CN116675631A - Cyclic production method of D, L-methionine - Google Patents
Cyclic production method of D, L-methionine Download PDFInfo
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- CN116675631A CN116675631A CN202310665827.3A CN202310665827A CN116675631A CN 116675631 A CN116675631 A CN 116675631A CN 202310665827 A CN202310665827 A CN 202310665827A CN 116675631 A CN116675631 A CN 116675631A
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- methionine
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- resin
- mother liquor
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 21
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229930182817 methionine Natural products 0.000 claims abstract description 58
- 229960004452 methionine Drugs 0.000 claims abstract description 58
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 58
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims abstract description 57
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 28
- 235000011181 potassium carbonates Nutrition 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940091173 hydantoin Drugs 0.000 claims abstract description 23
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 21
- QHMWJBZUZWPWFB-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;potassium Chemical compound [K].CSCC[C@H](N)C(O)=O QHMWJBZUZWPWFB-WCCKRBBISA-N 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims description 73
- 229920005989 resin Polymers 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 70
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- 239000012452 mother liquor Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000001569 carbon dioxide Substances 0.000 claims description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- 239000010413 mother solution Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000003795 desorption Methods 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 10
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000005262 decarbonization Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 229940072033 potash Drugs 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract description 16
- 235000015497 potassium bicarbonate Nutrition 0.000 abstract description 11
- 239000011736 potassium bicarbonate Substances 0.000 abstract description 11
- 229910000028 potassium bicarbonate Inorganic materials 0.000 abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011591 potassium Substances 0.000 abstract description 6
- 229910052700 potassium Inorganic materials 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 abstract description 2
- 239000004331 potassium propionate Substances 0.000 abstract description 2
- 235000010332 potassium propionate Nutrition 0.000 abstract description 2
- 159000000001 potassium salts Chemical class 0.000 abstract description 2
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000005261 decarburization Methods 0.000 description 21
- 239000012535 impurity Substances 0.000 description 10
- 238000000194 supercritical-fluid extraction Methods 0.000 description 10
- 239000012530 fluid Substances 0.000 description 8
- 238000005457 optimization Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BTUDTSGOEFVJTD-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;sodium Chemical compound [Na].CSCC[C@H](N)C(O)=O BTUDTSGOEFVJTD-WCCKRBBISA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KFSJYZYQSZKRRQ-BYPYZUCNSA-N (2s)-2-(hydroxyamino)-4-methylsulfanylbutanoic acid Chemical class CSCC[C@H](NO)C(O)=O KFSJYZYQSZKRRQ-BYPYZUCNSA-N 0.000 description 1
- GOAGGJDTOMPTSA-UHFFFAOYSA-N 1-(Methylthio)-2-butanone Chemical compound CCC(=O)CSC GOAGGJDTOMPTSA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000004596 appetite loss Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- PPVFOZYARYOARE-UHFFFAOYSA-N guaiapate Chemical compound COC1=CC=CC=C1OCCOCCOCCN1CCCCC1 PPVFOZYARYOARE-UHFFFAOYSA-N 0.000 description 1
- 229950010056 guaiapate Drugs 0.000 description 1
- 206010019692 hepatic necrosis Diseases 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- -1 liquid methionine) Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 231100000149 liver necrosis Toxicity 0.000 description 1
- 235000021266 loss of appetite Nutrition 0.000 description 1
- 208000019017 loss of appetite Diseases 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The cyclic production process of D, L-methionine includes mother liquid pre-treatment, decarbonizing liquid after pre-treatment, supercritical carbon dioxide extraction to obtain potassium salt solution, cyclic mixing the potassium salt solution with hydantoin, hydrolysis and acidification to obtain mother liquid, and repeating the steps to obtain cyclic production; the method can promote the decomposition of potassium salt, and the potassium salts such as potassium methionine, potassium propionate, potassium butyrate, potassium bicarbonate and the like are highly converted into potassium carbonate, the recovery rate is as high as 98.68%, and the purity of the recovered potassium carbonate solution is high, so that the preparation quality of methionine is good, the interference of the recovered potassium carbonate is reduced, the potassium carbonate is more stable in the potassium method process for preparing D, L-methionine by using sea-state raw materials, the circulation is ensured to be smoothly carried out under the condition of no new potassium carbonate, the energy consumption is low in the process of recovering and applying the potassium carbonate, the steps are simple and easy to operate, the preparation cost is saved in the process, and the atmospheric pollution is effectively reduced.
Description
Technical Field
The invention relates to the technical field of methionine production and preparation, in particular to a cyclic production method of D, L-methionine.
Background
Methionine, also known as methionine or methylthio-butanone, is closely related to the metabolism of various sulfur-containing compounds in organisms. In the absence of methionine, it causes loss of appetite, reduced or no weight gain, swelling of the kidneys and accumulation of iron in the liver, eventually leading to liver necrosis or fibrosis. Another methionine, known as hydroxy methionine derivative (i.e., liquid methionine), is widely used as a methionine nutritional supplement when used as a feed supplement to promote animal growth.
Methionine and liquid methionine are both amino acids, differing only in the alpha position, methionine linked to-NH 2 Whereas the liquid methionine is attached as-OH. When the solution pH is less than pI (isoelectric point), the solution exists in a cationic form; when the pH of the solution is more than pI (isoelectric point), the solution exists in an anion form; the solubility was minimal when ph=pi. Methionine is soluble in water but poorly soluble in non-polar materials, has a fairly high melting point and its aqueous solution properties are similar to those of aqueous solutions with high dipole moments. The method for preparing methionine is generally used at present, wherein a sodium methionine solution is neutralized under an acidic condition, the solution obtained after neutralization of sodium methionine by acid mainly contains methionine and inorganic salts, and then the methionine is obtained through crystallization and separation in a crystal form. Mother crystals after crystallizationSince the liquid still contains a certain amount of methionine and inorganic salts, the mother liquor of crystallization is preferably recycled.
The process for preparing methionine by using hydantoin as raw material includes a potassium process and a sodium process, wherein the potassium process is that hydantoin solution is hydrolyzed under alkaline condition to obtain potassium methionine aqueous solution; neutralizing the potassium methionine aqueous solution with carbon dioxide to obtain methionine and potassium bicarbonate aqueous solution, crystallizing and separating the methionine from the aqueous solution, and recycling the potassium bicarbonate along with the mother solution through subsequent treatment. Compared with the sodium process, the potassium process is cleaner, the potassium salt can be recovered and reused, and the production cost is lower. However, the following technical problems still exist in the production process of the potassium method: the byproducts in the reaction process are more, part of impurities still exist in the recovered potassium salt solution, and after repeated circulation, the impurities can be accumulated continuously, so that the purification difficulty of the final product is increased, the circulation times are reduced, and the quality of the final product is influenced. Therefore, the aim of finding a method which can simply and efficiently realize the recycling of high-purity potassium salt and realize the cost reduction and efficiency enhancement of products is urgent.
Disclosure of Invention
The invention aims to provide a cyclic production method of D, L-methionine.
The invention aims at realizing the following technical scheme:
a cyclic production method of D, L-methionine is characterized in that: the cyclic production method of D, L-methionine comprises the steps of pretreating mother liquor, decarbonizing liquid after pretreatment, carrying out supercritical carbon dioxide extraction reaction, collecting potassium salt solution after reaction, circularly mixing the potassium salt solution with hydantoin, hydrolyzing and acidifying to obtain mother liquor, and repeating the steps to realize cyclic production; the mother liquor is prepared by hydrolyzing hydantoin and potash to obtain a potassium methionine solution and acidizing the potassium methionine solution to obtain a mother liquor; the mother liquor pretreatment is that the mother liquor is required to be subjected to adsorption and desorption treatment by macroporous resin.
As a further optimization of the scheme, the macroporous resin is formed by mixing LSA-7 and LX-28 according to a mass ratio of 1:2-3, wherein the particle size of the LSA-7 is 30-40 meshes, the particle size of the LX-28 is 20-40 meshes, the LSA-7 brand is Klamar, and the LX-28 brand is Ruidaconstant.
Specifically, the mother liquor pretreatment is carried out according to the following steps:
(1) Pretreatment of macroporous resin: filling macroporous resins LSA-7 and LX-28 into a chromatographic column, and filling LSA-7 and LX-28; then eluting with 3-5% diluted hydrochloric acid with the flow rate of 3-5 ml/min, eluting with 5-7 times of the total volume of macroporous resin LSA-7 and LX-28, and washing with purified water with the same flow rate until the pH value of the effluent is=6.8-7.2;
(2) Resin adsorption: allowing the mother solution to pass through macroporous resin at a constant speed from top to bottom at a flow rate of 3-5 ml/min, collecting resin effluent separately, detecting methionine in the resin effluent at proper time, and stopping adding the mother solution into the resin when methionine is detected in the effluent;
(3) Resin desorption: adding 2-3% potassium hydroxide solution at a flow rate of 3-5 ml/min, desorbing resin from top to bottom, and collecting the analysis solution.
As a further optimization of the above scheme, the resin effluent collected in the above step (2) may be subjected to a next decarburization treatment; and (3) recrystallizing the analysis liquid in the step (3), collecting methionine, and mixing the recrystallized and separated liquid with mother liquor, and re-entering the mother liquor pretreatment step for recycling.
The combination of the specific macroporous resin and the specific adsorption mode have extremely strong adsorption capacity on methionine, so that methionine in the mother liquor is adsorbed on the macroporous resin, and meanwhile, the resin effluent liquid also has certain adsorption capacity on other impurities such as polymers and mainly contains potassium salt solution, thereby ensuring higher purity of the potassium salt solution before decarburization and reducing the difficulty of subsequent treatment steps; meanwhile, the analysis liquid can be recrystallized to obtain methionine, the methionine yield is improved, and the recrystallized liquid can enter circulation again along with the mother liquid.
As a further optimization of the scheme, the pre-treated liquid is subjected to decarburization treatment, namely, resin effluent is subjected to reduced pressure decarburization treatment for 45-60 min at the temperature of 50-100 Kpa and the temperature of 80-100 ℃. Through decarbonization treatment, part of potassium bicarbonate is converted into potassium carbonate, and part of organic potassium salt is further decomposed, so that the rapid carbon dioxide supercritical extraction decomposition process is effectively promoted.
As a further optimization of the scheme, the carbon dioxide supercritical extraction reaction is to take the decarbonized solution, place the decarbonized solution in a carbon dioxide supercritical extraction instrument, add diatomite treated by dilute acid, set the pressure at 30-40 MPa and the temperature at 140-150 ℃ for decomposition reaction for 12-15 min.
As a further optimization of the scheme, the diatomite treated by the dilute acid is placed in hydrochloric acid solution with the concentration of 0.1mol/L, kept stand for 12-15 h, washed to be neutral by deionized water after the standing is finished, and then dried; the mass ratio of the diatomite to the hydrochloric acid solution is 1:50-60.
In a carbon dioxide supercritical extraction instrument, under the condition of proper temperature and proper pressure, the decomposition of potassium salt can be accelerated, the reaction rate of potassium bicarbonate for generating potassium carbonate is accelerated under the supercritical environment, and meanwhile, due to the existence of diatomite treated by dilute acid in a system, the high-temperature and high-pressure environment further promotes the adsorption of organic polymer and other impurities in mother liquor of the diatomite treated by dilute acid during the decomposition of the potassium salt, the interference of residual impurities on the decomposition in the decomposition process is reduced, and more potassium salt is ensured to be converted into potassium carbonate; on the other hand, in the decomposition process, the solution and the carbon dioxide fluid have larger temperature difference, so that the reaction process is easy to be exploded, and the diatomite treated by the dilute acid is added to relieve the explosion condition and promote the smooth proceeding of the decomposition reaction. In addition, the supercritical carbon dioxide fluid has a protective effect on the residual methionine, can effectively prevent the oxidation and decomposition of methionine and reduce the generation of impurities, meanwhile, in the decomposition process of potassium bicarbonate, the carbon dioxide gas generated by decomposition is rapidly compressed and converted into a fluid state from a gaseous state under the action of high temperature and high pressure, so that the carbon dioxide gas is insoluble in filtrate, but is removed by the fluid used for extraction, the amount of the carbon dioxide in the gaseous state is reduced under the high temperature and high pressure environment which is favorable for the decomposition of the potassium bicarbonate and is unfavorable for the synthesis of the potassium bicarbonate, the decomposition of the potassium bicarbonate is further promoted, the carbon dioxide in the fluid state cannot inhibit the decomposition of the potassium bicarbonate, and conversely, the carbon dioxide fluid in the fluid state is absorbed and carried out by the flowing carbon dioxide fluid used for extraction, so that the recovery rate of potassium carbonate in the potassium salt solution used for recovery is increased, and the reflux accumulation of the impurities in the mother liquor is reduced.
As a further optimization of the scheme, the mass ratio of the decarbonized solution to the diatomite is 100:2-3.
As a further optimization of the scheme, the mother solution is prepared by acidizing potassium methionine solution, specifically, introducing carbon dioxide into the potassium methionine solution for reaction, wherein the reaction pressure is 0.1-0.3 MPa, the temperature is 30-50 ℃, and when the pH value of the solution is stable, the reaction is regarded as the end, then filtering, separating and washing are carried out, and the collected filtrate and washing liquid are mixed to obtain the mother solution; the potassium methionine solution is prepared by adding hydantoin into potassium carbonate and hydrolyzing at the temperature of 160-190 ℃ under the pressure of 0.7-1.4 MPa, wherein the molar ratio of potassium ions to hydantoin is 3-5:1.
The invention has the following technical effects:
according to the cyclic production method of D, L-methionine, through pretreatment, adsorption and desorption steps of specific macroporous resin, impurities in the subsequent supercritical carbon dioxide reaction are reduced, under the cooperation of acid diatomite, a specific supercritical carbon dioxide extraction mode can promote potassium salt to be decomposed, potassium methionine, potassium propionate, potassium butyrate, potassium bicarbonate and other potassium salts to be highly converted into potassium carbonate, the recovery rate is as high as 98.68%, the purity of the recovered potassium carbonate solution is high, so that the methionine preparation quality is good, the interference of the recovered potassium carbonate is also reduced, the potassium carbonate is more stable in the potassium method process of preparing D, L-methionine by using sea-borne materials, the circulation is ensured to be smoothly carried out under the condition of not adding new potassium carbonate, the energy consumption is low in the process of recycling the potassium carbonate, the steps are simple and easy to operate, and the environmental pollution is effectively reduced while the preparation cost is saved.
Detailed Description
The present invention will now be described in more detail by way of examples, which are set forth herein to illustrate the invention and are not to be construed as limiting the scope of the invention, as modifications or alternatives to the methods, steps or conditions of the invention may be made without departing from the spirit and nature of the invention.
Example 1
The cyclic production method of D, L-methionine comprises the following steps:
(1) Preparing mother solution: adding a potassium carbonate solution into a hydantoin solution, hydrolyzing at the temperature of 170 ℃ under 1.1MPa to obtain a potassium methionine solution, introducing carbon dioxide into the potassium methionine solution for reaction, setting the reaction pressure to 0.2MPa, setting the temperature to 40 ℃, considering the reaction as the end when the pH value of the solution is stable, filtering, separating and washing, and mixing the collected filtrate and the washing solution to obtain a mother solution; the molar ratio of the potassium ions to the hydantoin is 4:1. Through detection, methionine is contained in each main component in the mother liquor according to the mass percent: 10.16%, potassium ion: 10.63%.
(2) Pretreatment of mother solution:
A. pretreatment of macroporous resin: filling macroporous resins LSA-7 and LX-28 into a chromatographic column, and filling LSA-7 and LX-28; then eluting with 4% diluted hydrochloric acid at a flow rate of 4ml/min, eluting with volume 6 times of total volume of macroporous resins LSA-7 and LX-28, and washing with purified water at the same flow rate until effluent pH=6.93;
B. resin adsorption: allowing the mother solution to pass through macroporous resin at a constant speed from top to bottom at a flow rate of 4ml/min, collecting resin effluent separately, detecting methionine in the resin effluent at proper time, stopping adding the mother solution into the resin when the methionine content in the effluent is detected to be 0.07%, and allowing the collected resin effluent to enter into the next decarburization treatment;
C. resin desorption: adding potassium hydroxide solution with the mass fraction of 2.83% at the flow rate of 4ml/min, desorbing resin from top to bottom, collecting the desorption solution, recrystallizing the desorption solution, collecting methionine, mixing the recrystallized and separated liquid with the subsequent mother solution, and re-entering the mother solution pretreatment step for circulation. After desorption of the resin, the methionine content was detected to be 9.41%.
(3) Decarburization treatment: the resin effluent was subjected to a reduced pressure decarburization treatment at 80kpa and 90 c for 55min. After the resin effluent is subjected to decarburization treatment, the filtrate after decarburization is detected to have the following methionine mass percent: 10.73%, potassium salt (in K) + Meter): 11.19%.
(4) Supercritical carbon dioxide extraction reaction: placing the decarbonized solution in a carbon dioxide supercritical extractor, adding diatomite treated by dilute acid, setting the pressure at 35MPa and the temperature at 145 ℃, and carrying out decomposition reaction for 13min to obtain a potassium salt solution after the reaction is finished; the mass ratio of the decarbonized solution to the diatomite is 100:2.5; the diatomite treated by the dilute acid is prepared by placing diatomite into hydrochloric acid solution with the concentration of 0.1mol/L, standing for 13h, washing with deionized water to be neutral after standing is finished, and then drying; the mass ratio of the diatomite to the hydrochloric acid solution is 1:55. In the filtrate recovered after supercritical extraction, methionine: 2.83%, potassium salt (K) + Meter): 12.53% of the potassium carbonate in the proportion (K + Calculated as) was 99.13%.
(5) And (3) mixing the reacted potassium salt solution with hydantoin in a circulating way, hydrolyzing and acidifying to obtain mother liquor, and repeating the previous steps to obtain the circulating treatment.
Comparative example 1
Compared with example 1, the pretreatment step of the mother liquor is omitted, and the other steps are the same as those of example 1, wherein the mother liquor is prepared by separating a part of the mother liquor prepared in example 1 for subsequent steps, and the steps are as follows:
(1) Decarburization treatment: the mother liquor obtained in example 1 was subjected to decarburization under reduced pressure at 80kpa and 90℃for 55 minutes. After the mother solution is subjected to decarburization treatment, the mass percentage of methionine in filtrate after decarburization is as follows: 9.86%, potassium salt: 10.13%.
(2) Supercritical carbon dioxide extraction reaction: placing the decarbonized solution in a carbon dioxide supercritical extractor, adding diatomite treated by dilute acid, setting the pressure at 35MPa and the temperature at 145 ℃, and carrying out decomposition reaction for 13min to obtain a potassium salt solution after the reaction is finished; the decarbonized solution and diatomiteThe mass ratio of (2) is 100:2.5; the diatomite treated by the dilute acid is prepared by placing diatomite into hydrochloric acid solution with the concentration of 0.1mol/L, standing for 13h, washing with deionized water to be neutral after standing is finished, and then drying; the mass ratio of the diatomite to the hydrochloric acid solution is 1:55. In the filtrate recovered after supercritical extraction, methionine: 6.97%, potassium salt (K) + Meter): 11.27% of potassium carbonate (K) + Calculated as) was 76.42%.
(5) And (3) mixing the reacted potassium salt solution with hydantoin in a circulating way, hydrolyzing and acidifying to obtain mother liquor, and repeating the previous steps to obtain the circulating treatment.
From the above, the final potassium carbonate is relatively low in proportion after the whole treatment of the mother liquor is canceled, so that a certain amount of potassium carbonate is required to be added to improve the concentration of the potassium carbonate during circulation, and the impurity removal effect in the solution is not ideal, so that the circulation times and the product quality of final methionine are affected.
Comparative example 2
In comparison with example 1, in the potassium salt purification recovery step, when the mother liquor is decomposed by supercritical carbon dioxide extraction, the diluted acid-treated diatomite is not added, and the steps are otherwise the same as those in example 1, wherein the products obtained in steps (1), (2) and (3) are separated from example 1 to carry out the subsequent steps, and the steps are specifically as follows:
(1) Supercritical carbon dioxide extraction reaction: and (3) placing the decarbonized solution in a carbon dioxide supercritical extractor, setting the pressure at 35MPa and the temperature at 145 ℃, and carrying out decomposition reaction for 13min to obtain a potassium salt solution after the reaction is finished. In the supercritical extraction reaction process, a slight bumping phenomenon exists, and methionine is contained in filtrate recovered after the supercritical extraction reaction: 8.96%, potassium salt (K) + Meter): 10.02% of potassium carbonate in a ratio (K) + Calculated as) was 81.63%.
(2) And (3) mixing the reacted potassium salt solution with hydantoin in a circulating way, hydrolyzing and acidifying to obtain mother liquor, and repeating the previous steps to obtain the circulating treatment.
From the above, in the supercritical carbon dioxide extraction reaction process, the addition of acid diatomite is canceled, and the final potassium carbonate is relatively low in proportion, so that a certain amount of potassium carbonate is required to be added to improve the concentration of potassium carbonate during circulation, and the impurity removal effect in the solution is not ideal, so that the circulation times and the product quality of final methionine can be affected.
Example 2
The cyclic production method of D, L-methionine comprises the following steps:
(1) Preparing mother solution: adding hydantoin into potassium carbonate, adding a potassium carbonate solution into the hydantoin solution, hydrolyzing at the temperature of 190 ℃ under the pressure of 0.7MPa to obtain a potassium methionine solution, introducing carbon dioxide into the potassium methionine solution for reaction, wherein the reaction pressure is 0.1MPa, the temperature is 50 ℃, and when the pH value of the solution is stable, the reaction is considered to be finished, then filtering, separating and washing are carried out, and the collected filtrate and the washing liquid are mixed to obtain a mother solution; the molar ratio of the potassium ions to the hydantoin is 4:1. Through detection, methionine is contained in each main component in the mother liquor according to the mass percent: 9.83%, potassium ion: 10.28%.
(2) Pretreatment of mother solution:
A. pretreatment of macroporous resin: filling macroporous resins LSA-7 and LX-28 into a chromatographic column, and filling LSA-7 and LX-28; then eluting with diluted hydrochloric acid with volume fraction of 3, the flow rate of the diluted hydrochloric acid is 3ml/min, the eluting volume is 5 times of the total volume of macroporous resin LSA-7 and LX-28, and after the eluting, washing with purified water with the same flow rate until the pH of the effluent liquid is=6.82;
B. resin adsorption: allowing the mother solution to pass through macroporous resin at a constant flow rate of 3ml/min from top to bottom, collecting resin effluent separately, detecting methionine in time, stopping adding the mother solution into the resin when the methionine content of the resin effluent is detected to be 0.03%, and performing decarburization treatment on the collected resin effluent;
C. resin desorption: adding 2% potassium hydroxide solution at a flow rate of 3ml/min, desorbing resin from top to bottom, collecting desorption solution, recrystallizing the desorption solution, collecting methionine, mixing the recrystallized and separated liquid with mother liquor, and re-entering the mother liquor pretreatment step for circulation. After desorption of the resin, the methionine content was detected to be 8.97%.
(3) Decarburization treatment: the resin effluent was subjected to a reduced pressure decarbonization treatment at 50kpa and 100℃for 60 minutes. After the resin effluent is subjected to decarburization treatment, the filtrate after decarburization is detected to have the following methionine mass percent: 10.51%, potassium salt: 11.05%.
(4) Supercritical carbon dioxide extraction reaction: placing the decarbonized solution in a carbon dioxide supercritical extractor, adding diatomite treated by dilute acid, setting the pressure at 30MPa and the temperature at 150 ℃, and carrying out decomposition reaction for 15min to obtain a potassium salt solution after the reaction is finished; the mass ratio of the decarbonized solution to the diatomite is 100:2; the diatomite treated by the dilute acid is prepared by placing diatomite into hydrochloric acid solution with the concentration of 0.1mol/L, standing for 12 hours, washing with deionized water to be neutral after standing is finished, and then drying; the mass ratio of the diatomite to the hydrochloric acid solution is 1:50. In the filtrate recovered after supercritical extraction, methionine: 3.16%, potassium salt (K) + Meter): 12.07% of which the potassium carbonate ratio (K + Calculated as 98.68%.
(5) And (3) mixing the reacted potassium salt solution with hydantoin in a circulating way, hydrolyzing and acidifying to obtain mother liquor, and repeating the previous steps to obtain the circulating treatment.
Example 3
The cyclic production method of D, L-methionine comprises the following steps:
(1) Preparing mother solution: adding a potassium carbonate solution into a hydantoin solution, hydrolyzing at the temperature of 160 ℃ under the pressure of 1.4MPa to obtain a potassium methionine solution, introducing carbon dioxide into the potassium methionine solution for reaction, wherein the reaction pressure is 0.3MPa, the temperature is 30 ℃, and when the pH value of the solution is stable, the reaction is regarded as the end, filtering, separating and washing, and mixing the collected filtrate and the washing liquid to obtain a mother solution; the molar ratio of the potassium ions to the hydantoin is 5:1. Through detection, methionine is contained in each main component in the mother liquor according to the mass percent: 10.37%, potassium ion: 13.52%.
(2) Pretreatment of mother solution:
A. pretreatment of macroporous resin: filling macroporous resins LSA-7 and LX-28 into a chromatographic column, and filling LSA-7 and LX-28; then eluting with 5% diluted hydrochloric acid at a flow rate of 5ml/min and an elution volume of 7 times of the total volume of macroporous resins LSA-7 and LX-28, and washing with purified water at the same flow rate until the effluent pH=7.16;
B. resin adsorption: allowing the mother solution to pass through macroporous resin at a constant speed from top to bottom at a flow rate of 3-5 ml/min, collecting resin effluent separately, detecting methionine in the resin effluent at proper time, stopping adding the mother solution into the resin when the methionine content in the effluent is detected to be 0.02%, and allowing the collected resin effluent to enter into the next decarburization treatment;
C. resin desorption: adding 3% potassium hydroxide solution at a flow rate of 5ml/min, desorbing resin from top to bottom, collecting desorption solution, recrystallizing the desorption solution, collecting methionine, mixing the recrystallized and separated liquid with mother liquor, and re-entering the mother liquor pretreatment step for circulation. After desorption of the resin, the methionine content was detected to be 9.81%.
(3) Decarburization treatment: the resin effluent was subjected to decarbonization under reduced pressure at 100kpa and 80℃for 60min. After the resin effluent is subjected to decarburization treatment, the filtrate after decarburization is detected to have the following methionine mass percent: 10.69%, potassium salt: 13.66%.
(4) Supercritical carbon dioxide extraction reaction: placing the decarbonized solution in a carbon dioxide supercritical extractor, adding diatomite treated by dilute acid, setting the pressure at 40MPa and the temperature at 150 ℃, and carrying out decomposition reaction for 12min to obtain a potassium salt solution after the reaction is finished; the mass ratio of the decarbonized solution to the diatomite is 100:3; the diatomite treated by the dilute acid is prepared by placing diatomite into hydrochloric acid solution with the concentration of 0.1mol/L, standing for 15h, washing with deionized water to be neutral after standing is finished, and then drying; the mass ratio of the diatomite to the hydrochloric acid solution is 1:60. In the filtrate recovered after supercritical extraction, methionine: 2.97%, potassium salt (K) + Meter): 14.23% of which is potassium carbonate (K) + Calculated as) was 98.91%.
(5) And (3) mixing the reacted potassium salt solution with hydantoin in a circulating way, hydrolyzing and acidifying to obtain mother liquor, and repeating the previous steps to obtain the circulating treatment.
Claims (8)
1. The cyclic production method of D, L-methionine is characterized by comprising the steps of pretreating mother liquor, decarbonizing liquid after pretreatment, carrying out supercritical carbon dioxide extraction reaction, collecting potassium salt solution after reaction, circularly mixing the potassium salt solution with hydantoin, hydrolyzing and acidifying to obtain mother liquor, and repeating the steps to realize cyclic production; the mother liquor is prepared by hydrolyzing hydantoin and potash to obtain a potassium methionine solution and acidizing the potassium methionine solution to obtain a mother liquor; the mother liquor pretreatment is that the mother liquor is required to be subjected to adsorption and desorption treatment by macroporous resin.
2. The method for the cyclic production of D, L-methionine according to claim 1, wherein the macroporous resin is formed by mixing LSA-7 and LX-28 according to a mass ratio of 1:2-3, wherein the LSA-7 has a particle size of 30-40 meshes and the LX-28 has a particle size of 20-40 meshes.
3. The cyclic production method of D, L-methionine according to claim 2, wherein the mother liquor pretreatment is performed as follows:
(1) Pretreatment of macroporous resin: filling macroporous resins LSA-7 and LX-28 into a chromatographic column, and filling LSA-7 and LX-28; then eluting with 3-5% diluted hydrochloric acid with the flow rate of 3-5 ml/min, eluting with 5-7 times of the total volume of macroporous resin LSA-7 and LX-28, and washing with purified water with the same flow rate until the pH value of the effluent is=6.8-7.2;
(2) Resin adsorption: allowing the mother solution to pass through macroporous resin at a constant speed from top to bottom at a flow rate of 3-5 ml/min, collecting resin effluent separately, detecting methionine in the resin effluent at proper time, and stopping adding the mother solution into the resin when methionine is detected in the effluent;
(3) Resin desorption: adding 2-3% potassium hydroxide solution at a flow rate of 3-5 ml/min, desorbing resin from top to bottom, and collecting the analysis solution.
4. The method for recycling potassium salt in D, L-methionine production according to claim 3, wherein the liquid after the mother liquor pretreatment is subjected to decarbonization treatment, specifically, resin effluent is subjected to pressure reduction decarbonization treatment for 45-60 min at 50-100 Kpa and 80-100 ℃.
5. The method for recycling D, L-methionine according to claim 4, wherein the supercritical carbon dioxide extraction reaction is carried out by taking the decarbonized solution, placing the decarbonized solution in a supercritical carbon dioxide extractor, adding diatomite treated with dilute acid, setting the pressure at 30-40 MPa, and the temperature at 140-150 ℃ for decomposition reaction for 12-15 min.
6. The method for the cyclic production of D, L-methionine according to claim 5, wherein the dilute acid-treated diatomaceous earth is obtained by placing diatomaceous earth in a hydrochloric acid solution having a concentration of 0.1mol/L, standing for 12 to 15 hours, washing with deionized water to neutrality after the end of the standing, and drying; the mass ratio of the diatomite to the hydrochloric acid solution is 1:50-60.
7. The method for the cyclic production of D, L-methionine according to claim 6, wherein the mass ratio of the decarburized solution to the diatomaceous earth is 100:2-3.
8. The cyclic production method of D, L-methionine according to claim 7, wherein the mother liquor is prepared by acidifying potassium methionine solution, specifically, introducing carbon dioxide into potassium methionine solution for reaction, wherein the reaction pressure is 0.1-0.3 MPa, the temperature is 30-50 ℃, the reaction is regarded as being finished when the pH value of the solution is stable, then filtering and separating, washing, and mixing the collected filtrate and washing liquid to obtain the mother liquor; the potassium methionine solution is prepared by adding hydantoin into potassium carbonate and hydrolyzing at the temperature of 160-190 ℃ under the pressure of 0.7-1.4 MPa, wherein the molar ratio of potassium ions to hydantoin is 3-5:1.
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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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