CN101343194B - Process for preparing low-salt composite aminophenol powder - Google Patents
Process for preparing low-salt composite aminophenol powder Download PDFInfo
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- CN101343194B CN101343194B CN2008101968813A CN200810196881A CN101343194B CN 101343194 B CN101343194 B CN 101343194B CN 2008101968813 A CN2008101968813 A CN 2008101968813A CN 200810196881 A CN200810196881 A CN 200810196881A CN 101343194 B CN101343194 B CN 101343194B
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Abstract
The invention provides a production method for desalting a mother liquor after producing L-cystine by an extraction method and then producing a low-salt composite amino acid powder of amino acid by the desalted mother liquor, the method takes organic tertiary amine as an extractant, and the extractant is neutralized with ammonia for extracting cystine and then is mixed with the mother liquor by avolume ratio of 1:1-1:4 accompanied by agitation, a carbon dioxide gas is input in the process, the mixture is put standing until showing an oil phase and a water phase, effluent water phase matters are separated, and a product is obtained through concentration and drying, and the oil phase matters are regenerated as the extractant by dilute lye for recycling. The composite amino acid powder product produced by the method has the ammonium chloride content being reduced to below 10 percent, the composite amino acid total content of larger than 85 percent, and can serve as a high quality feedstuff additive, and the rate of recovery of amino acid can reach above 95 percent.
Description
Technical field
The present invention relates to from producing the mother liquor desalination behind L-Gelucystine, then with desalination mother liquor production method of compound amino-acid.
Background technology
Utilizing protein production L-Gelucystine in the animal hair, is by the hair protein raw material is finished through the technology that concentrated hydrochloric acid is hydrolyzed under about 110 ℃ of temperature.In hydrolysis method, the minimum principle of solubleness when utilizing the material iso-electric point, ammonification or alkali are neutralized to the iso-electric point of Gelucystine in hydrolyzed solution, make wherein to emanate from hydrolyzed solution, again through the technology of twice dissolving, crystallization, purification, obtain L-Gelucystine crystal subsequently.In order to neutral ammonia, comprise ammonia, bicarbonate of ammonia and ammoniacal liquor.With in the ammonia and the hydrolyzed solution that extracts behind the Gelucystine be mother liquor still, it contains multiple amino acids, total amount reaches 17% usually, simultaneously, also contains and is no less than 20% chlorination ammonium salt.With 1 ton of L-Gelucystine of the every production of this technology, produce the about 30m of mother liquor
3Because ammonium salt is difficult to separate from mother liquor, thereby the mother liquor that minority producer will extract ammoniacal liquor is made waste and has directly been discharged.Both waste valuable animal protein resource, polluted environment again.
In order to reduce the formation of ammonium chloride in the Gelucystine production process, some producer once adopted concentrating under reduced pressure equipment to catch up with acid, reducing the excessive hydrogen chloride in the hydrolyzed solution, thereby reduce in the ammonia and the time ammonium salt that produces.Because hydrochloric acid at 20.22% o'clock, is its aqueous solution constant boiling point, therefore, concentrating under reduced pressure can't reach the purpose of independent disacidify, and the mother liquor behind the extraction Gelucystine still has a large amount of chlorination ammonium salts to exist.
More domestic Gelucystine manufacturing enterprise and scholars, to having extracted a large amount of the studying of utilization of the mother liquor behind the Gelucystine:
As the new source of students biotechnology in Hubei stock company take the lead in as described in mother liquor produce compound amino-acid powder by spraying drying, but because ammonium chloride content surpasses 50% in the finished product, and each seed amino acid total content only is about 40%, make the use range of product be subjected to great restriction, as a comparison the additive of the compound manure of low side.
Document (the prosperous flourish Chen Weidong Shih-chao of Jin Yanjin Europe a kind of efficiently, amino acid mother liquor desalination process " the chemical industry world " 1994) fast utilizes the amino acid characteristics that solvable and ammonium chloride can not be molten in acetate, and through twice drying, the mother liquor desalting effect can reach 95%.Yet the glacial acetic acid that this method consumption is a large amount of, and be difficult to reclaim, desalination cost height hardly may suitability for industrialized production.
Chinese patent communique (CN1144799A with the method and apparatus of preparation low-salt compound amino-acid powder by cystine mother solution) places cystine mother liquor in the crystallization case of band adsorption medium support, under-5～20 ℃ of conditions, left standstill crystallization 3～10 hours, filtrate decompression is concentrated into 20～25Be, spraying drying.This law can make the amino acid rate of recovery be higher than 90%, the chlorination ammonium salt only is 25% in the product, aminoacids content is higher than 65%, good relatively solution the cost problem in the mother liquor desalination, but the long-time step crystal desalination that leaves standstill is unfavorable for large-scale industrial production, in addition, 25% saltiness only is middle after-product, can only as fertilizer sources, can not become fodder additives (content＜10%) product.
Japanese Patent (KOD AI191567/1989 removes the method for hydrochloric acid in the hydrochloric acid hydrolysis product solution by the diffusion dialysis of ion-exchange membrane) is that the hydrolyzed solution with the hydrochloric acid hydrolysis protein raw materials is filtered, make the filtrate depickling by ion exchange membrane diffusion dialysis, neutralize with alkali then.It to a certain degree is favourable before the neutralization hydrochloric acid being removed to, but to technology and equipment requirements strictness, and saltiness is still higher in the mother liquor after the neutralization.
Summary of the invention
The present invention's purpose is to overcome above-mentioned the deficiencies in the prior art, provide a kind of for reduce in the ammonia and extract Gelucystine after mother liquor ammonium chloride content and can not cause the production method of the low-salt composite aminophenol powder of amino acid loss thus, by method of the present invention, make the compound amino-acid powder product of being produced can be used as high-quality fodder additives.
Purpose of the present invention realizes by following technical proposals:
With the trimethylamine is extraction agent, mother liquor in extraction agent and the ammonia and after extracting Gelucystine is mixed mutually with 1: 1～1: 4 volume ratio, accompany by stirring, feed carbon dioxide in the process, leave standstill mixed solution to being oil phase and water, isolate aqueous-phase material, concentrated, the dry product that gets, the oil phase thing is regenerated as extraction agent with sig water, recycles.
Know-why of the present invention is:
NH
4CL+CO
2+H
2O—→NH
4HCO
3+HCL↑
This is reflected under the normal condition is left a chemical equilibrium reaction, but if the amount by heating, change reactant or product, add means such as catalyzer, can change the Direction of Reaction of this chemical equilibrium, and reaction direction is to the right carried out.The present invention impels balance to carry out to the right by the amount that changes reactant and resultant, specifically be exactly, constantly feed carbon dioxide reactant concn is increased, utilize the ligand complex of extraction agent constantly to consume hydrogenchloride simultaneously, thereby the ammonium chloride in the mother liquor is consumed.
In the present invention---
In the described ammonia and extract mother liquor behind the Gelucystine, be protein source through hydrochloric acid hydrolysis, with in the ammonia and the mother liquor after separating Gelucystine, described mother liquor is before being extracted, through the processing of decolouring;
Trimethylamine class material in order to as extraction agent substantially all is applicable to the present invention, and best is triethylamine, Tributylamine, trioctylamine etc.;
Mix liquid and feed holding time of carbon dioxide and control with the surplus liquid ammonium of measured extraction radical ion concentration≤1%;
Drying to isolated aqueous-phase material adopts spraying drying;
The alkali that is used for regenerating extracting agent can be NaOH solution, Na
2CO
3Solution, ammoniacal liquor, its concentration can be between 1%～10%.
The advantage that the present invention is compared with prior art had is:
Applied reaction kinetics, consume ammonium chloride in the described mother liquor by extraction process, the desalination effect is remarkable, and the ammonium chloride content in the compound amino-acid powder product of producing is reduced to below 10%, Canon reduces to below 3%, the aminoacids complex total content can be used as high-quality fodder additives greater than 85%, and in separating ammonium chloride salt, aminoacids complex in the mother liquor is loss not, thereby the rate of recovery height of this method aminoacids complex reaches more than 95%.In addition, method of the present invention is produced simple, and equipment is had no special requirements, and extraction agent can be recycled, and production cost is low relatively.
Embodiment
The present invention will be described below by embodiment.Following mother liquor is all protein source through hydrochloric acid hydrolysis, with in the ammoniacal liquor with separate Gelucystine after mother liquor.
Embodiment 1 gets mother liquor 5L, recording its amino acid total content is 167.54g/L, in this mother liquor, add the 15g activated carbon decolorizing, Plate Filtration, the back mother liquor that will decolour places extraction tank to mix with the 5L triethylamine, feed carbon dioxide while stirring, up to ammonium radical ion concentration≤1% that records the surplus liquid of extraction, stop logical carbonic acid gas, stop to stir, left standstill 30 minutes, system is divided into two-layer, and the water of lower floor is the mother liquor after the extraction desalination, and the oil phase on upper strata is an extraction agent, take the aqueous-phase material mother liquor of system lower floor away by the bottom land valve, mother liquor is concentrated the back spraying drying, get compound amino acid powder 946g, the ammonium chloride salts contg 2.84% after testing, aminoacids complex total content 88.5%, amino acid almost all reclaim; Add the sodium hydroxide solution 10L of 1% concentration in remaining the extraction tank that the oil phase thing is arranged, mixed 5 minutes, standing demix is isolated water layer from the bottom land valve equally, and the oil reservoir in the groove is regeneration back extraction agent triethylamine.Can be recycled after adding mother liquor.
Embodiment 2 gets mother liquor 5L, record its amino acid total content 167.54g/L, add the 15g activated carbon decolorizing in this mother liquor, Plate Filtration places extraction tank to mix with the 2L trioctylamine filtrate, feed carbon dioxide while stirring, up to ammonium radical ion concentration≤1% that records the surplus liquid of extraction, stop logical carbonic acid gas, stop to stir, left standstill 50 minutes, system is divided into oil phase and water is two-layer, takes the water mother liquor away by the bottom land valve, and mother liquor concentrates the back spraying drying, get compound amino acid powder 953g, after testing, its ammonium chloride salts contg is 5.48%, and the aminoacids complex total content is 87.9%, the sodium carbonate solution 4L that in remaining the extraction tank that the oil phase thing is arranged, adds 10% concentration, mixed 5 minutes, standing demix separates to walk water layer from the bottom land valve, oil reservoir in the groove is the extraction agent trioctylamine after regenerating, and adds Recycling Mother Solution and uses.
Embodiment 3 gets mother liquor 5L, recording its amino acid total content is 165.07g/L, in this mother liquor, add 25 gram activated carbon decolorizings, Plate Filtration, place extraction tank to mix with the 1.25L Tributylamine in the mother liquor after the decolouring, feed carbonic acid gas while stirring,, stop to feed carbonic acid gas and stop stirring up to ammonium radical ion concentration≤1% that records the surplus liquid of extraction, left standstill 60 minutes, system is divided into oil, two layers in water, taking water layer away by the bottom land valve is mother liquor, mother liquor is through concentrating, dry, get compound amino acid powder 952g, after testing, its ammonium chloride content is 7.48%, and the aminoacids complex total content is 85.8%.The ammoniacal liquor 4L of adding 3% strips to it in remaining the extraction tank that the oil phase thing is arranged, and mixes 5 minutes, and standing demix is isolated water layer from the bottom land valve, and the oil phase thing in the groove is the extraction agent Tributylamine after the regeneration, adds Recycling Mother Solution and uses.
In order to trimethylamine as extraction agent, except that above-mentioned giving an example, substantially all be applicable to the present invention, no longer exhaustive.
Claims (6)
1. the production method of low-salt composite aminophenol powder, it is characterized in that: be extraction agent with the trimethylamine, mother liquor in extraction agent and the ammonia and after extracting Gelucystine is mixed mutually with 1: 1～1: 4 volume ratio, accompany by stirring, feed carbon dioxide in the process, leave standstill mixed solution to being oil phase and water, isolate aqueous-phase material, through concentrated, the dry product that gets, the oil phase thing is regenerated as extraction agent with sig water, recycles.
2. the production method of low-salt composite aminophenol powder according to claim 1, it is characterized in that: in the described ammonia and extract mother liquor behind the Gelucystine, be protein source through hydrochloric acid hydrolysis, with in the ammonia with separate Gelucystine after mother liquor, described mother liquor is handled through decolouring before being extracted.
3. the production method of low-salt composite aminophenol powder according to claim 1 is characterized in that: in extraction agent and the ammonia and extract that the volume ratio of mother liquor can be 1: 4 or 1: 2.5 or 1: 1 behind the Gelucystine.
4. the production method of low-salt composite aminophenol powder according to claim 1, it is characterized in that: described trimethylamine compound is triethylamine, Tributylamine, trioctylamine.
5. the production method of low-salt composite aminophenol powder according to claim 1 is characterized in that: mix liquid and feed holding time of carbon dioxide and control with ammonium radical ion concentration≤1% of the measured surplus liquid of extraction.
6. the production method of low-salt composite aminophenol powder according to claim 1, it is characterized in that: the alkali that is used for regenerating extracting agent is NaOH solution, Na
2CO
3Solution, ammoniacal liquor, its concentration is all 1%～10%.
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| CN2008101968813A CN101343194B (en) | 2008-09-04 | 2008-09-04 | Process for preparing low-salt composite aminophenol powder |
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| CN101343194B true CN101343194B (en) | 2011-06-15 |
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| CN109534857A (en) * | 2018-11-09 | 2019-03-29 | 河南正达环保科技有限公司 | Compound amino acid liquid fertilizer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104295A (en) * | 1986-06-25 | 1988-03-02 | 罗纳·布朗克化学公司 | Method separating aminoacid |
| US4912228A (en) * | 1988-08-04 | 1990-03-27 | Henkel Research Corporation | Process of extraction of amino acids from aqueous solutions thereof |
| CN1058259C (en) * | 1996-05-13 | 2000-11-08 | 冯宗宇 | Method for preparation low-salt compound amino-acid powder by cystine mother solution and its equipment |
| CN1596695A (en) * | 2004-08-04 | 2005-03-23 | 吴扬海 | Amino acid synthetic fish powder |
-
2008
- 2008-09-04 CN CN2008101968813A patent/CN101343194B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104295A (en) * | 1986-06-25 | 1988-03-02 | 罗纳·布朗克化学公司 | Method separating aminoacid |
| US4912228A (en) * | 1988-08-04 | 1990-03-27 | Henkel Research Corporation | Process of extraction of amino acids from aqueous solutions thereof |
| CN1058259C (en) * | 1996-05-13 | 2000-11-08 | 冯宗宇 | Method for preparation low-salt compound amino-acid powder by cystine mother solution and its equipment |
| CN1596695A (en) * | 2004-08-04 | 2005-03-23 | 吴扬海 | Amino acid synthetic fish powder |
Non-Patent Citations (1)
| Title |
|---|
| 杨盛坤等人.萃取脱酸法分离胱氨酸.《华东理工大学学报（自然科学版）》.2005,第三卷(第四期),535－537. * |
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