CN109734637A - A kind of methionine crystalline mother solution processing method - Google Patents
A kind of methionine crystalline mother solution processing method Download PDFInfo
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- CN109734637A CN109734637A CN201910113860.9A CN201910113860A CN109734637A CN 109734637 A CN109734637 A CN 109734637A CN 201910113860 A CN201910113860 A CN 201910113860A CN 109734637 A CN109734637 A CN 109734637A
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Abstract
The present invention relates to a kind of methionine crystalline mother solution processing methods, using the methionine crystalline mother solution produced in methionine sylvite art production process as raw material, the following steps are included: the methionine crystalline mother solution of (1) extraction carries out heating concentration, obtain methionine potassium and potassium carbonate mixed liquor, then pass to carbon dioxide gas, the saleratus solid content containing methionine and saleratus filtrate are respectively obtained, solid content is back to 5-(2- methylmercaptoethyl) hydrolysis of-hydantoins；(2) the saleratus filtrate for obtaining step (1) carries out bipolar membrane electrodialysis treatment, and acid compartment obtains the aqueous solution containing organic matter, concentrated, burning disposal, and alkaline chamber obtains dilute potassium hydroxide aqueous solution, is back to 5-(2- methylmercaptoethyl) hydrolysis of-hydantoins.This method reuses carbon dioxide acidification and its bipolar membrane electrodialysis, sufficiently recycles methionine and potassium ion in mother liquor, avoids valuable compounds therefrom in mother liquor and loses, reduces production cost.
Description
Technical field
The invention belongs to chemical fields, crystallize more particularly, to the methionine produced in a kind of methionine sylvite production process
Mother liquor processing method.
Background technique
5-(2- methylmercaptoethyl is hydrolyzed under the conditions of the mainstream production method of known methionine is existing for the potassium carbonate)-
Hydantoins aqueous solution obtains the methionine aqueous solutions of potassium containing potassium carbonate, then water-soluble to the methionine potassium containing potassium carbonate
Being passed through after carbon dioxide neutralizes in liquid makes the crystallization of its methionine be precipitated, separate, and respectively obtains methionine wet product and contains methionine
Potassium bicarbonate aqueous solution (filtrate)；Potassium bicarbonate aqueous solution (filtrate) containing methionine is back to 5- by concentration
(2-methylmercaptoethyl)-hydantoins aqueous hydrolysis process.
In existing technical solution, main impurity is methionine dimer in mother liquor, and methionine dimer is in alkalinity
Under the conditions of can be converted into methionine, the equivalent for methionine is considered as, only such as two of methionine in fruit mother liquor
Aggressiveness accumulation is excessive, other substances such as polyethylene that will affect the crystallization of methionine, however be added in methionine crystallization process
Alcohol, sorbitan lauric acid rouge, hydroxypropyl methyl cellulose etc. can be accumulated, either above-mentioned side with the circulation of mother liquor
Method is added organic solvent miscible with water and carries out precipitate methionine and potassium and saleratus, and obtained methionine and saleratus are same
These impurity can be carried secretly, to can be brought into system again, this method is fundamentally that can't resolve impurity in mother liquor in fact
Accumulation, fundamentally solve effective method and be exactly that part extraction mother liquor carries out burning disposal, thus avoid or
Solve the aggregation of impurity in systems.Certainly, such processing is carried out under the premise of sacrificialing environment and economy, because burning
It burns also containing valuable considerable methionine and saleratus in the mother liquor of processing, and burns and be rich in potassium ion in mother liquor.
Organic solvent miscible with water such as methanol, acetone and isopropanol are added into mother liquor, although can precipitate a large amount of
Methionine and saleratus, but after having taken methionine and saleratus not only contain methanol or acetone, different in mother liquor
Propyl alcohol, but also contain other impurities such as methionine dimer, potassium formate, potassium propionate, potassium acetate, potassium butyrate, potassium carbonate, poly- second
Enol, sorbitan lauric acid rouge, hydroxypropyl methyl cellulose etc., synthesizing cyanalcohol with hydrogen cyanide in methylthiopropionaldehyde is, addition
For citrate buffer solution either acetate buffer solution as cyaniding catalyst, it is female that these catalyst finally can all bring methionine crystallization into
In liquid, as methionine crystalline mother solution recycled causes to accumulate, these impurity are impossible to make it by the way that organic solvent is added
It is precipitated, also stays in this mother liquor.Such mother liquid disposal is relatively difficult, because of a large amount of organic solvent used first, because
This needs that solvent recovery is now recycled organic solvent by way of distilling with rectifying, and recycling the raffinate after organic solvent must
Burning disposal must be carried out, its these impurity can just will not return in methionine production system.The recycling of solvent needs to consume big
Energy and a large amount of equipment investment of needs, and the loss of solvent is that this institute is inevitable, increases the production of methionine
Cost.
In view of the above-mentioned deficiencies, by the production practices of inventor's many years, a kind of methionine crystalline mother solution production is developed
Egg processing method, this method make full use of methionine and saleratus recycling methionine, carbon in the methionine crystalline mother solution of extraction
Potassium hydrogen phthalate and potassium hydroxide play the comprehensive utilization of waste, have reached economy and environment two-win, have avoided passing through at burning
Reason loss methionine and potassium ion avoid traditional use organic solvent, avoid the pollution to environment.
Summary of the invention
In order to solve these problems, present inventor has found one and effectively recycles methionine, carbon from the mother liquor of discharge
Potassium hydrogen phthalate and potassium hydroxide avoid accumulating in organic impurities mother liquor in mother liquor.As a result, it has been found that its row can be made by the following method
The methionine in mother liquor, saleratus and the potassium hydroxide put are fully utilized, and reach the two-win on economical and environmentally friendly.It is right
The mother liquor discharged is heat-treated and is concentrated, its saleratus is made to be decomposed into potassium carbonate, is then passed to carbon dioxide acidification, is made
Its methionine and saleratus are precipitated simultaneously, obtain the saleratus solid content containing methionine, which is recycled to 5-(2-
Methylmercaptoethyl)-hydantoins hydrolysing step, filtrate then passes through heat resolve, using bipolar membrane electrodialysis treatment, control acid
The pH and potassium concentration of material in room, acid compartment obtain organic aqueous solution, then burning disposal；Alkaline chamber obtains dilute hydrogen-oxygen
Change aqueous solutions of potassium, directly or through being recycled to 5-(2- methylmercaptoethyl after concentration)-hydantoins hydrolysing step.The present invention according to
It is accomplished according to above-mentioned discovery, it is such to be the discovery that based on comprehensively considering and a large amount of experimental demonstration and its pair to waste
Product market value considers and obtains.
A kind of methionine crystalline mother solution processing method provided by according to the present invention, this method is with methionine sylvite technique
The methionine crystalline mother solution produced in production process is raw material, comprising the following steps:
(1) the methionine crystalline mother solution produced carries out heating concentration, obtains methionine potassium and potassium carbonate mixed liquor, then passes to two
Carbon oxide gas respectively obtains saleratus solid content and saleratus filtrate, solid content containing methionine and is back to 5-(2-
Methylmercaptoethyl)-hydantoins hydrolytic process (see background technique)；
(2) the saleratus filtrate for obtaining step (1) carries out bipolar membrane electrodialysis treatment, and acid compartment is obtained containing the water-soluble of organic matter
Liquid (waste material), concentrated, burning disposal；Alkaline chamber obtains dilute potassium hydroxide aqueous solution (recycling), is back to 5-(2- methyl mercapto
Ethyl)-hydantoins hydrolytic process (see background technique).
Further, the methionine crystalline mother solution are as follows: in sylvite technique, carbon dioxide neutralization is passed through, after separating methionine
Obtained crystalline mother solution, the mother liquor group become methionine, saleratus, potassium carbonate, potassium formate, potassium propionate, potassium acetate, butyric acid
Potassium, potassium citrate, methionylmethionine, other organic matters such as polyvinyl alcohol, sorbitan lauric acid rouge or hydroxypropyl methyl are fine
Dimension element, wherein methionine is 4.0 wt %~9.0wt%, and potassium ion is 4.0 wt %~11.0wt%, methionylmethionine 0.01
Wt %~1.0wt%, other organic impurities are 0.01 wt %~0.5wt%, and the pH of mother liquor is 7.5~9.0.In this case,
If the mother liquor of all amounts recycled, impurity hydrolyzes 5-(2- methylmercaptoethyl again) it accumulates in-hydantoins step, because
This needs that mother liquor is discharged with defined speed.In addition, the measure that the processing as waste liquid discharge mother liquor has not been, therefore cause
The wherein loss of methionine and saleratus wherein included, and the load of liquid waste processing and consume very high.
Further, it is 20.0wt%~30wt% that methionine crystalline mother solution, which is concentrated into potassium concentration, in the step (1), dense
Contracting temperature is 80 DEG C~140 DEG C, and the pH of the aqueous solution is 12~14.Such concentration is for subsequent methionine and saleratus
It separates out as much as possible, reduces the residual of methionine and saleratus in mother liquor.
Further, carbon dioxide neutralizes in the step (1), and the pressure for being passed through carbon dioxide is 0.1~1.0Mpa, neutralizes
Temperature is 0 DEG C~10 DEG C, and obtained solid content is the saleratus solid containing a small amount of methionine, which is back to hydrolysis
5-(2- methylmercaptoethyl)-hydantoins, potassium concentration is 6.0wt%~9.0wt% in filtrate.Such solid content is mainly
Saleratus, accounts for 40wt%~65wt% of solid content, and methionine accounts for 10wt%~30wt%.
Further, the filtrate is potassium bicarbonate aqueous solution, contains a small amount of methionine, methionine dimer, formic acid
Potassium, potassium propionate, potassium acetate, potassium butyrate, potassium carbonate, potassium citrate, polyvinyl alcohol, sorbitan lauric acid rouge, hydroxypropyl methyl
One or more of cellulose etc..Impurity has plenty of what reaction itself generated in mother liquor, such as methionine dimer, potassium formate
Deng potassium formate is the excess due to raw material hydrogen cyanide and hydrolyzes generation, and the ratio that propionic aldehyde accounts in impurity is bigger；Additional is miscellaneous
Matter has propionic acid, acetic acid, butyric acid, citric acid, polyvinyl alcohol, sorbitan lauric acid rouge, hydroxypropyl methyl cellulose etc., these are miscellaneous
Matter has plenty of catalyst added when cyanalcohol production, adds when having plenty of methionine crystallization in order to obtain high-bulk-density,
These impurity are all inevitable and existing.
Further, acid compartment obtains organic compound aqueous solution in step (2) bipolar membrane electrodialysis, wherein pH be 6~
7, potassium concentration is lower than 0.10wt%, obtains potassium hydroxide aqueous solution in alkaline chamber, concentration of potassium hydroxide be 2.0wt%~
10.0wt%, bipolar membrane electrodialysis operating temperature are 20 DEG C~35 DEG C.
Further, the material into bipolar membrane electrodialysis treatment is preferably pre-processed, it may be assumed that first heating makes its carbonic acid
Hydrogen potassium is decomposed into potassium carbonate, it is cold go after by accurate filter enter back into the processing of bipolar membrane electrodialysis device.
Further, the material pretreatment and the operation of bipolar membrane electrodialysis may carry out for primary or multiple circulation,
Until potassium concentration is reduced within 0.10wt% in acid compartment in bipolar membrane electrodialysis device.And methionine and other organic matters are such as
Methionine dimer, potassium formate, potassium propionate, potassium acetate, potassium butyrate, potassium carbonate, polyvinyl alcohol, sorbitan lauric acid rouge, hydroxyl
Propyl methocel etc. has then stayed in acid compartment, and the potassium hydroxide formed in alkaline chamber to migrate the potassium ion to come is water-soluble
Liquid, for such aqueous solution other than potassium hydroxide, other impurities content is almost without either low-down.In this way using double
Pole membrane electrodialysis device just not only plays the mother liquor of separation potassium ion and methionine and other organic impurities, but also reaches
The purpose of the valuable potassium ion of recycling.
Further, the potassium hydroxide in the alkaline chamber directly or through be back to after concentration hydrolysis 5-(2- methylmercaptan ethyl
Base)-hydantoins process.
The advantages and positive effects of the present invention are: the abundant benefit of the method for the present invention makes full use of the methionine crystalline mother solution of extraction
Middle methionine and saleratus recycling methionine, saleratus and potassium hydroxide, play the comprehensive utilization of waste, reach
Economy and environment two-win avoid passing through burning disposal loss methionine and potassium ion, avoid traditional use organic solvent, keep away
Exempt from the pollution to environment, reached economy and environment two-win, production cost is low, and production is simple easily operated, has very high
Industrial application value.
Specific embodiment
The present invention is described in further detail below by specific embodiment, it is not to limit that following embodiment, which is descriptive,
Property, this does not limit the scope of protection of the present invention.
Embodiment
500 kilograms of methionine crystalline mother solution is added in a kettle, wherein the mass percentage of methionine is
7.5wt%, the mass percentage of methionine dimer are 0.5wt%, and the mass percentage of potassium ion is 9.5wt%, other have
The mass percentage of machine object is 0.02wt%, and the pH of mother liquor is 8.7；To mother liquor carry out heating 120 DEG C, be then concentrated into potassium from
Sub- concentration is 28.5wt%, methionine concentration 22.5wt%, and the concentration of methionine dimer is 1.5wt%, other organic matters it is total
Concentration is 0.06wt%, and the pH of feed liquid is that the mother liquor amount of the 12.8(extraction is the 1%~2% of entire internal circulating load).
Methionine potassium obtained above and potassium carbonate mixed liquor are cooled to 5 DEG C, carbon dioxide is then passed to, is passed through dioxy
The pressure for changing carbon is 0.5Mpa, and neutralizing pH is 8.2, and a large amount of milky white precipitate is precipitated, and filters, obtains the carbonic acid containing methionine
142.0 kilograms of hydrogen potassium solid content, wherein saleratus content is 65.0wt%, methionine content 24.65wt%, which returns
The hydrolysis 5-(2- methylmercaptoethyl being back in methionine production process)-hydantoins process.It is public to obtain filtrate total 147.45
Jin, wherein saleratus content is 20.0wt%, and methionine content 1.7wt%, other organic impurity contents are 1.8wt%.
So that its saleratus is completely decomposed into potassium carbonate filtrate obtained above heating, is subsequently cooled to 25 DEG C, passes through
Enter in bipolar membrane electrodialysis device after accurate filter and carries out de- potassium, potassium ion meeting in the acid compartment in bipolar membrane electrodialysis device
It gradually decreases, pH is gradually decreased, and potassium concentration can gradually increase in alkaline chamber, and pH gradually rises.When the pH in acid compartment cannot
When reducing again, the material in acid compartment is subjected to heat resolve, so that its saleratus is again converted to potassium carbonate, then carry out bipolar
Membrane electrodialysis takes off potassium operation, repeats aforesaid operations until the concentration of potassium ion is reduced to 0.1wt% or less in acid compartment.Acid compartment obtains
Aqueous solution containing methionine (a small amount of) and other organic matters is directly burned after concentration (due to containing here
The total methionine amount of methionine Zhan be it is seldom, account for 6.67% of methionine amount in mother liquor, can be ignored completely), alkaline chamber
209.18 kilograms of potassium hydroxide of 7.5wt% are obtained, the rate of recovery of potassium ion reaches 95%.Potassium hydroxide aqueous solution can directly or
The hydrolysis 5-(2- methylmercaptoethyl being back to after concentration in methionine production process)-hydantoins process.
Claims (9)
1. a kind of methionine crystalline mother solution processing method, which comprises the following steps:
(1) using the methionine crystalline mother solution produced in methionine sylvite art production process as raw material, to methionine crystalline mother solution
Heating concentration is carried out, methionine potassium and potassium carbonate mixed liquor is obtained, then passes to carbon dioxide gas, is respectively obtained containing egg ammonia
The saleratus solid content and saleratus filtrate, solid content of acid are back to 5-(2- methylmercaptoethyl)-hydantoins is hydrolyzed
Journey；
(2) the saleratus filtrate for obtaining step (1) carries out bipolar membrane electrodialysis treatment, and acid compartment is obtained containing the water-soluble of organic matter
Liquid, concentrated, burning disposal；Alkaline chamber obtains dilute potassium hydroxide aqueous solution, is back to 5-(2- methylmercaptoethyl)-hydantoins water
Solution preocess.
2. a kind of methionine crystalline mother solution processing method according to claim 1, which is characterized in that the methionine crystallization
Mother liquor are as follows: in sylvite technique, be passed through carbon dioxide neutralization, separate the crystalline mother solution obtained after methionine, which becomes egg
Propylhomoserin, saleratus, potassium formate, potassium propionate, potassium citrate, potassium acetate, potassium butyrate, potassium carbonate, methionylmethionine, other are organic
Object such as polyvinyl alcohol, sorbitan lauric acid rouge or hydroxypropyl methyl cellulose, wherein methionine be 4.0 wt %~
9.0wt%, potassium ion are 4.0 wt %~11.0wt%, and methionylmethionine is 0.01 wt %~1.0wt%, other organic impurities
For 0.01 wt %~0.5wt%, the pH of mother liquor is 7.5~9.0.
3. a kind of methionine crystalline mother solution processing method according to claim 1, which is characterized in that in the step (1)
It is 20.0wt%~30wt% that methionine crystalline mother solution, which is concentrated into potassium concentration, and thickening temperature is 80 DEG C~140 DEG C.
4. a kind of methionine crystalline mother solution processing method according to claim 1, which is characterized in that in the step (1)
Carbon dioxide neutralizes, and the pressure for being passed through carbon dioxide is 0.1~1.0Mpa, and neutralization temperature is 0 DEG C~10 DEG C, obtained solid content
For the saleratus solid containing a small amount of methionine.
5. a kind of methionine crystalline mother solution processing method according to claim 4, which is characterized in that the filtrate is carbon
Potassium hydrogen phthalate aqueous solution contains methionine, methionine dimer, potassium formate, potassium propionate, potassium acetate, potassium butyrate, potassium carbonate, lemon
One or more of sour potassium, polyvinyl alcohol, sorbitan lauric acid rouge, hydroxypropyl methyl cellulose etc..
6. a kind of methionine crystalline mother solution processing method according to claim 1, which is characterized in that the step (2) is double
Acid compartment obtains organic compound aqueous solution in the membrane electrodialysis of pole, and wherein pH is 6~7, and potassium concentration is lower than 0.10wt%, alkaline chamber
In obtain potassium hydroxide aqueous solution, concentration of potassium hydroxide is 2.0wt%~10.0wt%, and bipolar membrane electrodialysis operating temperature is 20 DEG C
~35 DEG C.
7. a kind of methionine crystalline mother solution processing method according to claim 6, which is characterized in that described to enter Bipolar Membrane
The material of electrodialysis process is pre-processed, it may be assumed that first heating makes saleratus be decomposed into potassium carbonate, it is cold go after by secondary filter
Device enters back into the processing of bipolar membrane electrodialysis device.
8. a kind of methionine crystalline mother solution processing method according to claim 7, which is characterized in that the material pretreatment
Operation with bipolar membrane electrodialysis is primary or repeatedly circulation carries out, until potassium ion is dense in acid compartment in bipolar membrane electrodialysis device
Degree is reduced within 0.10wt%.
9. a kind of methionine crystalline mother solution processing method according to claim 6, which is characterized in that the hydrogen in the alkaline chamber
Potassium oxide directly or through be back to after concentration hydrolysis 5-(2- methylmercaptoethyl)-hydantoins process.
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Cited By (4)
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| CN112679397A (en) * | 2020-12-21 | 2021-04-20 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method of DL-methionine |
| CN112679401A (en) * | 2020-12-30 | 2021-04-20 | 天宝动物营养科技股份有限公司 | Potassium carbonate full-circulation process for preparing D, L-methionine |
| CN114163367A (en) * | 2021-12-09 | 2022-03-11 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine environment-friendly preparation method based on carbon dioxide acidification method |
| EP4032857A4 (en) * | 2019-09-17 | 2023-11-01 | Sumitomo Chemical Company Limited | Method for producing concentrated carbonate aqueous solution |
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| EP4032857A4 (en) * | 2019-09-17 | 2023-11-01 | Sumitomo Chemical Company Limited | Method for producing concentrated carbonate aqueous solution |
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| CN114163367A (en) * | 2021-12-09 | 2022-03-11 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine environment-friendly preparation method based on carbon dioxide acidification method |
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Address after: 675000 salon village, Qinfeng Town, Lufeng County, Chuxiong Yi Autonomous Prefecture, Yunnan Province Applicant after: Tianbao Animal Nutrition Technology Co.,Ltd. Address before: 675000 salon village, Qinfeng Town, Lufeng County, Chuxiong Yi Autonomous Prefecture, Yunnan Province Applicant before: LUFENG TIANBAO PHOSPHORUS CHEMICAL Co.,Ltd. |
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