Approved:

THEl ECONOMICS OF SUGAR HYDROGENLOYSIS

FOR THE COllMERCIAL PRODUCTION OF AN

AUTOMOTIVE ANT:IFREEZre

by

William H. Clarke

A Thesis Submitted tor Partial Fultillment

of the Requirements for the Degree ot

MASTER OF SCIENCE

in

CHEMICAL ENGINEERING

In Charge ot Investi~ation

Head of .Major Department

Dean ot Engineering Division

Director ot Graduate Studies

Virginia Polytechnic Institute

Blacksburg, Virginia

1948

INDEX OF CONTENTS

Page I. INTRODUCTION l

II. LITERA.TURE REITIFll 3

A. Requirements of an Ideal Antifreeze Compound 3

1. Major Requirements 3 2. Minor Requirements 3 3. Oils 4 4. Salts·· 5 5. Sugars 5 6. Alcohols 6 7. Methanol 6 8. Ethyl Alcohol 6 9. Glycerol 7

10. Ethylene Glycol 8

B. Production of. Ethylene Glycol 9

1. History 9 2. Conversion of Ethylene Dichloride to

Ethylene Glycol 10 3. Conversion of Ethylene Chlorohydrin to

Ethylene Glycol 11 4. Catalytic Vapor Phase Oridation of

Ethylene to Ethylene.Oxide 13 5. Procedure for Vapor Phase Oxidation of

Ethylene to Ethylene Oxide 15 6. Conclusions from Work of Oxidation of

Ethylene to Ethylene Oxide 16 7. Hydration of Ethylene Oxide to Ethylene

Glycol 18

o. Production of Propylene Glycol 20

l. Method of Production 20 2. History of Hydrogenation of Sugar 20 3. Conditions for the Hydrogenation of Sucrose 22 4. Production of Propylene Glycol from Sugar 28

INDEX OF CONTENTS (CONT'D}

Page D. Some Methods of.TestingAntifreeze Solutions 30

1. Free~ing Point 30 2. Viscosity • 32 3. Other Methods of Testing.Antifreeze Mixtures 33

III. EXPERIMENTAL 34

A. Purpose 34

B. Plan of Procedure 34

l. Literature Review 34 2. Experimental· Work 34 3. Economics of SUgar Hydrogenolysis for

Production of an Automotive Antifreeze 35

C. Materials 36

D. Apparatus 39

E. Method of Procedure 42

l. Introduction 42 2. Determination of Yield of Catalyst 42 3. Identification of Glycerol and Congeners

Fraction 44 4. Makeup of Propylene Glycol-Glycerol and

Congeners-Water Solutions 45 5. Determination of Viscosity and Specific

Gravity of Antifreeze Mixtures 46 6. Cooling Curve Data for Antifl.'eeze Mixtures 48 .7. · Plant Design and Location 49

F. Data and Results 50

l. Tables 2. Figures 3. laboratory and Semiworks Data 4. Theoretical Calculations 5. Material Balance 6. Equipment Specifications 7. Sample Calculations for Equipment Design

52 60 71 73 76 86

103

INDEX OF CONTENTS (CONT'D)

Page 8. Schedule of Operation ll3 9. Preconstruction Cost Accounting 115

10. Plant Location 125

IV. DISCUSSION· 126

A.. Results 126

1. Preparation and Yield of Copper Aluminate Catalyst 126

2. Identification of Glycerol and Congeners 127 3. Makeup of Propylene Glycol-Glycerol and

Congeners-Water Solutions 128 4. Viscosity Determinations 129 5. Freezing Point Determinations 130

B. Plant Design 132

1. Competition With Ethylene Glycol 132 2. Dasign 133 3. Cost Explanation 134

c. Recommendations 135

1. substitutes for sugar 135 2. Refinement of the Hydrogenation Process

Using Sugar (sucrose) 136 3. Higher Pressures 137 4. Inhibitors 137

D. Limitations 138

v. CONCLUSIONS 139

VI. SUMrflA.RY 141

VII. BIBLIOGRAPHY 143

VIII. ACKNOWLEDGMENTS 151

Table I Table II

Table III -Table·IV

Table V

Table VI Table.VII

Table VIII

Table IX Tabl9 X Table XI

Figure l Figure 2

Figure 3

Figure 4

Figure 5 Figure 6

Figure 7

Figure 8 Figure 9

Figure 10 Figure 11 Figure 12 Figure 13 Figure 14

Figure 15

TABLES

Yield of Produce~% by weight of sugar Typical Charge and Jiald in Hydrogenation of Sucrose by Lenth 3D.d DuPuis Catalyst Yields Calibration of Ostwald and Ostwald-Fenske Viscosimeters Identification of Glycerol and Congeners Fraction from Miner Laboratories Viscosity Data.for Antifreeze Mixtures Viscosity Data of 60 Per Cant sucrose Solution Data for Duhring's Plot of Antifreeze Wdxtures Cooling Curve Data for Antifreeze Mixtures Freezing Points with Corresponding Viscosities Estimate of Wholesale Selling Price

FIGURES

Calibration Curve for Ostwald Viscosimeter Calibration Curve for Ostwald-Fenske Viscosimeter Concentration Propylene Glycol-Glycerol vs. Kinematic Viscosity . Concentration Propylene Glycol-Glycerol vs. Absolute Viscosity Temperature vs. Absolute Viscosity Temperature vs. Absolute Viscosity 60% sucrose Solution Duhring's Plot Propylene.Glycol-Glycerol Water vs. Temperature 60% sucrose Solution Temperature vs. Specific Gravity Concentration Propylene Glycol-Glycerol vs. Specific GraVity Cooling Curves Freezing Point Curves rflB.terial Balance Flow Sheet Qualitative Flow Diagram Calculation of Plates for Bubble Cap Fractionating Column Plant Layout

Page 26

29 52

53

54 55

56.

57 58 59

124

60

61

62

63 64

65

66 67

68 69 70 84 85

110 114

I. INTRODUCTION

The growth ot the automotive industry during the past half

century has commanded the attention of every one, and many times

chemistry has been able to further its growth through timely dis-

coveries. The production of cheap gasoline, special motor fuels,

the introduction of spacial alloys, and the creation of the nitro-

cellulose lacquers constitute but a few examples of the recent ac-

complishments. Another problem of this industry has been to pro-

vide a satisfactory antifreeze to take the place of water during

the freezing months. With the current estimate of 35 million

automobiles of all classes in use at the present time, it is a

challenge to the chemist to discover and to the chemical manu-

facturer to produce at a reasonable cost a satisfactory antifreeze

to meet the specifications of the automotive engineers.

At present, there are principally two antifreeze compounds,

one having an alcohol base, and the other having a glycol base.

It is very obvious that alcohol solutions possess lower boiling

points from that of water, and these solutions lose their non-

freezing properties during continued use through the evaporation

of alcohol. As regards odor, inflanmability, and destructive ef-

fect on certain types of automotive finishes, alcohol fails to

meet the most exacting teats. Ethylene glycol possesses all

-2-

advantages of alcohols and in addition does not lose its anti-

freeze properties by evaporation. Furthermore, extended use of

these solutions does not alter the ethylene glycol through de-

composition or change in structure. At the end of the winter

these solutions, unless dissipated through leakage or other

mechanical losses, will be fully as effective against freezing

as when introduced.

Since the demand for ethylene glycol antifreezes is tar in

excess of the supply, competition is practically nil. Because

of this, the price has been maintained at a consistently high

level.

The purpose ot this thesis is to determine if it is eco-

nomically feasible to produce an antifreeze consisting of

propylene glycol and "glycerol and congeners" by the catalytic

hydrogenation of sugar.

-3-

·II. LITERATURE .REVIEW

Requirements of an Ideal Antifreeze Compound

It would not seem to be a difficult matter to produce an

ideal compound which would prevent water from freezing ill auto-

mobile radiators under ordinary winter conditions. However, the

chemists have given this matter serious consideration for a number

of years, and it is now generally accepted that the problem is far

from simple. In order to appreciate the complexity of the problem

it is necessary only to review the requirements of an ideal anti-

freeze as given by Keyes(44 ).

Major Requirements.

1. It should prevent freezing of the cooling medium

at all ordinary temperatures.

2. It must not· injure by corrosion any metal parts

of the engine or radiator and must not soften or

deteriorate the rubber connections.

3. There must be an adequate supply at a reasonable

price.

4. It should be stable.

Minor Requirements.

1. It should have a low viscosity at all working

temperatures.

-4-

2. Water solutions should have a high specific heat

and a high heat conductivity.

3. It should not materially lower the boiling point

01' solution.

4. It should not produce an unpleasant odor.

5. It should not attack automobile finishes.

6. It should keep its antifreezing property tor a

long period of time (low vapor pressure).

7. It should have a low coefficient of expansion. {44) . Keyes using these specifications reviewed the various

antifreeze compounds that had been used and pointed out the good

and bad characteristics of each.

Oils - The various hydrocarbons, notably kerosene, have been

used to replace water as a cooling medium, especially in tractors.

The general disadvantages of oil are as follows:

1. High viscosity at low temperatures.

2. Low specific heat and low heat conductivity.

3. Oils, especially kerosene, soften and dissolve

rubber.

4. Leaks permit oil to come through, and the vapors

are dangerous because they are inflammable.

5. High boiling points ma.y cause overheating of the

engine.

-5-

Salts - Calcium chloride was for many years·the popular

antifreeze compound, possibly because it not only depressed the

freezing point of water to a marked degree, but it also stayed

in the system and was not lost by evaporation. It was cheap,

easily obtained, and there was an adequate supply. Its real

fault, however, was that, in common with all chloride salt so-

lutions, it would corrode common metals. It was thought for a

time that the addition of chroma.tea, such as sodium chromate,

would prevent this corrosion by rendering the material passive.

This addition of chromate helped in some cases, but fell down in

others, especiall_y when parts were made of aluminum. Magnesium

chloride was found to be even more corrosive than calcium chloride.

Not only was trouble experienced with corrosion, but when leaks

occured, a tine salt spray would appear and have a tendency to

short circuit spark plugs and ignition wires. There was also a

tendency for the salts to crystallize out and clog pumps and cut

down the heat transfer in the radiator.

sugars - Honey, glucose, and various sugar airups or waste

sugar liquors have been suggested as antifreeze compounds, and

some tests have been ma.de. Unfortunately, the sugar molecule is

too large for this purpose, and the freezing point lowering is

therefore relatively small. The concentrated solutions, more-

over, are highly viscous.

-6-

Alcohols "'." Considering the problem from: a· .fundamental . stanq.-

point, a compound should be chosen that, first of all, is com-

pletely miscible with water at all temperatures and in all con-

centrations • .Also a compound would be chosen that would not only

lower the freezing point of the water but would be no more cor-rosive than water. In other words, a compound -would be chosen that resembled water as closely as possible. The alcohols re-

semble water more closely than any other class or compounds, and

methanol stands at the head of the list.

Methanol - It not only gives a marked lowering of the freez-

ing point, a greater lowering than other alcohols, but it is ab-

solutely non-corrosive in the pure state. Thanks to modern de~

velopments in synthetic chemistry, it can be obtained,from carbon

monoxide and hydrogen by direct synthesis in unlimited quantities

at reasonable prices. Unfortunately, however, it has a hiBh vapor

pressure in water solutions and a low boiling point, and the fumes.

from a boiling solution are hanni'ul to the ordinary individual.

Modern automobile radiators are designed to give adequate coolinB,

and little difficulty is experienced with boiling radiators.

Ethyl Alcohol - Much has been said for and against denatured

ethyl alcohol as an antifreeze. Some of the advantages of ethyl

alcohol are as follows:

-7-

· 1. The ability to reduce the freezing point

of wate~ is adequate when compared with

other antifreeze compounds.

2. It is no more corrosive towards metals or

rubber than water.

3. It boils without decomposition.

4. Its water solutions_have a low viscosity

. even at low temperatures.

5. It ia sold at·a moderate price, easily ob-

tained, and produced in adequate quantities.

Glycerol - Some of the advantages which make glycerol more appeal-

ing are:

1. Its vapor :P_ressure in water solutions is

low. There is very little loss due to

· _ evaporatiqn •.

2. It is odorless.

Some of its disadvantages are:

l. It has a tendency to soften rubber, there-

fore necessitating a replacement of hose

connections.

2. It has a high viscosity at low temperatures,

therefore necessitating forced circulation.

3. There is a shortage and its initial cost is high.

-8-

Ethylene Glycol - Ethylene glycol, which from a chemical

standpoint, is a cross between glycerol and ethyl alcohol, has

interesting properties. Some of its advantages are:

l. It has a low vapor pressure up to 45% by

volume, thus resembling glycerol.

2. It is no more corrosive towards metals

than ethyl alcohol or glycerol.

3. Unlike glycerol, it has only a slightly

greater viscosity at low temperatures

than alcohol solutions.

4. It does not appreciably change the boiling

point of water.

5. Water solutions of it have a high specific

heat and high conductivity.

6. As a synthetic product made from cracked

petroleum gases, it can be produced in

large quantities.

Some of the disadvantages are:

l. It has a tendency to soften rubber, there-

fore necessitating the replacement of hose

connections.

2. It has a high initial cost.

-9-

Production of Ethylene Glycol

History. (30) .

Ellis stated that the glycols or dihydric alco-

hols derived from the olefins contain two hydroxyl groups attached

to adjoining carbon atoms in the chain and are referred to as

1,2-glycols. Although ethylene glycol, the simplest and most im-

portant member of the series, was discovered as early as 1857 by

Wurtz, this material was merely a laboratory product until about.

1925. The commercial development and large scale production or

the glycols and especially of ethylene glycol, is undoubtedly due,

in a large measure, to the availability of large supplies of cheap

. ethylene as a by-product in the cracking of higher petroleum

fractions.

The conversion of olefins into glycols is exemplified by

the following reaction:

0~ CH20H /I +¾0+0 _,.I. . 0~ OH20H

Crawley{ 2S) stated that the economical production of ethylene

glycol by the methods. now used depends on cheap sources of ethylene

and chlorine. The ethylene is either produced from ethyl alcohol

or separated from the unsaturated gases produced in the cracking

of petroleum oils. For large scale production of ethylene glycol

three principal processes have been used industrially, namely

-10-

(1) the hydrolysis of ethylene dichloride, (2) the hydrolysis or

ethylene chlorohydrin, end (3} ·the hydrolysis of ethylene oxide •.

Briefly, the most common of these according to CrawleyC28) is the

co~version of ethylene to ethylene chlorohydrin with hypochlorous

acid. The monochlorohydrin is then hydrolyzed with a weak alkali

such as sodium bicarbonate. The product of this hydrolysis is

ethylene glycol, which must be concentrated by steam distillation.

Conversion of Ethylene Dichloride to Ethylene Glycol. Y..atter<48Ha3)

proposed to hydrolyze ethylene dichloride by heating it in a

closed vessel with an aqueous alkali bicarbonate solution in the

presence of sheet copper as a catalyst. For example, 100 parts by

weight of ethylene dichloride were heated nth a solution or 180

parts of sodium bicarbonate in 1900 parts of water in a closed

vessel for six hours at 130-140°c, the liquid being stirred con-

tinuously and a sheet of copper being used as a catalyst. After

cooling, the liquid was neutralized, concentrated, and fractional-

ly distilled. In this way about 50-55 parts by weight of glycol

were obtained. It was shown that aldehydes began to b_e formed in

quantity if the hydrochloric acid content of the liquid exceeded

1%. A method of autoclave treatment was therefore adopted, which

included the addition of alkali at intervals to neutralize excess

HCl.

-11-

Conversion ·of Ethylene Chlorohydrin to Ethylene Glycol. Eilis{ 30)

found that a number of processes used ethylene chlorohydrin as the

starting material tor the manufacture-of ethylene glycol. The hy-

drolysis of ethylene chlorohydrin was affected for the most part,

with aqueous solutions of weak alkalies, such as sodium bicarbonate

according to the reaction:

CH20H CH20H I + Ne.H003 -+- I + NaCl + CO2 C¾Ol CH20H

The use of anhydrous caustic alkalies resulted in the for-

~tion of olefin oxides, whereas more dilute caustic alkalies

· promoted the formation of tarry- non-distillable materials. (25) · Brooks stated that when aqueous solutions of ethylene or

propylene chlorohydrin were heated with aqueous sodium bicarbon-

ate, marked evolution of carbon dionde ensued at about 65° c. By refluxing w1 th sodi~ bicarbonate, yields of 44-48% of the

theoretical were obtained, the remainder being converted into

olefin oxides which, on account ot their volatility, were lost.

By carrying out the reaction in a closed autoc_lave at 105-110°0

tor two hours, yields of ethylene glycol of 90% were obtained.

The remaining 10-~ was converted into tarry material which could

not be distilled without decomposition even under 10 mm pressure.

Calcium and magnesium hydroxide were not satisfactory for the

hydrolysis as they firmly retain the glycol.

-12-

Sa~ders and Wignall(Gl){ 30) described a continuous process

for the vapor phase hydrolysis of. ethylene chlorohydrin to

ethylene glycol or ethylene on.de by a solution of sodium carbon-

ate or sodium hydroxide respectively•. At the bottom of a scrubber

tower lagged and filled uith_packing, a steady stream of steam

entered and was adjusted so t!18.t it was exactly sufficient to vol-

atilize and carry upwards the ethylene chlorohydrin contained in

the solution. The current of steam laden with chlorohydrin tra-

versed a fractionating column and passed·away at the top, carry-

ing 95% of the chlorohydrin contained in the crude solution. The

vapor then passed down a well-lagged pipe to the bottom of a

second packed ·tower. The admixed ethylene chlorohydrin vapors

and steam ascending this tower met a down-flowing solution of

sodium carbonate (if ethylene glycol was to be obtained) or caustic

soda (if ethylene oxide was desired) admitted in the correct pro-

portions. The _ethylene chlorohydrin was hydrolyzed to the glycol

with concomitant production of salt, while steam, carbon dioxide,

and volatile unhydrolyzable impurities passed away to a condenser.

The ethylene glyc?l dissolved in the salt solution and was carried

down to the bottom of the tower and then flowed from the trap

direct to a desalter. When ethylene oxide was formed, it passed

away at the top of the tower and was dried and collected.

-13-

Fieser and Fieser( 33} maintained that the preparation of

ethylene glycol from ethylene chlorohydrin was an improvement

because ot the greater rate of hydrolysis, and because, since

only half the amount of soda is required, separation ot sodium

chloride from the product was facilitated. This operation was

avoided completely by converting the chlorohydrin into ethylene

oxide with either caustic or soda lime which was rapidly hydro-

lyzed by a dilute acid, such as hydrochloric or sulfuric.

Catalytic Vapor Phase Oxidation of Ethylene to Ethylene

Oxide. The development of a suitable catalyst and the discovery

of the best method of applying it have been the aims of many in-

vestigators. McBee, Haes, and WisemanC50) stated that ot the

numerous materials tested and reported at least partially suc-

cessful, silver and certain of.its compounds seemed to be the

most desirable catalysts yet found. This metal was used either

alone or in alloys. More commonly, however, a silver compound,

such as the oxide, nitrate, carbonate, chloride, or cyanide,

was used to coat a suitable inert carrier.

Almost any inert material which provides a large surface

area can be used as a catalyst carrier. There is evidence, how-

ever, that both the.chemical nature and the physical state of

the carrier had an appreciable effect·upon the activity of the

-14-

catalyst • .Among the catalyst carriers which were tried were

pumice, charcoal, activated carbon, silica gel, silica stone,

alundum, and corundum. Of these materials, it appeared that

the most satisfactory consisted of some form of aluminum oxide.

It was shown that the addition of small quantities of mod-

ifying agents called "promotersff often had a desirable effect

on the silver type of catalysts. Such a promoter was usually

an oxide or hydroxide of an alkaline earth metal. There seemed

to be little doubt but that catalysts so modified were more

rugged and durable and possessed~ more active and longer life

than similar untreated ones.

During the oxidation of ethylene, the products which were

obtained depended upon the temperature and the manner in which

the oxidation was performed. The products formed in the cata-

lytic process were thought to be a result of two competing re-

actions.

Since excessive temperatures favored the formation of carbon

dioxide and water rather than ethylene oxide, it was essential

that during the operation the catalyst be maintained within narrow

temperature limits. The more the formation of carbon dioxide and

-16-

water was suppressed the more desirable the process became, both

from the standpoint of economy of operations and of materials.

A common method for controlling the temperature of an exo-

thermic reaction was to surround the reactor with a material such

as.mercury or molten salt. By suitable regulation of this bath

. it was possible to maintain the catalyst at the desired tempera-

ture.level.

Another method widely reported as useful tor controlling

such a process was the introduction ot a diluent along With the

reactants. Of these nitrogen, carbon dioxide, air, and steam

were the most common.

A third and interesting method of controlling the reaction

was the use of substances called anticatalysts. An anticatalyst

is a specific substance which when added to the reactins gases

in very amall amounts, suppresses the formation of carbon dioxide

and water and causes the catalyst to be more efficient in the pro-

duction of the olefin oxide. Ethylene dichloride serves as a good

example of such a material.

Procedure for Vapor Phase Oxidation of Ethylene to Ethylene

Oxide. McBee, Haas, and Wiaeman(oO) passed the reactants through

flo\'illleters, mixed them in a catalyst chamber. The gases from the

reactor passed through a series of absorbers. The first of the

·-16-

absorbing tubes contained 25 ml. of O.lN HCl saturated with mag-

nesium chloride. The effluent gases passed through the first

three absorbers for a definite time interval. At the end of

this period the gases were then passed through another set of

.absorbers containing 1N ECl saturated with magnesium chloride

to catch any of the ethylene oxide from the exit gases. To de-

termine the amount of ethylene oxide produced, it was necessary

to remove the liquid from the absorber to titrate the unreacted

acid with standardized ·sodium hydroxide.

Conclusions from Work on Oxidation of Ethylene to Ethylene

Oxide. Francon( 35} reached the following conclusions from his

work on the preparation of ethylene oxide from ethylene.

1. The optimum air-ethylene ratio was 10.

2. The optimum temperature was 375°c.

3. The injection of water reduced the pro-

duction of both ethylene oxide and carbon

dioxide but the latter to a greater extent.

4. · The formation of carbon dioxide was not

due to the oxidation of ethylene oxide

but to the direct oxidation of ethylene.

5. At the optimum rate of flow, reducing the

air:· ethylene ratio (below 10) rapidly

-17-

reduced the fonnation of ethylene oxide

while that of carbon dioxide tended to

stay constant or increase • ...

6. Reducing the temperature below 375°0

rapidly reduced.the- forzmtion of ethy-

lene oxide and had but little effect on

that of carbon dioxide; _ increasing it

above 375°0. accelerated both reactions,

the formation qf carbon dioxide increa~-/ ing more rapidl~ than that of ethylene

oxide.

7. Increasing the pressure up to 50 kg/cm2

decreased the production of ethylene

oxide and increased the production of

carbon dioxide because of partial com-

bustion of the ethylene oxide.

McBee, Haas, and Wiseman<5o) found from their oxidation of

ethylene to ethylene oxide:

l. As the catalyst aged, it became lass ef-

ficient and the temperature of operation

of the catalyst had to be raised if maxi-

mwn efficiency for the production of ethy-

lene oxide was to be maintained.

-18-

2. A high air-ethylene ratio was most favor-

able for obtaining both good yields and

conversion.

Hydration of Ethylene Oxide to Ethylene Glycol. Ellis{ 30)

stated that the conversion of ethylene oxide into ethylene glycol

by hydrolysis with water was easily carried out by heating in a

closed vessel. The reaction was accelerated by the addition of

_mineral acids, especially sulfuric acid. In large scale practice

the heat evolution (about 25 kg/mole) must be considered. The

hydration of ethylene oxide was affected according to the reaction:

CH2 CH20H '' -+ 0 + H20 -r I CH2 C¾OH

in the presence of dilute sulfuric acid as a catalyst.

Matignon, Moureau, ·and Dode(49 ) found that when ethylene

oxide was passed into aqueous ethylene glycol containing 0.5%

sulfuric acid at 90-5°c, there was formed a mixture of ethy-

lene, diethylene, triethylene, and tetraethylene glycols. The

proportions in which the various glycols were formed were main-

ly dependent on the ratio of water to ethylene oxide. Thus,

with one mole of ethylene oxide, the following results were ob-

tained:

Mols Water

% ethylene glycol

10.5 4.2 2.1 0.61

82.3 65.7 47.2 15.70

% diethylene glycol

% triatbylene glycol

% tetraetbylene glycol

% higher glycols

-19-

12.7 · 27.0 34.5 26.00

2.3 13.0 19.80

0.3 19.00

14.50

Thus, in every case the yield was about 95%. The tempera-

ture had little effect on the course of the reaction, experiments

at ?o0c and 5o0 c gave practically the same mixtures and yields as

those at 9o0 c. The acidity of the solution also had little in-

fluence. Trials using 0.5, 2, 2.5, and 5% sulfuric acid gave

similar results except that in the case of 5% acid the yield was

only 88%.

-20-

Production ot Propylene Glycol

Method ot Preparation. Ellis( 3l) stated that prop~lene

glycol (propane - 1,2-diol CH3CHOHCH20H) is obtained from either

or the propylene chlorohydrins by treatment with sodium bicarbon-

ate solution under pressure. The production of this and other

1,2-glycols can be conducted by the methods previously discussed

in the section on ethylene glycol. The method of the hydrolysis

ot the olefin oxide is being used industrially to produce propy~

lene glycol. There is one method of making propylene glycol which

is not used in making ethylene glycol: this is the hydrogenation

of sugar in the presence of a catalyst.

History of Hydrogenation ot Sugar. Stenge1(64) stated that

this hydrogenation process is termed "hydrogenolysis" in those

instances involving cleavage of a carbon-to-carbon bond in ad-

dition to hydrogenation. By this hydrogenation method, for ex-

ample, sugars, such as dextrose or sucrose, have been transformed

into ma.nnitol, sorbitol, glycerol, propylersglycol, and other pro-

ducts in varying proportions.

The earliest reference to the reaction of sugars with hy-

drogen, according to Lenth and DuPuis<46),~as made by Ipatiett< 43)

who produced the corresponding sugar alcohols from several mono-

saccharides by treatment with hydrogen at 84 atmospheres and

-21-

between 100-135°C. Since then, many( 26H45 }(48)(51)('75}('76)

have investigated this reaction and patents have been issued.

The outstanding point in connection with all of _the patenta

is that the reactions were universally carried out in aqueous

solutions, although in the usµal broad language of patents oc-

casional mention of the possibility of using alcoholic solvents

was made. However, there is no indication that such solvents

were actually employed until Zartman and Adkins(?G) published

on the hydrogenolysis of sugars in anhydrous ethyl alcohol so-

lutions. Their operating-conditions were somewhat severe in

that they used pressures of 300 atmospheres. Consequently,

any glycerol that might have been produced was probably further

reduced to propylene glycol. In any event, they were the only

investigators who did no:t claim the production of large-_ quanti-

ties .of glycerol. While it may be argued that the use of an

alcoholic medium instead of an aqueous one inhibits the formation

of glycerol, Lenth and DuPuis( 4S) indicated little or no differ-

.ence in the amount of glycerol fanned between the tVTO solvents

under similar temperature and pressure conditions. Their.work

further showed that there is considerably less decomposition to

tarry substances when the alcoholic vehicle is used. Experiments

indicated that a cleaner product resulted from the use of an al-

coholic vehicle than from the use of water; consequently, a study

-22-

was made to establish conditions for the reaction in methanol.

Lenth and DuPuis( 4G) found ,that the maximum conversion_ of sugars

to polyhydric alcohols of low molecular weight occurs at pressures

less than 2000 lbs/sq. in. and et temperatures of 225-250°0. in

presence of a specially prepared copper-aluminum oxide catalyst.

It was also found that refined cane sugar, refined beet sugar,

and dextrose may be processed interchangeably. Of these, re-

. fined cane sugar was the most reactive. The other grades of

sucrose required higher catalyst and promoter concentrations,

and dextrose required a reduced form of the copper-aluminum oxide

catalyst.

Conditions for the Hydrogenation of Sucrose. Stenge1( 64)

found that al.though there have been numerous catalysts proposed

for utilization in this process, these catalysts have had vari-

ous disadvantages, such as high cost, tendency to become poison-

ed by c~lorides and other substances, and inability to operate

successfully with crude carbohydrate materials such as molasses •.

There are, principally three catalysts that tend to meet the above

specifications and produce high yields of polyhydric alcohols.

The first is one that was used by L~nth and DuPuis(46 ), a copper-

aluminum oxide compound. The other two are the cupric hydroxide

catalyst and the co~pr~cipitated cupric oxide and calcium fluoride,

-23-

both of which were perfected.by Stengel and Maple(G5)_ These

catalysts comprise copper substances and activating agents which

are.substantially insoluble in the medium in which the reaction

is effected.

Stengel and .Maple(G5} indicated that when employing cata-·

lyats in the hydrogenolysis of sugars it was not necessary to

utilize a completely anhydrous medium. Thia was particularly

advantageous when molasses, or some other commercial source of'

carbohydrates, which normally.contain water, were·employed. How-

ever, it was preferred to maintain the water content of' the re-·

action mixture as low as possible with the particular·source of

carbohydrate and preferably below approximately 30%-by volume,

based on the total liquid in the initial reaction mixture.

stengel(G4t} also stated that if' the copper hydroxide was allowed

to dry after precipitation and before utilization in the hydro-

genation reaotio~, its catalytic activity was reduced to such an

extent that it was almost worthless f'rom a commercial viewpoint.

The diminishing of the catalyst activity took place, but to ·a

much less extent, if the wet precipitate was allowed to stand

for a long period of time before use. For this reason it was

undesirable to employ a precipitate that had stood longer than,

a week, and so preferably a freshly precipitated material should

-24-

be used. A desirable process fo~ providing freshly precipitated

copper hydroxide in the reaction mixture was to effect the pre-

cipitation in the reaction mixture itself. For example, if it

was proposed to subject molasses in methanol solution to hydro-

genolyais, a solution of copper sulfate was added to the molasses-

methanol mixture and caustic alkali was added to,precipitate the

cupric hydroxide directly in the reaction mixture.

Stengel(G 4) found. that it was necessary with the three cata-

lysts mentioned above to maintain alkaline conditions throughout

the reaction. If the reaction mixture was allowed to become

acidic prior to the conclusion of the reaction, the yields were

seriously decreased. Since acidic products may be formed from

sugars or other polyhydric compounds during the course of the

reaction, sufficient alkali material must be added to neutralize

these acidic products and maintain an alkaline reaction· at all

times. This was most conveniently effected by introducing a

large excess of alkali into the initial reaction mixture.

Stengel(S 4 ) indicated that the temperature was suitably

maintained constant through the reaction, or an initial reaction

period at a lower temperature was followed by a secondary re-.

action period at a higher temperature. The time and temperature

of reaction depended primarily on the ratio of products desired.

-25-

In general, higher temperatures favored the production of lower

molecular weight products, whereas lower temperatures favored

the production of higher molecular weight products. For the

production of propylene glycol as the major product a tempera-. .

ture of 230-240°c was more desirable. In this temperature range

a considerable amount of glycerol was formed in addition to the

propylene glycol together with a certain proportion of higher

molecular weight polyhydric alcohols. t~en operating at lower

temperatures, 150-20o 0 c, the major products constituted the

higher alcohols together with some glycerol and propylene glycol.

The effect of temperature on the yield is shown in Table I. The

minimum reaction time for optimum yields varied in general in-

versely with the temperature. However, considerably shorter

reaction times than required for the optimum yield were employed

without reducing the yield below the limit of practical utility.

Also, the reaction mixture was maintained at the reaction tem-

perature for considerably longer periods than the necessary

minimum time without seriously affecting the yields. The best

reaction was usually carried out at 230-240°0 for 3-4 hours.

About half of this period was required to raise the temperature

to the point at which the reaction started. The actual duration

of the reaction was therefore about 1.5 hours.

-26-

_ TABLE I

EFFECT OF TEMPERATURE ON YIELD .IN HYDROGENATION OF SUGAR*

Temperature Propylene Glycerol oc Higher

Alcohols

150

175

190

210

230

250

Glycol

1.2

3.1

3.9

9.9

27.9

38.8

1.6

4.4

27.4

45.3

28.4

73.6

95.9

63.7

43.0

o.o 0.0

I . - - . - -Contained a small percentage of water

Total

76.4 I

103.3

7S.7

80.1

72.2

67.2

*Stengel, L. A. and Maple, F. E. Catalyst and Process tor Producing Polyhydroxy Compounds. U.S. 2, 381, 316 August 7, 1945.

.;.27-

Stengel and Maple(G5) stated that a wide range of hydrogen

pressure was utilized when carrying out the process without sub-

stantially affecting the reaction. The optimum pressure in any

case depended to some extent upon the nature of the material

being reacted and the solubility of hydrogen in the reaction

medium. It was generally sufficient to consider the total

pressure maintained in the reaction vessel, and it was found

that this pressure should preferably be substantially above

1000 lbs/sq.in. and suitably from 1500-2000 lbs/sq.in. If the

reaction vessel was adjusted to such a pressure before heating,

an increased pressure resulted during heating and prior to

hydrogen absorption, after which the pressure was adjusted

either continuously or intermittently to the initial value.

Pressures above 2000 lbs/sq.in. were employed, but satisfactory

results were obtainable with the range 1500-2000 lbs/sq~in. and

since this condition constitutes the usual range of pressure

for hydrogen available commercially in cylinders this consti-

tuted an advantageous pressure range for carrying out the pro-

cess. The agitation should be sufficient to maintain adequate

contact between the reacting materials and to prevent local

overheating of the polyhydroxy compounds which might result in

caramelization or charring.

-28-

Production of Propylene Glycol from sugar. Len.th and

DuPuis( 4G) obtained the following data from experimental work

on the production of propylene glycol from sugar. A typical

charge and yield in the hydrogenolysis of sucrose is shown in

Table II.

-29-

TABLE II

TYPICAL CHARGE .AND YIELD IN HYDROGENA.TIOif OF SUCROSE

BY LENTH .AND DUPUIS*

CHARGE.

sugar, lb.

Methanol (anhydrous), lb.

Copper-aluminum oxide catalyst, lb.

Soda ash, lb.

Initial hydrogen pressure, lb/sq.in.

YIEID

Temperature, 0c ..

Operating pressure, lb/sq.in.

Agitator speed, rpm

Yield% by weight of sugar

10

10

0.75

0.04

900

239

1500

126

Total nonvolatile at 100°0 75.8

Propylene glycol 39.5

Glycerol and congeners 25.1

Total distillable polyhydric alcohols 64.6

Residue 11.0

Hydrogen consumed

Moles/mole sugar

Standard cu.ft./lb. sugar

5.7

6.45 *Lenth, c. w. and DuPuis, .R. N. Polyhydric Alcohol

Production. Ind. Engr. Chem. ~' 152-7, (1945)

-30-

Some Methods of Testing .Antifreeze Solutions

Freezing Point. Previous investigators did not use identi-

cal methods for detennining the freezing point, but all of their

methods depended upon the observance of either the appearance or

disappearance of crystals, thus including the element of human

error.

The freezing point{l) has been referred to as that tempera-

ture in the cooling process at which the crystals begin to form.

'!he temperature at which the mass became solid was several de-

grees lower than the freezing point of dilute solutions and 10-

1500 lower for more concen~ratad solutions. Some investigators( 53)

reported the flow point which was the temperature at which the

slush of ice crystals and liquid ceased to flow through a¼ inch

pipe.

Curme and Young(29) and Olsen, Brunjes, and Olsen<53 ) used

the appearance of the first crystals as the freezing point of

the mixture. They also used the Beckmann method, which consisted

essentially in cooling the melt below the freezing point, inocu-

lating with the proper kind of crystal, stirring, and noting the

maximum temperature to which the thennometer rose. According to

Skaw and Saxton( 62} these freezing points obtained were usually

low owing to two causes: (1) change in c~mposition of the liquid

-31-

due to the solid froze~ out and (2) the thermometer lag. They

then set up a method which-was used by several other investi-

gators(27)(32). The temperature at which the crystals disap-

peared was taken as the freezing point •. The method which was

used was essentially cooling the solution approximately 5°c be-

low the point of crystal formation in a mixture of solid carbon

d~oxide and methanol, removing the container from the freezing

mixture, inserting it in_ a slightly precooled bath and allowing

it to warm with constant.stirring .until the last of the crystals

disappeared. The temperature at this point was recorded.as the

freezing point. This method tended to give higher temperatures

than the method of Curme and Young<29 ) and Olsen, Brunjes, and

Olsen<53 )_

Findlay( 34 ) used the cooling curve·method as a means of de-

termining the freezing points of binary mixtures. This method

should be applicable in determining the freezing points of anti-

freeze mixtures. The method consisted essentially of cooling a

binary mixture in a cooling medium and recording the temperature

or the mixture at a regular time interval. When the mixture

reached the temperature at which the crystals began to form,

the temperature remained constant until all the heat of crystal-

lization bad been taken away. The temperature then.began to

-32-

drop after the constant level.was obtained. This constant tem-

perature was used as the freezing point of.the mixture.

Viscosity. The viscosities< 22 ) of antifreeze mixtures were

usually determined by an Ostwald viscosimeter or some modifica-

tion of an Ostwald. This type of viscosimeter has been cali-

brated against such standard solutions as sucrose and glycerine

whose viscosities were known. The kinematic viscosity, Vihich

is the ratio of the absolute viscosity to the specific gravity

at the same temperature, has been calculated from the known

absolute viscosities of the standard solutions and their knom

specific gravities. With the time of flow for each mixture and

its corresponding kinematic viscosity a calibration curve was

plotted •. The viscosity of any mixture was then determined by

taking the time of flow and obtaining from the calibration curve

a corresponding kinematic viscosity. Since the specific gravity·

of the solution was determined for each mixture at the tempera-

ture of the experiment, the absolute viscosity was calculated

from the kinematic viscosity.

Perry and Smith<55 ) state that Duhring's rule was appli-

cable to viscosity data: "If the temperature tA at which liquid

A has a given viscosity is plotted against the temperature tB

at which the viscosity of liquid B has the same val.ue, the points

-33-

lie nearly on a straight line. This fact was useful for ex-

trapolation and interpolation of meager data. The best results

were obtained from two liquids which were chemically similar."

Other Methods of Testing .Antifreeze Mixtures. Corrosion

is a big factor in determining the suitability of an antifreeze.

The literature did not reveal any specific method by which the

corrosive properties of an antifreeze were determined. All anti-

freezes contain some form of an inhibitor which prevents cor-

rosion.

Foaming is another major problem which must be considered

in ths evaluation of an antifreeze mixture. Almost all perma-

nent antifreezes contain some agent which prevent_s 1'.oaming.

Other tests which are used in determining the suitability

of an antifreeze are stability; odor, volatility, boiling point,

specific heat, thermal conductivity, and infle.nmability. The

literature revealed no standard procedures for these tests.

-34-

III. EXPERIMENTAL

A. Purpose

The purpose of this thesis is to determine if it is eco-

nomically feasible to produce an antifreeze consisting of propy-

lene glycol and "glycerol·and congeners"-by the catalytic hydro-

genation of sugar.

B. Plan of Procedure

Literature Review. A review of the literature was made to

determine specifically the requirements of an ideal automotive

antifreeze; a study of previously used antifreeze compounds,

their advantages and disadvantages; a study of the methods of

production of ethylene glycol and propylene glycol; and the pro-

cess of the catalytic hydrogenation of sucrose.

ExJ]erimental V/ork. Mixtures of propy~ene glycol - glycerol

and congeners - water were made up and their suitability for use

as an antifreeze was found by determining the freezing point and

viscosity of the mixtures. The economic feasibility of the cata-

lytic hydrogenation of sugar for the production of an automotive

antifreeze was detennined by using the data of Lenth and DuPuis{46)

-35-

and Stengel and Maple( 55} and experimentally obtained data on

catalyst yields.

Economics of SUgar Hydrogenolysis tor Production of an

Automotive Antifreeze. After having compiled the necessary (46). .

data of Lenth and DuPuis and Stangel and Maple<65) and the

data obtained experimentally, consideration was given the fol-

lowing preliminary engineering studies in detennining the eco-

nomic feasibility of the process:

1. Material and heat balances.

2. 1faterial balance flow sheet.

3. Q.ualitative flow diagram.

4. Tentative specifications of machinery.

5. Operation schedule.of equipll_l-ent.

6. Plant layout.

7. Tentative specifications of materials.

8. Preconstruction cost accounting.

9. Plant location.

-36-

C. . Materials

The materials used in this investigation were as follows:

l. Cupric Sulfate. Fine crystal, c. P., Lot #36 D.

Used to prepare copper aluminate catalyst.

General Chemical Co., New York, N. Y.

2. Aluminum Sulfate. Granular, Technical Lot No.

73040. Used to prepare copper aluminate catalyst.

J. T. Baker Chemical Co., Phillipsburg, N. J.

3. Soda Ash. Powder, Technical. Used to prepare

copper aluminate catalyst. Phipps & Bird, Inc.,

Richmond, Virginia.

4. Propylene Glycol. N. F. grade, Lot S-7128 RllJ.

Used to prepare antifreeze mixtures. Carbide and

Carbon Chemicals Corporation, South Charlestown,

west Virginia.

5. Ethylene Glycol. Technical grade, Lot S-7134 EPS.

Used to prepare antifreeze solutions. Carbide and

Carbon Chemicals Corporation, South Charlestown,

West Virginia.

6. "Glycerol and Congeners". Used to prepare anti-

freeze solutions. Actual fxaction obtained by · (46) Lenth and DuPuis • Donated by the Miner Labora-

tories, Chicago, Ill.

-37-

7. sulfuric Acid. Technical, 20% Fuming, Lot 122844.

Used in determining glycerine content in "glycerol

and congeners·. 11 J. T. Baker Chemical Co. ,

Phillipsburg, N, J.

8. Silver sulfate. Reagent grade, Code 2181, Lot 17.

Used in determining glycerine content in "glycerol

and congeners." General Chemical Co., New York,N.Y.

9. Potassium Dichromate. Technical, Lot 5640. Used

in determining glycerine content in "glycerol and

congeners". J. T. Baker Chemical Co., Phillipsburg,

New .Jersey.

10. Potassium Iodide. Crystals. P-106, Cat. No. P-256,

Reagent grade. Used in determining glycerine con~

tent in 1tglyoerol and congeners". Eimer· and Amend,

New York;, N. Y.

11. Sodium Thiosulfate. Crystals, ACS Std., Lot 122845.

Used in determining glycerine content in "glycerol

and congeners" • .r. T. Baker Chemical Co.,

Phillipsburg, N • .T.

12. starch. Potato. Used in making indicator solution

for determining glycerine content in ~glycerol and

congeners". Phipps and Bird, Inc., Richmond, Va.

--38-

13. Glycerine. C. P., No. 78202. Used in calibrating

viscosimeters. Colgate, Palmolive, Peet Co.,

Jersey City, N. J.

14. SUgar. Refined, Table grade. Used in calibrating

viscosimeters.

15. Salt. Table grade. Used in preparing low tempera-

ture bath for determining viscosities of antifreeze

mixtures and for preparing freezing mixtures.

16. Ice. Used in preparing low temperature bath for

dete:rmining viscosities of antifreeze mixtures and

for preparing freezing mixtures. . .

17. Isopropanol. 99% isopropyl alcohol. Order No.

A2532. Used in cleaning viscosimeters. Phipps

and Bird, Inc., Richmonc, Va.

18. Barium Chloride. Dilute solution. Used in qual-

itative tests to determine if the catalyst has been

washed enough. General Chemical Co., New York, N. Y.

19. Distilled Water. Used in making up antlfreeze

mixture.

D. App~atus

The following is a list of equipment that was used in ex-

periments •

.Analytical Balance. Chainomatic, dampened, max. wt.

201.1 gr., accuracy -0.0001 gr., Serial No.· A2238.

Seederen-Koblbuach Inc., Jersey City, N. J.

Balance. Double beam, porcelain pans, max. wt. 2

kilograms, accuracy 0.05 gr. Fisher Scientific Co.,

Pittsburgh, Pennsylvania.

Weights. Will Corporation, Rochester, N. Y.

Basket Centrifuge. Five inch basket. Variable speed,

maximum speed 3600 rpm, 110 volts AC or DC, No. 1!5467.

Fisher Scientific Co., Pittsburgh, Pa.

Drying oven. Serial No. 100-2761, Catalog No. 1250,

temperature range 35°-iso 0c, 110 volts, 60 cycles,

600 watts, 5.5 amps., single phase Type A. Precision

Scientific Co., Chicago, Ill.

:t.iU:t'fle Furnace. Serial No. 1400, type 9921, 1.35 kw.,

220 volts, 6.13 amps., working temperature l750°F,

maximum temperature 1850°F. Cooley Electric Co.,

Indianapolis, Indiana.

-40-

Aviation Engine Thermometer Test Unit. Self-contained,

electrically operated. Temperature range 392°F to

-40°F. Type AVT-CHT-P; Model R-1; No. 2100, 110 volts,

.60 cycle, Laird Engineering Co., Charlestown, w. Va.

Ostwald Viscosimeter. A 71-600, range 80-100 seconds,

determination or viscosity by comparison with water;

used to detennine viscosities of antifreeze mixtures.

Phipps & Bird Inc., Richmond, Virginia •.

Ostwald-Fenske Viscosimeter •. A 60-400, A.S.T.M. Ho.·

300, Range 26-175 centistokes, capillary diameter 1.20-

1.30. · Used to determine Viscosi ties of antifreeze

mixtures. Phipps and Bird, Inc~, Ricbmonc'!,., Virginia.

Westphal Balance. Displacement of plummet 5 ml at·

i5°c, accuracy 0.0001. Used to determine specific

gravity of antifreeze mixtures. Fisher Scientific·

Co., Pittsburgh, Pennsylvania.

Timer. Range 0.1 second-10,000 seconds, graduations

0.1 second. 60 cycle, 110 volts. "Time it", Pre-

cision Scientific Co., Chicago, Illinois.

Thermalair Fluid. For use in Aviation Engine Ther-

mometer Test Unit Models AVT-Cm' and AVT-CHT-P. Laird

Engineering Co., Charlestown, West Virginia.

-41-

Hydrometer. Range 1.000-1.220. Accuracy 0.002. For

heavy liquids temp. 60/60°F. Fisher Scientific Co.,

Pittsburgh, Pennsylvania.

TheDnometer. Mercury, Range -4o0c to 5o0o. Brothcom

Co., New York, N. y.

Thermometer. Mercury. Range -10°0 to 30000. Broth com

Co., New York, N. Y.

Assorted Glassware and Laboratory Equipment. Test.

tubes - 35 ml. with cork stoppers; beakers - 1000 ml.,

800 ml., 600 ml., 250 ml., and 50 ml.; jar - glass,

one gallon; flasks - Ehrlenm.eyer, 250 ml.;·flasks -

volumetric, 1000 ml., 500 ml., and 250 ml. ; pipettes -

50 ml., 25 ml., 10 ml.; evapor~tinB dishes - 1000 ml.,

25 mL; graduated cylinders - 250 ml'., 100 ml.; ring

stand and clamp; rubber tubing; crucible, porcelain,

30 ml.; tongs, monel.

-42-

. E. Method of Procedure

l. Introduction. In order to determine the feasibility ot

the process the catalyst yield had to be known. This was obtain--1 . •

ed experimentally sine~ it was n.ot given by Lenth and ~isC 46}.

The glycerol and congeners fraction donated by the Miner

Laboratories had to be identified with the product reported by

Lenth and DuPuis( 4s). The specific gravity and the glycerine

concentration by the bichromate method were determined.

The viscosity, specific gravity, and freezing point of

various mixtures of propylene glycol - glycerol and congeners-

water were compared with ethylene glycol-water mixtures to test

their suitability as an automotive antifreeze.

2. Determination of Yield of Catalyst. Two experimental

runs were made for the purpose of detennining the percentage

yield that could be ez:pected in the preparation of the copper

aluminate catalyst. The preparation consisted primarily of four

main steps, mixing, centrifuging, drying and ignition. The fol-

lowing procedure was used~

1. Following the procedure given by. Lenth and DuPuisC46 }

25 grams cupric sulfate was placed in a one gallon

jug, 64.7 grams aluminum sulfate dissolved in 328

ml. of hot water, and 51.8 grams soda ash dissolved

-43-

in 230 ml. of hot water. The aluminum sulfate

solution was then poured into the gallon jar

with the cupric sulfate. Then the soda ash

solution was added slowly with vigorous stirring.

The mixture was stirred for about 30 minutes .

atter all the soda ash had been added and was·

~hen allowed to stand for approximately 24 hours

with occasional stirring to assist in driving

out the carbon dioxide.·

2. The mixture was then centrifuged in a 5 inch

basket centrifuge with a maximum rpm of 3600.

The mixture was centrifuged five times in order

to recover as much of the precipitate as possible.

The cake was then washed with hot tap water until

the wash water showed only a faint cloudiness

when a few drops of a dilute barium chloride

solution was added.

3. The cake was then removed from the basket and

broken up into approximately one-half inch

lumps which were placed into a 1000 ml. evapo-

rating dish. The evaporating dish was then

placed in a.drying oven at uo 0c -5 for 24 hours.

-44-

Upon removal from the drying oven, the dried ·

cake was weighed on a double beam balance after

the cake had been allowed to cool for 30 minutes ...

4. Then a sample of this cake was placed in a cruci-

ble and weighed.· The crucible was then placed

in amuffle-fumace at 96o0 c -10° for five minutes.

After removal from the furnace, the samples were

allowed to cool one hour before weighing~

· Two additional runs were made to correlate

the first- two runs.

3. Identification of Glycerol and Con:gerers Fraction. Glycer-

ine content of the glycerol and conge:iierafraction·as received was

determined by the Bichromate method.(s 3} .A. sample of "glycerol and

congeners" of not more than 3 grams was weighed. This ws.s dis-

solved in 200 ml. of hot water in a 600 ml. beaker, end 25 ml.

of 1:4 sulfuric acid was added. This• solution was then allowed

to boil for 20 - 30 minutes. The contents were then cooled to

room temperature and diluted to about 400 ml. to which O. 25 gram

silver sulfate was added. ·. After the precipitate settled to the

bottom, a portion of the contents of the calibrated flask was

filtered discarding the first 10 - 15 ml. Fifty m1.·of the fil-

trate was pipetted into a 250 ml. beaker, and 50 ml. of water

-45-

was placed in a similar beaker as a blank. Seventy-five ml. of

a solution containing 74.553 grams of potassium bichromate per

liter were added to the sample, and_25 ml. of the same solution

was added to the blank.· Twenty-;'ive ml. of concentrated sul- _

furic acid was added to each, stirred thoroughly, end covered

with a watch glass. Both of these solutions were then kept at

a temperature of 90-100°0 for approximately two hours. The

solutions were cooled, transferred to one liter volumetric

flasks, and diluted to volume. After the solutions were mixed

well, 50 ml. of each was pipetted to which was added 50 ml. or

water and 20 ml. of 10--; potassium iodide solution. Each solution

was then titrated with O.lN sodiwn thiosulfate solution, usins

starch indicator when near the end point. The final color is

green. The calculation of the glycerine content was the same

as used by Snell.and Biffen( 63}.

4. 1IBkeup of Propylene Glycol-Glycerol and Congeners-Water

Solutions. Since the antifreeze to be tested was to consist of

only the propylene glycol and glycerol and congeners obtained in

the catalytic hydrogenation of sucrose, a solution of 61.2% by

weight propylene glycol and 38.8% by weight glycerol and con-

geners was made up. This ratio is the same as the yield given

by Lenth and DuPuis( 4G}. Solutions of 10, 15, 25, 30, 35, 40

-4:6-·

and 4:5% by volume of propylene glycol-glycerol and congeners-

were made up with distilled water to contain a total of 32 ml.

5. Determination of Viscosity and Specific Gravity of

Antifreeze 1ti:rtures of Propylene Glycol-Glycerol and Congeners-

Water. The Ostwald viscosimeter was calibrated against dis-

tilled water at 20°c and 85°c and against sucrose solutions of

20 and 40% at 20°c. Each viscosity time was taken using a 5 ml.

sample of the material being tested. Si~ce the viscositiea( 55 )

and the specific gravities( 40} of each were known at the tempera-

ture at which the experiments were carried out, the kinematic

viscosities could be calculated and.plotted against the corre-

sponding times giving a calibration curve by which the kinematic

viscosity of other solutions could be determined by kn.owing the

time (Figure 1).

The Ostwald-Fenske viscosimeter was calibrated against a . 0

60%.sugar, 76, ?0.3, 66.3 and 62.5% glycerol solutions at 25 C

in a similar manner as the Ostwald Viscosimeter (Figure 2).

The flow times of.the solutions were determined at the

temperatures shown in Table VI.

The specific gravity of these mixtures were determined at

the temperature of each test with a Westphal balance~ The tem-

peratures for the tests using the Ostwald viscosimeter were

obtained with an Aviation Engine Thennometer Test Unit Type

AVT-CHT-P. The temperatures for the tests using .the Ostwald-

Fenske viacoaimeterwere obtained by using crushed ice and

salt mixtures for temperatures below 25°c and by hot water

above 25°c.

To obtain the.viscosity o~ the solutions at their freez~

ing points, it was necessary to extrapolate this data by making

use of Duhring's plot( 55 )_ This was• done in the following

manner: the viscosity for a s~i sucrose solution;was plotted

against its corresponding temperature (Figure 6) •. Then by

using the curve of absolute viscosity vs. temperature in Figure

5 for each mixture of propylene glycol-glycerol and congeners-

water, several viscosities and their corresponding temperatures

were obtained. To obtain a Dµhring's plot, the temperatures at I

which the 60% sugar solution and the antifreeze solutions had

the same viscosities were plotted against each other_ in Figure

7. These points fell on.a straight line and could be extrapolated.

Since the freezing point of the antifreeze mixture was known,

the temperature of the 60% sucrose solution which had the same

viscosity was obtained from Figure 7. Then the viscosity of the

freezing mixture could be obtained fro::n Figure 6.

-48-

6. Cooling Curve Data for Antifreeze Mixtures of Propylene

Glycol-Glycerol and Congeners-Water. Cooling curve data was

collected for mixtures of 10, 15, 25, 30, · 35, 40 and 45% by

volume·propylene glycol-glycerol and congeners in the follow-

ing manner: · The Aviation Engine Thennometer Test Unit· was used

as the refrigerating· source •. The refrigerator was started and

allowed to cool to at least 10°c lower than room temperature

before the sample was placed in the cooling bath. The tempera~

ture of the cooling bath and the temperature of the antifreeze

mixture were recorded·every minute. After the antifreeze mix-

ture reached a constant temperature, when the antifreeze mix-

ture began to crystallize, the run was continued until the tem-

perature·of the mixture had reached a temperature at least 5°c below the constant temperature. This procedure was used for

all mixtures except the 45% mixture. In this test, a tempera-

ture 5°c below the constant temperature was not obtainable due

to the limits of the machine. The temperature of the cooling

bath was regulated so that at no time prior to the constant

temperature level the temperature of the mixture was within 5°c

of the cooling bath. In order to maintain this temperature dif-

ference for the higher percentages, 30, 35, 40 and 45% by volume,

the initial temperature difference between the mixture and the

cooling bath had to ba between 30 and 40°0.

-49-

7. Plant Design and Location. On the basis of the experi-

mental work and the data of Lenth and DuPuis{45) and stengel and

.Maple(54)(S 5),-a :plant was d~signed to produce 3000 pounds per 3 ' . .

hours of an antifreeze consisting of propylene glycol and glycerol

and congeners. Mate;ial ·and heat balances( 35-42 ) (54)( 59) were ·

made across each piece of equipment.· After these balances were . .

ma.de, equipment was either designed or selected from those used

in industry as to size(2-6)(8)(10)(13-l4){16-20)(47)(52)(56-60)

(66- 68)( 7i- 74) ~d location in the plant. The cost of equip-

ment, installation, and operation w.a"s determined< 36-42) (54) (69).

The plant location was selected on the basis of availa-

bility of raw materials, market, transportation, labor and

power< ?O).

-50-

F. Data and Results .

The yield that was obtained in the preparation of the copper

aluminate catalyst is given in Table III.

The comparison of the glycerol and congeners used and that

reported by Lenth and DuPuis is given in Table v. The calibration data for the Ost~~ld and Ostwald-Fenske

viscosimeters is given in Table IV, and this data is plotted in

Figures 1 and 2.

The specific gravity, temperature, time concentration,

absolute viscosity, and kinematic viscosity for varying mixtures

of propylene glycol-glycerol and congeners-water are given in

Table VI. This data is plotted in Figures 3, 4, 5, 8 and 9.

The absolute viscosity of a 60% sucrose solution at vary-

ing temperatures is shown in Table VII and is plotted in Figure 6.

The data f~r Duhring's plotC 55 ) is shown in Table VIII.

This data was obtained by using Figures 5 and 6 and plotting the

temperature of propylene glycol-glycerol and congeners-water mix-

tures against the temperatures of 60--p sucrose solutions having

the same vi sco si ty in Fi gur'a 7.

The cooling curve data for various mixtures of propylene

glycol-glycerol and congeners-water is given in Table IX and

plotted in Figure 10. The data before five minutes and after

sixteen minutes was not included since it was not important.

-51-

The freezing points and the viscosities at the freezing

points ot various mixtures are summarized in Tables X and

plotted in Figures 5 and 11.

A comparison of ethylene glycol and propylene glycol-

glycerol and congeners from the standpoint of viscosity and

freezing point is shown in Table n.

RUN NO.

l

2

3

4

-52-

TABLE III

DATA AND RESULTS

PREPARATION OF COPPER .ALUMINATE*FROM 25 GRAMS OF CUPRIC SOI.FATE, 64. 7 GRAMS OF .~UMINUM SUL-FATE IN 328 ML. OF HOT WATER, AND 51.8 GRAMS OF SODA ASH m 230 ML. OF HOT WATER.

Tnm YIELD BEFORE IGNITION YIELD .AFTER IGNITION LOSS IGNITION

(Hrs.) (Grams) (%) (Grams)

24 29.3 28.3 21.10 Aluminwn sul-

24 32.4 18.6 26.38 :rate used in Runs 2 and 3

24 28.5 15.0 24.25 not the same as Runs l and

24 26.4 20.0· 20.12 4.

*Lenth, C. W. and DuPuis, R. N. Polyhydric Alcohol Production. Ind. En.gr. Chem. ~' 152-7, (1945).

.... 53_

TABLE IV

DATA .AND RESULTS

CALIBRATION OF OSTNALD A.~D OSTV/ALD-FENSKE VISCOSIMETERS

TIME SP. GR. VISCOSITY (Centi. poises)

KINEMATIC VISCOSITY

(Centi-stokes)

TEMP.

OSTWALD

Water

water

20% sugar

40% Sugar

OSTW.ALD-FEN'SKE

(Sec.)

68.2 0.9982

28.8 0.9686

1.000

0.336

125.0 l.0810 . l.967

3158.0 l.1764 6.223

60Cp sugar 130.0 1.2856 44.02

76% Glycerol 103.0 1.1980 30.56

70.3% Glycerol 69.4 1.183 18~48-

66.3% Glycerol 47.6 1.172 13.54:

1.002

0.346

l.815

5.290

34.02

25.40

· 15.60

11.55

20

85

20

20

25

25

25

25

62.3% Glycerol 32.3 1.161 10.35 8.92 25 SUGAR DATA

l. Hodgman, C. D. ttHandbook of Chemistry and Physicstt. Pg. 1633-4. Chemical Rubber Publishing Co., Cleveland, Ohio. 1946. 30th Ed.

2. Perry, j. H. ttChe~ical Engineers' Handbook~. Pg. 788-98. McGraw-Hill Book Co., Inc., New York. 1941. 2nd Ed.

GLYCEROL·. DATA l. Hodgman, C. D. "Handbook of Chewistry and Physics".

Pg. 1742. Chemical Rubber Publishing Co., Oleveland, Ohio. 1946. 30th Ed.

-54-

TABLE·V

DATA AND RESULTS

ID:ENTIFIC.A.TION OF GLYCEROL .AND CON-GEI.IBRS FRACTION FROM MINER LABORA-TORIES WITH PRODUCT OF UNTH AND DUPUIS*

PROCEDURE RESULTS

LENTH AND DUPUIS EXPERIMJJNTAL

SP.GR.(Westphal) 25/25°0

SP.GR.(Not given)25/25°c

GLYCERINE(Acetylation,%)

GLYCERINE(Bichromate, %)

1.194

71.8

l.198

78 *Lenth, C. w. and DuPuis, R. N. Polyhydric Alcohol Pro-

duction. Ind. En.gr. Chem.~, 152-7, {1945).

-55-

TABLE VI

DATA .AND RESULTS

VISCOSITY DATA FOR .ANTIFREEZE MIXTURES OF PROPYLENE GLYCOL .AND GLYCEROL.AND CONGENERS.

CONC. VISCOS- TIME KINElf.ATIC VISCOSITY SP.GR. TEMP. BY VOL. IMETER

TYPE VISCOSITY,

(Centi-poises}

(Centi-poisas)

0

0

0

10

10

10

30

30

30

35

40

45

45

45

45

0

0

0

F

a a F

F

F

F

0

0

199.0

92.5

38.0

34.4

186.8

56.7

48.0

65.9

· 119.3

53.2

318.7

85.0

1. 7924

0.98S

0.357

2.925

1.325

0.500

9.25

2.75

0.800

11.75

15.00

30.625

12.50

4.725

1.226

1. 7921 o. 9998

0.981 0.9981

0.3478 0.9730

a 21

82

2.963

1.34

0.493

9.650

2.85

0.814

12.35

15.90

32.6

13.30

4.98

1.260

1.0130 0

1.0117 21

0.986 82

1.043 -10

1.0376 21

1.0175 82

1.050 -10

1.060 -10

L067 -20

1.063 0

1.0550 21

1.029 82

0 = OS'IWAID VISCOSIMETER F = OSTWAID-Fl!NSKE VISCOSIMEI'ER ·

WATER DA.TA Perry, J". H. "Chemical Engineers' Handbook". Pg. 788-98. McGraw-Hill Book Co., Inc., ·New York. 1941. 2nd Ed.

TABIE.VII

DATA FOR EXTRAPOLATION

VISCOSITIES OF 60% SUCROSE SOLUTION*

TEMPERATURE 0c VISCOSITIES IN CE~TIPOISES

. 15 . 74.90

20 56.70

25 44.02

30 M.01

35 26.62

40 21.30

45 17.24

50 14.06

55 11.71

60 9.87

65 8.37

70 7.18

75 6.22

80 5.42

90 4.17

95 3.73

'FI>erry, J". H. "Chemical Engineers' Hand-book." Pg. 788~98. McGraw-Hill Book Co., Inc., New York. 1941. 2nd Ed.

-57-

TABLE VIII

DATA AND RESULTS

DATA FOB DUHBING' S PLOT* OF A..T\l"TIFREEZE MUTORE:::i VS. 60% SUCROSE SOLUTION

CONO. P.G.-G.O. VISCOSITY ~. TEMPERA.TUBE BY VOL. (Centipoises) SOI.N. GO'fo SUCROSE oo OC

30 9.50 -10 61

30 7.50 -4 68

30 6.75 0 72

35 12.25 -10' 54

35 10.00 -5 59

35 7.50 2 68

35 6.50 7 72

40 16.75 -10 46

40 15.00 -7.5 49

40 12.50 -3.0 53.5

40 7.50 8.5 68

40 6.75 12.5 72

45 22.50 -'-10 39

45 20.00 -7.5 . 42

45 13.75 o.o . 51.

45 10.00 7 59

45 8.75 10 63 ili5erry-, J". H. "Chemical Engineers' Handbook. Pg. 788-98. McGraw-Hill Book Co., Inc., New York. 1941. 2nd Ed.

·TABLE IX

DATA AND RESULTS

COOLING CURVE DATA FOR ANTIFREEZES OF PROPYLENE GLYCOL-GLYCEROL & CONGENERS-WATER

CONC. P.G.-G.C. BY VOL.

%

10

15

25

30

35

40

45

TiliE (min. ) 5 6 7 8 9 10 11 12 13 14 15 16 TEMP. COOLING

BATH 0 c O -1 -2.5 -4 TEMP. MIXTURE 0 c 8. 5 6 3. 5 2

-5.5 -7 -8 -10 -10 -10.5 -11 -12 0.5 -2 -4 -3 -3 -3 -3 -3

TEMP. COOLING BATH 0 c -7 -9 -11 -13 -14 -15 -16 -17.5 -18.5 -20 -21 -22

TEMP. MIXTURE 0 c 3 0 -2 -3 -5 -4-5 -4-5 -4-5 -5 -5.5 -6 -7 TEMP. COOLING

BATH °C -16.5 -18 -19 -20.5 -22 -23 -23.5 -24.5 -25 -25-5 -26 -26.5 TEMP. t1IXTURE 0c -7-5 -8.5 -9 -9 -9 -10 -10.5 -11.5 -12.5 -13.5 -14-5 -15

.. T.EMP. COOLING BATH 0 c -18 -18.5 -19 -19 -19.5 -19.5 -20 -20 -20.5 -21 -21.5 -21.5

Tllil'. MIXTURE °C -9 -11. 5 -12. 5 -13 -14 -14 -14 -14 -14. 5 -15 -15. 5 -15.5 T.EliP. COOLING

BATH °C -20.5 -21.5 -22.5 -24 -24.5 -25 -25.5 -26 -27 -27.5 -27.5 -27.5 TEMP. MIXTURE 0 c -12.5 -14 -15.5 -15.5 -15.5 -16 -16.5 -17 -17.5 -18.5 -20 -20.5 TEMP. COOLING

BATH 0 c -26 -26. 5 -1{ -27. 5 -27. 5 -27. 5 -28 -28 -28. 5 -28. 5 -29 -29 Tllff>. llIXTURE 0c -16.5 -18 -19 -20 -20 -20 -20.5 -21.5 -22 -23 -23.5 -24 TEMP. COOLING

BATH 0c -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 TEMP. MIXTURE 0c -19 -21 -23 -24 -25 -25.5 -25.5 -25.5 -25.5 -26 -26.5 -27

I \.1l

'P

-59-

TABLE X

DATA AND RESULTS

FREEZING POINTS WITH CORRESPONDING VIS-COSITIES, OBTAINED FROM DUERINGS' PLOT*

CONC.P.G.-G.C. BY VOL

% 10

15

25

30

35

40

· FREEZil!G POINT 00

-5

-4.5

-9

-14

-15.5

-20

ABSOLUTE VISCOSITY

(Centipoises)

10.00

15.00

25.50

45 -25.5 61.00 >i<Ferry, ;r. H. "Chemical Engineers' Handbook". Pg. '788-98. McGraw-Hill Book Co., Inc., New York. 1941. 2nd Ed.

-59A-

TABLE XA

DAll AND RESULTS

COMPARISON OF El'EYI&'IB GLYCOL AND PRO~ GLYCOL-GLYCEROL AND CONGENERS(l2

CONG. BY VOL. VISCOSITY FREEZING POINT

P.G. & G.C. E.G. P.G. & G.C. E.G. % Centipoises Cc

10 3.00 2.50 -3 -4.5

20 4.25 -9 -9.5

30 9.50 7.60 -12 -17

35 15.00 -15.5 -22.

40 25.50 20.00 -20 -25.5

45 60.00 -25.5

55 60.00 -45.0

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-71-

Laboratory and Semiworka Data

Composition of product from hydrogenolysis of sugar, based

on weight of sugar; fro~ 11 terature ( 46 ) •

Propylene Glycol, per cent 39.5

Water, per cent U.2

Glycerol end Congeners 25.l

Residue, per cant ll.O

Composition of reactor used in the preparation of the copper

aluminate catalyst.

Copper Sulfate, per cent

Aluminum. Sulfate, per cent

Soda Ash, per cent

Water, per cent

3.58

9.25

7.41

79.76

Composition of products obtained in the preparation of the copper

aluminate catalyst.

Copper Aluminate, per cent

Sodium Sulfate, per cent

Carbon Dioxide

Soda Ash

Water

2.56

8.08

2.47

l.47

85.42

-72-

Composition of copper aluminate· catalyst as used, dry basis

calculated.

Copper Aluminate, per cent

Sodium sulfate, per cent

Soda Ash, per cent

86.76

10.00

3.24

-73-

Theoretical Calculations

The production of ethylene glycol for the year 1945 was

205,000,000 pounds, of which 65% was used as automotive anti-

freeze. In order not to upset the demand, 5% of the latter

would be a fa~r figure to enter the field.

205,000,000 x 0.65 = 133,250,000 lbs. per year

133,250,000 x 0.05 = 6,662,500 lbs. per year

A conservative estimate would be to build a plant to pro-

duce 6,000,000 lbs. or 3000 tons of antifreeze.

Plant Specifications

.Annual Output: 3000 tons antifreeze

Operation: ·3 shifts (8 hours) per day-

40 hour week

10 day vacation, unitized

250 days total working time per year

6000 hours of production, overall

1000 lbs. per hour antifreeze production

Reaction Calculations for Hydrogenation

Basis: 3 hour cycle

Antifreeze to consist of propylene glycol and glycerol and

congeners fractions.

-74-

Production: 3000 lbs. per _3 hour cycle

Hydrogenation Reaction:

Sugar (Refined cane sugar) Needed:

3000 X 2000 0.646 X 250 X 8 = 4644 lbs./cycle

Hydrogen Needed:_

5.7 moles hydrogen per mole su.gar-

4644 ~x 5.7 x 2 • 155 lbs./cycle

Methanol Needed:

Equal weights of sugar and methanol: 4644 lbs./cycle

Catalyst Needed: _

10-fo ot weight of sugar: 464.4 lbs./cycle

Soda Ash Needed:

0.¥/4 of weight of sugar: 18.6 lbs./cycle

Reaction Calculation for-Catalyst Preparation

Basis: Material f'or 3 hour cycle

(See Table II and Laboratory and Semiworks Data)

Production: 464:.4 lbs. per 3 hour cycle

Reactions:

CuS04 • 5H20 + Na2co3 _.,. CuO + Na2so 4 + CO2 + 5H20

il2(s0 4 }3 •18¾0 + 3Na2co3 -.. A12o3 + 3Na2so 4 + 3Co2 + 18H20

-75-

Copper Alwninate Present in Catalyst:

464.4 x 0.8676 = 402.9 lbs./cycle

Weight of Total Catalyst Slurry:

~~~2:6 = 15738.3 lbs./cycle

Copper Sulfate Needed:

15738.3 x 0.0358 = 563.4 lbs./cycle

Aluminum Sulfate Needed:

15738.3 x 0.0925 = 1455.8 lbs./cycle

Soda Ash Needed:

15738.3 x 0.074 =.1164.7 lbs./cycle

Water Needed:

15738.3 x 0.7977 = 12554.4 lbs./cycle

-76-

Material. Balance

Basis: 3000 pounds antifreeze per 3 hour cycle {All weights in pounds)

(See Figure 12}

Note: Left hand-entering; right hand-leaving

A-1 Copper Sulfate Storage

Copper Sulfate 563..4

A-2 Aluminum sulfate Storage

Aluminum sulfate 1455.8

A-3 Soda Ash Storage

Soda Ash Cat. Soda Ash Hydro.

1164.7 18.6

1183.3

A-5 Methanol storage Tank

Methanol supply 4644 Methanol -Loss 232.2

A.-6 Hydrogen Storage

Hydrogen

4876.2

155

A-7 Hot Water Pump (85-90°F)

Water Alum. Water Soda Ash· • Water, Wash

Steam

7382.0· 5172.4. 1411.0

. 13965.4

873.0 14838.4

Copper sulfate 563.4 to B-1

Aluminum sulfate 1455.8 to B-1

Soda Ash Cat. ll64.7 to B-3 Soda Ash Hydro. 18.6

1183.3

Methanol Supply 4644 Methanol Loss 232.2

Hydrogen

vrater Alum •. Water Soda Ash Water, Wash

Steam

4876.2

155

7382.0 to B-1 5172.4 to B-3 1411.0 to C-1

·13965.4

873.0 14838.4

-77-

B-l·Dissolving Tank (85-90°F}

From. A-l Copper Sulfate 563.4 .copper SUltate 563.4' A-2 Aluminum Sulfate 1445.8 Aluminum SUlfate 1344.8 to B-2 A-7 Water 7382.0 Water 7382.0

9401.2 9401.2

B-2 Dissolving Tank Pump

From .B-1 Sama as·B-1 Same as B-l to B-3

B-3 Reactor

From Copper Sulfate 563.4 Carbon Dioxide 388.7 to vent

B-2 Aluminum Sulfate 1455.8 Sodium Sulfate 1271.7 Water 7382.0 Soda Ash 231.3 to B-4 A-3 Soda Ash 1164.7 Copper Aluminate 402.9

A-7 Water 5172.4 Water 13443.7 15738.3 15738.3

B-4 Reactor Pump

From. Sodi µm Sulfate 1271.7 Sodium Sulfate 1271.7 Soda Ash 231.3 Soda Ash 231.3

to C-1 B-3 Copper .Aluminate 402.9 Copper Aluminate 402.9 Water 13443.7 Water 13443.7

15349.6 15349.6

C-1 Centrifugal Filter

From Sodium Sulfate 1271.7 As Solid Soda Ash 231.5 Sodium SUlt'ate ·46.4

B-4 Copper Aluminate 402.9 Soda Ash 15.1 Water 13443.7 Copper Aluminate402.9 to C-2

Water 2010.8 2475.2

From A-7 Wash V[ater

0-2 Belt ConTeyor

From Sodium Sulfate Soda Aeh

-78-

14ll.O As Liquid 16760.6 Water 11432.9

Wash Water 1411.0 Soda Ash 216.2 Sodium Sulfate 1225.3

Sodium Sulfate Soda Ash

14285.4 2475.2

16760.6

46.4 15.l

C-1 Copper Aluminate Water

46.4 15.l

402.9 2010.8 2475.2

Copper Aluminate Water

402.9 to D-1

D-1 Rotary Dryer (200-210°F)

Fran Sodium Sulfate

0_2 Soda Ash c·opper Aluminate Water Steam

46.4 15.l

402.9 2010.8 3592.5 6067.7

Air 211,252 cu. ft.

D-2 Belt Conveyor

From Sodium Sulfate 46.4 Soda Ash 15.1

D-1 Copper Aluminate 402.9 Water 154.3

618.7

D-3 Rotary Kiln (1810-1830°F) From.

Sodium Sulfate 46.4 D-2 Soda Ash 16.l

Sodium Sulfate Soda Ash Copper Aluminate Water Water Vapor Steam Condensate

2010.8 2475.2

46.4 15.1

402.9 164.3

1856.5 3592.6 606'7.7

Air 211,252 cu. ft.

Sodium Sulfate 46.4 Soda Ash 15.l Copper Aluminate 402.9 Water 164.3

618.7

Sodium Sulfate 46.4 Soda Ash 15.l

to D-2

to waste

to D-3

to D-4

From Copper Aluminate

D-2 Water

-79-

402.9 Copper .Alurninate 154.3 618.7 Water Vapor

402.9 to D-4 464.4 154.3 to waste 618.7

· Fuel 011 Air·

3 gals. Fuel 011 2085 cu. ft. Air

3 gals. 2085 cu. ft.

D-4 Conveyor Cooling Kiln (200-2200.F)

From Sodium Sulfate

D-3 Soda Ash Copper Aluminate

Air 61,000

E-1 Crushing Rolls

From Sodium Sulfate

D-4· Soda Ash Copper Aluminate

E-2 Belt Conveyor

From E-1 Same as E-1

F-1 Hydrogen Compressor

From· A-6 Same as A-6

F-2 Methanol Pump

From A-5 Same as A-5

F-3 Sugar Feed Hopper

Fran A-4 Same as A-4

46.4 15.l

402.9 464.4

cu. ft.

46.4 15.l

402.9 464.4

Sodium sulfate 46.4 Soda Ash 16.1 to E-1 Copper Aluminate 402.9

464.4 Air 61,000 cu. ft.

Sodium SUlfate Soda Ash Copper Aluminate

Same as E-1

Same as A-6

Same as A-5

Same as A-4

46.4 15.l to E-2

402.9 464.4

to F-4

to F-4

to F-4

to F-4 ·

-80-

F-4 Autoclave (1500 psig, 460-465°F)

From F-1 Hydrogen 1550 Methanol 4876.2 F-2 Methanol 4876.2 Catalyst 464.4 F-3 sugar 4644:.0 P. G. 1834.6 A-3 Soda Ash 18.6 G. C. 1165.6 to F-5 E-2 Catalyst 464.4 Water 1123.8

10158.2 Residue 510.8 Loss 182.8

10158.2

F-5 Condenser (135-140~)

From Methanol 4876.2 Methanol 4876.2 Catalyst 464:.4 ·. Catalyst 464.4 P. G. 1834.6 P. G. 1834.6

F-4 G. O. 1165.6 G. C. 1165.6 to F-7 Water 1123.8 Water 1123.8 Residue 510.8 Residue . 510.8 Loss 152.8 Loss 152.8

10128.2 10128.2 Cooling Water 3615 gals. Cooling Water 3615 gals.

F-6 Condenser Cooling Water Pump

Cooling Water 3615 gals. Cooling Water 3615 gals. to F-5

F-7 Condensate Pump

From Methanol Catalyst P. G.

F-5 G. O. Water Residue Loss·.

G-1 Basket Centrifuge

From F-7 Methanol

Catalyst

4876.2 Methanol 464.4 Catalyst

1834.6 P. G. 1165.6 G. C. 1123.8 Water

510.8 Residue 152.8 Loss

10158.2

4876.2 As Solid 464.4 Catalyst

4876.2 464.4

1834.6 1165.6 to G-1 1123.8 510.8 152.8

10158.2

464.4: to waste

-81-

P. G. 1834.6 As Liquid G. C. 1165.6 Methanol 4876.2

F-7 Water 1123.8 P. G. 1834.6 Residue 510.8 G. C. 1165.6 Loss 152.8 Water 1123.8 to G-2

10158.2 Residue 510.8 Loss 152.8

9693.8

G-2 Basket Centrifuge Pump

Fran Methanol 4876.2 Methanol 4876.2 P. G. 1834.6 P. G. 1834.6 G. C. 1165.6 G. C. 1165.6

G-1 Water 1123.8 Water 1123.8 to H-1 Residue 510.8 Residue 510.8 Loss 152.8 Loss 152.8

9693.8 9693.8

H-1 Atmospheric Still (140-212°F)

From Methanol 4876.2 As Vapor P. G. 1834.6 Methanol 4644 to H-2 G. C. 1165.6 Water 1123.8

G-2 Water 1123.8 5767.8 Residue 510.8 As Liquid Loss 152.8 P. G. 1834.6

9693.8 G. C. 1165.6 to I-1 Steam 6924.0 Residue 510.8

16,617.8 Loss 415.0 3926.0

Steam Condensate 6924:.0 Vapor 5767.8

· 16,617.8

H-2 Atmospheric Still Condenser (70-75°F)

From Methanol 4644 Methanol 4644 to H-:3

H-1 Water 1123.8 Water 1123.8 to waste 5767.8 5767.8

Cooling Water 14,617 gels. Cooling Water 14,617 gals.

-82-

H~3 Condensate Pump

From H-2 Methanol 4644 ?.."ethanol to A-5

H-4 Condenser Cooling Water Pump

Cooling Water 14.617 gals. Cooling Water 14,61J gals. to H-2

H-5 Atmospheric Still Pump

From P. G.

H l G. O. - Residue

Loss

1834:.6 1165.6 510.8 415.0

3926.0

P. G. G. O. Residue Loss.

1834.6 1165.6 to I-1 510.8

415.0 3926.0

I-1 vacuum Still (26 in. vac., 130-227°F)

From P. G.

H-5 G. C. Residue Loss

Steam

I-2 Vacuum still Condenser

From I-1 P. G.

G. C.

1834.6 ll65.6 510.8 415.0

3926.0 1874.0 5800.0

1834.6 1165.6 3000.2

Cooling Water 4646.9 @l!ls.

I-3 Vacuum Pump

As Vapor P. G. .1834.6 to I-2 G. O. 1165.6

3000.2 As Liquid

Residue 510.8 to waste Loss 415.0 925.8

Steam Condensate 1874.0 Vapor 3000.2

5800.0

· ~: ~: ~:::: to j-l 3000.2

Cooling Water 4646.9 gals.

Air 150 g.p.m. Air 150 g.p.m. to I-1

-83-

I-4 Condenser Cooling Water Pump

Cooling Water 4646. 9 €13,ls. Cooling Water 4646. 9 gals. to I-2

I-5 Condensate Pump .

From

I-2 p. G. 1834.6 G. c. 1165.6

3000.2

J-1 Antifreeze Storage·

From I-5 P. G. 1834.6

G. c. 1165.6 3000.2

Note:

P. G. = Propylene Glycol

G. C. = Glycerol and Congeners.

Cat. = Catalyst

Hydro.= Hydrogenation

Alum. = Aluminum Sulfate

P. G. G. c.

P. G. G. c.

1834.6 1165.6 to J-l 3000.2

1834.6 1165.6 3000.2

-86-

Equipment Specifications

A-l Copper SUlfate storage

Minimum supply: 4 weeks Repleni ahmen t period: 4 weeks . Capacity of area: 10 weeks Containers: 500 lb. barrel Requirement per 3 hour cycle: 563.4 lbs. or 1.125 barrels Cycles per day: 8 Requirement per day: 1.125 x 8 = 9.00 barrels Working days per week: 5 Requirement for 10 weeks: 9 x 5 x 10 = 450 barrels Dimensions or barrel: 30 in. dia. and 36 in. height Floor area required: 2.5 x 2.5 x 450 = 2812.5 sq. ft. Height or ceiling: 9 feet Type of floor: · concrete

A-2 Aluminum sulfate storage

Minimum supply: 4 weeks Replenishment period: 4 weeks Capacity of area: 10 weeks Containers: 400 lbs. barrel Requirement per 3 hr. cycle: 1455.8 lbs. or 3.64 barrels Cycles per day: 8 · Requirement per day: 5.64 x 8 = 29.l barrels Working days per week: 5 Reqµirement for 10 weeks: 29.l x 5 x 10 = 1450 barrels Dimensions of barrel: 22 in. die.. and 34 in. height Floor area required: 1.835 x 1.835 x 1450 = 4870 sq. tt. Type of floor: concrete Height of ceiling: 9 feet

A-3 Soda Ash Storage.

Minimum supply: 4 weeks Replenishment pertod: 4 weeks Capacity of area: 10 weeks supply, Containers: 100 lb. bags Requirement per 3 hour cycle: 1164.7 18.6: ll83.3 Cycles par day: 8 Requirement per day: 9466.4 lbs.

-87-

Working days per week: 5 Requirement for 10 weeks: 473,320 lbs. Number of bags: 4733 bags . Height of storage pile: 8 bags Area of bag: 2.5 x 1.5 = 3.75 sq. ft. Floor area required: 3.75 x~ = 2,220 sq. tt.

8 (Assume 10--~ of area for bags}

Height of ceiling: 9 feet Type of floor: concrete

A-4 SUgar Storage

Minimum supply: 2 weeks Replenishment period: 2 weeks Capacity of area: 5 weeks Containers: 100 lb. bags RequireIOOnt per 3 hour cycle: 4644 lbs. Cycles per day: 8 Requirement per day: 37,152 lbs. Working days pe.r week: 5 Requirement for 6 weeks: 37,152 x 5 x 6 = 1,014,560 lbs. Number of bags: 10,014.56 or 10,015 bags Height of storage pile: 8 bags Area of bag: 2.5 x 1.5 = 3.75 sq. tt. Floor area required: 10,015

3.75 X 8 = 4730 CU. ft. (Allow 10% of area for bags)

Haieht of ceiling: 9 feat Type of floor: concrete

A-5 Methanol Storage Tank

Minimum supply: 2 weeks Replenishment period: 4 weeks Capacity of area: 8 weeks Containers: 8000 gal. tenk car Capacity of tank car: 8000 x 8.335 x o •. 659 = Requirement per 3 hour cycle: 232.8 lbs • . Cycles per day: 8 . Requirement per day: 232.2 x 8 = 1857.6 lbs.

43,492 lbs.

Working days per week: 5 Requirement for 8 weeks: Necessary volume of tank:

1857.6 x 5 x 8 = 74,304 lbs. ..,,.,,.._7.,..4 .... , ... 3...,0,..4___,,,'""=" = 1510 cu. ft • 62.4 X 0.7913

Safety allowance 10-% 151 1661 cu. ft. or 12,200·gals.

-88-

Equipment available from: Lancaster Iron Works Inc., Lancaster, Pennsylvania Tank Dimensions: o.c., 96 in •

. Length, 41 ft. 2 in. Shell Thickness, 0.540 in. Capacity, 15,000 gals.

Number required: one tank

A-6 Hydrogen storage

Minimum supply: 2 weeks Replenishment period: 4 weeks Capacity of area: 8 weeks Containers: cylinders, 1600 psig, Requirement per 3 hour cycle: 155 Cycles per day: 8 ·

3 180 ft. , 101.75 lbs. lbs.

Requirement per day: 155 x 8 = 1240 lbs. Working days· per week: 5 Requirement for 8 weeks: l240 X 8 X 5 = 487 cylinders

101.75 Dimensions of cylinder: 9 in. dia. and 55 in. height

Floor area required: 9 x 9 x 487 • 274 sq. tt. 12 X 12

Height of ceiling: 9 feet Type of floor: concre.te

A-7 Hot Water Pump

Capacity: 90,gpm ~Iaterials handled: hot water Head : 10 . feet Type : open impeller, single stage, centrifugal Material of construction: caat iron. RPM: 1200 · · Motor: lBP, 220-440 volts, 3 phase, 60 cycles, .MJ, in-

duction, squirrel-cage, splash-proof, 1750 rpm. Equipment.available from:

Motor -·westingliouee Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,

N. ;r., Type OF-1 Number re(lUir~d: one mot or and one pump

B-1 Dissolving Tank

Capacity: 1480.gal. Shape: cylindrical

-90-

B-3 A Agitator

Type: "Lightin" mixer, Model M-2 RPM:· 1150 Material of construction: mild steel shaft and blade Motor: 2 HP, 220-440volts, 3 phase, 60 cycles, AC Equipment available frcm:

Mixing Co., Inc., Rochester, N. Y. · Number required: one

B-4 Reactor Pump

Capacity: 134 gpm Materials handled: suspensions Head: 15 feet Type: open impeller, single stage, centrifugal Material of construction: cast iron RPM: 1200 · Motor: 2 HP, -220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:

Motor - Westinghouse Elec. and Ivifg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,

N. J., Type CF-1 Number required: one pump and one motor

C-1 Centrifugal Filter

Capacity: 15,349.6 x 4 = 61,400 lbs. per hour Volume capacity: 2176 3C> • 72.5 gpm

Type: Solid bowl continuous Material of construction: mild steel Equipment available as:

Size (in} - 24 x 38 HP - 25,220 440 volts, 3 phase, 60 cycles, AC

induction, squirrel cage, splash-proof, 1750 rpm

Solids, cu. ft. per hour - 60-90 Max. teed GPM - 70 Bird Machine Co. , East Walpole, Mass.

-91-

C-2 Belt Conveyor

Capacity: 165 lbs. per minute Length of belt: 10 f'eet Width of belt: 18 in. Speed of belt: 40 f'eat per minute Motor: 0.5 HP, 220-440 volts, 3 phase, 60 cycles, A. C.

induction, squirrel cage, splash-proof, 1750 rpm Belt: 4 ply, 23 oz. Link Belt "Service Brand" duck Equipment available from:

Link-Belt Co., -Chicago, Ill. -

D-1 Rotary Dryer

Capacity: Evaporation rate - 1856.5 lbs. water per hour Steam rate - 2237 lbs. per hour (5 lbs. gage) Air rate - 1760 cu. tt. per minute

Type : Rot'ary, · direct steam heated Material of construction: mild steel Dimensions: O.D. 8 feet

Length 35 feet RPM: 1 Uotor: 8 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment to be made and installed by:

Blaw,.Knox _co., Pittsburgh, Pa.

D-1 A Blower

Capacity: 4000 cu. ft. per minute Type: Single stage pedestal turbo blower RPM: 3500. Pressure: l lb. ·. gage Motor: 25 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 3500 rpm Equipment available from:

· Allis Chalmers Mfg. Co., :Milwaukee, Wisconsin

D-2 Belt Conveyor

Capacity: 10.3 lbs. per minute Length of belt: 10 f'eet Width of' belt: 18 in.

-92-

Speed of belt : 40 tt. per minute Motor: .0.5 HP, 220-440 volts, 3 phase, 60 cycles, AC in-

duction, squirrel cage, splash-proof, 1750 rpm .Belt: 4 ply, 23 oz. Link "Service Brand", duck Equipment available from:

Link-Belt Co~, Chicago, Ill.

D-3 Rotary Kiln

Capacity: Evaporation rate - 154.3 lbs. water per hour Fuel oil rate - 3 gallons per hour Air rate - 35 cu. tt. per minute

Type: Rotary, direct heated Material of construction: · mild steel Dimension: 0.D. 2 feet

Length 11 feet RPM: l Motor: l HP, 220-440 volts,. 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment to be made and installed by:

Blaw-Knox Co., Pittsburgh~ Pa.

D-3 A Blower

Capac! ty: 45 cu. ft • per minute Type: Rotary Positive Blower RPM:: 1750 Pressure: 1 lb. gage Motor: 1/3 BP, 220-440 volts;· 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1'750 rpm Equipment availabl_e from:

Roots-Connersville Blower Corp. Connersville, Indiana Victor Acme Blower No. 36

D-4 Convey or Cooling Kiln

Capacity: Air rate: 813 cu. ft. per minute Solids rate: 371 lbs. per hour

Type: Belt· conveyor

-93-

Material of construction: Belt - woven steel wire Housing -·i in. sheet steel

Dimensions: · Belt - 5 series of belts, 26 ft. long and 3 ft. Wide

. Housing - 5 x 5 x 26 feet Speed of belt: 2.2. feet per minute Motor: 2 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash proof, 1750 rpm Equipment available from:

Link-Belt Co., Chicago, Ill.

D-4 A Blower

Capacity: 1000 cu. ft. per minute Type: Single stage pedestal turbo blower RPM: 3500 . Pressure: 1 lb. gage Motor: 10 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, spiash-proo:f, 3500 rpm · Equipment available from:

Allis Chalmers·~ttg. Co., ~lwaukee, Wisconsin

E-1 Crushing Rolls .

Capacity: Feed - 928.8 lbs. per hour, i in. Product - 928.8 lbs. per hour, -50 mesh

Type of material:· very brittle Type of crusher: single roll crusher Material of construction: mild steel Dimensions {in): 18 x 18 Motor: 10 HP, 220-440 volta, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:

C. o. Barlett and Snow Co., Cleveland, Ohio

E-2 Belt Conveyor

Capacity: 31 lbs. per minute Length of belt: 30 feet Width of belt: 18 in. Speed of belt: 40 ft. per minute

-94-

Motor:. 0.5 HP, 220-440 volts, 3 phase, 60 cycles, AO, in-duction, squirrel cage, splash-proot, 1750 rpm

Equipment available from: Link-Belt Co., Chicago, Ill.

F-1 Hydrogen Compressor

Capacity: Piston displacement - 311 cu. ft. per minute

Type: single horizontal three stage Material of construction: mild steel Dimensions:

Cylinder dia. in. Low pressure - 11 3/4 Intennediate - 7 1/4 High pressure- 3 l/8

Stroke, in. - 13 Maximum pressure: 1500 psi RPM: 250 Motor: 100 HP, .220-440 volts, 3 phase, 60 cycles, AC,

induction, squirrel cage, splash-proof, 1750 rpm Equipment available trom: . .

Worthington Pump and :Machinery Corp., Harrison, N. :r. Type HB-3 .

F-2 Methanol Pump

.Capacity: 3 gpm Materials handled: methanol Head: 15 feet Type: open impeller, single stage, centrifugal. Materials of construction: cast iron BFM: 1200 Motor: 1/3 HP, 220~440 volts, 3 phase, 60 cycles, AC,

induction, squirrel cage, splash-proof, 1750 rpm Equipment available from: ·

Motor - Westinghouse Elec. and _Mi'g. Co., Pittsburgh, Pa. Pump - Worthington Pump and U.iachinery Corp., Harrison,N.J'.

Type CF-1 Number required: one motor and one pump

-95-

F-3 SUgar Feed Hopper

Capacity: 78 cu. ft. Shape: cylindrical w1 th cone shaped bottom Total height: 9 feet Diameter: 4 feet Bottom:

Height - 4 feet Opening - 8 in. for drain

Material of construction: 3/16 in. mild steel plate Equipment available from:,

Blaw-Knox Co., Pittsburgh, Pa.

F-4 Autoclave

Capacity: 400 cu. ft. or 1450 gala. Shape: cylindrical Diameter: I.D. 5 feet Height:· 21-reet Plate thickness: 2.85 in. Material of construction: steel, ASfl/i Specification A-212,

Grade B, ·:tensile· strength - 70,000 psi Connections: Charging entrance top right side; Blow pipe

top left aide Heating unit: Strip heaters fastened on outside of auto-

clave shell; current supplied to be 845 kw., 220-440 volts, 3 phase, 60 cycles, AC

Attachments: one,.0-2000 lb. pressure gage; one, 0-500°F temperature recorder

Agitator: Type - .Anchor type RPM - 126 Motor - 10 HP, 220-440 volts, 3 phase, 60 cycles,

AC, induction, squirrel cage, splash-proof, 1750 rpm

Insulation: 3 in. magnesia (85%} Equipment available from:

\ Blaw-Knox Co., Pittsburgh, Pa.

F-5 Condenser

Size of condenser tubes: · l½ in. O.D., 16 B.W.G. Tube spacing - 3/8 in. Inside surfaoe area of tubes: 819 sq. ft.

-96-

· Length of tubes: 23 feet Number 01' tubes: 100 Diameter of tube shell: 22 in. TU.bing material: 0.15 carbon steel Condenser shell material: cast iron Type of condenser: Horizontal, double pass, countercurrent

flow, floating head shell. Type of baffles: orifice Vapor path: outside tubing; in at 464°F, out at 140°F;

velocity 169.3 lbs. per minute Liquid path: Inside tubing; in at 50°F, out at 200°F;

velocity 60.2 gpm Equipment available from:

\Blaw-Knox Co., Pittsburgh, Pa.

F-6 Condenser Cooling Water Pump

Capacity: 60 gpm Materials handled: water Head: 15 feet Type: open impeller, single Materials·of construction: RPM: 1200 ·

stage, centrifugal cast iron

Motor: l HP, 220-440 volts, 3 phase, 60 cycles, AC, in-duction, squirrel cage, splash-proof, 1750 rpm

Equipment available from: Motor - Westinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.J".

Type CF-1 Number required: one motor and one pump

F-7 Condensate Pump

Capacity: 33.5 gpm Materials handled: fine suspensions Head: 15 feet Type: oper impeller, single stage, centrifugal Niateriala of construction: cast iron BPM: 1200 Motor: l HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:

Motor: Westinghouse Elect. and Mfg. Co., Pittsburgh, Pa. Pump: Worthington Pump and Machinery Corp., Harrison,N.J".

Type CF-1 . . Number required: one motor and one pump

-97-

G-1 Basket Centrifuge

Capacity: 10,158 lbs. per hour Volume capacity: 24 gpm Type: under dri van basket centrifuge Material of construction: mild steel Equipment available as:

Basket capacity - 10.5 cu. ft. Basket diameter - 48 in. Motor - 10 HP, 220-440 volts, 3 phase, 60 cycles, AC,

explosion proof, 3500 rpm American Tool and Machinery Co., Hyde Park, Boston, Mass.

G-2 Basket Centrifuge Pump

Capacity~ 24 gpm Materials handled:· solutions Head: 10 feet Type: open impeller, single stage, centrifugal Material of construction: . cast iron BPM: 1200 Motor: 1/3 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, ,1750 rpm Equipment available from:

Motor - Westinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.j.

Type CF-1 Number required: one motor and one pump

H-1 Atmospheric still Pot

Capacity: 1415 gals. Shape: cylindrical with round bottom Diameter: 6 feet Height: a·feet .Material of construction: mild steel Heating surface required: 255 sq. ft.

Steam heating pipes -O.D. (in.) - 2 Spacing (in.} - l Length (ft.) - 3 Number - 163

Connections: Charging entrance through left side, exit entrance in bottom, vapors through rie;ht side.

-98-

Attachments:. one, 0-250°F temperature recorder Insulation: 3 _in. magnesia (85%}. Equipment available from:

Blaw-Knox Co., Pittsburgh, Pa.

H-1 A Fractionating Column

Number of plates: 14: Plate spacing: 18 in. Type of plates: Bubble cap Plate diameter: 2 feet Column height: . 21 feet Liquid seal on plates: · li in. Vapor velocity: 3.25 feet per second Reflux ratio: 3 . :rr.aterials of construction: mild steel Insulation: 3 in. magnesia (85%) Equipment available from:

, Blaw-Knox Co., Pittsburgh, Pa.

H-2 Atmospheric Still Condenser

Size of condenser tubes: li in. O.D., 16 B.W.G. Tube spacing: 3/8 in. Inside surface area of tubes: 458 sq. ft. Isngth of tubes: 17 ft. Number of tubes: 75 Diameter of tube shell: 18 in. Tubing material: 0.15 carbon steel Condenser shell material: cast iron Type of condenser: vertical, double pass, counter current

flow, floating head shell Type of baffle: -orifice . Vapor path: outside tubing; in at 212°F, out at 70°F;

. velocity 81.3 gpm Equipment available from:

Blaw-Knox co., Pittsburgh, Pa.

H-3 Condensate Pump

Capacity: 5. 7 gpm Materials handled: methanol and water Head: 10 feet

-99-

Type: open impeller, single stage, centrifugal Material of construction: cast iron BPM: 1200 Motor: 1/3 BP, 220~440 volts~ 3 phase, 60 cycles, AC,

induction, squirrel cage, splash-proof, 1750 rpm Equillllent available from:

Motor - Westinghouse Elec~ and Mtg. Co., Pittsburgh, Pa. Pump -Worthington Pump and· Machinery Corp., Harrison, N. j.

Type.CF-1 Number required: one J!!-Otor and one pump

H-4 Condenser Cooling Water Pump

Capacity: 81.5 gpm. Niaterials handled: water Head: 30 feet Type: open impeller, single stage, centrifugal Material of construction: cast •iron RPM: 1800 Motor: 2 BP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1800 rpm Equipment available from:

Motor - Westinghouse Elec. and ~Itg. Co., Pittsburgh, Pa. Pump - Worthington Punip and Machinery Corp., Harrison,N.j •

. Type CF-1

H-5 Atmospheric Still Pump Capacity: ·33.4 gpm· :tiaterial handled: solutions Head: 10 feet Type:· open impeller, si~gle stage, centrifugal lTaterials of construction: cast•iron · BPM: 1200 Mot or: 1 BP, 220-440 volt a, 3 phase , 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:

Motor: Vlestinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump: -Worthington Pump and Ua.chinery Corp., Harrison,N.j.

· Type CF-1 Number required: one motor and one pump

-100-

I-1 Vacuum Still

Capacity: 435 gala. Shape: cylindrical With round bot tom Diameter: 4 ft. Height : 5. 5 ft • 11aterial of construction: mild steel Heating surface reqµired: 127.5 sq. ft.

Steam heating pipes O~D. (in.) - 2 Spacing (in.) - 1 Length (in.) - 2 Number - 122

Connections: Charging entrance through left side, draw off in bottom, vapor exit through right side

Attachment: one, 0-500°F temperature recorder .one, 0-30 in. vacuum gage

Insulation: 3 in·. magnesia ( 85%) Equipment available from:

\ Blaw-Knox Co., Pittsburgh, Pa.

I-2 vacuum Still Condenser

Size of condenser tubes: l½ in. O.D., 16 B.W.G. TUbe spacing: 3/8 in. Inside surface area of tubes: 123 sq. ft. Length of tubes: 12 ft. Number of tubes: 30 Diameter of tube shell: 12 in. Tubing material: 0.15 ca:rbon steel Condenser shell material: cast iron Type of condenser: horizontal, double pass, counter current

flow, floating head shell Type of baffle: orfice Vapor path: outside tubing; in at lS0°F, out at 100°F;

velocity 16.6 lbs. per minute Liquid path: inside tubing; in at 50°F, out at 77°F;

velocity 25.8 gpm Equipment available from:

Blaw-Knox Co., Pittsburgh, Pa.

-101~

I-3 Vacuum Pu.mp

C~pacity: Piston displacement - 137 gpm Type: horizontal single air· and steam heating vacuum pump Materials of construction: mild steal Dimensions (in.}: x 8 x 7 Piston speed: 53 ft. per minute steam required: 1250 lbs.@ 105 psi Equipment available from:

Worthington Pump and Machinery Corp.,. Harrison, N. ;r. Type AE

I-4 Condenser Cooling Water Pump

Capacity: 25.8 gpm Materials handled: water Head: 15 f't. Type: open impeller, s~ngle stage, centrifugal Material of construction: cast iron El?M: 1200 Motor: . 1/3 HP, 220-440 volts, 3 phase, 60 cycles, AC, in-

duction, squirrel cage, splash-proof, 1750 rpm Equipment available from:

Motor - Westinghouse Elec. and YJ!'g. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.;r.

Type CF-1 Number required: one motor and one pump

I-5 Condensate Pump

Capacity: 1.83 gpm N..a.terials handled: propylene glycol and glycerol Head: 10 ft. Type: open impeller, single stage, centrifugal Materials of construction: cast iron BPM: 1200 Motor: 1/3 HP, 220-440 volts, 3 phase, 60 cycles, AC,

induction, squirrel cage, splash-proof, 1750 rpm Equipment available from:

Motor - Westinghouse Elec. and Mfg. Co., Pittsburgh, Pa. Pump - Worthington Pump and Machinery Corp., Harrison,N.;r.

Type CF-1 Number required: one motor and one pump

-102-

J'-1 .Antifreeze storage .

Capacity: one week supply Requirement per 3 hour cycle: 330 gals. Cycles per day: 8 Requirement per day: - 330 x 8_ =. 2640 gals. Working days per week: 5 Requirement per week:· 2640 -x 5 = 13,200 gals. Equipment available from:

Lancaster Iron Works, ·Inc., Lancaster,Pa. Tank Dimensions: o.n. - 96 in.

Length - 41 tt., 2 in. Shell thickness - 0.540 in. Capacity - 15, 000 gals. ·

Number required: one tank

K-1 Hand Trucks

Type: ",Single Lift", hand operated Maximum ·capacity: 2500 lbs. Minimum lift: • l 1/3 in. Number of strokes tor maximum lift - 5 Number required: 5 Equipment available from~

The Yale & Towne .Mfg. Co., Philadelphia, Pa.

-103-

Sample Calculations for Equipment Design

Rotary Drier.

Heat re4uired to raise mass to 212°F

Water {1856.5 154.3} X 1 X {212-75) = 275,479.6 Btu

Al203 223.5 X 0.198 X {212-75} = 6,062.3

Cu0 179.5 X 0.144 X (212-75) - 3,540.1 -Na2so4 46.4 X 0.22 X {212-75) = 1,398.8

Naf0 3 15.l x 0.256 x (212-75) = 526.l 287 ,006.,9

Heat re4uired to evaporate water

Using steam @5 lb. gage and assuming a steam efficiency

of 60%.

·l, 288, 588 •7 = 2237 lbs. steam required 960.l X 0.60

Moisture in feed material Moisture in discharge material Water to be evaporated

75% 25~~ 1856.5 lbs.

.Entering air 75°F 40% R.H. Humidity - 0.0075 lbs. water per lb. dry air

Leaving air 150°F 60% R. H. Humidity - 0.1255 lbs. water per lb. dry air

o.i!~~~o:oo75 = 15648.3 lbs. air

Specific volwne of air - 13.5 cu. ft. per lb. 15648.3 x 13.5 = 211,252 cu. ft. per cycle

-104-

Drier Dimensions

Time operated - l hour 211,252 ·

60 = 3521 cu. ft. per minute

However, material is actually in drier only 30 minutes so dimensions are based on this assumption •

. . 30

3521 X 60 = 1760 CU. ft.

Assume a diameter of 8 feet for drier. 1760 _

8 8 - 33.7 or 34 feet for length of drier. 3.14 X :

-105-

Sample Calculations (Cont'd.)

Autoclave:

Pressure - 1500 psig Temperature 465°F

Calculation of Viall Thiclmess{ 2l'

Assume diameter of 5 ft. I. D. of autoclave

t = R SE p SE-P - l

t = thickness of cylindrical shell, inches R = inside radius of cylinder, inches s = allowable working stress, lbs. per sq. in. E = efficiency of.longitudinal seam, per cent P ='design pressure, lbs. per sq. in.

t = 30 70,4000 X 0. 95 · 1600 ·

704000 X 0. 95 - 1

- 1600

= 2.86 in. plate thickness

Volume occupied by materials - 194 cu. ft. Assume 100% safety factor so that volume of autoclave will

now be 400 cu. ft. 400 ------ = 20.4 feet height of autoclave

3.14 XO: 5 Use 21 ft. as height

-106-

Sample Calculations (Cont'd.)

Atmospheric still •.

Heat required to raise mass to 212°F

C%0H 4644 X 0.39 X (212-70) = 275~302

Water ·1123 X 1 X (212-70) = 171,817

C~5(0H)2 1834.4 X 0.525 X (212-70) : 136,761.8

C3%(0H)3 1165.6 X 0.299 X (212-70) = 95,997.0

Residue 510.8 X 0.299 X (212-70) = 21,710.2 701,588

Heat required to vaporize methanol and water

4644 X 262 X 1.8 : 2,196,797.4 1123.8 X 539.5 X 1.8: 1,090,545.3

3,287,342.7

Total heat required 701,588 3,287,342.7 3,988,930.7 Btu

Btu

Using steam@ 5 lb. gage and assuming a· steam efficiency or 60% ·

3,988,930.7 - 6924 l.b t 3 h 960.l x 0•60 - s. seam ~or ours

Total heat required in Btu per hour

329883930•7 = 1,329,643 Btu per hour

Heating surface required:

_q_ 1,329 643 A= Udt = 60 x (2g?-J.40) = 255 sq. ft.

Assume U = 60 dt = (227-140)based on constant temp. of steam 227°F and aver. temp. of feedJ4:00F.

-107-

Sample Calculations ( Cont 'd. }

Use 2 in. O.D. tubes Area - sq. tt. per linear foot 0.5233

0_5:;; x 3 = 163 pipes requirea,each being 3 ft. long

Volume occupied by pipes

2 X 2 3.4 X 4 X 144 X 3 X 163: 10.65 CU. ft.

Volume of liquid material

189.0 10.65 = 199.65 or 200 cu. ft.

Assume a dia. of 6 ft. for still pot

200 · 6 x 6 = 7.2 tt. height of still

3.14 X 4 Use 8 ft. as height

-108-

Sample Calculations (Cont'd.)

Fractionating·column.

Assume: Over all efficiency of 60% Reflux ratio of 3 to 1 . Distillate: 99.5 pure (mol %) Molecular weight of distillate: 32 Molecular weight of residue: 18 Methanol recovered: 95%

Material to be fractionated: 4644 lbs. methanol 1123· lbs. water

Calculation of Number of theoretical plates: McCabe-Thiele Diagram

Feed 4876 32 -48- 76-- 1-1-23-• 0.707 mol. fraction

°32 18

Residue X. 232 32 -

232 1123 - 0.322 mol. traction 32 18

.:rd = 99.5 mol. % or 0.995 mol. :tractio11 (assW11ed)

y intercept - = 0.995. 0 •25 R l 3 1

Number of theoretical plates - 8 (See. Figure 12)

Number of actual plates - o.:o = 13.3 or 14

Height of column

Assume: plate spacing - 18 in. liquid seal - lj- in.

-109-

Vapor velocity:

V = Kv P1 - P2 ½ Assume Kv = 0.13 P2

P1 = 45 lbs. per cu. tt.

32 273 P2 = 359 x 273 65 = 0.072 lbs. per cu. ft.

4644 . 359 460 284 ~x 3600 x 3 x 460 70 = 6.77 cu. ft. per sec.

Tower .Ai-ea

= 2.08 sq. ft.

3.14 x d2 . 2.08 = ------4

d = l.63 or 2 ft. dia. ot column

Height of column: 14 x 1.5 = 21 ft.

-111-

Sample Calculations (Cont'd)

Atmospheric still Condenser.

Calculation of cooling water required:

Time operated - 3 hours Assume water enters at 50°F and leaves at 77°F.

wcdt = w w=w

cdt 4644 X 262.8 X 1.8 =--------1 X 77-50

w: weight in lbs. c = specific heat

= latent heat of vapori-zation, Btu

dt = change in temp •. °F

= 81,361.7 lbs. water for methanol

_ 1123 X 539.5 X 1.8 w - l_x 77-50

= 40,390.5 lbs. water for water

Total cooling water= 81,361.7 40,390.5 = 14,617.3 gals. 8.335

Heat required to remove:

4644 x-262.8 x 1.8 = 2,196,797.4 Btu tor methanol 1123' x 539.5 x 1.8 = 1,090,545.3 Btu for water

3,287,342.7

3 ,2873342•7 = 1,095,781 Btu per hour

.Area required:

Vapors enter at 212°F Vapors leave a~ 70°F Water enters at 50°F Water leaves at 77°F

-112-

Sample Calculations (Cont'd.)

q = UAdtm Assume U = 4.0

dtm : 135 - 20135 = 60.2oF 2.3 X log. 20

A = 1,095,781 _ 458 . 60.2 X 40 - · sq •. ft.

Use 1½ in. 0.D. condenser tubes, I.D. 1.37 in. Area - sq. ft. pa·r linear ft·. :: 0.3~

458 · · 0 _36 x 75 = 17 ft .• length of tubes using 75 tubes

HOURS

Dissolver :E'ill . - •--•

Reactor

-113-

SCHEDULE OF OPERATION FOR EQ.UIP.MENT IN THE PREPARATION OF PROPYLENE

GLYCOL AND GLYCEROL .AND CONGENERS

Ba.sis: 3 hour cycle

¼ .l. i l l¼ ,,. lj- lf 2 21 2 4:

r,

Fill and Reaction

Reactor, Empty .... r

and Centrifuge

Dryer ... r.

Kiln ... .,

Cooler

Crusher

Fill Autoclave

Autoclave, . . Reaction

Autoclave, Empty and Condenser

Centrifuge ... , tind Fill Still

Atmospheric Still

Pump to VAC still VAC Still

2½ 2£ 3 .

... .

..._ .

H . .,

... ,

... •

. .

J-1 ------- --- -

-115-

Preconstruction Cost Accounting

A. Estimated Fixecl Capital: Building and Land

l. Land, 300 ft. x 110 ft. (l acre) C e1,000 per acre

2. Buildings, l warehouse l storeroom 1 office and lab.

140,130 cu.ft. 10,000 16,200

166,330 cu.:tt. @ $0.75 per cu.

3. Fencing, 820 ft. x 7 ft. high @$3.00 per ft.

4. Railroad,. 240 · C ~o.6'~ per ft.

5. Locker Room and Toilet Facilities

6. Drinking Fountains

'1. Roads, Pavements, and landscaping ·

8. Excavation

Total Building and Land Fixed Capital

B. Estimated Fixed Capital: Equipment

1. Material storage

No. Item

ft.

A-5 Methanol storage Tank Cyl., Mild steel F-3 Sugar Feed Hopper Cyl., mild steel J"-1 Antifreeze storage Cyl,, mild steel

$1,000

124,738

2,460

12,000

1,500

200

2,500

1,440

$145,858

Cost

<,$1,800 200

1,800 i:5,800

-ll6-

2. Material Handling

No. Item Cost

A-7 Hot Water Pump Single Stage,Centrifugal $60 B-2 Dissolving Tank " " tt. 50

Pump B-4 Reactor Pump It n " 80 F-2 Methanol Pump n n n 50 F-6 Condenser Cool-

ing Water Pump " It " 50 F-7 Condensate Pump " n " 50 G-2 Basket Centri-

·:ruge Pump ti " It 50 H-3 Condensate Pump " ti It 50 H-4. Condenser Cool.-

ing Water Pump " " n 60 H-5 Atmospheric still

Pump ti n " 50 I-4 Condenser Cool-

ing .Water_. .Pump It " It 50 I-5 Condensat~ Pump n n It 50 - ·• .. I-3 Vacuum Pump Horizontal single.air 200

&. steam heating C-2 Bel.tConveyor Bel.t, 1.0 :rt. a. to c. 100 D-~ Belt Conveyor Belt, 1.0 tt. c. to c. 100 E-2 Belt.Conveyor_ Belt, 30 ft. c. to c. 200 K..;l Hand Trucks 5 C $100 500

il,750

3. Motors

HP. No. Motor Cost {Com;2.) Total

1/3 5 j53 $265 i 3 61 .183 1 ·5 52 260 2 2· 68 136

isi4"

-117-

4. Mixing Tanks

No. Item

B-1 B-3

5. Filtration

No.

C-1

G-1

Dissolving Tank Reactor

Item

Centrifugal Filter

Basket Centrifuge

6. Dryer, Kiln, and Cooler

No.

D-1

D-3

D-4

Item

Rotary Drier

Rotary Kiln

Conveyor Cooling Kiln

7. Stills, Column, and Condensers

Cyl. , Cypress Cyl., Cypress

Solid bowl, continuous

Under Driven

Rotary,direct heated

Rotary, direct fired

Belt Conveyor

Cost

$ 94 151

~245

Cost

$8,000 S,000

$11,000

Cost.

$14,080 .

1,385 2,000

$17,465

No. Item

F-5 Cond,enser

Size

Horizontal 819 sq. ft.

Cost

$4,516

2,383 H-2 Atmospherio

still Condenser I-2 vacuum still

Condenser H-1 Atmospheric

Still Pot H-lA Fractionating

Column I-1 vacuum Still

vertical 458 sq. ft.

Horizontal 123 sq. ft. 1,103 6 tt. dia., 8 ft. high 1,150 14 plates·,2 ft. dia.,21 rt.high 600 4 ft. dia., 5.5 ft. high 725

$10,477

8.

9.

-118-

1tiscellaneous Equipnent

No. Item

F-4 Autoclave, 5 ft. I.D., 21 ft. high B-1 A Agitator, "Lightin" Mixer, 1 HP B-3 A .Agitator, "Lightin" Mixer, 2 HP E-1 Crushing Rolls, Single Roll, 18 x 18 (in} D-1 A Blower, 4,000 cu. ft. per min. D-3 A Blower, 45 cu. ft. per min. D-4 A Blower, 1,000 cu. ft. per min. F-1 Single Horizontal, 3 stage,

311 cu. ft. per min.

Instruments

No.

Flow meter, recording 11 Flow meter, non-recording 5 Thennometer, record and control 11 Thennometer, .non-record 3 Pressure, recorder and control 2 Pressure Gage 1 Fuel Gage 1 Vacuum Gage 2

a. Material storage b. Material Handling c. Motors d. Mixing Tanks e. Filtration t. Dryer Kiln and Cooler g. Stills, Column & Condensers h. Miscellaneous Equipment L Instruments

Eg_uipment Basic Cost

Cost

$400 20 50 20

150 20 20 20

$3,800 1,750

844 245

11,000 17,465 10,477 30,218

6,590 $82,389

Cost

$25,000 205 255 750

1,400 128 480

2 2000 $30,218

Total

$4,400 100

1,650 60

300 20 20 40

16,590

c.

D.

E.

-119-

Installation Costs

Item Basic Cost Per Cent Instal. Cost

Tanks $3,800 15. $570 Pumps 850 15 128 Belt Conveyor 900 20 180 Motors 844 10 85 Mixing Tanks 245 15 · 37 Filtration 11,000 25 2,750 Dryer, Kiln, Cooler l.7,465 30 5,240 Condensers, Still and

Fractionating Column 10,477 35 1,419 Autoclave 25,000 30 7,500 .Agitators 460 5 23 Crusher 750 8 60 Blowers 2,028 5 102 Compressor ·2,000 30 600

$18,694

Total Equipment Cost

Equipment Basic Cost ~82,389 Installation Cost 18,694 Freight (2% Basic Cost) 1 2648 Total Installed Cost 102,731 Accessories (75% Installed Cost) 77 z 048

$179,779

Working Capital

1. Raw Materials (25% of Raw Material Cost) $136,184 2. Labor and supervision (25% ot Labor

and supervision) 30,660 3. Fixed Charges

a. Realty Taxes (O. 75% of o;s x Bldg. and Land plus Equipmeµt Costs) 1,465

b. Others (25% of Social security Tax plus Insurance) (1) social Security(0.015

of total under i3000 per year) $1,234

(2) Insurance (a) Extended Coverage

(0.5% of 0.9 x Bldg. and Land Cost} 656

-120

{b} Equipment (1.0% ot . 0.66 X Equipmen.t

Cost) ~l,187 Total Social Security Tax and Insurance $3,061

Other fixed charges ~3061 x 0.25 4. Engineering (10% ot Bldg. and Land plus

Equipment Cost) 5. Legal Costs

Total Working Capital Per Year

F. Capital Investment

l. Buildings and Land 2. Equipment Costs 3. Working Capi taJ.

Total Capital Investment

G. Estimate of Operating Cost l. Raw Materials

a. Copper Sulfate, 4,507.2 lbs. per day @ $0.07 per lb.

b. Aluminum Sulfate, 11,646.4 lbs. per day,@ $0.0115 per lb.

c. Soda Ash, 9,466.4 lbs. per day @ $0.012 per lb.

d. sugar, 37,152 lbs. per day, @$0.04 per lb.

e. Methanol, 282 gals. per day, @$0.24 per gal.

t. Hydrogen, l,240 lbs. per day, @ i0.05 per lb.

g. Water Processed, 700 gals. per day, @$0.22 per 1000 gals.

Cost Per Day

$765

$3?,564 2,500

$204,138

$145,858 .179,779

$529,775

$315.50

133.93

ll3.60

1,486.08

67.68

62.00

0.15 $2,178.94

Total Cost Per Year {250 days) $544, 735 .00

2. Productive Labor

Based on: 8 hr. day, 40 hr. week, 52 weeks pay.

3.

-121-

Employer No. Hourly .Annual. Total. Rate Salary- Cost

Per· Per Employer Year

Catalyst Area Operators 3 i3,600.00 $10,800

Hydrogenation Area Operators 3 3,600.00 10,800

Catalyst Area Laborers 6 $0.91 1,892.80 11,357

Hydrogenation Area Laborers 15 ~0.91 1,892.80 28,392

Total Coat· Productive Labor

Manufacturing Expense

a. Fuel

1. Water, raw, 197,403 gals. per day, @~0.05 per 1000 gals.

2. Fuel oil, 24 gals. per day, @$0.03 per gal. Total Cost per Day

Total Cost per Year(250 days)

b. Maintenance (10-fa Fixed Capital on Equipment plus 5% on Bldg. and Land)

c. Power l. Steam, 125,264 lbs. per day

@ $0.50 per 1000 lbs. 2. Electric Power, 8575 Kw-hrs. per day

@ $0. 0125 per Kw-hr. 3. Electric Lights, 100 outlets x 100 watts x

24 hrs. @ $0.04 per Kw-hr. ·

$61,349

~9.87 0.72 -$10.59

~264.75

$25,270

$62.64

107.19

9.60 Total Cost per Day ~179.43 Total Cost per Year $43,858.00

4. Plant Transportation and Warehousing

a. Warehouse Operators, 3, @ $3,600 per year · $10,800 b. Warehouse Area Labors,9, .@.~l,892.80 per year 17,035

Total Cost per year $27,835

-122-

5. Testa and Inspection (l man per day plus 100% overhead)

a. Chemist, @ $3300 per year 100% overhead $6,600

6. Plant Administration ·

a. Plant Y.anager, @ $8000 per year b. Bookkeeper and Paymaster, @$3000 per year c. Watchmen, 3, @ $1664 per year

Total Cost per Year

7. Depreciation (5% of Bldg and Land plus 20% Equipment Coat}

a. Insurance

a. Extended Coverage (0.5% of 0.9 x Bldg. and Land Cost}

b. Equipment (l.~ of 0.66 x Equipment Cost} Total Insurance per Yr.

9. Taxes

a. Realty (0.75% of 0.6 x Bldg. and Land plus Equipment Cost)

b. social Security (0.015 of total under $3000 per year)

Tote.l Taxes per Year

TOTAL MANUFACTURING EXPENSE

TOTAL MA.NUFACTORING cosr BUIK

l. Raw Materials 2. Productive labor 3. Manufacturing Expense

Total Manufacturing Cost Bulk,1'.o.b.

$8,000 3,000 4,992

$15,992

$61,226

$656 1,187

$1,943

$1,465

1,234 $2,699

$185,687.75

sj544,735 61,349

185,687.75 $791,771.75

Estimate of Wholesale Selling Price - The effect of the price

of sugar and catalyst recovery on the wholesale price of the anti-

freeze is shown in Table XI. From this table it can be easily seen

-123-

that even with sugar at $0.02 per lb. and a recovery of 75% of

the catalyst, the price of $0.166 is in excess of the $0.135

for ethylene glycol. In order for such a plant to operate, the

price of ethylene glycol would have to rise to at least $0.165

per lb.

TABLE XI

ESTIMATE OF TIHOSESALE SELLING PRICE*

Sugar@ $/lb .. 0.04 0.04 0.03 0.02

·catalyst Recovery No Yes Yea Yes

75%

Raw Material Cost 0.091 0.073 0.058 0.0-43 I I-' I\?

""" Productive Labor and· ' Manufacturing Expense 0.041 0.041 0.041 0~041

Income Tax, Surplus, Research Interest, 0.041 0.041 0.041 0.041 Development,New Markets, etc.

Yiarketing Cost (Adver-tising, Sale Expense, 0.04:1 0.041 0.041 0.041 Commissions, etc.

Total Wholesale Selling Price $/lb. 0.217 0.206 0.181 0.166

~hurchl 11, H. L. How to Price for Progress, Chem. &Met. 42, 129-33, (1935}

-125-

Plant Location

The hydrogenation of sugar to obtain an automotive anti-

freeze is greatly dependent upon the cost of its chief raw

material, sugar, as may be seen in the· Preconstruction Cost

Accounting Section, p~ge 120. This fact would tend to locate

the plant near some sugar cane producing area in order to de-

crease the cost of the sugar as much as possible.

The state of Louisiana leads the country today in the

amount of sugar produced. There has been a considerable flow

of chemical industries to Louisiana in the last few decades,

creating a supply of experienced labor, especially around Baton

. Rouge.

The fuel, water, labor, power, availability of raw ma-

terials, end land costs would be practically constant through-

out the state. Transportation of the finished product would

then be the major factor in the location.

The markets to be supplied will be the eastern end mid-. .

western states. If the plant was located near Baton Rouge, it

would have the advantages of transportation, experienced labor,

and a nearby seaport, New Orleans, for possible overseas market.

Also, Baton Rouge is· the center of the suga~ cane growing industry.

-126-

IV. DISCUSSION

A. Rasul.ts

Preparation and Yield of Copper Aluminate Catalyst. Since

Lenth and DuPuis( 45 ) did not indi~te in their work what yield

and composition they obtained in the preparation of the catal.yst

that was used in the hydrogenation of sugar, this data had to be

determined experimentally in order that the plant could be de-

signed.·

Four runs were made to determine the composition and· yield

of the copper aluminate catalyst ~sing the same concentration of

reactants arid procedure as were used by Lenth and DuPuis( 46 l.

In Runs 1 and 4, technical aluminum sulfate was used as did Lenth

and Du.Puis(46). However, in Runs 2 and 3, some aluminum sulfate

which was not technical grade was used by.mistake, and conse-

quently as may be seen from the data given in Table III, the

yield was approximately 25.3 grams instead of 20.6 grams. Al-

though the yield was higher in Runs 2 and 3, the calculations

for the design of the plant were based on the yields of.Runs 1 . .

and 4, since it had been proven by Lenth and DuPuis( 45 ) that this

catalyst would work, and since no actual hydrogenation of sugar

was carried out, there was no way of knowing if such a product

as prepared in Runs 2 and 3 would give favorable results when used

as a catalyst.

-127-

By calculating the theoretical yield of copper aluminate

that could be expected and noting the actual yield that was ob-

tained, it was found that the catalyst was not entirely copper

aluminate but contained soIIB impurities. So for the purpose of

design, it was assumed that the copper aluminate catalyst con-

tained 10-; impurity calculated as sodium sulfate and 3.24% un-

reacted soda ash which were not washed out in the washing of the

catalyst before drying, and 86.76% copper aluminate.

Identification of Glycerol and Congeners. When this in-

vestigation was begun, a letter was written to ~. Lenth( 4s)

requesting a sample of the glycerol arid congeners fraction re-

ported in the literature. The letter was referred to the Miner

Laboratories in Chicago who took over the work of Lenth and

DuPuis( 4G). Since the actual hydrogenation was not carried out,

a representative sample of this impure glycerine fraction that

Lenth and DuPuis( 4G) reported was necessary in order to test the

suitability of an antifreeze made of propylene glycol and glycerol

and congeners as obtained in the hydrogenation of sugar.

Before this fraction was used, it.was.compared with that

reported by Lenth and DuPuis( 4G) by specific gravity and deter-

mination of glycerine content by the bichromate method. Lenth

and DuPuis( 46 ) reported a specific gravity of 1.198 and the

-128-

s];lecific gravity_ of the fraction donated by the Miner Labora-

to7ies determined with a Westphal balance was 1.194, showing

only a very slight difference in the two fractions. The glycer-

in content of glycerol and congeners reported by Lenth end

DuPuis(4G) was 71.8% by the acetylation method, and the glycer-

ine content of the fraction used in·this investigation by the

Bichromate method was 78%. The Bichromate determination re~

quired the use of a starch indicator and the end point depended

upon the change of color of the solution from a light tan to a

light green. When the end point was being approached, a very

heavy black substance precipitated making it extremely difficult

to see the green end point •. Because of this fact, the differ-

ence in glycerine content of the two fractions does not indicate

that they actually differ that much.

Makeup of Propylene Glycol-Glycerol and Congeners-Water So-

lutions. Since the antifreeze was to consist of· the propylene

glycol and glycerine fractions obtained in the hydrogenation of

sugar, a mixture of these two fractions was made up in the pro-

portions they would be expected to be received as products of

the hydrogenation reaction, 61.2% by weight propylene glycol and

38.8% by weight glycerol and.congeners. This. mixture was then

diluted with distilled water to give solutions of 10-45% by·

volume propylene glycol-glycerol and congeners.

-129-

Viscosity Determinations. The Ostwald viscosimeter, which

was used for solutions having kinematic viscosities below 5

centistokes, was calibrated against water and sugar solutions

having known absolute viscosities and specific gravities. The

Ostwald-Fenske viscosimeter, which was used for substances having

kinematic viscosities greater tha.n.5 centistokes, was calibrated

against a 60% sugar solution, and various glycerine solutions.

Since the absolute viscosity and specific gravity were known for

these standard solutions, the kinematic viscosity could be calcu- ·

lated and plotted against the time in seconds for each solution

to give a calibration curve for each viscosimeter. Then the vis-

cosities of the different antifreeze solutions were determined by

knowing the viscosity ti~es. Knowing the time and the viscosimeter

used, the kinematic viscosity could be picked off the calibration

curve. Since the specific gravity of each antifreeze solution was

determined at the temperature of the test, the absolute viscosity

could be calculated from the kinematic viscosity by multiplying by . .

the specific gravity. In Figure 5, a curve of absolute viscosity

vs. temperature was plotted for each solution to show the extent of

viscosity increase as temperature is lowered. In order to det~rmine

the viscosity of the various antifreeze solutions at their.freezing

points, to complete the curves in Figure 5, it.was necessary to

-130-

extrapolate the experimental data by applying Duhring's rule< 55)

as shown in Figures 5, 6 and 7.

From Figure 5 it may be seen that solutions up to 45% by

volume were tested for viscosity. Solutions of 60% by volume of

ethylene glyco1< 12) have been used in automobile radiators, and

this solution bas an absolute viscosity of 70 centipoises at -3o0c. The viscosity of solutions of propylene glycol-glycerol and con-

geners up to 45% by volume are suitable for use as antifreezes

since at -25.5°c a 45% by volume solution has an absolute vis-

cosity of 61 centipoises.

Freezing Point Determination. Previous investigatorsC 27 )

(29)(32)(53)(62) in determining the freezing point of commonly

used automotive antifreezes based their tests on either the ap-

pearance or disappearance of crystal formation so that the

element of human error was placed in the experiment. This may

be the cause of the difference in the freezing points of the same

solutions reported by different investigators. In order to elim-

inate this error as nearly ~s possible, the cooling curve method

of determining the freezing point described by FindlayC 34 } was

applied in this investigation.

This method consisted essentially of cooling the solution in

a cooling medium and recording the time at regular intervals.

-131

When the solution began to crystallize, the temperature remain-

ed constant until the heat of crystallization had been taken

away-. After this, the temperature began to drop. The time was

plotted against the temperature of the solution in Figure 10

which shows a flat place or a constant temperature level in the

curve for each solution. These flat places were taken as the

freezing points of the corresponding solutions. By using this

method there can be no error in seeing the first crystal appear

or the last one leave as the case may be, but a constant level

will be reached which may be duplicated by any other investigator.

In Figure 11 the freezing points of the different solutions

of propylene glycol-glycerol and congeners solutions are com-

pared with ethylene glycol-water solutions. It can be seen from

these curves that ap~rorlmately 5-7% by volume more propylene

glycol-glycerol and congeners will be needed to obtain the same

freezing point depression.

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B. Plant Design

Competition with Ethylene Glycol. The plant was designed

to produce 3000 tons of permanent antifreeze consisting of propy-

lene glycol and glycerol and congeners which constituted approxi-

mately 65% by weight yield of the original weight of sugar. This

production figure represented 5% of the ethylene glycol which was

used as automotive antifreeze in 1945. It was decided that such

a figure would not disrupt the market for permanent type auto-

motive antifreezes.

The cost of production was based upon the cost of ethylene

glycol at approximately $1.25 per gallon rather than at the cost

of "Preatone", "Zerex" or some other camnercial pennanent type

antifreeze retailing at $2.65 per gallon. "Prestone" and "Zerex"

contain about 9?% ethylene glycol, the other part being made up

of various types of foaming corrosion, and rust inhibitors. The

large gap in price here is not largely due to the cost of inhibi-

tors but to the middle man profit. Sinoe very little has been

published on the type of inhibitors used because the antifreeze

producers wish to maintain the secret and since this would entail

a considerable amount of additional experimental w:irk, it was de-

cided that if a plant could be desigµed to produce an.automotive

antifreeze from sugar at the same price as ethylene glycol, it

could compete with "Prestone" and "Zerex".

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Design. After the suitability of the antifreeze had been

proved, the design of the plant waa based upon the data of Lenth

and DuPuis( 4S) and Stengel and Maple(s 4 ){s 5 ). The proper equip-

ment was selected and a heat and material balance were made across

each piece of equipment. Each piece was either selected or de-

signed according to capacity and material of construction.

The plant layout was based upon the storage of raw materials

and their accessability to the plant, related equipment and future

expansion. Both the equipment and storage areas are enclosed.

After the plant design and layout were completed, the cost

of raw materials, buildings and. land, .labor and supervision,. and

equipment were computed. These costs were summarized in the form

of fixed charges, working capital, capital investment, annual

gross income, annual cost, and annual net income. In order to

build the plant it was found that a capital investment of i529,775

was re quired •

The location of the plant was decided upon by considering

the fuel, water, labor, power, availability.of raw materials and

market for product, land coats, and transportation. Baton Rouge,

Louisiana was selected as the location of, the plant since it was

in the heart of sugar cane growing district, possessed excellent

transportation to the eastern and midwestern markets in the U. s.

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and to the possible overseas market through nearby New Orleans,

and also the availability of experienced labor in and around

Baton Rouge due to the presence of other chemical industries.

Cost Explanation.· After reviewing the cost estimate of the

wholesale selling price, it can be seen·that even· if sugar could

be bought at $0.02 per lb. and a recavery of 75% of the catalyst

was possible, the price of ethylene glycol would have to rise to

$0.166 per lb. if such a plant were to operate.

The price of sugar is one of the controlling factors in the

success of the process. The price used in the calculations was

$0. 04 per lb., but no doubt if this plant were set up in Baton

Rouge in the heart of the sugar cane district, the sugar could be

bought considerably cheaper.

A second large item controlling the cost of the plant is

the coat of producing copper aluminate catalyst. Since no actual

experimental hydrogenation was carried out, and the literature

stated that the catalyst is reduced in the process, there was no

way of knowing if the catalyst could be recovered and reactivated.

Consequently, in the design of the plant, the catalyst had to be

thrown away after use. The recovery of the catalyst would not

only lower the raw material cost but undoubtedly lower the equip-

ment cost since the size could be greatly reduced, thereby de-

creasing the manufacturing expense and the cost of Productive

-135-

Labor which are very important !actors as may be seen in

Table XI.

Another factor which would ·possibly help put the process

on a paying basis is the by-products which for the purpose of

design v.sre considered as wastes •. In the preparation o:t: the

copper aluminate catalyst, carbon dioxide and sodium sulfate

are by-products which could be easily recovered. Also the

residue from the hydrogenation reaction, which constitutes 11%

of the original sugar, could possibly be used as a fertilizer

or a livestock feed •.

o. Recommendations

substitutes for sugar. Since it is evident from the Pre-

construction Cost Accounting that the cost of sugar is the con-

trolling factor of the financial success of the plant, some

cheaper impure grades should be used. Stenge1(S 4) reported that

when 100 parts (dry bases.) by weight of high test molasses in

143 parts by weight ~f methanol with a catalyst of 16.l parts

by weight of 25% solution of copper sulfate-Eild -10.4 parts by

weight of 30% solution 9f sodium hydroxide were hydrogenated

for 3 hours at 230°0 and 1700 lbs. per sq. in., a yield of 49.6%

propylene glycol was obtained. No analysis was given on the re-

mainder of the yield.

-136-

still another cheaper raw material was also used by stenge1(64).

When 100 parts by weight (dry bases) of "hydrol greens" (mother

liquor from the first crystallization of corn sugar) and 324 parts

by weight of methanol with a catalyst of 14.8 parts by weight of

26% solution of ·copper sulfate and 9.0 parts by weight of 30%

sodium hydroxide were hydrogenated for 3 hours at 230°c and 1700

lbs. per sq. in., a yield of 30.7% propylene glycol was obtained.

No analysis for higher alcohols was made.

Refinement of the Hydrogenation Process Using Sugar (sucrose).

Since no actual hydrogenation was carried out in this investiga-

tion, it was not kn.own whether the copper aluminate catalyst

could be reactivated and used again. In the Discussion of Results

it was brought out tha.t_if the catalyst could be recovered, it

would decidedly decrease the cost of production.

It is also probable that a good antifreeze product might be

obtained by centrifuging off the catalyst, unreacted sugar, and

any tarry decomposition products of sugar; distilling off the

methanol and water; and using_ the whole mixture as an· antifreeze

rather than vacuum distilling the residue from the methanol and

water distillation. This would decrease the cost of the plant,

and there would be no residue loss since the whole mass after

distillation would be used.

-137-

Higher Pressures. This investigation was based upon the

work of Lenth and DuPuis{ 45 ) whose primary aim was to develop

a new process to obtain glycerine to make up for the shortage

created in World War II. Conse~uently, the conditions they

used were selected to make as much glycerine as possible. They

stated in trying to purify the glycerol and coneeners fraction

that upon rehydrogenation at 1800 lbs. per sq. in. 34% of the

fraction was converted into propylene glycol. It is then possi-

ble if the original hydrogenation were carried out at 1800 lbs.

per sq. in. very little glycerine would be obtained, and the

yield would be primarily propylene glycol, which makes a better

automotive antifreeze material.

Inhibitors. In order to eliminate the profit of the middle

man, soma work should be done on testing the various types of

inhibitors to.prevent foaming and corrosion. When suitable in-

hibitors have been found, the product could then be sold at a

higher price thereby increasing the annual gross income.

After suitable inhibitors have been discovered, they should

be tried in automobile radiators to determine their tendency to

corrode, foam, etc.

-138-

D. Limitations

The recomnendations section indicates the extent to which

this investigation should have been carried out, but time did

not permit.

This investigation was limited in that no actual exp~ri-

mental hydrogenation of sugar was carried out. Consequently,

the data, upon which the plant is based, was taken from the

work of Lenth and DuPuis( 4S) which in'many cases was found to

be lacking in experimental information. Quite fre@ently, as-

sumptions had to be made which would not have been necessary

had some experimental work on the hydrogenation of sugar been

done.

A pilot plant is the next step in order that a closer check

can have been made on the necessary equipment for the commercial

plant. Al.so some cheaper sources of sugar should be tried, as

brought out in the recommendations.

Before a solution of propylene glycol and glycerol and con-

geners is used in an automotive as an antifreeze, some form of

inhibitors should be used to prevent foaming and corrosion.

-139-

V. CONCLUSIONS

The following conclusions may be drawn on the basis of the

·work done in this investigation:

1. A solution of propylene glycol and glycerol and

congeners from the standpoint of viscosity ia

suitable for use as an automotive antifreeze up

to 45% by volume solutions where the 45% by vol-

ume solution had an absolute viscosity of 61

centipoises at -25.5°c compared with a 60% by

volume ethylene glycol solution with an absolut~

viscosity of 60 centipoises at -25.5°0.

2. From the standpoint of freezing point depression,

a solution of propylene glycol and glycerol and

congeners is suitable for use as an automotive

antifreeze up to 45% by volume, but approximately

5-7% by volume more -of this solution is required

to give the same freezing point depression as

ethylene glycol.

3. A plant designed to produce 3000 tons per year

of propylene glycol-glycerol and congeners by

the hydrogenation of sucrose would require a

capital investment of $529,775.

4. It susar were to sell at $0.04 per lb., and no

catalyst was recovered, the antifreeze would

have to wholesale at 21.7¢ per lb.

-141-

VI. - SUMMARY

This investigation was based upon the work of Lenth and

DuPuis and stengel and Maple, who hydrogenated sugar suspended

in methanol at 240°c and 1500 lbs. per sq. in. for three hours

with the primary purpose of developing a new process. to pro-

duce glycerine to make up for the shortage created in World

War II. The products of the hydrogenation were water, propy-

lene glycol, glycerol and congeners, and a residue made up 'of

the tarry decomposition products of sugar.

The actual glycerol and congeners fraction obtained by

Lenth and DuPuis was secured from the 1ti.ner Laboratories in

Chicago. This impure glycerine fraction and propylene glycol

were mixed together, and its suitability as an automotive

antifreeze was tested. AB far as viscosity and freezing point

depression were concerned, such an automotive antifreeze com-

pares favorably with ethylene glycol.

The economics of the process were st~died, and a tenta-

tive plant was designed to produce 3000 tons. ~er year which

would require a capital investment of about $529,775 and have

a wholesale price of $0.217 per lb. with sugar costing ~0.04.

-142-

Thia coat may be reduced by catalyst recovery and a reduction

in sugar cost.

-143-

VII. BIBUOGRAPHY

1. Anon. Antifreezing Solutions for Automobile Radiators. Ind.

Engr. Chan. News Ed. 4, 1-2, (1926)

2. Anon. Blaw-Knox Autoclaves Catalog 2081, Blaw-Knox Co.,

Blawnox, Pa. (1946)

3. Anon. Blower Application Bull. 6048, Allis-Chalmers,

Milwaukee, Wis.

4 • .Anon. Blower Application Chart Cull. 21-B-35. Roots-

Connersville Blower Corp., Connersville, Ind.

5. Anon. Chemical Engineering Catalog, pg. 349-72.. Reinhold

Publishing Corp., N. Y. 1946. 31st Eel.

6. ibid., pg. 1584

7. Anon. Chemical Market Prices, Chem. and ED.gr. News, 25,

3686-90, (1947)

8 • .Anon. Compressor Application Bull. L-611-B 1213,

Worthington Pump and Machinery Corp., Harrison, N. J.

9. Anon. Compressed Gas Data. Price List 2 A. The Matheson

Co., East Rutherford, N. J.· (1942)

10. Anon. Conveyor Specifications General Catalog 800, pg.1014-1104.

Link-Belt Co., Chicago, Ill.

11. Anon. Current Prices. Chan. Ind. 61, 720-3, (1947)

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12. Anon..· Glycols. Carbide and Carbon Chemicals Corp. New York,

N. Y. (1947)

13. .Anon. Heat Exchanger Application Bull. M 8802. National

Carbon Co., Inc. New York, N. Y. (1944)

14. _.Anon. Lancaster Hand :Sook, :3rd Ed., Lancaster Iron Works,

Inc., Lancaster, Pa.

15. .Anon. Process. Equipment Cost Estimation, Chem. and Met~

Engr. 54, 5, 108-138, (1947)

16~ Anon. Pump Application Chart. Bull. np-1099-B 18.

Worthington Pump and Machinery Corp., Harrison, N. J. (1941)

17. .Anon. Wooden Tanks, Catalog 33. The Hauser-Stander Tank Co. ,

Cincinnat, Ohio

18. Badger, w. L. and McCabe, Yl. L. "Elements of Chemical

Engineering". pg. 118-71. McGraw Hill Book Co., Inc., I

New York, lif. Y. 1936. 2nd Ed.

19. ibid., 248-279

20. ibid., 323-75

21. Batters, N. M. Chemical Economics. Chem. and Met. Engr •

.2!, l, 279-88, (1947)

· 22. Bingham, E. c. "FJ.uidity an_d Plasticity". pg. 75-77.

McGraw-Hill Book Co., Inc., New York, N. Y. 1922. 1st Ed.

23. Bliss, H. Equipment Cost Estimating Data. Chem. and Met.

Engr. E!, 6, 100-3, ( 1947)

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24:. Bliss, H •. The Costs or Process Equipment and Accessories.

Trans. A. I. Ch. E. 37, 763-804,, ( 1941)

25. Brooks, B. T. Ethylene, and Propylene Chlorobydrins and

Glycols from Oil Gas. Chem. and Met. Engr. 22, 629-33, (1920)

26. Cake, W. E. The Catalytic Hydrogenation of Dextro Glycose.

J". Am. Chem. Soc. ,!!, 859-861, 1922.

27. Conrad, F. N., Hill, E. F., Ballman, E. A. Freezing Points

of the System Ethylene Glycol-Methanol-Water. Ind. Engr.

Chem.~' 542-3, (1940)

28. Crawley, J". E. Design of a Commercial Plant for the

Production of Ethylene Glycol. Unpublished T'nesis. Library,

Virginia Polytechnic Institute, Blacksburg, Virginia, 1947

29. Curme, G. o., J"r. and Young, C. o. ·Ethylene Glycol, Ind.

Engr. Chem. l:Z,, 1117-1120, {1925)

30. Ellis, Carleton, "Chemistry or Petroleum Derivatives''.

pg. 505-511. Chemical Catalog,Co., Inc., New York, N. Y.,

1934, 1st Ed.

31. ibid., pg. 529-32

32. Feldman, H.B. and Dahlstrom, w. G., J"r. Freezing Points

of the Ternary System. Glycerol-Methanol-Water. Ind. Engr.

Ch81Il. 28, 1316-7, {1936)

33~ Fieser, L. F. and Eieser, M. "Organic Chemist17 1t. pg. 115.

D. C. Heath & Co., Boston, Mass. 1944, 1st Ed., abridged.

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34. Findlay, A. "The Phase Rule and. Its Applications"·. pg.

199-204. Longmans, Green, and Co., New York, N. Y. 1911,

3rd Ed.

35. Francon, J. Industrial Process for the t'!anufacture of

Ethylene Oxide and Ethylene Glycol. Chimie & industrie

Spec. No., 869-75, (june, 1933), C. A.~' 465, (1934)

36. Gregory, T. C. 11The Condensed Chemical Dictionary',..

pg. 64-5. Reinhold Publishing Corp., New York, N. Y., 1942

37. ibid., pg. 210

38. ibid., pg. 431

39. ibid., pg. 578-9

40. Hodgman, C. D. "Handbook of Chemistry and Physics".

pg. 1633-4. Chemical Rubber Publishing Co., Cleaveland,

Ohio. 1946, 30th Ed.

41. ibid., pg. 1742

42. ibid., pg. 1774-87

43. Ipatieff, v. Redu.ktionskatalyse der Kohlenhydrate, Berichte

il, 3224-6, (1912)

44. Keyes, D. B. Antifreeze Compounds, Ind. Engr. Chem. 19,

1119-1121, (1927)

45. Larcher, A • .w. Glycols, CAN.· 315, 883~ October 6; 1931,

c. A. ~I 1297, (1932)

-147-

46. Len.th, C. W. and DuPuis, R. N. Polyhydric Alcohol Pro-

duction, Ind. Engr. Chem. 37, 152-7, {1945)

47. Marks, L. s. "Mechanical Engineers' Handbook". pg. 310.

McGraw-Hill Book Co., Inc., New York, N. Y. 1941, 4th Ed.

48. Matter, o. Polyhydric Alcohols, U. s. l, 237,076, August

49.

50.

14, 1917, C. A. 11, 2904, 1917.

Matignon, C., Mourew, .H.' and Dode, M. The Hydration of

Ethylene Oxide, Bull. Soc. Chim. 5, ·,!_, 1308-17, (1934),

C. A. ~' 1777; {1935)

McBee, ti' ... T., Haas, H. B., and Wiseman, p • .A. • Catalytic

Vapor Phase Oxidation of Ethylene, Ind. Engr. Chem.~'

432-8, (1945)

51. Natta, G., Rigamonti, R., and Beati, E. Obtaining Glycerol

and Glycols by Hydrogenation of Carbohydrates. Ber. 76 B,

641-56, (1943), Chimica a Industria (Italy) 24, 419-25,

(1942); C.A. 38, 1731, (1944)

52. Norris, E. B., and Therkelsan, E. "Heat Power". pg. 96-118.

McGraw-Hill Book Co., Inc., New York, N. Y. 1939, 2nd Ed.

53. Olsen, J. c., Brunjes, A. s., and Olsen, .r. w. Freezing

and Flow Points for Glycerol, ~restone, Denatured Alcohol

and Methanol. Ind. En.gr. Chem. 22, 1315-7, (1930)

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54. Perry, J. H. "Chemical Engineers' Handbook". pg. 510-4,

529-36. McGraw-Hill Book Co., Inc., New York, N. Y. 1941.

2nd Ed.

55. ibid., pg. 788-981

56. ibid., pg. 1365

57. ibid., pg. 2241

58. Riegel, E, R. "Chemical Machinery". pg. 173-94. Reinhold

Publishing Corp., New York, N. Y. 1944

59. ibid., pg. 299-314

60. ibid., pg. 351-381

61. Saunders, K. H. and Wignall, H. Ethylene Glycol Brit.

286,850 Feb. 8, 1927, u. s. 1,737,345, Nov. 26, 1929,

C. A. 23, 397, 1929 ·

62. Skaw, E. L. and Saxton, B. Son:e Errors Inherent in the

Usual Determination of the Binary·Freezing Point Diagram.

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.Analysis", pg. 396-7. McGraw-Hill Book Co., Inc., New

York, N. Y. 1944,- 1st Ed,

64. Stengel, L.A. Catalyst end Process for the Hydrogenation

of Polyhydro~ Compounds, U.S. 2;325,206, July 27, 1943

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65. Stengel, L.A. and W.a.ple, F. E. Catalyst and Process for

Producing Polyhydroxy Compounds, u. S. 2,381,316, August

7, 1945

66. Vilbrandt, F. C. "Chemical Engineerins Plant Design"

pg. 94-139, McGraw Hill Book Co., Inc., New York, N. Y.

1942, 2nd Ed.

67. ibid., pg. 188-213

68. ibid., pg. 214-288

69. ibid., pg. 306-365

70. ibid., pg. 366-386

71. ibid., PB• 405-407

'12. ibid., pg. 425-433

73. Washburn, E. w. "International Critical Tablesn. pg. 311.

McGraw-Hill Book Co., Inc., New York, N. Y. 1928, 1st Ed.

74. Weber, H. C. "Thermodynamics for Chemical Engineers 1t. , . I

pg. 86-104. John Wiley &. Sons, Inc., New York, N. Y. 1939

75. Yosikawa, K. and Hanai, s. Hydrogenation of Saccharides,

Bull. Inst. Phys. Chem. Research (Tokyo) 17, 1262-77, (1938).

C. A. 34, 2796, (1940)

76. Zartman, W. H. and Ad.kins, H. Hydrogenolysis of Sugars,

J • .Am. Chem. Soc. 55, 4559-63, (1933)

-151-

VIII. ACKNOWLEDGMENTS

The author wishes to express his appreciation tor the en-

couragement, interest, and helpful suggestions ottered by Dr.

N. F. Milrphey.

Dr. F. C. Vilbrandt 1and F. \7. Bull contributed their in-

valuable assistance in the plant design part of the investigation.

Without the glycerol and congeners fraction so kindly donated

by c. s. Miner of The lliner Laboratories in Chicago; Illinois, the

investigation could not have been carried out.

The author also wishes to thank Miss Janet Pusey for help in

the typins and proof reading of the first draft of the thesis.