premise :in order to discuss the place of chemistry in industry, we must consider the nature of the...
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Premise: In order to discuss the place of chemistry in industry, we must consider the nature of the “Chemical Industry” and related industries in terms of economics and fundamental philosophies.
Goal: Students should be able to
1) describe the place of the “Chemical Industry” in the Canadian and world economy
2) describe the nature of the Canadian “Chemical Industry”
Topic 1 - Introduction to the Chemical Industry…
The “Chemical Industry”
• a term referring to a statistical entity tracked by economic analysts
• includes the production of chemicals (pharmaceuticals, pesticides, etc.) and chemical products (plastics, paints, dyes etc.)
• traditionally, does not include production of steel, glass, paper etc.
Related industries
• Steel• Aluminum• Glass• Ceramics• Pulp and paper• Petroleum• Natural gas• Mining
A super Short History of the Chemical Industry…
Division of Labor analyzed by Adam Smith (Scotsman & smart cookie): “An Inquiry into the Nature and Causes of the Wealth of Nations” (=Industrial Revolution for Dummies) Economics, Library
Need for high load machines & transport means: dump wood adopt steel (Commodities, Mining, Social Unrest - in the wood sector, requests to ban steel)
Large scale steel production requires coke (Coal + heat -> gas + coke + tar), charcoal does not support the high weight of Stack furnace load, also too expensive and environmentally problematic (deforrestation) Green Chemistry.
Gas lights up streets, tar is dumped (Waste Management)
Henry Perkin jr (smart cookie #2) tries to make Quinine (Pharma, Colonies, Malaria) from tar, invents Mauveine (first synthetic dye - violet color) which becomes all the rage. (Fine Chemicals, Dyes)
Tar dug up again to make more dyes (Recycling), birth of the chemical industry (CHEM 401)
Highly trained man power needed (Latin & Greek & Theology doesn’t cut it). Beginning ofgeneral education. (U of G, Midterm, Final, Grades, Syllabus, Labs)
Discovered the synthetic dye mauve in 1856 while trying to make quinine. A year later he set up a dyestuffs factory at Greenford Green, Middlesex, with his father and brother.
QuickTime™ and aTIFF (Uncompressed) decompressor
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William Henry Perkin (1838-1907)
+ =
C20H24N2O2
1 oddball + 1 assumption = 1 Product,1000+ Products$$$$$$$$, etc.
Consequence for us: clean fingernails etc etc.
Mauveine (right) was obtained by William Henry Perkin who at the age of 18 (1856) had set out to make quinine (C20H24N2O2) by oxidising allytoluidine (C10H12N).
It is worth noting that molecular structure of few compounds were known with certainty at this time. Even the tetravalency of carbon was not common knowledge at this time, having been suggested by Kekule only in 1857).
A list of chemical structures published by Loschmidt, (1861) comprised ~ 250 molecules known at the time.
The structure of Mauveine has been correctly identified only in 1994 (O. Meth-Cohn and M. Smith, J. Chem. Soc., Perkin Transactions 1, 1994, 5. DOI: 10.1039/P19940000005.
Mauveine - The first Fine Chemical
N
N
H2N NH
N
N
H2N NH
reassignment
Correct Mauveine structure
QuickTime™ and aTIFF (Uncompressed) decompressor
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N
HO N
Quinine
QuickTime™ and aTIFF (Uncompressed) decompressor
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Photograph of William Henry Perkin Jr (1860-1929), probably taken in his laboratory in the then new Dyson Perrin Laboratory at Oxford, around the time it was opened in 1916.
Perkin Jr was one of three sons of the famous English chemist Sir William Henry Perkin (1838-1907). Also a chemist, he is remembered for synthesising numerous organic compounds, including camphor and several alkaloids.
He was Professor of Chemistry at Manchester (1892-1912) and Waynflete Professor of Chemistry at Oxford (1912-1929).
William Henry Perkin Jr.
Public (shares) or Private (no shares)
State owned. Can be public (Gazprom) or not (SABIC)
Regional - National - GlobalMost chemical companies are global players
Diversified vs. Single productExxon - Oil & oil products => not diversifiedBASF - organic, inorganic, highly diversified 30 y gas
contractsPfizer - all pharma = not diversified
Diversified: integrated vs not integratedJohnson & Johnson - Diversified (consumerproducts, Healthcare but not integratedBASF - diverisified, super-integrated(company philosophy
All chemicals or mixedExxon, GE - partialDow - all chemical
Chemical Companies…
1) Basic objective - make a profit (except state owned…)
2) Very competitive - there are hundreds of chemical companies, both small and very large…there tend not to be monopolies, global pressure
3) Highly dependent on science and technology
4) High R&D budgets (sometimes….)
5) Capital intensive - to construct, expand and maintain production facilities
6) Low labor requirements - BUT needs highly qualified personnel
7) Industry Growth - generally through integration rather than diversification
More Features of Chemical Companies…
2nd largest creator of global trade (road vehicles being the 1st).
Global trade in chemicals (2004): US$ 963 B
Global production (2004): US$ 2002 B
Absorbs 10% of total world commodities
Global Chemicals Output (2004): ~ 2.2 Trillion USD !
• Europe 37 %• Americas 31 %• Asia/Pacific/Africa 32 %
Global Importance of The Chemical Industry
World’s largest chemical producer : U.S.A.
World’s largest chemical exporter : Germany
North American Chemicals Output 2004 (2002):
• USA $ 516 (467) Billion USD• Canada $ 36 (23) Billion USD• Mexico $ 17 (15) Billion USD
Some Fatcs about The Chemical Industry
• Global trade in chemicals (2004): US$ 962.5 B
• 60% shipped in “bulk” 1/3 by truck1/3 by rail1/3 by water
more truck in Europe, more water in Asia
• Key chemical ports in USLong Beach (west coast);Houston and New Orleans (USGC)Newark (east coast)
• Key chemical ports in CanadaHalifaxMontrealVancouver
Transport of Chemicals
1. Nova Chemicals (public) 2. Potash Corp. Sask. (public) 3. Dow Chemical Canada (100% Dow) 4. Agrium (public) 5. DuPont (77% DuPont) 6. Methanex (37% Nova) 7. Imperial Oil (70% Exxon-Mobil) 8. ICI Canada (100% ICI) 9. BASF (100% BASF)10. Shell Canada (78% Royal Dutch Shell)11. Celanese Canada (100% Celanese AG)12. Petromont (50% Dow Chemical, 50% Prov. Quebec)13. Rhône-Poulenc Canada (100% Rhône-Poulenc)14. CXY Chemicals (100% Nexen)15. AT Plastics (public)
Canada’s Top Chemical Companies
Canada’s Top Chemicals (2005, 1000 metric tons)
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Ammonia
Sulfuric acid
Urea
Polyethylene
Ammoniumnitrate, NH4NO3
Sodiumchlorate NaClO3
Nitric acid
Sodium hydroxide
Chlorine
Benzene
Take home message: Inorganics Dominate, PE top organic
Canada’s Top Chemicals: Changes
Canada produces:•Metals•Coal•Gas•Oil
Why the deficit ?
Possible reasons.•Not enough value addition (manpower, R&D)•Economy of scales (China/Gulf syndrome )
But: • Deficit exists for US as well
?Accounting Artefact ?Good or Bad ?
Canada’s Chemical Industry: Import vs. Export
Premise: There are fundamental differences between the design of a chemical synthesis for industry and that for a research laboratory.
Goal: Students should be able to
1) explain how industrial synthetic approaches differ from laboratory synthesis methods.
2) evaluate possible reaction schemes based on thermodynamic, economic, and other
considerations.
Differences between Lab and Industry
Differences in the Synthetic Approach
Example: Hydration of ethylene:
H2C CH2 + H2OH
H3C
H2C
OH
Laboratory1. Bubble ethylene into 98% H2SO4
2. Hydrolysis of resultant sulfate ester Et-O-SO2-OH
IndustryA stream of ethylene/steam is passed over a solid catalyst (phosphoric on diatomaceous earth) at 325°C and 1000 psiContinuous process, unreacted ethylene recovered and recycled to the feed stream.
Bioethanol: State sponsered moon-shining. Currently requires subsidies (tax money), may become economical with $ 60 oil & cellulose splitting enzymes.
Differences in Synthetic Approach
SynthesisIf you can’t make it, you can’t sell it
Laboratory Objectives• Synthesize the product by optimizing:
1. Chemist’s time2. Equipment available (usually glassware)3. Conditions achievable (usually close to ambient pressure
and between -195.8° C (N2(l)) and 132° C (chlorobenzene).
Industrial Objectives• Minimize costs
1. Today2. In the future (psychics ?)
• Tools1. Wide range of temperatures and pressures (fun)2. Batch process or continuous operation3. Reactants in vapor phase or liquid phase or biphasic or….4. Solvent or no solvent? Get rid of solvents (bad habit).5. Nonsientific: financial instruments, taxation, bribes (just kidding)
Differences in Synthetic Approach
If a chemist has an idea for an industrial scale process, what are the steps that must be taken before the process can be implemented?
Evaluation of alternative strategies are.
1) Technical feasibility2) Economic feasibility4) Location (supply/demand)3) Other considerations: environmental issues, etc.
Feasibility
To estimate the difference between the market value of the products and the starting materials, the following simplifications are often made
• 100% yield• No costs of solvents or catalysts (can be recycled)• No value for co-products
These assumptions must be reassessed further on in the development stage.
Economic Feasibility
Evaluate:
• Number of possible side-products & separation problems
• Air or moisture sensitivity of reactants and intermediates
• Commercial value of side-products (moving target)
• Environmental impact of side-products (moving target)
• Health and safety issues
Feasibility - Fine Print
The chemist must consider not only the well-known, obvious approaches, but also unknown or untested approaches.
e.g., the manufacture of ethylamine
1.
2.
3.
4.
5.
6.
7.
8.
CH3CH2Cl + 2 NH3 CH3CH2NH2 + 2 NH4Cl
C NH3C + 2 H2 CH3CH2NH2
CH3CH2NO2 + 3 H2 CH3CH2NH2 + 2 H2O
H3C H
O
+ NH2OH + 2 H2CH3CH2NH2 + 2 H2O
H3C H
O
+ NH3 CH3CH2NH2 + 2 H2O
CH3CH2OH + NH3 CH3CH2NH2 + H2O
H2C CH2 + NH3 CH3CH2NH2
H3C CH3 + 0.5 N2 + 0.5 H2 CH3CH2NH2
Evaluation of Different Reactions
There are many parameters, only two of which must be known:
Thermodynamics: How far does the reaction go, if it is allowed to proceed to equilibrium? (Does it go in the direction of interest at all?)
Kinetics: How fast does it progress?
Question (1) is concerned with thermodynamics and amounts to evaluating the equilibrium constant (K). Bad K Cannot be circumvented
Question (2) is a matter of kinetics and reduces to the need to know the rate equation and rate constants (k). Bad k can be beaten decisively (catalysis). Example: Ammonia (Haber-Bosch) [Fe]
Technical Feasibility
Generally, the first approach is to consider the thermodynamics of the reaction.
This may be done by evaluating the change in Gibbs free energy
GR = HR - T SR
A spontaneous reaction has a decrease in Gibbs energy of the system.
To calculate the Gibbs energy of reaction, use standard Gibbs energies of formation
Greaction = Gf°products - Gf°reactants
Thermodynamics
Base Chemicals = Inventing New Reactions => Go ?
H3C-CH3 + 0.5 N2 + 0.5 H2 H3C-CH2-NH2 Go = ?
Base Chemicals = Inventing New Reactions => Go ?
CBS-Q:• High precision computational method• Can act as substitute for exp. Data• Gives E, H, G, from G => Keq
• Can calculate for different p,T• Error ± 1 kcal • ± 2.7 kcal = 1:99 or 99:1
(1 Hartree = 627.51 kcal•mol-1)
H3C-CH3 + 0.5 N2 + 0.5 H2 H3C-CH2-NH2 Go = ?
N2: CBS-Q (0 K) -109.395956CBS-Q Energy -109.393596CBS-Q Enthalpy -109.392651CBS-Q Free Energy -109.414354
C2H6 CBS-Q (0 K)= -79.629747CBS-Q Energy -79.626237
CBS-Q Enthalpy= -79.62529CBS-Q Free Energy -79.651180
H2 CBS-Q (0 K) -1.166091CBS-Q Energy -1.163730
CBS-Q Enthalpy -1.162786CBS Free Energy -1.177546
C2H5NH2 CBS-Q (0 K) -134.894719CBS-Q Energy -134.890298
CBS-Q Enthalpy -134.889354CBS-Q Free Energy -134.920208
N2 CBS-Q (0 K) -109.395956CBS-Q Energy -109.393596
CBS-Q Enthalpy -109.392651CBS-Q Free Energy -109.414354
Base Chemicals = Inventing New Reactions => Go ?
CBS-Q:• High precision computational method• Can act as substitute for exp. Data• Gives E, H, G, from G => Keq
• Can calculate for different p,T• Error ± 1 kcal • ± 2.7 kcal = 1:99 or 99:1
(1 Hartree = 627.51 kcal•mol-1)
H3C-CH3 + 0.5 N2 + 0.5 H2 H3C-CH2-NH2 Go = ?
Base Chemicals = Inventing New Reactions => Go ?
H3C-CH3 + 0.5 N2 + 0.5 H2 H3C-CH2-NH2 Go +16.9
Base Chemicals = Inventing New Reactions => Go ?
CBS-Q:• Slightly endothermic• Might work with high pressure• Entropically disfavored =>• Need T to be low• Need extremely active catalyst• N2 cleavage ?• Haber-Bosch p,T = 300,300• But: need C-H activation too
=> Tough one
H3C-CH3 + 0.5 N2 + 0.5 H2 H3C-CH2-NH2 Go +16.9
How about ethylene instead of ethane ? Go
G298 = -1.65 kcal/molG1000= -1.91 kcal/mol
H3C CH3 + 0.5 N2 + 0.5 H2 CH3CH2NH2
CH3CH2OH + NH3 CH3CH2NH2 + H2O
G298 = + 16.78 kcal/molG1000= + 34.83 kcal/mol
H2C CH2 + NH3 CH3CH2NH2 G298 = - 3.51 kcal/molG1000= + 17.86 kcal/mol
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