CN101748161B - Process for purifying succinic acid by anaerobic fermentation - Google Patents
Process for purifying succinic acid by anaerobic fermentation Download PDFInfo
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- CN101748161B CN101748161B CN201010018204XA CN201010018204A CN101748161B CN 101748161 B CN101748161 B CN 101748161B CN 201010018204X A CN201010018204X A CN 201010018204XA CN 201010018204 A CN201010018204 A CN 201010018204A CN 101748161 B CN101748161 B CN 101748161B
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- succinic acid
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- acid
- decolouring
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000001384 succinic acid Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000855 fermentation Methods 0.000 title claims abstract description 44
- 230000004151 fermentation Effects 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 238000005336 cracking Methods 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 13
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000002906 microbiologic effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011218 seed culture Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000031018 biological processes and functions Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000948980 Actinobacillus succinogenes Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000003570 biosynthesizing effect Effects 0.000 description 2
- LZNBFGXYVFUAQM-UHFFFAOYSA-N butanedioic acid;magnesium Chemical compound [Mg].OC(=O)CCC(O)=O LZNBFGXYVFUAQM-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KJXMXCRSMLOXBM-UHFFFAOYSA-N 2,3-diethylbutanedioic acid Chemical compound CCC(C(O)=O)C(CC)C(O)=O KJXMXCRSMLOXBM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000005862 Whey Substances 0.000 description 1
- 102000007544 Whey Proteins Human genes 0.000 description 1
- 108010046377 Whey Proteins Proteins 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of bioengineering, and discloses a novel process for purifying succinic acid by anaerobic fermentation. The invention adopts a separation process based on solid-liquid separation, ultrafiltration, decoloration, acidification and crystallization units, introduces a thermal cracking technology of ammonium sulfate, realizes the cyclic utilization of acid and alkali, forms a closed clean production flow, and effectively ensures the product quality of food-grade and pharmaceutical-grade succinic acid. The invention not only reduces the fermentation cost, but also improves the economic benefit; and the environmental pollution is reduced, the ecological environment is improved, the sustainable development of national economy is promoted, and the social benefit is wide.
Description
Technical field
The invention belongs to technical field of bioengineering, relate to a kind of closed technology of novel anaerobically fermenting succinic acid purification.
Background technology
Succinic Acid has another name called succsinic acid, is a kind of common natural organic acids, extensively is present in human body, animal, plant and the mikrobe.The Succinic Acid great majority still adopt chemical method synthetic at present, and its raw material depends on fossil resource.The industrial potential of Succinic Acid fermentation just was realized as far back as 1980, and technical progress that biological process prepare Succinic Acid exhausted day by day along with fossil resource utilizes biotransformation method scale operation Succinic Acid to cause the attention of more and more countries.
Succinic Acid is most important carbon Siping City platform compound in the biorefinery product engineering.It is as many important intermediate product and specialized chemicals, conventional production methods adopts be from butane through MALEIC ANHYDRIDE through electrolysis production, produce and pollute greatly, cost is high, this severe inhibition the development potentiality of this bulk chemical of Succinic Acid.The main raw material that biological process is produced Succinic Acid is glucides such as glucose and wood sugar; Its wide material sources and cheap (corn, waste whey, industrial production waste material etc.) develop efficiently that the method for biosynthesizing Succinic Acid has very important significance, and production cost will be expected to from present 12; Reduce to 4 for 000 yuan/ton; Below 000 yuan/ton, thereby the market of opening bulk chemical replaces a lot of commodity based on benzene and petrochemical industry intermediate product; Minimizing is the produced pollution in surpassing the production and consumption process of 250 kinds of phenylating chemicals, and the total market size will be expected to extend to 4,000,000 tons by present 1.8 ten thousand tons.The production that utilizes biological process to carry out Succinic Acid also has a key character---absorbs and fixation of C O
2Be used for the metabolism of bacterial strain, finally generate Succinic Acid, this is that Succinic Acid production is different from the important speciality that traditional organic acid is produced.Every production 1kg Succinic Acid is with the CO that has 0.37kg
2Be fixed.The biosynthesizing Succinic Acid is the production technique of environmental protection, if fermentation production of succinic acid and another large leavened prod alcoholic acid production process are coupled, and more can be with the CO of fermentative production of ethanol generation
2Be used, reduce the discharging of greenhouse gases, and produce Succinic Acid, ethanol and three kinds of products of diethyl succinic acid simultaneously at the minimizing carbon loss.
Contain impurity such as a large amount of thalline, insolubles particle, residual substrate, protein and coloring matter in the Succinic Acid fermented liquid, before it is extracted purifying, need insolubles particle in the fermented liquid and macromole impurity are effectively separated.Therefore, preparing the Succinic Acid system to microbe fermentation method carries out the downstream Study on Technology and has important practice significance.
Relate in publication and the document at present and from microbial fermentation solution, extract the method for preparing Succinic Acid and mainly contain calcium salt method, solvent extration, ammonium salt process, electroosmose process, ion exchange method and membrane separation process.The method that U.S. Pat 5034105, US5143834 adopt the two-stage EDBM to separate the purification Succinic Acid, but this method electrodialytic membranes loss and power consumption are high, and can not handle divalent ion; U.S. Pat 5168055 adopts the calcium salt neutralisation to extract Succinic Acid, and route is long, inefficiency, produces a large amount of calcium sulfate waste residues, and acid and alkali consumption is big, has increased cost and environmental pollution; Chinese patent CN200810195852.5, CN200810195851.0 adopt ion exchange method to handle and separating and extracting succinic acid; Owing to contain a large amount of foreign ions in the Succinic Acid fermented liquid; Cause resin stain to increase the weight of; Exchange capacity descends rapidly, and plastic resin treatment is frequent, has problems such as regeneration difficulty, eluent consumption and blowdown flow rate are big; Chinese patent ZL200610086003.7 adopts micro-filtration, ultra-filtration membrane separating and extracting succinic acid, but owing to produce a large amount of sal epsom during the fermented liquid acidifying, may cause product vitriol to exceed standard or extract yield descends.
U.S. Patent application US5958744 discloses the technology of a kind of fermentative prodn and succinic acid purification, and the schema of its technical scheme is shown in accompanying drawing 1.It adopts ammonium salt process to extract Succinic Acid, regulates soda acid through adding ammoniacal liquor and sulfuric acid, and realizes that ammoniacal liquor and vitriolic recycle.But its crystallisation process operational condition is harsh, needs Pintsch process vitriol, complex steps, and difficulty is big.In a word, the separating and extracting method of Succinic Acid still remains to be improved at aspects such as simplifying technology, improve the quality of products and reduce cost at present.
Summary of the invention
Technical purpose of the present invention is to improve to the shortcoming of the technical scheme of US5958744; Make that the new technical scheme after improving is more reasonable and easy to the separation of pigment, biomacromolecule etc., further reduce the running cost of the downstream process of Succinic Acid fermentative prodn.
In order to realize technical purpose of the present invention, technical program of the present invention lies in:
A kind of technology of anaerobically fermenting succinic acid purification is characterized in that may further comprise the steps:
(1) in fermentor tank, utilize mikrobe anaerobically fermenting in fermention medium to produce Succinic Acid;
(2) in the process of fermentation and acid, adding alkaline neutraliser, to keep fermentation system pH value be 6.0～7.0;
(3) after the fermentation ends, fermented liquid is realized solid-liquid separation through filtration unit, the fermented liquid behind the removal insolubles carries out ultrafiltration again and removes biomacromolecule;
(4) ultrafiltrated gets into multiple-effect evaporator after decolouring, and waits to concentrate 4～6 times;
(5) material after will concentrating is after the mold reaction treatment, the Succinic Acid that dissociates, and deliver to crystallisation by cooling in the Succinic Acid mold, and filter through strainer, obtain crystalloid Succinic Acid product, and the mother liquor that contains a small amount of Succinic Acid;
(6) mother liquor is got in the next mold and with methanol mixed after deliver to that condensing crystal goes out the Succinic Acid crystal in the methanol evaporator; And it is returned bleacher; After the decolouring crystallization, obtain the Succinic Acid product, rest materials is delivered to hot tearing device cracking recovery after reclaiming methyl alcohol.
Above-mentioned technology of the present invention, wherein:
Optimal ph described in the step (2) is 6.8;
PH value in the mold described in the step (5) should maintain below 2.0; Optimal ph is 1.5～1.8;
Alkaline neutraliser is NH described in the step (1)
4During OH; In mold, add the vitriol oil during step (5) to obtain free Succinic Acid; Hot tearing device in the step (6) generates ammoniacal liquor and monoammonium sulfate with the ammonium sulfate cracking, the monoammonium sulfate of generation or sulfuric acid at least a portion be used for step (5) in extra reaction, ammoniacal liquor is added in the fermentor tank again;
When alkaline neutraliser is NaOH described in the step (1), in mold, adds ammoniacal liquor during step (5) and feed CO
2Gas; Add the vitriol oil at last to obtain free Succinic Acid, the hot tearing device in the step (6) generates ammoniacal liquor and monoammonium sulfate with the ammonium sulfate cracking, monoammonium sulfate at least a portion of generation be used for step (5) in extra reaction; Ammoniacal liquor is added in the fermentor tank again, and reclaims NaHSO
4
Alkaline neutraliser described in the step (1) is Mg (OH)
2The time, in mold, add ammoniacal liquor during step (5) and feed HCl gas, obtain free Succinic Acid, and reclaim Mg (OH)
2To fermentor tank, the hot tearing device in the step (6) is used to reclaim NH
4Cl;
Alkaline neutraliser is MgCO described in the step (1)
3The time, in mold, add ammoniacal liquor during step (5) and feed HCl gas, obtain free Succinic Acid, and reclaim Mg (OH)
2To fermentor tank, the hot tearing device in the step (6) is used to reclaim NH
4Cl;
Alkaline neutraliser is Na described in the step (1)
2CO
3The time, in mold, add ammoniacal liquor during step (5) and feed CO
2Gas adds the vitriol oil at last obtaining free Succinic Acid, and reclaims NaHCO
3To fermentor tank, the hot tearing device in the step (6) generates ammoniacal liquor and monoammonium sulfate with the ammonium sulfate cracking, monoammonium sulfate at least a portion of generation be used for step (5) in extra reaction, ammoniacal liquor is added in the fermentor tank again, and reclaims NaHSO
4
Beneficial effect of the present invention is:
1, described closed technology, wherein the biomacromolecule of ultrafiltration removal comprises protein, polysaccharide etc., produces to avoid the pigment in follow-up condensing crystal process;
2, simultaneously, before multiple-effect evaporation, increased the decolouring unit, to guarantee the quality of Succinic Acid crystalline product; Decolouring is with removing the pigment in the fermented liquid, to guarantee the quality of Succinic Acid crystalline product;
3, once more; Succinic Acid crystal in that methanol extraction ammonium sulfate, methyl alcohol evaporative crystallization obtain is got back in the bleacher; Again through decolouring, evaporative crystallization, residual with methyl alcohol in the further minimizing product guarantees the quality of product; And operational path of the present invention only need add a hypo acid, alkali, has reduced production cost.
Description of drawings
Fig. 1 is the disclosed operational path of US5958744;
Fig. 2 is the technology when utilizing ammoniacal liquor to regulate fermented liquid pH;
Fig. 3 is the technology when utilizing NaOH to regulate fermented liquid pH;
Fig. 4 is for utilizing Mg (OH)
2Technology when regulating fermented liquid pH;
Fig. 5 is for utilizing MgCO
3Technology when regulating fermented liquid pH;
Fig. 6 is for utilizing Na
2CO
3Technology when regulating fermented liquid pH.
Embodiment
Following embodiment elaborates to the present invention, but to not restriction of the present invention.
Embodiment 1
The method of fermentation production of succinic acid of the present invention can be used the microbial strains of any anaerobically fermenting succinic acid-producing in the prior art.The microbial strains of the succinic acid-producing that present embodiment adopted is: produce succsinic acid pleuropneumoniae NJ113 (Actinobacillus succinogenes NJ113), this bacterium patent applied for is also obtained the authorization, and the license notification number is CN100537744C.
Fermention medium of the present invention can use the fermention medium of any anaerobically fermenting succinic acid-producing in the prior art.The substratum that present embodiment adopted is: every liter of volume substratum contains glucose (separately sterilization) 50～100g, yeast powder 15g, steeping water 15mL, anhydrous sodium acetate 1.36g, NaCl 1g, K
2HPO
43g, MgCl
20.2g, CaCl
20.2g.
The method of organism of fermentation strain preparation Succinic Acid of the present invention can be anaerobically fermenting preparation method arbitrarily in the prior art, and these methods generally all comprise actication of culture, seed culture, anaerobic fermentation and acid production three steps.The preparation process of this enforcement is:
(1) actication of culture: the slant medium of actication of culture is the solid slant culture base that carbon source, nitrogenous source and inorganic salt can be provided that contains carbohydrate of pH 6.0～8.0; After during slant culture bacterial strain being carried out plate streaking in slant medium; In the anaerobism incubator, cultivate, incubator contains N
2, CO
2And H
2Mixed gas, temperature is 30～40 ℃, activation culture 24～48h is used for seed culture medium inoculation and bacterial strain preservation;
(2) seed culture: in the 100mL serum bottle, adding seed culture medium is 20～80mL, feeds and contains N
2And CO
2Gas mixture, 115～121 ℃ of sterilization 15～30min, the slant culture bacterial strain is inserted in the cooling back, and culture temperature is 30～40 ℃, shaking speed 100～200r/min, incubation time is 10～16h, is used for the fermention medium inoculation;
(3) the 5L ferment tank is cultivated: 5L fermentation cylinder for fermentation culture volume is 2～4L, and inoculum size is 3～7% (v/v), and temperature is 35～40 ℃, and fermentor tank feeds and contains N
2And CO
2Gas mixture, to keep the anaerobic environment of fermentation system, mixing speed is at 100～300rpm, and fermenting process adopts and adds alkaline neutraliser control pH 6.0～7.0, and fermentation time is 30～48h, separating and extracting succinic acid.
Analytical procedure:
HPLC system high efficiency liquid chromatograph: WatersHPLC2010 workstation; Chromatographic column Prevail organic acidcolumn 250mm * 4.6mm; Ultraviolet detection wavelength 215nm; Flow velocity 1mL/min, input 20 μ L, moving phase 25mmol/L KH
2PO
4, pH 2.5; Column temperature: room temperature.Organic acid (Succinic Acid (Fluka), acetate (Sigma), formic acid (Fluka), lactic acid (the Fluka)) standardized solution of redistilled water preparation different concns is according to the concentration relationship production standard curve of peak area and organic acid standardized solution.Fermented sample after centrifugal dilution based on each organic acid content of calculated by peak area.
The process step of present embodiment does, and is as shown in Figure 2:
In fermentor tank, utilize Actinobacillus succinogenes NJ113 anaerobically fermenting in above-mentioned fermention medium to produce Succinic Acid according to above-mentioned fermentation process; In the process of fermentation and acid, add NH
4OH keeps fermentation system in pH value 6.0; After the fermentation ends, fermented liquid is realized solid-liquid separation through filtration unit, the fermented liquid behind the removal insolubles carries out ultrafiltration again and removes biomacromolecules such as protein, polysaccharide, produces to avoid the pigment in follow-up condensing crystal process; Ultrafiltrated through decolouring guaranteeing the quality of Succinic Acid crystalline product, after get into multiple-effect evaporator again, wait that concentrating 4～6 times moves to mold, add vitriol oil acidifying, Succinic Acid and form ammonium sulfate dissociates; With acidizing fluid crystallisation by cooling in the Succinic Acid mold, and keep pH 1.5, under this low pH, Succinic Acid two ammoniums and monoammonium sulfate reaction generate Succinic Acid and ammonium sulfate:
(NH
4)
2A+2NH
4HSO
4→H
2A+2(NH
4)
2SO
4
Wherein, A represents the succinic ion, promptly
-(HOOC) (CH
2)
2(COOH)
-
Filter through strainer, obtain crystalloid Succinic Acid product, and the mother liquor that contains a small amount of Succinic Acid and ammonium sulfate; With mother liquor get in the next mold and and methanol mixed, and will filter with the ammonium sulfate that crystalline form is separated out and deliver to the cracking of hot tearing device, cracking under 200～300 ℃ of conditions, the NH of formation
3, NH
4HSO
4Or H
2SO
4Reclaim, ammonia reclaims in order to the pH value in the control fermenting process, NH again
4HSO
4Or H
2SO
4Can be in order to the destainer acid adjustment; And the methanol solution that is dissolved with Succinic Acid in the methanol crystallization device is delivered to condensing crystal in the methanol evaporator, and the gained crystal returns bleacher, obtains the Succinic Acid product through decolouring after the crystallization, and residual with methyl alcohol in the further minimizing product guarantees the quality of product.
Present embodiment adopts and embodiment 1 identical fermentation condition and method, and its whole process method is as shown in Figure 3:
Utilize NaOH to regulate fermentation pH.
In anaerobic reactor, utilize the microbiological anaerobic fermentation production of succinic acid, in the fermenting process, the pH with NaOH regulates fermentation system maintains 7.0.Fermented liquid after the fermentation ends leaches insolubles through strainer, removes biomacromolecules such as protein, polysaccharide again through ultrafiltration, produces to avoid the pigment in follow-up condensing crystal process; Simultaneously, before multiple-effect evaporation, increased the decolouring unit, to guarantee the quality of Succinic Acid crystalline product; PH maintains 1.8 in mold, under this low pH, feeds CO
2, and add ammoniacal liquor, then the reaction of disodium succinate and ammoniacal liquor and yellow soda ash generates Succinic Acid two ammoniums and sodium hydrogencarbonate, adds the vitriol oil at last to obtain free Succinic Acid.
Na
2A+2NH
3+2H
2CO
3→(NH
4)
2A+2NaHCO
3
A represents the succinic ion, promptly
-(HOOC) (CH
2)
2(COOH)
-
The sodium hydrogencarbonate that reaction generates is used further to regulate in the fermentor tank pH.
The Succinic Acid crystal that evaporative crystallization obtains in methanol evaporator is got back in the bleacher, and again through decolouring, evaporative crystallization, residual with methyl alcohol in the further minimizing product guarantees the quality of product.
Vitriol comprises that mainly ammonium sulfate, monoammonium sulfate and sulfuric acid that some are residual get into the hot tearing device, cracking under 200～300 ℃ of conditions, and ammonium sulfate and sodium sulfate are cracked into monoammonium sulfate and ammoniacal liquor, and sodium pyrosulfate.
2(NH
4)
2SO
4+Na
2SO
4→NH
4HSO
4+3NH
3+2NaHSO
4
The ammoniacal liquor that reaction generates is used further in the mold, and monoammonium sulfate returns in the Succinic Acid mold and reuses.
Embodiment 3
Present embodiment adopts and embodiment 1 identical fermentation condition and method, and its whole process method is as shown in Figure 4:
Utilize Mg (OH)
2Regulate fermentation pH.
As carbon source, in anaerobic reactor, utilize the microbiological anaerobic fermentation production of succinic acid with glucide, in the fermenting process, with Mg (OH)
2Regulate the pH of fermentation system, maintain about 6.8.Fermented liquid after the fermentation ends leaches insolubles through strainer, removes biomacromolecules such as protein, polysaccharide again through ultrafiltration, produces to avoid the pigment in follow-up condensing crystal process; Simultaneously, before multiple-effect evaporation, increased the decolouring unit, to guarantee the quality of Succinic Acid crystalline product; PH keeps 1.6 in mold, under this low pH, mends HCl, adds ammoniacal liquor again, and then Succinic Acid magnesium and HCl reaction generates Succinic Acid and MgCl
2, MgCl
2Generate Mg (OH) with the ammoniacal liquor reaction again
2And NH
4Cl.
MgA+2HCl→H
2A+MgCl
2
MgCl
2+2NH
4OH→2NH
4Cl+Mg(OH)
2
A represents the succinic ion, promptly
-(HOOC) (CH
2)
2(COOH)
-
The Marinco H that reaction generates is used further to regulate in the fermentor tank pH.
The Succinic Acid crystal that evaporative crystallization obtains in methanol evaporator is got back in the bleacher, and again through decolouring, evaporative crystallization, residual with methyl alcohol in the further minimizing product guarantees the quality of product.
Ammonium chloride then as fertilizer sources uses.
Embodiment 4
Present embodiment adopts and embodiment 1 identical fermentation condition and method, and its whole process method is as shown in Figure 5:
Utilize MgCO
3Regulate fermentation pH.
As carbon source, in anaerobic reactor, utilize the microbiological anaerobic fermentation production of succinic acid with glucide, in the fermenting process, use MgCO
3Regulate the pH of fermentation system, maintain 7.0.Fermented liquid after the fermentation ends leaches insolubles through strainer, removes biomacromolecules such as protein, polysaccharide again through ultrafiltration, produces to avoid the pigment in follow-up condensing crystal process; Simultaneously, before multiple-effect evaporation, increased the decolouring unit, to guarantee the quality of Succinic Acid crystalline product; PH maintains 1.7 in mold, under this low pH, mends HCl, adds ammoniacal liquor again, and then Succinic Acid magnesium and HCl reaction generates Succinic Acid acid and MgCl
2, MgCl
2Generate Mg (OH) with the ammoniacal liquor reaction again
2And NH
4Cl.
MgA+2HCl→H
2A+MgCl
2
MgCl
2+2NH
4OH→2NH
4Cl+Mg(OH)
2
A represents the succinic ion, promptly
-(HOOC) (CH
2)
2(COOH)
-
The Marinco H that reaction generates is used further to regulate in the fermentor tank pH.
The Succinic Acid crystal that evaporative crystallization obtains in methanol evaporator is got back in the bleacher, and again through decolouring, evaporative crystallization, residual with methyl alcohol in the further minimizing product guarantees the quality of product.
Ammonium chloride then as fertilizer sources uses.
Embodiment 5
Present embodiment adopts and embodiment 1 identical fermentation condition and method, and its whole process method is as shown in Figure 6:
Utilize Na
2CO
3Regulate fermentation pH.
As carbon source, in anaerobic reactor, utilize the microbiological anaerobic fermentation production of succinic acid with glucide, in the fermenting process, use Na
2CO
3Regulate the pH of fermentation system, maintain 6.8.Fermented liquid after the fermentation ends leaches insolubles through strainer, removes biomacromolecules such as protein, polysaccharide again through ultrafiltration, produces to avoid the pigment in follow-up condensing crystal process; Simultaneously, before multiple-effect evaporation, increased the decolouring unit, to guarantee the quality of Succinic Acid crystalline product; PH maintains 1.8 in mold, under this low pH, feeds CO
2, and add ammoniacal liquor, then the reaction of disodium succinate and ammoniacal liquor and yellow soda ash generates Succinic Acid two ammoniums and sodium hydrogencarbonate.
Na
2A+2NH
3+2H
2CO
3→(NH
4)
2A+2NaHCO
3
A represents the succinic ion, promptly
-(HOOC) (CH
2)
2(COOH)
-
The sodium hydrogencarbonate that reaction generates is used further to regulate in the fermentor tank pH.
The Succinic Acid crystal that evaporative crystallization obtains in methanol evaporator is got back in the bleacher, and again through decolouring, evaporative crystallization, residual with methyl alcohol in the further minimizing product guarantees the quality of product.
Vitriol comprises that mainly ammonium sulfate, monoammonium sulfate and sulfuric acid that some are residual get into the hot tearing device, cracking under 200～300 ℃ of conditions, and ammonium sulfate and sodium sulfate are cracked into monoammonium sulfate and ammoniacal liquor, and sodium pyrosulfate.
2(NH
4)
2SO
4+Na
2SO
4→NH
4HSO
4+3NH
3+2NaHSO
4
The ammoniacal liquor that reaction generates is used further in the mold, and monoammonium sulfate returns in the Succinic Acid mold and reuses.
Claims (4)
1. the technology of an anaerobically fermenting succinic acid purification is characterized in that may further comprise the steps:
(1) in fermentor tank, utilize mikrobe anaerobically fermenting in fermention medium to produce Succinic Acid;
(2) in the process of fermentation and acid, add alkaline neutraliser Mg (OH)
2Perhaps MgCO
3Keeping fermentation system pH value is 6.0～7.0;
(3) after the fermentation ends, fermented liquid is realized solid-liquid separation through filtration unit, the fermented liquid behind the removal insolubles carries out ultrafiltration again and removes biomacromolecule;
(4) ultrafiltrated gets into multiple-effect evaporator after decolouring, and waits to concentrate 4～6 times;
(5) in mold, add ammoniacal liquor and feed HCl gas, after the mold reaction treatment, Succinic Acid dissociates with the material after concentrating; And deliver to crystallisation by cooling in the Succinic Acid mold; Filter through strainer, obtain crystalloid Succinic Acid product, and the mother liquor that contains a small amount of Succinic Acid; And the Mg in the recovery mold (OH)
2To fermentor tank;
(6) mother liquor is got in the next mold and with methanol mixed after deliver to that condensing crystal goes out the Succinic Acid crystal in the methanol evaporator; And it is returned bleacher; After the decolouring crystallization, obtain the Succinic Acid product, rest materials is delivered to hot tearing device cracking recovery NH after reclaiming methyl alcohol
4Cl.
2. technology according to claim 1 is characterized in that the optimal ph described in the described step (2) is 6.8.
3. technology according to claim 1 is characterized in that the pH value in the mold described in the described step (5) should maintain below 2.0.
4. technology according to claim 3 is characterized in that described optimal ph is 1.5～1.8.
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| CN102634442B (en) * | 2011-02-10 | 2014-06-04 | 中国科学院过程工程研究所 | Device and method for biologically manufacturing succinic acid by continuous crystallization |
| PL2744745T3 (en) * | 2011-08-16 | 2020-05-18 | Purac Biochem B.V. | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
| JP2020045349A (en) * | 2011-08-16 | 2020-03-26 | ピュラック バイオケム ビー． ブイ． | Recovery of carboxylic acids from magnesium salts thereof through precipitation using hydrochloric acid, useful for fermentation broth processing |
| EP3845487A1 (en) | 2011-08-16 | 2021-07-07 | Purac Biochem B.V. | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
| PL2744746T3 (en) * | 2011-08-16 | 2021-06-14 | Purac Biochem Bv | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
| CN108821961A (en) * | 2011-08-16 | 2018-11-16 | 普拉克生化公司 | Carboxylic acid is recycled from its magnesium salts by precipitation using the hydrochloric acid for fermentation liquor treatment |
| CN102952008A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Method for extracting succinic acid from anaerobic fermentation broth |
| CN102363594B (en) * | 2011-11-09 | 2014-04-02 | 中国科学院过程工程研究所 | Method for separating and purifying succinic acid from fermentation broth |
| WO2013117687A1 (en) * | 2012-02-08 | 2013-08-15 | Purac Biochem B.V. | Carboxylate acidification |
| CN104591994B (en) * | 2013-11-03 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of method of refining long-chain biatomic acid |
| CN104876817B (en) * | 2015-04-24 | 2017-07-28 | 镇江博睿兴邦生物科技有限公司 | A kind of method that use succinic acid fermentation liquor extracts succinic acid |
| CN106316836A (en) * | 2015-07-01 | 2017-01-11 | 中国石化扬子石油化工有限公司 | Method for preparing butanedioic acid |
| CN105420296B (en) * | 2015-11-12 | 2020-02-14 | 武汉三江航天固德生物科技有限公司 | Method for producing succinic acid by fermentation method |
| CN106117012B (en) * | 2016-06-22 | 2018-07-31 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination |
| CN109206313B (en) * | 2017-07-05 | 2021-06-11 | 中国石化扬子石油化工有限公司 | Method for preparing succinic acid by succinate anaerobic fermentation liquid |
| CN110373432A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院过程工程研究所 | It is a kind of using synthesis gas as the system and its processing method of raw material coproduction succinic acid and alcohols |
| CN109265337A (en) * | 2018-10-30 | 2019-01-25 | 徐州绿油油生物肥料有限公司 | A kind of embrane method extraction process for extracting succinic acid from bio-fermented liquid |
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