5561 5565.output

* GB785969 (A)

Description: GB785969 (A) ? 1957-11-06

Process of producing solid chloro-paraffins

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

PATENT SPECIFICATION 785,969 l M| A d Date of Application and filing Complete Specification May 3, 1956. No 13748/56. Application made in Germany on May 13, 1955. Complete Specification Published Nov 6, 1957. Index at acceptance: -Class 2 ( 3), CIGI(A 2: D), C 1 G 6 A 1. International Classification: -CO 7 c. COMPLETE SPECIFICATION Process of Producing Solid Chloro-Paraffins' We, IMHAUSEN W Ea Rca G M B HS, of Witten-Ruhr, Germany, a Body Corporate organised under the Laws of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to a process of producing solid chloro-paraffins. It is known that paraffinic hydrocarbons can be chlorinated and that the products are liquid or solid according to their molecular weights and their chlorine content. The production of solid chloro-paraffins with high melting points presents fairly substantial technical difficulties.

By introducing large quantities of chlorine into low molecular paraffinic hydrocarbons, solid products can be obtained but the chloroparaffins thus produced all have relatively low melting points Higher molecular and more particularly solid paraffinic hydrocarbons by themselves are difficult to chlorinate to high chlorine contents because they become increasingly viscous as their chlorine content increases and they strongly tend to effervesce. Moreover, the temperature cannot be arbitarily raised to reduce their viscosity during chlorination because the compounds then dissociate and darken. It has therefore been proposed to chlorinate these higher molecular paraffins in a solvent, more particularly carbon, tetrachloride However these methods also suffer from grave disadvantages The relative volatility of the solvent necessitates comparatively low chlorination temperatures and these entail prolonged reaction times In view of the high viscosity of chloro-paraffins at these low temperatures, large quantities of solvent are needed and their recovery calls for special apparatus, quite apart from the fact that they are most difficult to separate completely from the chlorinated product. It has now been found that solid chloroparaffins with relatively high melting points can be prepared in a simple manner by chlorinating high molecular paraffinic hydrocarbons, more particularly solid paraffins, such as commercial paraffin melting at 52 C, or crude paraffin wax, together with relatively low molecular paraffinic hydrocarbons such as fractions boiling between 150 and 2500 C, or their chlorination products The low molecular hydrocarbons and their chlorination products apparently serve as solvents for the higher molecular hydrocarbons and permit chlorination at higher temperatures so that viscosity is reduced, the utilisation of the chlorine improved and more stable compounds are produced The lower molecular chlorination products need not be removed when chlorination has been completed. Based on the foregoing discovery, the present invention provides a process for the production of solid chloro-paraffins, which comprises subjecting a mixture of high molecular paraffin hydrocarbons containing more than 20 carbon atoms in the molecule and especially solid paraffins, with comparatively low molecular paraffin hydrocarbons containing between 5 and 20 carbon atoms, and preferably between 10 and 16 carbon atoms in the molecule (especially fractions boiling between and 2500 C) or their chlorination products, to chlorination in a manner known per se, at temperatures of between 50 and 180 C, and preferably between 80 and 1400 C. According to the proportions in which the lower and higher hydrocarbons are present, hard resins melting at more or less elevated

temperatures are obtained. It is an advantage to add inorganic and/or organic nitrogen compounds such as ammonium chloride, urea or amines, before and/or during chlorination, in order to prevent the product from darkening, as this easily happens at elevated temperatures, when chlorination is interrupted or when the dissolved chlorine and hydrogen chlorides are being driven out with a current of gas after chlorination is complete. Chlorination is conveniently effected at' 785,969 increasing temperatures with the final temperature as high as may be compatible with the preservation of colour, because the chloroparaffins produced at high temperatures are more stable than those produced at lower temperatures. The invention will be illustrated by the following examples, in which the parts referred to are parts by weight:EXAMPLE 1 parts of paraffin, m p 520 C, and 18 parts of a paraffinic hydrocarbon boiling between about 180 and 225 C, are chlorinated together at a temperature of about 100 C, whilst exposed to light, until the chlorine content has risen to about 65 % The temperature is then raised gradually to 160 C. When the chlorine content is 71 7 % the product obtained has a melting point of 690 C If chlorination proceeds to 75 % chlorine a light yellow product results which fuses at 1080 C. EXAMPLE 2 parts of paraffin, m p 520 C, and 60 parts of a chloro-hydrocarbon with a chlorine content of 71 % prepared from a paraffinic hydrocarbon boiling between 180 and 2250 C., are chlorinated together at a temperature of 1800 C Chlorine contents equal to those mentioned in Example 1 produce the same chlorination products. EXAMPLE 3 parts of crude paraffin wax from the hydrogenation of carbon monoxide, and 21 parts of a synthetic paraffinic hydrocarbon boiling between 160 and 2100 C, are chlorinated together as described in Example 1. When the chlorine content is 72 6 % the product is a brittle light resin which fuses at 750 C. On the other hand, if a fraction between and 225 is chlorinated by itself the product at 73 % C 12 is already considerably viscous at 400 C Moreover, a paraffin melting at 520 C cannot be chlorinated at 1000 C. in a reasonable time without the use of a solvent, to more than 62 to 65 % Cl 2 as it otherwise becomes too viscous and effervesces considerably At higher temperatures the product becomes very dark. If darkening should occur in the course of chlorination a pronounced lightening in colour can be achieved in the course of further chlorination by the admixture of 03-0 5 % of ammonium chloride or urea.

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* GB785970 (A)

Description: GB785970 (A) ? 1957-11-06

Inhibitor for lubricating oil compositions

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PATENT SPECIFICATION Date of Application and filing Complete Specification: May 8, 1956. No 14253156. Application made in United States of America on May 25, 1955. Complete Specification Published: Nov 6, 1957. Index at acceptance:-Classes 2 ( 3), B 4 E, C 2 C( 2: 6 C: 7 A 2: 7 A 3: 8); and 91, F( 1: 2). International Classification:-CO 7 d Cl Om. COMPLETE SPECIFICATION Inhibitor for Lubricating Oil Compositions; We, Esso RESEARCH AND ENGINEERING COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Elizabeth, New Jersey, State of New Jersey, United States of America, do hereby declare the invention, for which we pray that a patent may

be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to lubricants and more particularly relates to improved lubricant compositions containing a new class of products as corrosion and oxidation inhibitors, to the novel products themselves and to the method of their preparation The novel products of this invention, which are oil soluble, are prepared by reacting a metal polysulfide with diphenylamine or an alkyl derivative thereof. The successful lubrication of internal combustion engines is complicated by the deterioration of the lubricating oil during use Oxidation of the oil, for example, causes the formation of sludge and lacquers that deposit on parts of the engine and interfere with circulation of the oil Also, certain deterioration products are acidic in nature and corrode bearing metals and other metal parts The difficulties encountered in regard to corrosion have become aggravated in recent years because of the increasing utilization of bearings made of alloys such as cadmium-nickel, copper-lead, cadmium-silver, etc, and also because of the increased severity of engine operation. Although the discovery of certain lubricant additives has alleviated this problem to a certain extent, there is a continuing need for still further improved lubricating compositions which are resistant to oxidation. In accordance with the present invention, it has been found that a product prepared by reacting an alkali or alkaline earth metal polysulfide with diphenylamine, or certain alkyl derivatives thereof, imparts improved antioxidant and anti-corrosion properties to a lubricant More specifically, the products of this invention are prepared by reacting an lPrice 3 s 62; f 3 >CC El 4 alkali or alkaline earth metal polysulfide with a compound having the formula where each R is hydrogen or an alkyl radical containing 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms The reaction is carried out at an elevated temperature and for a period of time sufficient to produce an oil-soluble reaction product which contains a ratio of sulfur atoms to nitrogen atoms in the range of from 0 4 to 1 5, preferably from 0 5 to 1.0 The proportions of the reactants are selected so that the amount of the metal polysulfide employed in the reaction is such as to provide sufficient reactive sulfur atoms to produce an oil-soluble reaction product containing the aforementioned sulfur to nitrogen ratio The reaction mixture (resulting from the reaction of the metal polysulfide and the diphenylamine compound) will generally contain a small amount of oil-insoluble material and this is removed by filtration or decantation from oil solution (e g hexane) to yield the oilsoluble product of this invention. The metal polysulfides of this invention preferably have the following

general formula: Ma Sb where M is an alkali metal or an alkaline earth metal, a is an integer of 2 in the case of alkali metals and 1 in the case of alkaline earth metals and b is 2, 3, 4 or 5 The preferred metals are calcium, barium, magnesium, lithium, sodium, and potassium The alkaline earth metals are particularly preferred The preferred metal polysulfides are calcium polysulfides It has been found that metal monosulfides alone are inoperative in the present invention The metal polysulfides utilized in this invention may be r 85,970 prepared by any conventional methods such as by heating 1 mole of the metal monosulfide with about 1 to 4 moles, particularly about 3 moles, of elemental sulfur Such reaction may be conveniently carried out at a temperature in the range of about 2000 to 300 F for a period of time of about 0 5-2 hours In this type of preparation it is desirable to carry out the reaction in water which serves as a vehicle or carrier for the reactants The products produced by reacting metal monosulfides with elemental sulfur are predominantly metal polysulfides, and the total product may be employed in this invention if desired The reaction of the metal polysulfide and the phenylamine compound is carried out at an elevated temperature so that the reactants are maintained in a molten state Temperatures in the range of about 175 F to 570 F may be employed to carry out the reaction At temperatures below about 1750 F the reactants will not readily react whereas at temperatures in excess of about 5700 F difficulty is encountered due to the vaporization of the diphenylamine compound Preferably the reaction temperature is maintained in the range of about 200 to 300 F. The proportion of the metal polysulfide employed in the reaction is such as to provide sufficient reactive sulfur atoms to produce an oil-soluble reaction product containing a ratio of sulfur atoms to nitrogen atoms in the range of about 0 4 to 1 5, preferably 0 5 to 1 0. Because the higher sulfur content polysulfides contain a greater number of reactive sulfur atoms per molecule, it is therefore possible to utilize a smaller proportion of them in the reaction than in the case of the lower sulfur content polysulfides such as the disulfides. The term "reactive sulfur atoms" refers to those atoms of sulfur which are combined with the metal in excess of one sulfur atom per molecule Thus the metal polysulfides may be expressed as MSSY where y is an integer of 1 to 4 and S, designates the "reactive sulfur atoms " The reaction is carried out for an extended period of time until an oil-soluble reaction product is obtained which contains the desired ratio of sulfur atoms to nitrogen atoms, which ratio, as previously stated, is in the range of about 0 4 to 1 5, preferably about 0 5 to 1 0.

A reaction time in the range of about 0 5 to 4.0 hours is generally sufficient to produce an oil-soluble reaction product containing a ratio of sulfur atoms to nitrogen atoms in the range of 0 4 to 1 5, providing, of course, that a sufficient quantity of the metal polysulfide is employed Preferred reaction times are in the range of about 1 to 2 hours Upon completion of the reaction, the compounds of this invention may be dissolved in a suitable solvent such as hexane, heptane, petroleum ether, ligroin, etc, and then filtered to separate therefrom any insoluble inorganic material such as metal monosulfides, metal oxides and other unreactive products Thereafter the compounds of this invention may be recrystallized from the solvent The crystallized product contains no detectable amount of metal, 70 which is removed by filtration as described above It has not been possible to date to identify the molecular structures of the products of this invention. The following examples are intended to 75 illustrate in greater detail but it will be understood that it is not intended that the invention be limited thereto. EXAMPLE 1 A calcium polysulfide product was prepared 80 by placing 72 grams of calcium monosulfide, 96 grams of sulfur, and 400 grams of water in a one-liter glass flask which was equipped with a condenser, stirrer, and thermometer. The contents of the flask were heated for about 85 one hour at about 2150 F, with the water being refluxed during the reaction The reaction produced a red jolored upper liquid layer and a small lower layer of unreacted solid materials The red colored liquid was 90 separated and was then evaporated to dryness to recover a yellow powder which contained 22 ' calcium and 57 5 % sulfur Although the calcium polysulfide product in this example was prepared as described above in the labora 95 tory, it will be understood that any polysulfide of alkali or alkaline earth metals may be used in the reaction described below. 34 grams of the powder prepared above were then blended with 84 grams of diphenyl 100 amine and the mixture was placed in a oneliter glass flask equipped with a condenser, stirrer, and thermometer The contents of the flask were heated together for two hours at C After cooling, the contents of the 105 flask were blended with about 250 cc of hexane and the solution was filtered through a Buchner funnel A small amount of insoluble material was collected on the filter. This insoluble material consisted primarily of 110 calcium monosulfide and other unreactive calcium and sulfur containing products Thereafter the oil-soluble product of this invention vas recrystallized from the hhexane and dried to produce a crystalline product which con 115 tained 12 32 % sulfur, 6 47 %' nitrogen and no detectable amount of

calcium The product was readily soluble in mineral oil and will hereinafter be termed Product A The ratio of sulfur atoms to nitrogen atoms in Product 120 A was 0 84. A similar reaction was carried out utilizing diphenylaimine and calcium monosulfide but no reaction took place, thus indicating the necessity of utilizing a polysulfide in the 125 reaction with diphenylamine. EXAMPLE 2 About 34 grams of the dried powder prepared in Example 1 were blended with 98 2 grams of pp'-dioctyl diphenylamine and the 130 785,970 EXAMPLE 3 In order to determine the storage stability of the oil-soluble reaction products of this invention in mineral lubricating oils, various concentrations of Product A and B were added to a mineral lubricating oil base stock (hereinafter termed Base Stock I) and were tested for stability under the following conditions: ( 1) in the sunlight at room temperature and ( 2) in a refrigerator at 350 F The storage stability of the blends was determined by noting the period of time that they remained clear without any evidence of turbidity, suspended sediment or solids precipitation An anti-oxidant additive of the prior art, namely phenothiazine, was also subjected to these storage stability tests for comparison purposes. mixture was placed in a one-liter glass flask equipped with a condenser, stirrer, and thermometer The contents of the flask were heated for one hour at 1400 C, after which the contents were cooled and then added to about 250 cc of hexane The resultant solution was filtered through a Buchner funnel and a small amount of oil-insoluble material was collected on the filter The oil-soluble product of this invention was then recrystallized from the filtrate and dried An oilsoluble crystalline product was obtained which contained 4 02 % sulfur, 3 37 % nitrogen and no detectable amount of calcium This product will hereinafter be termed Product B. The ratio of sulfur atoms to nitrogen atoms in Product B was 0 53. TABLE I Storage 'Stability Test Additive in Base Stock 1 Storage Stability, Days Sunlight Refrigerator Type Conc, Wt;% Room Temp 350 F. Product A , , Product B h h Ph enothi azin e 0.5 2.0 3.0 5.0 3.0 5.0 0.5 + + < 10 + + + 2 l + 7 < 2 Base Stock I was a solvent refined Mid-Continent mineral oil base stock (SAE-20 grade) having the following inspections: Gravity, O A Pl = 29 4 SUS viscosity @ 1000 F = 522 6 Pu t, @ 2100 F = 66 2 Pour Pt,, F = -'10 EXAMPLE 4 The effectiveness of Product A as an oxidation inhibitor was then determined in a test which was carried out as follows: A 500 cc.

sample of the test lubricant was charged to a "Pyrex" tube in a salt bath held at 3250 F. ("Pyrex" is a Registered Trade Mark) A shaft holding two halves of a copper-lead bearing was rotated in the test lubricant at 400 to 650 r p m while 2 cu ft /hour of air was bubbled through the lubricant The test was run for 4-hour periods, and at the end of each, the bearings were cleaned and 65 weighed to measure weight loss The test was continued 'in repeated 4-hour cycles until a cumulative bearing weight loss of 100 mgms. was obtained. For comparison purposes, phenothiazine 70 was similarly tested and the following results were determined: TABLE II Oxidation-Corrosion Test Additive in Base Stock I Conc, Type Wt % None Product A Phenothiazine Hours to Lose mgms. 12 34 0.5 0.5 785,970 The results of the tests shown in Examples 3 and 4 clearly indicate that products made in accordance with this invention are outstanding additives for lubricating oil compositions on account of ( 1) their excellent solubility in lubricating oil base stocks and ( 2) their effectiveness in reducing oxidation and corrosion. EXAMPLE 5 The products of this invention are not a mere mixture of diphenylamine (or its alkyl derivatives) and phenothiazine (or its alkyl derivatives), which can be formed by reacting diphenylamine (or its alkyl derivatives) with elemental sulfur This is shown by the following laboratory treatment of the product of this invention A benzene solution of Product A was washed with a 10 % solution of hydrochloric acid and the water phase separated. If free diphenylamine had been present, it would have formed the diphenylamine hydrochloride salt which is water soluble The water layer was neutralized with sodium hydroxide to liberate free diphenylamine, which being water insoluble would precipitate. Since no precipitate was formed, it can be concluded that the product of the invention contains no free diphenylamine. Product A of this invention as well as diphenylamine, phenothiazine and mixtures of diphenylamine and phenothiazine were evaluated as additives in a mineral lubricating oil in the Oxidation-Corrosion Test described in Example 4 The mineral lubricating oil (hereinafter termed Base Stock II) was a solvent refined Mid-Continent mineral oil base stock of SAE-30 grade The results of these tests are shown below: TABLE III Oxidation-Corrosion Test Additive, Wt % in Base Stock II None Phenothiazine 0 5 % Product A 0.5 % Hours to Lose mgms.

Diphenylamine 1 0 % Phenothiazine O 5 % Diphenylamine 05 % 1 Phenothiazine 0 75 %} Diphenylamine 0 25 %' When additives of this invention are employed in lubricating oils, they are usually added in proportions in the range of about 0.01 to 10 0 % by weight and preferably in the range of about 0 1 to 5 O % by weight, particularly about 0 2 to 1 0 % by weight If the additives are utilized at high concentrations, conventional solubilizers may be employed to increase the solubility of these additives The proportions giving the best results will vary somewhat according to the nature of the additive. The products of the present invention may be employed not only in ordinary hydrocarbon lubricating oils but also in the "heavy duty" type of lubricating oils which have been compounded with such detergent type additives as phosphosulfurized hydrocarbons, metal soaps, metal petroleum sulfonates, metal phenates, metal alcoholates, metal alkyl phenol sulfides, metal organo phosphates, thiophosphates, phosphites and thiophosphites, metal salicylates, metal xanthates and thioxanthates, metal thiocarbamates, amines and amine derivatives, reaction products of metal phenates and sulfur, reaction productions of metal phenates and phosphorus sulfides and metal phenol sulfonates Thus the additives of the present invention may be used in lubricating oils containing such other addition agents as barium tert -octylphenol sulfide, calcium tert amylphenol sulfide, nickel oleate, barium octadecylate, calcium phenyl stearate, zinc diisopropyl salicylate, aluminum naphthenate, calcium cetyl phosphate, barium di-tert -amylphenol sulfide, calcium petroleum sulfonate, zinc methylcyclohexyl thiophosphate and calcium dichlorostearate. The lubricating oil base stocks used in the compositions of this invention may be mineral lubricating oils or distillates derived from paraffinic, naphthenic, asphaltic, or mixed base crudes, or, if desired, various blended oils may be employed as well as residuals, particularly those from which asphaltic constituents have been carefully removed The oils may be 785,970 alcohols, aldehydes, halogenated or nitrated compounds, and the like may also be employed. In addition to being employed in lubricants, the additive of this invention may be also used in motor fuels, hydraulic fluids, torque converter fluids, cutting oils, flushing oils, turbine oils or transformer oils, industrial oils, process oils, gear lubricants, greases, and generally as anti-oxidants in oleaginous products.

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* GB785971 (A)

Description: GB785971 (A) ? 1957-11-06

Improvements in or relating to the mounting of electronic circuit components

Description of GB785971 (A)

PATENT SPECIFICATION Inventors: JACK EVANS and IDWAL JOHN TAYLOR JENKINS 785,971 / il ' Air Date of Application and filing Complete Specification: May 9, 1956. No 14352/56 Complete Specification Published: Nov 6, 1957. Index at acceptance:-Classes 37, T 1; and 108 ( 3), R, 56 E 2. International Classification:-F 06 f H Oin. COMPLETE SPECIFICATION Improvements in or relating to the Mounting of Electronic Circuit Components We, STANDARD TELEPHONES AND CABLES LIMITED, a British Company, of Connaught House, 63 Aldwych, London, W C 2, England, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to the supporting of articles in holes in plates or sheets and more particularly to the mounting of electronic circuit components and articles of similar shape. The main feature of the invention consists in a compressible tubular member of rubber or other resilient material having a cylindrical outer wall, an external flange at one end and a bore tapering towards the other end, and capable of acting as a grommet. The invention will now be described with reference to the accompanying drawings, in which:Fig 1 shows a sectional elevation and end views of a compressible tubular member or grommet; Fig 2 is a side view of a member inserted in a panel, and Fig 3 is a side view showing an electrical component inserted in a member in a panel. As seen in Fig 1, a compressible tubular member or grommet comprises a cylinder 1, preferably of rubber or the like having at one end an

external flange 2 and having a tapering bore-hole 3 with the layer end of the taper at the same end as the flange 2. The diameter of the smaller end 4 of the bore-hole is arranged to be less than the external diameter of an article to be mounted therein Such an article may be an electronic circuit component such as 5 (Fig 3). In order to mount the component in a plate or sheet such as 6, the grommet is inserted into a hole in the plate 6 (Fig 2) so that the flange 2 is on one side of the plate 6 and the end of the cylinder 1 having the lPrice 3 s 6 d l smaller end 4 of the bore-hole is projecting from the other side of the plate, the diameter of the hole in the plate 6 being approximately equal to the external diameter of the cylinder 1 An article such as 5 (Fig 3) is then 50 pushed or driven into the bore-hole from the flange end The cylinder 1, at least towards the smaller end of the bore hole is expanded or forced into intimate contact with the wall of the hole and that part of cylinder which 55 projects beyond the plate 6 is expanded around the end of the hole so that the component and the member cannot be easily removed from the plate. It has been found that such a member is 60 simple to manufacture as by moulding and that such a method of mounting a component is easy and cheap Furthermore the component is not likely to be damaged during mounting and is held in a resilient and shock 65 proof manner.


* GB785972 (A)

Description: GB785972 (A) ? 1957-11-06

Process for the preparation of purified concentrates with intrinsic factoractivity


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COMPLETE SPECIFICATION Process for the Preparation of Purified Concentrates with Intrinsic Factor Activity We, ORGANON LABORATORIES LIMITED, a British Company, of Brettenham House, Lancaster Place, London, W.C.2, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statment : - The invention relates to a process for the preparation of purified concentrates with intrinsic factor activity, which contain a vitamin of the B,, group. It is generally known, that for the resorption of orally administered vitamin B12 intrinsic factor is nncessary. This intrinsic factor (hereinafter indicated by I.F.) which was first described by Castle and collaborators (see Am.J.Med.Sci. 178, 748 (1929)), is a component of normal human gastric juice and occurs therein in a sufficient measure to place the extrinsic factor, viz. vitamin B12 or another vitamin of the B12 group, from the food at the disposal of the organism. In some persons the I.F. in the gastric juice is lacking so that with those, owing to the failure of the resorption of the vitamin B12 from the food, finally the symptoms of the pernicious an mia may occur. It is of importance that there shall be available for such persons and all those whose production of I.F. is partly disturbed, I.F. preparations which can be taken simultaneously with the food, or even more favourably of vitamin B,, containing I.F. conpentrates because in the latter case there is the assurance that sufficient B12 is present so that they are not dependent on the B12 content of the food. As sources or I.F. activity are considered, in addition to normal human gastric juice, animal organs such as the pylorus, the duodenum, and other parts of the digestive tract and in particular the mucosa thereof. Especially the above organs of the pig possess a great I.F. activity. Crude I.C. preparations may for example be obtained by drying and then

grinding the above animal organs if necessary together with one or more vitamins of the B,, group. It is a great objection that, in order to obtain a good, h matopoietic effect, very large quantities of such crude preparations have to be administered daily to patients suffering from pernicious anemia. Attempts have therefore been made to concentrate these preparations. From Specification No. 733,875 it is known that I.F. concentrates which contain a vitamin of the B12 group can be purified by precipitating them from a solution hereof by means of an alkanol or alkanone, for example ethanol or acetone, at a temperature below oo C. In Ptoc.Soc.Exptl.Biol.lUINed. 87, 400 (1954) W. L. Williams and others describe how I.F. concentrates which contain no vitamin B12 can be prepared by fractionating solutions with LF. activity by means of alcohol. These investigators isolate the fraction which is precipitated between 40 and 80% by volume of ethanol. It has now been found that according to the present invention purified LF. preparations can be prepared by treating a concentrate with I.F. activity in the presence of a vitamin of the B12 group, in an aqueous system which has 35-50%' by volume of an alkanol or alkanone with not more than three carbon atoms, and separating the resulting liquid phase which contains the active constituent. As such systems solutions may be employed of one or more of the substances methanol, ethanol, isopropanol, propanol, and acetone. By the treatment of the concentrate according to the process is understood the selective dissolving of the I.F. active constituent therefrom. As starting products may be used a liquid or solid concentrate for example in powder form, whether dried or not, or a somewhat purified precipitate, such as is for example obtained according to the process of saint patent Specification. The process according to the invention may be applied to any concentrate that has I.F. activity in whatever stage of purity it may be. If desired, aqueous solutions of I.F. concentrates may be converted into a solid concentrate, for example by drying iez vacuo, by lyophilizing, by spray-drying. As vitamin B1, containing substance which is added to the I.F. concentrate before applying the process of the invention, any preparation that contains one or more members of the vitamin B12 group is considered, such for example as the so-called "oral grade solubles", crystalline vitamin B12 and other preparatlons obtainable in trade. It is preferable to perform the treatment in the presence of one or several salts such for example as alkali chlorides, phosphates, etc. This has for example as a result that after the treatment the liquid

can easily be separated from the remaining solid substance. A slight quantity of a salt has already a very favourable action. In this respect sodium chloride appears to have a very favourable action. To improve the yield the treatment may be repeated once or several times. It gives particularly favourable results if operations are carried out at 0 C. or at lower temperature. It is preferably carried out in a weakly acid medium for example at a PH 6-7. The pH of the mixture can for example be adjusted to this value by using the component parts of a buffer e.g. KH,PO4+Na,HPO4. From several experiments it has appeared, that a very favourable result is obtained when using 40 50% by vol. of ethanol. With this percentage few ballast substances are extracted, as a result of which a strong purifiction of the preparation is obtained. In a known way a solid preparation can be prepared from the liquid phase for example by lyophilizing, evaporating to dryness, or atomizing. An extra purification of the preparation is effected by isolating this from the resulting liquid by increasing the alkanone or alkanol concentration to a value ranging from 6075% by vol. at which the I.F. activity-containing compound precipitates, together with the bound vitamin B,z, so that ultimately a preparation is obtained with a strong human topoietic action in patients with pernicious an mia. Dependent on the applied solvent, the precipitating agent used and the nature of the tarting product, the limits of the alkanol and alkanone concentration at which the most favourable purification takes place may vary. If, starting from a previously purified concentrate which shows a good clinical activity on administration in a daily dose of +30 mg., this concentrate is treated while making use of ethanol and the active compound is then precipitated from the resulting solution, the strongest I.F. active substance is obtained by increasing the ethanol concentration of the solution to 60% by TOl. See for example, Example 2 below in which the preparation is described of a preparation which contains the active constituent in a concentration which is 10 times that of the starting product. It is not necessary that the precipitation of the active compound from the recovered liquid takes place with the same liquid which is us-.d as solvent in the aqueous system. For the precipitation one of the liquids commonly used for this purpose may be applied, such for example as methanol, ethanol, acetone, or a combination of these liquids. The precipitate obtained from the solution by precipitation of the active compound may be dried in a known way such for example as by lyophilizing, drying in vacio, and passing over of warm air. The action of the preparation may be tested by daily administering a

certain quantity hereof to patients with untreated pernicious anemia. The preparation is preferably administered in the form of a tablet. The action of the preparation is established on the basis of the increase of the number of erythrocytes per cu. mm. of blood during a certain period of treatmen. The erythrocytes content is frequently determined a fortnight and 21 days after the beginning of the administration of the preparation. In additicn the reticulocytes maximum (in percentage) is frequently determined. The following examples, in which the percentages are by volume, illustrate the invention: EXAMPLE 1 376 gm. of a powdered I.F. concentrate, to which during the preparation so much cyans cobalamin has been added that the whole binding capacity for cobalamin is saturated so that it contains about 0.28 ug. of vitamin B12 (cyanocobalamin) per mg. (in a bound form) are used as starting product. This preparation is clinically active in a daily dose of 38 mg. In a Waring blender the powder is moistened with cold 45 X ethanol which solution contains 9 gin. of NaCl per 1.; subsequently so much of this ethanolic solution is added to the mixture that in all 4 1. thereof are used. The mixture is stirred at 50 C. for 18 hours after which it is centrifuged. The same process is repeated twice more, each time with 45 XO ethanol which contains 9 gm. of NaCI per 1. To the collected liquid phases cold 9646 ethanol is added until a final concentration of about 75% is obtained. The temperature is kept between 0 and 5 C. The resulting precipitate is collected and dried in vacuo at low temperature. The final yield is 37.4 gm. of a red coloured preparation with a vitamin B22 content of 2.3y of B12 per mg. EXAMPLE 2 To a solution of an I.F. concentrate of which 30 mg. of dry substance daily are clinically well active (while simultaneously administering 15pig. of B12 daily) sufficient cyanocobalamin is added to saturate all binding capacity; subsequently, while stirring and at low temperature 96% ethanol is added. The fraction which precipitates between 0 and 40% ethanol concentration is intermediately removed by centrifuging. Subsequently the ethanol concentration is raised from 40 to 75% as a result of which a precipitate is formed. This is collected by centrifuging and serves as starting material for the extraction according to the invention. This starting material with a drying residue of 110 gm. and a total vitamin B12 content of 50 mg., is suspended in 1.5 1. of cold 45% ethanol solution which contains 17 gm. of NaC:l per 1. After stirring at --50" C. for 24 hours the liquid is separated. The precipitate is

treated twice with 45% ethanol with 17 gm. of NaCS per 1. The insoluble part is dried and the ethanol concentration of the collected solutions, in all 2,880 ml., is increased in stages to gain an impression as to the weight of the fractions which precipitate within certain ethanol concentrations. The precipitates are dried in vacuo. In the following table these weights are summarised : - Precipitated between Fraction the alcohol limits Yield (gm.) Colour Precipitate insoluble in 45% alcohol 45.5 white-light-brown 1 45-50 12.0 light rose 2 50-55 6.38 strongly red 3 55-60 1.87 red-yellow 4 60-70 2.99 nearly white 5 70-75 0.94 white For determination of the clinical and microbiological activities the fractions 1, 2 and 3 are, after termination, mixed, dissolved in little water, and lyophilised. Microbiologically, with Lactobacillus Leichmannii, a vitamin B12 content of 2.2 yg per mg. is found so in all 46.6 mg. of B12 (yield more than 90%). In the clinical assay in a daily dose of 2.9 mg. of this preparation, completed with 5y of free cyanocobalamin already 3.30 millions of erythrocytes per cu. mm. of blood are counted after a fortnight at an initial value of 1.29 million, while this increase continues so that after 21 days already 3.6 millions of erythrocytes per cu. mm. of blood are present. The reticulocytes maximum of 18.6% which was found in this patient with pernicious anaemia on the eleventh day also points to the great clinical activity of the preparation. EXAMPLE 3 As starting product acetone is used containing the precipitate which has been formed by adding an excess of a hydroxy cobalamin concentrate to an aqueous solution of an I.F. concentrate so that all binding capacity for cobalamin is saturated. The said mixture is treated with a threefold excess of acetone in which the temperature is kept below 0 C. The precipitate is separated by centrifuging. This starting product with a drying residue of 1,535 gm. and a cobalamin activity which corresponds in all to 495 mg. of cyanocobalamin, is suspended in 20.5 1. of 40% ethanol and stirred overnight. After centrifuging the resulting residue is treated another twice with, each time, 161. of 45% ethanol. Of the collected solutions, in all 49 1., a sample is lyophilised in order to determine the effect of the treatment. The content of dry substance of the sample amounts to 5.4 mg. per ml. The collected solutions consequently

contain about 265 gm. of dry substance so that in this respect a six-fold concentration has been reached. To the collected solutions which have an organic solvent concentration of about 45 /O (ethanol and a little acetone) about 19 1. of 96% ethanol are now added to precipitate the active principle. After drying in vacuo the precipitate has a weight of 165.5 gm. The Bl2a content hereof, measured as cyanocobalamin activity in the Lactobacillus Leichmannii test, amounts to 2.4y per mg. The total quantity of vitamin B,2 in the precipitate amounts to 397 mg. I This is a yield of 80% calculated with reference to the original, bound quantity. This preparation is clinically active in a daily dose of 2.5 mg. (see the assay results in the following table). Erythrocytes (million/cu. mm. of blood) Reticulocytes max. Onthe On the Patient Time 0 14th day 21st day Xt, day A 1.43 1.82 2.43 23.4 9th B 2.00 2.95 3.61 19.3 13th EXAMPLE 4 As starting product use is made of methanol containing the precipitate which has been prepared in the same way as described in Example 3, however, with this difference that as a source of vitamin B12 so-called B12 oral grade solubles have been used which, according to the absorption spectrum, contain the vitamin in the form of cyanocobalamin while for the precipitation 3 volumes of methanol have been used. The precipitate with a total wet weight of 5,638 gm. and a dry residue of 1,643 gm. which in all contains about 500 mg. of B12 activity, is suspended in 20 l. of 36 methanol which contains 20 gm. of NaCI per l. Alter stirring for 17 hours the mixture is centrifuged. A second and third treatment take place with a 40% methanol solution, which contains 20 gm. of NaCl per 1. In all 56 1. of solution are obtained to which 27 1. of cooled methanol are added. Here a precipitate is formed. After drying hereof in high vacuum a final product is obtained with 2.557 of B12 activity per mg. in a yield of 156.5 gm. This final product is clinically very active. Oral administration in a daily dose of 2.37 mg. to a patient with an untreated pernicious anemia causes an increase of the erythrocytes of 1.0 million in 15 days and 1.47 million in 21 days at an initial value of 1.17 million per cu. mm. of blood. The reticulocvtes maxlmum amounts to 14.9% on the 9th day of the assay. In a second patient the values found for the erythrocytes were: in the beginning 1.82 million, after a fortnight 2.94 million and after 21 days 3.12 million.

The reticulocytes maximum on the 7th dap of the treatment amounted to 7.4%. EXAMPLE 5 As starting product use is made of acetone containing the precipitate which has been prepared in the same way as described in Example 3. As a source of vitamin B,2, however, so-called B12 oral grade solubles have been used in which the vitamin occurs in the form of cyanocobalamin. 5.1 kg. of this starting product with a vitamin B12 activity totally corresponding to 350 mg. of B12 are treated with 15 1. of 30,' acetone and then twice with, each time, 12 1. of 35% acetone. Here a temperature of between5 and 0 C. is applied. During the latter two treatments the 35% acetone always contains 15 gm. of NaCl per 1. To the collected solutions, in all 401., 25 1. of cold acetone are added while stirring. After having been left to stand overnight at - 50 C the precipitate is collected and dried in vacuo In all 80 gm. of the final product are obtained. The vitamin B12 content is 3.67? of B12 per mg. The yield of B12 amounts to nearly 84 ' calculated with reference to the cyanocobalamin activity. EXAMPLE 6 Start is made from a cyanocobalamin-containing intrinsic factor precipitate prepared according to Example 3 but the precipitation is performed with ethanol instead of with acetone. This precipitate with a wet weight of 2.7 kg. is suspended in 25 1. of a cooled 43% ethanol solution which contains 20 gm. of NaCl per l., and the mixture is stirred at -5 C. for 13 hours. Then it is centrifuged; the precipitate is treated another twice with, each time, 20 1. of 45 % ethanol which contains 20 gm. of NaCl per 1. To the collected solutions, with a total drying residue of 1,40 gm. 24.8 1. of cold 96 ' ethanol are added while stirring, while the temperature is kept at about -5 C. After the addition stirring is continued for another hour after which the resulting precipitate is centrifuged. The precipitate which has been formed by precipitation between the limits of about 4S% to 60% ethanol is dried in high vacuum. As final yield are obtained 138 gm. of a product which contains 1.697 of B12 per mg. In a daily dose of 5.5 mg. the product is clinically very active as appears from the following table Erythrocytes (million/cu. mm. of blood) Reticulocytes max. Onthe On the Patient Time 0 14th day 21st day % day C 0.85 1.92 2.84 44.6 8th


* GB785973 (A)

Description: GB785973 (A) ? 1957-11-06

Manufacture of uranium tetrachloride


PATENT SPECIFICATION 785,973 Date of Application and filing Complete Specification Dec I, 1944. : ark No 24099/44. Application made in United States of America on Dec 13, 1943. Complete Specification Published Nov 6, 1957. (Under Section 6 ( 1) (a) of the Patents &c (Emergency) Act, 1939 the proviso to Section 91 ( 4) of the Patents and Designs Acts, 1907 to 1942 became operative on April 4, 1957). Index at Acceptance:-Class 1 ( 3), A 1 (D 10: G 36 D 10). International Classification: -C Oig. COMPLETE SPECIFICATION Manufacture of Uranium Tetrachiloride We, UNITED KINGDOM ATOMIC ENERGY AUTHORITY, of London, a British Authority, do hereby declare the nature of this invention and in what manner the same is to be performed, to be particularly described and ascertained in and by the following statement: - This invention relates to the manufacture of uranium tetrachloride by the interaction of a uranium oxide and carbon tetrachloride at elevated temperature. Earlier investigators, including Camboulives, Comptes Rendu ( 1910) 150, 175-177, and Marden, U S A Patent 1,646,734 ( 1927), October 25, mention the formation of uranium chloride by reacting uranium oxide

and carbon tetrachloride. The present invention is concerned with a method of making uranium tetrachloride by the above reaction, by which method there is a considerable reduction in the tendency for some of the uranium tetrachloride product to be lost by entrainment in the gaseous products of the reaction. According to the invention there is provided a process for the manufacture of uranium tetrachloride by the interaction of carbon tetrachloride and a uranium oxide at elevated temperature, wherein carbon tetrachloride vapour generated from liquid carbon tetrachloride in a first chamber is caused to flow under gravity into a second chamber containing the uranium oxide maintained at elevated temperature, the chambers being so interconnected that the gaseous products of reaction pass from the second chamber upwardly into and through the first. The method of the invention has particular application to the conversion to uranium tetrachloride of uranium dioxide and trioxide. Particularly good results have been obtained using the method of the invention for the conversion of uranium dioxide to uranium tetrachloride at a temperature of 4250 C to 4750 C. How the invention can be performed will now be described with reference to the accompanying drawing, which is a diagrammatic representation of apparatus suitable for use in the practice of the invention Parts are given by weight throughout the written description. The apparatus shown in the drawing comprises a reaction vessel 3 connected to a condenser L which is in turn connected to a supply reservoir 2 An inner gas line C extends through the condenser and into the reaction vessel The reaction vessel is shaped somewhat like an hourglass and comprises a first or vaporizing chamber B and a second (" reaction ") chamber A These chambers are supported on sand bath heaters 5 and 6, respectively The sand heater 5 is supported on a bracket 7 and the sand heater 6 is supported on a bracket 8 Both brackets are secured to the upright of a stand 9 which rests on the surface 11 At the other end of the apparatus the upright of a stand 12 supports a bracket 13 which in turn supports bracket 14 which in its turn, through a clamp 15, supports the elevated end of the condenser at which end is vent 4 The upright of the stand 12 also supports a bracket 16 to which is secured a clamp 17 which in turn supports the reservoir 2. Usually the reservoir 2 is graduated and has a gravity feed valve 18 whereby the rate at which the liquid reactant is being utilized can be determined A container for an inert gas under pressure (not shown) is connected at the upper end of the line C The outer jacket E of the

condenser has the usual inlet 19 and outlet 21 for a cooling fluid. In operation the reaction chamber A is charged with uranium dioxide and the reaction vessel 3 connected to the condenser L A gentle stream of inert gas such as nitrogen is flowed into the reaction chamber A through the line C to sweep out the air The flow of inert gas continues throughout the reaction during which time it serves to sweep out byproduct gases and excess carbon tetrachloride vapor Heat is then applied to the reaction chamber A and a flow of carbon tetrachloride started through the valve 18 This carbon 785,973 tetrachloride collects in the vaporizing vessel B After a pool of the desired size has collected, heat is applied and the addition of carbon tetrachloride from the reservoir 2 regulated to keep the level substantially constant. Upon the application of heat to the vaporizing chamber B some of the carbon tetrachloride vapors enter the condenser L and are refluxed. Another portion of the vapor flows by gravity into the reaction chamber where it reacts with the uranium dioxide, usually forming carbon monoxide, carbon dioxide, phosgene and chlorine These gases are swept up into the condenser along with some carbon tetrachloride vapor by means of the nitrogen entering through the line C Some of the phosgene is dissolved in the carbon tetrachloride and carried back into the reaction chamber where it reacts with the uranium dioxide The gases which are not condensed in the condenser are vented through the line 4, usually into a scrubber of some sort. Efforts to drop the carbon tetrachloride directly into the reaction chamber have not been successful since liquid carbon tetrachloride boils to form relatively tremendous volumes of vapor and as a result the velocity of the gas sweeps some of the desired product out of the reaction vessel, thereby lowering the yield In addition, uranium pentachloride, which is volatile relative to the UC 1, is formed in such an operation and passes into the condenser, clogging the apparatus. EXAMPLE I Place a charge of 2242 parts of uranium dioxide in the reaction chamber A of the previously described apparatus Connect the reaction vessel 3 to condenser as shown in the drawing Introduce nitrogen in a slow stream through the inner line C to sweep out, first, the air from the apparatus, and then, after the reaction starts, the gaseous reaction products. Apply heat to the bulb containing the solid raw material and start dropping carbon tetrachloride from the measuring container 2 into the condenser L This liquid will collect in the vaporizing chamber B Apply heat to the bulb containing the carbon tetrachloride and, when it starts refluxing, maintain that condition The carbon tetrachloride

vapor at its boiling point is very much heavier than nitrogen and the hot gases such as carbon monoxide, carbon dioxide, phosgene and chlorine formed in the course of the reaction. Some of the carbon tetrachloride, therefore, continuously and gently flows downwardly into the reaction chamber When there is no reaction, the only gas leaving the system is the small amount of nitrogen used to maintain the slight sweeping action When the reaction mass reaches 4,50 ' C, maintain it at that temperature until the reaction is complete In addition to carbon monoxide and carbon dioxide formed during the reaction, some phosgene (COCL) and chlorine are produced. At least a part of the phosgene is absorbed by he carbon tetrachloride and returned for reaction with the uranium oxide By adjusting the flow of carbon tetrachloride from the reservoir to keep the volume of the pool in the vaporizing chamber B substantially constant the rate of the reaction can be accurately followed At the completion of the reaction 3153 parts of uranium tetrachloride will be obtained from the reaction chamber. EXAMPLE II Repeat the procedure of Example I using 1056 parts of uranium trioxide and maintain at an operating temperature of 500 C A yield of 1392 parts of uranium tetrachloride 80 will be obtained UCI, which tends to form due to the use of UO, as charge stock is thermally unstable at this reaction temperature, and is substantially converted into U Cl Q. In carrying out the present process employ 85 ing uranium dioxide in the production of uranium tetrachloride, the reaction temperature should be maintained as near 450 C as practicable However, good results are obtained in the range 425 to 475 C Diffi 90 culties are encountered below 400 C and above 500 C, and these temperatures may be considered the satisfactory operating limits. Atmospheric pressure is preferred, although elevated pressures are not objectionable and 95 small pressure variations do not materially affect the yields or purity of the product. The reaction is usually complete in less than five hours, the time depending to some extent on the crystalline form and particle size 100 of the raw material, the temperature of the reaction, and the size of the charge Ordinary commercial purity carbon tetrachloride is satisfactory for the reaction The process may be carried out in glass or metal apparatus 195 Since uranium compounds are expensive and usually handled in small quantities it has appeared satisfactory to illustrate Iaboratorysize apparatus With cheaper metals, which can be handled on a much larger scale, it is 110 obvious that plant size or large scale metal apparatus would be used. After the uranium tetrachloride has been produced it may be poured from the chamber.

It should be run into a dry container and 115 maintained in storage under an environment of carbon dioxide or in vacuum. The uranium tetrachloride produced in accordance with the present invention has a crystal size and structure especially suitable 120 for sublimation or vaporization in vacuum apparatus Its form allows it to be readily out-gassed and there is little tendency for it to be transported as a dust while being processed in a vacuum 125 Having now particularly described and ascertained the nature of the said invention, and in what manner the same is to be per785,973


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