CN106588681B - A kind of method that L alanine is prepared using hydroxyproline waste water as raw material - Google Patents

A kind of method that L alanine is prepared using hydroxyproline waste water as raw material Download PDF

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CN106588681B
CN106588681B CN201611116629.8A CN201611116629A CN106588681B CN 106588681 B CN106588681 B CN 106588681B CN 201611116629 A CN201611116629 A CN 201611116629A CN 106588681 B CN106588681 B CN 106588681B
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alanine
hydroxyproline
waste water
alcohol
solution
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CN106588681A (en
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段二红
李雪
陈子丹
王坤坤
马焕金
俞磊
牛建瑞
罗晓
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Hebei University of Science and Technology
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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
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to the method for hydroxyproline waste water reuse, and in particular to a kind of method using hydroxyproline technique waste water as raw material for L alanine.The present invention uses the method for high-temperature oxydation to prepare L alanine, " activated carbon decolorizing concentration+alcoholic solution separation+alcohol by raw material of hydroxyproline waste water（Ketone）Solution recrystallizes " coupling technique separating-purifying L alanine.Determine that products obtained therefrom is sterling L alanine by nmr analysis and specific rotatory power measure.The present invention realizes waste water reclaiming, reduces cost for wastewater treatment, realizes resource and the target of sustainable development of environment.

Description

A kind of method that ALANINE is prepared using hydroxyproline waste water as raw material
Technical field
The present invention relates to the method for hydroxyproline waste water reuse, and in particular to a kind of to produce hydroxyproline technique waste water The method that ALANINE is prepared for raw material.
Background technology
To produce in the gelatin hydrolysis liquid of hydroxyproline containing largely abundant amino acid, wherein glycine 39.56mg/ ML, hydroxyproline 21.65mg/mL, proline 21.71mg/mL, phenylalanine 15.75mg/mL, arginine 9.8mg/mL etc. two Ten kinds of amino acid.Industrially conventional gelatin hydrolysis-oxidizing process production hydroxyproline, the production technology is using gelatin particle as former material Material, hydrolyzed by hydrochloric acid, natrium nitrosum oxidation, high temperature reduction, activated carbon decolorizing and ion exchange process obtain hydroxyproline.
Gelatine wastewater is desorbed solution after the post after ion exchange collects L- hydroxyprolines, wherein containing substantial amounts of dried meat ammonia Sour and a small amount of L- hydroxyprolines.Ion exchange process must use substantial amounts of hydrochloric acid, ammoniacal liquor, and caused waste water has high chlorine, high ammonia The characteristics of nitrogen.So ion exchange separating-purifying amino acid cost in waste water is high, pollution is big, and discharge and the improvement of waste water turn into Technique problem urgently to be resolved hurrily.Industrially mostly together handled, caused very with other industrial wastewaters both at home and abroad at present Big resource and energy waste, while also increase environmental improvement cost.
The preparation existing process of ALANINE mainly use microbe fermentation method, by cultivate D-alanine brevibacterium or The microbial mutant of corynebacterium, accumulation and isolated ALANINE in nutrient solution（CN 1038669A）.In addition, Screened, obtained high from a kind of culture medium for the Pseudomonasdacunhae that can effectively produce ASPARTIC ACID-β-decarboxylase Yield, the fermentation source of high enzyme activity prepare ALANINE, but fermentation method production ALANINE complex process.Hydroxyproline and dried meat ammonia Sour open loop under the high temperature conditions, ALANINE is generated, but due to comparison of ingredients complexity in gelatin, in addition L- hydroxyprolines production During the reaction of oxidation link it is not thorough so that useless impurities in water amino acid is more, and pigment content is big, so as to cause generation The dopant species of ALANINE are more, amount is big, separating difficulty is big.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparation process is simple, control, operation letter Just, energy consumption and resource cost are few, during non-volatility etchant gas produce, production operation environment is good, the low L- of environmental pollution The preparation method of alanine, realize the sustainable development of resource and environment.Specifically, for being given up caused by production hydroxyproline Hydroxyproline high temperature in wastewater oxidation is prepared ALANINE by the problem of water is present and the property of ALANINE, the present invention, is used " activated carbon decolorizing+be concentrated under reduced pressure+alcoholic solution separation+alcohol（Ketone）Solution recrystallizes " separating-purifying ALANINE.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, comprises the following steps：
A, hydroxyproline waste water is taken, by solution centrifugal, to obtain mother liquor in 80-120 DEG C of reaction 6-8h in reactor；
B, by the mother liquor in step a, the 2-3h that decolourizes is added at mass fraction 0.5-3% 60-70 DEG C of activated carbon, is filtered Colourless transparent solution, it is concentrated under reduced pressure to give solid；
Solid in step b is added to the aqueous solution of alcohol, 2-3h is dissolved at 50-60 DEG C, filtering, dries, obtains the ammonia of L- third c, Acid crude；
D, it is the ALANINE crude product in step c is soluble in water, 55-70 DEG C of ALANINE saturated aqueous solution is prepared, upwards State and alcohol or ketone are added in saturated aqueous solution, until fine crystals separate out in solution, be cooled to 15-25 DEG C, constant temperature aging 6-8h, mistake Filter, dry, obtain ALANINE sterling.
Further, 15-25 is down to 150-300rpm stir speed (S.S.)s, 0.1-0.5 DEG C/min rate of temperature fall in step d ℃。
Further, the alcohol in step c is one kind in methanol, ethanol or n-butanol.Preferably methanol.
Further, the mass ratio of alcohol and water is 98-90 in the aqueous solution of the alcohol in step c：2-10.As to above-mentioned The optimization of process for separation and purification, the mass ratio of methanol and water is 92 in the step c：8, " methanol+water " mixed solvent water is not Foot, causes impurity all to dissolve；Water can excessively introduce other impurities, cause subsequent separation process more complicated.
Further, the alcohol in step d or ketone are ethanol or isopropanol or acetone.As to above-mentioned process for separation and purification Optimize, the alcohol in the step d is ethanol, and crystallization parameters are drop rate 3g/min, stir speed (S.S.) 200rpm respectively, and cooling is fast 0.3 DEG C/min of rate, 15 DEG C of outlet temperature, ageing time 6h.
The present invention is using " high-temperature oxydation+activated carbon decolorizing+is concentrated under reduced pressure+alcoholic solution separation+alcohol（Ketone）Solution recrystallizes " Technique prepares ALANINE from hydroxyproline waste water.It is mainly L- hydroxyprolines and L-PROLINE open loop under hot conditions to prepare Generate ALANINE, " alcoholic solution separation " is mainly that alcohol mixes with water, wherein alcohol include methanol, absolute ethyl alcohol, n-butanol, alcohol and Water quality ratio is 98-90:2-10 mixed solution separation ALANINE." alcohol（Ketone）Solution recrystallization " technique is to ALANINE Subtractive process.ALANINE is soluble in water, is insoluble in some alcohol（Ketone）Solvent, so using the method for dilution crystallization to L- third Propylhomoserin is refined.
The present invention prepares ALANINE using hydroxyproline waste water as raw material, greatly reduces the pressure of follow-up waste water treatment.This Technique separation and purification process is simple, controls, be easy to operate, energy consumption and resource cost are few；Crystallization process non-volatility etchant gas Produce, production operation environment is good, and environmental pollution is low, optimizes Workshop Production environment, reduces labor strength, realizes money Source and the sustainable development of environment.
Brief description of the drawings
The 1H-NMR spectrograms of Fig. 1 products of the present invention
The 13C-NMR spectrograms of Fig. 2 products of the present invention.
Embodiment
Embodiment one
The present embodiment is related to a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, specifically includes following step Suddenly：
A, take hydroxyproline waste water, 110 DEG C of high temperature in reactor, react 6h, by solution centrifugal, obtain ALANINE mother Liquid；
B, by the mother liquor obtained by step a, added at 65 DEG C 3%（Mass fraction）Food grade active carbon decoloring 2h, mistake Filter obtains the solution of water white transparency, is concentrated under reduced pressure to give solid；
C, by the solid of gained in step b, add " methanol+water ", wherein methanol：Water quality ratio=90：10, at 55 DEG C 2h is dissolved, filtration drying obtains ALANINE crude product；
D, gained ALANINE crude product in step c is recrystallized, the saturated aqueous solution of ALANINE is configured at 65 DEG C, Fully dissolving 2h, absolute ethyl alcohol is added with 1g/min drop rate, until when having fine crystals precipitation in solution, stop dissolved The dropwise addition of agent.With 150rpm stir speed (S.S.), 0.2 DEG C/min rate of temperature fall is down to 15 DEG C, constant temperature aging 6h, be filtered by vacuum, It is dried to obtain the sterling of ALANINE.
Embodiment two
The present embodiment is related to a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, specifically includes following step Suddenly：
A, take hydroxyproline waste water, 100 DEG C of high temperature in reactor, react 7h, by solution centrifugal, obtain ALANINE mother Liquid.
B, by the water obtained by step a, added at 60 DEG C 0.5%（Mass fraction）Food grade active carbon decoloring 3h, mistake Filter obtains the solution of water white transparency, is concentrated under reduced pressure to give solid.
C, by the solid of gained in step b, add " absolute ethyl alcohol+water ", wherein absolute ethyl alcohol：Water=92：8.At 60 DEG C 3h is dissolved, filtration drying obtains ALANINE crude product.
D, gained ALANINE crude product in step c is recrystallized, the saturated aqueous solution of ALANINE is configured at 70 DEG C, Fully dissolving 2h, isopropanol is added with 3g/min drop rate, until when having fine crystals precipitation in solution, stop dissolved agent Dropwise addition.With 300rpm stir speed (S.S.), 0.1 DEG C/min rate of temperature fall drops 20 DEG C, constant temperature aging 7h, and vacuum filtration obtains L- The sterling of alanine.
Embodiment three
The present embodiment is related to a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, specifically includes following step Suddenly：
A, take hydroxyproline waste water, 80 DEG C of high temperature in reactor, react 8h, by solution centrifugal, obtain ALANINE mother liquor.
B, gelatine wastewater, 1% added at 65 DEG C are taken（Mass fraction）Food grade active carbon decoloring 1.5h, is filtrated to get nothing The transparent solution of color, is concentrated under reduced pressure to give solid.
C, by the solid of gained in step a, add " n-butanol+water ", wherein n-butanol：Water=95：5.Dissolved at 50 DEG C 2h, filtration drying obtain ALANINE crude product.
D, gained ALANINE crude product in step b is recrystallized, the saturated aqueous solution of ALANINE is configured at 55 DEG C, Fully dissolving 2h, isopropanol is added with 3g/min drop rate, until when having fine crystals precipitation in solution, stop dissolved agent Dropwise addition.With 200rpm stir speed (S.S.), 0.5 DEG C/min rate of temperature fall is down to 23 DEG C, and constant temperature aging 6h, vacuum filtration obtains The sterling of ALANINE.
Example IV
The present embodiment is related to a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, specifically includes following step Suddenly：
A, take hydroxyproline waste water, high temperature of 120 DEG C in reactor, react 6h, by solution centrifugal, obtain ALANINE mother Liquid.
B, gelatine wastewater, 2% added at 63 DEG C are taken（Mass fraction）Food grade active carbon decoloring 2.5h, is filtrated to get nothing The transparent solution of color, is concentrated under reduced pressure to give solid.
C, by the solid of gained in step b, add " methanol+water ", wherein methanol：Water=92：8.2h is dissolved at 55 DEG C, Filtration drying obtains ALANINE crude product.
D, gained ALANINE crude product in step c is recrystallized, the saturated aqueous solution of ALANINE is configured at 65 DEG C, Fully dissolving 2h, absolute ethyl alcohol is added with 5g/min drop rate, until when having fine crystals precipitation in solution, stop dissolved The dropwise addition of agent.With 250rpm stir speed (S.S.), 0.3 DEG C/min rate of temperature fall is down to 16 DEG C, constant temperature aging 8h, is filtered by vacuum To the sterling of ALANINE.
Embodiment five
The present embodiment is related to a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, specifically includes following step Suddenly：
A, take hydroxyproline waste water, 80 DEG C of high temperature in reactor, react 8h, by solution centrifugal, obtain ALANINE mother liquor.
B, by the water of gained in step a, 1.5% added at 65 DEG C（Mass fraction）Food grade active carbon decoloring 3h, mistake Filter obtains the solution of water white transparency, is concentrated under reduced pressure to give solid.
C, by the solid of gained in step b, add " absolute ethyl alcohol+water ", wherein absolute ethyl alcohol：Water=95：5.At 55 DEG C 2h is dissolved, filtration drying obtains ALANINE crude product.
D, gained ALANINE crude product in step c is recrystallized, the saturated aqueous solution of ALANINE is configured at 65 DEG C, Fully dissolving 2h, acetone is added with 3g/min drop rate, until when having fine crystals precipitation in solution, stop dissolved agent It is added dropwise.With 150rpm stir speed (S.S.), 0.2 DEG C/min rate of temperature fall is down to 15 DEG C, constant temperature aging 7h, and vacuum filtration obtains L- The sterling of alanine.
Embodiment six
The present embodiment is related to a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material, specifically includes following step Suddenly：
A, take hydroxyproline waste water, 100 DEG C of high temperature in reactor, react 7h, by solution centrifugal, obtain ALANINE mother Liquid.
B, by the mother liquor of gained in step a, 2.5% added at 65 DEG C（Mass fraction）Food grade active carbon decoloring 3h, mistake Filter obtains the solution of water white transparency, is concentrated under reduced pressure to give solid.
C, by the solid of gained in step b, add " methanol+water ", wherein methanol：Water=92：8.2h is dissolved at 55 DEG C, Filtration drying obtains ALANINE crude product.
D, gained ALANINE crude product in step c is recrystallized, the saturated aqueous solution of ALANINE is configured at 65 DEG C, Fully dissolving 2h, absolute ethyl alcohol is added with 3g/min drop rate, until when having fine crystals precipitation in solution, stop dissolved The dropwise addition of agent.With 200rpm stir speed (S.S.), 0.3 DEG C/min rate of temperature fall is down to 15 DEG C, constant temperature aging 6h, is filtered by vacuum To the sterling of ALANINE.
The nmr analysis result of inventive samples is as follows：
1H-NMR（500 MHz, D2O）Spectrogram is as shown in Figure 1, it can be deduced that, δ 1.467-1.482（M, J=7.5HZ, 3H）, 3.755-3.799（M, 1H）, δ 4.776 is solvent peak, and δ 3.552 is water peak.Due to sample, solubility is larger in water, selection D2O is solvent, NH2Covered with the active H in COOH by solvent peak.
13C-NMR（500 MHz, D2O）Spectrogram is as shown in Figure 2, it can be deduced that, δ 175.75（1C）, 50.50 (CH), 16.13 （CH3）, the C that is followed successively by-COOH, with-NH2Connected C, CH3In C, δ 50.50（CH）Due to by-NH2Influence, to Low field moves.
It is consistent with the nuclear magnetic data of ALANINE reported in the literature, the molecular formula of the compound is understood according to nuclear magnetic data For CH3CH (NH2) COOH, the product that the present invention obtains is pure ALANINE, is substantially free of impurity.
The test of specific rotation is carried out to the product, between 13.5-15.5 °, it is L- thus to further demonstrate that the product Alanine.

Claims (4)

  1. A kind of 1. method that ALANINE is prepared using hydroxyproline waste water as raw material, it is characterised in that comprise the following steps：
    A, hydroxyproline waste water is taken, by solution centrifugal, to obtain mother liquor in 80-120 DEG C of reaction 6-8h in reactor；
    B, by the mother liquor in step a, the 2-3h that decolourizes is added at mass fraction 0.5-3% 60-70 DEG C of activated carbon, filters colourless Clear solution, it is concentrated under reduced pressure to give solid；
    Solid in step b is added to the aqueous solution of alcohol, 2-3h is dissolved at 50-60 DEG C, filtering, dries, it is thick to obtain ALANINE c, Product；
    D, it is the ALANINE crude product in step c is soluble in water, 55-70 DEG C of ALANINE saturated aqueous solution is prepared, to above-mentioned Alcohol or ketone are added in saturated aqueous solution, until fine crystals separate out in solution, is cooled to 15-25 DEG C, constant temperature aging 6-8h, mistake Filter, dry, obtain ALANINE sterling；
    Alcohol in step c is one kind in methanol, ethanol or n-butanol；
    Alcohol in step d is ethanol or isopropanol；Ketone in step d is acetone.
  2. 2. a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material according to claim 1, its feature exist In the mass ratio of alcohol and water is 98-90 in the aqueous solution of the alcohol in step c：2-10.
  3. 3. a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material according to claim 1, its feature exist In the mass ratio that the aqueous solution of, the alcohol in step c is methanol and water be 92：8 solution.
  4. 4. a kind of method that ALANINE is prepared using hydroxyproline waste water as raw material according to claim 1, in step d with 150-300rpm stir speed (S.S.)s, 0.1-0.5 DEG C/min rate of temperature fall are down to 15-25 DEG C.
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CN107382759A (en) * 2017-06-09 2017-11-24 安徽丰原发酵技术工程研究有限公司 A kind of method for extracting alanine
CN107298649A (en) * 2017-07-25 2017-10-27 河北科技大学 A kind of method that L proline is purified from gelatine wastewater
CN110305028B (en) * 2019-06-21 2022-04-08 湖北泰盛化工有限公司 Device and process for washing glycine crude product by alcohol phase method

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FR2523961B1 (en) * 1982-03-23 1985-08-30 Centre Nat Rech Scient PROCESS FOR THE PREPARATION OF A FREE L-ALPHA-AMINO-ACID
DE3326633C1 (en) * 1983-07-23 1985-01-03 Kali-Chemie Ag, 3000 Hannover Process for the production of specific amino acid fractions and their use for the production of individual amino acids
CN104926709B (en) * 2015-07-13 2017-03-29 福建师范大学 A kind of process for purification of L tryptophans
CN105949111B (en) * 2016-05-24 2018-10-19 南通紫琅生物医药科技有限公司 A kind of preparation process of high-purity high light transmission L-Trp

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