CN104230732A - Method for extracting L-lysine from molasses fermentation liquor - Google Patents

Method for extracting L-lysine from molasses fermentation liquor Download PDF

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CN104230732A
CN104230732A CN201410417019.6A CN201410417019A CN104230732A CN 104230732 A CN104230732 A CN 104230732A CN 201410417019 A CN201410417019 A CN 201410417019A CN 104230732 A CN104230732 A CN 104230732A
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molasses
fermented liquid
extraction
extracting
molasses fermented
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CN104230732B (en
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陈可泉
何珣
肖文
张弘
欧阳平凯
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The invention discloses a method for extracting L-lysine from a molasses fermentation liquor. The method is characterized by comprising solid-liquid separation, film filtration, solid recovery, chemical extraction and reverse extraction. The method specifically comprises the following steps: removing solid substances such as thallus and colloid out of molasses fermentation liquor, and then fully mixing with an extracting solution; oscillating at room temperature, extracting to reach balance, and then separating the extracting solution from raffinate; carrying out reverse extraction on the raffinate by using hydrochloric acid and then recovering an organic solvent; directly recovering the raffinate as a component of a fermentation medium, wherein filter residues separated from the fermentation liquor can be used as a substrate for methane fermentation. L-lysine is extracted at room temperature, so that the distribution ratio of high-concentration L-lysine is increased. A molasses pigment is completely separated from L-lysine, so that subsequent purification and rectification of L-lysine are facilitated. An organic solvent for extracting is completely recovered, and all the raffinate is recovered as a culture medium component, so that the process is environment-friendly and free of pollutant emission; the production cost is effectively reduced; the economical efficiency is improved; and good social benefits can also be brought about.

Description

A kind of method extracting 1B from molasses fermented liquid
Technical field
The invention belongs to technical field of biochemical industry, be specifically related to a kind of method extracting 1B in molasses fermented liquid.
Background technology
In fermented liquid, amino acid whose separation and Extraction is technological difficulties in amino acids production process always, if Methionin can be made effectively to be separated with the sugar in fermented liquid, sulfate radical, calcium ion, magnesium ion, other impurity such as amino acid, pigment, just improve the purity of 1B product.
Amino acid whose extraction and separation method comprises the precipitator method, ion exchange method, reverse micelle extraction method, electroosmose process, liquid membrane separation method, solvent extration etc.Precipitator method selectivity is strong, simple to operate, but in production process, if desired reaches good separating effect, often needs to add precipitation agent, and precipitation agent can have certain residual in the product, and product reliability is lower, and at present, industrial application is less; Reverse micelle extraction method extracts Methionin, and when only having that inorganic ion concentration is lower in the solution, just can reach reasonable separating effect, for the molasses fermented liquid that inorganic salt content is higher, reverse micelle extraction method effect is poor; Electroosmose process is simple to operate, and yield is high, does not produce by product in production process, free from environmental pollution, but ion-exchange membrane is subject to concentration polarization impact and fouling, separating effect declines, and cost is higher and poor for the separation for amino acids extraction effect that iso-electric point difference is less; Liquid film separation extraction process comprises the operations such as system breast, extraction, clarification, breakdown of emulsion, reuse, and make its technological process relative complex, the stability of film is comparatively large by such environmental effects, less stable; The separation method of industrial the most frequently used Methionin is ion exchange method, and this method needs a large amount of bronsted lowry acids and bases bronsted lowries to regenerate zwitterion resin in process of production.This just certainly leads to a large amount of waste water, causes required equipment complicated simultaneously, and serialization, automatic production difficulty.And adopting solvent extration to be separated lysine fermentation liquor, whole extraction process and reextraction process form a closed cycle, can address these problems well.Zhang Bobin etc. (2013) adopt di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester as extraction agent, sulfonated kerosene is as thinner, the lysine fermentation liquor that 1B concentration is respectively 31.0,46.5,62.0,74.4,93.0 g/L is extracted under the rotating speed of 200 r/min, stir and within 4 minutes, can reach extractive reaction balance, partition ratio is respectively 1.35,0.90,0.80,0.78,0.75.Back extraction lysine hydrochloride out only need adopt ion exchange method or extraction process to remove foreign ion when refining, substantially reduces discharge of wastewater, or does not produce waste water.But at present for the method extracting high density 1B from the very complicated molasses fermented liquid of composition, not yet there is report.
Summary of the invention
The object of this invention is to provide a kind of method extracting 1B in molasses fermented liquid, can distribution ratio be improved by the method, completely by 1B and molasses pigment separated.
For realizing technical purpose of the present invention, technical scheme of the present invention is:
After the solid matters such as the thalline in molasses fermented liquid, colloid are removed, fully mix with extraction liquid, vibrate under normal temperature, extraction reaches the rear separating and extracting liquid of balance and raffinate, extraction liquid reclaims organic solvent after hydrochloric acid is stripped, raffinate directly reclaims the component as fermention medium, and the filter residue that separation of fermentative broth goes out can be used as the substrate of biogas fermentation.
The concrete steps of technical solution of the present invention are as follows:
From molasses fermented liquid, extract a method for 1B, it is characterized in that described concrete steps are as follows:
A) solid-liquid separation
Centrifugal treating is carried out to molasses fermented liquid, collects centrifugate and solid substance respectively;
B) membrane filtration
By step a) collected by centrifugate membrane filtration, collect filter residue and filtrate respectively;
C) chemical extraction
With the mixing solutions of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and hexanaphthene for extraction agent, by extraction agent and step b) gained filtrate by compared with 1:1 mix, extraction temperature 25 DEG C, stratification after vibration 2-5 min, collect upper organic phase and lower floor's aqueous phase respectively, the aqueous phase of lower floor imports fermentor tank as fermention medium component, and the organic phase on upper strata is stripped;
D) strip
In organic phase, add the hydrochloric acid soln that concentration is 0.3-0.8 mol/L, mix rear vibration 2-4 min, after stratification, collect upper organic phase and lower floor's aqueous phase respectively, lower floor's aqueous phase and 1B solution, upper organic phase is the extraction agent after regeneration, is used again to extraction step.
Preferably, described method also comprises solids recovery steps, is specially and collects step a) and step b) solid substance that obtains and filter residue, as the reaction substrate of biogas fermentation;
Preferably, step a) described in centrifugal treating condition be 2000-3000 rpm, time 5-10 min.
Preferably, step b) described in filter sizes be 0.22-0.45 μm.
Preferably, step c) described in extraction agent be take hexanaphthene as thinner, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester dilution obtained, in extraction agent, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester concentration is 0.4-2.0 mol/L.
The suitability of the inventive method to 1B concentration is in extensive range, and preferably, in described molasses fermented liquid, 1B concentration is 90-250 g/L.
The inventive method can using all molasses fermented liquid as extraction feed, the source of preferred described molasses fermented liquid is cane molasses, beet sirup, corn molasses, grape molasses through fermentable or enzyme catalysis obtain containing 1B liquid.
Of the present invention to 1B extraction process, achieve outstanding beneficial effect: first, the scope of application is very extensive, and the method can using the molasses fermented liquid of all the components complexity as extraction feed; Secondly, the suitability of the inventive method to 1B concentration is in extensive range; Moreover compared with 1B extractive technique in existing fermented liquid, extraction process partition ratio of the present invention is high, and 1B reaches with pigment and is separated completely, effectively reduce the purifying of follow-up 1B product and refining production cost; Finally, present method operates at normal temperature condition, without the need to strict temperature control parameter, greatly can not only reduce production energy consumption, and can reduce the operation control overflow in production process, namely reduces the training cost of production operation personnel and production, potential safety hazard.And, reclaim organic solvent in present method, save production and cost recovery; And remaining solid substance is produced, whole flow process non-pollutant discharge, technique is green friendly.
Embodiment
The following examples elaborate to the inventive method, but do not limit the present invention.
In embodiment, the detection of pigment is that described mensuration wavelength is absorbing wavelength 395 nm that in existing bibliographical information, pigment is the most frequently used with spectrophotometer.
embodiment 1 the present embodiment illustrates the method extracting 1B from molasses fermented liquid
Carry out centrifugal treating to the beet sirup fermented liquid that 1B concentration is 90 g/L, centrifugal condition is 2000 rpm, time 5 min., collect centrifugate and solid substance respectively; By the membrane filtration of the filtrate after centrifugal with 0.45 μm, aperture, collect filter residue and filtrate respectively; The solid substance that collection solid-liquid separation and membrane filtration obtain and filter residue, as the reaction substrate of biogas fermentation; With the mixing solutions of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and hexanaphthene for extraction agent, in extraction agent, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester concentration is 1 mol/L, the filtrate that extraction agent and membrane filtration are obtained by compared with 1:1 mix, extraction temperature 25 DEG C, vibrate stratification after 4 min, collect upper organic phase and lower floor's aqueous phase respectively, the aqueous phase of lower floor imports fermentor tank as fermention medium component, and the organic phase on upper strata is stripped; In organic phase, add the hydrochloric acid soln that concentration is 0.6 mol/L, mix rear vibration 4 min, after stratification, collect upper organic phase and lower floor's aqueous phase respectively, lower floor's aqueous phase and 1B solution, upper organic phase is the extraction agent after regeneration, is used again to extraction step.The partition ratio of 1B extraction is 1.09, and back extraction ratio is 99%, and the light absorption value that the 1B solution finally obtained measures at optical wavelength 395 nm place is 0.
embodiment 2 the present embodiment illustrates the method extracting 1B from molasses fermented liquid
Carry out centrifugal treating to the cane molasses fermented liquid that 1B concentration is 140 g/L, centrifugal condition is 2000 rpm, time 5 min., collect centrifugate and solid substance respectively; By the membrane filtration of the filtrate after centrifugal with 0.22 μm, aperture, collect filter residue and filtrate respectively; The solid substance that collection solid-liquid separation and membrane filtration obtain and filter residue, as the reaction substrate of biogas fermentation; With the mixing solutions of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and hexanaphthene for extraction agent, in extraction agent, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester concentration is 0.4 mol/L, the filtrate that extraction agent and membrane filtration are obtained by compared with 1:1 mix, extraction temperature 25 DEG C, vibrate stratification after 2 min, collect upper organic phase and lower floor's aqueous phase respectively, the aqueous phase of lower floor imports fermentor tank as fermention medium component, and the organic phase on upper strata is stripped; In organic phase, add the hydrochloric acid soln that concentration is 0.3 mol/L, mix rear vibration 5 min, after stratification, collect upper organic phase and lower floor's aqueous phase respectively, lower floor's aqueous phase and 1B solution, upper organic phase is the extraction agent after regeneration, is used again to extraction step.The partition ratio of 1B extraction is 0.79, and back extraction ratio is 100%, and the light absorption value that the 1B solution finally obtained measures at optical wavelength 395 nm place is 0.
embodiment 3 the present embodiment illustrates the method extracting 1B from molasses fermented liquid
carry out centrifugal treating to the grape molasses fermented liquid that 1B concentration is 250 g/L, centrifugal condition is 3000 rpm, time 8 min., collect centrifugate and solid substance respectively; By the membrane filtration of the filtrate after centrifugal with 0.22 μm, aperture, collect filter residue and filtrate respectively; The solid substance that collection solid-liquid separation and membrane filtration obtain and filter residue, as the reaction substrate of biogas fermentation; With the mixing solutions of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and hexanaphthene for extraction agent, in extraction agent, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester concentration is 2 mol/L, the filtrate that extraction agent and membrane filtration are obtained by compared with 1:1 mix, extraction temperature 25 DEG C, vibrate stratification after 5 min, collect upper organic phase and lower floor's aqueous phase respectively, the aqueous phase of lower floor imports fermentor tank as fermention medium component, and the organic phase on upper strata is stripped; In organic phase, add the hydrochloric acid soln that concentration is 0.8 mol/L, mix rear vibration 5 min, after stratification, collect upper organic phase and lower floor's aqueous phase respectively, lower floor's aqueous phase and 1B solution, upper organic phase is the extraction agent after regeneration, is used again to extraction step.The partition ratio of 1B extraction is 0.89, and back extraction ratio is 97%, and the light absorption value that the 1B solution finally obtained measures at optical wavelength 395 nm place is 0.
embodiment 4 the present embodiment illustrates the method extracting 1B from molasses fermented liquid
Carry out centrifugal treating to the corn molasses fermented liquid that 1B concentration is 120 g/L, centrifugal condition is 2500 rpm, time 10 min.Collect centrifugate and solid substance respectively; By the membrane filtration of the filtrate after centrifugal with 0.45 μm, aperture, collect filter residue and filtrate respectively; The solid substance that collection solid-liquid separation and membrane filtration obtain and filter residue, as the reaction substrate of biogas fermentation; With the mixing solutions of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and hexanaphthene for extraction agent, in extraction agent, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester concentration is 1 mol/L, the filtrate that extraction agent and membrane filtration are obtained by compared with 1:1 mix, extraction temperature 25 DEG C, vibrate stratification after 4 min, collect upper organic phase and lower floor's aqueous phase respectively, the aqueous phase of lower floor imports fermentor tank as fermention medium component, and the organic phase on upper strata is stripped; In organic phase, add the hydrochloric acid soln that concentration is 0.6 mol/L, mix rear vibration 4 min, after stratification, collect upper organic phase and lower floor's aqueous phase respectively, lower floor's aqueous phase and 1B solution, upper organic phase is the extraction agent after regeneration, is used again to extraction step.The partition ratio of 1B extraction is 0.91, and back extraction ratio is 98%, and the light absorption value that the 1B solution finally obtained measures at optical wavelength 395 nm place is 0.

Claims (7)

1. from molasses fermented liquid, extract a method for 1B, it is characterized in that described concrete steps are as follows:
A) solid-liquid separation
Centrifugal treating is carried out to molasses fermented liquid, collects centrifugate and solid substance respectively;
B) membrane filtration
By step a) collected by centrifugate membrane filtration, collect filter residue and filtrate respectively;
C) chemical extraction
With the mixing solutions of di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and hexanaphthene for extraction agent, by extraction agent and step b) gained filtrate by compared with 1:1 mix, extraction temperature 25 DEG C, stratification after vibration 2-5 min, collect upper organic phase and lower floor's aqueous phase respectively, the aqueous phase of lower floor imports fermentor tank as fermention medium component, and the organic phase on upper strata is stripped;
D) strip
In organic phase, add the hydrochloric acid soln that concentration is 0.3-0.8 mol/L, mix rear vibration 2-5 min, after stratification, collect upper organic phase and lower floor's aqueous phase respectively, lower floor's aqueous phase and 1B solution, upper organic phase is the extraction agent after regeneration, is used again to extraction step.
2. a kind of method extracting 1B from molasses fermented liquid according to claim 1, it is characterized in that, described method also comprises solids recovery steps, is specially and collects step a) and step b) solid substance that obtains and filter residue, as the reaction substrate of biogas fermentation.
3., according to a kind of method extracting 1B from molasses fermented liquid described in claim 1, it is characterized in that, step a) described in centrifugal treating condition be 2000-3000 rpm, time 5-10 min.
4., according to a kind of method extracting 1B from molasses fermented liquid described in claim 1, it is characterized in that, step b) described in filter sizes be 0.22-0.45 μm.
5. according to a kind of method extracting 1B from molasses fermented liquid described in claim 1, it is characterized in that, step c) described in extraction agent be take hexanaphthene as thinner, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester dilution obtained, in extraction agent, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester concentration is 0.4-2.0 mol/L.
6. according to a kind of method extracting 1B from molasses fermented liquid described in claim 1, it is characterized in that, in described molasses fermented liquid, 1B concentration is 90-250 g/L.
7. according to a kind of method extracting 1B from molasses fermented liquid described in claim 1, it is characterized in that, the source of described molasses fermented liquid is cane molasses, beet sirup, corn molasses, grape molasses through fermentable or enzyme catalysis obtain containing 1B liquid.
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Publication number Priority date Publication date Assignee Title
CN109136292A (en) * 2018-09-11 2019-01-04 南京工业大学 A kind of molasses method of comprehensive utilization

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Publication number Priority date Publication date Assignee Title
CN109136292A (en) * 2018-09-11 2019-01-04 南京工业大学 A kind of molasses method of comprehensive utilization
CN109136292B (en) * 2018-09-11 2021-11-26 南京工业大学 Comprehensive utilization method of molasses

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