CN1049650C - Synthetic method of phenyl-pyruvic alkali salt and ammonium salt - Google Patents
Synthetic method of phenyl-pyruvic alkali salt and ammonium salt Download PDFInfo
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- CN1049650C CN1049650C CN96116853A CN96116853A CN1049650C CN 1049650 C CN1049650 C CN 1049650C CN 96116853 A CN96116853 A CN 96116853A CN 96116853 A CN96116853 A CN 96116853A CN 1049650 C CN1049650 C CN 1049650C
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Abstract
The present invention relates to a method for synthesizing the alkali-metal salt and the ammonium salt of phenylphruvic acid by the dicarbonylation of chlorobenzyl. Hydrated lime, water, isopropyl alcohol and a sulfur containing reductant are firstly poured into a reaction still together, and cobalt chloride is added after ventilation; chlorobenzyl is continuously added in the reaction still at a carbon monoxide atmosphere, and cobalt tetracarboryl salt and the calcium salt of phenylphruvic acid are obtained. The salt are discharged out of the still under the condition of 0.1 to 0.8MPa of pressure difference and are filtered and separated immediately, the extraction liquid of the phenylphruvic acid is obtained via drying and acidizing, a water solution of alkali metal hydroxide or ammonia water is added in the extraction liquid, and then the alkali metal salt or the ammonium salt of the phenylphruvic acid of the present invention is obtained.
Description
The present invention relates to the production method of a kind of phenyl-pyruvic alkali salt and ammonium salt, the method for synthetic phenyl-pyruvic alkali salt of the two carbonylations of particularly a kind of benzyl chloride and ammonium salt.
Phenyl-pyruvic alkali salt and ammonium salt are a kind of organic acid salts, and it can be used as the main raw material of Production by Enzymes L-phenylalanine.Particularly in recent years,, make the market requirement of L-phenylalanine suddenly increase year by year, thereby stimulated domestic and international research work phenyl-pyruvic acid and salt synthesis technique thereof because the production of novel sweetener sky benzene dipeptides has realized industrial scaleization in countries such as America and Europe, days.
In the last thirty years, the bibliographical information of some synthetic styrene-acrylic ketone acids and basic salt method is kind more than 50 nearly, but really is used for industrial only severally, and because the problem of operational path or production cost aspect is all unsatisfactory.Recent two decades comes, with the transition metal carbonyl compound is the rise of the oxo process of catalyzer, then having occurred with benzyl chloride and carbon monoxide successively is raw material, with the cobalt octacarbonyl is catalyzer, in the water mixed alkoxide solution, with calcium hydroxide is the synthetic phenyl-pyruvic acid salt of neutralizing agent carbonylation under 2.0-5.0MPa pressure, and obtains the patent report of phenyl-pyruvic acid through aftertreatment.For example, the US4447644 of the U.S., US4948920 patent, the EP0195530 patent in Europe, clear 62-158239, the clear 62-116541 of Japan, clear 60-61550 patent or the like.But cobalt octacarbonyl need synthesize in the voltage-resistant reactor of special use under the condition of high voltage more than the 10MPa, and it is extremely unstable, stores and transports, ships and resell on another market and all have any problem, so make these patents all be difficult to realize suitability for industrialized production.Along with people's going deep into to the understanding of the two carbonyl reaction mechanism of benzyl chloride, what known a catalyst action is cobalt tetracarbonyl rather than cobalt octacarbonyl, so the Frenchman has reviewed the content of relevant cobalt tetracarbonyl salt synthetic method in the bibliographical information since this century three, the forties.For example add auxiliary agents such as potassium cyanide, halfcystine, tartrate in basic solution, cobalt chloride or Xiao Suangu and carbon monoxide react under normal pressure and make cobalt tetracarbonyl salt; Cobalt tetracarbonyl mercury salt or silver salt are made in the reaction of the ammonia soln of Xiao Suangu and V-Brite B under carbon monoxide atmosphere; At methyl alcohol---in the water miscible fluid, add calcium hydroxide, cobalt chloride, iron/manganese alloy powder and sulfur-bearing reductive agent and make cobalt tetracarbonyl salt etc.On this basis, the Frenchman has invented the processing method of synthesizing cobalt tetracarbonyl salt and phenyl-pyruvic alkali salt in same reactor, sees French Patent Fr2629816-A1.The advantage of this patent is the operation of having removed high pressure synthesizing carbonyl catalyzer cobalt octacarbonyl from, saved the trouble of storing cobalt octacarbonyl, simplified synthesis technique, reduced production cost, and the purity of phenyl-pyruvic acid and phenyl-pyruvic alkali salt and yield are not affected.But still there is following deficiency in this patent, the one, and reductive agent uses sodium sulphite.The easy deliquescence of sodium sulphite needs again to grind in advance, and not only troublesome poeration, and generation black cobaltous sulfide in the reaction process makes the product purification difficult.The 2nd, before the reaction, need Continuous Flow under carbon monoxide atmosphere adds alcohol/water milk of lime and contacts with the reductive agent cobalt chloride in reactor, this feed way easily makes reinforced valve port stop up, troublesome poeration, feeding equipment is required high, therefore reductive agent effect instability has a direct impact the synthetic phenyl-pyruvic acid calcium salt of the two carbonylations of the benzyl chloride of back.The 3rd, the reaction product filtering separation adopts belt Thin-layer separation device, this separator designs complexity, and the cost height is difficult to be applied to suitability for industrialized production.The 4th, the carbonylation reaction cycle is still grown (reaching more than 5 hours), and in the so long cycle, the accumulation of foreign matter in the product increases, and quality and yield must be influenced.The 5th, with generating Sodium.beta.-phenylpyruvate with extraction ether liquid in the aqueous sodium hydroxide solution.Though sodium salt is more relatively stable than phenyl-pyruvic acid, water-soluble relatively poor, difficult when then in enzyme commentaries on classics ammonia production L-phenylalanine technology, preparing nutrient solution, change still easy oxidation under 37-40 ℃ of condition of ammonia temperature at enzyme.The 6th, cobalt chloride is abandoned blowdown in the waste water, and its loss cobalt is worth not few, has not only improved production cost, and contaminate environment.In addition, up to the present, yet there are no report with the method for benzyl chloride carbonylation synthetic styrene-acrylic ketone acid ammonium salt.
Purpose of the present invention is exactly in order to address the above problem, and it is simpler to propose a kind of technology, and processing condition require low, and operation and production cost are lower and pollution-free easily, the phenyl-pyruvic alkali salt that can suitability for industrialized production and the synthetic method of ammonium salt.
Technical solution of the present invention:
A kind of synthetic method of phenyl-pyruvic alkali salt is characterized in that:
A, white lime, water, Virahol and the sulfur-bearing reductive agent except that sodium sulphite are mixed by uncovered once the pouring in the reactor of solid feed inlet, ventilation then, add cobalt chloride, and under feed gas containing carbon monoxide atmosphere, add benzyl chloride continuously, just successively obtain cobalt tetracarbonyl salt and impurity such as phenyl-pyruvic acid calcium salt that contains the excessive hydrogen calcium oxide and toluylic acid calcium;
B, the product after the oxide treatment in the reactor is discharged reactor and filtering separation immediately under the still inside and outside differential pressure condition of 0.1-0.8MPa, just obtain thin and phenyl-pyruvic acid calcium salt filter cake that loose;
C, above-mentioned filter cake is passed to the nitrogen that is lower than 50 ℃ and carries out drying after washing, to remove remaining alcohol in the filter cake;
D, dried filter cake is added acidifying in sour ether (or acid esters) mixed solution, the phenyl-pyruvic acid of generation enters organic extractant phase to be separated, and calcium chloride, cobalt chloride and other inorganic impurity are stayed water;
E, the extraction liquid that contains phenyl-pyruvic acid add alkali metal hydroxide aqueous solution and stir and just obtain phenyl-pyruvic alkali salt under nitrogen protection.
A kind of synthetic method of phenyl-pyruvic acid ammonium salt is characterized in that its A---E step operation and an alkali metal salt identical, the extraction liquid that just will contain phenyl-pyruvic acid adds ammoniacal liquor and promptly makes the phenyl-pyruvic acid ammonium salt under nitrogen protection.
When preparing cobalt carbonyl catalyst, the present invention do not use sodium sulphite, remove from and produce the sedimentary possibility of cobaltous sulfide, when reinforced with white lime, alcohol, raw materials such as water and reductive agent is disposable pours in the reactor, make operation very simple easily, can also avoid stream to add milk of lime and stop up valve, problems such as reductive agent partial failure, carbon monoxide directly adopts industrial tail gas simultaneously, reduced the unstripped gas cost, and force unstripped gas to circulate strongly, make gas, liquid, Gu three phase materials thorough mixing, so shortened reaction time, temperature of reaction reduces, raw gas pressure also reduces, and can effectively reduce power consumption and production run cost like this, and the product impurities accumulation reduces, quality product and yield height can suitability for industrialized production.The solvent and the cobalt of the inventive method recycle in reaction system, and the rate of recovery is up to more than 85%, and whole process of production does not have " three wastes " to pollute.The inventive method also provides from the phenyl-pyruvic acid extraction liquid and has been converted into ammonium salt solution, be directly used in the joint process route of producing L one phenylalanine, its effect has been saved crystallization, refining step, saves facility investment and production run cost greatly, and quality product is unaffected.The inventive method decapacitation utilizes outside the industrial tail gas, self-produced hydrogen peroxide of fertilizer plant and ammoniacal liquor have also been utilized, can make that production cost obviously descends, shown great competitive power, through pilot plant test, the like product of every technical indicator of quality product and U.S. Sigma company is suitable, successfully pushes suitability for industrialized production to for immobilized cell enzymatic conversion production L-phenylalanine operational path reliable basis is provided.
Embodiment:
The primary device of the inventive method adopts 100 liter stainless steel cauldrons, by its solid feed inlet 8 kilograms of white limes, 7.5 kg of water, 30 kilograms of Virahols, 6.3 gram S-WATs and 6.9 gram Sodium Thiosulfate Pentahydrate reductive agents once are poured into and mix in the reactor and tighten kettle cover, nitrogen with 0.5MPa pressure is replaced atmosphere in the reactor three times, catch up with oxygen in the most still, replace three times with 0.5MPa pressure with feed gas containing carbon monoxide again.Temperature rises to 65 ℃, and feed gas containing carbon monoxide pressure rises to 1.8MPa.The sulfur-bearing reductive agent that reacts used is that the valency of sulphur is equal to or less than+water soluble of 4 valencys or the compound of alcohol.The feed gas containing carbon monoxide that reacts used can be used industrial tail gas, is preferably synthetic ammonia refining resurgent gases, and this resurgent gases carbon monoxide concentration is not less than 75%, and oxygen level is not higher than 0.1%.After the ventilation, again 69 gram cobalt chloride hexahydrates are dissolved in 200 milliliters of pure water, add reactor, allow it react 1 hour.The consumption mol ratio of cobalt chloride and sulfur-bearing reductive agent is generally 1: between the 0.05-0.8, the estimation cobalt chloride is converted into the about 75-80% of transformation efficiency of cobalt tetracarbonyl calcium.The benzyl chloride that then adds 7.7 kilograms added material in 3 hours, and temperature maintenance is at 65 ℃, and air pressure maintains 1.8MPa and continues reaction 1 hour.The consumption mol ratio of benzyl chloride and cobalt chloride is generally 1: 4 * 10
-3-9 * 10
-3Can adopt similar mines machinery mixing method in the reactor, force the interior feed gas containing carbon monoxide of still to circulate strongly, make gas in the still, solid, liquid phase reaction material atomizing thorough mixing, make that reacting the same period shortens, temperature of reaction reduces, reaction pressure can be lower than 2.0MPa, and general temperature of reaction is controlled at 40-70 ℃.The internal reaction still can be finished the benzyl chloride carbonylation reaction process in such 4 hours, successively obtained cobalt tetracarbonyl salt and impurity such as phenyl-pyruvic acid calcium salt that contains the excessive hydrogen calcium oxide and toluylic acid calcium.After carbonylation reaction finishes, can be according to the existing product situation of producing of manufacturer, adding is with respect to the hydrogen peroxide (or clorox) of cobalt salt 0.5-8 mole, with the oxidation cobalt carbonyl catalyst, prevent that cobalt salt enters organic phase with phenyl-pyruvic acid in the subsequent process, add fashionable elder generation reactor is exitted, make gauge pressure reduce to zero, feed nitrogen again, pressure rises to 0.1MPa, add 850 milliliters in 10% hydrogen peroxide, stirred 10 minutes, nitrogen pressure in the still is risen to 0.8MPa, utilize the still inside and outside differential pressure that reaction mass is given off reactor filtering separation immediately while hot, its filter cake approaches and looses, and economizes cleaning solvent, easily washes clean.Be 1: 1 the Virahol and the mixed solution drip washing filter cake of water with volume ratio during washing, use 45 ℃ hot nitrogen dry cake then, obtain about 13.8 kilograms dry powder.With chemical titration analysis and measurement result, wherein the phenyl-pyruvic acid calcium contents is about 60.1%, calculates with the benzyl chloride charging capacity, and phenyl-pyruvic acid calcium yield is 74.4%.The cleaning solvent of hydroformylation reaction product of the present invention and reaction solvent all are Virahols, therefore are convenient to distillation and reclaim, and the distillation azeotrope can directly return carbonylation reactor and use, and the rate of recovery reaches more than 90%.In the enamel still of 300 liter strap clamps covers, add methyl tert-butyl ether, 38% concentrated hydrochloric acid and the mixed solution of water again, three's volume ratio is 80: 50: 50, under stirring state, slowly add the above-mentioned dry powder that contains calcium salt that obtains and carry out acidizing extraction, the chuck water coolant guarantees temperature in the kettle below 20 ℃, and acidificatoin time was kept 1 hour.Emit the water that contains cobalt chloride, calcium chloride at the bottom of still, stay organic phase, organic phase includes phenyl-pyruvic acid.Organic addition water washing.If the preparation phenyl-pyruvic alkali salt is an example with the sodium salt, in the ether liquid that then in still, stays slowly stream add the sodium hydroxide of 8mol/l, guarantee that ph value of aqueous phase about 7.5, added material in 20 minutes, left standstill 3 hours, filtering separation obtains the desired phenyl-pyruvic acid sodium salt of the present invention.If preparation phenyl-pyruvic acid ammonium salt solution, then the ammoniacal liquor of stream adding saturation concentration in ether liquid is still controlled ph value of aqueous phase about 7.5, promptly obtains the desired phenyl-pyruvic acid ammonium salt solution of the present invention.This solution can be directly used in the production of Production by Enzymes L-phenylalanine.Above-mentioned phenyl-pyruvic acid calcium salt is converted into the phenyl-pyruvic acid sodium salt or the ammonium salt solution yield reaches more than 90%.
In the inventive method, the filtering separation behind carbonylation reaction, acidizing extraction, each operation of salinization all are to carry out the deoxygenation air system of sealing, and treatment temp all is not higher than 50 ℃, thereby reduce solvent loss, reduce production costs.
Though the used cobalt salt consumption of carbonylation reaction is little among the present invention, the cobalt salt price is very expensive, if do not reclaim usefulness again, financial loss still can not be ignored, about 4000 yuan of the cobalt salt that about phenyl-pyruvic alkali salt per ton or ammonium salt will consume.Contain cobalt salt in the waste discharge simultaneously, can not ignore the pollution of environment.The present invention has adopted a kind of cobalt-containing wastewater treatment process commonly used, and promptly cobalt-containing wastewater promptly more easily reclaims cobalt chloride usefulness again through precipitation, washing, oxidation, separation, acidifying, refining, condensing crystal, and the rate of recovery is up to 90%.Reclaim behind the cobalt salt acid-bearing wastewater again through lime neutralize the calcium chloride byproduct, last waste water is handled the back through charcoal absorption and is discharged, and has just solved " three wastes " pollution problem.
Claims (7)
1, the preparation method of a kind of phenyl-pyruvic alkali salt and ammonium salt is characterized in that:
A, with white lime, water, Virahol and the valency except that sodium sulphite or be equal to or less than+water-soluble sulfur-bearing reductive agent of 4 valencys mixes by uncovered once the pouring in the reactor of solid feed inlet, with nitrogen atmosphere in the reactor is replaced then, add cobalt chloride, and under feed gas containing carbon monoxide atmosphere, add benzyl chloride continuously, just successively obtain cobalt tetracarbonyl salt and impurity such as phenyl-pyruvic acid calcium salt that contains the excessive hydrogen calcium oxide and toluylic acid calcium;
B, the product after the oxide treatment in the reactor is discharged reactor and filtering separation immediately under the still inside and outside differential pressure condition of 0.1-0.8MPa, just obtain thin and phenyl-pyruvic acid calcium salt filter cake that loose;
C, above-mentioned filter cake is passed to the nitrogen that is lower than 50 ℃ and carries out drying after washing, to remove remaining alcohol in the filter cake;
D, dried filter cake is added acidifying in acid-ether or the acid-ester mixed solution, the phenyl-pyruvic acid of generation enters organic extractant phase to be separated, and calcium chloride, cobalt chloride and other inorganic impurity are stayed water;
E, the extraction liquid that contains phenyl-pyruvic acid add alkali metal hydroxide aqueous solution or ammoniacal liquor under nitrogen protection, stir and just obtain phenyl-pyruvic alkali salt or ammonium salt.
2, press the preparation method of described phenyl-pyruvic alkali salt of claim 1 and ammonium salt, it is characterized in that in the A operation, should forcing the carbon monoxide air-flow in reactor, to circulate strongly, make the three phase materials atomizing thorough mixing in the reactor, make reaction pressure can be lower than 2.0MPa, the temperature of reaction in the reactor is controlled at 40-70 ℃ of scope.
3, by the preparation method of described phenyl-pyruvic alkali salt of claim 1 and ammonium salt, it is characterized in that feed gas containing carbon monoxide used in the A operation is an industrial tail gas, carbon monoxide concentration is not less than 75% in this resurgent gases, and oxygen level is not higher than 0.1%.
4, by the preparation method of described phenyl-pyruvic alkali salt of claim 3 and ammonium salt, it is characterized in that described industrial tail gas is a synthetic ammonia refining resurgent gases.
5, by the preparation method of described phenyl-pyruvic alkali salt of claim 1 and ammonium salt, it is characterized in that in the A operation, before reactant goes out still, should add hydrogen peroxide or clorox, cobalt tetracarbonyl salt is oxidized to cobaltous hydroxide with respect to cobalt salt 0.5-8 mole.
6,, it is characterized in that all sealing deoxygenation air system, carrying out, and treatment temp all is not higher than 50 ℃ from the C-D operation by the preparation method of described phenyl-pyruvic alkali salt of claim 1 and ammonium salt.
7,, it is characterized in that cobalt chloride in the acid-bearing wastewater in the D operation should reclaim again to use by the preparation method of the described phenyl-pyruvic alkali salt of claim 1 and ammonium salt.
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| CN96116853A CN1049650C (en) | 1996-03-08 | 1996-03-08 | Synthetic method of phenyl-pyruvic alkali salt and ammonium salt |
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| CN96116853A CN1049650C (en) | 1996-03-08 | 1996-03-08 | Synthetic method of phenyl-pyruvic alkali salt and ammonium salt |
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| CN1138022A CN1138022A (en) | 1996-12-18 |
| CN1049650C true CN1049650C (en) | 2000-02-23 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0195530A2 (en) * | 1985-02-21 | 1986-09-24 | Japan as represented by Director-General, Agency of Industrial Science and Technology | Process for the preparation of phenyl pyruvic acid |
| US4997979A (en) * | 1988-04-06 | 1991-03-05 | Rhone-Poulenc Chimie | Process for the preparation of alkaline phenylpyrovate |
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- 1996-03-08 CN CN96116853A patent/CN1049650C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0195530A2 (en) * | 1985-02-21 | 1986-09-24 | Japan as represented by Director-General, Agency of Industrial Science and Technology | Process for the preparation of phenyl pyruvic acid |
| US4997979A (en) * | 1988-04-06 | 1991-03-05 | Rhone-Poulenc Chimie | Process for the preparation of alkaline phenylpyrovate |
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