CN100465154C - Processing method for producing amino acid by using (supercritical) near-critical hydrolyzed biomass - Google Patents
Processing method for producing amino acid by using (supercritical) near-critical hydrolyzed biomass Download PDFInfo
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- CN100465154C CN100465154C CNB2006100262211A CN200610026221A CN100465154C CN 100465154 C CN100465154 C CN 100465154C CN B2006100262211 A CNB2006100262211 A CN B2006100262211A CN 200610026221 A CN200610026221 A CN 200610026221A CN 100465154 C CN100465154 C CN 100465154C
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Abstract
The invention relates to a technique of amino acids'preparation which using (super) approximate critical hydrolysis biomass, belonging to organic biology processing technological realm. This invention using animal biomass as material, after disintegration, mixing with deionized water of finite proportion, and then beating by beater, emulsifications by colloidal mill, carrying into (super) approximate critical water autoclave for hydrolysis. The hydrolysis technological conditions are: controlling reaction temperature between 220-300deg C, reaction pressure is 5-25Mpa, reaction time is 10-40min. According to different raw materal, in order to avoid amino acid oxidation, using air, nitrogen and carbon dioxide as reaction atmosphere seperatly, doing (super) approximate critical hydrolysis by control reaction condition. The method of this invention has high conversion rate, no environmental pollution, it is a green protection process of environment friendly.
Description
Technical field
The present invention relates to a kind of (surpassing) near-critical water and separate biomass and prepare amino acid whose processing method, belong to organic-biological processing treatment Technology field.
Background technology
The main organic composition of biomass is protein and fat, and wherein protein is the basic substance of life.Proteinic fundamental unit is an amino acid.Amino acid contained kind and different amts in the different proteins, some amino acid can not synthesize in human body or the composite number quantity not sufficient, must be replenished by food proteins and just can keep the body normal growth and grow.Human body self can not be called the nutrition indispensable amino acid by synthetic amino acid, and they must be provided by external, then will cause protein synthesis obstacle in the body if lack the nutrition indispensable amino acid.
The nutrition indispensable amino acid mainly contains 8 kinds, and they are: Methionin, tryptophane, phenylalanine, first sulphur (egg) propylhomoserin, Threonine, leucine, Isoleucine and Xie Ansuan.
The hydrolysis of biomass mainly is proteinic hydrolysis, and protein can be by acid, alkali or proteolytic enzyme catalytic hydrolysis.Acid-hydrolyzed shortcoming is that tryptophane can all be destroyed by acid, and Serine, Threonine and tyrosine etc. also have sub-fraction to be decomposed.The shortcoming of basic hydrolysis is, has multiple amino acids can suffer in various degree destruction in the hydrolytic process, and easily produces the racemization phenomenon, and products therefrom is D-amino acid and the amino acid whose mixture of L-.No matter be acid hydrolysis or basic hydrolysis, all environment is produced bigger pollution, and the water resources consumption amount be bigger in the acid-base neutralisation process.The shortcoming of enzymatic hydrolysis is, often hydrolysis is not thorough to use a kind of enzyme, needs several enzymes synergies just can make the protein complete hydrolysis, and its technology is also complicated; In addition, the enzymic hydrolysis required time is also longer, and enzyme is to the envrionment conditions sensitivity.
Summary of the invention
In order to overcome some defectives that the said hydrolyzed method exists, the present invention has created the method that a kind of (surpassing) near-critical water is separated biomass.(surpassing) near-critical water is separated does not need acid, alkaline catalysts, can reach the effect of complete hydrolysis or partial hydrolysis by temperature, pressure and the hydrolysis time of control reaction.
(surpassing) near-critical water has big solubleness to most of organic compound, and its performance is equivalent to acetone, can substitute organic solvent commonly used.The ionic product of (surpassing) near-critical water has acidity or base catalysis effect than big several thousand times of the ionic product of normality water.(surpassing) near-critical water has very high energies, can improve reaction conversion ratio, accelerates speed of reaction, and water is a kind of environment amenable friendly process to not pollution of environment.
It is simple to the purpose of this invention is to provide a kind of technology, and environment amenable (surpassing) near-critical water is separated biomass and prepared amino acid whose processing method.
A kind of (surpassing) near-critical water is separated the processing method of biomass preparation base acid, it is characterized in that having following technological process and step:
A. be raw material with animal organism matter, raw material includes by product, Litter and the scrap stock that aquatic product, bird, herding class and the course of processing thereof produce, as the flesh of fish, pork, chicken etc., and the course of processing produces by product, Litter and scrap stock, as raw fish, end to end, internal organ, Xia Shui, firecoat hair etc.; In above-mentioned raw materials, select any, it is placed in the pulverizer pulverizes, add a certain amount of deionized water subsequently, and mix, send into hollander then and pull an oar, put into colloidal mill at last again and process emulsification, generate whey liquid;
B. above-mentioned whey liquid is delivered in (surpassing) near-critical water reactor and be hydrolyzed; Need in advance kettle and pipeline to be carried out pipeline purging, empty and hunt leak with gas; Used gas is selected air, nitrogen or carbonic acid gas for use according to different material, to form required reaction atmosphere, avoids some amino acid whose oxidation;
C. energising heating makes the reaction that is hydrolyzed of biomass material in (surpassing) near-critical water reactor; The processing condition regulating and controlling of hydrolysis reaction is: 220～300 ℃ of temperature of reaction, reaction pressure 5～25MPa, 10～40 minutes reaction times.
Description of drawings
Fig. 1 is amino acid standard model and flesh of fish hydrolyzation sample collection of illustrative plates comparison diagram.
Among the figure: a arginine, b Methionin, c L-Ala, e Threonine, d glycine, f Xie Ansuan, h Serine, g proline(Pro), i Isoleucine, j leucine, k methionine(Met), 1 Histidine, m phenylalanine, n L-glutamic acid, o aspartic acid, p Gelucystine, q tyrosine
Fig. 2 is amino acid standard model and pork hydrolyzation sample collection of illustrative plates comparison diagram.
Among the figure: a arginine, b Methionin, c Threonine, d glycine, e Xie Ansuan, f Serine, g Isoleucine, h leucine, i methionine(Met), j Histidine, k phenylalanine, 1 L-glutamic acid, m aspartic acid, n Gelucystine, o tyrosine
Fig. 3 is amino acid standard model and hydrolysis of chicken meat sample collection of illustrative plates comparison diagram.
Among the figure: a arginine, b Methionin, c Threonine, d glycine, e Xie Ansuan, f Serine, g Isoleucine, h leucine, i methionine(Met), j Histidine, k phenylalanine, 1 L-glutamic acid, m aspartic acid, n Gelucystine, o tyrosine
Fig. 4 is amino acid standard model and fish processing waste hydrolyzation sample collection of illustrative plates comparison diagram.
Among the figure: a arginine, b Methionin, c L-Ala, d Threonine, e glycine, f Xie Ansuan, g Serine, h proline(Pro), i Isoleucine, j leucine, k methionine(Met), 1 Histidine, m phenylalanine, n L-glutamic acid, o aspartic acid, p Gelucystine, q tyrosine
Embodiment
After now specific embodiments of the invention being described in.
The hydrolysis process process and the step of present embodiment are as described below:
(1) chooses the 100g flesh of fish and be raw material, at first it is pulverized, add deionized water subsequently, make its volume reach 2 liters, mix, send into hollander then to pull an oar, put into colloidal mill again and process emulsification, generate whey liquid;
(2) above-mentioned whey liquid is delivered in (surpassing) near-critical water reactor be hydrolyzed; With air kettle and pipeline are carried out pipeline purging, empty and hunt leak in advance; With air as reaction atmosphere;
(3) getting 180 milliliters of fish slurries, to send into volume be in 200 milliliters the reactor; The energising heating makes the fish slurry in (surpassing) near-critical water reactor that hydrolysis reaction take place; Temperature of reaction is controlled to be 220 ℃, and reaction pressure is 18MPa, and the reaction times is 40 minutes.
The final hydrolyzed solution that obtains is with amino acidanalyser analysis amino acid kind and productive rate thereof wherein.
Prepared the solution that contains 17 seed amino acid standard models in the experiment, analyzed with amino acidanalyser equally, to make the usefulness of contrast.
Flesh of fish hydrolyzation sample and amino acid standard model collection of illustrative plates comparison diagram are referring to the Fig. 1 in the accompanying drawing.
Various amino acid whose productive rate in the present embodiment is as shown in table 1 below:
The amino acid whose productive rate of table 1 present embodiment
| Amino acid | Histidine | Different bright Isoleucine * | L-Ala | Phenylalanine * | Bright leucine * | Silk and proline(Pro) | Arginine | Methionine(Met) * | Methionin * | Xie Ansuan * | Threonine * | Glycine | Tyrosine |
| Productive rate (ton/hundred tons) | 0.38 | 0.20 | 0.40 | 0.52 | 1.30 | 0.50 | 0.39 | 0.42 | 0.20 | 0.30 | 0.28 | 0.34 | 0.70 |
Annotate: band
*Number be the necessary amino acid of human body, other has ends such as Gelucystine, L-glutamic acid and aspartic acid to do quantitative analysis.
The hydrolysis process process and the step of present embodiment are as described below:
(1) choosing 100g pork is raw material, at first it is pulverized, and adds deionized water subsequently, makes its volume reach 2 liters, mixes, and sends into hollander then and pulls an oar, and puts into colloidal mill again and processes emulsification, generates whey liquid;
(2) above-mentioned whey liquid is delivered in (surpassing) near-critical water reactor be hydrolyzed; With nitrogen kettle and pipeline are carried out pipeline purging, empty and hunt leak in advance; With nitrogen as reaction atmosphere;
(3) getting 180 milliliters of pork slurries, to send into volume be in 200 milliliters the reactor; The energising heating makes the pork slurry in (surpassing) near-critical water reactor that hydrolysis reaction take place; Temperature of reaction is controlled to be 280 ℃, and reaction pressure is 25MPa, and the reaction times is 10 minutes.
The final hydrolyzed solution that obtains is with amino acidanalyser analysis amino acid kind and productive rate thereof wherein.
Prepared the solution that contains 15 seed amino acid standard models in the experiment, analyzed with amino acidanalyser equally, to make the usefulness of contrast.
Pork hydrolyzation sample and amino acid standard model collection of illustrative plates comparison diagram are referring to the Fig. 2 in the accompanying drawing.
Various amino acid whose productive rate in the present embodiment is as shown in table 2 below:
The amino acid whose productive rate of table 2 present embodiment
| Amino acid | Histidine | Isoleucine * | Glycine | Phenylalanine * | Bright leucine * | Silk and proline(Pro) | Arginine | Methionine(Met) * | Methionin * | Xie Ansuan * | Threonine * | Gelucystine | Tyrosine |
| Productive rate (ton/hundred tons) | 0.20 | 0.16 | 0.30 | 0.25 | 0.80 | 0.60 | 0.70 | 0.10 | 0.32 | 0.60 | 0.11 | 0.10 | 0.32 |
Annotate: band
*Number be the necessary amino acid of human body, other has L-Ala, L-glutamic acid and aspartic acid end quantitative analysis.
Embodiment 3
The hydrolysis process process and the step of present embodiment are as described below:
(1) choosing 100g chicken is raw material, at first it is pulverized, and adds deionized water subsequently, makes its volume reach 2 liters, mixes, and sends into hollander then and pulls an oar, and puts into colloidal mill again and processes emulsification, generates whey liquid;
(2) above-mentioned whey liquid is delivered in (surpassing) near-critical water reactor be hydrolyzed; With carbon dioxide kettle and pipeline are carried out pipeline purging, empty and hunt leak in advance; With carbon dioxide as reaction atmosphere;
(3) getting 180 milliliters of chicken whey liquids, to send into volume be in 200 milliliters the reactor; The energising heating makes the chicken whey liquid generation hydrolysis reaction in (surpassing) near-critical water reactor; Temperature of reaction is controlled to be 240 ℃, and reaction pressure is 15MPa, and the reaction times is 20 minutes.
The final hydrolyzed solution that obtains is with amino acidanalyser analysis amino acid kind and productive rate thereof wherein.
Prepared the solution that contains 15 seed amino acid standard models in the experiment, analyzed with amino acidanalyser equally, to make the usefulness of contrast.
Hydrolysis of chicken meat sample and amino acid standard model collection of illustrative plates comparison diagram are referring to the Fig. 3 in the accompanying drawing.
Various amino acid whose productive rate in the present embodiment is as shown in table 3 below:
The amino acid whose productive rate of table 3 present embodiment
| Amino acid | Histidine | Isoleucine * | Glycine | Propylhomoserin in the benzene * | Bright leucine * | Silk and proline(Pro) | Arginine | The egg methionine(Met) * | Methionin * | Xie Ansuan * | Threonine * | Gelucystine | Tyrosine |
| Productive rate (hundred tons of tons) | 0.18 | 0.20 | 0.15 | 0.22 | 1.00 | 0.73 | 0.55 | 0.50 | 0.43 | 0.89 | 0.10 | 0.10 | 0.72 |
Annotate: band
*Number be the necessary amino acid of human body, other has L-Ala, L-glutamic acid and aspartic acid end quantitative analysis.
Embodiment 4
The hydrolysis process process and the step of present embodiment are as described below:
(1) choosing the byproduct and the scrap stock waste that produce in the 100g fish course of processing is raw material, at first it is pulverized, and adds deionized water subsequently, make its volume reach 2 liters, mix, send into hollander then and pull an oar, put into colloidal mill again and process emulsification, generate whey liquid;
(2) above-mentioned whey liquid is delivered in (surpassing) near-critical water reactor be hydrolyzed; With air kettle and pipeline are carried out pipeline purging, empty and hunt leak in advance; With air as reaction atmosphere;
(3) getting 180 milliliters of whey liquids, to send into volume be in 200 milliliters the reactor; The energising heating makes the whey liquid generation hydrolysis reaction in (surpassing) near-critical water reactor; Temperature of reaction is controlled to be 260 ℃, and reaction pressure is 5MPa, and the reaction times is 20 minutes.
The final hydrolyzed solution that obtains is with amino acidanalyser analysis amino acid kind and productive rate thereof wherein.
Prepared the solution that contains 17 seed amino acid standard models in the experiment, analyzed with amino acidanalyser equally, to make the usefulness of contrast.
Fish processing waste hydrolyzation sample and amino acid standard model collection of illustrative plates comparison diagram are referring to the Fig. 4 in the accompanying drawing.
Various amino acid whose productive rate in the present embodiment is as shown in table 4 below:
The amino acid whose productive rate of table 4 present embodiment
| Amino acid | Histidine | Isoleucine * | L-Ala | Phenylalanine * | Bright leucine * | Silk and proline(Pro) | Arginine | The egg methionine(Met) * | Methionin * | Xie Ansuan * | Threonine * | Glycine | Tyrosine |
| Productive rate (ton/hundred tons) | 0.28 | 0.20 | 0.21 | 0.21 | 0.36 | 0.50 | 1.00 | 0.15 | 0.10 | 0.38 | 0.23 | 0.35 | 0.32 |
Annotate: band
*Number be the necessary amino acid of human body, other has Gelucystine, L-glutamic acid and aspartic acid end quantitative analysis.
Claims (1)
1. a super or near-critical water is separated biomass and is prepared amino acid whose processing method, it is characterized in that having following technological process and step:
A. be raw material with animal organism matter, raw material is any in aquatic product, bird, herding class and the course of processing thereof the by product, Litter and the scrap stock that produce, it is placed in the pulverizer pulverizes, add a certain amount of deionized water subsequently, and mix, send into hollander then and pull an oar, put into colloidal mill at last again and process emulsification, generate whey liquid;
B. above-mentioned whey liquid is delivered in super or the near-critical water reactor and be hydrolyzed; Need in advance kettle and pipeline to be carried out pipeline purging, empty and hunt leak with gas; Used gas is selected air, nitrogen or carbonic acid gas for use according to different material, to form required reaction atmosphere;
C. energising heating makes the reaction that is hydrolyzed of biomass material in super or the near-critical water reactor; The processing condition regulating and controlling of hydrolysis reaction is: 220～300 ℃ of temperature of reaction, reaction pressure 5～25MPa, 10～40 minutes reaction times.
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| CN101863727A (en) * | 2010-06-29 | 2010-10-20 | 上海大学 | Method for preparing amino acid by hydrolyzing soybean dregs in near-critical water |
| CN103130595B (en) * | 2013-03-05 | 2015-01-07 | 新沂市汉菱生物工程有限公司 | Method for hydrolyzing feather to extract amino acid through microwave heating at high temperature and high pressure |
| CN103951726A (en) * | 2014-04-09 | 2014-07-30 | 上海大学 | Process for preparing polypeptide surfactant by near-critical hydrolysis of feather keratin |
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Non-Patent Citations (10)
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| production of organic acids and amino acids from fish meatby sub-critical water hydrolysis. Hiroyuki Yoshida et al.Biotechnol.Prog.,Vol.15 No.6. 1999 |
| production of organic acids and amino acids from fish meatby sub-critical water hydrolysis. Hiroyuki Yoshida et al.Biotechnol.Prog.,Vol.15 No.6. 1999 * |
| sub-critical water hydrolysis treatment for waste squid entrailsand production of amino acids,organic acids,and fatty acids. Hiroyuki Yoshida.Journal of chemical engineering of Japan,Vol.37 No.2. 2004 |
| sub-critical water hydrolysis treatment for waste squid entrailsand production of amino acids,organic acids,and fatty acids. Hiroyuki Yoshida.Journal of chemical engineering of Japan,Vol.37 No.2. 2004 * |
| 动物蹄甲超声水解制备复合氨基酸的新工艺. 穆军，呼世斌.西北农林科技大学学报(自然科学版) ,，第2期. 2006 |
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| 角蛋白的水解. 丁金贵.明胶科学与技术，第2期. 1985 |
| 角蛋白的水解. 丁金贵.明胶科学与技术，第2期. 1985 * |
| 超(亚)临界水氧化法在固体废物资源化中的应用. 孙晓红，汪群慧.现代化工，第5期. 2003 |
| 超(亚)临界水氧化法在固体废物资源化中的应用. 孙晓红，汪群慧.现代化工，第5期. 2003 * |
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