CN104109697A - Method for producing citric acid by citric acid wastewater reflux fermentation - Google Patents

Method for producing citric acid by citric acid wastewater reflux fermentation Download PDF

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CN104109697A
CN104109697A CN201410321671.8A CN201410321671A CN104109697A CN 104109697 A CN104109697 A CN 104109697A CN 201410321671 A CN201410321671 A CN 201410321671A CN 104109697 A CN104109697 A CN 104109697A
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citric acid
liquid
fermentation
liquefaction
acid wastewater
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CN104109697B (en
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石贵阳
胡志杰
蒋小东
孙福新
金赛
王宝石
张�杰
李赢
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Joint limited energy company of Jiangsu China Telecom
Jiangnan University
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YIXING-UNION BIOCHEMICAL Co Ltd
Jiangnan University
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Abstract

The invention relates to a method for producing citric acid by citric acid wastewater reflux fermentation. The method comprises the following steps: uniformly mixing a starchy raw material with citric acid wastewater, and adding high-temperature alpha-amylase (2) carrying out injection on the mixed solution twice, and carrying iodine test to obtain a qualified liquefied mixed solution; carrying out plate-frame pressure filtration on the liquefied mixed solution to obtain a liquefied clear solution; (3) mixing the liquefied clear solution with the liquefied mixed solution, adding the citric acid wastewater for water replenishing to obtain a seed culture medium, and carrying out strain seed culture; (4) mixing the liquefied clear solution with the liquefied mixed solution, adding citric acid wastewater for water replenishing to obtain a fermentation nutrient solution, and carrying out fermentation culture; and (5) after the fermentation is finished, carrying out solid-liquid separation to remove the thallus, and extracting by a hydrogen calcium process or chromatography to obtain the citric acid, wherein the generated wastewater returns to the steps (1), (3) and (4), and the cycle repeats. The method has the advantages high fermentation stability and equivalent level with the original technique, saves the consumption of process water and vapor, saves the sewage treatment cost, and has important environmental benefit and economic benefit.

Description

The method of citric acid wastewater backflow fermentation production of citric acid
Technical field
The present invention relates to fermentation engineering field, especially relate to a kind of citric acid wastewater without any processing, the method for the fermentation production of citric acid that directly refluxes.
Background technology
Citric acid because the tart flavour, entrance that it has pleasant is frank, the feature of tart flavour, safety non-toxic without male offspring, so be widely used in the fields such as food, medicine and chemical industry, become the edible organic acid of growing amount and consumption maximum on our times.China is maximum in the world citric acid export State, and the production capacity of 2012 has surpassed ten thousand tons of l10, and about 90% citric acid exports to foreign countries, and accounts for Gross World Product 70% left and right.Citric acid production mainly adopts liquid submerged fermentation, in leaching process, can produce a large amount of waste water, wherein contains the materials such as some organic acids, sugar, protein colloid, mineral substance, and COD is up to 350kg/t citric acid, and concentration is up to 10000 ~ 15000ppm.If these waste water are not treated or deal with improperly, not only cause serious environmental pollution, also cause the waste of great lot of water resources, increased enterprise's production cost simultaneously.Therefore how effectively processing the high concentrated organic wastewater that citric acid fermentation produces, is citric acid industry problem demanding prompt solution.
The main methods of existing citric acid wastewater: anaerobic biological process, aerobe method, anaerobic-aerobic combined method, they are to utilize aerobic or anaerobion organism in degradation of sewage under suitable condition, partial organic substances is converted into self cellular constituent simultaneously, thereby reduces the COD of waste water.From current citric acid industry wastewater treatment present situation, effect is unsatisfactory, and these methods generally need pre-treatment in early stage, and the cycle is longer, and waste water treatment is not thorough, needs further advanced treatment, just can reach emission standard, and processing cost is higher.Therefore, how effectively realizing energy-saving and emission-reduction, reduce costs, is the key subjects that citric acid industry healthy development faces.If citric acid wastewater can direct reuse or simple process after reuse, for solving, a sewage disposal difficult problem is significant.
Summary of the invention
The problems referred to above that exist for prior art, the applicant provides a kind of method of citric acid wastewater backflow fermentation production of citric acid.Present method fermentation stability and suitable with former technology level, has saved process water and steam consumption, has saved cost of sewage disposal, has important environmental benefit, economic benefit.
Technical scheme of the present invention is as follows:
The method of citric acid wastewater backflow fermentation production of citric acid, comprises the steps:
(1) starchy material and citric acid wastewater are the in the situation that of 50 ~ 60 ℃, ratio according to 1:1.5 ~ 1:4 in material-compound tank mixes, pH to 5.8 ~ 6.0 that regulate mixed solution with calcium hydroxide, then add high-temperatureα-amylase, and its addition is 15 ~ 40U/g Semen Maydis powder;
(2) step (1) gained mixed solution is carried out to two step processing: first by mixed solution through twice injection, one time injection temperature is 97 ~ 101 ℃, second spraying temperature is 120 ~ 130 ℃, through iodine examination for light brown qualified, mixed liquid obtains liquefying; By the mixed liquid process of 60 ~ 80% liquefaction filter press, obtain the clear liquid that liquefies again;
(3) step (2) gained liquefaction clear liquid is mixed in the ratio of 1:1.5 ~ 1:2.5 with the mixed liquid of liquefaction, and add citric acid wastewater to carry out moisturizing, and making mixed liquid total reducing sugar is 10 ~ 12%, total nitrogen is 0.19 ~ 0.40%, obtain seed culture medium, carry out the seed culture of bacterial classification;
(4) step (2) gained liquefaction clear liquid is mixed in the ratio of 3.5:1 ~ 5:1 with the mixed liquid of liquefaction, and add citric acid wastewater to carry out moisturizing, making mixed liquid total reducing sugar is 14 ~ 17%, total nitrogen is 0.05 ~ 0.15%, obtain fermented nutritive liquid, step (3) seed culture gained seed liquor is added to fermented nutritive liquid, carry out fermentation culture;
(5) step (4) fermentation ends is removed thalline by solid-liquid separation, through hydrogen calcium method or chromatography, extracts and obtains citric acid, and the waste water of generation is got back to step (1) and step (3), (4), so circulates.
Starchy material described in step (1) comprises at least one of Semen Maydis powder, wheat-flour, Tapioca Starch, sweet potato powder, starch, molasses, wheat.
Citric acid wastewater described in step (1) refers to the useless syrup that hydrogen calcium extraction method produces while manufacturing citric acid, or the chromatogram raffinate that produces while manufacturing citric acid of chromatogram extraction method.
Bacterial classification described in step (3) for screening the high aspergillus niger strain of strong adaptability, stability obtaining in citric acid wastewater.
The technique effect that the present invention is useful is:
The object of the invention is to not change in the situation of existing main body zymotechnique technology and equipment, by adding reflux cycle pipeline, reduce the biological treatment process of even eliminating high concentrated organic wastewater, set up the scheme of the citric acid wastewater backflow fermentation production of citric acid of a set of steady running.
The present invention can make the waste water that citric acid leaching process produces directly substitute water of productive use without any processing, for raw material, sizes mixing and liquefies and the moisturizing of preparation substratum; Cultivation is to the adaptable bacterial classification of waste water, and switching is fermented; Fermentation ends, fermented liquid obtains fermentation clear liquid through solid-liquid separation, and hydrogen calcium method or chromatography are extracted citric acid, and the citric acid wastewater of generation continues to be back to production system, so realizes the recycle of waste water.
Adopt 40 batches of this technology lemon acid waste water circulation uses, glucose acid invert ratio is 95.85% ~ 101.35%, and fermentation period is at 62 ~ 72h, fermentation stability and suitable with former technology level.The present invention can effectively utilize the carbon and nitrogen sources in waste water, and the citric acid wastewater of 50 ~ 60 ℃ of refluxing can agree with feed temperature, has saved process water and steam consumption, has saved cost of sewage disposal, has important environmental benefit, economic benefit.
Accompanying drawing explanation
Fig. 1 is the Technology schematic flow sheet of citric acid wastewater backflow fermentation production of citric acid of the present invention.
Embodiment
Below in conjunction with accompanying drawing 1, the present invention is specifically described.The source of the aspergillus niger seed in embodiment is that Yixing-Union Biochemical Co., Ltd. produces below, by Southern Yangtze University's grain zymotechnique and technology national engineering laboratory bioseparation engineering research chamber, tames cultivation.(citric acid extracts the waste water producing to citric acid wastewater, Yixing-Union Biochemical Co., Ltd. provides) liquefying obtains liquefied corn, add a certain amount of ammonium sulfate, preparation substratum (total reducing sugar 5% ~ 9%, total nitrogen 0.25% ~ 0.45%), inoculated aspergillus niger seed, through (35 ℃ of plate isolation screenings, 48h), select neat in edge, projection, larger single bacterium colony, (35 ℃ of single bacterium colony slant culture, 5d), shaking flask is sieved (35 ℃ again, 320rpm, cultivate 72h) select and produce the higher bacterial classification of acid, then further domestication is cultivated, so be cycled to repeat screening, obtain adaptable bacterial classification, be numbered AT0019.
 
Embodiment 1
Semen Maydis powder 200kg, lemon acid waste syrup 600kg mixes in 50 ℃ of material-compound tanks, and adding calcium hydroxide regulates pH to 5.8, and adding Mei Huo unit is the high temperature resistant α-amylase 250g of 20000U/g.Through second spraying liquefaction, wherein an injection temperature is 97 ℃, and second spraying temperature is 130 ℃, maintain and in tank, maintain 0.5 ~ 1h, iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 70% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:1.5, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 3.5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 10.7%, total nitrogen 0.24%, aspergillus niger seed culture 27h, pH 2.05, acidity 2.05%; Fermentation initial total sugar 16.10%, total nitrogen 0.05%, 37 ℃ of culture temperature; Fermentation ends acidity is 16.08% (v/v), and residual total reducing sugar is 2.3%, and residual reducing sugar is 0.5%, and transformation efficiency is 99.88%, cycle 67h.Fermented liquid extracts citric acid through hydrogen calcium method, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 batches, and citric acid fermentation level is normal.
 
Embodiment 2
Tapioca Starch 100kg, lemon acid waste syrup 150kg mixes in 60 ℃ of material-compound tanks, and adding calcium hydroxide is adjusted pH to 5.9, and adding Mei Huo unit is the high temperature resistant α-amylase 125g of 20000U/g.Through second spraying liquefaction, wherein an injection temperature is 99 ℃, and second spraying temperature is 125 ℃, maintains 0.5 ~ 1h in maintaining tank, iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 60% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:1.5, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 5.5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 10%, total nitrogen 0.2%, aspergillus niger seed culture 26h, pH 2.06, acidity 2.7%; Fermentation initial total sugar is 14%, total nitrogen 0.08%, 37 ℃ of culture temperature; Fermentation ends acidity is 14.19% (v/v), and residual total reducing sugar is 2.0%, and residual reducing sugar is 0.5%, and transformation efficiency is 101.35%, cycle 60h.Fermented liquid extracts citric acid through hydrogen calcium method, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
 
Embodiment 3
Semen Maydis powder 300kg, Tapioca Starch raw material 200kg, lemon acid waste syrup 2000kg mixes in 55 ℃ of material-compound tanks, and adding calcium hydroxide is adjusted pH to 5.9, and adding Mei Huo unit is the high temperature resistant α-amylase 800g of 20000U/g.Through second spraying liquefaction, wherein an injection temperature is 101 ℃, and second spraying temperature is 120 ℃, maintains 0.5 ~ 1h in maintaining tank, through iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 80% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:2, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 5.5:1, and adds citric acid wastewater to carry out moisturizing.
Seed initial total sugar 12%, total nitrogen 0.26%, aspergillus niger seed culture 26h, pH 1.99, acidity 2.3%; Fermention medium initial total sugar is 16.2%, total nitrogen 0.11%, 37 ℃ of culture temperature; Fermentation ends acidity is 16.1% (v/v), and residual total reducing sugar is 2.02%, and residual reducing sugar is 0.51%, and transformation efficiency is 99.38%, cycle 72h.Fermented liquid extracts citric acid through hydrogen calcium method, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
 
Embodiment 4
Sweet potato powder raw material 120kg, lemon acid waste syrup 320kg mixes in 55 ℃ of material-compound tanks, and adding calcium hydroxide is adjusted pH to 6.0, adding Mei Huo unit is the high temperature resistant α-amylase 180g of 20000U/g, through second spraying liquefaction, wherein an injection temperature is 97 ℃, and second spraying temperature is 125 ℃, in maintaining tank, maintain 0.5 ~ 1h, iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 65% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:2, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 10.8%, total nitrogen 0.22%, aspergillus niger seed culture 26h, pH 2.06, acidity 2.7%; Fermentation initial total sugar is 16.7%, total nitrogen 0.13%, 37 ℃ of culture temperature; Fermentation ends acidity is 16.61% (v/v), and residual total reducing sugar is 2.0%, and residual reducing sugar is 0.5%, and transformation efficiency is 99.5%, cycle 69h.Fermented liquid extracts citric acid through hydrogen calcium method, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
 
Embodiment 5
Wheat-flour 210kg, lemon acid waste syrup 380kg mixes in 60 ℃ of material-compound tanks, and adding calcium hydroxide is adjusted pH to 5.9, adding Mei Huo unit is the high temperature resistant α-amylase 290g of 20000U/g, through second spraying liquefaction, wherein an injection temperature is 98 ℃, and second spraying temperature is 128 ℃, in maintaining tank, maintain 0.5 ~ 1h, iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 75% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:2.5, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 11%, total nitrogen 0.24%, aspergillus niger seed culture 25h, pH 2.02, acidity 2.9%; Fermentation initial total sugar is 15.2%, total nitrogen 0.15%, 37 ℃ of culture temperature; Fermentation ends acidity is 15.03% (v/v), and residual total reducing sugar is 2.0%, and residual reducing sugar is 0.5%, and transformation efficiency is 98.9%, cycle 66h.Fermented liquid extracts citric acid through hydrogen calcium method, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
 
Embodiment 6
Semen Maydis powder 150kg, chromatogram raffinate 600kg mixes in 52 ℃ of material-compound tanks, and adding calcium hydroxide regulates pH to 5.8, adding Mei Huo unit is the high temperature resistant α-amylase 130g of low pH of 20000U/g, through second spraying liquefaction, wherein an injection temperature is 100 ℃, and second spraying temperature is 122 ℃, maintain and in tank, maintain 0.5 ~ 1h, iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 70% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:2.5, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 4.5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 9.7%, total nitrogen 0.19%, aspergillus niger seed culture 26h, pH 2.0, acidity 2.15%; Fermentation initial total sugar 15.90%, total nitrogen 0.10%, 37 ℃ of culture temperature; Fermentation ends acidity is 15.42% (v/v), and residual total reducing sugar is 2.08%, and residual reducing sugar is 0.5%, and transformation efficiency is 96.14%, cycle 67h.Fermented liquid extracts citric acid through chromatography, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 batches, and citric acid fermentation level is normal.
 
Embodiment 7
Tapioca Starch 200kg, chromatogram raffinate 800kg mixes in 60 ℃ of material-compound tanks, and adding calcium hydroxide is adjusted pH to 5.8, adding Mei Huo unit is the high temperature resistant α-amylase 250g of low pH of 20000U/g, through second spraying liquefaction, wherein an injection temperature is 97 ℃, and second spraying temperature is 124 ℃, in maintaining tank, maintain 0.5 ~ 1h, iodine examination for light brown qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 70% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 1:1.5, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 4.5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 10.9%, total nitrogen 0.3%, aspergillus niger seed culture 25h, pH 2.06, acidity 2.2%; Fermentation initial total sugar is 17%, total nitrogen 0.13%, 37 ℃ of culture temperature; Fermentation ends acidity is 16.77% (v/v), and residual total reducing sugar is 2.15%, and residual reducing sugar is 0.5%, and transformation efficiency is 98.62%, cycle 71h.Fermented liquid extracts citric acid through chromatography, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
 
Embodiment 8
Semen Maydis powder 300kg, Tapioca Starch raw material 200kg, chromatogram raffinate 1000kg, in 55 ℃ of material-compound tanks, mix, adding calcium hydroxide is adjusted pH to 5.9, and adding Mei Huo unit is the high temperature resistant α-amylase 800g of low pH of 20000U/g, through second spraying liquefaction, wherein an injection temperature is 100 ℃, second spraying temperature is 130 ℃, maintains 0.5 ~ 1h in maintaining tank, through iodine examination, is that light brown is qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 80% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in 1:1.5 ratio, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 4:1, and adds citric acid wastewater to carry out moisturizing.
Seed initial total sugar 11%, total nitrogen 0.23%, aspergillus niger seed culture 25h, pH 1.99, acidity 2.3%; Fermention medium initial total sugar is 15.44%, total nitrogen 0.11%, 37 ℃ of culture temperature; Fermentation ends acidity is 15.38% (v/v), and residual total reducing sugar is 2.08%, and residual reducing sugar is 0.5%, and transformation efficiency is 99.64%, cycle 72h.Fermented liquid extracts citric acid through chromatography, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
 
Embodiment 9
Semen Maydis powder 250kg, wheat-flour 150kg, chromatogram raffinate 1200kg, in 60 ℃ of material-compound tanks, mix, adding calcium hydroxide is adjusted pH to 5.8, and adding Mei Huo unit is the high temperature resistant α-amylase 250g of low pH of 20000U/g, through second spraying liquefaction, wherein an injection temperature is 97 ℃, second spraying temperature is 129 ℃, maintains 0.5 ~ 1h in maintaining tank, and iodine examination is that light brown is qualified, the mixed liquid that obtains liquefying, the more mixed liquid of 60% liquefaction is entered to filter press obtain the clear liquid that liquefies.
Preparation seed culture medium and fermented nutritive liquid, wherein seed culture medium is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in 1:2 ratio, and adds citric acid wastewater to carry out moisturizing; Fermented nutritive liquid is that the mixed liquid of liquefaction clear liquid and liquefaction is mixed in the ratio of 3.5:1, and adds citric acid wastewater to carry out moisturizing.
Seed culture medium initial total sugar 11.2%, total nitrogen 0.35%, aspergillus niger seed culture 24h, pH 2.06, acidity 2.3%; Fermentation initial total sugar is 15.9%, total nitrogen 0.07%, 37 ℃ of culture temperature; Fermentation ends acidity is 15.87% (v/v), and residual total reducing sugar is 2.01%, and residual reducing sugar is 0.5%, and transformation efficiency is 97.99%, cycle 63h.Fermented liquid extracts citric acid through chromatography, produces citric acid wastewater, again according to above-mentioned steps repetitive operation, circulates 40 times, and citric acid fermentation level is normal.
The above has described embodiment of the present invention in detail; can do a lot of improvement obviously for a person skilled in the art; within the spirit and principles in the present invention all, any modification of making, equal replacement, improvement etc., within all should being included in the scope of protection of the invention.

Claims (4)

1. the method for citric acid wastewater backflow fermentation production of citric acid, is characterized in that comprising the steps:
(1) starchy material and citric acid wastewater are the in the situation that of 50 ~ 60 ℃, ratio according to 1:1.5 ~ 1:4 in material-compound tank mixes, pH to 5.8 ~ 6.0 that regulate mixed solution with calcium hydroxide, then add high-temperatureα-amylase, and its addition is 15 ~ 40U/g Semen Maydis powder;
(2) step (1) gained mixed solution is carried out to two step processing: first by mixed solution through twice injection, one time injection temperature is 97 ~ 101 ℃, second spraying temperature is 120 ~ 130 ℃, through iodine examination for light brown qualified, mixed liquid obtains liquefying; By the mixed liquid process of 60 ~ 80% liquefaction filter press, obtain the clear liquid that liquefies again;
(3) step (2) gained liquefaction clear liquid is mixed in the ratio of 1:1.5 ~ 1:2.5 with the mixed liquid of liquefaction, and add citric acid wastewater to carry out moisturizing, and making mixed liquid total reducing sugar is 10 ~ 12%, total nitrogen is 0.19 ~ 0.40%, obtain seed culture medium, carry out the seed culture of bacterial classification;
(4) step (2) gained liquefaction clear liquid is mixed in the ratio of 3.5:1 ~ 5:1 with the mixed liquid of liquefaction, and add citric acid wastewater to carry out moisturizing, making mixed liquid total reducing sugar is 14 ~ 17%, total nitrogen is 0.05 ~ 0.15%, obtain fermented nutritive liquid, step (3) seed culture gained seed liquor is added to fermented nutritive liquid, carry out fermentation culture;
(5) step (4) fermentation ends is removed thalline by solid-liquid separation, through hydrogen calcium method or chromatography, extracts and obtains citric acid, and the waste water of generation is got back to step (1) and step (3), (4), so circulates.
2. the method for citric acid wastewater backflow fermentation production of citric acid according to claim 1, is characterized in that starchy material described in step (1) comprises at least one of Semen Maydis powder, wheat-flour, Tapioca Starch, sweet potato powder, starch, molasses, wheat.
3. the method for citric acid wastewater backflow fermentation production of citric acid according to claim 1, it is characterized in that citric acid wastewater described in step (1) refers to the useless syrup that hydrogen calcium extraction method produces while manufacturing citric acid, or the chromatogram raffinate that produces while manufacturing citric acid of chromatogram extraction method.
4. the method for citric acid wastewater backflow fermentation production of citric acid according to claim 1, is characterized in that bacterial classification described in step (3) for screening the high aspergillus niger strain of strong adaptability, stability obtaining in citric acid wastewater.
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CN105567749A (en) * 2016-03-10 2016-05-11 江苏国信协联能源有限公司 Processing method for starchiness materials and application of processing method in citric acid preparing industry
CN105586367A (en) * 2016-03-10 2016-05-18 江南大学 Method for conducting fermentative production of citric acid by adding saccharifying enzyme stage by stage based on pH responses
CN109022502A (en) * 2018-08-17 2018-12-18 江南大学 A kind of method of anaerobic digestion solution circulating and recovering production citric acid
CN109022503A (en) * 2018-08-17 2018-12-18 江南大学 A method of citric acid is produced using recycling anaerobic digestion solution
CN113278659A (en) * 2021-05-28 2021-08-20 郑州运维生物技术有限公司 Recycling method of lactic acid fermentation acid-containing wastewater
CN114717273A (en) * 2022-03-10 2022-07-08 山东柠檬生化有限公司 Recycling process of anaerobic digestion solution in citric acid production
CN115976121A (en) * 2023-02-08 2023-04-18 江苏国信协联能源有限公司 Method for producing citric acid by membrane separation aspergillus niger bacteria circulating continuous fermentation of residual sugar recovery

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CN102249895A (en) * 2011-05-10 2011-11-23 安徽丰原生物化学股份有限公司 Treatment method of solution containing citric acid
CN102747111A (en) * 2012-08-06 2012-10-24 江南大学 Process for producing citric acid with aerobic effluent serving as ingredient water

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CN105296549A (en) * 2015-10-23 2016-02-03 安徽丰原发酵技术工程研究有限公司 Method for improving citric acid fermenting level
CN105567749A (en) * 2016-03-10 2016-05-11 江苏国信协联能源有限公司 Processing method for starchiness materials and application of processing method in citric acid preparing industry
CN105586367A (en) * 2016-03-10 2016-05-18 江南大学 Method for conducting fermentative production of citric acid by adding saccharifying enzyme stage by stage based on pH responses
CN109022502A (en) * 2018-08-17 2018-12-18 江南大学 A kind of method of anaerobic digestion solution circulating and recovering production citric acid
CN109022503A (en) * 2018-08-17 2018-12-18 江南大学 A method of citric acid is produced using recycling anaerobic digestion solution
CN109022503B (en) * 2018-08-17 2020-09-04 江南大学 Method for producing citric acid by utilizing recycled anaerobic digestion solution
CN109022502B (en) * 2018-08-17 2020-10-09 江南大学 Method for producing citric acid by recycling anaerobic digestion solution
CN113278659A (en) * 2021-05-28 2021-08-20 郑州运维生物技术有限公司 Recycling method of lactic acid fermentation acid-containing wastewater
CN114717273A (en) * 2022-03-10 2022-07-08 山东柠檬生化有限公司 Recycling process of anaerobic digestion solution in citric acid production
CN115976121A (en) * 2023-02-08 2023-04-18 江苏国信协联能源有限公司 Method for producing citric acid by membrane separation aspergillus niger bacteria circulating continuous fermentation of residual sugar recovery

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