CN102358716B - Method of extracting succinic acid from fermentation broth - Google Patents
Method of extracting succinic acid from fermentation broth Download PDFInfo
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- CN102358716B CN102358716B CN201110314084.2A CN201110314084A CN102358716B CN 102358716 B CN102358716 B CN 102358716B CN 201110314084 A CN201110314084 A CN 201110314084A CN 102358716 B CN102358716 B CN 102358716B
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Abstract
The invention belongs to the field of bio-separation engineering, in particular relates to a method for extracting succinic acid from fermentation broth. The method for extracting the succinic acid from the fermentation broth includes the following steps of obtaining zinc succinate sedimentation capable of being filtered out through a reaction of zinc oxide and succinic acid fermentation broth obtained after filtering thallus; reducing the filtered sedimentation by adding H2S gas; and obtaining succinic acid solution and zinc sulfide sedimentation capable of being filtered out after sufficient reaction, wherein the succinic acid solution is concentrated and crystallized to obtain succinic acid products, and the zinc sulfide sedimentation can generate raw materials of zinc oxide and dilute sulphuric acid for extracting through a series of regeneration processes. The materials for extracting in the whole technology process can all be recycled, thereby saving sources and being economical and environment-friendly.
Description
Technical field
The invention belongs to bioseparation engineering field, be specifically related to a kind of method of extracting succsinic acid from fermented liquid.
Background technology
Succsinic acid, claims again 1, 4-succinic acid, gains the name because being present in amber.Molecular formula is C
4h
60
4, molecular weight is 118.09, its structural formula is as follows:
Succsinic acid is a kind of binary organic acid, is also industrial a kind of important C
4hardware and software platform compound is the important meta-bolites of microorganism tricarboxylic acid cycle and anaerobically fermenting.Be widely used in the fields such as food, medicine, tensio-active agent, sanitising agent, green solvent, biodegradable plastic as basic organic chemical industry starting material.
The production method of succsinic acid can be divided into the chemical synthesis taking petroleum base chemical as raw material and the biological fermentation process taking renewable sugar as raw material at present.Along with decline and the price of oil storing amount are constantly soaring, and the impact of petroleum base chemical industry on environment, it is a kind of trend that biological fermentation process is produced succsinic acid.Fermentative Production succsinic acid, complicated component in fermented liquid, need to remove thalline, albumen etc., more further succsinic acid is refined in separation and purification, and the method for extracting succsinic acid at present from fermented liquid can be divided into following four kinds:
(1) organic solvent extractionprocess
By adding a kind of organic solvent, selectively separating and extracting succsinic acid, this is also that organic acid extracts conventional method.But this extracting method, can consume a large amount of organic solvents in process.
(2) electroosmose process
Berglund etc. (United States Patent (USP) NO:5034105) have invented a kind of electroosmose process and have extracted succsinic acid in fermented liquid, after filtering fermentation liquor degerming, enter two-stage electrodialysis cell, salt and uncharged sugar, albumen etc. are separated, succinate changes succsinic acid into, and salt ion, as Na
+, by cationic membrane and hydroxide radical in conjunction with forming corresponding alkali.But electroosmose process power consumption is higher, device and film price are also more expensive.
(3) film extraction method
Wu Hao etc. (Chinese patent NO:200610086003.7) have invented a kind of method of membrane filtration extraction succsinic acid, first adopt micro-filtration degerming, then adopt ultrafiltration membrance filter, then use decolorization and impurity removal by active carbon, obtain succinic acid solution, condensing crystal obtains succsinic acid crystal.Although membrane filtration extracts, mild condition, without the need for machine solvent, membrane filtration is difficult to except impurity such as formic acid removal and acetic acid, and cost is also higher in addition, is not suitable for large-scale industry preparation.
(4) calcium salt precipitation method
Calcium salt precipitation method is by add Ca (OH) in fermented liquid
2or CaCO
3in coming, with pH and generation succinate precipitation, add afterwards sulfuric acid acidation, precipitated acid solution obtains succsinic acid.Although this method is easy and simple to handle, be easy to use in large-scale production, in leaching process, can produce a large amount of industrial waste residue CaSO that cannot use
4.
US Patent No. 5168055 discloses a kind of method that adopts calcium salt method separation and Extraction succsinic acid, and its technological line is to add first during the fermentation calcium hydroxide to regulate pH value, and in fermented liquid, crystallization goes out calcium succinate.Fermented liquid obtains the mixed precipitation of thalline, albumen, calcium succinate after filtration, the impurity such as thalline, albumen of then going out wherein by washing; Calcium succinate after washing adds vitriol oil acidifying to become soluble succsinic acid and insoluble calcium sulfate; Filter and remove after calcium sulfate, succinic acid solution is removed zwitterion through ion exchange resin, then obtains succsinic acid, and in product, the purity of succsinic acid is to 80-99%.But the method is had relatively high expectations to fermented bacterium, be only suitable for adding the zymotechnique of calcium salt adjusting pH value in fermenting process, performance is not good in this regard in known Screening of Succinic-producing Strain strain at present, is not suitable for suitability for industrialized production.
Chinese patent CN101643400A discloses a kind of method of extracting succsinic acid from fermented liquid, the method will obtain succinate solution after succsinic acid fermented liquid degerming removal of impurities, and generate calcium succinate precipitation after adding calcium chloride reaction, after reaction solution solid-liquid separation, obtain calcium succinate solid, add hydrochloric acid reaction to generate after calcium chloride and succsinic acid, be cooled to 5-55 DEG C and separate out succsinic acid solid, after solid-liquid separation, obtain succsinic acid and calcium chloride solution.The method extract yield can reach more than 90%, and product purity can reach 99.5%, and by product calcium chloride can reuse simultaneously.All belong to water soluble substance but pass into the succsinic acid and the calcium chloride that obtain after hydrochloric acid reduction in the method, be difficult to separate, the hydrochloric acid simultaneously adding can not reuse.
More than the fermentation level of succsinic acid can reach 100 g/L at present, transformation efficiency reaches 80%, reaches industrialized level.But be limited to current extraction process technology also immature, industrialization cost is higher, industrialization amplification ratio is more difficult, causes current biological fermentation process to produce succsinic acid also in laboratory stage.
Summary of the invention
For this reason, technical problem to be solved by this invention is from fermented liquid, to extract in prior art the problem that solvent consumption is high, product separation is difficult of succsinic acid, and then provides that a kind of extraction efficiency is high, yield is high, extracts the method for extracting succsinic acid from fermented liquid of raw material reusable edible.
For solving the problems of the technologies described above, the method for extracting succsinic acid from fermented liquid of the present invention, comprises the steps:
(1) in succsinic acid filtering fermentation liquor liquid, add zinc oxide, control 70-85 DEG C of temperature, generate zinc succinate precipitation;
(2) filter and obtain zinc succinate precipitation, and described zinc succinate precipitation is added water after making suspension and passes into H
2s reaction, generates zinc sulphide precipitation and succinic acid solution;
(3) concentrated the succinic acid solution after elimination zinc sulphide precipitation, crystallization are obtained to required high purity succsinic acid crystal.
In described step (1), the molar ratio of described succsinic acid and described zinc oxide is 1:1-1.5.
In described step (2), obtain in addition the reacted solution of step (1) being cooled to the step of 30-40 DEG C before zinc succinate precipitation in filtration.
In described step (2), the mass percent of described zinc succinate suspension is 10-25%.
In described step (2), described zinc succinate and described H
2the mol ratio of S is 1:1-1.5.
In described step (3), described enrichment step temperature is 65-80 DEG C, and described crystallisation step temperature is 5-10 DEG C.
Described step (3) also comprises H afterwards
2the step (4) that S regenerates: the zinc sulphide precipitation that filtration in step (3) is obtained adds water and makes suspension, and stream adds dilute sulphuric acid reaction, generation H
2s gas and solution of zinc sulfate, collect H
2s gas.
In described step (4), the weight percentage of described zinc sulphide suspension is 10-25%.
In described step (4), the concentration of described dilute sulphuric acid is 2-10 mol/L.
After described step (4), also comprise the step (5) of pyrolysis zinc sulfate: by the solution of zinc sulfate condensing crystal obtaining in step (4), and dry after in 700-900 DEG C of thermal degradation, in process, obtain Zinc oxide powder and sulfur trioxide gas, collect Zinc oxide powder.
After described step (5), also comprise the step (6) of black sulfuric acid: collect the sulfur trioxide gas producing in step (5), pass into reaction in the regeneration of sulfuric acid tank that deionized water is housed and obtain dilute sulphuric acid.
Compared to the prior art technique scheme of the present invention, has the following advantages:
1, the method for extracting succsinic acid from fermented liquid of the present invention selects zinc oxide and the succinic acid solution phase reaction of filtering after thalline to generate the precipitation that can leach, and the zinc succinate leaching precipitation passes into H
2s gas reduction, the zinc sulphide precipitation that fully obtains succinic acid solution after reaction and can leach, the zinc sulphide precipitation leaching can regenerate reaction raw materials zinc oxide and hydrogen sulfide and dilute sulphuric acid by a series of regenerative processes, in whole reaction process, extract the equal recoverable of raw material of use, economic environmental protection simultaneously economizes on resources;
2, in whole reaction process, every secondary response product separation is later all separation of solid liquid phase, only adopt simple filtration to realize, and separation efficiency is higher;
3, in whole reaction process, the simple and contamination-free waste material of step produces, and reaction efficiency is higher;
4, the zinc succinate obtaining is cooled to 30-40 DEG C after in Low Temperature Thermal filter, ensure leach efficiency in, can improve the zinc succinate rate of recovery;
5, in step (2), the suspension of zinc succinate can directly pass into H
2s reaction, can react without zinc succinate suspension is carried out to pre-treatment, and reactions steps is simple;
6,, in step (2), zinc succinate that filtration is obtained precipitation is mixed with after the suspension that massfraction is 10-25 % and H
2s reaction, choose reasonable of the present invention the mass concentration of zinc succinate suspension, be zinc succinate precipitation and H
2the reaction of S provides reasonable and sufficient reaction conditions, has increased to greatest extent the extract yield of succsinic acid.
Brief description of the drawings
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein:
Fig. 1 is the process flow sheet of extraction succsinic acid of the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.But, those skilled in the art will readily understand, the described concrete technology condition of embodiment, material proportion and result thereof be only for the present invention is described, and should also can not limit the present invention described in claims.
As shown in Figure 1, the method for extracting succsinic acid from fermented liquid of the present invention will be carried out with this process flow steps.
All fermentation preparations by the following method of succsinic acid fermented liquid that following examples are used:
Production bacterial classification be Actinobacillus succinogenes (
actinobacillus succinogenesaTCC 55618), seed culture medium is all mutually with fermention medium component: glucose 15%, corn steep liquor 1%, magnesium sulfate 0.02%, yeast powder 2%, Sodium phosphate dibasic 0.25%, all the other are distilled water, the above mass percent that all refers to, initial pH value is 6.5.
The cultivation of seed: bacterial classification is inoculated in 200 mL serum bottles, liquid amount is 120 mL, 35 DEG C leave standstill cultivation 24 h.
Seed 10 L tank enlarged culturing: 10 L tanks, liquid amount is 6.5 L, and then 121 DEG C of sterilizing 20 min inoculate seed by 10% inoculum size, and rotating speed 200 rpm, are that 0.5 L/min passes into N by air quantity
2, CO
2and H
2mixed gas, N
2, CO
2and H
2ratio is 7.5:1.5:1, and 35 DEG C of anaerobism are cultivated 20 h.
Seed 100 L tanks spread cultivation: 100 L tanks, and liquid amount is 65 L, 121 DEG C of sterilizing 20 min, the seed liquor of then above-mentioned 10 L tanks being cultivated is seeded in 100 L tanks and carries out seed liquor enlarged culturing with 10% inoculum size, and rotating speed 200 rpm, pass into N
2, CO
2and H
2mixed gas, N
2, CO
2and H
2ratio is 7.5:1.5:1, and air quantity is 5 L/min, and 35 DEG C of anaerobism are cultivated 12 h.
Fermentor cultivation: 1 ton of tank, liquid amount is 650 L, and then 121 DEG C of sterilizing 20 min cultivate by above-mentioned 100 L tanks the seed liquor obtaining and are seeded to fermentation culture in 1 ton of tank with 10% inoculum size, and rotating speed 200 rpm, pass into N
2, CO
2and H
2mixed gas, N
2, CO
2and H
2ratio is 7.5:1.5:1, and air quantity is 100 L/min, by auto-feeding 5 mol/L Na
2cO
3control pH 6.0 ± 0.1,35 DEG C of anaerobism are cultivated 40 h, and lower tank is collected fermented liquid.Recording wherein succinic acid content by high performance liquid chromatography (HPLC) is 103.5 g/L, acetic acid 17.3 g/L, formic acid 1.8 g/L.
Those skilled in the art are known, and in the present invention, succsinic acid fermented liquid also can adopt other production of succinic acid bacterial classification to cultivate and obtain through anaerobically fermenting according to the method for introducing in prior art.
embodiment 1
Get fresh above-mentioned succsinic acid fermented liquid, through the degerming of plate-and-frame filter press diatomite filtration, obtain succsinic acid filtered liquid.The method of extracting succsinic acid is as follows:
(1) get fermentation filtrate 0.6 M
3, add in neutralization tank, in the ratio of ZnO and succsinic acid mol ratio 1:1, stir and add ZnO to heat temperature raising limit, neutralization tank limit, at 80 DEG C of insulation reaction 30 min, generate zinc succinate precipitation.
(2) then reaction solution is cooled to 35 DEG C, filtration obtains zinc succinate precipitation, now, although the acetic acid in fermented liquid and formic acid also may react and generate zinc acetate and zinc formate with ZnO, but due to zinc acetate and zinc formate water soluble, in this filtration procedure, can be removed, and be had to zinc succinate precipitation.
In conversion tank, it is 25% suspension that zinc succinate and deionized water are mixed with to mass percent, then presses zinc succinate and H
2s mol ratio 1:1 passes into H
2s, temperature is 25 DEG C, filters and obtains ZnS precipitation and succinic acid solution.
(3) it is 80% that succinic acid solution filtration being obtained is concentrated to mass concentration through vaporizer reduction vaporization, working pressure is-0.1MPa, service temperature is 65 DEG C, then add crystal seed by succinic acid content 2.5%, temperature drops to 5 DEG C from 65 DEG C, obtains succsinic acid crystallization in process, and centrifugal drying obtains succsinic acid crystal, purity is 99.5%, and the total yield of succsinic acid is 90.7%.
(4) at H
2in S regenerating tank, the suspension that is 25% in ZnS and deionized water ratio 1:3 preparation massfraction, then under agitation condition, slowly stream adds rare H that concentration is 6 mol/L
2sO
4solution, makes temperature maintain 60 DEG C in reaction process, generate H in process
2s gas and ZnSO
4solution, the H wherein generating
2s reclaims for above-mentioned conversion process, ZnSO
4solution filters and obtains wet ZnSO through condensing crystal
4and dry.
(5) by dried ZnSO
4be placed in pyrolyzer, 900 DEG C of pyrolysis 30 min, obtain ZnO powder and SO in process
3gas, the ZnO powder of collecting is wherein used for above-mentioned N-process.
(6) H of deionized water is being housed
2sO
4in regenerating tank, pass into the SO generating in above-mentioned pyrolytic process
3gas, generates H
2sO
4solution, regulates H
2sO
4after concentration, for above-mentioned H
2the regenerative process of S.
embodiment 2
Get fresh succsinic acid fermented liquid, through the degerming of plate-and-frame filter press diatomite filtration, obtain succsinic acid filtered liquid.The method of extracting succsinic acid is as follows:
(1) get fermentation filtrate 0.6 M
3, add in neutralization tank, in the ratio of ZnO and succsinic acid mol ratio 1:1.2, stir and add ZnO to heat temperature raising limit, neutralization tank limit, at 85 DEG C of insulation 25 min, generate zinc succinate precipitation.
(2) reaction solution is cooled to 40 DEG C, filter and obtain zinc succinate precipitation, and zinc acetate and zinc formate water soluble are removed in this process.
In conversion tank, zinc succinate and deionized water are prepared to the suspension that mass percent is 20%, then press succsinic acid and H
2s mol ratio 1:1.2 passes into H while stirring
2s gas, controlling temperature is 25 DEG C, filters and obtains ZnS precipitation and succinic acid solution.
(3) it is 75% that succinic acid solution filtration being obtained is concentrated to mass concentration through vaporizer reduction vaporization, working pressure is-0.1MPa, service temperature is 75 DEG C, then add crystal seed by succinic acid content 2.0%, temperature drops to 7 DEG C from 75 DEG C, obtains succsinic acid crystallization in process, and centrifugal drying obtains succsinic acid crystal, purity is 99.6%, and the total yield of succsinic acid is 93.4%.
(4) at H
2in S regenerating tank, it is 10% suspension that ZnS and deionized water are mixed with to mass percent, and then slowly stream adds the H that concentration is 2 mol/L
2sO
4solution, makes temperature maintain 60 DEG C in reaction process, generate H in process
2s gas and ZnSO
4solution, the H wherein generating
2s reclaims for above-mentioned conversion process, ZnSO
4solution filters and obtains wet ZnSO through condensing crystal
4and dry.
(5) by dried ZnSO
4be placed in pyrolyzer, 800 DEG C of pyrolysis 45 min, obtain ZnO powder and SO in process
3gas, wherein ZnO is for above-mentioned N-process.
(6) H of deionized water is being housed
2sO
4in regenerating tank, pass into the SO generating in above-mentioned pyrolytic process
3gas, generates H
2sO
4solution, regulates H
2sO
4after concentration, for above-mentioned H
2the regenerative process of S.
embodiment 3
Get fresh above-mentioned succsinic acid fermented liquid, through the degerming of plate-and-frame filter press diatomite filtration, obtain succsinic acid filtered liquid.The method of extracting succsinic acid is as follows:
(1) fresh succsinic acid fermented liquid, through the degerming of plate-and-frame filter press diatomite filtration, obtains succsinic acid filtered liquid.Get fermentation filtrate 0.6 M
3, add in neutralization tank, in the ratio of ZnO and succsinic acid mol ratio 1:1.5, stir and add ZnO to heat temperature raising limit, neutralization tank limit, at 70 DEG C of insulation 40 min.
(2) step (1) is reacted to the suspension obtaining and cool to 30 DEG C, filter and obtain zinc succinate precipitation, and zinc acetate and zinc formate water soluble are removed in this process.
In conversion tank, it is 10% suspension that zinc succinate and deionized water are mixed with to mass percent, then under agitation condition, by succsinic acid and H
2s mol ratio 1:1.5 passes into H
2s, temperature is 25 DEG C, filters and obtains ZnS precipitation and succinic acid solution.
(3) succinic acid solution of collection being concentrated to mass concentration through vaporizer reduction vaporization is 85%, working pressure is-0.1MPa, service temperature is 80 DEG C, then add crystal seed by succinic acid content 3.0%, temperature drops to 10 DEG C from 80 DEG C, obtains succsinic acid crystallization in process, and centrifugal drying obtains succsinic acid crystal, purity is 99.7%, and the total yield of succsinic acid is 92.5%.
(4) at H
2in S regenerating tank, it is 15% suspension that ZnS precipitation and deionized water are mixed with to mass percent, and then slow stream adds the H that concentration is 10 mol/L
2sO
4solution, makes temperature maintain 60 DEG C in reaction process, generate H in process
2s gas and ZnSO
4solution, the H wherein generating
2s reclaims for above-mentioned conversion process, ZnSO
4solution filters and obtains wet ZnSO through condensing crystal
4.
(5) by dried ZnSO
4be placed in pyrolyzer, 700 DEG C of pyrolysis 60 min, obtain ZnO powder and SO in process
3gas, wherein ZnO is for above-mentioned N-process.
(6) H of deionized water is being housed
2sO
4in regenerating tank, pass into the SO generating in above-mentioned pyrolytic process
3gas, generates H
2sO
4solution, regulates H
2sO
4after concentration, for above-mentioned H
2the regenerative process of S.
embodiment 4
Get fresh above-mentioned succsinic acid fermented liquid, through the degerming of plate-and-frame filter press diatomite filtration, obtain succsinic acid filtered liquid.The method of extracting succsinic acid is as follows:
(1) get fermentation filtrate 0.6 M
3, add in neutralization tank, in the ratio of ZnO and succsinic acid mol ratio 1:1, stir and add ZnO to heat temperature raising limit, neutralization tank limit, at 80 DEG C of insulation 30 min, generate zinc succinate precipitation.
(2) then reaction solution is cooled to 35 DEG C, filter and obtain zinc succinate precipitation, and zinc acetate and zinc formate water soluble are removed in this process.
In conversion tank, the suspension that is 20% in zinc succinate and deionized water ratio 1:4 preparation mass percent, adding weight percent is 20% succinic acid solution, and add succinic acid solution volume be 1 times of above-mentioned zinc succinate suspension vol.Then under agitation condition, by succsinic acid and H
2s mol ratio 1:1 passes into H
2s, controlling temperature is 25 DEG C, filters and obtains ZnS precipitation and succinic acid solution.
(3) it is 80% that succinic acid solution filtration being obtained is concentrated to mass concentration through vaporizer reduction vaporization, working pressure is-0.1 MPa, service temperature is 65 DEG C, then add crystal seed by succinic acid content 2.5%, temperature drops to 5 DEG C from 65 DEG C, obtains succsinic acid crystallization in process, deionized water wash, centrifugal drying obtains succsinic acid crystal, and purity is 99.1%, and the total yield of succsinic acid is 85.4%.
(4) at H
2in S regenerating tank, the suspension that is 25% in ZnS and deionized water ratio 1:3 preparation massfraction, then slowly stream adds rare H that concentration is 6 mol/L
2sO
4solution, makes temperature maintain 60 DEG C in reaction process, generate H in process
2s gas and ZnSO
4solution, the H wherein generating
2s reclaims for above-mentioned conversion process, ZnSO
4solution filters and obtains wet ZnSO through condensing crystal
4and dry.
(5) by dried ZnSO
4be placed in pyrolyzer, 900 DEG C of pyrolysis 30 min, obtain ZnO powder and SO in process
3gas, the ZnO powder of collecting is wherein used for above-mentioned N-process.
(6) H of deionized water is being housed
2sO
4in regenerating tank, pass into the SO generating in above-mentioned pyrolytic process
3gas, generates H
2sO
4solution, regulates H
2sO
4after concentration, for above-mentioned H
2the regenerative process of S.
embodiment 5
Get fresh above-mentioned succsinic acid fermented liquid, through the degerming of plate-and-frame filter press diatomite filtration, obtain succsinic acid filtered liquid.The method of extracting succsinic acid is as follows:
(1) get fermentation filtrate 0.6 M
3, add in neutralization tank, in the ratio of ZnO and succsinic acid mol ratio 1:1, stir and add ZnO to heat temperature raising limit, neutralization tank limit, 80 DEG C of insulation 30 min, generate zinc succinate precipitation.
(2) then direct reaction solution filtered while hot is obtained to zinc succinate precipitation, and zinc acetate and zinc formate water soluble are removed in this process.
In conversion tank, the suspension that is 20% in zinc succinate and deionized water ratio 1:4 preparation mass percent, then under agitation condition, by succsinic acid and H
2s mol ratio 1:1 passes into H
2s, temperature is 25 DEG C, filters and obtains ZnS precipitation and succinic acid solution.
(3) it is 80% that succinic acid solution filtration being obtained is concentrated to mass concentration through vaporizer reduction vaporization, working pressure is-0.1MPa, service temperature is 65 DEG C, then add crystal seed by succinic acid content 2.5%, temperature drops to 5 DEG C from 65 DEG C, obtains succsinic acid crystallization in process, and centrifugal drying obtains succsinic acid crystal, purity is 98.9%, and the total yield of succsinic acid is 87.8%.
(4) at H
2in S regenerating tank, it is 15% suspension that ZnS precipitation and deionized water are mixed with to mass percent, and then slow stream adds rare H that concentration is 6 mol/L
2sO
4solution, makes temperature maintain 60 DEG C in reaction process, generate H in process
2s gas and ZnSO
4solution, the H wherein generating
2s reclaims for above-mentioned conversion process, ZnSO
4solution filters and obtains wet ZnSO through condensing crystal
4and dry.
(5) by dried ZnSO
4be placed in pyrolyzer, 900 DEG C of pyrolysis 30 min, obtain ZnO powder and SO in process
3gas, the ZnO powder of collecting is wherein used for above-mentioned N-process.
(6) H of deionized water is being housed
2sO
4in regenerating tank, pass into the SO generating in above-mentioned pyrolytic process
3gas, generates H
2sO
4solution, regulates H
2sO
4after concentration, for above-mentioned H
2the regenerative process of S.
embodiment 6
The method that the present embodiment extracts the succsinic acid in fresh fermented liquid is identical with method and the processing parameter recorded in embodiment 2, it is 5% suspension that the zinc succinate precipitation that its difference is only in step (2), filtration to be obtained and deionized water are mixed with mass percent, and passes into H
2s gas reaction reaction, the purity of the succsinic acid crystal that crystallization obtains after being also dried is 98.8%, the total recovery of succsinic acid is 86.9%.
embodiment 7
The method that the present embodiment extracts the succsinic acid in fresh fermented liquid is identical with method and the processing parameter recorded in embodiment 2, it is 30% suspension that the zinc succinate precipitation that its difference is only in step (2), filtration to be obtained and deionized water are mixed with mass percent, and passes into H
2s gas reaction reaction, the purity of the succsinic acid crystal that crystallization obtains after being also dried is 98.7%, the total recovery of succsinic acid is 87.3 %.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (7)
1. a method of extracting succsinic acid from fermented liquid, is characterized in that, comprises the steps:
(1) in succsinic acid filtering fermentation liquor liquid, add zinc oxide, control 70-85 DEG C of temperature, generate zinc succinate precipitation; The molar ratio of described succsinic acid and described zinc oxide is 1:1-1.5;
(2) the reacted solution of step (1) is cooled to 30-40 DEG C, filters and obtain zinc succinate precipitation, and described zinc succinate precipitation is added water after making suspension and passes into H
2s reaction, generates zinc sulphide precipitation and succinic acid solution; The mass percent of described zinc succinate suspension is 10-25%, described zinc succinate and described H
2the mol ratio of S is 1:1-1.5;
(3) concentrated the succinic acid solution after elimination zinc sulphide precipitation, crystallization are obtained to required high purity succsinic acid crystal.
2. the method for extracting succsinic acid from fermented liquid according to claim 1, is characterized in that:
In described step (3), described enrichment step temperature is 65-80 DEG C, and described crystallisation step temperature is 5-10 DEG C.
3. the method for extracting succsinic acid from fermented liquid according to claim 1 and 2, is characterized in that:
Described step (3) also comprises H afterwards
2the step (4) that S regenerates: the zinc sulphide precipitation that filtration in step (3) is obtained adds water and makes suspension, and stream adds dilute sulphuric acid reaction, generation H
2s gas and solution of zinc sulfate, collect H
2s gas.
4. the method for extracting succsinic acid from fermented liquid according to claim 3, is characterized in that:
In described step (4), the weight percentage of described zinc sulphide suspension is 10-25%.
5. the method for extracting succsinic acid from fermented liquid according to claim 4, is characterized in that:
In described step (4), the concentration of described dilute sulphuric acid is 2-10 mol/L.
6. the method for extracting succsinic acid from fermented liquid according to claim 5, is characterized in that:
After described step (4), also comprise the step (5) of pyrolysis zinc sulfate: by the solution of zinc sulfate condensing crystal obtaining in step (4), and dry after in 700-900 DEG C of thermal degradation, in process, obtain Zinc oxide powder and sulfur trioxide gas, collect Zinc oxide powder.
7. the method for extracting succsinic acid from fermented liquid according to claim 6, is characterized in that:
After described step (5), also comprise the step (6) of black sulfuric acid: collect the sulfur trioxide gas producing in step (5), pass into reaction in the regenerating tank that deionized water is housed and obtain dilute sulphuric acid.
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