CN108658821A - D, clean preparation method of L-Methionine and products thereof - Google Patents
D, clean preparation method of L-Methionine and products thereof Download PDFInfo
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- CN108658821A CN108658821A CN201710443926.1A CN201710443926A CN108658821A CN 108658821 A CN108658821 A CN 108658821A CN 201710443926 A CN201710443926 A CN 201710443926A CN 108658821 A CN108658821 A CN 108658821A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of D, the clean preparation method and products thereof of L methionine, by the saponification liquor containing certain density methionine salt and carbonate, methionine crystal product and crystalline mother solution are obtained by carbon dioxide acidizing crystal, separation of solid and liquid, crystalline mother solution is using bipolar membrane electrodialysis except sodium, decarburization concentrate, carbon dioxide acidizing crystal is finally carried out again, and whole process obtains methionine crystal product purity in 99.4wt% or more；The carbon dioxide and sodium hydroxide obtained in its production process can recycle Reusability in this process and preceding process.The present invention has D, and L methionine loss lates are low, product purity is high, are generated without low value inorganic salts, without the features such as large quantity of exhaust gas discharges, energy unit consumption is low, realize the clean manufacturing of methionine.
Description
Technical field
The invention belongs to the production fields of organic compound, and in particular to D, the clean preparation method of L-Methionine and its production
Product.
Background technology
D, L-Methionine also known as methionine are one of the base units for constituting protein, are unique in essential amino acid
Amino acid containing sulphur, the synthesis in addition to participating in the transfer of methyl, the metabolism of phosphorus and adrenaline, choline, creatine in animal body
Outside or the raw material of synthetic protein and cystine.Methionine is widely used in the fields such as medicine, food, feed and cosmetics,
The middle dosage as feed addictive is very big.The demand of global methionine has reached 1,600,000 tons/year, Chinese methionine
The demand of methionine in 2014 has been more than 130,000 tons, but 11 ten thousand ton methionine of the China in addition to Chongqing purple light chemical industry at present
Outside, the methionine in China also needs to largely from foreign countries into domestic yield is unable to meet demand.
Glycolylurea method prepares approach there are mainly two types of methionine at present：One is using hydrogen cyanide replace traditional Cymag or
Person's potassium cyanide is reacted with 3- methylthiopropionaldehydes generates cyanalcohol, then is reacted with carbon dioxide, ammonia and generate glycolylurea, potassium carbonate hydrolysis sea
Cause in carbon dioxide and methionine potassium, detaches methionine and saleratus, the saleratus Recycling Mother Solution containing methionine to glycolylurea
Hydrolysing step is arranged in the entire technical process of this method almost without outside a large amount of waste water and dregs, is a kind of cleaner, low life
Produce the methionine production technology of cost；Another kind is using cyanalcohol, carbon dioxide, ammonia as raw material or with Cymag, 3- methyl mercaptos
Propionic aldehyde, carbon dioxide, ammonia are raw material, prepare glycolylurea, and then under the action of sodium hydroxide, hydrolysis generates containing sodium carbonate and egg ammonia
The saponification liquor of sour sodium respectively obtains methionine and sodium sulphate, disadvantage existing for the technique is egg through sulfuric acid acidification, crystallization
Propylhomoserin and sodium sulphate isolate and purify problem, i.e., when plus sulfuric acid is acidified to pH=5.0 or so, are crystallized in 40 DEG C or so methionine, point
From methionine, drying obtains methionine product, and maximum impurity is sodium sulphate in methionine product；Sodium sulphate containing methionine is female
Liquid is concentrated using high temperature, be especially heated to 100 DEG C~120 DEG C, and a large amount of sodium sulfate crystal (at this moment methionine is then precipitated
Solubility is maximum, and the solubility of sodium sulphate is minimum), it filters while hot under the high temperature conditions, filtrate is cooled to 40 DEG C, methionine knot
Crystalline substance, washing, drying obtains methionine product, but 10% methionine of also close total amount remains in sulfuric acid mother liquid of sodium, will
The Recycling Mother Solution recycles above-mentioned steps to saponification liquor acidification step, during the sodium sulphate Recycling Mother Solution containing methionine, in order to
The loss of methionine is avoided, it is not outer as far as possible to arrange mother liquor, cause methionine under long-term thermophilic digestion, some methionine hair
Having given birth to thermal decomposition, (applicant's methionine seminar has studied methionine Thermal Decomposition Mechanism for the first time, by using compounds GC-MS for the first time
Confirm to be determined that the product of methionine thermal decomposition is dimethyl disulfide, allylamine, 3- methyl mercaptos propylamine and carbon dioxide),
Mechanism is：Methionine is decomposed into 3- methyl mercaptos propylamine and carbon dioxide first when heated, that is to say, that decarboxylation first, 3- first
Sulfenyl propylamine, which continues to be heated, is decomposed into dimethyl disulfide and allylamine, produces the substance dimethyl disulfide with foul smell, this
Kind substance can remain in sulfuric acid mother liquid of sodium and neutralize in the outer condensed water arranged, and the sulfuric acid mother liquid of sodium of cycle for a long time is caused to have stench
Taste, sodium sulphate plant operations bad environments, influences surrounding enviroment, and also results in the decomposed of methionine, the mother liquor of outer row
COD is higher, it is difficult to carry out biochemical treatment, the sulfuric acid mother liquid of sodium containing methionine recycles for a long time, leads to the product of follow-up methionine
Quality decline, decline the reason of be mainly：First, the decomposition of methionine and the polymerization of methionine, especially form methionine
Dimer, and methionine decompose after organic impurities add up in system, and crystallize obtained methionine have it is unpleasant
Smell；Second is that sodium formate in saponification liquor, 2-Hydroxy-4-methylthiobutyric acid sodium add up in system, to affect egg ammonia
The quality of acid product will eventually influence the quality of sulfuric acid, not only also contain sodium formate containing methionine in sodium sulphate product,
It is used to influence sodium sulphate, especially contains 0.5% or so methionine.It is maximum that the above results in methionine production technology
Outstanding problem be environmental issue and by-product low value sodium sulphate (1 ton of methionine by-product sodium sulphate is 1.2~1.8 tons), and
It is to burn to solve environmental issue best bet at present, this loss for inevitably consuming more energy, increasing methionine
And production cost, and for the sodium sulphate problem of a large amount of low values of by-product, it can not but find essence effective solution means.
Based on above-mentioned methionine production Technology, researcher of the present invention is dedicated to developing a kind of saving energy consumption, environment
Friendly D, L methionine clean preparation methods.
Invention content
Through applicants have found that, as long as controlling the proper ratio of Sodium L-methioninate and sodium carbonate in saponification liquor, can adopt
D, L-Methionine product are produced with carbon dioxide acidizing crystal, and has the characteristics that desalination using bipolar membrane electrodialysis, is reduced
Sodium carbonate in saponification liquor, to reach when being passed through carbon dioxide acidification Sodium L-methioninate, the sodium bicarbonate of generation is not enough to reach
To saturation state, and methionine can crystallize precipitation, and purity is high.It is removed in methionine crystalline mother solution by bipolar membrane electrodialysis
Sodium ion, actually really reach the content for reducing sodium carbonate, making in system will not be because of methionine and sodium bicarbonate
Sodium carbonate is accumulated caused by Recycling Mother Solution, improves the methionine product quality that the acidified saponified liquid of carbon dioxide crystallizes.
The purpose of the present invention is to provide a kind of saving energy consumption, environmental-friendly D, L methionine clean preparation methods, the party
Method can overcome traditional D, environmental issue in L-Methionine production method, the sodium sulphate problem of by-product low value, energy waste
Problem, methionine and inorganic salts resolution problem
In order to achieve the above objectives, the present invention provides the following technical solutions：
1.D, the clean preparation method of L-Methionine, includes the following steps：By the saponification containing methionine salt and carbonate
Liquid is passed through carbon dioxide acidizing crystal, is separated by solid-liquid separation and collects D, L-Methionine crystal and crystalline mother solution, the D of collection, L- respectively
Methionine crystal is by dry D, L-Methionine；Crystalline mother solution obtains mother liquor decarbonizing liquid after carrying out decarburization, and mother liquor decarbonizing liquid passes through
Bipolar membrane electrodialysis removes the salt ion of total 20~70wt% of salt ion in solution, carries out secondary decarburization, obtain methionine salt and
The decarbonizing liquid of methionine salt and carbonate is finally returned to carbon dioxide acidizing crystal by the decarbonizing liquid and carbon dioxide of carbonate
Step cycle utilizes.
Further, the acidizing crystal is 0 DEG C~70 DEG C of temperature, pressure 0.1~1.0MPa conditions are passed through carbon dioxide.
Further, the bipolar membrane electrodialysis treatment is that mother liquor decarbonizing liquid is passed through in salt room, be passed through in alkali room water or
Dilute aqueous slkali, cathode and anode are passed through direct current, and control salt room pH is 6.5-10.0,15-50 DEG C of temperature.
Further, the carbon dioxide recycle of decarburization recycling is to acidizing crystal step.
Further, the saponification liquor contains sodium carbonate within 4wt% and 10~25wt% Sodium L-methioninates or the saponification
Liquid contains potassium carbonate and 10~25wt% methionine potassium within 20wt%.
Further, the saponification liquor is prepared as follows：With 2- 2-hydroxy-4-methylthios butyronitrile, carbon dioxide, ammonia and water
For raw material, 5- (2-methylmercaptoethyl)-hydantoins and ammonium bicarbonate mixed aqueous solution is prepared, 5- (2- first is obtained after stripping
Sulfenyl ethyl)-hydantoins aqueous solution, it adds sodium hydroxide alkaline hydrolysis, using stripping after alkaline hydrolysis, obtains carbonate content
For within 4wt%, the saponification liquor that Sodium L-methioninate content is 10~25wt%；
Or the saponification liquor is prepared as follows：Using cyanalcohol, carbon dioxide and ammonia as raw material or with Cymag, 3- first sulphur
Base propionic aldehyde, carbon dioxide and ammonia are that raw material prepares glycolylurea, glycolylurea through alkaline hydrolysis, acidification adjust pH3.0~6.0 obtain containing 2.5~
The mixed liquor of 10wt% sodium carbonate, 10~25wt% Sodium L-methioninates, by mixed liquor be diluted to carbonate content be 4wt% within,
Sodium L-methioninate content is 4~10wt%；Then sodium is removed by bipolar membrane electrodialysis, then carries out decarburization, be concentrated to give carbonate content
For within 4wt%, the saponification liquor that Sodium L-methioninate content is 10~25wt%.
Further, the rejection conditions be 0~0.6Mpa, 70~150 DEG C.
Further, the saponification liquor is obtained by following steps：With 2- 2-hydroxy-4-methylthios butyronitrile, carbon dioxide, ammonia and
Water is raw material, and 5- (2-methylmercaptoethyl)-hydantoins and ammonium bicarbonate mixed aqueous solution is prepared, 5- (2- are obtained after stripping
Methylmercaptoethyl)-hydantoins aqueous solution, potassium hydroxide alkaline hydrolysis is added, using stripping after alkaline hydrolysis, is contained
The saponification liquor of potassium carbonate and 10~25wt% methionine potassium within 20wt%；Further, the heating rejection conditions be 0~
0.6Mpa, 100~180 DEG C.
2, by above-described D, the D of the high and low impurity of purity, L- egg ammonia made from the clean preparation method of L-Methionine
Acid, the D, L-Methionine purity are more than 99.4%.
The beneficial effects of the present invention are：The clean preparation method of D, L-Methionine can eliminate asking for by-product sodium sulphate
Topic avoids the energy consumption needed for the concentration of sodium sulphate subsequent purification, and easy to operate, gained methionine purity may be up to 99.4% or more,
The present invention is not required to the sodium bicarbonate filtrate containing methionine concentration is repeated, can avoid methionine for a long time thermally decomposed and
Foul gas is generated, and this method is of low cost, a large amount of acid and stink discharge of wastewater of nothing, environmentally protective, Bipolar Membrane is electric
The sodium hydroxide of dialysis by-product is recycled to hydrolysis 5- (2-methylmercaptoethyl)-hydantoins step, without adding fresh hydrogen-oxygen
Change sodium, the carbon dioxide that decarburization is produced also is recycled to saponification liquor acidification step, economic and practical, is worth marketing application.
In the methionine salt and carbonate content difference saponification liquor that are obtained present invention can apply to different modes, with real more
The clean manufacturing mode of the existing methionine of kind.
Description of the drawings
In order to keep the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides following attached drawing and carries out
Explanation：
Fig. 1：D, L-Methionine clean preparation method flow chart；
Wherein V1 is saponification liquor concentration adjusting device, and ED1 is bipolar membrane electrodialysis device, and E1 is decarburization enrichment facility, T1
For carbon dioxide recovering apparatus, R1 is carbon dioxide acidizing crystal device, and S1 is equipment for separating liquid from solid, and E2 is decarbonization device；
Saponification liquor is 1.:10~25wt% Sodium L-methioninates, 2.5~10wt% sodium carbonate；
Saponification liquor is 2.:10~25wt% Sodium L-methioninates, 0~4wt% sodium carbonate；
Saponification liquor is 3.:10~25wt% methionine potassium, 0~20wt% potassium carbonate.
Specific implementation mode
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.It is not specified in embodiment specific
The experimental method of condition, usually according to conventional conditions or according to the manufacturer's recommendations.
Embodiment 1
Using 2- 2-hydroxy-4-methylthios butyronitrile, carbon dioxide, ammonia and water as raw material, closed reactor is added by a certain percentage
In, after completion of the reaction, pressure release to normal pressure obtains 5- (2-methylmercaptoethyl)-hydantoins and ammonium bicarbonate (ammonium hydrogencarbonate and carbonic acid ammonia
Solution) mixed aqueous solution, unreacted ammonium bicarbonate in reaction system is discharged, 5- (2-methylmercaptoethyl)-hydantoins water is obtained
Solution liquid, is added a certain amount of sodium hydrate aqueous solution, after alkaline hydrolysis, obtains 599 grams of Sodium L-methioninates and sodium carbonate saponification liquor,
Wherein Sodium L-methioninate content is 16.8%, carbonate content 3.07%；Saponification liquor obtained above is added to the stirring of 2L
It in reactor, keeps the temperature to 45 DEG C, while being passed through carbon dioxide, the pressure for being passed through carbon dioxide is 0.2MPa, and acidification reaction finishes
Afterwards, it is separated by solid-liquid separation and collects respectively D, L-Methionine crystal and crystalline mother solution, a small amount of water washing D, L-Methionine crystal, by drying
The single yield of dry 51.18 grams of obtained methionine product, purity 99.4%, methionine is 58%；Crystalline mother solution passes through 110
DEG C high temperature carbonization treatment, obtains 555 grams of the decarbonizing liquid of sodium carbonate and Sodium L-methioninate, the mass percentage of Sodium L-methioninate is
8.96%, sodium carbonate mass percentage is 6.57%, and decarbonizing liquid, which is entered bipolar membrane electrodialysis, removes sodium system.Bipolar Membrane electric osmose
Analysis system side and other side are respectively equipped with the cathode chamber (I) of built-in cathode and the anode chamber (II) equipped with built-in anode, cloudy
Film pair is equipped between pole room and anode chamber, a film is to by a spaced Bipolar Membrane (BP) and a cation-exchange membrane (C) group
At the film is located at cathode direction to the anode that the relative position of Bipolar Membrane and cation-exchange membrane is Bipolar Membrane, Bipolar Membrane
Cathode is located at anode direction, and a cation-exchange membrane, cathode side of the film to Bipolar Membrane are equipped between two Bipolar Membranes
Alkali room (III) is constituted to anode membrane, anode membrane and Bipolar Membrane anode direction constitute salt room (IV).Bipolar membrane electrodialysis treatment is in salt
It is passed through mother liquor decarbonizing liquid in room, water or dilute aqueous slkali are passed through in alkali room, cathode and anode are passed through direct current, and control salt room pH is
6.5-10.0 15-50 DEG C of temperature.Decarbonizing liquid is after bipolar membrane electrodialysis system, the matter of Sodium L-methioninate in obtained saponification liquor
It is 7.5% to measure percentage composition, and the mass percentage of sodium carbonate is 1.8%, by concentration, Sodium L-methioninate in obtained saponification liquor
Mass percentage be 16%, the mass percentage of sodium carbonate is 3.84%, which is recycled to carbon dioxide acidification
Step, pH value are continuously decreased by original 14, and when salt room, pH value is reduced to 7.5, and the mobility of sodium ion is 67%,；It is bipolar
The mass percentage of the sodium hydroxide of film by-product is 9%, by being concentrated into 40%-50%, is recycled to 5- (2- methylmercaptan ethyls
Base)-hydantoins aqueous hydrolysis alkali.
Embodiment 2
1mol 3- methylthiopropionaldehydes, Cymag, carbon dioxide, ammonia and 800 grams of water are added in closed reactor, 3- first
Sulfenyl propionic aldehyde, Cymag, carbon dioxide, ammonia molar ratio be 1:1.05:2:4,80 DEG C are then heated to, insulated and stirred
10min, then it is warming up to 120 DEG C immediately, the pressure of reaction system is risen into 2MPa after insulated and stirred 20min, after completion of the reaction, is let out
It is depressed into normal pressure, by unreacted hydrocarbon discharge in reaction system, obtains glycolylurea aqueous solution, the mass fraction for adding 1.5mol is
40% sodium hydrate aqueous solution, is warming up to 178 DEG C immediately, insulated and stirred 30 minutes, and the pressure for controlling reaction system is
2.5MPa；Be cooled to 100 DEG C after reaction, pressure release to normal pressure, by reaction system carbon dioxide and ammonia exclude, obtain
970 grams of Sodium L-methioninates and sodium carbonate saponification liquor, wherein Sodium L-methioninate content are 17.36%, and carbonate content 8.40% will be upper
It is 5.4% to state saponification liquor and be diluted with water the mass percentage of Sodium L-methioninate, and the mass percentage of sodium carbonate is 2.61%,
This dilution is separated sodium ion 50wt% total in solution by bipolar membrane electrodialysis in the form of sodium hydroxide solution,
PH is respectively obtained as 7.2 except sodium liquid and sodium hydroxide solution；Except sodium liquid is passing through 110 DEG C, 0.2MPa high temperature carbonization treatments are dense
Contracting, obtains the mixed liquor of 18.51wt% Sodium L-methioninates and 1.61wt% sodium carbonate.
Mixed liquor obtained above is added in the stirred reactor of 2L, is kept the temperature to 50 DEG C, while being passed through carbon dioxide,
The pressure for being passed through carbon dioxide is 0.2MPa, after acidification reaction, is separated by solid-liquid separation and simultaneously collects D respectively, L-Methionine crystal and
Crystalline mother solution, a small amount of water washing D, L-Methionine crystal, 57.58 grams of the methionine product obtained by drying, purity are
99.5%, the single yield of methionine is 42%；Crystalline mother solution passes through 120 DEG C of high temperature carbonization treatments, obtains sodium carbonate and egg ammonia
The mass percentage of 850 grams of the decarbonizing liquid of sour sodium, Sodium L-methioninate is 10.1%, and sodium carbonate mass percentage is 3.67%,
Decarbonizing liquid is entered into bipolar membrane electrodialysis and removes sodium system, decarbonizing liquid is after bipolar membrane electrodialysis system, in obtained saponification liquor
The mass percentage of Sodium L-methioninate is 9.9%, and the mass percentage of sodium carbonate is 1.4%, by concentration, obtained saponification
The mass percentage of Sodium L-methioninate is 16% in liquid, and the mass percentage of sodium carbonate is 2.26%, which is recycled to
Carbon dioxide acidification step, pH value are continuously decreased by original 14, and when salt room, pH value is reduced to 7.5, the mobility of sodium ion
It is 52%,；The mass percentage of the sodium hydroxide of Bipolar Membrane by-product is 7%, by being concentrated into 40%-50%, is recycled to sea
Because of hydrolysis alkali.
Embodiment 3
It is added in closed reactor by raw material of 2- 2-hydroxy-4-methylthios butyronitrile, carbon dioxide, ammonia and water, after stripping
It obtains that 5- (2-methylmercaptoethyl)-hydantoins and ammonium bicarbonate (ammonium hydrogencarbonate and carbonic acid ammonia solution) mixed aqueous solution is prepared,
5- (2-methylmercaptoethyl)-hydantoins aqueous solution is obtained after stripping, adds the hydroxide that mass percentage is 50%
Aqueous solutions of potassium mixes, and is rapidly heated to 185 DEG C, soaking time 15min, pressure 2.0MPa.Pressure release is to normal after reaction
Pressure, then carries out air lift, and it is air lift terminal that carbon dioxide and ammonia that reaction releases, which are removed up to ammonia is not detected, is contained
There is 786 grams of the mixing saponification liquor of methionine potassium and potassium carbonate, the wherein mass percentage of methionine potassium is 22.4%, potassium carbonate
Mass percentage be 18.9%.
Mixed liquor obtained above is added in the stirred reactor of 2L, is kept the temperature to 60 DEG C, while being passed through carbon dioxide,
The pressure for being passed through carbon dioxide is 0.4MPa, after acidification reaction, is separated by solid-liquid separation and simultaneously collects D respectively, L-Methionine crystal and
Crystalline mother solution, a small amount of water washing D, L-Methionine crystal, 345.84 grams of the methionine product obtained by drying, purity are
99.5%, the single yield of methionine is 44%；Crystalline mother solution passes through 160 DEG C of high temperature carbonization treatments, obtains potassium carbonate and egg ammonia
The mass percentage of 561 grams of the decarbonizing liquid of sour potassium, methionine potassium is 11.9%, and potassium carbonate mass percentage is 9.8%, will
Decarbonizing liquid enters bipolar membrane electrodialysis system (shown in Fig. 1), and decarbonizing liquid is after bipolar membrane electrodialysis system, obtained saponification liquor
The mass percentage of middle methionine potassium is 11.8%, and the mass percentage of potassium carbonate is 6.7%, by concentration, is obtained
The mass percentage of methionine potassium is 20.7% in saponification liquor, and the mass percentage of potassium carbonate is 11.75%, the saponification liquor
It is recycled to carbon dioxide acidification step, pH value is continuously decreased by original 14, and pH value is reduced to 9.07 when salt room, potassium ion
Mobility is 50%,；The mass percentage of the potassium hydroxide of Bipolar Membrane by-product is 7%, by being concentrated into 40%-50%, is followed
Ring is to 5- (2-methylmercaptoethyl)-hydantoins aqueous hydrolysis alkali.
Fig. 1 is D of the present invention, L-Methionine clean preparation method flow chart.V1 is saponification liquor concentration adjusting device in Fig. 1,
ED1 is bipolar membrane electrodialysis device, and E1 is decarburization enrichment facility, and T1 is carbon dioxide recovering apparatus, and R1 is acidified for carbon dioxide
Crystallization apparatus, S1 are equipment for separating liquid from solid, and E2 is decarbonization device.Wherein saponification liquor 1. in containing 10~25wt% Sodium L-methioninates and
2. 2.5~10wt% sodium carbonate, saponification liquor contain 10~25wt% Sodium L-methioninates and 0~4wt% sodium carbonate；3. saponification liquor contains
10~25wt% methionine potassium, 0~20wt% potassium carbonate.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1.D, the clean preparation method of L-Methionine, which is characterized in that include the following steps：Methionine salt and carbonate will be contained
Saponification liquor be passed through carbon dioxide acidizing crystal, be separated by solid-liquid separation and simultaneously collect D, L-Methionine crystal and crystalline mother solution respectively, collect
D, L-Methionine crystal is by dry D, L-Methionine；Crystalline mother solution obtains mother liquor decarbonizing liquid, mother liquor decarburization after carrying out decarburization
Liquid removes the salt ion of 20~70wt% of total salt ion in solution by bipolar membrane electrodialysis, carries out secondary decarburization, obtains egg ammonia
The decarbonizing liquid of methionine salt and carbonate is finally returned to titanium dioxide carbonic acid by the decarbonizing liquid and carbon dioxide of hydrochlorate and carbonate
Change crystallisation step to recycle.
2. D according to claim 1, the clean preparation method of L-Methionine, which is characterized in that the acidizing crystal is temperature
0 DEG C~70 DEG C of degree, pressure 0.1~1.0MPa conditions are passed through carbon dioxide.
3. D according to claim 1, the clean preparation method of L-Methionine, which is characterized in that the Bipolar Membrane electric osmose
Analysis processing is that mother liquor decarbonizing liquid is passed through in salt room, and water or dilute aqueous slkali are passed through in alkali room, and cathode and anode are passed through direct current,
It is 6.5-10.0,15-50 DEG C of temperature to control salt room pH.
4. D according to claim 1, the clean preparation method of L-Methionine, which is characterized in that the two of the decarburization recycling
Carbonoxide is recycled to acidizing crystal step.
5. according to Claims 1 to 4 any one of them D, the clean preparation method of L-Methionine, it is characterised in that：The soap
Change that liquid contains sodium carbonate within 4wt% and 10~25wt% Sodium L-methioninates or the saponification liquor contains carbonic acid within 20%wt
Potassium and 10~25wt% methionine potassium.
6. D according to claim 5, the clean preparation method of L-Methionine, which is characterized in that the saponification liquor is pressed with lower section
It is prepared by method：Using 2- 2-hydroxy-4-methylthios butyronitrile, carbon dioxide, ammonia and water as raw material, 5- (2-methylmercaptoethyl)-is prepared
Hydantoins and ammonium bicarbonate mixed aqueous solution obtain 5- (2-methylmercaptoethyl)-hydantoins aqueous solution after stripping, add hydrogen
Sodium oxide molybdena alkaline hydrolysis, using stripping after alkaline hydrolysis, obtain carbonate content be within 4wt%, Sodium L-methioninate content be 10~
The saponification liquor of 25wt%；
Or the saponification liquor is prepared as follows：Using cyanalcohol, carbon dioxide and ammonia as raw material or with Cymag, 3- methyl mercaptos third
Aldehyde, carbon dioxide and ammonia are that raw material prepares glycolylurea, and glycolylurea adjusts pH3.0~6.0 through alkaline hydrolysis, acidification and obtains containing 2.5~10wt%
The mixed liquor of sodium carbonate, 10~25wt% Sodium L-methioninates, by mixed liquor be diluted to carbonate content be 4wt% within, methionine
Sodium content is 4~10wt%；Then sodium is removed by bipolar membrane electrodialysis, then carries out decarburization, it is 4wt% to be concentrated to give carbonate content
Within, Sodium L-methioninate content be 10~25wt% saponification liquor.
7. D according to claim 6, the clean preparation method of L-Methionine, which is characterized in that the rejection conditions are
0~0.6Mpa, 70~150 DEG C.
8. D according to claim 5, the clean preparation method of L-Methionine, which is characterized in that the saponification liquor is by following
Step obtains：Using 2- 2-hydroxy-4-methylthios butyronitrile, carbon dioxide, ammonia and water as raw material, 5- (2- methylmercaptan ethyls are prepared
Base)-hydantoins and ammonium bicarbonate mixed aqueous solution, 5- (2-methylmercaptoethyl)-hydantoins aqueous solution is obtained after stripping, is added
Potassium hydroxide alkaline hydrolysis, using stripping after alkaline hydrolysis, the potassium carbonate within obtaining containing 20wt% and 10~25wt% egg ammonia
The saponification liquor of sour potassium.
9. D according to claim 8, the clean preparation method of L-Methionine, which is characterized in that the heating decarburization item
Part be 0~0.6Mpa, 100~180 DEG C.
10. by claim 1~9 any one of them D, the high and low impurity of purity made from the clean preparation method of L-Methionine
D, L-Methionine, the D, L-Methionine purity be more than 99.4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710443926.1A CN108658821B (en) | 2017-06-13 | 2017-06-13 | Clean production method of D, L-methionine and product thereof |
Applications Claiming Priority (1)
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| CN116535338A (en) * | 2023-04-25 | 2023-08-04 | 重庆渝化新材料有限责任公司 | Potassium salt recycling process in production process of D, L-methionine |
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