CN105837460A - Clean production process for separating and extracting glutamic acid from molasses fermented glutamic acid fermentation liquid - Google Patents
Clean production process for separating and extracting glutamic acid from molasses fermented glutamic acid fermentation liquid Download PDFInfo
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- CN105837460A CN105837460A CN201610402246.0A CN201610402246A CN105837460A CN 105837460 A CN105837460 A CN 105837460A CN 201610402246 A CN201610402246 A CN 201610402246A CN 105837460 A CN105837460 A CN 105837460A
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- glutamic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
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- 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
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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Abstract
The invention discloses a clean production process for separating and extracting glutamic acid from molasses fermented glutamic acid fermentation liquid. The fermentation liquid is purified through utilizing a stainless steel membrane and a primary nano-filtration membrane, and is concentrated through utilizing a secondary nano-filtration membrane; the fermentation liquid is subjected to two times of isoelectronic crystallization under a normal temperature condition; meanwhile, all levels of wastewater and waste dreg, which are generated in the process, are comprehensively utilized to develop byproducts including mycoprotein feed, C.M.S, organic fertilizers, chlorine-ammonium fertilizers and the like. Compared with a traditional concentration isoelectronic process, a membrane-method secondary isoelectronic process can realize huge economic benefits on the basis of no pollution and zero emission, and the clean production process has higher comprehensive utilization degree of resources.
Description
Technical field
The invention belongs to biological chemical field, carry from the separation of molasses fermented glutami acid fermentation liquor particularly to one
Take the process for cleanly preparing of glutamic acid.
Background technology
The extracting method of prior art Glutamic Acid has the electrical methods such as low temperature, ion exchange, slaine method, salt
The electrical methods such as acid hydrolysis isoelectric point method, concentration.
Wherein, the electrical method such as low temperature is the isoelectric point, IP that fermentating liquid acidification is adjusted to glutamic acid, makes the dissolving of glutamic acid
Degree reduces, thus Precipitation, crystallization yield can generally achieve more than 75%, if using the electrical methods such as low temperature
(10 DEG C), then yield can reach 80%.
Ion exchange is that fermentation liquid is diluted to finite concentration, then with acid fermentation liquid is adjusted to isoelectric point, IP with
Under, use cationic exchange resin adsorption glutamic acid, then with eluant (typically ammonia) by glutamic acid
Elute from resin, reach to concentrate the purpose purified.Use this method to extract, usual yield up to 90%,
But soda acid consumption is big.Current domestic nearly all producer all employings etc. ionize skill of handing over, will fermentation liquid
After isoelectric point crystallization, mother solution continuation acid is adjusted to pH1.7, then adsorbs also with storng-acid cation exchange resin
Using ammonia eluting, total recovery is up to 96%.But this method soda acid consumption is big, wastewater flow rate big, waits ionization to hand over
The waste water that skill produces is difficult to biochemical treatment, and a large amount of scientific workers do in a monosodium glutamate wastewater treatment difficult problem in recent years
Numerous studies, but be also only capable of administering produce in the skill of handing in, low-concentration organic waste water, or only
Resting on the experimental stage, do not have industrialization case, therefore, problem of environmental pollution is the most serious.
Slaine method is often referred to zincate process, utilizes glutamic acid and zinc ion action, generates the paddy ammonia being insoluble in water
Hydrochlorate Precipitation, is decomposed at sour environment Glutamic Acid slaine, and when pH2.4, glutamic acid is tied again
Partial crystallization goes out, thus reaches isolated and purified purpose.This method yield up to about 85%, but due to heavy metal from
The pollution problem of son, this method is not widely used.
In hydrochloric acid hydrolysis isoelectric point method, in fermentation liquid in addition to containing glutamic acid, still there is a certain amount of glutamy
Amine, pyroglutamic acid and tropina.The methods such as these material isoelectric point methods, ion exchange and the sedimentation method
It is irretrievable.Fermentation liquor uses hydrochloric acid to hydrolyze this part glutamic acid recyclable after concentrating.But, adopt
The highest to equipment requirements by this method, hydrolysis simultaneously can produce a large amount of miscellaneous aminoacid, is unfavorable for further
Purification.
In the electrical methods such as concentration, fermentation liquor concentrate after acid adjustment isoelectric point crystallization again, after crystallization, mother solution direct fertilizer is not
Being recycled, use this method, yield can reach 80-90% according to fermentation liquid character difference.Use this method
Wait ionization to hand over a large amount of high concentrations and organic wastewater with medium-low concentration produced by skill, be to compare environmental protection
Production technology, external producer this method of many employings.
But, using Sugar cane molasses is that raw material ferments, if the ionization such as employing is handed over, skill produces,
One, due in fermentation liquid impurity content higher, during the electricity such as low temperature, crystallization yield is difficult to ensure；Two,
When crystalline mother solution cationic resin adsorbs, resin is easily poisoned, thus causes resin replacement frequent；Three,
The waste water that the high concentrated organic wastewater produced all produces than starch material fermentation liquid from pigment or COD
Height, therefore, Wei Dan company can only use the galvanic process such as concentration to extract glutamic acid.Although the galvanic process energy such as concentration
Fundamentally solve pollution problem, but extract yield is low, energy consumption is high, serious waste of resources is following
There is serious shortcomings in several aspects:
1, rearing crystal time is long, owing to the impurity content in fermentation liquid is high, after fermentation liquid concentrates 2.5 3 times,
Total solids content in concentrated broth has reached more than 75%.It then becomes necessary to significant period of time is foster
Brilliant guarantee forms the crystal of comparatively robust, thus guarantee is brilliant during crystal separates with mother solution
Physical ability is than separating from mother solution more smoothly.It addition, during washing at four times, crystal is sufficiently solid also
Can guarantee that the bran acid being dissolved in washing water is the fewest.But due to rearing crystal time long (720 hours), a side
Face can cause production risk too high, and once-through operation error is likely to cause the crystal solution of 30 batches and is contaminated；
On the other hand overlong time is likely to cause product because various unknown causes are lost.
2, crystal separates difficulty, and owing to crystalline mother solution solid content is too high, the separation of crystal and mother solution is very
Difficulty, is calculated by the production scale producing ten thousand tons of bran acid per year, needs the horizontal spiral formula centrifuge 48 of 40KW altogether
Platform, centrifuge energy consumption is the hugest.
3, crystal purity is low, crystallization obtain bran acid crystal purity low, only 80%, needs four times wash,
Twice turn of crystalline substance just can obtain up-to-standard bran acid crystal, and this not only can cause product to lose, and also can bring huge
Big energy resource consumption and the soda acid wasting of resources.
4, crystallization yield is low, and due to impurity content height, rearing crystal time length, washing times are many even also needs to two
Secondary turn of crystalline substance, therefore, the crystallization yield of bran acid is low, and only 84%.
5, comprehensive utilization of resources degree is low, and tropina, caramel color and other Organic substance in fermentation liquid is
Process as polluter as being blended in crystalline mother solution eventually.
In view of as above reason, it is necessary to research is a kind of from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid
Process for cleanly preparing, to solve problems of the prior art.
Summary of the invention
Complete the present invention in view of at least one the problems referred to above, and it is an object of the present invention to carry
For a kind of process for cleanly preparing from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid, it is characterised in that
Comprise the following steps:
Heat molasses fermented glutami acid fermentation liquor；
Micro-filtration membrane is used described fermentation liquid to be filtered and adds water dialysis, it is thus achieved that the first filtrate and first retains
Liquid；
Carry out the first trapped fluid being spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；
First order nanofiltration membrane the first filtrate is used to obtain the second filtrate and the second trapped fluid；
Second trapped fluid obtains side-product through evaporation and concentration and concentrates Mel fermentation liquid C.M.S.；
Second level nanofiltration membrane the second filtrate is used to obtain the 3rd filtrate and the 3rd trapped fluid, the 3rd filtrate
It is used for dialysing as aforementioned water；
Use hydrochloric acid to adjust the pH value of the 3rd trapped fluid, isoelectric point crystallization, and use tripod pendulum type batch centrifugal centrifugation
Obtain the first glutamic acid crystal and the first crystalline mother solution；
Use liquefied ammonia to adjust the pH value of the first crystalline mother solution, then use third level NF membrane to carry out filtering acquisition
4th filtrate and the 4th trapped fluid；
4th filtrate is highly purified ammonium chloride solution, obtains side-product after using evaporation and concentration, crystallizing and drying
Ammonium chloride fertilizer；
4th trapped fluid uses hydrochloric acid to adjust pH value, isoelectric point crystallization, then uses tripod pendulum type batch centrifugal centrifugation
Obtain the second glutamic acid crystal and the second crystalline mother solution；
Second crystalline mother solution uses evaporation and concentration to obtain rich in glutamic acid, the side-product liquid fertilizer of ammonium chloride；
Wherein, the first glutamic acid crystal and the merging of the second glutamic acid crystal are used for converting sodium glutamate.
According to a further aspect of the invention, using hydrochloric acid to adjust the 3rd trapped fluid pH value is 3-4, and the 4th section
Staying liquid to use hydrochloric acid to adjust pH value is 3-4.
According to a further aspect of the invention, the pH value using liquefied ammonia to adjust the first crystalline mother solution is 5-6.
According to a further aspect of the invention, micro-filtration membrane is ceramic membrane or the stainless steel membrane of tubular structure, its supporting layer
Material is Al2O3, or rustless steel, film layer material is rutile TiO2, or α-Al2O3, its pore size filter is
20-200nm。
According to a further aspect of the invention, first order NF membrane is the polymeric membrane of wound module mode, and it retains
Molecular weight is 300-400D, and it is 80-90% to the rejection of magnesium sulfate, and its temperature tolerance range is 5-60 DEG C.
According to a further aspect of the invention, micro-filtration membrane thoroughly eliminates solid suspension, and the second trapped fluid uses three
Effect evaporation and concentration, to solids content 60%, does not has solid deposits to separate out after 10 days stand.
According to a further aspect of the invention, second and polymeric membrane that third level NF membrane is wound module mode,
Its molecular cut off is 100-200D, and it is 96-99% to the rejection of magnesium sulfate, and its temperature tolerance range is
5-45℃。
According to a further aspect of the invention, using hydrochloric acid to adjust the 3rd trapped fluid pH value is 3.2, and the 4th section
Staying liquid to use hydrochloric acid to adjust pH value is 3.2.
According to a further aspect of the invention, the pH value using liquefied ammonia to adjust the first crystalline mother solution is 5.5.
Compared with prior art, the beneficial effects of the present invention is: the present invention utilizes stainless steel membrane and one-level to receive
Filter membrane purified fermentation broth, utilizes two grades of NF membrane to concentrate, and carries out two inferior electricity knots under normal temperature condition
Crystalline substance, meanwhile, comprehensively utilizes waste water at different levels, the waste residue produced in technique, have developed tropina
The side-products such as feedstuff, C.M.S, fertilizer, oronain fertilizer.Extracting glutamic acid total recovery >=96%, with tradition
Technique is compared not only extracting glutamic acid yield and is promoted more than 12%, and water consumption, power consumption, energy consumption are greatly lowered,
Compared with the galvanic process such as tradition concentration, use the inferior galvanic process of embrane method two at the base of " pollution-free, zero-emission "
On plinth, it is possible to achieve great economic benefit, it it is the higher process for cleanly preparing of comprehensive utilization of resources degree.
Accompanying drawing explanation
Fig. 1 is according to the preferred embodiment of the invention from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid
Process for cleanly preparing flow chart.
Detailed description of the invention
Below in conjunction with the accompanying drawings, the preferred forms of the present invention, tool here are described by preferred embodiment
Body embodiment is to explain the present invention, and should not be construed as limitation of the present invention, without departing from
In the case of spirit and substance of the present invention scope, can make various changes and modifications, these all should comprise
Within protection scope of the present invention.
Seeing Fig. 1, the preferred embodiment of the present invention provides a kind of from molasses fermented glutami acid fermentation liquor separation and Extraction
The process for cleanly preparing of glutamic acid.Should be raw from the cleaning of molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid
Production. art comprises the following steps:
Heat molasses fermented glutami acid fermentation liquor；
Micro-filtration membrane is used described fermentation liquid to be filtered and adds water dialysis, it is thus achieved that the first filtrate and first retains
Liquid；
Carry out the first trapped fluid being spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；
First order nanofiltration membrane the first filtrate is used to obtain the second filtrate and the second trapped fluid；
Second trapped fluid obtains side-product through evaporation and concentration and concentrates Mel fermentation liquid C.M.S.；
Second level nanofiltration membrane the second filtrate is used to obtain the 3rd filtrate and the 3rd trapped fluid, the 3rd filtrate
It is used for dialysing as aforementioned water；
Use hydrochloric acid to adjust the pH value of the 3rd trapped fluid, isoelectric point crystallization, and use tripod pendulum type batch centrifugal centrifugation
Obtain the first glutamic acid crystal and the first crystalline mother solution；
Use liquefied ammonia to adjust the pH value of the first crystalline mother solution, then use third level NF membrane to carry out filtering acquisition
4th filtrate and the 4th trapped fluid；
4th filtrate is highly purified ammonium chloride solution, obtains side-product after using evaporation and concentration, crystallizing and drying
Ammonium chloride fertilizer；
4th trapped fluid uses hydrochloric acid to adjust pH value, isoelectric point crystallization, then uses tripod pendulum type batch centrifugal centrifugation
Obtain the second glutamic acid crystal and the second crystalline mother solution；
Second crystalline mother solution uses evaporation and concentration to obtain rich in glutamic acid, the side-product liquid fertilizer of ammonium chloride；
Wherein, the first glutamic acid crystal and the merging of the second glutamic acid crystal are used for converting sodium glutamate.
Preferably, using hydrochloric acid to adjust the 3rd trapped fluid pH value is 3-4, and the 4th trapped fluid uses hydrochloric acid
Adjustment pH value is 3-4.
Preferably, the pH value using liquefied ammonia to adjust the first crystalline mother solution is 5-6.
Preferably, micro-filtration membrane is ceramic membrane or the stainless steel membrane of tubular structure, and its supporting layer material is Al2O3,
Or rustless steel, film layer material is rutile TiO2, or α-Al2O3, its pore size filter is 20-200nm.
Preferably, first order NF membrane is the polymeric membrane of wound module mode, and its molecular cut off is
300-400D, it is 80-90% to the rejection of magnesium sulfate, and its temperature tolerance range is 5-60 DEG C.
Preferably, micro-filtration membrane thoroughly eliminates solid suspension, and the second trapped fluid uses three-effect evaporation and condensation extremely
Solids content 60%, does not has solid deposits to separate out after 10 days stand.
Preferably, second and polymeric membrane that third level NF membrane is wound module mode, its molecular cut off
For 100-200D, it is 96-99% to the rejection of magnesium sulfate, and its temperature tolerance range is 5-45 DEG C.
Preferably, using hydrochloric acid to adjust the 3rd trapped fluid pH value is 3.2, and the 4th trapped fluid uses hydrochloric acid
Adjusting pH value is 3.2.
Preferably, the pH value using liquefied ammonia to adjust the first crystalline mother solution is 5.5.
Visible, the present invention is directed to the drawback of the electricity production technologies such as molasses fermented glutamic acid concentration, fundamentally change
Make extracting glutamic acid technology, it is provided that a kind of high yield, low cost, low energy consumption, comprehensive utilization of resources, technique
The most controlled, the high efficiency process for cleanly preparing of Low investment.
Preferably, present invention also offers a kind of separation and Extraction paddy ammonia from molasses fermented glutami acid fermentation liquor
The process for cleanly preparing of acid, comprises the following steps:
A, molasses fermented glutami acid fermentation liquor, after fermenting-ripening, put keep during tank fermentation tank is ventilated,
The conditions such as stirring, tank temperature are constant, and fermentation liquid uses steam injection heating in putting tank pipeline, instantaneous reaches
Fermentation liquid after heating enters micro-filtration membrane head tank, and heat treatment yield is more than 99.5%；
B, the sterilization fermentation liquid of step a gained, use micro-filtration membrane to carry out clarification filtration, and the dialysis that adds water, obtain
Obtain filtrate 1 and trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 0-10bar, and micro-filtrate membrane filtration concentrates
Multiple is 4-10 times, and water-dialyzing addition is 3-5 times of trapped fluid 1 volume, filters yield more than 99%；
C, the trapped fluid 1 of step b gained use to be spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；Retain
Total solids content >=18% in liquid 1, protein content (butt) >=50%, after being spray-dried, obtain by-product
Product list animal feeding-stuff containing somatic protein；
D, the filtrate 1 of step b gained, after using plate type heat exchanger cooling, use one-level nanofiltration membrane to obtain
Obtain filtrate 2 and trapped fluid 2；Filtration temperature is 40-60 DEG C, filter pressure 0-42bar, filters yield and is more than
99%；
E, the trapped fluid 2 of step d gained, be concentrated into solids content 60% through multiple-effect evaporation, it is thus achieved that side-product
C.M.S.。
F, the filtrate 2 of step d gained, after plate type heat exchanger cools down, use two grades of nanofiltration membrane to obtain
Filtrate 3 and trapped fluid 3；Filtration temperature is 20-45 DEG C, filter pressure 0-42bar, owing to filtrate is applied mechanically,
This unit does not has yield losses；
G, the filtrate 3 of step f gained, set is used step a and is used as water-dialyzing；
H, the trapped fluid 3 of step f gained, use hydrochloric acid to be adjusted to glutamic acid isoelectric pH 3.2, waits electricity knot
Crystalline substance, and use tripod pendulum type batch centrifugal centrifugation to obtain glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield
Reach 85-90%；
The crystalline mother solution 1 that i, step h obtain uses liquefied ammonia to be adjusted to pH5.5, then uses three grades of NF membrane
Carry out filtering and obtain filtrate 4 and trapped fluid 4；Filtration temperature is 20-45 DEG C, filter pressure 0-42bar；Cross
Filter yield >=99.5%；
The filtrate 4 that j, step i obtain is highly purified ammonium chloride solution, uses evaporation and concentration, crystallizing and drying
Rear acquisition side-product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i obtain, uses hydrochloric acid to be adjusted to pH3.2, isoelectric point crystallization, then uses
Tripod pendulum type batch centrifugal centrifugation obtains glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches
85-90%；
The crystalline mother solution 2 that l, step k obtain uses evaporation and concentration to obtain rich in glutamic acid, the by-product of ammonium chloride
Product liquid fertilizer；
Glutamic acid crystal 1 that m, step h and step k obtain and glutamic acid crystal are 2-in-1 and be used for converting paddy ammonia
Acid sodium (monosodium glutamate), extracting glutamic acid total recovery >=96%, glutamic acid gives money as a gift purity >=98.5%, moisture
10-18%, calcium ion 20-40ppm, oxalate denominationby 15-30ppm, chloride ion 100-300ppm, sulfate radical
10-30ppm。
Preferably, present invention also offers a kind of separation and Extraction paddy ammonia from molasses fermented glutami acid fermentation liquor
The process for cleanly preparing of acid, wherein, the glutamic acid maturing fermentation liquid with molasses as raw material, use following steps
Process:
A, molasses fermented glutami acid fermentation liquor, after fermenting-ripening, put keep during tank fermentation tank is ventilated,
The conditions such as stirring, tank temperature are constant, and fermentation liquid uses steam injection heating in putting tank pipeline, instantaneous reaches
Fermentation liquid after heating enters micro-filtration membrane head tank, and heat treatment yield is 99.6%；
B, the sterilization fermentation liquid of step a gained, use micro-filtration membrane to carry out clarification filtration, and the dialysis that adds water, obtain
Obtain filtrate 1 and trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 5bar, and micro-filtrate membrane filtration concentrates again
Number is 8 times, and water-dialyzing addition is 3.7 times of trapped fluid 1 volume, filters yield 99.1%；
C, the trapped fluid 1 of step b gained use to be spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；Retain
Total solids content 20% in liquid 1, protein content (butt) 55%, after being spray-dried, obtain side-product list
Animal feeding-stuff containing somatic protein；
D, the filtrate 1 of step b gained, after using plate type heat exchanger cooling, use one-level nanofiltration membrane to obtain
Obtain filtrate 2 and trapped fluid 2；Filtration temperature is 53 DEG C, filter pressure 31bar, and filtering yield is 99.1%；
E, the trapped fluid 2 of step d gained, be concentrated into solids content 60% through multiple-effect evaporation, it is thus achieved that side-product
C.M.S.。
F, the filtrate 2 of step d gained, after plate type heat exchanger cools down, use two grades of nanofiltration membrane to obtain
Filtrate 3 and trapped fluid 3；Filtration temperature is 37 DEG C, filter pressure 33bar, owing to filtrate is applied mechanically, and this unit
There is no yield losses；
G, the filtrate 3 of step f gained, set is used step a and is used as water-dialyzing；
H, the trapped fluid 3 of step f gained, use hydrochloric acid to be adjusted to glutamic acid isoelectric pH 3.2, waits electricity knot
Crystalline substance, and use tripod pendulum type batch centrifugal centrifugation to obtain glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield
Reach 87%；
The crystalline mother solution 1 that i, step h obtain uses liquefied ammonia to be adjusted to pH5.5, then uses three grades of NF membrane
Carry out filtering and obtain filtrate 4 and trapped fluid 4；Filtration temperature is 22 DEG C, filter pressure 32bar；Filter yield
99.6%；
The filtrate 4 that j, step i obtain is highly purified ammonium chloride solution, uses evaporation and concentration, crystallizing and drying
Rear acquisition side-product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i obtain, uses hydrochloric acid to be adjusted to pH3.2, isoelectric point crystallization, then uses
Tripod pendulum type batch centrifugal centrifugation obtains glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 88%；
The crystalline mother solution 2 that l, step k obtain uses evaporation and concentration to obtain rich in glutamic acid, the by-product of ammonium chloride
Product liquid fertilizer；
Glutamic acid crystal 1 that m, step h and step k obtain and glutamic acid crystal are 2-in-1 and be used for converting paddy ammonia
Acid sodium (monosodium glutamate), extracting glutamic acid total recovery is 96.3%, and glutamic acid crystal is given money as a gift purity 98.5%, moisture
Content 15%, calcium ion 30ppm, oxalate denominationby 20ppm, chloride ion 200ppm, sulfate radical 20ppm.
Preferably, present invention also offers a kind of separation and Extraction paddy ammonia from molasses fermented glutami acid fermentation liquor
The process for cleanly preparing of acid, wherein, the glutamic acid maturing fermentation liquid with molasses as raw material, use following steps
Process:
A, molasses fermented glutami acid fermentation liquor, after fermenting-ripening, put keep during tank fermentation tank is ventilated,
The conditions such as stirring, tank temperature are constant, and fermentation liquid uses steam injection heating in putting tank pipeline, instantaneous reaches
Fermentation liquid after heating enters micro-filtration membrane head tank, and heat treatment yield is 99.5%；
B, the sterilization fermentation liquid of step a gained, use micro-filtration membrane to carry out clarification filtration, and the dialysis that adds water, obtain
Obtain filtrate 1 and trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 7bar, and micro-filtrate membrane filtration concentrates again
Number is 9 times, and water-dialyzing addition is 4 times of trapped fluid 1 volume, filters yield 99.3%；
C, the trapped fluid 1 of step b gained use to be spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；Retain
Total solids content 23% in liquid 1, protein content (butt) 52%, after being spray-dried, obtain side-product list
Animal feeding-stuff containing somatic protein；
D, the filtrate 1 of step b gained, after using plate type heat exchanger cooling, use one-level nanofiltration membrane to obtain
Obtain filtrate 2 and trapped fluid 2；Filtration temperature is 55 DEG C, filter pressure 32bar, and filtering yield is 99.2%；
E, the trapped fluid 2 of step d gained, be concentrated into solids content 60% through multiple-effect evaporation, it is thus achieved that side-product
C.M.S.。
F, the filtrate 2 of step d gained, after plate type heat exchanger cools down, use two grades of nanofiltration membrane to obtain
Filtrate 3 and trapped fluid 3；Filtration temperature is 37 DEG C, filter pressure 36bar, owing to filtrate is applied mechanically, and this unit
There is no yield losses；
G, the filtrate 3 of step f gained, set is used step a and is used as water-dialyzing；
H, the trapped fluid 3 of step f gained, use hydrochloric acid to be adjusted to glutamic acid isoelectric pH 3.2, waits electricity knot
Crystalline substance, and use tripod pendulum type batch centrifugal centrifugation to obtain glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield
Reach 86%；
The crystalline mother solution 1 that i, step h obtain uses liquefied ammonia to be adjusted to pH5.5, then uses three grades of NF membrane
Carry out filtering and obtain filtrate 4 and trapped fluid 4；Filtration temperature is 22 DEG C, filter pressure 32bar；Filter yield
99.7%；
The filtrate 4 that j, step i obtain is highly purified ammonium chloride solution, uses evaporation and concentration, crystallizing and drying
Rear acquisition side-product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i obtain, uses hydrochloric acid to be adjusted to pH3.2, isoelectric point crystallization, then uses
Tripod pendulum type batch centrifugal centrifugation obtains glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 89%；
The crystalline mother solution 2 that l, step k obtain uses evaporation and concentration to obtain rich in glutamic acid, the by-product of ammonium chloride
Product liquid fertilizer；
Glutamic acid crystal 1 that m, step h and step k obtain and glutamic acid crystal are 2-in-1 and be used for converting paddy ammonia
Acid sodium (monosodium glutamate), extracting glutamic acid total recovery is 96.2%, and glutamic acid crystal is given money as a gift purity 98.6%, moisture
Content 14%, calcium ion 28ppm, oxalate denominationby 19ppm, chloride ion 190ppm, sulfate radical 18ppm.
Preferably, present invention also offers a kind of separation and Extraction paddy ammonia from molasses fermented glutami acid fermentation liquor
The process for cleanly preparing of acid, wherein, the glutamic acid maturing fermentation liquid with molasses as raw material, use following steps
Process:
A, molasses fermented glutami acid fermentation liquor, after fermenting-ripening, put keep during tank fermentation tank is ventilated,
The conditions such as stirring, tank temperature are constant, and fermentation liquid uses steam injection heating in putting tank pipeline, instantaneous reaches
Fermentation liquid after heating enters micro-filtration membrane head tank, and heat treatment yield is 99.7%；
B, the sterilization fermentation liquid of step a gained, use micro-filtration membrane to carry out clarification filtration, and the dialysis that adds water, obtain
Obtain filtrate 1 and trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 9bar, and micro-filtrate membrane filtration concentrates again
Number is 10 times, and water-dialyzing addition is 5 times of trapped fluid 1 volume, filters yield 99.7%；
C, the trapped fluid 1 of step b gained use to be spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；Retain
Total solids content 22% in liquid 1, protein content (butt) 53%, after being spray-dried, obtain side-product list
Animal feeding-stuff containing somatic protein；
D, the filtrate 1 of step b gained, after using plate type heat exchanger cooling, use one-level nanofiltration membrane to obtain
Obtain filtrate 2 and trapped fluid 2；Filtration temperature is 56 DEG C, filter pressure 37bar, and filtering yield is 99.3%；
E, the trapped fluid 2 of step d gained, be concentrated into solids content 60% through multiple-effect evaporation, it is thus achieved that side-product
C.M.S.。
F, the filtrate 2 of step d gained, after plate type heat exchanger cools down, use two grades of nanofiltration membrane to obtain
Filtrate 3 and trapped fluid 3；Filtration temperature is 39 DEG C, filter pressure 35bar, owing to filtrate is applied mechanically, and this unit
There is no yield losses；
G, the filtrate 3 of step f gained, set is used step a and is used as water-dialyzing；
H, the trapped fluid 3 of step f gained, use hydrochloric acid to be adjusted to glutamic acid isoelectric pH 3.2, waits electricity knot
Crystalline substance, and use tripod pendulum type batch centrifugal centrifugation to obtain glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield
Reach 89%；
The crystalline mother solution 1 that i, step h obtain uses liquefied ammonia to be adjusted to pH5.5, then uses three grades of NF membrane
Carry out filtering and obtain filtrate 4 and trapped fluid 4；Filtration temperature is 20 DEG C, filter pressure 30bar；Filter yield
99.6%；
The filtrate 4 that j, step i obtain is highly purified ammonium chloride solution, uses evaporation and concentration, crystallizing and drying
Rear acquisition side-product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i obtain, uses hydrochloric acid to be adjusted to pH3.2, isoelectric point crystallization, then uses
Tripod pendulum type batch centrifugal centrifugation obtains glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 85%；
The crystalline mother solution 2 that l, step k obtain uses evaporation and concentration to obtain rich in glutamic acid, the by-product of ammonium chloride
Product liquid fertilizer；
Glutamic acid crystal 1 that m, step h and step k obtain and glutamic acid crystal are 2-in-1 and be used for converting paddy ammonia
Acid sodium (monosodium glutamate), extracting glutamic acid total recovery is 96.7%, and glutamic acid crystal is given money as a gift purity 98.7%, moisture
Content 12%, calcium ion 25ppm, oxalate denominationby 17ppm, chloride ion 160ppm, sulfate radical 15ppm.
Preferably, present invention also offers a kind of separation and Extraction paddy ammonia from molasses fermented glutami acid fermentation liquor
The process for cleanly preparing of acid, comprises the following steps:
Molasses fermented glutami acid fermentation liquor, after fermenting-ripening, put keep during tank fermentation tank is ventilated,
The conditions such as stirring, tank temperature are constant, and fermentation liquid uses steam injection heating in putting tank pipeline, instantaneous reaches
Fermentation liquid after heating enters micro-filtration membrane head tank；
The sterilization fermentation liquid of step a gained, uses micro-filtration membrane to carry out clarification filtration, and the dialysis that adds water, it is thus achieved that
Filtrate 1 and trapped fluid 1；
The trapped fluid 1 of step b gained uses to be spray-dried and obtains side-product list animal feeding-stuff containing somatic protein；
The filtrate 1 of step b gained, uses one-level nanofiltration membrane to obtain filtrate 2 and trapped fluid 2；
The trapped fluid 2 of step d gained, is concentrated into solids content 60% through multiple-effect evaporation, it is thus achieved that side-product
C.M.S.。
The filtrate 2 of step d gained, uses two grades of nanofiltration membrane to obtain filtrate 3 and trapped fluid 3；
The filtrate 3 of step f gained, set is used step a and is used as water-dialyzing；
The trapped fluid 3 of step f gained, uses hydrochloric acid to be adjusted to glutamic acid isoelectric pH 3.2, isoelectric point crystallization,
And use tripod pendulum type batch centrifugal centrifugation to obtain glutamic acid crystal 1 and crystalline mother solution 1；
The crystalline mother solution 1 that step h obtains uses liquefied ammonia to be adjusted to pH5.5, then uses three grades of NF membrane to carry out
Filter and obtain filtrate 4 and trapped fluid 4；
The filtrate 4 that step i obtains is highly purified ammonium chloride solution, after using evaporation and concentration, crystallizing and drying
Obtain side-product ammonium chloride fertilizer；
The trapped fluid 4 that step i obtains, uses hydrochloric acid to be adjusted to pH3.2, isoelectric point crystallization, then uses tripodia
Centrifuge separates and obtains glutamic acid crystal 2 and crystalline mother solution 2；
The crystalline mother solution 2 that step k obtains uses evaporation and concentration to obtain rich in glutamic acid, the side-product of ammonium chloride
Liquid fertilizer；
Glutamic acid crystal 1 that step h and step k obtain and glutamic acid crystal are 2-in-1 and be used for converting glutamic acid
Sodium (monosodium glutamate).
Preferably, the molasses fermented glutami acid fermentation liquor described in step a, after fermenting-ripening, put tank process
Middle holding fermentation tank ventilated, stir, the condition such as tank temperature constant, to ensure the activity of thalline in fermentation tank,
The glutamic acid loss that the bacterial metabolism disorder that minimizing temperature-rise period brings causes, fermentation liquid is adopted in putting tank pipeline
With steam injection heating, instantaneous reachThe enzyme of thalline and thalline secretion inactivates in very short time, heating
After fermentation liquid enter micro-filtration membrane head tank.
Preferably, the micro-filtration membrane described in step b, for ceramic membrane or the stainless steel membrane of tubular structure, it supports
Layer material is Al2O3, or rustless steel, film layer material is rutile TiO2, or α-Al2O3, its pore size filter is
20nm-200nm。
Preferably, rich in tropina and aminoacid in the trapped fluid 1 described in step c, through being spray-dried
After can be as side-product list animal feeding-stuff containing somatic protein.
Preferably, the polymeric membrane that one-level NF membrane is wound module mode described in step d, it retains point
Son amount is 300-400D, and it is 80-90% to the rejection of magnesium sulfate, and its temperature tolerance range is 5-60 DEG C；
Preferably, the trapped fluid 2 described in step e, it is concentrated into solids content 60% through multiple-effect evaporation, it is thus achieved that secondary
Products C .M.S..C.M.S. being to make with fermentable with molasses for raw material, it is except original containing molasses
Nutritional labeling and excellent flavor outside, more had more the protein synthesized in sweat, ammonia by Institute of Micro-biology
Base acid, organic acid, vitamin and ferment cofactor, be a kind of feed additive with high nutritive value.
This product is applied not only to animal husbandry: milk cattle, barren sow, laying hen, broiler；Aquatic products industry: the feedstuff of fish and shrimp etc. adds
Add agent, it is also possible to part substitutes higher-priced protein feeds raw material, simultaneously because needed for this product has plant
Nitrogen, phosphorus, three kinds of trace element of potassic fertilizer and the low molecule organic nutrition easily absorbed by plant
Composition, has the effect promoting plant growth, it is also possible to be used for allocating liquid state organic fertilizer or add solid-state fertile
In material.Step b uses micro-filtration membrane thoroughly to eliminate solid suspension, and trapped fluid 2 uses three-effect evaporation and condensation
To solids content 60%, not having solid deposits to separate out after 10 days stand, this has broken European C.M.S.
Technology barriers.
Preferably, two grades of NF membrane described in step f are the polymeric membrane of wound module mode, and it retains molecule
Amount is 100-200D, and it is 96-99% to the rejection of magnesium sulfate, and its temperature tolerance range is 5-45 DEG C.
Preferably, the polymeric membrane that three grades of NF membrane are wound module mode described in step i, it retains point
Son amount is 100-200D, and it is 96-99% to the rejection of magnesium sulfate, 5-45 DEG C.
Preferably, the filtrate 4 rich in high-purity ammonium chloride described in step j is permissible through crystallization and evaporation process
Obtain ammonium chloride side-product.
Preferably, the crystalline mother solution 2 rich in glutamic acid and ammonium chloride described in step l is dense through multiple-effect evaporation
Side-product liquid fertilizer can be obtained after contracting.
In sum, the beneficial effects of the present invention is: the present invention utilizes stainless steel membrane and one-level NF membrane pure
Change fermentation liquid, utilize two grades of NF membrane to concentrate, and under normal temperature condition, carry out twice isoelectric point crystallization, with
Time, in technique produce waste water at different levels, waste residue comprehensively utilize, have developed animal feeding-stuff containing somatic protein,
The side-products such as C.M.S, fertilizer, oronain fertilizer.Compared with the galvanic process such as tradition concentration, use embrane method secondary
Etc. galvanic process on the basis of " pollution-free, zero-emission ", it is possible to achieve great economic benefit, it is that resource is combined
Close the higher process for cleanly preparing of producing level.
The invention is not restricted to above-mentioned specific embodiment.It is understood that without departing from the present invention spirit and
In the case of essential scope, can make various changes and modifications, these all should be included in the protection of the present invention
Within the scope of.
Claims (9)
1. from a process for cleanly preparing for molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid, its feature
It is, comprises the following steps:
Heat molasses fermented glutami acid fermentation liquor；
Micro-filtration membrane is used described fermentation liquid to be filtered and adds water dialysis, it is thus achieved that the first filtrate and first retains
Liquid；
Carry out the first trapped fluid being spray-dried and obtain side-product list animal feeding-stuff containing somatic protein；
First order nanofiltration membrane the first filtrate is used to obtain the second filtrate and the second trapped fluid；
Second trapped fluid obtains side-product through evaporation and concentration and concentrates Mel fermentation liquid C.M.S.；
Second level nanofiltration membrane the second filtrate is used to obtain the 3rd filtrate and the 3rd trapped fluid, the 3rd filtrate
It is used for dialysing as aforementioned water；
Use hydrochloric acid to adjust the pH value of the 3rd trapped fluid, isoelectric point crystallization, and use tripod pendulum type batch centrifugal centrifugation
Obtain the first glutamic acid crystal and the first crystalline mother solution；
Use liquefied ammonia to adjust the pH value of the first crystalline mother solution, then use third level NF membrane to carry out filtering acquisition
4th filtrate and the 4th trapped fluid；
4th filtrate is highly purified ammonium chloride solution, obtains side-product after using evaporation and concentration, crystallizing and drying
Ammonium chloride fertilizer；
4th trapped fluid uses hydrochloric acid to adjust pH value, isoelectric point crystallization, then uses tripod pendulum type batch centrifugal centrifugation
Obtain the second glutamic acid crystal and the second crystalline mother solution；
Second crystalline mother solution uses evaporation and concentration to obtain rich in glutamic acid, the side-product liquid fertilizer of ammonium chloride；
Wherein, the first glutamic acid crystal and the merging of the second glutamic acid crystal are used for converting sodium glutamate.
Technique the most according to claim 1, it is characterised in that employing hydrochloric acid adjusts the 3rd trapped fluid pH value and is
3-4, and the 4th trapped fluid use hydrochloric acid adjust pH value be 3-4.
Technique the most according to claim 2, it is characterised in that use liquefied ammonia to adjust the pH of the first crystalline mother solution
Value is 5-6.
4. according to the technique described in any one of claim 1-3, it is characterised in that micro-filtration membrane is the pottery of tubular structure
Porcelain film or stainless steel membrane, its supporting layer material is Al2O3, or rustless steel, film layer material is rutile TiO2, or α
-Al2O3, its pore size filter is 20-200nm.
Technique the most according to claim 4, it is characterised in that first order NF membrane is wound module mode
Polymeric membrane, its molecular cut off is 300-400D, and it is 80-90% to the rejection of magnesium sulfate, its temperature
Tolerance range is 5-60 DEG C.
Technique the most according to claim 4, it is characterised in that micro-filtration membrane thoroughly eliminates solid suspension,
Second trapped fluid uses three-effect evaporation and condensation to solids content 60%, does not has solid matter to sink after 10 days stand
Precipitation goes out.
Technique the most according to claim 5, it is characterised in that second and third level NF membrane be wound module
The polymeric membrane of mode, its molecular cut off is 100-200D, and it is 96-99% to the rejection of magnesium sulfate,
Its temperature tolerance range is 5-45 DEG C.
Technique the most according to claim 5, it is characterised in that employing hydrochloric acid adjusts the 3rd trapped fluid pH value and is
3.2, and the 4th trapped fluid use hydrochloric acid adjust pH value be 3.2.
Technique the most according to claim 5, it is characterised in that use liquefied ammonia to adjust the pH of the first crystalline mother solution
Value is 5.5.
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| CN107223772A (en) * | 2017-05-10 | 2017-10-03 | 通辽梅花生物科技有限公司 | New high protein mixed feed and its production technology |
| CN111377779A (en) * | 2020-04-15 | 2020-07-07 | 宝鸡阜丰生物科技有限公司 | Method and system for producing fertilizer containing glutamic acid fermentation waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1597661A (en) * | 2004-07-22 | 2005-03-23 | 徐昌洪 | Glutamic acid extraction technology in production of glutamic acid by fermentation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1597661A (en) * | 2004-07-22 | 2005-03-23 | 徐昌洪 | Glutamic acid extraction technology in production of glutamic acid by fermentation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107223772A (en) * | 2017-05-10 | 2017-10-03 | 通辽梅花生物科技有限公司 | New high protein mixed feed and its production technology |
| CN107223772B (en) * | 2017-05-10 | 2021-02-23 | 通辽梅花生物科技有限公司 | High-protein compound feed and production process thereof |
| CN111377779A (en) * | 2020-04-15 | 2020-07-07 | 宝鸡阜丰生物科技有限公司 | Method and system for producing fertilizer containing glutamic acid fermentation waste liquid |
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