CN108949841A - A method of production citric acid is discharged using aerobic sigestion - Google Patents
A method of production citric acid is discharged using aerobic sigestion Download PDFInfo
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- CN108949841A CN108949841A CN201810939730.6A CN201810939730A CN108949841A CN 108949841 A CN108949841 A CN 108949841A CN 201810939730 A CN201810939730 A CN 201810939730A CN 108949841 A CN108949841 A CN 108949841A
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 38
- 230000029087 digestion Effects 0.000 claims abstract description 79
- 238000000855 fermentation Methods 0.000 claims abstract description 58
- 230000004151 fermentation Effects 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000002921 fermentation waste Substances 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract 2
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 244000061456 Solanum tuberosum Species 0.000 claims description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims 1
- 229920002472 Starch Polymers 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract 1
- 239000008235 industrial water Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013505 freshwater Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 241001052560 Thallis Species 0.000 description 3
- 102000004139 alpha-Amylases Human genes 0.000 description 3
- 108090000637 alpha-Amylases Proteins 0.000 description 3
- 229940024171 alpha-amylase Drugs 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- -1 calcium hydrogen Chemical class 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/44—Polycarboxylic acids
- C12P7/48—Tricarboxylic acids, e.g. citric acid
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention discloses a kind of aerobic sigestion water outlets come the method for producing citric acid, belongs to citric acid fermentation industrial technical field.Technical solution of the present invention comprise the steps of: citric acid fermentation waste water by anaerobic digestion, aerobic sigestion, separation of solid and liquid, cation exchange resin and etc. processing, aerobic sigestion that treated can be used as the industrial water of citric acid fermentation, fermented product is obtained through conventional production process such as liquefaction, fermentation and extractions again, extracts the circulation that waste liquid enters next batch.It is an advantage of the invention that aerobic sigestion water outlet can Infinite Cyclic reuse, not only eliminate the pollution of aerobic waste water, also a save the water resources drop of a large amount of preciousnesses, low production cost improves economic benefit and environmental benefit.
Description
Technical Field
The invention relates to a method for producing citric acid by using aerobic digestion effluent, belonging to the technical field of citric acid fermentation industry.
Background
Citric acid is an important organic acid and is widely applied to the fields of food, medicine, chemical industry, environmental protection and the like, the yield of citric acid in China reaches 120 million tons and accounts for more than 65% of the total yield in the world, the citric acid is expected to increase at a speed of 4% in future with the continuous expansion of the application field of citric acid, and the development speed and the scale of the citric acid are attracted by attention. In the traditional process for producing citric acid by fermenting the starchy raw material, the starchy raw material is crushed, fresh water is added for size mixing, cooking and liquefying, then aspergillus niger is inoculated for fermentation, 7.5-15 tons of wastewater is discharged per ton of citric acid on average, and COD (chemical oxygen demand) of the wastewater isCrThe concentration of the fresh water is up to 15000-25000 mg/L, which not only causes serious pollution to the environment, but also causes a great deal of waste of fresh water resources. Therefore, how to effectively treat the high-concentration organic wastewater generated by citric acid fermentation becomes a bottleneck restricting the healthy development of the citric acid industry.
At present, citric acid wastewater in China mainly adopts a biological treatment mode of anaerobic digestion and aerobic digestion: namely, the citric acid waste water is firstly subjected to anaerobic digestion to convert high-concentration organic matters into methane, and then is subjected to aerobic digestion treatment such as aeration and the like; the method has the main problem that the COD of the aerobic digestion effluent isCrStill in 300-600 mg/L, still can not reach national emission standard, still need further advanced treatment to increase treatment cost, and cause the waste of water resource. At the same time, China is also water resourceOne of countries with serious shortage of resources is that in economically developed areas such as the Ministry of Ministry and the like, governments have started to make relevant restriction policies not only for the total amount of wastewater discharged by biological fermentation enterprises, but also for the total amount of water used. Therefore, the method has the same important significance on reducing the consumption of fresh water and reducing emission for domestic citric acid fermentation enterprises.
The patent application (CN102690003A) provides a device and a method for advanced treatment of citric acid wastewater by a double-membrane method, wherein aerobic digestion effluent is subjected to flocculation, ultrafiltration and reverse osmosis treatment in sequence, and reverse osmosis effluent is reused in production. However, aerobic digestion, flocculation, reverse osmosis under high pressure and the like all cause high operation cost, low water yield and the like, and limit the application of the method in production. Patent application (CN102747111A) proposes a process for producing citric acid from aerobic effluent, in which the aerobic digested effluent is directly used as process ingredient water to produce citric acid, and researches show that the aerobic effluent not only has higher conductivity, but also some cations inhibit citric acid fermentation, which causes the decrease of citric acid yield, so that the method cannot be really applied.
Disclosure of Invention
In order to overcome the defects, the invention provides the method for producing the citric acid by treating the aerobic digestion solution by the recycling method, and the method can reduce the pollution of aerobic effluent and the advanced treatment cost, simultaneously save the consumption of fresh water resources and improve the economic benefit.
The invention provides a ring-shaped production method of citric acid, which comprises the following steps: treating aerobic digestive juice in the citric acid production process by using cation exchange resin to serve as production water, wherein Na in the production water+≤300mg/L、K+≤350mg/L、Mg2+Less than or equal to 60 mg/L; the aerobic digestion solution is obtained by extracting, anaerobic digestion and aerobic digestion of citric acid fermentation liquor.
In one embodiment of the present invention, the COD of the aerobic digestion solution is 100 to 600mg/L
In one embodiment of the invention, the cation exchange resin is a strong acid type cation exchange resin, the treatment mode is dynamic adsorption, the sample injection speed is 1-36 times of the volume of a resin bed per hour, and the sample injection temperature is 15-50 ℃.
In one embodiment of the invention, the strong acid type cation exchange resin is one or more of hydrogen type cation exchange resin, 732 type cation exchange resin and D001 macroporous cation exchange resin.
In one embodiment of the invention, the method comprises the steps of: citric acid fermentation, citric acid waste liquid extraction, anaerobic digestion, aerobic digestion, cation exchange treatment, raw material ingredient liquefaction and a new round of citric acid fermentation.
In one embodiment of the present invention, the extraction process is any one of a calcium salt method, a calcium hydroxide method, or a chromatography method.
In one embodiment of the present invention, the method specifically comprises the following steps:
step 101: carrying out solid-liquid separation and extraction processes on the citric acid fermentation liquor to obtain a citric acid fermentation waste liquor and a crude product;
step 102: allowing the citric acid fermentation waste liquid generated in the step 101 to enter a biogas fermentation process, and fermenting to generate biogas and anaerobic digestion liquid;
step 103: directly carrying out aerobic digestion treatment on the anaerobic digestion solution generated in the step 102;
step 104: carrying out solid-liquid separation on the aerobic digestion solution to obtain a filtrate;
step 105: treating the filtrate generated in the step 104 by using cation resin to obtain aerobic digestion effluent;
step 106: mixing the starchy material with the aerobic digestion effluent generated in the step 105, stirring, and liquefying, wherein the part with insufficient aerobic digestion effluent can be supplemented by deionized water or other process water;
step 107: separating the partial liquefied liquid or the whole liquefied liquid after the material mixing and liquefaction in the step 106 by a solid-liquid separation means to obtain clear liquid;
step 108: performing citric acid fermentation on the liquefied liquid generated in the step 106 and the clear liquid generated in the step 107;
returning the fermentation liquor generated in the step 108 to the step 101 to form a cycle; wherein,
returning the fermentation liquor generated in the step 108 to the step 101 to form a cycle; wherein, when the turbidity of the aerobic digestion solution obtained in the step 103 is less than 50NTU, the step 104 is omitted, and the step 105 is directly carried out; when the starchy feedstock is not single corn, step 107 may be omitted.
In one embodiment of the invention, the solid-liquid separation mode is one or more of centrifugal separation, plate-and-frame filtration, flocculation filtration, microfiltration membrane and ultrafiltration membrane which are combined in series.
In an embodiment of the present invention, the biogas fermentation in step 102 is any biogas fermentation process, and the fermentation method and the process conditions are not limited.
In one embodiment of the present invention, the preferred biogas fermentation method is: single-stage medium-temperature anaerobic fermentation is carried out at the temperature of 32-42 ℃ and the hydraulic retention time is 1-5 days.
In an embodiment of the present invention, the aerobic digestion treatment in step 102 is not limited in the manner and process conditions.
In one embodiment of the present invention, the conditions of the aerobic digestion treatment are preferably: the temperature is 20-35 ℃, and the dissolved oxygen is 1-10 mg/L.
In an embodiment of the present invention, the part of the liquefied liquid after the enzymatic liquefaction or the whole liquefied liquid is subjected to a solid-liquid separation to obtain a clear liquid, and then the clear liquid is fed into a fermentation process, wherein the step can be selected according to actual needs.
In one embodiment of the present invention, the liquefaction process is performed by subjecting the mixed material to conventional liquefaction operations such as pH adjustment, enzyme addition, temperature increase and maintenance for a certain period of time, and other liquefaction methods are employed without affecting the practice of the present invention.
In one embodiment of the invention, when the starchy raw material is mixed with aerobic effluent, the ratio Kg/L of the mass of the raw material to the volume of the water is 1: 2.5 to 5 (w/v).
In one embodiment of the invention, the starchy material is one or more of potatoes, corn, rice and wheat.
In one embodiment of the present invention, when the starchy material is corn alone, the operation of separating the supernatant obtained by subjecting a part of the liquefied liquid or the whole liquefied liquid after liquefaction with an enzyme to solid-liquid separation cannot be omitted.
The invention has the following beneficial technical effects:
1. the aerobic digestion effluent recycling has no influence on the citric acid fermentation level, the concentration of the fermentation product is equivalent to that of the deionized water fermentation product, and the purpose of recycling the aerobic digestion effluent is really realized;
2. the process for producing the citric acid by aerobic digestion of effluent not only reduces the pollution of aerobic wastewater, but also saves the consumption of fresh water resources, and reduces the production cost of each ton of citric acid by 20.8 yuan, thereby improving the economic benefit and the environmental protection benefit.
Drawings
FIG. 1 is a schematic flow diagram of a process for producing citric acid by aerobic digestion of effluent according to the present invention.
Detailed Description
Detection of Na+、K+、Mg2+The content method comprises the following steps: the measurement is carried out by adopting a national standard method, namely flame atomic absorption spectrometry.
The COD content determination method comprises the following steps: the determination is carried out by adopting a national standard method, namely a potassium dichromate method.
The invention will be further described in the following by way of example with reference to the accompanying fig. 1:
example 1
Step 101: after separating thalli and residues from the citric acid fermentation liquor, obtaining citric acid fermentation waste liquor and a crude product by adopting a calcium hydrogen method extraction process, wherein the total COD of the citric acid fermentation waste liquor is 16500 mg/L;
step 102: performing medium-temperature anaerobic digestion (in a UASB reactor), maintaining the temperature at 35 ℃, Hydraulic Retention Time (HRT) for 2d and pH at 7.0-7.2 to obtain anaerobic digestion liquid, wherein COD of the anaerobic digestion liquid is 1200 mg/L;
step 103: carrying out aerobic digestion treatment on the anaerobic digestion solution generated in the step 102, maintaining the temperature at 25 ℃, the dissolved oxygen at 2mg/L, the COD of the aerobic digestion solution at 550mg/L, and Na+＝478mg/L、K+＝501mg/L、Mg2+＝97mg/L；
Step 104: filtering the aerobic digestion solution by a plate frame to obtain sludge and filtrate;
step 105: and (3) enabling the filtrate obtained in the step (104) to enter a 732 type cation resin bed, maintaining the temperature at 30 ℃, and enabling the feeding speed to be 25 times of the volume of the resin bed per hour to obtain aerobic digestion effluent, wherein the quality of the aerobic digestion effluent is as follows: na (Na)+＝187mg/L、K+＝235mg/L、Mg2+＝36mg/L；
step 106, adding 1750mL of aerobic digestion effluent generated in the step 105 into 400g of cassava powder and 100g of corn powder, firstly adjusting the pH to 5.8, adding 1.1mL of 20000U/mL high-temperature α -amylase, uniformly stirring, heating, and liquefying to obtain liquefied liquid;
step 108: the liquefied liquid generated in the step 106 is sterilized, cooled, inoculated and fermented at constant temperature for 65 hours, and the concentration of citric acid after the fermentation is finished is 16.5% (w/v, Kg/L, the same as the concentration of citric acid fermented by deionized water is 16.3% (w/v);
returning the fermentation liquor in the step 108 to the step 101 for treatment; and then the steps are carried out in sequence, 12 batches are circulated, the fermentation level of the citric acid is normal, and the process for producing the citric acid by using the aerobic digestion effluent is established in the embodiment.
Example 2
Step 101: after separating thalli and residues from the citric acid fermentation liquor, obtaining a citric acid fermentation waste liquor and a crude product by adopting a calcium salt method extraction process, wherein the total COD of the citric acid fermentation waste liquor is 19000 mg/L;
step 102: performing medium-temperature anaerobic digestion (in a UASB reactor), maintaining the temperature at 37 ℃, the Hydraulic Retention Time (HRT) at 4d and the pH at 6.9-7.1 to obtain anaerobic digestion liquid, wherein the COD of the anaerobic digestion liquid is 890 mg/L;
step 103: subjecting the anaerobic digestion solution generated in the step 202 to aerobic digestion treatment, maintaining the temperature at 32 ℃, the dissolved oxygen at 4mg/L, the COD of the aerobic digestion solution at 360mg/L, and the effluent turbidity at 35NTU, Na+＝462mg/L、K+＝481mg/L、Mg2+＝83mg/L；
Step 105: and (3) enabling the filtrate obtained in the step (103) to enter a hydrogen type strong acid type cation resin bed, maintaining the temperature at 35 ℃, and enabling the feeding speed to be 10 times of the volume of the resin bed per hour to obtain aerobic digestion effluent, wherein the quality of the aerobic digestion effluent is as follows: na (Na)+＝140mg/L、K+＝180mg/L、Mg2+＝25mg/L；
step 106, adding 2000mL of aerobic digestion effluent generated in the step 105 into 400g of rice flour and 100g of corn flour, firstly adjusting the pH to 5.6, adding 1.1mL of 20000U/mL high-temperature α -amylase, uniformly stirring, heating, and liquefying to obtain liquefied liquid;
step 108: the liquefied liquid generated in the step 106 is sterilized, cooled, inoculated and fermented at a constant temperature for 68 hours, and the concentration of citric acid after the fermentation is finished is 14.6% (w/v), which is equivalent to the concentration of citric acid fermented by deionized water, which is 14.5% (w/v);
returning the fermentation liquor in the step 108 to the step 101 for treatment; and then the steps are carried out sequentially, 15 batches are circulated, and the fermentation level of the citric acid is normal, so that the process for producing the citric acid by using the aerobic digestion effluent is constructed.
Example 3
Step 101: after separating thalli and residues from the citric acid fermentation liquor, obtaining citric acid fermentation waste liquor and a crude product by adopting a chromatography extraction process, wherein the total COD of the citric acid fermentation waste liquor is 21000 mg/L;
step 102: performing medium-temperature anaerobic digestion (in a UASB reactor), maintaining the temperature at 38.5 ℃, the Hydraulic Retention Time (HRT) for 3d and the pH at 7.0-7.3 to obtain anaerobic digestion liquid, wherein the COD of the anaerobic digestion liquid is 970 mg/L;
step 103: the anaerobic digestion solution generated in the step 202 is treated by aerobic digestion, the temperature is maintained at 35 ℃, the dissolved oxygen is 6mg/L, the COD of the aerobic digestion solution is 480mg/L, and Na is added+＝512mg/L、K+＝498mg/L、Mg2+＝91mg/L；
Step 104: treating the aerobic digestion solution generated in the step 103 by using an ultrafiltration membrane to obtain a filtrate;
step 105: and (3) allowing the filtrate obtained in the step (104) to enter D001 macroporous cation exchange resin, maintaining the temperature at 44 ℃, and enabling the feeding speed to be 5 times of the volume of a resin bed per hour to obtain aerobic digestion effluent, wherein the quality of the aerobic digestion effluent is as follows: na (Na)+＝116mg/L、K+＝145mg/L、Mg2+＝18mg/L；
step 106, adding 2200mL of aerobic digestion effluent generated in the step 105 into 500g of corn flour, firstly adjusting the pH to 6.0, adding 1.1mL of 20000U/mL high-temperature α -amylase, uniformly stirring, heating, and liquefying to obtain liquefied liquid;
step 107: taking out 30% (volume fraction) of the liquefied solution, and performing centrifugal separation to obtain a clear solution;
step 108: mixing the 70% of non-centrifuged liquefied liquid generated in the step 106 with the clear liquid generated in the step 107, sterilizing, cooling, inoculating, fermenting at constant temperature for 62 hours, wherein the citric acid concentration is 14.1% (w/v) after the fermentation is finished, and is equivalent to the citric acid concentration of 14.0% (w/v) fermented by deionized water;
returning the fermentation liquor in the step 108 to the step 101 for treatment; and then the steps are sequentially carried out, 10 batches are circulated, and the fermentation level of the citric acid is normal, so that the process for producing the citric acid by using the aerobic digestion effluent is constructed.
Comparative example 1: selection of cation exchange resins
The cation exchange resin selected in the comparative example is D113, the rest of the operation steps are the same as the example 1, and the water quality of the treated aerobic digestion effluent is as follows: na (Na)+＝223mg/L、K+＝395mg/L、Mg2+78 mg/L; the good sample effluent after D113 treatment is used for citric acid fermentation, the citric acid concentration is 13.9% (w/v) after the fermentation is finished, and compared with the citric acid concentration of 16.3% (w/v) obtained by adopting deionized water fermentation, the fermentation concentration is obviously reduced.
Comparative example 2: feed rate of cation exchange resin
Comparative example the feeding speed of step 105 is 40 times of the resin bed volume, the rest of the operation steps are the same as the example 1, and the water quality of the aerobic digestion effluent after treatment is as follows: na (Na)+＝331mg/L、K+＝310mg/L、Mg2+35 mg/L; will obtainThe good sample effluent is used for citric acid fermentation, the concentration of the citric acid is 14.6% (w/v) after the fermentation is finished, and compared with the citric acid concentration of 16.3% (w/v) obtained by adopting deionized water fermentation, the fermentation concentration is obviously reduced.
Comparative example 3: feed temperature of cation exchange resin
The feeding temperature of the step 105 of the comparative example is 10 ℃, the rest operation steps are the same as the operation steps of the example 1, and the water quality of the treated aerobic digestion effluent is as follows: na (Na)+＝326mg/L、K+＝387mg/L、Mg2+69 mg/L; the obtained good sample effluent is used for citric acid fermentation, the concentration of citric acid is 14.2% (w/v) after the fermentation is finished, and compared with the concentration of citric acid fermented by deionized water which is 16.3% (w/v), the fermentation concentration is obviously reduced.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The annular production method of citric acid is characterized in that aerobic digestion liquid in the production process of citric acid is treated by cation exchange resin to be used as production water, and Na in the production water+≤300mg/L、K+≤350mg/L、Mg2+Less than or equal to 60 mg/L; the aerobic digestion solution is obtained by extracting, anaerobic digesting and aerobic digesting the citric acid fermentation liquor.
2. The annular production method of citric acid according to claim 1, wherein the COD of the aerobic digestion solution is 100-600 mg/L.
3. The annular production method of citric acid according to claim 1 or 2, wherein the cation exchange resin is a strong acid type cation exchange resin, the treatment mode is dynamic adsorption, the feeding speed is 1-36 times the volume of the resin bed per hour, and the feeding temperature is 15-50 ℃.
4. The annular production method of citric acid according to any one of claims 1-3, wherein said strong acid type cation exchange resin is one or more of hydrogen type cation exchange resin, 732 type cation exchange resin and D001 macroporous strong acid type cation exchange resin.
5. A method for the cyclic production of citric acid according to any of claims 1 to 4, characterized in that it comprises the following steps: citric acid fermentation, citric acid waste liquid extraction, anaerobic digestion, aerobic digestion, cation exchange treatment, raw material ingredient liquefaction and a new round of citric acid fermentation.
6. The annular production method of citric acid according to any of claims 1-5, characterized in that it comprises the following steps:
step 101: carrying out solid-liquid separation and extraction processes on the citric acid fermentation liquor to obtain a citric acid fermentation waste liquor and a crude product;
step 102: allowing the citric acid fermentation waste liquid generated in the step 101 to enter a biogas fermentation process, and fermenting to generate biogas and anaerobic digestion liquid;
step 103: directly carrying out aerobic digestion treatment on the anaerobic digestion solution generated in the step 102;
step 104: carrying out solid-liquid separation on the aerobic digestion solution to obtain a filtrate;
step 105: treating the filtrate generated in the step 104 by using cation resin to obtain aerobic digestion effluent;
step 106: mixing the starchy material with the aerobic digestion effluent generated in the step 105, stirring, and liquefying, wherein the part with insufficient aerobic digestion effluent can be supplemented by deionized water or other process water;
step 107: separating part of the liquefied liquid or the whole liquefied liquid after the material mixing and liquefaction in the step 106 by a solid-liquid separation means to obtain clear liquid;
step 108: performing citric acid fermentation on the liquefied liquid generated in the step 106 and the clear liquid generated in the step 107;
returning the fermentation liquor generated in the step 108 to the step 101 to form a cycle; wherein, when the turbidity of the aerobic digestion solution obtained in the step 103 is less than 50NTU, the step 104 is omitted, and the step 105 is directly carried out; when the starchy feedstock is not single corn, step 107 may be omitted.
7. The annular production method of citric acid according to claim 6, wherein the solid-liquid separation mode is one or more of centrifugal separation, plate-frame filtration, flocculation filtration, microfiltration membrane and ultrafiltration membrane in series combination; the extraction process is any one of calcium salt method, calcium hydride method and chromatography.
8. The annular production method of citric acid as claimed in claim 6 or 7, wherein the volume ratio Kg/L of the starch material to the aerobic effluent is 1: (2.5-5).
9. The ring production method of citric acid according to any one of claims 6-8, wherein the starchy material is one or more of potato, corn, rice, and wheat.
10. The annular production method of citric acid according to any of claims 6-9, wherein the biogas fermentation mode is: single-stage medium-temperature anaerobic fermentation is carried out at the temperature of 32-42 ℃ and the hydraulic retention time is 1-5 days.
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| CN111348766A (en) * | 2020-04-29 | 2020-06-30 | 吉林中粮生化有限公司 | Method and system for treating polyhydroxyalkanoate fermentation liquor by using membrane filtration and application of obtained fermentation waste liquor |
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