CN105503630B - A kind of method for purifying lysine hydrochloride - Google Patents
A kind of method for purifying lysine hydrochloride Download PDFInfo
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- CN105503630B CN105503630B CN201510896726.2A CN201510896726A CN105503630B CN 105503630 B CN105503630 B CN 105503630B CN 201510896726 A CN201510896726 A CN 201510896726A CN 105503630 B CN105503630 B CN 105503630B
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- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 title claims abstract description 112
- 229960005337 lysine hydrochloride Drugs 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 66
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 64
- 239000000919 ceramic Substances 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 34
- 238000000855 fermentation Methods 0.000 claims description 33
- 230000004151 fermentation Effects 0.000 claims description 33
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 239000012452 mother liquor Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 2
- 239000010413 mother solution Substances 0.000 abstract 2
- 239000012982 microporous membrane Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000004472 Lysine Substances 0.000 description 24
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 24
- 229960003646 lysine Drugs 0.000 description 24
- 238000000746 purification Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 241001052560 Thallis Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BVHLGVCQOALMSV-UHFFFAOYSA-N (5-amino-1-carboxypentyl)azanium;chloride Chemical group Cl.NCCCCC(N)C(O)=O BVHLGVCQOALMSV-UHFFFAOYSA-N 0.000 description 1
- PHIQHXFUZVPYII-ZCFIWIBFSA-N (R)-carnitine Chemical compound C[N+](C)(C)C[C@H](O)CC([O-])=O PHIQHXFUZVPYII-ZCFIWIBFSA-N 0.000 description 1
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000007999 Nuclear Proteins Human genes 0.000 description 1
- 108010089610 Nuclear Proteins Proteins 0.000 description 1
- 102000015731 Peptide Hormones Human genes 0.000 description 1
- 108010038988 Peptide Hormones Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229960004203 carnitine Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000003792 cranial nerve Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002361 ketogenic effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000813 peptide hormone Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- -1 skeletal muscle Proteins 0.000 description 1
- 210000002027 skeletal muscle Anatomy 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention relates to a kind of method that lysine hydrochloride is extracted in zymotic fluid from lysine hydrochloride.Methods described comprises the steps of：Lysine hydrochloride zymotic fluid is filtered using microporous membrane, obtains micro-filtrate and film concentrated phase；The micro-filtrate is decolourized using activated carbon, obtains destainer；By gained destainer through being concentrated in vacuo, acid adjustment, decrease temperature crystalline, wet crystal and crystalline mother solution are obtained；Wherein described wet crystal further centrifuges drying, obtains lysine hydrochloride crystal；Gained film concentrated phase and gained crystalline mother solution are merged, gained mixed liquor obtains lysine hydrochloride of the content more than 65% through being concentrated in vacuo, being spray-dried.Lysine hydrochloride is extracted using this method, not only recovery rate is high, and the lysine hydrochloride of high-purity can be made；And extraction process is simple to operate, green.
Description
Technical Field
The invention relates to the field of lysine hydrochloride extraction, and particularly provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor.
Background
Lysine is an indispensable component for synthesizing cranial nerves, biological nuclear protein and hemoglobin, is one of amino acids which cannot be synthesized by animals themselves and must be taken from food, and is classified as "the first lacking amino acid" by nutritionists. "first limiting amino acids" of vegetable proteins. Lysine hydrochloride, chemical name is 2, 6-diaminocaproic acid hydrochloride, molecular formula is: c6H14N2O2·HCL。
Lysine functions in vivo are: involved in the synthesis of body proteins such as skeletal muscle, enzymes and polypeptide hormones; is one of the ketogenic amino acids which, in the absence of available carbohydrate, is involved in the metabolism to form ketone bodies and glucose; the acid-base balance in the body is maintained; as a precursor for synthesizing carnitine, participate in fat metabolism; in addition, lysine can also improve the stress resistance of the body.
With the development of science and technology and the increased understanding of health care knowledge, the importance of lysine in human life has been recognized, and the demand of the lysine market has been increasing. The development of the market has led lysine to move from the animal feed field to the food health field and the pharmaceutical field. The current world annual production of lysine hydrochloride products reaches 100 million tons, of which about 90% is used as feed additive and 10% is used as food and pharmaceutical intermediate. It is very important to increase the added value of the product.
At present, although the production of lysine is developed vigorously at home and abroad, the lysine salt products sold in the market mainly comprise lysine hydrochloride crystals and lysine sulfate with the purity of about 65 percent. Wherein, the high-purity lysine hydrochloride is mainly obtained by adopting a resin adsorption method for purification, but has some defects in the purification process: for example, the metastable zone of lysine hydrochloride crystal is narrow; lysine hydrochloride in aqueous solution is not easy to crystallize due to high solubility and is easy to agglomerate in a high-temperature environment; the energy consumption in the purification process is high; the mother liquor is directly discharged, and the environmental pollution is large.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a simple, convenient, efficient, green and environment-friendly method for purifying lysine hydrochloride. By adopting the purification method, the purity and the yield of the lysine hydrochloride are further improved, and the technical difficulty that the lysine hydrochloride is difficult to crystallize in an aqueous solution is solved; meanwhile, the lysine hydrochloride in the membrane concentrated phase and the crystallization mother liquor is fully extracted, the utilization value of the lysine hydrochloride fermentation liquor is effectively improved, and the problem of environmental pollution caused by direct discharge of the crystallization mother liquor is avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a purification method of lysine hydrochloride comprises the following steps:
step (1): filtering the lysine hydrochloride fermentation liquor by adopting a microporous ceramic membrane to obtain a micro-filtrate and a membrane concentrated phase;
step (2): decolorizing the micro-filtrate by adopting activated carbon to obtain a decolorized solution;
and (3): vacuum concentrating the obtained decolorized solution, adjusting acid, cooling and crystallizing to obtain wet crystal and crystallization mother liquor; wherein the wet crystal is further centrifugally dried to obtain a lysine hydrochloride crystal;
and (4): and (3) combining the membrane concentrated phase obtained in the step (1) and the crystallization mother liquor obtained in the step (3), and performing vacuum concentration and spray drying on the obtained mixed liquor to obtain lysine hydrochloride with the content of more than 65%.
In the purification method, in the step (1), the inlet pressure of the microporous ceramic membrane is 0.2-0.3 MPa, and the pressure difference between an inlet and an outlet is 0.05 MPa; the membrane flux is 50-70 LMH; the aperture of the microporous ceramic membrane is 0.05-0.1 μm; the concentration multiple of the fermentation liquor is 5-7 times; the addition amount of the dialysis water is 30-35% (v/v) of the total volume of the fermentation liquor feeding; in this step, the yield of lysine hydrochloride reaches more than 96%. Through proper selection of the pore diameter of the microporous ceramic membrane and reasonable control of the inlet and outlet pressure and the membrane flux of the microporous ceramic membrane, impurities and thalli in the fermentation liquor can be effectively removed, so that the operation of the subsequent purification process is facilitated, and the filtration of the lysine hydrochloride fermentation liquor is quickly completed; and effectively avoids the membrane deformation caused by overlarge membrane pressure. In addition, the concentrated phase of the membrane after filtration can be added with dialysis water for multiple times of microporous ceramic membrane filtration, thereby improving the filtration effect.
In the purification method, in the step (2), the addition amount of the active carbon is 0.001-0.002 g/mL of micro-filtrate; the decoloring temperature is 60-70 ℃, the time is 30-60 min, and the yield of the lysine hydrochloride reaches more than 98%. The selection of the decolorizing agent and the control of decolorizing conditions can ensure that the micro-filtrate can achieve higher decolorizing efficiency and decolorizing effect.
In the purification method of the present invention, in the step (3), the vacuum concentration conditions are: the vacuum degree is-0.08 to-0.09 MPa, and the temperature is 60 to 70 ℃.
In the purification method, in the step (3), the decolorized solution is concentrated in vacuum until the solid content is 70-75%, and then the pH value is adjusted to 4.0-5.0. The acid adjusting process can adopt concentrated hydrochloric acid and other acid liquor which are conventional in the field.
In the purification method of the present invention, in the step (3), the cooling crystallization specifically comprises the following steps: firstly, cooling to 55 ℃, putting lysine hydrochloride seed crystals according to the mass percentage of 1-10%, growing the crystals for 2-4 h, and then cooling to 45 ℃ at the speed of 1 ℃/h; then reduced to 15 ℃ at a rate of 3 ℃/h. Separating the obtained crystal slurry by a centrifuge, washing by absolute ethyl alcohol, and drying by using a high-efficiency fluidized bed at 50-60 ℃ to obtain white acicular lysine hydrochloride crystals with the content of more than 98.5%. In the process, through controlling the crystal growing time and the cooling speed, the technical difficulties that the metastable zone of lysine hydrochloride crystallization is narrow, solidification can occur when the concentration is too high, and no crystal is generated when the concentration is too low can be solved, so that high-quality crystals are obtained, and the crystallization yield is improved.
In the purification method of the present invention, in the step (4), the vacuum concentration conditions are: the vacuum degree is between-0.08 and-0.09 Mpa, and the concentration temperature is 65 to 70 ℃; concentrating until the solid content is 30-40%, and then carrying out spray drying to obtain the low-purity lysine hydrochloride.
As one preferable embodiment of the invention, the lysine hydrochloride fermentation liquor has a solid content of 22-25%, a pH value of 6.7-6.9, and a lysine hydrochloride content of 15-20 g/100 mL. Experiments prove that the technical scheme of the invention has better purification effect on the lysine hydrochloride under the conditions. In addition, in the purification method, the lysine hydrochloride fermentation liquor is preferably put into a tank and then heated to 80 ℃ and kept for 10min, so that a better sterilization effect is realized.
The invention adopts advanced membrane separation process to replace the traditional resin adsorption method for preparing lysine process, further improves the purity and yield of lysine hydrochloride by specifically optimizing the conditions of the membrane separation process, and solves the technical difficulty that lysine hydrochloride is not easy to crystallize in aqueous solution; meanwhile, the lysine hydrochloride in the membrane concentrated phase and the crystallization mother liquor is fully extracted, the utilization value of the lysine hydrochloride fermentation liquor is effectively improved, and the problem of environmental pollution caused by direct discharge of the crystallization mother liquor is avoided. The extraction rate of the total lysine hydrochloride obtained by the invention can reach more than 98 percent.
Detailed Description
The examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
The concentration of the invention is mass concentration, and the solid content is mass content.
The lysine hydrochloride fermentation liquor is from Anhui Feng original fermentation technology engineering Limited company.
Example 1
The invention provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor, which specifically comprises the following steps:
step (1): taking lysine hydrochloride fermentation liquor, wherein the solid content is 22%, the pH value is 6.8, and the lysine hydrochloride content is 15g/100 mL. Filtering the lysine hydrochloride fermentation liquor by adopting a microporous ceramic membrane to obtain a micro-filtrate and a membrane concentrated phase;
the aperture of the ceramic membrane is 0.05 μm; the inlet pressure of the microporous ceramic membrane is 0.2MPa, the outlet pressure of the microporous ceramic membrane is 0.1MPa, and the membrane flux of the microporous ceramic membrane is 50 LMH.
Step (2): decolorizing the micro-filtrate by adopting powdered activated carbon to obtain a decolorized solution; the adding amount of the active carbon is 0.001g/mL of the micro-filtrate, the decoloring temperature is 60 ℃, and the time is 30 min.
And (3): concentrating the decolorized solution in vacuum at-0.08 MPa and 60 deg.C to solid content of 70% to obtain concentrated solution. Adjusting the pH value of the concentrated solution to 4.0. Cooling the concentrated solution to 50 ℃, adding 1% (m/m) lysine hydrochloride seed crystal into the concentrated solution, growing the crystals for 2h, and then cooling to 40 ℃ at the cooling rate of 1 ℃/h; then the temperature is reduced to 10 ℃ at the cooling rate of 3 ℃/h to obtain crystal slurry. And (3) centrifugally separating the crystal slurry, washing the centrifuged wet crystal with water, and drying the washed wet crystal with a high-efficiency boiling bed at 50 ℃ to obtain the lysine hydrochloride crystal.
And (4): and (3) combining the membrane concentrated phase obtained in the step (1) and the crystallization mother liquor obtained in the step (3), concentrating in vacuum at the vacuum degree of-0.08 MPa and the concentration temperature of 65 ℃, concentrating in vacuum until the solid content is 30% (m/m), and then performing spray drying to obtain a lysine hydrochloride mixture.
In the step (1) of this example, the lysine hydrochloride fermentation broth was concentrated by 5.9 times, the concentrated lysine content was 4.47g/100mL, and the solid content was 13.3%. The concentration multiple is the ratio of the total feed liquid entering the ceramic membrane to the concentrated phase except the clear phase after the completion.
In the step (3) of this example, the obtained lysine hydrochloride crystals have a content of 98.8% (calculated as hydrochloride), an ammonia nitrogen content of 0.025% (m/m), and an ash content of 0.14% (m/m).
In this example, the purity of lysine hydrochloride crystals was 99.7%, and the yield was 70%; the purity of lysine hydrochloride in the lysine hydrochloride mixture was 66%, and the yield was 94%. The total yield of lysine hydrochloride in this example was 98.2%.
Example 2
The invention provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor, which specifically comprises the following steps:
step (1): taking lysine hydrochloride fermentation liquor, wherein the solid content is 23%, the pH value is 6.7, and the lysine hydrochloride content is 18g/100 mL. Filtering the lysine hydrochloride fermentation liquor by adopting a microporous ceramic membrane to obtain a micro-filtrate and a membrane concentrated phase;
the aperture of the ceramic membrane is 0.08 mu m; the inlet pressure of the microporous ceramic membrane is 0.25MPa, the outlet pressure of the microporous ceramic membrane is 0.15MPa, and the membrane flux of the microporous ceramic membrane is 60 LMH.
Step (2): decolorizing the micro-filtrate by adopting activated carbon to obtain a decolorized solution; the adding amount of the active carbon is 0.0015g/mL of the micro-filtrate, the decoloring temperature is 65 ℃, and the time is 45 min.
And (3): concentrating the decolorized solution in vacuum at-0.085 MPa and 65 deg.C to solid content of 72% to obtain concentrated solution. Adjusting the pH value of the concentrated solution to 4.5. Cooling the concentrated solution to 52 ℃, adding 6% (m/m) lysine hydrochloride seed crystals into the concentrated solution, growing crystals for 3h, and then cooling to 42 ℃ at a cooling rate of 1 ℃/h; then the temperature is reduced to 12 ℃ at the cooling rate of 3 ℃/h to obtain crystal slurry. Drying the obtained wet crystal by using an efficient boiling bed at 55 ℃ to obtain the lysine hydrochloride crystal.
And (4): and (3) combining the membrane concentrated phase obtained in the step (1) and the crystallization mother liquor obtained in the step (3), concentrating in vacuum at the vacuum degree of-0.085 MPa and the concentration temperature of 67 ℃, concentrating in vacuum until the solid content is 35% (m/m), and then performing spray drying to obtain a lysine hydrochloride mixture.
Wherein, the purity of lysine hydrochloride crystal in this example is 99%, and the yield is 71%; the purity of lysine hydrochloride in the lysine mixture was 65.5%, and the yield was 94%. The total yield of lysine hydrochloride in this example was 98.26%.
Example 3
The invention provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor, which specifically comprises the following steps:
step (1): taking lysine hydrochloride fermentation liquor, wherein the solid content is 25%, the pH value is 6.8, and the content of lysine hydrochloride is 20g/100 mL. Filtering the lysine hydrochloride fermentation liquor by adopting a microporous ceramic membrane to obtain a micro-filtrate and a membrane concentrated phase;
the aperture of the ceramic membrane is 0.1 mu m; the inlet pressure of the microporous ceramic membrane is 0.3MPa, the outlet pressure of the microporous ceramic membrane is 0.2MPa, and the membrane flux of the microporous ceramic membrane is 70 LMH.
Step (2): decolorizing the micro-filtrate by adopting activated carbon to obtain a decolorized solution; the adding amount of the active carbon is 0.002g/mL of the micro-filtrate, the decoloring temperature is 70 ℃, and the time is 60 min.
And (3): concentrating the decolorized solution in vacuum at-0.09 MPa and 70 deg.C to solid content of 75% to obtain concentrated solution. Adjusting the pH value of the concentrated solution to 5.0. Cooling the concentrated solution to 55 ℃, adding 10% (m/m) lysine hydrochloride seed crystals into the concentrated solution, growing crystals for 4h, and cooling to 45 ℃ at a cooling rate of 1 ℃/h; then the temperature is reduced to 15 ℃ at the cooling rate of 3 ℃/h to obtain crystal slurry. Drying the obtained wet crystal by using an efficient boiling bed at 60 ℃ to obtain the lysine hydrochloride crystal.
And (4): and (3) mixing the membrane concentrated phase obtained in the step (1) and the crystallization mother liquor obtained in the step (3) for vacuum concentration, wherein the vacuum degree is-0.09 MPa, the concentration temperature is 70 ℃, and the membrane concentrated phase is subjected to vacuum concentration until the solid content is 40% (m/m), and then spray drying is carried out, so as to prepare 65.2% lysine hydrochloride.
Wherein, the purity of the lysine hydrochloride crystal in the embodiment is 99.73%, and the yield is 72.5%; the purity of lysine hydrochloride in the lysine hydrochloride mixture was 65.6%, and the yield was 94.1%. The total yield of lysine hydrochloride in this example was 98.38%.
Example 4
The invention provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor, which specifically comprises the following steps:
step (1): 500L of heated fermentation liquor is taken, the solid content is 25 percent, the lysine content is 19.5g/100mL, and the pH value is 6.8. Filtering the fermentation liquor by using a 0.05-micron ceramic membrane, wherein the membrane inlet pressure is 0.2MPa, the membrane outlet pressure is 0.15MPa, the flux is 55.8LMH,
step (2): the ceramic membrane micro-filtrate has 20 percent of solid content and 15.1g/100mL of lysine content. Decolorizing the micro-filtrate with powdered carbon, wherein the addition amount of the powdered carbon is 0.0014g/mL of the micro-filtrate, the decolorizing temperature is 67 ℃, and the decolorizing time is 40 min. The dialysate mixed transmittance was measured at 430nm and found to be 83%.
And (3): vacuum concentrating the decolorized solution to solid content of 74%, pumping the concentrated solution into a crystallizer, adjusting the pH value to 4.6 by using concentrated hydrochloric acid, cooling to 55 ℃, adding 450g of seed crystal, growing crystals for 2h, and starting cooling crystallization after the crystal growth is finished, wherein the cooling speed is controlled to be 1 ℃/h between 55 ℃ and 45 ℃, the cooling speed is controlled to be 3 ℃/h between 45 ℃ and 15 ℃, cooling crystallization is carried out to 15 ℃, centrifugal separation is carried out, and crystals are washed by absolute ethyl alcohol. The mother liquor had a solids content of 56% (m/m) and a lysine content of 34.2% (m/v).
The obtained wet crystal is dried by a high-efficiency boiling bed at 50-60 ℃, the crystal is white needle-shaped, the crystal content is 98.8 percent (calculated by hydrochloride), the ammonia nitrogen content is 0.025 percent (m/m), and the ash content is 0.14 percent (m/m).
And (4): and (3) mixing the ceramic membrane concentrated phase obtained in the step (1) and the crystallization mother liquor obtained in the step (3) for vacuum concentration, wherein the vacuum degree is-0.085 MPa, the concentration temperature is 67 ℃, and the lysine hydrochloride with the content of 65% is prepared by spray drying after vacuum concentration until the solid content is 32% (m/m).
In this example, the purity of lysine hydrochloride crystals was 99%, and the yield was 72.6%; the purity of lysine hydrochloride in the lysine hydrochloride mixture was 66%, and the yield was 94.6%. The total yield of lysine hydrochloride in this example was 98.5%.
Example 5
The invention provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor, which specifically comprises the following steps:
step (1): 400L of heated fermentation liquor is taken, the solid content is 23%, the lysine content is 18.2g/100mL, and the pH value is 6.75.
Filtering the fermentation liquor by using a 0.05-micron ceramic membrane, filtering out thalli, concentrating by 6.6 times, and adding 130L of dialysis water, wherein the membrane inlet pressure is 0.2MPa, the outlet pressure is 0.15MPa, and the flux is 56.1 LMH. The volume of the concentrated phase is 80L, the lysine content of the concentrated phase is 4.2g/100mL, and the solid content is 12.6%.
Step (2): the ceramic membrane micro-filtrate has 18 percent of solid content and 14.7g/100mL of lysine content. And decolorizing the micro-filtrate by using powdered carbon, wherein the addition amount of the powdered carbon is 0.0012g/mL of the micro-filtrate, the decolorizing temperature is 65 ℃, and the decolorizing time is 38 min. The dialysate mixed transmittance was determined to be 81% at 430 nm.
And (3): concentrating the decolorized solution to 75% of solid content, pumping the concentrated solution into a crystallizing tank, adjusting the pH value to 4.8 by using concentrated hydrochloric acid, cooling to 55 ℃, adding 300g of seed crystal, growing crystals for 2.5h, and starting cooling crystallization after the crystal growth is finished, wherein the cooling speed is controlled to be 1 ℃/h between 55 ℃ and 45 ℃, the cooling speed is controlled to be 3 ℃/h between 45 ℃ and 15 ℃, cooling crystallization is carried out to 15 ℃, centrifugal separation is carried out, and crystals are washed by absolute ethyl alcohol. The mother liquor has a solid content of 57.5% (m/m) and a lysine content of 32% (m/v).
The obtained wet crystal is dried by a high-efficiency boiling bed at 50-60 ℃, the crystal is white needle-shaped, the crystal content is 98.7 percent (calculated by hydrochloride), the ammonia nitrogen content is 0.02 percent (m/m), and the ash content is 0.15 percent (m/m).
And (4): mixing the obtained ceramic membrane concentrated phase and crystallization mother liquor, vacuum concentrating at-0.085 MPa and 65 deg.C until the solid content reaches 37% (m/m), and spray drying to obtain 65% lysine hydrochloride.
In this example, the purity of lysine hydrochloride crystals was 99.1%, and the yield was 71.8%; the purity of lysine hydrochloride in the lysine hydrochloride mixture was 65.8%, and the yield was 94.1%. The total yield of lysine hydrochloride in this example was 98.3%.
Example 6
The invention provides a method for extracting lysine hydrochloride from lysine hydrochloride fermentation liquor, which specifically comprises the following steps:
step (1): 300L of heated fermentation liquor is taken, the solid content is 22%, the lysine content is 16.9g/100mL, and the pH value is 6.9.
Filtering the fermentation liquor by using a 0.05-micron ceramic membrane, filtering out thalli, concentrating by 6.2 times, and adding 90L of dialyzed water, wherein the membrane inlet pressure is 0.2MPa, the membrane outlet pressure is 0.15MPa, and the flux is 56.7 LMH. The volume of a concentrated phase is 63L, the lysine content of the concentrated phase is 4.2g/100mL, and the solid content is 14.4%.
Step (2): the ceramic membrane micro-filtrate has the solid content of 19.5 percent and the lysine content of 15.7g/100 mL. And decolorizing the micro-filtrate by using powdered carbon, wherein the addition amount of the powdered carbon is 0.0016g/mL of the micro-filtrate, the decolorizing temperature is 65 ℃, and the decolorizing time is 40 min. The dialysate mixed transmittance was measured at 430nm and found to be 84%.
And (3): concentrating the decolorized solution to a solid content of 72%, pumping the concentrated solution into a crystallizing tank, adjusting the pH value to 4.7 by using concentrated hydrochloric acid, cooling to 55 ℃, adding 200g of seed crystal, growing crystals for 3 hours, and starting cooling crystallization after the crystal growth is finished, wherein the cooling speed is controlled to be 1 ℃/h between 55 ℃ and 45 ℃, the cooling speed is controlled to be 3 ℃/h between 45 ℃ and 15 ℃, the temperature is reduced to 15 ℃, performing centrifugal separation, and washing the crystals by using absolute ethyl alcohol. The mother liquor has a solid content of 55% (m/m) and a lysine content of 31.8% (m/v).
The obtained wet crystal is dried by a high-efficiency boiling bed at 50-60 ℃, the crystal is white needle-shaped, the crystal content is 98.7 percent (calculated by hydrochloride), the ammonia nitrogen content is 0.018 percent (m/m), and the ash content is 0.1 percent (m/m).
And (4): mixing the obtained ceramic membrane concentrated phase and crystallization mother liquor, vacuum concentrating at-0.085 MPa and 67 deg.C until the solid content reaches 34% (m/m), and spray drying to obtain 65% lysine hydrochloride.
In this example, the purity of lysine hydrochloride crystals was 98.8%, and the yield was 70%; the purity of lysine hydrochloride in the lysine hydrochloride mixture was 66%, and the yield was 94%. The total yield of lysine hydrochloride in this example was 98.2%.
From the above embodiments, the method of the invention has simple process and environmental protection, and the 65% lysine prepared by the mother liquor and the membrane concentrated phase can achieve the purpose of recycling waste. Meanwhile, compared with the traditional process, the purification method can obtain qualified products of lysine hydrochloride with the content of 98.5 percent or more and 65 percent of lysine by-products. And 65% of lysine as a by-product of the process brings about greater economic benefits to production.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (2)
1. A method for purifying lysine hydrochloride is characterized by comprising the following steps:
step (1): filtering the lysine hydrochloride fermentation liquor by adopting a microporous ceramic membrane to obtain a micro-filtrate and a membrane concentrated phase;
step (2): decolorizing the micro-filtrate by adopting activated carbon to obtain a decolorized solution;
and (3): vacuum concentrating the obtained decolorized solution, adjusting acid, cooling and crystallizing to obtain wet crystal and crystallization mother liquor; wherein the wet crystal is further centrifugally dried to obtain a lysine hydrochloride crystal;
and (4): combining the membrane concentrated phase obtained in the step (1) and the crystallization mother liquor obtained in the step (3), and performing vacuum concentration and spray drying on the obtained mixed liquor to obtain lysine hydrochloride with the content of more than 65%;
wherein,
in the step (1), the inlet pressure of the microporous ceramic membrane is 0.2-0.3 MPa, and the pressure difference between an inlet and an outlet is 0.05 MPa; the membrane flux of the microporous ceramic membrane is 50-70 LMH; the aperture of the microporous ceramic membrane is 0.05-0.1 μm;
in the step (2), the addition amount of the active carbon is 0.001-0.002 g/mL of micro-filtrate; the decoloring temperature is 60-70 ℃, and the time is 30-60 min;
in the step (3), the vacuum concentration conditions are as follows: the vacuum degree is-0.08 to-0.09 MPa, and the temperature is 60 to 70 ℃; concentrating the decolorized solution in vacuum until the solid content is 70-75%, and then adjusting the pH value to 4.0-5.0; the specific operation steps of cooling crystallization are as follows: firstly, cooling to 55 ℃, putting lysine hydrochloride seed crystals according to the mass percentage of 1-10%, growing the crystals for 2-4 h, and then cooling to 45 ℃ at the speed of 1 ℃/h; then reducing the temperature to 15 ℃ at the speed of 3 ℃/h, centrifuging, washing with absolute ethyl alcohol, and drying at 50-60 ℃ by using a high-efficiency boiling bed to obtain lysine hydrochloride crystals;
in the step (4), the vacuum concentration conditions are as follows: the vacuum degree is between-0.08 and-0.09 Mpa, and the concentration temperature is 65 to 70 ℃; concentrating until the solid content is 30-40%, and then carrying out spray drying to obtain lysine hydrochloride.
2. The method according to claim 1, wherein the lysine hydrochloride fermentation broth has a solid content of 22 to 25%, a pH value of 6.7 to 6.9, and a lysine hydrochloride content of 15 to 20g/100 mm.
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