CN114717273A - Recycling process of anaerobic digestion solution in citric acid production - Google Patents
Recycling process of anaerobic digestion solution in citric acid production Download PDFInfo
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- 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 description 5
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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Abstract
The invention discloses a recycling process of anaerobic digestion liquid in citric acid production, which comprises the following citric acid fermentation steps: according to the mass ratio of 4-5: 1, mixing cassava powder and corn powder, adding process water according to the mass ratio of 1: 4-5, mixing, and preparing a citric acid fermentation culture medium; liquefying the feed liquid, controlling the total sugar mass concentration of the final feed liquid to be 155-160 g/L by adding deionized water after liquefaction, and sterilizing for 25-35min at the temperature of 115 ℃ and 120 ℃; inoculating 6mL of seed liquid into a 500mL triangular flask filled with 34mL of fermentation medium in a sterile room, and culturing for 90-92h in a shaking table at 36.5-38 ℃ and 260-290 r/min; 2720mL of the liquefied fermentation medium is filled in a 5L fermentation tank, and the fermentation tank is sterilized at 115 ℃ for 25-35 min; then 480mL of seed liquid is added, the mixture is fermented for 70 to 72 hours in a shaking table with the temperature of 36.5 to 38 ℃ and the temperature of 600 and 650r/min, sterile air is introduced during the fermentation, and the ventilation volume is 2L/min.
Description
Technical Field
The invention belongs to the technical field of citric acid production, and particularly relates to a production process for extracting citric acid by recycling mycelium hydrolysate.
Background
Citric acid is a ternary organic acid, has the characteristics of good solubility, mild sour taste, oxidation resistance, safety, no toxicity and the like, and is widely applied to the fields of food, medicine, textile, electronics, chemical industry, buildings and the like. With the continuous expansion of the application field of citric acid, the citric acid yield in China is continuously increased, and 7-8 m can be generated when 1t of citric acid is produced3Fermentative waste water, sometimes even up to 15m3The wastewater has the characteristics of high COD (about 20000mg/L) and low pH (4.5-4.8), and has high treatment requirement and high difficulty to reach the national discharge standard, so the treated wastewater still can cause serious pollution to the environment, and how to effectively treat high-concentration organic wastewater generated by citric acid becomes a bottleneck restricting the healthy development of the citric acid industry.
At present, the citric acid fermentation wastewater is treated by a biochemical method (anaerobic digestion and aerobic digestion) mainly, and the wastewater treated by the biochemical method still cannot reach the national discharge standard which is increasingly strict, and further advanced treatment is needed to reach the discharge standard. Meanwhile, the traditional biochemical treatment process has large investment and high operating cost, especially the aerobic digestion treatment part occupies a large amount of land and consumes a large amount of energy, the operating cost of the traditional biochemical treatment process basically occupies more than 2/3 of the cost of the whole wastewater treatment process, and the production cost of the citric acid is increased. If the aerobic digestion treatment part of the wastewater with high operation cost can be abolished and the high-income anaerobic digestion process of the wastewater is reserved, the competitiveness of the citric acid industry in China can be effectively improved. Meanwhile, China is one of the countries with relatively lack of fresh water resources, if the waste water after anaerobic digestion can be reused in production, the pollution of the waste water to the environment can be reduced, and the consumption of the fresh water resources can be reduced, so that the clean and efficient production of the citric acid industry is really realized.
In the prior art, the feasibility of reusing citric acid wastewater for citric acid fermentation is also studied, and although the reuse of citric acid neutralization wastewater can be realized, the treatment process mainly adopts treatment methods such as ion exchange and activated carbon addition, so that the treatment cost is high, and new secondary wastewater is generated; in addition, although the research eliminates the aerobic digestion part of the wastewater, the research also eliminates the high-benefit anaerobic digestion process, so that a large amount of organic matters in the citric acid fermentation wastewater cannot be utilized, the resource waste is caused, the economic benefit is low, and the research cannot be suitable for industrial application.
Disclosure of Invention
The invention aims to solve the main technical problem of providing a process for recycling anaerobic digestion solution in citric acid production, which removes key inhibiting factors influencing citric acid fermentation in the anaerobic digestion solution, ensures the stable operation of the citric acid production by recycling the anaerobic digestion solution and realizes the clean production of the citric acid industry.
In order to solve the technical problems, the invention provides the following technical scheme:
a recycling process of anaerobic digestion liquid in citric acid production comprises a citric acid fermentation step: selecting cassava flour and corn flour, and mixing the cassava flour and the corn flour in a mass ratio of 4-5: 1, mixing, adding process water according to the mass ratio of the material to the water of 1: 4-5, mixing and preparing a citric acid fermentation culture medium; liquefying the feed liquid, controlling the total sugar mass concentration of the final feed liquid to be 155-160 g/L by adding deionized water after liquefaction, and sterilizing for 25-35min at the temperature of 115 ℃ and 120 ℃; inoculating 6mL of seed liquid into a 500mL triangular flask filled with 34mL of fermentation medium in a sterile room, and culturing for 90-92h in a shaking table at 36.5-38 ℃ and 260-290 r/min; 2720mL of the liquefied fermentation medium is filled in a 5L fermentation tank, and the fermentation tank is sterilized at 115 ℃ for 25-35 min; then 480mL of seed liquid is added, and the mixture is fermented for 70 to 72 hours in a shaking table with the temperature of 36.5 to 38 ℃ and the temperature of 600-.
The following is a further optimization of the above technical solution of the present invention:
the process also comprises the following extraction steps: after fermentation is finished, the fermentation liquor is filtered by a plate frame to remove thalli and other solid matters, and then is extracted by a calcium hydride method to obtain fermentation waste liquor and a citric acid crude product.
Further optimization: the feed liquid liquefaction process comprises the following steps: the evenly stirred feed liquid is treated by NaOH with the mass fraction of 10% or H with the mass fraction of 30%2SO4 Adjusting pH of the solution to 5.8-6.0, adding high temperature resistant alpha-amylase according to 12-14U/g raw material, liquefying in boiling water bath, and determining liquefaction end point with dilute iodine solution.
Further optimization: the cassava powder and the corn powder are prepared by crushing cassava and corn by a crusher and sieving the crushed cassava and corn by a sieve of 60-70 meshes.
Further optimization: the preparation of the seed liquid comprises the following steps: selecting cassava powder, adding deionized water according to the mass ratio of 1: 4-5 to prepare a seed culture medium, liquefying the feed liquid, cooling the feed liquid to room temperature, supplementing water lost in the liquefaction process with the deionized water, and adding 1g/L (NH4)2SO4As a nitrogen source for the medium; then adjusting the pH value of the feed liquid to 5.5, sterilizing for 25-35min at the temperature of 115-120 ℃, then inoculating 5mL of spore suspension with the concentration of 6.0X 106/mL into a 500mL triangular flask filled with 40mL of seed culture medium in a sterile room, and culturing for 20-22h in a shaking table with the temperature of 36.5-38 ℃ and the temperature of 200-300r/min to obtain the seed liquid.
Further optimization: the process water production procedure comprises the following steps: biogas fermentation is carried out in a 5L up-flow anaerobic sludge bed reactor, and the sludge inoculation amount is 30 percent of the volume fraction and is connected into anaerobic granular sludge; external constant-temperature circulating water is conveyed to a jacket of the upflow anaerobic sludge bed reactor through a pump to maintain the biogas fermentation temperature at 34-36 ℃; 1L of citric acid wastewater is fed into the upflow anaerobic sludge bed reactor every day, the effluent of the upflow anaerobic sludge bed reactor is centrifuged for 15-25min at the centrifugal force of 4000-4500 Xg to obtain supernatant, namely anaerobic digestion liquid, the anaerobic digestion liquid is subjected to air stripping, ultrafiltration membrane treatment and nanofiltration membrane treatment to prepare nanofiltration clear liquid, and the nanofiltration clear liquid is used as process water to be recycled for citric acid fermentation.
Further optimization: the air stripping process comprises the steps of loading 4L of anaerobic digestion solution into a 5L wide-mouth bottle, placing the wide-mouth bottle in a water bath at 50-55 ℃ to maintain the temperature of the anaerobic digestion solution, controlling the ventilation amount at 10L/min, stripping for 60min, supplementing the water lost in the stripping process with deionized water, and centrifuging for 20-30min under the conditions of 4000 plus 4500 Xg, wherein the obtained supernatant is ready for production and use.
Further optimization: the ultrafiltration membrane treatment process comprises the following steps: the cut-off molecular weight is 20000Da, anaerobic digestion liquid is injected into a storage tank and is input into an ultrafiltration membrane through a circulating pump, the operating pressure is controlled at 0.7MPa, the operating temperature is controlled at 43 ℃ through an external cooling device, ultrafiltration permeate liquid and concentrated liquid are obtained, the ultrafiltration permeate liquid is prepared for use of the nanofiltration membrane, and the concentrated liquid flows back to the biogas fermentation.
And (4) further optimizing: the nanofiltration membrane treatment process comprises the following steps: the molecular weight cut-off is 150 Da; the collected ultrafiltration permeate is injected into a storage tank of a nanofiltration membrane system and is input into a nanofiltration membrane through a circulating pump, the operating pressure is controlled to be 1.6MPa, the operating temperature is controlled to be 43 ℃ through an external cooling device, nanofiltration concentrate with volume fraction of 35% and nanofiltration clear liquid with volume fraction of 65% are obtained, and the nanofiltration concentrate is refluxed to methane for fermentation; and recycling the treated nanofiltration clear liquid as process water for citric acid fermentation.
By adopting the technical scheme, the invention has ingenious conception, a large amount of organic matters in the citric acid fermentation wastewater are converted into the clean energy source, namely methane through anaerobic digestion treatment (anaerobic compound flora), and the methane can be converted into heat energy and electric energy through cogeneration for production; the generated liquid (called anaerobic digestion liquid) is used as process water to be mixed to produce citric acid, thereby realizing recycling; the aerobic digestion process of the waste water with high energy consumption, net investment and no output is completely abolished, and the anaerobic digestion process of the waste water with high income is reserved; in addition, the invention removes key inhibiting factors influencing citric acid fermentation in the anaerobic digestion solution by technical means, ensures the stable operation of the anaerobic digestion solution for recycling and producing citric acid, realizes the clean production of the citric acid industry, and saves precious clean water resources to lay a solid foundation.
The invention is further illustrated with reference to the following figures and examples.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
Example 1: referring to fig. 1, a recycling process of anaerobic digestion solution in citric acid production includes the following steps:
s1, preparing raw materials: and (3) crushing the cassava and the corn by a crusher, and sieving the crushed cassava and the corn by a 60-mesh sieve to obtain cassava powder and corn powder for production and use.
S2, preparing seed liquid: selecting the cassava flour prepared in the step S1, adding deionized water according to the mass ratio of material to water of 1: 4 for burdening, preparing a seed culture medium, liquefying the material liquid, adjusting the pH of the uniformly stirred material liquid to 5.8 by using a NaOH solution with the mass fraction of 10%, adding high-temperature-resistant alpha-amylase according to the raw material of 12U/g, liquefying in a boiling water bath, judging the liquefaction end point by using a dilute iodine solution, cooling the material liquid to room temperature, supplementing water lost in the liquefaction process by using the deionized water, and adding 1g/L (NH4)2SO4A nitrogen source as a culture medium; then adjusting the pH value of the feed liquid to 5.5, sterilizing for 30min at 115 ℃, then inoculating 5mL of spore suspension with the concentration of 6.0X 106/mL into a 500mL triangular flask filled with 40mL of seed culture medium in an aseptic chamber, and culturing for 20h in a shaking table with the temperature of 35 ℃ and the speed of 200r/min to obtain the seed liquid.
S3, citric acid fermentation: selecting the cassava flour and the corn flour prepared in the step S1, and mixing the cassava flour and the corn flour in a mass ratio of 4: 1, then adding process water according to the mass ratio of the material to the water of 1: 4.5 to mix ingredients, and preparing a citric acid fermentation culture medium; liquefying the feed liquid, adjusting the pH of the uniformly stirred feed liquid to 5.8 by using a NaOH solution with the mass fraction of 10%, adding high-temperature-resistant alpha-amylase according to 12U/g of the raw material, liquefying in a boiling water bath, judging a liquefaction end point by using a dilute iodine solution, controlling the total sugar mass concentration of the final feed liquid to be 155g/L by using a deionized water adding mode after liquefying is finished, and sterilizing at 115 ℃ for 30 min; inoculating 6mL of seed solution into a 500mL triangular flask filled with 34mL of fermentation medium in a sterile room, and culturing for 90h in a shaking table at 36.5 ℃ and 260 r/min; the shaking procedure was repeated 3 times; 2720mL of the liquefied fermentation medium was charged into a 5L fermenter, and sterilized at 115 ℃ for 30 min. Then 480mL of seed liquid is added, and the mixture is fermented for 72 hours in a shaking table at 36.5 ℃ and 600r/min, and sterile air is introduced during the fermentation, wherein the air flow is 2L/min.
S4, extraction: after fermentation is finished, the fermentation liquor is filtered by a plate frame to remove thalli and other solid matters, and then is extracted by a calcium hydride method to obtain fermentation waste liquor and a citric acid crude product.
S5, biogas fermentation is carried out in a 5L up-flow anaerobic sludge bed reactor (UASB), and the sludge inoculation amount is 30 percent of the volume fraction and is inoculated into anaerobic granular sludge; external constant-temperature circulating water is conveyed to a jacket of the upflow anaerobic sludge bed reactor through a pump to maintain the biogas fermentation temperature at 35 ℃; 1L of citric acid wastewater is fed into the upflow anaerobic sludge bed reactor every day, the effluent of the upflow anaerobic sludge bed reactor is centrifuged for 20min at the centrifugal force of 4000 Xg, and the obtained supernatant is anaerobic digestion liquid which is used as process water for fermentation.
S6, air stripping, namely, filling 4L of anaerobic digestion solution into a 5L wide-mouth bottle, placing the wide-mouth bottle in a water bath at 50 ℃ to maintain the temperature of the anaerobic digestion solution, controlling the ventilation quantity at 10L/min, carrying out air stripping for 60min, then supplementing water lost in the air stripping process with deionized water, and centrifuging for 20min under the condition of 4500 Xg, wherein the obtained supernatant is ready for production and use.
S7, ultrafiltration and nanofiltration membrane treatment: the ultrafiltration membrane treatment conditions were that the membrane area of the ultrafiltration membrane was 0.08m2The molecular weight cut-off is 20000 Da; injecting anaerobic digestive juice into storage tank, introducing into ultrafiltration membrane via circulation pump, controlling operation pressure at 0.6MPa, controlling feeding temperature at 45 deg.C via external cooling device to obtain ultrafiltration permeationAnd (3) ultrafiltering the permeate to prepare a nanofiltration membrane for use, and refluxing the concentrate to methane for fermentation.
The nanofiltration membrane treatment conditions are that the membrane area of the nanofiltration membrane is 0.27m2, and the molecular weight cutoff is 150 Da; and (3) injecting the collected ultrafiltration permeate into a storage tank of a nanofiltration membrane system, inputting the ultrafiltration permeate into a nanofiltration membrane through a circulating pump, controlling the operating pressure to be 1.5MPa, controlling the feeding temperature to be 45 ℃ through an external cooling device at the operating temperature, obtaining nanofiltration concentrate with the volume fraction of 35% and nanofiltration clear liquid with the volume fraction of 65%, and refluxing the nanofiltration concentrate to methane for fermentation. And recycling the treated nanofiltration clear liquid as process water for the next batch of citric acid fermentation.
The detected average concentration of citric acid is 16.25%.
Example 2:
a recycling process of anaerobic digestion liquid in citric acid production comprises the following steps:
s1, preparing raw materials: and (3) crushing the cassava and the corn by a crusher, and sieving the crushed cassava and the corn by a 70-mesh sieve to obtain cassava powder and corn powder for production and use.
S2, preparing seed liquid: selecting the cassava flour prepared in the step S1, adding deionized water according to the mass ratio of material to water of 1: 4.5 for burdening, preparing a seed culture medium, liquefying the feed liquid, and using H with the mass fraction of 30% to uniformly stir the feed liquid2SO4 Adjusting pH of the solution to 5.9, adding high temperature resistant alpha-amylase according to 13U/g raw material, liquefying in boiling water bath, determining liquefaction end point with dilute iodine solution, cooling the solution to room temperature, supplementing water lost in liquefaction with deionized water, and adding 1g/L (NH4)2SO4A nitrogen source as a culture medium; then adjusting the pH value of the feed liquid to 5.5, sterilizing at 117 ℃ for 35min, then inoculating 5mL of spore suspension with the concentration of 6.0X 106/mL into a 500mL triangular flask filled with 40mL of seed culture medium in an aseptic chamber, and culturing for 21h in a shaking table with the temperature of 37 ℃ and the speed of 250r/min to obtain the seed liquid.
S3, citric acid fermentation: selecting the cassava flour and the corn flour prepared in the step S1, and mixing the cassava flour and the corn flour in a mass ratio of 4.5: 1, then adding process water according to the mass ratio of the material to the water of 1: 4 to mix ingredients, and preparing a citric acid fermentation culture medium; liquefying the feed liquid, adjusting the pH of the uniformly stirred feed liquid to 5.8 by using a NaOH solution with the mass fraction of 10%, adding high-temperature-resistant alpha-amylase according to 13U/g of raw material, liquefying in a boiling water bath, judging a liquefaction end point by using a dilute iodine solution, controlling the total sugar mass concentration of the final feed liquid to be 155g/L by using a deionized water adding mode after liquefying is finished, and sterilizing for 35min at 117 ℃; inoculating 6mL of seed solution into a 500mL triangular flask containing 34mL of fermentation medium in a sterile room, and culturing for 91h in a shaking table at 37 ℃ and 280 r/min; the shaking procedure was repeated 3 times; 2720mL of the liquefied fermentation medium was charged into a 5L fermentor and sterilized at 117 ℃ for 35 min. Then 480mL of seed solution was added, and the mixture was fermented at 37 ℃ for 71 hours in a shaker at 625r/min, while introducing sterile air at 2L/min.
S4, extraction: after fermentation is finished, the fermentation liquor is filtered by a plate frame to remove thalli and other solid matters, and then is extracted by a calcium hydride method to obtain fermentation waste liquor and a citric acid crude product.
S5, biogas fermentation is carried out in a 5L up-flow anaerobic sludge bed reactor (UASB), and the sludge inoculation amount is 30 percent of the volume fraction and is inoculated into anaerobic granular sludge; external constant-temperature circulating water is conveyed to a jacket of the upflow anaerobic sludge bed reactor through a pump to maintain the biogas fermentation temperature at 34 ℃; 1L of citric acid wastewater is fed into the upflow anaerobic sludge bed reactor every day, the effluent of the upflow anaerobic sludge bed reactor is centrifuged for 25min at the centrifugal force of 4300 Xg, and the obtained supernatant is anaerobic digestion liquid which is used as process water for fermentation.
S6, air stripping, namely, filling 4L of anaerobic digestion solution into a 5L wide-mouth bottle, placing the wide-mouth bottle in a water bath at 52 ℃ to maintain the temperature of the anaerobic digestion solution, controlling the ventilation rate at 11L/min, stripping for 65min, then supplementing water lost in the stripping process with deionized water, and centrifuging for 25min under the condition of 4300 Xg, wherein the obtained supernatant is ready for production and use.
S7, ultrafiltration and nanofiltration membrane treatment: the ultrafiltration membrane treatment conditions were that the membrane area of the ultrafiltration membrane was 0.08m2The molecular weight cut-off is 20000 Da; anaerobic digestion liquid injection storage tankAnd (3) inputting the mixture into an ultrafiltration membrane through a circulating pump, controlling the operating pressure to be 0.7MPa, controlling the feeding temperature to be 43 ℃ through an external cooling device at the operating temperature, obtaining ultrafiltration permeate and concentrated solution, wherein the ultrafiltration permeate is used by a nanofiltration membrane, and the concentrated solution reflows to methane for fermentation.
The nanofiltration membrane treatment condition is that the membrane area of the nanofiltration membrane is 0.27m2The molecular weight cut-off is 150 Da; the collected ultrafiltration permeate is injected into a storage tank of a nanofiltration membrane system and is input into a nanofiltration membrane through a circulating pump, the operating pressure is controlled to be 1.6MPa, the operating temperature is controlled to be 43 ℃ through an external cooling device, nanofiltration concentrate with volume fraction of 35% and nanofiltration clear liquid with volume fraction of 65% are obtained, and the nanofiltration concentrate is refluxed to methane for fermentation; and recycling the treated nanofiltration clear liquid as process water for the next batch of citric acid fermentation.
The detected average concentration of citric acid is 16.30%.
Example 3: a recycling process of anaerobic digestion liquid in citric acid production comprises the following steps:
s1, preparing raw materials: and (3) crushing the cassava and the corn by a crusher, and sieving the crushed cassava and the corn by a 80-mesh sieve to obtain cassava powder and corn powder for production and use.
S2, preparing seed liquid: selecting the cassava flour prepared in the step S1, adding deionized water according to the mass ratio of material to water of 1: 5 for batching, preparing a seed culture medium, liquefying the material liquid, adjusting the pH of the uniformly stirred material liquid to 6.0 by using a NaOH solution with the mass fraction of 10%, adding high-temperature-resistant alpha-amylase according to 14U/g of raw material, liquefying in a boiling water bath, judging the liquefaction end point by using a dilute iodine solution, cooling the material liquid to room temperature, supplementing water lost in the liquefaction process by using the deionized water, and adding 1g/L (NH4)2SO4 as a nitrogen source of the culture medium; then adjusting the pH value of the feed liquid to 5.5, sterilizing for 25min at 120 ℃, then inoculating 5mL of spore suspension with the concentration of 6.0X 106/mL into a 500mL triangular flask filled with 40mL of seed culture medium in an aseptic chamber, and culturing for 22h in a shaking table with the temperature of 38 ℃ and the speed of 300r/min to obtain the seed liquid.
S3, citric acid fermentation: selecting the cassava flour and the corn flour prepared in the step S1, and mixing the cassava flour and the corn flour in a mass ratio of 5: 1, then adding process water according to the mass ratio of the material to the water of 1: 5 to mix ingredients, and preparing a citric acid fermentation culture medium; liquefying the feed liquid, adjusting the pH of the uniformly stirred feed liquid to 5.8 by using a NaOH solution with the mass fraction of 10%, adding high-temperature-resistant alpha-amylase according to 14U/g of the raw material, liquefying in a boiling water bath, judging a liquefaction end point by using a dilute iodine solution, controlling the total sugar mass concentration of the final feed liquid to be 160g/L by using a deionized water adding mode after liquefying is finished, and sterilizing for 25min at the temperature of 120 ℃; inoculating 6mL of seed solution into a 500mL triangular flask containing 34mL of fermentation medium in a sterile room, and culturing for 92h at 38 ℃ in a shaking table at 290 r/min; the shaking procedure was repeated 3 times; 2720mL of the liquefied fermentation medium was placed in a 5L fermenter and sterilized at 120 ℃ for 25 min. Then 480mL of seed liquid is added, and the mixture is fermented for 70h in a shaking table at the temperature of 38 ℃ and at the speed of 650r/min, and sterile air is introduced during the fermentation period, wherein the air flow is 2L/min.
S4, extraction: after fermentation is finished, the fermentation liquor is filtered by a plate frame to remove thalli and other solid matters, and then is extracted by a calcium hydride method to obtain fermentation waste liquor and a citric acid crude product.
S5, biogas fermentation is carried out in a 5L up-flow anaerobic sludge bed reactor (UASB), and the sludge inoculation amount is 30 percent of the volume fraction and is inoculated into anaerobic granular sludge; external constant-temperature circulating water is sent to a jacket of the upflow anaerobic sludge bed reactor through a pump to maintain the fermentation temperature of the biogas at 36 ℃. 1L of citric acid wastewater is fed into the upflow anaerobic sludge bed reactor every day, the effluent of the upflow anaerobic sludge bed reactor is centrifuged for 15min at the centrifugal force of 4500 Xg, and the obtained supernatant is anaerobic digestion liquid which is used as process water for fermentation.
S6, air stripping, namely, filling 4L of anaerobic digestion solution into a 5L wide-mouth bottle, placing the wide-mouth bottle in a water bath at 55 ℃ to maintain the temperature of the anaerobic digestion solution, controlling the ventilation quantity at 10L/min, stripping for 60min, then supplementing water lost in the stripping process with deionized water, and centrifuging for 30min under the condition of 4000 Xg, wherein the obtained supernatant is ready for production and use.
S7, ultrafiltration and nanofiltration membrane treatment: the ultrafiltration membrane treatment conditions are that the membrane of the ultrafiltration membraneArea of 0.08m2The molecular weight cut-off is 20000 Da; and (3) injecting anaerobic digestion liquid into a storage tank, inputting the anaerobic digestion liquid into an ultrafiltration membrane through a circulating pump, controlling the operating pressure to be 0.8MPa, controlling the feeding temperature to be 40 ℃ through an external cooling device at the operating temperature, obtaining ultrafiltration permeate and concentrated liquid, wherein the ultrafiltration permeate is used by a nanofiltration membrane, and the concentrated liquid flows back to methane for fermentation.
The nanofiltration membrane treatment conditions are that the membrane area of the nanofiltration membrane is 0.27m2, and the molecular weight cutoff is 150 Da; and (3) injecting the collected ultrafiltration permeate into a storage tank of a nanofiltration membrane system, inputting the ultrafiltration permeate into a nanofiltration membrane through a circulating pump, controlling the operating pressure to be 1.7MPa, controlling the feeding temperature to be 40 ℃ through an external cooling device at the operating temperature, obtaining nanofiltration concentrate with the volume fraction of 35% and nanofiltration clear liquid with the volume fraction of 65%, and refluxing the nanofiltration concentrate to methane for fermentation. And recycling the treated nanofiltration clear liquid as process water for the next batch of citric acid fermentation.
The mean concentration of citric acid was found to be 16.27%.
In the invention, the high temperature resistant amylase (20000U/mL) is provided by Wuxigenengae bioengineering Co.Ltd; the cassava and the corn raw materials are provided by the Henan Tian Guang Enterprise group Co., Ltd; mesophilic anaerobic digestion sludge is provided by yixing-collaborated biochemistry limited; the rest are all commercial chemical reagents.
In the present invention, a 5L autonomous fermenter (LiLusGX) was provided by Korea bioreactor Ltd; a 5L upflow anaerobic sludge blanket reactor (UASB) provided by shanghai dao Ming education instruments ltd; ultrafiltration membrane, nanofiltration membrane system (PL-D3-1812) was provided by Anhui Brown Membrane technology, Inc.; the shaker-Combined (HYL-C) is supplied by Taicang Qiangle laboratory instruments, Inc.
Researches find that the recycling of the anaerobic digestion solution directly used as process ingredient water has no influence on the liquefaction of raw materials, but inhibits the citric acid fermentation. Further research proves that ammonia nitrogen, Na + and K + in the anaerobic digestion solution can inhibit citric acid fermentation, and the corresponding critical inhibition mass concentrations are 100, 200 and 300mg/L respectively. The anaerobic digestion solution is subjected to resource treatment by adopting a combined membrane technology of ultrafiltration and nanofiltration, so that inhibitors in the anaerobic digestion solution are effectively removed, wherein the removal rate of K + and Na + is over 90 percent, and the removal rate of ammonia nitrogen is over 80 percent; the citric acid yield of the recycled anaerobic digestion solution is 139.25 +/-1.85 g/L after recycling, the fermentation level of deionized water (138.70 +/-2.46 g/L) is reached, and the novel process for producing the citric acid by recycling the recycled anaerobic digestion solution is feasible.
The citric acid fermentation wastewater is subjected to anaerobic digestion treatment (anaerobic compound flora) to convert a large amount of organic matters in the wastewater into clean energy, namely biogas, and the biogas can be converted into heat energy and electric energy through cogeneration and is supplied for production; the generated liquid (called anaerobic digestion liquid) is used as process water to be mixed to produce citric acid, thereby realizing recycling; the aerobic digestion process of the waste water with high energy consumption, net investment and no output is completely abolished, and the anaerobic digestion process of the waste water with high income is reserved; in addition, the invention removes key inhibiting factors influencing citric acid fermentation in the anaerobic digestion solution by technical means, ensures the stable operation of the anaerobic digestion solution for recycling and producing citric acid, realizes the clean production of the citric acid industry, and saves precious clean water resources to lay a solid foundation.
It will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in the embodiments described above without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims.
Claims (9)
1. A recycling process of anaerobic digestion liquid in citric acid production is characterized in that: comprises a citric acid fermentation step: selecting cassava powder and corn powder, and mixing the cassava powder and the corn powder according to a mass ratio of 4-5: 1, then adding process water according to the mass ratio of 1: 4-5 to mix ingredients to prepare a citric acid fermentation medium; liquefying the feed liquid, controlling the total sugar mass concentration of the final feed liquid to be 155-160 g/L by adding deionized water after liquefaction, and sterilizing for 25-35min at the temperature of 115 ℃ and 120 ℃; inoculating 6mL of seed liquid into a 500mL triangular flask filled with 34mL of fermentation medium in a sterile room, and culturing for 90-92h in a shaking table at 36.5-38 ℃ and 260-290 r/min; 2720mL of the liquefied fermentation medium is filled in a 5L fermentation tank, and the fermentation tank is sterilized for 25-35min at 115 ℃; then 480mL of seed liquid is added, and the mixture is fermented for 70 to 72 hours in a shaking table with the temperature of 36.5 to 38 ℃ and the temperature of 600-.
2. The recycling process of anaerobic digestion solution in citric acid production according to claim 1, characterized in that: the process also comprises the following extraction steps: after fermentation is finished, the fermentation liquor is filtered by a plate frame to remove thalli and other solid matters, and then is extracted by a calcium hydride method to obtain fermentation waste liquor and a citric acid crude product.
3. The recycling process of anaerobic digestion solution in citric acid production according to claim 2, characterized in that: the feed liquid liquefaction process comprises the following steps: the evenly stirred feed liquid is treated by NaOH with the mass fraction of 10% or H with the mass fraction of 30%2SO4 Adjusting pH of the solution to 5.8-6.0, adding high temperature resistant alpha-amylase according to 12-14U/g raw material, liquefying in boiling water bath, and determining liquefaction end point with dilute iodine solution.
4. The recycling process of anaerobic digestion solution in citric acid production according to claim 3, characterized in that: the cassava powder and the corn powder are prepared by crushing cassava and corn by a crusher and sieving the crushed cassava and corn by a sieve of 60-70 meshes.
5. The recycling process of anaerobic digestion solution in citric acid production according to claim 4, characterized in that: the preparation of the seed liquid comprises the following steps: selecting cassava powder, adding deionized water according to the mass ratio of 1: 4-5 to prepare a seed culture medium, liquefying the feed liquid, cooling the feed liquid to room temperature, supplementing water lost in the liquefaction process with the deionized water, and adding 1g/L (NH4)2SO4A nitrogen source as a culture medium; then adjusting the pH value of the feed liquid to 5.5, sterilizing the feed liquid at the temperature of 115 ℃ and 120 ℃ for 25-35min, and then inoculating 5mL of spore suspension with the concentration of 6.0X 106 spores/mL into a container with 4 spores in a sterile roomCulturing the seeds in a 500mL triangular flask containing 0mL seed culture medium for 20-22h at 36.5-38 ℃ in a shaking table at 200-300r/min to obtain the seed solution.
6. The recycling process of anaerobic digestion solution in citric acid production according to claim 5, characterized by comprising the following steps: the process water production procedure comprises the following steps: biogas fermentation is carried out in a 5L up-flow anaerobic sludge bed reactor, and the sludge inoculation amount is 30 percent of the volume fraction and is connected into anaerobic granular sludge; external constant-temperature circulating water is conveyed to a jacket of the upflow anaerobic sludge bed reactor through a pump to maintain the biogas fermentation temperature at 34-36 ℃; maintaining an upflow anaerobic sludge bed reactor to feed 1L of citric acid wastewater every day, centrifuging the effluent of the upflow anaerobic sludge bed reactor for 15-25min at the centrifugal force of 4000-4500 Xg, and then obtaining a supernatant which is anaerobic digestion liquid, preparing the anaerobic digestion liquid into a nanofiltration clear liquid by air stripping, ultrafiltration membrane treatment and nanofiltration membrane treatment, and recycling the nanofiltration clear liquid as process water for citric acid fermentation.
7. The recycling process of anaerobic digestion solution in citric acid production according to claim 6, characterized by comprising the following steps: the air stripping process comprises the steps of loading 4L of anaerobic digestion solution into a 5L wide-mouth bottle, placing the wide-mouth bottle in a water bath at 50-55 ℃ to maintain the temperature of the anaerobic digestion solution, controlling the ventilation rate at 10L/min, stripping for 60min, supplementing water lost in the stripping process with deionized water, and centrifuging for 20-30min under the conditions of 4000 plus 4500 Xg, wherein the obtained supernatant is ready for production and use.
8. The recycling process of anaerobic digestion solution in citric acid production according to claim 7, characterized in that: the ultrafiltration membrane treatment process comprises the following steps: the cut-off molecular weight is 20000Da, anaerobic digestion liquid is injected into a storage tank and is input into an ultrafiltration membrane through a circulating pump, the operating pressure is controlled at 0.7MPa, the operating temperature is controlled at 43 ℃ through an external cooling device, ultrafiltration permeate liquid and concentrated liquid are obtained, the ultrafiltration permeate liquid is prepared for use of the nanofiltration membrane, and the concentrated liquid flows back to the biogas fermentation.
9. The recycling process of anaerobic digestion solution in citric acid production according to claim 8, characterized by comprising the following steps: the nanofiltration membrane treatment process comprises the following steps: the molecular weight cut-off is 150 Da; the collected ultrafiltration permeate is injected into a storage tank of a nanofiltration membrane system and is input into a nanofiltration membrane through a circulating pump, the operating pressure is controlled to be 1.6MPa, the operating temperature is controlled to be 43 ℃ through an external cooling device, nanofiltration concentrate with volume fraction of 35% and nanofiltration clear liquid with volume fraction of 65% are obtained, and the nanofiltration concentrate is refluxed to methane for fermentation; and recycling the treated nanofiltration clear liquid as process water for citric acid fermentation.
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