5816 5820.output

* GB786224 (A)

Description: GB786224 (A) ? 1957-11-13

Improvements in or relating to the manufacture of hollow axially symmetricalbodies

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COMPLETE SPECIFICATION Improvements in or relating to the manufacture of hollow axially symmetrical bodies We, CHEMISCHE WERKE ALBERT, a Body Corporate organised under German law of Albertstrasse 10-14, Wiesbaden-Biebrich, 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 is concerned with improvements in or relating to the manufacture of axially symmetrical hollow bodies, especially tubes, from synthetic resins. By the expression "other axially symmetrical bodies" used herein we mean bodies which are symmetrical about an axis and which are provided with a passage coaxial with said axis. Tubes made from synthetic resins find a variety of uses in technology; according to the type of resin used, they may be produced in limited lengths by compression or injection moulding, by casting and by a winding method. Endless tubes can in some cases be manufactured by pressure extrusion processes. The majority of the known processes for the production of limited

lengths of tube require the use of a more or less conical mandrel, which determines the internal diameter of the tube and at the same time the mould which determines the external tube diameter must also be conical, where a divided mould is not used. It will be apparent that it is impossible to produce a truly cylindrical tube, that is a tube which is not to any extent conical, and hence a tube with a uniform wall thickness, throughout its whole length, by these means. Uniform wall thickness can indeed be obtained by pressure extrusion processes of manufacture; however such processes require that synthetic resins used therein should be capable of rapid hardening and this requirement has been found to militate against the production of tubes with thick walls and hence high wall strengths and precludes the use of slow hardening synthetic resins. Indeed, hitherto the only satisfactory method of manufacturing tubes from slow hardening synthetic resins has been casting. In the case of synthetic resins which in the hardened or set condition strongly adhere to other bodies, even casting is not satisfactory. Thus even when using the known separating media and with an extreme conicality of the mandrel and the outer mould it is not possible to manufacture a tube from, say, an epoxide resin of, say, 1 metre in length and 10 cms. average internal diameter, by, for example, casting. Even if such a tube could be separated from the outer mould, it would be found that separation from the mandrel would be impossible because the shrinkage of the epoxide resin on hardening is so great that any separating medium previously applied to the mandrel would be forced into the resin itself so that the latter would become undetachably adhered to the mandrel. It has been proposed to form axially symmetrical bodies by spinning thermosetting synthetic resins in a rotating mould. Such a process suffers from a number of disadvantages including the need to make special provisions for fine machining or polishing of the internal wall of the mould in order to avoid sticking. Moreover in such a process one can only make tubes of one diameter with a given mould. We have now found that axially symmetrical hollow bodies can be produced in a particularly advantageous manner from hardenable synthetic resins as herein defined by spinning such resins in fiowable, e.g. liquid, softened or molten, condition in a mould of the desired shape and hardening the resin during the spinning to a rigid state, an inert liquid supporting layer having a specific gravity greater than the resin being interposed between the inner surface of the mould and the resin. By the term a "hardenable synthetic resin" used herein we mean a synthetic resin or mixture of resins which is irreversibly hardenable under the action of heat and/or a hardenable

agent; in addition to any such hardening agents, such hardenable synthetic resins may also contain other substances conventionally associated with synthetic resins such as pigments, plasticisers, fillers and stabilisers. According to the present invention, therefore, we provide a process for the manufacture of axially symmetrical hollow bodies from synthetic resins in which a hardenable synthetic resin as herein defined in fiowable condition is spun centrifugally in a mould and hardened during the spinning so as to produce a rigid body of the desired shape, a supporting layer of a substance which is liquid at the temperature employed and which has a higher specific gravity than the resin and is inert thereto, being interposed between the inner wall of the mould and the resin. The mould is preferably provided with heating and cooling means, thus enabling the viscosity and rate of hardening of the resin to be controlled prior to and during the spinning operation; suitable means for heating and cooling the mould will be apparent to those skilled in the art. The radial acceleration required for any given set of operating conditions, which will be dependent on the viscosity of the hardenable synthetic resin, temperature, etc., may be obtained and controlled by any convenient rotary speed control. The invention enables tubes to be produced which are internally smooth, have a truly cylindrical shape and uniform wall thickness throughout their length. The process of the invention has the important advantage over the prior casting, compression and injection moulding processes that no mandrel is required to form the internal diameter of the tube and the deformation from a truly cylindrical shape commonly brought about by the use of conical mandrels is therefore avoided. Similarly the present process, in contradistinction to pressure extrusion, enables thick walled tubes to be produced since the necessary heating or cooling can be controlled exactly as required. An unexpected advantage obtained by the present process is that the tubes and other axially symmetrical bodies obtained are substantially completely free from air and gas bubbles, as air and reaction gases are virtually completely driven out of the tube during the rotational acceleration of the hardenable synthetic resin prior to the hardening or setting thereof. In prior production processes considerable difficulties, which in some cases could not be overcome, arose in securing the exclusion of gas or air bubbles from the moulded bodies obtained. In the course of the process according to the invention the liquid supporting substance on account of its higher specific gravity, forms a supporting layer between the mould and the resin which presents the advantage of preventing adhesion between the resin and the mould when

the resin hardens. The thermal conductivity of such a substance should preferably be such that heat that requires to be supplied or removed to or from the resin for controlling hardness during the course of the spinning can be transferred between the resin and the mould. which as stated above is preferably provided with heating and cooling means. By using such a substance capable of providing a supporting layer, it is not necessary to make special provisions for fine machining or polishing of the internal wall of the mould in order to avoid sticking, and cleaning of the mould is also facilitated. By introducing varying quantities of the substance capable of providing a supporting layer and hence varying the thickness of the layer, it is possible to produce tubes of varying external diameter in one and the same mould and hence the number of moulds required can be reduced. As stated above, substances capable of providing a supporting layer should be liquid at the temperature employed, should have a higher specific gravity than the resin and should be inert thereto. Their boiling points in the liquid state should be higher than the hardening or softening temperatures of the resin employed. Suitable substances are, for example, simple salt solutions, such as aqueous ammonium nitrate solutions; the particular advantage of such salt solutions is that their specific gravity and boiling point can be adjusted within wide limits to suit a variety of conditions by varying their concentrations. Other substances which may be used are, for example, mercury and the following which are solid at room temperature, fused salts, lowmelting metal alloys, such as Wood's metal and metal amalgams. In order that the invention may be well understood, the following example is given by way of illustration only: Exasnple Mercury (spec. gravity 13.6) or lead hexanoate (spec. gravity 1.5) is introduced into a horizontal rotating iron tube provided at both ends with releasable flanges, through a centrally disposed orifice in one flange. The internal diameter of the iron tube is 2 inches and it is rotated at 2500 r.p.m. Due to the centrifugal acceleration developed, the liquid is spread evenly over the inner face of the tube, the quantity of liquid introduced being predetermined so that a layer of approximately 1 mm. thickness is obtained. The tube is then heated to 140"C and an epoxide resin (spec. gravity approx. 1.2) premixed with hardening agents and accelerators therefor is allowed to run in. The epoxide resin becomes evenly distributed over the heavier supporting liquid and hardens within 15 to 20 minutes.

After hardening is completed, the mould is allowed to cool and the filling flange is then removed whereupon the supporting liquid flows out and the hardened tube of epoxide resin is readily removed. The tube thus obtained was truly cylindrical along its whole length, had excellent outer and inner smoothness and required no further finishing treatment. Owing to the relative ease with which tubes may be produced by the process according to the invention tubes with highly specific surface properties may be obtained which hitherto raised great production difficulties and could only be obtained in a roundabout manner. Thus arcing on tube surfaces may be reduced by adding ground quartz to the resin prior to the spinning operation; due to the centrifugal forces developed and the higher specific gravity of the quartz the latter accumulates on the surface of the resin. The supporting liquid layer in such a case must have a specific gravity not only greater than that of the resin but also greater than that of quartz; suitable substances are, for example, mercury and molten Wood's metal. In like manner other substances of greater specific gravity than the resin may be added to modify the surface characteristics of the tubes; examples of such substances are semi-conductors and pigments. What we claim is : - 1. A process for the manufacture of axially symmetrical hollow bodies from synthetic resins in which a hardenable synthetic resin as herein defined in flowable condition is spun centrifugally in a mould and hardened during the spinning so as to produce a rigid body of the desired shape, a supporting layer of a substance which is liquid at the temperature employed and which has a higher specific gravity than the resin and is inert thereto, being interposed between the inner wall of the mould and the resin.

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* GB786225 (A)

Description: GB786225 (A) ? 1957-11-13

Improvements in or relating to the refining of petroleum hydrocarbons

Description of GB786225 (A)

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NL94831 (C) NL94831 (C) less Translate this text into Tooltip



PATENT SPECIFICATION 786,225 Date of Application and filing Complete Specification: July 28, 1955. No 21849/55. Application made in France on Aug 17, 1954. Application made in France on Feb 21, 1955. Complete Specification Published: Nov 13, 1957. Index at Acceptance:-Class 91, 02 c. International Classification:-Cl Og. COMPLETE SPECIFICATION Improvements in or relating to the refining of petroleum hydrocarbons We, COMPAGNIE FRANCAISE DE RAFFINAIGE, a body corporate organised under the laws of the French Republic, of 11, rue du Docteur Lancereaux, Paris, France, 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: - The present invention relates to the elimination of traces of metallic compounds contained in petroleum hydrocarbons. It is well known that petroleum products and distillation fractions thereof often contain traces of metals, present in the form of various compounds which have been introduced either by pollution or by being brought in during the course of handling, either during the various

processes of refining, such as for example sweetening processes by the action of metallic salts, such as cupric chloride or ferric sulphate, or by the action of chelate organo-metallic compounds, or other like processes These metallic compounds which are contained in a state of solution or of fine suspension in the hydrocarbon compounds, are apt to produce either a certain instability in course of time, with development of cloudiness and a coloration and the slow formation of a precipitate, or a noxious effect during the combustion of the said products in explosion engines or internal combustion engines. It is also known that it is possible to reduce these noxious effects of metallic compounds contained in petroleum products by compounding them in the form of organo-metallic compounds with chelated links, by intimate association with iminophenols, such as, amongst others, Schiff bases, for example disalicylal propylene diimine It is also possible to limit the effects of the said instability of petroleum lPrice 3 s 6 d l products by other methods, for example, by simple filtration Methods of this latter kind, however, remove more or less completely only the consequences of this instability and not the instability itself. According to the invention there is provided a method of eliminating substantially all metallic compounds contained in petroleum hydrocarbons or in their distillation fractions, which comprises forming in situ in the hydrocarbons an organo-metallic compound with chelated links by the action of an alkyl imino-phenol, followed by the decomposition of the chelated compound by contact with a solid compound having an acid reaction. A special application of the invention is constituted by a process of stabilisation of petroleum hydrocarbons which have been subjected to a sweetening treatment by oxidation in a free oxygen-containing gas of the mercaptans which they contain, in the presence of a chelate compound obtained by reaction of an alkyl imino-phenol with a Group VIII metal said process consisting in removing the traces of metallic compounds which remain in the sweetened products by decomposition of the chelated compounds by means of a solid compound having an acid reaction. We have found on the one hand that the treatment for removing traces of metals present in petroleum hydrocarbons in the form of organo-metallic compounds with chelated links, may be effected by simple filtration through a solid compound having an acid reaction, and in particular a crystalline acid salt, such as for example (and without any limitation being implied by this enumeration) an acid sulphate of an alkali metal or an alkaline earth metal, an acid phosphate of an alkali metal or of an alkaline earth metal, or an alkali acid fluoride (for instance H Na-F Na).

There is also a certain advantage to be derived from using such a crystalline salt mixed with an inactive material serving only as an inert filling medium, such as coke or a neutral salt, such as sodium chloride, so as to avoid the formation of deposits by the acid salt setting into a mass during the course of the operation. On the other hand, it is known that in certain cases the metals to be eliminated are present in the petroleum hydrocarbons in such a form that mere filtration through a solid compound having an acid reaction is not sufficient to eliminate these metals. It has been discovered, however, that it is possible to eliminate these metals if prior to the filtration through a solid compound having an acid reaction there has been added to the petroleum hydrocarbons an alkyl imino-phenol, for example certain Schiff bases, by the action of which a chelate organic compound of the metal to be eliminated is formed in situ The Schiff bases to be used are, for example, those which result from the condensation of an ortho-hydroxy-benzaldehyde with a diamine. In addition, we have found that the formation in siti of the said chelate metallic compounds can only be obtained rapidly and easily when the metals to be eliminated from the hydrocarbons are present in an ionisable form, for example in the form of a chloride, an oleate, a stearate, a naphthenate, an enolate or a cresolate, this enumeration being furthermore not given in any limiting sense. Thus, for example, to a petrol having an initial and final boiling point of 100 '-160 'C. and a density of 0 738, and containing spectrographically less than 0 03 mg per litre of copper, there is added: To a sample ( 1): 1.0 mg per litre of copper in the form of copper naphthenate. To a sample ( 2): 1.0 mg per litre of copper in the form of copper naphthenate This sample ( 2) is divided into four fractions 2 a, 2 b, 2 c, 2 d, to which there is added respectively: Fraction ( 2 a): 1 mg per litre of a Schiff's base (disalicylal-propylene-diimine) (added in the form of a commercial product containing % by weight of the disalicylal-propylenediimine). Fraction ( 2 b): 3 mg per litre of the same Schiff's base; Fraction ( 2 c): mg per litre of the same Schiff's base; Fraction ( 2 d): mg per litre of the same Schifl's base; It should be observed that with this commercial Schiff's base, the stoichiometric quantity necessary for the formation of chelate of copper is 6 mg per litre. To a sample ( 3), containing copper in the metallic form by pollution:

after filtration, the concentration of copper is 0 6 mg per litre This sample ( 3) is divided into similar fractions, and the same additions made, as in the case of sample ( 2). This series of fractions is subjected to filtration over a bed of sodium bisulphate at a speed of 20 litres of hydrocarbon per litre of the mass of the filter and per hour The results obtained are given in the following table: N -: Sample No. 1 2 a 2 b 2 c 2 d 3 a 3 b 3 c 3 d The i Amount of Schiff base added mg/1 0 1 3 1 3 results obtains X Upper in petrol Before After filtration filtration mg/i mg/i 1 0 5 1 0 04 1 0 04 1 0 03 1 0 03 0.6 0 5 0.6 0 3 0.6 0 4 0.6 0 5 ed in the case of the samples 2 a, 2 b, 2 c and 2 d clearly show the effectiveness of the method of elimination in accordance with the invention, in addition, a comparison of the results relating to 95 the samples of the series ( 2) illustrates very clearly the catalytic role played by the alkyl imino-phenol or Schiff's base, in the elimination of the traces of metals by the method in accordance with the invention 100 It will be seen, in fact, that it is not necessary that the alkyl imino-phenol should be present in a stoichiometric quantity with respect to the said metals in the process of purification In addition, the trifling results 105 obtained in the case of the samples of the series ( 3) support the indication given above to the effect that the metal to be eliminated should be in an ionisable form. We have furthermore observed that the 110 treatments known as sweetening of petroleum hydrocarbons by oxidation in air of the mercaptans in the presence of organometallic compounds with chelate links, are accompanied by a precipitate which is easy 115 to remove by simple filtration; but in addition, if the sweetened petroleum hydrocarbon still contains an excess of chelate compound it may remain coloured and may have a certain instability which is indicated 120 by the development of cloudiness, resulting from slow precipitation of traces of metallic compounds The presence of this undesirable excess of chelate compound may occur especially in the case when the sweetening 125 of the petroleum hydrocarbon is carried out during storage by an addition of small quantities of chelate compound, but in excess however, with respect to the mercaptans, and in particular if the hydrocarbon 130 786,225 250 'C; d,5 = 0 770), containing 0 016 % of sulphur by weight in the form of mercaptans, there is added 7 grammes per cu m of disalicylal propylene-diimino cobalt in the form of a solution in a petroleum solvent 70 containing 60 % by volume of aromatic hydrocarbons and initial and final boiling points of 140 '-200 'C; said solution contains 16 6 grammes per litre of disalicylal propylene diimine, 3 48 grammes per litre of 75 cobalt in the form of

naphthenate and 20 grammes per litre of lead in the form of naphthenate After 24 hours' storage, the kerosene thus treated only contained 0 003 % by weight of sulphur in the form of 80 mercaptan, and its Saybolt colour was + 11. This product is then filtered through a bed of acid sodium phosphate in crystalline form; the paraffin thus treated does not contain any metals and its Saybolt colour 85 is + 22. Example 4 -The same kerosene which was treated as indicated at the beginning of Example 3 so as to remove the mercaptans, was filtered through a bed charged with 90 ammonium bifluoride (HF NH 4 F). The kerosene thus treated then contains only traces of metals and its Saybolt colour is + 20. Example 5 -A petrol obtained by distil 95 lation of Iraq crude oil (initial and final boiling points 40 '-120 'C; d 15 = 0 725), containing 0 025 % by weight of sulphur in the form of mercaptans is made sweet by stirring in the presence of a fifth of its 100 volume of an aqueous solution containing grammes per litre of cupric chloride, 40 grammes per litre of sodium chloride and 1 cu cm per litre of concentrated hydrochloric acid; the petrol thus treated 105 contains 0 40 mg per litre of copper. From this petrol, two fractions are made; one fraction is directly filtered through a bed of bisulphate of sodium and the other is filtered through a similar bed after the 110 addition of 1 mg per litre of disalicylal propylene diimine After these treatments, the first fraction still contains 0 20 mg per litre of copper, whilst the second contains only 0 06 mg per litre of copper 115


* GB786226 (A)

Description: GB786226 (A) ? 1957-11-13

Improvements in or relating to glutamic acid derivatives and process of

making the same




COMPLETE SPECIFICATION Improvements in or relating to Giutamic cid Derivatives and process of making the same We, INTERNATIONAL MINERALS & CHEMICAL CORPORATION, a corporation organised under the laws of the State of New York, United States of America, of 20 North Wacker Drive, City of Chicago, State of Illinois, 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 a method for preparing new glutamic acid derivatives, and more particularly to methods for preparation of glutamic acid derivatives from which optically active natural glutamine is produced. The present invention provides a process; of preparing an N-carboallyloxy-L-glutarmc acid and an N-carboallyloxy-L-glutamic anhydride which comprises reacting L-glutamic acid with an allyl chloroformate and if desired, converting the resultant acid to its corresponding anhydride by methods heroin described. The present invention further provides a process for the production of LSlutamine which comprises treating a Ncarboallyloxy- L-glutamic anhydride with liquid ammonia to produce, the corresponding N-carboallyloxy L-glutamine and treating the N-carboallyloxy- i;-glutamine to remove the carboallyloxy group by methods herein described and produce Lcglutamine thereby. The present invention also provides a compound of the group consisting of an N-carboallyloxy-L-glutamic acid and an N-carboallyloxy glutamic anhydride.

Known processes for the preparation of Lglutamine have been characterized by difficulties resulting from the complicated series of steps involved, the dangers of the reactants utilized, economically unfeasible manipulations, low yields, and the like. For example, utilizing the carbobenzyloxy method of Bergmann, Zervas, and Salzmann, BERICHTE 66B, 1288-90 (1933), and the phthalyl method of Kidd and King, NATURE 162, 776 (1948), low yields of the order of 5% to 15% are obtained. Other processes utilized in the past have been characterized by lower yields. Bergmann's method in particular has the further disadvantage of the hazard connected with benzylchioroformate. Upon standing and/or drying, this compound spontaneously decomposes in an explosive manner, and in the past has caused serious injury to workers. There has been need for a commercially feasible process for synthesizing glutamine. It is an object of the instant invention to provide an improved method for the synthesis of optically active natural glutamine. It is a further object of the instant invention to provide a method for synthesizing optically active natural glutamine in com paratively high yields without resorting to the resolution of a racemic mixture. It is a further object of the instant invention to provide an improved synthesis of optically active natural glutamine in which comparatively high yields are obtained using reactants and intermediates which are not hazardous. It is another object of the instant invention to prepare new compounds from which optically active natural glutamine is produced. It is another object of the instant invention to provide a commercially acceptable method for the synthesis of optically active natural glutamme. These and other objects of the instant inInvention will become more apparent upon a fuller understanding of the invention as hereinafter decribed. In accordance with this invention optically active natural glutamine, that is, L-glutamine, is produced by amidating with liquid ammonia an N-carboallyloxy-L-glutamic anhydride to produce the corresponding Ncarboallyloxy-L-glutamine and then removing the carboallyloxy group from the latter compound to produce L-glutamine. In carrying out the process of this invenfor utilizing L - glutamic acid as a raw material, L-glutamic acid is reacted with an allyl chloroformate, such as allylcKoro- formate, phenallylchloroformate, methallylchloroformate or other alkallyichioroformate. Reaction of an allylchloroformate compound with L-glutamic acid produces the corresponding Ncarboailyioxy-L - glutamic acid believed to have the structural formula <img class="EMIRef" id="026445168-00020001" />

wherein R is hydrogen, alkyl or phenyl, depending upon the particular allyl chloroformate employed. When R is an alkyl group, it is preferably a lower alkyl group, that is, an alkyl group having less than 8 carbon atoms of either branched chain or straight chain configurations. The N-carboallyloxy glutamic acid compound is then su'ojected to a cyclization reaction, for example, by treatment with acetic anhydride, to produce the corresponding Ncarboallyloxy-L-glutamic anhydride believed to have the structural formula <img class="EMIRef" id="026445168-00020002" /> in which R is hydrogen, alkyl or phenyl as described above The particular carboallyloxy group in the N-carbGallyloxy-L-glutamic anhydride will, of course, correspond to the carboallyloxy group of the particular Ncarboallyloxy - L - glutamic acid compound utilized in its preparation. N-carboallyloxy-Lglutamic anhydride and Ncarb omethallyloxy- L-glutamic anhydride are preferred species of the class described in that they are particularly useful in preparing L-glutamine in accordance with this invention. In producing L-glutamine according to the process of this invention, an N-carboallyloxy-L-glutaraic anhydride is amidated by treatment with liquid ammonia to produce the corresponding N-carboallyloxy - L-glutamine. The N-carboallyloxy - L-glutamine may then be converted into L-glutamine by treatment to remove the carboallyloxy group. By the term"glutamine"as used herein, either alone or in combination with one or more prefixes, is meant the corresponding Lglutamine. In one embodiment of the instant invention, L-glutamic acid is reacted with allyl chloroformate in the presence of a magnesium or:ide catalyst. When the reaction has proceeded to substantial completion, the reaction mixture is extracted with chloroform to remove unreacted allyl chloroformate. The aqueous residue is acidified with hydrochloric acid and extracted with a solvent such as nbutanol. The resulting n-butanol solution contains N-carboallylGxy-L-glutamic acid. Treatment of the N-carboallyloxv-L-glutamic acid with a liquid acid anhydride such as acetic anhydride produces the N-carboallyloxy-Lglutamic anhydride of this invention. In carrying out the instant invention, any suitable allyl chloroformate may be utilized and the term an allyl chloroformate" as utilized herein refers to unsubstituted allyl chloroformate, alkallylchloroformates, or phenallyl chioroformate. In the case of the alkyl substituted allyl chloroformates, it is preferred that the alkyl substituent be a lower alkyl group, that is, an allyl group containing less than 8 carbon atoms. Unsubstitut:d allyl chloroformate is preferred in carrying out the process of this invention because of the

higher yields obtained with the compound. The terms an N-carboallylexy-L-glutamic acid," an N-carboallyloxy-L-glutamic anhydride," and "an Nsarboallyloxy-LSlut- amine" refer to N-carboallyloxy derivatives of L-glutamic acid, L-glutamic anhydride, and L-glutamine, respectively, in which the allyloxy group may be an unsubstituted allyloxy group or a phenyl or alkyl substituted allyloxy group in which the alkyl group is preferably a lower alkyl group as described above. The terms "N-carboallyloxy- L-lutamic acid," "N-carboallyloxy-L-glutamic anhydride" and "N-carbcallyloxyL-glutarrine refer to N-carboallyloxy derivatives in which the allyloxy group is unsubstituted. In accordance with a preferred embodiment of this invention, N-carboallyloxy-Lglutamic anhydride produced by cyclization of N-carboallyloxy-L-glutamic acid is treated with liquid ammonia to produce the correspending N-carboallyloxy-L-glutamine. The latter L-glutamine derivative is then treated vjith hydrogen bromide or hydrogen chloride under anhydrous conditions. The product is L-glutamine in the form of a hydrogen halide addition salt L-glutamine may be recovered from the reaction product mixture by any suitable means. A convenient method involves evaporating the reaction product mixture to dryness, dissolving the residue in methanol, adjusting the pH of the methanol solution to about the iso-electric point of Lglutamine, that is, a pH of about 5.5 by addition of aqueous ammonia, adding acetone in an amount equal to that of the methanol and letting the mixture stand at 0 C to 10 C. to permit crystallization of the L-glutamine. The L-glutamine crystals may be recovered by filtration. L-glutamic acid reacts readily with an allyl chloroformate such as allyl chloro form ate, methallyl chloroformate, phenallyl chloroformate, and other lower alkyl (e.g. ethyl, propyl) substituted allyl chioroformates. The reaction is exothermic, with the reactants being generally admixed at a temperature between about 0 C. and about 50 -C., preferably between about 15 C. and about 35 C., the temperature of the resulting mixture is allowed to rise to about atmospheric temperature and in a preferred embodiment the mixture is agitated at about atmospheric temperature for about one-half hour and about 2 hours. l The resulting reaction products are extracted with a solvent to separate the unreacted allyl chloroformate. An organic solvent, such as chloroform, - carbon tetrachloride, methylene bichloride or ethylene bichloride is used. The aqueous residue is then acidified, for example, with hydrochloric acid to a H between about 1.5 and about 2.5. The

carboallyioxy-L-glutamic acid is extracted from the acidified solution with a solvent such as n-butyl alcohol. In a preferred embodiment, the product is extracted with n-butanol and the n-butanol extract evaporated to dryness. The N-carboallyloxy-L-glutamic acid is then cvclized by treatment with a liquid. organic acid anhydride, such as acetic anhydride, to produce an N-carboallyloxy-L-glutamic anhydride. This reaction is preferably carried out by dissolving the N-carboallyloxy- L-glutamic acid in acetic anhydride and then heating the solution rapidly to a temperature up to about 100" C., preferably to about 95" C., and maintaining that temperature for about 5 minutes. Any temperature from about 20 C. to about 100" C. may be utilized. The reaction product mixture is then allowed to cool slowly and the solvent comprising an acetic acid-acetic anhydride mixture is distilled off at reduced pressure and a temperature less than about 65 C. The N-carboallyloxy-L-glutamic anhydride is then amidated with ammonia to produce the corresponding N-carboallyloxy-L-glutamine. The amidation reaction is carried out using liquid ammonia. A pressure vessel may be employed if desired. Following the reaction, the ammonia is removed from the Ncarboallyloxy-L-glutamine, for example by evaporation. The N-carboallyloxy-L-glutamine is then treated to remove the carboallyloxy group to produce L-glutamine. in one embodiment liquid ammonia and sodium are added to the N-carboallyloxy-L-glutamine, which has been evaporated to dryness, to reduce this compound to L-glutamine. The reduction is substantially complete when the solution becomes a permanent blue color. Ammonia is evaporated from the solution and the residue is dissolved in water. The L-glutamine solution is then acidified to a pH between about 4.5 and about 6.0, preferably about 5.5 with an acid. An acid which forms a sodium or ammonium salt which is soluble in alcohol, such as, for example, hydriodic acid, formic acid, or the like, is employed. An alcohol such as methanol, ethanol or a combination of methanol and acetone or isopropanol, is then added. L-glutamine is insoluble in the alcoholic solution and is separated from the solution. In accordance with another embodiment, Ncarboallyloxy-L-glutamine may be treated to remove the carboallyloxy group by treatment with hydrogen and a noble metal catalyst, such as platinum, palladium, rodium and the like, or other hydrogenation catalysts such as nickel. The treatment with hydrogen is preferably carried out at room temperatures and superatmospheric pressures. The following examples represent specific embodiments of the

invention. All parts are by weight unless otherwise indicated. lixAMPLE I. L-glutamic acid in the amount of about 73. 5 parts was charged into a reaction vessel along with about 58 parts magnesium hydroxide and about 300 parts water. While the mixture was agitated vigorously, there was added about 150 parts of allyl chloroformate at room temperature. Agitation was continued for about 1. 5 hours at about 28 C. and the mixture was then filtered to remove excess magnesium hydroxide. The filtrate was washed with two 150-part portions of chloroform to remove unreacted allyl chloroformate. The extracted filtrate was acidified to a pH of about 1.5 using a 1:1 mixture of water and concentrated hydrochloric acid. The acidified mixture was again extracted with three 162-part portions of n-butanol and the combined butanol extracts were washed with 200 parts of water and then distilled at about 25 mm. Eg from a water bath at about 60 G The residue was N-carboallyloxy-L-glutamic acid. The Ncarboallyioxy glutamic acid was a viscous syrupy oil having a neutralization equivalent of 118 (theoretical 116) and a nitrogen content of 5. 91% (theoretical 6.0596). The refractive index was nD2S= 1.4899 and the specific rotation was ['ID'8 = -17.4 (C=4.08; water). N-carboallyloxy-L.glutamic acid prepared as above in the amount of about 98.6 parts was dissolved in about 300 ml. of acetic anhydride and the solution heated on a steam bath for about 5 minutes at about 95" C. and then allowed to stand in a closed vessel at room temperature for about 1 hour. The solvent was distilled off at about 28 mm. Hg at a temperature of about 60 C. The product which was N-carboallyloxy-L-glutamic anhydride was dissolved in about 184 parts of liquid ammonia over a period of about 1 hour with agitation. After dissolution was complete, the excess ammonia was distilled off under reduced pressure at room temperature and condensed for reuse. The residue remaining after removal of excess ammonia was the ammonium salt of the gamma-amide of Ncarboallyloxy-L-glutamic acid. Acidification of the ammonium salt with formic acid produces the gamma-amide of N-carboallyloxy-L-glutamic acid. The ammonium salt of the gamma-amide of N-carboallyloxy-L-glutamic acid (N-carboallyloxy-L-glutamine) in the amount of about 49.4 parts was dissolved in about 360 parts of liquid ammonia and about 13.8 parts of metallic sodium was added to this solution in the form of small chips. A blue color formed at the end of the reaction. Excess ammonia was expelled under reduced pressure at room temperature and the ammonia vapors condensed for reuse. The residual white solid was treated with about 55 parts of methanol to destroy any unreacted metallic sodium. The suspended solids were dissolved with cooling to

below 10 C. in about 160 parts of water and the pH was rapidly adjusted to about 5.5 with approximately 55 parts of 90% formic acid followed by the addition of about 569 parts of methanol. A volume of acetone equivalent to that of the methanol was then added to the mixture. The temperature of the solution was reduced to about -10' C. and allowed to stand. Over a period of 24 to 48 hours a solid crystallized from the mixture, which solid was identified as glutamine. The crude L-glutamine which was about 85% pure was dissolved as rapidly as possible in about 9 times its weight of water which had been preheated to about 60 C. to 65 C. The solution was filtered while hot immediately after dissolution was complete and about 158 parts of acetone added to the filtrate. The solution was immediately cooled to 09 C. and filtered after standing for about 1.5 to 2.0 hours. The filter cake was washed with about 8 parts of methanol and dried at about 58 C. The glatamine obtained had a purity of about 98%. EXAMPLE U. The ammonium salt of Ncarboallyloxy- L-glutamine prepared as in Example I in the amount of about 24.7 parts was dissolved in about 105 parts glacial acetic acid by means of warming the mixture to a temperature of about 48 C. with agitation. To the warmed solution was added about 105 parts of a 36% solution of hydrogen bromide in glacial acetic acid. The mixture was allowed to stand at room temperature for about 2 hours with occasional agitation. The reaction mixture was then evaporated to dryness under reduced pressure (about 25 mm. Hg) using a bath temperature of about 58 C. The residue which was a sticky straw-colored mass was dissolved in about 198 parts absolute methanol and the pH of the solution was adjusted to about 5.5 with a 14% aqueous ammonia solution. A volume of acetone equivalent to that of the methanol was then added. After storage of the mixture at about 5t C. for about 2 hours, the crystalline product was filtered and washed with methanol. The yield of L-glutamine amounted to about 9.3 parts and had a purity of about 84%. The crude glutamine was dissolved in about 84 parts of water at a temperature of about 63G C. and was filtered rapidly as soon as the solution was complete. To the filtrate was added about 168 parts of hot acetone (50 C.). The mixture was cooled as fast as possible to 0 C. and after about 1.5 hours at this temperature, it was filtered to give crystalline L-glutamine. The recrystallized L-glutamine had a purity of about 91% and the yield amounted to a 91% recovery. By recrystallizing the L-glutamine a second time, utilizing the same procedure, the purity was raised to 96% with a 95 yield. What we claim is : -

1. A process of preparing an N-carboallyloxy-L.-glutamic acid and an N-carboallyloxy L-glutamic anhydride which comprises reacting L-glutamic acid with an allylchloroformate, and if desired, converting the resultan. acid to its corresponding aniydride by methods herein described.


* GB786227 (A)

Description: GB786227 (A) ? 1957-11-13

Improvements in or relating to ratchet wrenches

Description of GB786227 (A)

PATENT SPECIFICATION Inventor: WILLIAM BENJAMIN FORD 7869227 (:t'W t _Date of Application and filing Complete Specification: Aug 15, 1955. No 23479155. Complete Specification Published: Nov 13, 1957. Index at acceptance:-Class 83 ( 3), N( 2 A 2: 2 E 2: 3 C 7). International Classification;:-B 23 g. COMPLETE SPECIFICATION Improvements in or relating to Ratchet Wrenches We, THE ARO EQUIPMENT CORPORATION, a corporation organised under the laws of the State of Ohio, United States of America, of Bryan, Ohio, 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 a ratchet wrench of the open end type which has a head that may be used on a hexagon-shaped nut, a bolt, a cap

screw head or a tubing nut which is accessible only from the side, to impart rotation 1 S thereto either continuously, or intermittently in as little as one-twelfth of a revolution or by swinging motion of the tool. The present invention provides a ratchet wrench including a C-shaped wrench head haying jaws of sufficient width to receive the small diameter of a nut and inwardly of said jaws a partial cylindrical surface of sufficient size to receive the corners of the nut, said roller means being mounted on said head to engage the corner of the nut to rotate it when said head is oscillated around the nut in one direction and permit the roller means to move over the nut when said head is oscillated around the nut in the opposite direction, and spring means normally biasing said roller means toward a fixed position, a frame oscillatably supponrting said head, and power-operated means for oscillating said head relative to said frame. One object of the invention is to provide an open-end ratchet wrench of this general character which may be power operated and which has a relatively small thickness so that it eliminates the necessity of considerable head room to work on a nut or bolt as required 40)by many types of power wrenches. Another object is to provide a wrench which is adapted for power operation as by means of a pneumatic motor, the wrench comprising a wrench head which is o:scilll'atably mounted in a frame attached to the motor and the frame including mechanism for translating the rotations of the motor shaft into oscillations of the wrenchhead lPrice A further object is to provide a novel wrench head which may be slipped edgewise over a 50 nut and when in operating position has a circular part clearing the corners of the nut, the circumferential extent of which is greater than degrees so that it substantially confines the nut against slipping of the wrench therefrom 55 during operation of the wrench. A still further object is to provide a Cshaped wrench head which is oscilliatably mounted in a frame of the tool and is prokided with one or more nut corner-engaging 60 rollers or cams to engage the nut to rotate it when the wrench head is oscillated in one direction, the rollers or cams being slidable in the wrench head so that the rollers or cams clear the corners of the nut in -ratchet 65 ing fashion when the wrench head is oscillated in the opposite direction. An additional object is to provide a relatively simple C-shaped wrench head with relafively simple pocket and roller arrangements 70 in conjunction therewith, and a 'gear sector, idler gear and rack arrangement for changing reciprocations of the rack into oscillations of the wrench head, the rack in turn being reciprocated by a cam on the motor shaft 75 Another additional object is 'to provide a cam

plate pivoted to the frame of the tool and projecting through a slot of the wrench head, the cam plate serving as a stop against the top of a nut during some types of operations and 80 as a holding means to prevent reverse rotation of the nut during other types of operations. With these and other objects in view, the invention consists in the constructions, arrangement and combination of the various parts 85 of the ratchet wrench, whereby the objects contemplated are attained, as hereinafter more fully set forth, pointed out in the claims and illustrated in the accompanying drawings, wherein: 90 Figure 1 is a plan view of ia ratchet wrench embodying the present invention' with a cover plate removed and part of the housing and other elements shown in section. Figure 2 is a detail sectional view on the 95 line 2-2 of Figure 1. Figure 3 is a detail sectional view on the line 3-3 ' of Figure 1 and shows the motor for the wrench partially in side elevation. Figure 4 is an enlarged view similar to the left-hand end of Figure 1 with the wrench head shown in, section and illustrating the cooperation of one of the rollers thereof with one corner of a nut. Figure 5 is a similar view showing the nut turned 30 degrees clockwise. Figure 6 is a similar view showing the wrench head being oscillated in the opposite direction and one of the rollers ratcheting over the corner of the nut. Figure 7 shows the final position for the other roller to engage the corner of the nut just before another reciprocation clockwise to retate the nut another 30 degrees. Figure 8 is a detail sectional view on the line 8-8 of Figure 4; and Figure 9 is a perspective view of a roller and its follower used in the wrench head of the ratchet wrench. Figure 10 is an enlarged view similar to the left-hand end of Figure 1, but of a modification of -the wrench head, and illustrating in section the cooperation of one notched cam in each of two pair thereof with two opposite corners of a nut. Figure 11 is a similar view showing the nut turned 30 degrees clockwise. Figure 12 is a similar view showing the wrench head being oscillated in the opposite direction, and the notched cams ratcheting over the corners of the nut. Figure 13 shows the final position for each of the other notched cams to engage the corners of the nut just before another reciprocation clockwise to rotate the nut another 30 degrees. Figure 14 is a detail sectional view on the line 14-14 of Figure 12. Figure 115 is a detail sectional view on the line 15-15 of Figure 12, and shows the motor for the wrench partially in side elevation.

-Figure 1,6 is a perspective view of a notched cam and its spring and keeper pin as used in the wrench head of the ratchet wrench. On the accompanying drawings the reference numeral 10 indicates a motor for operating the wrench which motor may be pneumatically powered and provided with a throttle valve 12 and a throttle lever 14 in the usual manner The shaft of the motor is indicated at 16. A body for frame 18 & is provided which is partially fiat and partially circular as shown in Figure 3 The circular part is engaged with a flange 20 of the motor 10 by a retainer nut 22 so that the frame may be readily connected and disconnected in relation to the motor The frame 18 is provided with a hollow space therein for an idler gear 24, a rack 26 and portions of a C-shaped wrench head 28 A stud 29 having reduced ends is provided on which the gear 24 rotates, The wrench head 28, as shown in figure 1, is provided with a circumference 30 and an inner cylindrical surface 32 The circumference has a projection 34 as shown in Figure 2 which interfits in a corresponding arc-shaped 70 groove 33 of the frame 18 for permitting rotation or oscillation of the wrench head relative thereto A cover plate retains the wrench head in position and also covers the cavity in the frame in which the driving elements 24 and 75 26 are mounted. The projection 34 of the wrench head is provided with gear teeth 36 meshing with the idler gear 214 and the teeth of the idler gear 24 also mesh with those of the rack 26 so that 80 any oscillations imparted to the rack obviously will oscillate the wrench head For imparting such oscillations thereto, we provide a cam 38 keyed at 40 to a sleeve 42 mounted on the motor shaft 16 and cooperating with a 85 roller 44 carried by the rack To retain the roller in contact with the cam 38, we provide a spring 46 interposed between a socket 48 in the frame 18 and a socket 50 in the head 52 of the journal pin 54 provided for the 90 roller 44, all as shown in Figure 1. With specific reference to the C-shaped wrench head 28, it is provided with opposite parallel jaws 56 and 58 The distance between these jaws is just slightly greater than the small 95 diameter of a hexagon nut 59 as shown in Figure 7 The cylindrical surface 32 is just large enough to receive the nut or has a radius substantially equal to the radius of the corner of the nut Thus the cylindrical surface is of 100 slightly greater extent than 180 degrees as indicated by the angle B in Figure 4. IA pair of rollers 60 and 62 are provided which are mounted in pockets 64 and 66 of the wrench head 28 These rollers are normally 105 seated at 64 a and 66 a by means of springs 68 (see Figure 8) which bias roller keeper pins toward the rollers, the pins being provided with blade-like extensions 72 entering grooves 74 of the rollers (see also Figure 9) There 110 fore, the rollers can be forced back in their

pockets against the bias of the springs 68 as shown in Figure 6, for instance, (roller 60) when the wrench head is oscillated counterclockwise The springs 68 are retained in posi 115 ton by plugs 76. Also in connection with the wrench head, there is provided a cam plate 78 pivoted at (see Figure 4) and biased by spring 83 to a position inward of the cylindrical sur 120 face 32 of the wrench head by a spring 83. The inward limit position is shown in Figure 1 This cam plate is provided with an edge portion 80 and a notch 82, the purpose of which will hereinafter appear In order not to 125 interfere with the action of the cam plate, the wrench head is slotted as indicated at 84 and the cam plate extends from a pocket 85 in the frame 18 through the slot 8 '4. ? 86,227 786,227 OPERATION In the operation of the ratchet wrench, it may be placed downwardly on ma bolt or cap screw head 61 as in Figure 1, N which case the cam plate 78 will act as a stop and this is desirable when the head of a bolt or cap screw, for instance, is spaced some distance from a surface against which the head is to be finally engaged by operation of the wrench. The cam plate 78 is this instance will prevent the wrench head from settling down too far on the bolt head shown' dotted in Figure 2 On the 'other hand, the head may be slipped sideways over the nut as shown' in Figure 7 where there is no head room for the usual type of motor driven wrench. Assuming a starting position such as shown in Figure 4, the angle A between the rollers and 62 is substantially 30 degrees for the ratchet wrench when designed for a hexagon nut in order to rotate the nut in increments of one-twelfth of a revolution as will hereinafter appear It will be obvious that if the C-shaped wrench head 28 in Figure 4 is now rotated clockwise, the roller 60 will have no effect but the roller 62 will engage the upper corner of the nut 59 and rotate the nut, the final position being shown in Figure 5 whereupon the wrench head has reached the limit of its clockwise rotation and is ready 'to start rotating counter-clockwise. Figure 6 shows about half of the counterclockwise rotation completed The roller 60 is not ratcheting across that corner of the nut above referred to, it being shown spaced from its seat 6 '4 ia A little further rotation will permit the spring 68 to extend the roller 160 out again to a position such as shown in Figure 6 where the roller 60 now engages the specified corner of the nut for effecting the next 30 degrees of rotation Slimilarly during the next counter-clockwise reciprocation, the roller 62 will ratchet over the next corner of the nut and assume the position of Figure 7 for rotating that corner, 'and

the cycle will be repeated with the rollers 60 and 62 alternately engaging the nut corners. With a wrench of the character shown, the motor 10 may be used for rotating the nut 59 until it stalls the motor whereupon the length of the frame 1,81 plus the motor 10 serves as a handle of sufficient leverage to tighten the nut by hand, the gearing being locked 'due to coming to the end of the throw such as the position shown in Figure 1 with the roller 44 at the bottom of the cam surface 38, or the wrench can be used for hland tightening at any position on the cam rise in confined areas for small degrees of motion. Referring to Figure 4, it will be noted that the lower corner of the nut is slightly out of position with relation to the notch 82 The notch, it will be noted, is so shaped as to apply pressure as indicated by the arrow to tend to rotate the nut clockwise Likewise at the intermediate position of the nut, as shown in Figure 7, the notch 82 of the cam engages the corner of the nut as indicated by an arrow to apply pressure tending to rotate the nut clockwise The cam plate 78, therefore, when 70 it engages the side of the nut, tends to keep it from rotating counter-clockwise during the ratcheting operation in case the friction between the nut and the bolt is but slight. To rotate the nut in a counter-clockwise 75 direction', it is merely necessary to turn the complete wrench including the frame 118 over. The wrench head can then be applied to the nut and the tool used as a hand lever for loosening the nut after which the motor may be 80 energized for removing the nut We have illustrated one size of wrench head 2 '8 and it will be obvious that it fits but one size of nut It may, of course, be made in various sizes and each wrench, being readily attachable and de 85 tachable relative to the motor 10, minimizes wrench changing This is no disadvantage in mass production, however, as it would be the usual practice for one workman to operate on only the size of nut which his wrench will fit 90 In a modification as illustrated in Figures to 116, two pairs of notched cams, 1,60 and 1 '60 a, and 161 ' and 1611 a, are provided which are rotatably mounted in sockets 62, in the wrench head 28 ' along axes, parallel to the 95 longitudinal axis of the nut The sockets are exposed at the inner surface of the wrench head over an angle of arc substantially less than 1800 The cams are retained in position by the wrench head 2,8, land are normally seated 100 by means of springs 1,64 which bias keeper pins 165 toward the cams, the keeper pins seating in recesses 166 in the cams as shown in Figure 16 Therefore, the notched cams or rockers can be forced to rotate in their sockets 105 against the bias of the springs 164 as shown in Figure 10, for instance (cams 160 a and 161 ua), when the wrench head is oscillated in a return or 'couniter-clockwase direction.

Also in connection with this form of wrench 110 head, there is provided an L-shaped holding pawl 168 having a serrated engaging-surface 16,9 with a radius of curvature just large enough to clear the corners of the nut when the nut is held in a centered position by the 115 cams. PRACTICAL OPERATION. In operation, the ratchet wrench may be placed against a bolt or cap' screw head 59, as in Figure 10, land the holding pawl 1,68 120 is then forced' against one or two corners of the nut, in which position the serrations thereof act as a stop to prevent rotation of the nut in a direction opposite that desired The notched cams or rockers, when they become 125 operative to engage and rotate the nut, will serve to center the nut so' as to provide dearance between the nut corners and the holding pawl, whereupon actuation of the motor drive will effect oscillation of ithe wrench head and 130 786,227 rotation of the nut without interference therewith by the serrations of the paw L. Assuming a starting position such as shown in Figure 10, the angle A between the notched cams 160 and 160 a is substantially 30 degrees for the ratchet wrench when designed for a hexagonal nut head in order to rotate the nut in increments of one-twelfth of a revolution, as will hereinafter appear It will be apparent that if the C-shaped wrench head 28 in Figeure is now rotated clock-wise, the notched cams a and 161 a will have no effect, but the cams 160 and 1651 will engage the upper and lower corners respectively of the nut 59 and rotate the nut in a clockwise direction through an arc of 30 degrees to a final position as shown in Figure 11, whereupon the wrench head has reached the limit of its clockwise rotation and is ready to rotate counter-clockwise. Figure 12 shows about one-half of the return or counter-clockwise rotation completed The notched cams 160 a and 161 a are now ratcheting across the corners of the nut above referred to, and are shown rotated in a counter-clockwise direction against the bias of springs 164. At the same time, the serrations of the holding pawl will act to grip the adjacent corner of the nut as the manual pressure exerted by the operator serves to move the wrench head forwardly against the nut Normally, the nut and wrench head will have some degree of free relative movement, one within the other When the gripping rockers are operatively effective to turn the nut, the latter will be centered within the head, permitting the corners of the nut to clear the serrated surface of the holding pawl. As the rockers ratchet back across the corner of the nut during a return oscillation, the manual force exerted by the operator will serve to eccentrically position the nut and head, relative to each other, thereby permitting the holding pawl to move forvardly to engage

and grip an adjacent corner of the nut and preclude reverse rotation thereof In this manner, counter-clockwise rotation of thenut is prevented zs the rockers ratchet back. Further rotation of the wrench head will permit the springs 168 to return the cams 160 a and 161 a to the normal position of Figure 13 where cams 160 a and 161 a now engage opposite corners of the nut for effecting the next degrees of rotation as the wrench rotates in a clockwise direction. Similarly, during the next counlter-clockwise reciprocation of the wrench head, the cams and 161 will ratchet over the next corners of the nut and assume the position of Figure 10 for rotating those corners The cycle will be repeated with the cam pairs 160-161 and 1,60 a-161 a alternately engaging the nut corners. 1 Otherwise, theoperating functions of the wrench as a whole are the same as described with reference to the embodiment of Figures 1 to 9.


* GB786228 (A)

Description: GB786228 (A) ? 1957-11-13

Process for the enrichment in p o of phosphate rock which contains calciumcarbonateand for the manufacture of superphosphate



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 7869228 Date of Application and filing Complete Specification Aug 18, 1955. & "'% No 23871,55. Complete Specification Published Nov 13, 1957. Index at Aecel c l: -Class 1 ( 3), A( 1 D 37: G 47 D 37). International Classification::Ob. COMPLETE SPECIFICATION Process for the Enrichrment in P 20 i; of Phosphate Rock which Contains Calciumn Carbonate and for the Manufacture of Suyperellosphate We, THE STATE OF ISRAEL, represented by the Prime Minister, Jerusalem and SHMUEL PERLMUTTER, of No 16 Rehov Zephania, Jerusalem, an Israel citizen, 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 enrichment in P 20, of phosphate rock which contains calcium carbonate and also to the manufacture of superphosphate. Calcium carbonate contained in phosphate rock is decomposed in the usual process of manufacture of superphosphate by a considerable quantity of sulphuric acid with the formation of calcium sulphate whereby the percentage of P O O in the superphosphate produced is reduced Therefore, in the manufacture of superphosphate employing such raw material (hereinafter referred to as " raw phosphate ") efforts were made to remove wholly or partly the calcium carbonate, in order to obtain a super Dhosphate of at least 18 % by weight available phosphoric acid (" A P A "). Up to now various methods have been used for this purpose, e g mechanical separation, alkaline fusion, calcination, all of them of relatively little avail and having many disadvantages such as high cost, high fuel consumption and considerable losses in P 2 O,. According to the present invention, a process for the enrichment in P O, of phosphate rock which contains calcium carbonate, comprises reacting the raw phosphate reduced to a fineness of 30 to 170 mesh with a 5 to 10 . aqueous sulphuric acid to convert calcium carbonate contained in the raw phosphate to calcium sulphate and separating the calcium sulphate suspension thus obtained from the rapidly sedimenting phosphate The quantity of the sulphuric acid required is equivalent to the quantity of Ca CO, contained in the raw phosphate, or to the quantity of Ca CO, which lPrice 3 s 6 d.

it is desired to remove (if only a part of it is to be removed) This quantity of 11,504: is saved afterwards if the enriched phosphate is converted to superphosphate. The mesh figures quoted in this specification and in the claims correspond to the sieve designations of the A S T M (American Society for Testing Materials) Specification E-11/39 (also quoted as U S Sieve Series in Table 8 on page 963 of Chemical Engineers Handbook edited by John H Perry, 3rd edition, 1950, published by the McGraw Hill Publishing Co Ltd), 30 mesh corresponding to sieve openings of 0 59 mm and 170 mesh corresponding to sieve openings of 0 088 mm. In the enrichment process of the invention, the calcium sulphate formed is in the form of relatively small particles of low settling velocity whereas the phosphate particles are of relatively large size and settle rapidly The sizing of the phosphate particles is an important feature in obtaining this result and enables an effective separation to be obtained. The invention also provides an improved process for the production of superphosphate from phosphate rock containing calcium carbonate, in which the phosphate rock is enriched in POQ, and freed from calcium carbonate as set out above and the enriched phosphate product is then treated in known manner with sulphuric acid to produce superphosphate. The process of the invention for the manufacture of superphosphate does not result in a saving in the overall consumption of HMSO 4, but with equal quantities of H SO, a product of far higher P O,-content is obtained from the same raw material Nevertheless, even with respect to acid consumption, an advantage of this invention accrues from the fact that a 504 which constitutes a waste product in other factories or branches of the plant can be used for the first acidulation step. In order to more fully illustrate the invention and the preferred mode of carrying the same into effect, the following example is given to which the invention is, of course, not limited. EXAMPLE. 1000 kg raw phosphate, ground to about 100 mesh, containing 26 % P 0,0 and 20 % Ca CO,, are mixed under stirring with 1800 litres of % H 2 SO 4 When the reaction is finished the slurry is transferred in continuous or batchwise process into a series of mixers and thickeners as known per se, by addition of water The concentrated raw phosphate is drawn off from the bottom of the thickeners by means of pumps or other usual methods, the water with the suspended calcium sulphate removed by overflow The concentrated phosphate contains 33 to 34 % P 20, with a yield of about 90 % This phosphate may readily be converted into superphosphate in known manner. Phosphate rocks differ widely in their composition, but the quantity of acid required for achieving the desired result can be ascertained

in each case by chemical tests of the available raw material.


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