CN105837460B - From the process for cleanly preparing of molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid - Google Patents
From the process for cleanly preparing of molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid Download PDFInfo
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- CN105837460B CN105837460B CN201610402246.0A CN201610402246A CN105837460B CN 105837460 B CN105837460 B CN 105837460B CN 201610402246 A CN201610402246 A CN 201610402246A CN 105837460 B CN105837460 B CN 105837460B
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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
Abstract
The invention discloses a kind of process for cleanly preparing from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid, it utilizes stainless steel membrane and one-level NF membrane purified fermentation broth, concentrated using two grades of NF membranes, and isoelectric point crystallization twice is carried out under normal temperature condition, simultaneously, waste water at different levels, the waste residue produced in technique is comprehensively utilized, the byproducts such as animal feeding-stuff containing somatic protein, C.M.S, organic fertilizer, oronain fertilizer are have developed.It is the higher process for cleanly preparing of comprehensive utilization of resources degree using the inferior galvanic process of embrane method two on the basis of " pollution-free, zero-emission ", it is possible to achieve great economic benefit compared with the galvanic process such as tradition concentration.
Description
Technical field
It is more particularly to a kind of from molasses fermented glutami acid fermentation liquor separation and Extraction paddy ammonia the invention belongs to biological chemical field
The process for cleanly preparing of acid.
Background technology
The extracting method of prior art Glutamic Acid have the electrical methods such as low temperature, ion-exchange, metal salt method, hydrochloric acid hydrolysis-
The electrical methods such as isoelectric point method, concentration.
Wherein, the electrical method such as low temperature is the isoelectric point that fermentating liquid acidification is adjusted to glutamic acid, makes the solubility of glutamic acid and reduces,
So as to Precipitation, crystallization yield can generally achieve more than 75%, if using the electrical methods such as low temperature (10 DEG C), yield is reachable
To 80%.
Ion-exchange is that zymotic fluid is diluted into finite concentration, and then zymotic fluid is adjusted to below isoelectric point with acid, adopted
Cationic exchange resin adsorption glutamic acid is used, is then eluted from resin glutamic acid with eluant, eluent (be typically ammoniacal liquor),
Reach the purpose of concentration purification.Extracted using this method, usual yield is up to 90%, but soda acid consumption is big.The current country is almost
All producers all using etc. electricity-from skill of handing over, i.e., by after zymotic fluid isoelectric point crystallization, mother liquor continuation is adjusted to pH1.7 with acid, so
Adsorbed and eluted with ammoniacal liquor with storng-acid cation exchange resin afterwards, total recovery is up to 96%.But this method soda acid consumption is big, useless
Water is big, wait ionization hand over skill generation waste water it is difficult to which biochemical treatment, a large amount of scientific workers are in monosodium glutamate wastewater treatment in recent years
Numerous studies have been done in problem, but be also only capable of administering from being produced in skill of handing over, low-concentration organic waste water, or only stop
In the experimental stage, case is not industrialized, therefore, problem of environmental pollution is very serious.
Metal salt method is often referred to zincate process, using glutamic acid and zinc ion action, and the glutamate that generation is insoluble in water sinks
Precipitation goes out, and is decomposed in sour environment Glutamic Acid metal salt, and in pH2.4, glutamic acid crystallizes precipitation again, so as to reach separation
The purpose of purifying.This method yield is due to the pollution problem of heavy metal ion up to 85% or so, and this method is no extensively should
With.
In hydrochloric acid hydrolysis-isoelectric point method, in zymotic fluid in addition to containing glutamic acid, still there are a certain amount of glutamine, Jiao Gu
Propylhomoserin and mycoprotein.These materials are irretrievable with methods such as isoelectric point method, ion-exchange and the precipitation method.Zymotic fluid
This recyclable part glutamic acid is hydrolyzed using hydrochloric acid after concentrated.But, it is on the one hand very high to equipment requirement using this method, simultaneously
Hydrolysis can produce a large amount of miscellaneous amino acid, be unfavorable for being further purified.
Concentration etc. is in electrical method, acid adjustment isoelectric point crystallization again after zymotic fluid is concentrated, crystallization Mother liquor direct fertilizer not recycling
Utilize, using this method, yield can reach 80-90% according to zymotic fluid property difference.Electricity-from handing over is waited using this method
A large amount of high concentrations and organic wastewater with medium-low concentration produced by skill, are the environmentally friendly production technologies of comparison, are used external producer more
This method.
However, use Sugar cane molasses to be fermented for raw material, if using etc. ionization skill of handing over produced, one, by
Impurity content is higher in zymotic fluid, and crystallization yield is difficult to ensure when low temperature etc. is electric；Secondly, crystalline mother solution resin cation
During absorption, resin is easily poisoned, so as to cause resin replacement frequent；Thirdly, no matter the high concentrated organic wastewater that produces is from pigment
Or all higher than the waste water that starch material zymotic fluid is produced on COD, therefore, Wei Dan companies can only be extracted using galvanic process such as concentrations
Glutamic acid.Although the galvanic process such as concentration can fundamentally solve pollution problem, extract yield is low, energy consumption is high, resource
Seriously there are serious shortcomings in the following aspects in waste：
1st, rearing crystal time is long, and because the impurity content in zymotic fluid is high, zymotic fluid is concentrated after 2.5-3 times, concentrated broth
In total solids content reached more than 75%.Compare it then becomes necessary to which the growing the grain of significant period of time just can guarantee that to be formed
Firm crystal, so as to just can guarantee that crystal can be than more smoothly separating from mother liquor during crystal and mother liquor separation.
In addition, during four times are washed, crystal is sufficiently solid also to can guarantee that the bran acid being dissolved in washing water is as far as possible few.But due to
Rearing crystal time is long (720 hours), on the one hand production risk can be caused too high, and once-through operation error is likely to cause 30 batches
Crystal solution be contaminated；Another aspect overlong time may also cause product because various unknown causes are lost.
2nd, crystal separation is difficult, and because crystalline mother solution solid content is too high, the separation of crystal and mother liquor is extremely difficult, presses
The production scale for producing ten thousand tons of bran acid per year is calculated, and 40KW 48, horizontal spiral formula centrifuge is needed altogether, centrifuge energy consumption is very huge
Greatly.
3rd, crystal purity is low, and the bran acid crystal purity for crystallizing acquisition is low, and only 80%, it is necessary to wash for four times, turn brilliant twice
Up-to-standard bran acid crystal can be just obtained, this can not only cause product to lose, can also bring huge energy resource consumption and soda acid
The wasting of resources.
4th, crystallization yield is low, due to even also needing to turn brilliant twice more than impurity content height, rearing crystal time length, washing times,
Therefore, the crystallization yield of bran acid is low, and only 84%.
5th, comprehensive utilization of resources degree is low, the mycoprotein, caramel colorant and other organic matters in zymotic fluid eventually as
It is blended in crystalline mother solution as pollution sources and handles.
In view of as above reason, it is necessary to study a kind of cleaning from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid
Production technology, to solve problems of the prior art.
The content of the invention
The present invention is completed in view of at least one above mentioned problem, and it is an object of the present invention to provide one kind
From the process for cleanly preparing of molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid, it is characterised in that comprise the following steps：
The molasses fermented glutami acid fermentation liquor of heating；
The zymotic fluid is filtered using microfiltration membranes and the dialysis that adds water, obtain the first filtrate and the first trapped fluid；
Spray drying is carried out to the first trapped fluid and obtains byproduct list animal feeding-stuff containing somatic protein；
Second filtrate and the second trapped fluid are obtained using the filtrate of first order nanofiltration membrane first；
Second trapped fluid obtains byproduct concentration honey zymotic fluid C.M.S. through being concentrated by evaporation；
3rd filtrate and the 3rd trapped fluid are obtained using the filtrate of second level nanofiltration membrane second, the 3rd filtrate is as preceding
Stating water is used to dialyse；
The pH value of the 3rd trapped fluid, isoelectric point crystallization are adjusted using hydrochloric acid, and is centrifuged using tripod pendulum type batch centrifugal and obtains the
One glutamic acid crystal and the first crystalline mother solution；
The pH value of the first crystalline mother solution is adjusted using liquefied ammonia, then carrying out filtering acquisition the 4th using third level NF membrane filters
Liquid and the 4th trapped fluid；
4th filtrate is the ammonium chloride solution of high-purity, using acquisition byproduct ammonium chloride after evaporation and concentration, crystallizing and drying
Fertilizer；
4th trapped fluid adjusts pH value using hydrochloric acid, and then isoelectric point crystallization is centrifuged using tripod pendulum type batch centrifugal and obtain the
Two glutamic acid crystals and the second crystalline mother solution；
Second crystalline mother solution is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Wherein, the first glutamic acid crystal and the second glutamic acid crystal merge for converting sodium glutamate.
According to a further aspect of the invention, hydrochloric acid is used to adjust the 3rd trapped fluid pH value for 3-4, and the 4th trapped fluid is used
Hydrochloric acid adjustment pH value is 3-4.
According to a further aspect of the invention, liquefied ammonia is used to adjust the pH value of the first crystalline mother solution for 5-6.
According to a further aspect of the invention, microfiltration membranes are the ceramic membrane or stainless steel membrane of tubular structure, and its supporting layer material is
Al2O3, or stainless 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, its molecular cut off
For 300-400D, its rejection to magnesium sulfate is 80-90%, and its temperature tolerance range is 5-60 DEG C.
According to a further aspect of the invention, microfiltration membranes thoroughly eliminate solid suspension, and the second trapped fluid uses triple effect evaporation
Solids content 60% is concentrated into, does not have solid deposits precipitation after 10 days stand.
According to a further aspect of the invention, second and third level NF membrane be wound module mode polymeric membrane, its retain
Molecular weight is 100-200D, and its rejection to magnesium sulfate is 96-99%, and its temperature tolerance range is 5-45 DEG C.
According to a further aspect of the invention, hydrochloric acid is used to adjust the 3rd trapped fluid pH value for 3.2, and the 4th trapped fluid is used
Hydrochloric acid adjustment pH value is 3.2.
According to a further aspect of the invention, liquefied ammonia is used to adjust the pH value of the first crystalline mother solution for 5.5.
Compared with prior art, the beneficial effects of the present invention are：The present invention is pure using stainless steel membrane and one-level NF membrane
Change zymotic fluid, concentrated using two grades of NF membranes, and isoelectric point crystallization twice is carried out under normal temperature condition, meanwhile, in technique
Waste water at different levels, the waste residue produced is comprehensively utilized, and have developed animal feeding-stuff containing somatic protein, C.M.S, organic fertilizer, oronain fertilizer etc.
Byproduct.Extracting glutamic acid total recovery >=96%, the not only extracting glutamic acid yield lifting more than 12% compared with traditional handicraft, and
And water consume, power consumption, energy consumption are greatly lowered, compared with the galvanic process such as tradition concentration, using the inferior galvanic process of embrane method two in " no dirt
On the basis of dye, zero-emission ", it is possible to achieve great economic benefit, is the higher process for cleanly preparing of comprehensive utilization of resources degree.
Brief description of the drawings
Fig. 1 is the cleaning according to the preferred embodiment of the invention from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid
Production technological process.
Embodiment
Below in conjunction with the accompanying drawings, the preferred forms of the present invention, specific implementation here are described by preferred embodiment
Mode is to explain the present invention, and should not be construed as limiting the invention, and is not departing from the spiritual and real of the present invention
In the case of matter scope, various changes and modifications can be made, these should be all included within protection scope of the present invention.
Referring to Fig. 1, the preferred embodiment of the present invention provides a kind of from molasses fermented glutami acid fermentation liquor separation and Extraction paddy ammonia
The process for cleanly preparing of acid.This includes following from the process for cleanly preparing of molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid
Step：
The molasses fermented glutami acid fermentation liquor of heating；
The zymotic fluid is filtered using microfiltration membranes and the dialysis that adds water, obtain the first filtrate and the first trapped fluid；
Spray drying is carried out to the first trapped fluid and obtains byproduct list animal feeding-stuff containing somatic protein；
Second filtrate and the second trapped fluid are obtained using the filtrate of first order nanofiltration membrane first；
Second trapped fluid obtains byproduct concentration honey zymotic fluid C.M.S. through being concentrated by evaporation；
3rd filtrate and the 3rd trapped fluid are obtained using the filtrate of second level nanofiltration membrane second, the 3rd filtrate is as preceding
Stating water is used to dialyse；
The pH value of the 3rd trapped fluid, isoelectric point crystallization are adjusted using hydrochloric acid, and is centrifuged using tripod pendulum type batch centrifugal and obtains the
One glutamic acid crystal and the first crystalline mother solution；
The pH value of the first crystalline mother solution is adjusted using liquefied ammonia, then carrying out filtering acquisition the 4th using third level NF membrane filters
Liquid and the 4th trapped fluid；
4th filtrate is the ammonium chloride solution of high-purity, using acquisition byproduct ammonium chloride after evaporation and concentration, crystallizing and drying
Fertilizer；
4th trapped fluid adjusts pH value using hydrochloric acid, and then isoelectric point crystallization is centrifuged using tripod pendulum type batch centrifugal and obtain the
Two glutamic acid crystals and the second crystalline mother solution；
Second crystalline mother solution is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Wherein, the first glutamic acid crystal and the second glutamic acid crystal merge for converting sodium glutamate.
Preferably, hydrochloric acid is used to adjust the 3rd trapped fluid pH value for 3-4, and the 4th trapped fluid adjusts pH value using hydrochloric acid
For 3-4.
Preferably, liquefied ammonia is used to adjust the pH value of the first crystalline mother solution for 5-6.
Preferably, microfiltration membranes are the ceramic membrane or stainless steel membrane of tubular structure, and its supporting layer material is Al2O3, or it is stainless
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, its
Rejection to magnesium sulfate is 80-90%, and its temperature tolerance range is 5-60 DEG C.
Preferably, microfiltration membranes thoroughly eliminate solid suspension, and the second trapped fluid is contained using three-effect evaporation and condensation to solid
Amount 60%, does not have solid deposits precipitation after 10 days stand.
Preferably, second and third level NF membrane be wound module mode polymeric membrane, its molecular cut off be 100-
200D, its rejection to magnesium sulfate is 96-99%, and its temperature tolerance range is 5-45 DEG C.
Preferably, hydrochloric acid is used to adjust the 3rd trapped fluid pH value for 3.2, and the 4th trapped fluid adjusts pH value using hydrochloric acid
For 3.2.
Preferably, liquefied ammonia is used to adjust the pH value of the first crystalline mother solution for 5.5.
It can be seen that, the drawbacks of present invention is for electric production technologies such as molasses fermented glutamic acid concentrations fundamentally transforms paddy ammonia
There is provided one kind in high yield, low cost, low energy consumption, comprehensive utilization of resources, technique are continuously controllable, and Low investment is efficient for sour extractive technique
The process for cleanly preparing of rate.
Preferably, present invention also offers a kind of the clear of separation and Extraction glutamic acid from molasses fermented glutami acid fermentation liquor
Clean production technology, comprises the following steps：
After a, molasses fermented glutami acid fermentation liquor, fermenting-ripening, put keep during tank ventilation in fermentation tank, stirring,
The conditions such as tank temperature are constant, and zymotic fluid sprays heating in tank pipeline is put using steam, instantaneously reachesZymotic fluid after heating
Into microfiltration membranes head tank, heat treatment yield is more than 99.5%；
Sterilization fermentation liquid obtained by b, step a, carries out clarification filtration, and the dialysis that adds water using microfiltration membranes, obtains the He of filtrate 1
Trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 0-10bar, and micro-filtrate membrane filtration cycles of concentration is 4-10 times, and water-dialyzing adds
Dosage is 3-5 times of the volume of trapped fluid 1, and filtering yield is more than 99%；
Trapped fluid 1 obtained by c, step b obtains byproduct list animal feeding-stuff containing somatic protein using spray drying；It is total in trapped fluid 1
Solids content >=18%, protein content (butt) >=50% obtains byproduct list animal feeding-stuff containing somatic protein after spray drying；
Filtrate 1 obtained by d, step b, after being cooled down using plate type heat exchanger, the He of filtrate 2 is obtained using one-level nanofiltration membrane
Trapped fluid 2；Filtration temperature is 40-60 DEG C, filter pressure 0-42bar, and filtering yield is more than 99%；
Trapped fluid 2 obtained by e, step d, solids content 60% is concentrated into through multiple-effect evaporation, obtains byproduct C.M.S..
Filtrate 2 obtained by f, step d, after being cooled down through plate type heat exchanger, obtains filtrate 3 using two grades of nanofiltration membranes and cuts
Stay liquid 3；Filtration temperature is 20-45 DEG C, filter pressure 0-42bar, and because filtrate is applied mechanically, this unit does not have yield losses；
Filtrate 3 obtained by g, step f, set is used step a and used as water-dialyzing；
Trapped fluid 3 obtained by h, step f, is adjusted to glutamic acid isoelectric pH 3.2, isoelectric point crystallization, and use using hydrochloric acid
Tripod pendulum type batch centrifugal, which is centrifuged, obtains glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield reaches 85-90%；
The crystalline mother solution 1 that i, step h are obtained is adjusted to pH5.5 using liquefied ammonia, is then filtered using three-level NF membrane
Obtain filtrate 4 and trapped fluid 4；Filtration temperature is 20-45 DEG C, filter pressure 0-42bar；Filter yield >=99.5%；
The filtrate 4 that j, step i are obtained is the ammonium chloride solution of high-purity, secondary using being obtained after evaporation and concentration, crystallizing and drying
Product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i are obtained, pH3.2, isoelectric point crystallization, then using tripod pendulum type batch centrifugal are adjusted to using hydrochloric acid
Centrifuge and obtain glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 85-90%；
The crystalline mother solution 2 that l, step k are obtained is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Glutamic acid crystal 1 and glutamic acid crystal that m, step h and step k are obtained are 2-in-1 and for converting sodium glutamate (taste
Essence), extracting glutamic acid total recovery >=96%, glutamic acid is given money as a gift purity >=98.5%, moisture 10-18%, calcium ion 20-
40ppm, oxalate denominationby 15-30ppm, chlorion 100-300ppm, sulfate radical 10-30ppm.
Preferably, present invention also offers a kind of the clear of separation and Extraction glutamic acid from molasses fermented glutami acid fermentation liquor
Clean production technology, wherein, the glutamic acid maturing fermentation liquid by raw material of molasses is handled using following steps：
After a, molasses fermented glutami acid fermentation liquor, fermenting-ripening, put keep during tank ventilation in fermentation tank, stirring,
The conditions such as tank temperature are constant, and zymotic fluid sprays heating in tank pipeline is put using steam, instantaneously reachesZymotic fluid after heating
Into microfiltration membranes head tank, heat treatment yield is 99.6%；
Sterilization fermentation liquid obtained by b, step a, carries out clarification filtration, and the dialysis that adds water using microfiltration membranes, obtains the He of filtrate 1
Trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 5bar, and micro-filtrate membrane filtration cycles of concentration is 8 times, and water-dialyzing addition is
3.7 times of the volume of trapped fluid 1, filter yield 99.1%；
Trapped fluid 1 obtained by c, step b obtains byproduct list animal feeding-stuff containing somatic protein using spray drying；It is total in trapped fluid 1
Solids content 20%, protein content (butt) 55% obtains byproduct list animal feeding-stuff containing somatic protein after spray drying；
Filtrate 1 obtained by d, step b, after being cooled down using plate type heat exchanger, the He of filtrate 2 is obtained using one-level nanofiltration membrane
Trapped fluid 2；Filtration temperature is 53 DEG C, filter pressure 31bar, and filtering yield is 99.1%；
Trapped fluid 2 obtained by e, step d, solids content 60% is concentrated into through multiple-effect evaporation, obtains byproduct C.M.S..
Filtrate 2 obtained by f, step d, after being cooled down through plate type heat exchanger, obtains filtrate 3 using two grades of nanofiltration membranes and cuts
Stay liquid 3；Filtration temperature is 37 DEG C, filter pressure 33bar, and because filtrate is applied mechanically, this unit does not have yield losses；
Filtrate 3 obtained by g, step f, set is used step a and used as water-dialyzing；
Trapped fluid 3 obtained by h, step f, is adjusted to glutamic acid isoelectric pH 3.2, isoelectric point crystallization, and use using hydrochloric acid
Tripod pendulum type batch centrifugal, which is centrifuged, obtains glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield reaches 87%；
The crystalline mother solution 1 that i, step h are obtained is adjusted to pH5.5 using liquefied ammonia, is then filtered using three-level NF membrane
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 are obtained is the ammonium chloride solution of high-purity, secondary using being obtained after evaporation and concentration, crystallizing and drying
Product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i are obtained, pH3.2, isoelectric point crystallization, then using tripod pendulum type batch centrifugal are adjusted to using hydrochloric acid
Centrifuge and obtain glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 88%；
The crystalline mother solution 2 that l, step k are obtained is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Glutamic acid crystal 1 and glutamic acid crystal that m, step h and step k are obtained are 2-in-1 and for converting sodium glutamate (taste
Essence), extracting glutamic acid total recovery is 96.3%, and glutamic acid crystal is given money as a gift purity 98.5%, moisture 15%, calcium ion
30ppm, oxalate denominationby 20ppm, chlorion 200ppm, sulfate radical 20ppm.
Preferably, present invention also offers a kind of the clear of separation and Extraction glutamic acid from molasses fermented glutami acid fermentation liquor
Clean production technology, wherein, the glutamic acid maturing fermentation liquid by raw material of molasses is handled using following steps：
After a, molasses fermented glutami acid fermentation liquor, fermenting-ripening, put keep during tank ventilation in fermentation tank, stirring,
The conditions such as tank temperature are constant, and zymotic fluid sprays heating in tank pipeline is put using steam, instantaneously reachesZymotic fluid after heating
Into microfiltration membranes head tank, heat treatment yield is 99.5%；
Sterilization fermentation liquid obtained by b, step a, carries out clarification filtration, and the dialysis that adds water using microfiltration membranes, obtains the He of filtrate 1
Trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 7bar, and micro-filtrate membrane filtration cycles of concentration is 9 times, and water-dialyzing addition is
4 times of the volume of trapped fluid 1, filter yield 99.3%；
Trapped fluid 1 obtained by c, step b obtains byproduct list animal feeding-stuff containing somatic protein using spray drying；It is total in trapped fluid 1
Solids content 23%, protein content (butt) 52% obtains byproduct list animal feeding-stuff containing somatic protein after spray drying；
Filtrate 1 obtained by d, step b, after being cooled down using plate type heat exchanger, the He of filtrate 2 is obtained using one-level nanofiltration membrane
Trapped fluid 2；Filtration temperature is 55 DEG C, filter pressure 32bar, and filtering yield is 99.2%；
Trapped fluid 2 obtained by e, step d, solids content 60% is concentrated into through multiple-effect evaporation, obtains byproduct C.M.S..
Filtrate 2 obtained by f, step d, after being cooled down through plate type heat exchanger, obtains filtrate 3 using two grades of nanofiltration membranes and cuts
Stay liquid 3；Filtration temperature is 37 DEG C, filter pressure 36bar, and because filtrate is applied mechanically, this unit does not have yield losses；
Filtrate 3 obtained by g, step f, set is used step a and used as water-dialyzing；
Trapped fluid 3 obtained by h, step f, is adjusted to glutamic acid isoelectric pH 3.2, isoelectric point crystallization, and use using hydrochloric acid
Tripod pendulum type batch centrifugal, which is centrifuged, obtains glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield reaches 86%；
The crystalline mother solution 1 that i, step h are obtained is adjusted to pH5.5 using liquefied ammonia, is then filtered using three-level NF membrane
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 are obtained is the ammonium chloride solution of high-purity, secondary using being obtained after evaporation and concentration, crystallizing and drying
Product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i are obtained, pH3.2, isoelectric point crystallization, then using tripod pendulum type batch centrifugal are adjusted to using hydrochloric acid
Centrifuge and obtain glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 89%；
The crystalline mother solution 2 that l, step k are obtained is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Glutamic acid crystal 1 and glutamic acid crystal that m, step h and step k are obtained are 2-in-1 and for converting sodium glutamate (taste
Essence), extracting glutamic acid total recovery is 96.2%, and glutamic acid crystal is given money as a gift purity 98.6%, moisture 14%, calcium ion
28ppm, oxalate denominationby 19ppm, chlorion 190ppm, sulfate radical 18ppm.
Preferably, present invention also offers a kind of the clear of separation and Extraction glutamic acid from molasses fermented glutami acid fermentation liquor
Clean production technology, wherein, the glutamic acid maturing fermentation liquid by raw material of molasses is handled using following steps：
After a, molasses fermented glutami acid fermentation liquor, fermenting-ripening, put keep during tank ventilation in fermentation tank, stirring,
The conditions such as tank temperature are constant, and zymotic fluid sprays heating in tank pipeline is put using steam, instantaneously reachesZymotic fluid after heating
Into microfiltration membranes head tank, heat treatment yield is 99.7%；
Sterilization fermentation liquid obtained by b, step a, carries out clarification filtration, and the dialysis that adds water using microfiltration membranes, obtains the He of filtrate 1
Trapped fluid 1；Filtration temperature is 75 DEG C, and filter pressure is 9bar, and micro-filtrate membrane filtration cycles of concentration is 10 times, and water-dialyzing addition is
5 times of the volume of trapped fluid 1, filter yield 99.7%；
Trapped fluid 1 obtained by c, step b obtains byproduct list animal feeding-stuff containing somatic protein using spray drying；It is total in trapped fluid 1
Solids content 22%, protein content (butt) 53% obtains byproduct list animal feeding-stuff containing somatic protein after spray drying；
Filtrate 1 obtained by d, step b, after being cooled down using plate type heat exchanger, the He of filtrate 2 is obtained using one-level nanofiltration membrane
Trapped fluid 2；Filtration temperature is 56 DEG C, filter pressure 37bar, and filtering yield is 99.3%；
Trapped fluid 2 obtained by e, step d, solids content 60% is concentrated into through multiple-effect evaporation, obtains byproduct C.M.S..
Filtrate 2 obtained by f, step d, after being cooled down through plate type heat exchanger, obtains filtrate 3 using two grades of nanofiltration membranes and cuts
Stay liquid 3；Filtration temperature is 39 DEG C, filter pressure 35bar, and because filtrate is applied mechanically, this unit does not have yield losses；
Filtrate 3 obtained by g, step f, set is used step a and used as water-dialyzing；
Trapped fluid 3 obtained by h, step f, is adjusted to glutamic acid isoelectric pH 3.2, isoelectric point crystallization, and use using hydrochloric acid
Tripod pendulum type batch centrifugal, which is centrifuged, obtains glutamic acid crystal 1 and crystalline mother solution 1；Primary crystallization yield reaches 89%；
The crystalline mother solution 1 that i, step h are obtained is adjusted to pH5.5 using liquefied ammonia, is then filtered using three-level NF membrane
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 are obtained is the ammonium chloride solution of high-purity, secondary using being obtained after evaporation and concentration, crystallizing and drying
Product ammonium chloride fertilizer；
The trapped fluid 4 that k, step i are obtained, pH3.2, isoelectric point crystallization, then using tripod pendulum type batch centrifugal are adjusted to using hydrochloric acid
Centrifuge and obtain glutamic acid crystal 2 and crystalline mother solution 2；Secondary crystallization yield reaches 85%；
The crystalline mother solution 2 that l, step k are obtained is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Glutamic acid crystal 1 and glutamic acid crystal that m, step h and step k are obtained are 2-in-1 and for converting sodium glutamate (taste
Essence), extracting glutamic acid total recovery is 96.7%, and glutamic acid crystal is given money as a gift purity 98.7%, moisture 12%, calcium ion
25ppm, oxalate denominationby 17ppm, chlorion 160ppm, sulfate radical 15ppm.
Preferably, present invention also offers a kind of the clear of separation and Extraction glutamic acid from molasses fermented glutami acid fermentation liquor
Clean production technology, comprises the following steps：
After molasses fermented glutami acid fermentation liquor, fermenting-ripening, put and ventilation in fermentation tank, stirring, tank are kept during tank
The conditions such as temperature are constant, and zymotic fluid sprays heating in tank pipeline is put using steam, instantaneously reachesZymotic fluid after heating enters
Enter microfiltration membranes head tank；
Sterilization fermentation liquid obtained by step a, clarification filtration, and the dialysis that adds water are carried out using microfiltration membranes, are obtained filtrate 1 and are cut
Stay liquid 1；
Trapped fluid 1 obtained by step b obtains byproduct list animal feeding-stuff containing somatic protein using spray drying；
Filtrate 1 obtained by step b, filtrate 2 and trapped fluid 2 are obtained using one-level nanofiltration membrane；
Trapped fluid 2 obtained by step d, solids content 60% is concentrated into through multiple-effect evaporation, obtains byproduct C.M.S..
Filtrate 2 obtained by step d, filtrate 3 and trapped fluid 3 are obtained using two grades of nanofiltration membranes；
Filtrate 3 obtained by step f, set is used step a and used as water-dialyzing；
Trapped fluid 3 obtained by step f, is adjusted to glutamic acid isoelectric pH 3.2, isoelectric point crystallization, and use three using hydrochloric acid
Sufficient centrifuge separation obtains glutamic acid crystal 1 and crystalline mother solution 1；
The crystalline mother solution 1 that step h is obtained is adjusted to pH5.5 using liquefied ammonia, and then carrying out filtering using three-level NF membrane obtains
Obtain filtrate 4 and trapped fluid 4；
The filtrate 4 that step i is obtained is the ammonium chloride solution of high-purity, using being concentrated by evaporation, obtain by-product after crystallizing and drying
Product ammonium chloride fertilizer；
The trapped fluid 4 that step i is obtained, pH3.2 is adjusted to using hydrochloric acid, isoelectric point crystallization, then using tripod pendulum type batch centrifugal from
Heart separation obtains glutamic acid crystal 2 and crystalline mother solution 2；
The crystalline mother solution 2 that step k is obtained is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Glutamic acid crystal 1 and glutamic acid crystal that step h and step k are obtained are 2-in-1 and for converting sodium glutamate (monosodium glutamate).
Preferably, after the molasses fermented glutami acid fermentation liquor described in step a, fermenting-ripening, holding hair during tank is put
The condition such as ventilation, stirring, tank temperature is constant in fermentation tank, to ensure the activity of thalline in fermentation tank, reduces the bacterium that temperature-rise period is brought
The glutamic acid loss that body metabolic disorder is caused, zymotic fluid sprays heating using steam in tank pipeline is put, instantaneously reachedBacterium
Body and the enzyme of thalline secretion are inactivated in very short time, and the zymotic fluid after heating enters microfiltration membranes head tank.
Preferably, the microfiltration membranes described in step b, are the ceramic membrane or stainless steel membrane of tubular structure, and its supporting layer material is
Al2O3, or stainless steel, film layer material is rutile TiO2, or α-Al2O3, its pore size filter is 20nm-200nm.
Preferably, mycoprotein and amino acid are rich in the trapped fluid 1 described in step c, can be made after spray drying
For byproduct list animal feeding-stuff containing somatic protein.
Preferably, the one-level NF membrane described in step d is the polymeric membrane of wound module mode, and its molecular cut off is
300-400D, its rejection to magnesium sulfate is 80-90%, and its temperature tolerance range is 5-60 DEG C；
Preferably, the trapped fluid 2 described in step e, solids content 60% is concentrated into through multiple-effect evaporation, obtains byproduct
C.M.S..C.M.S. it is made of that with microbial fermentation, it is except containing the original nutritional ingredient of molasses and good by raw material of molasses
Outside good local flavor, the protein synthesized in fermentation process by Institute of Micro-biology, amino acid, organic acid, vitamin and ferment have more been had more
Co-factor, is a kind of feed addictive with high nutritive value.The product is applied not only to animal husbandry：Cow, pork pig, laying hen,
Broiler chicken；Aquatic products industry：The feed addictive of fishes and shrimps etc., can also partly substitute higher-priced protein feeds raw material, simultaneously because
The product has nitrogen needed for plant, and phosphorus, three kinds of trace elements of potassic fertilizer and the low molecule easily absorbed by plant have
Machine nutritional ingredient, has effects that to promote plant growth, can be used for allotment liquid state organic fertilizer or adds in solid fertilizer.
Step b thoroughly eliminates solid suspension using microfiltration membranes, and trapped fluid 2 is using three-effect evaporation and condensation to solids content 60%, warp
Spend 10 days does not have solid deposits precipitation after standing, and this has broken European C.M.S. technology barriers.
Preferably, two grades of NF membranes described in step f are the polymeric membrane of wound module mode, and its molecular cut off is 100-
200D, its rejection to magnesium sulfate is 96-99%, and its temperature tolerance range is 5-45 DEG C.
Preferably, the three-level NF membrane described in step i is the polymeric membrane of wound module mode, and its molecular cut off is
100-200D, its rejection to magnesium sulfate is 96-99%, 5-45 DEG C.
Preferably, the filtrate 4 rich in high-purity ammonium chloride described in step j can obtain chlorination by crystallization and evaporation process
Ammonium byproduct.
Preferably, the crystalline mother solution 2 rich in glutamic acid and ammonium chloride described in step l can be with after multiple-effect evaporation is concentrated
Obtain byproduct liquid fertilizer.
In summary, the beneficial effects of the present invention are：The present invention utilizes stainless steel membrane and one-level NF membrane purification of fermentation
Liquid, is concentrated using two grades of NF membranes, and carries out isoelectric point crystallization twice under normal temperature condition, meanwhile, to what is produced in technique
Waste water at different levels, waste residue are comprehensively utilized, and have developed the byproducts such as animal feeding-stuff containing somatic protein, C.M.S, organic fertilizer, oronain fertilizer.
Compared with the galvanic process such as tradition concentration, using the inferior galvanic process of embrane method two on the basis of " pollution-free, zero-emission ", it is possible to achieve
Great economic benefit, is the higher process for cleanly preparing of comprehensive utilization of resources degree.
The invention is not restricted to above-mentioned specific embodiment.It is understood that not departing from spirit and substance of the present invention model
In the case of enclosing, various changes and modifications can be made, these should be all included within protection scope of the present invention.
Claims (5)
1. a kind of process for cleanly preparing from molasses fermented glutami acid fermentation liquor separation and Extraction glutamic acid, it is characterised in that including
Following steps：
The molasses fermented glutami acid fermentation liquor of heating；
The zymotic fluid is filtered using microfiltration membranes and the dialysis that adds water, obtain the first filtrate and the first trapped fluid, the micro-filtration
Film is the stainless steel membrane of tubular structure, and its supporting layer material is stainless steel, and film layer material is rutile TiO2, or α-Al2O3, its
Pore size filter is 20-200nm；
Spray drying is carried out to the first trapped fluid and obtains byproduct list animal feeding-stuff containing somatic protein；
Second filtrate and the second trapped fluid are obtained using the filtrate of first order nanofiltration membrane first, the first order NF membrane is rolling
The polymeric membrane of modularity, its molecular cut off is 300-400D, and its rejection to magnesium sulfate is 80-90%, its temperature
Tolerance range is 5-60 DEG C；
Second trapped fluid obtains byproduct concentration honey zymotic fluid C.M.S. through being concentrated by evaporation；
3rd filtrate and the 3rd trapped fluid are obtained using the filtrate of second level nanofiltration membrane second, the 3rd filtrate is used as foregoing water
For dialysing, the second level NF membrane is the polymeric membrane of wound module mode, and its molecular cut off is 100-200D, and it is to sulphur
The rejection of sour magnesium is 96-99%, and its temperature tolerance range is 5-45 DEG C；
The pH value of the 3rd trapped fluid, isoelectric point crystallization are adjusted using hydrochloric acid, and the first paddy of acquisition is centrifuged using tripod pendulum type batch centrifugal
Propylhomoserin crystal and the first crystalline mother solution；
The pH value of the first crystalline mother solution is adjusted using liquefied ammonia, then using third level NF membrane carry out filtering obtain the 4th filtrate and
4th trapped fluid, the third level NF membrane is the polymeric membrane of wound module mode, and its molecular cut off is 100-200D, and its is right
The rejection of magnesium sulfate is 96-99%, and its temperature tolerance range is 5-45 DEG C；
4th filtrate is the ammonium chloride solution of high-purity, using acquisition byproduct ammonium chloride fertilizer after evaporation and concentration, crystallizing and drying；
4th trapped fluid adjusts pH value using hydrochloric acid, and then isoelectric point crystallization is centrifuged using tripod pendulum type batch centrifugal and obtain the second paddy
Propylhomoserin crystal and the second crystalline mother solution；
Second crystalline mother solution is rich in glutamic acid, the byproduct liquid fertilizer of ammonium chloride using acquisition is concentrated by evaporation；
Wherein, the first glutamic acid crystal and the second glutamic acid crystal merge for converting sodium glutamate；
Wherein, the microfiltration membranes thoroughly eliminate solid suspension, and the second trapped fluid is using three-effect evaporation and condensation to solids content
60%, there is no solid deposits precipitation after 10 days stand.
2. technique according to claim 1, it is characterised in that use hydrochloric acid to adjust the 3rd trapped fluid pH value for 3-4, and
4th trapped fluid uses hydrochloric acid to adjust pH value for 3-4.
3. technique according to claim 2, it is characterised in that use liquefied ammonia to adjust the pH value of the first crystalline mother solution for 5-6.
4. technique according to claim 1, it is characterised in that use hydrochloric acid to adjust the 3rd trapped fluid pH value for 3.2, and
4th trapped fluid uses hydrochloric acid to adjust pH value for 3.2.
5. technique according to claim 1, it is characterised in that use liquefied ammonia to adjust the pH value of the first crystalline mother solution for 5.5.
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