CN109022503A - A method of citric acid is produced using recycling anaerobic digestion solution - Google Patents
A method of citric acid is produced using recycling anaerobic digestion solution Download PDFInfo
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- CN109022503A CN109022503A CN201810939727.4A CN201810939727A CN109022503A CN 109022503 A CN109022503 A CN 109022503A CN 201810939727 A CN201810939727 A CN 201810939727A CN 109022503 A CN109022503 A CN 109022503A
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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
Abstract
The invention discloses a kind of methods of recycling anaerobic digestion solution production citric acid, belong to organic acid fermentation industrial technical field.Technical solution of the present invention comprises the steps of: that spent liqour of citric acid fermentation generates biogas and anaerobic digestion solution by anaerobic digestion, anaerobic digestion solution successively passes through ultrafiltration membrane, nanofiltration membrane recycling treatment, treated, and clear liquid produces the technique of citric acid as technique ingredient water, and constitutes annular Citric Acid Production technique.It is an advantage of the invention that anaerobic digestion solution by recycling treatment can Infinite Cyclic reuse, not only eliminate the contaminated wastewater in Citric Acid Production technique, also a save a large amount of freshwater resources, also superseded aeration supports well treatment process, reduces production cost.
Description
Technical field
The present invention relates to a kind of methods using recycling anaerobic digestion solution production citric acid, belong to organic acid fermentation industry
Technical field.
Background technique
Citric acid is a kind of important organic acid, because having good physics, chemistry and derivative performance, is widely used in food
The fields such as product, medicine, chemical industry and metallurgy, global citric acid production capacity reaches 2,640,000 tons within 2014, is be only second to alcohol second largest
Fermented product, China's lemon acid yield account for 65% of world wide production or more, it is contemplated that 10 years from now on still with 4% speed increase.So
And one ton of citric acid of every production can generate 7.5~15 tons of Fermented waste water, not only the scale of construction is big for citric acid wastewater, COD concentration is high
(15000~25000mg/L), pH are low, and a large amount of wastewater from fermentation industry not only causes environmental pollution to get worse, and are also consumed by a large amount of
Water resource, as country is increasingly strict to industrial wastewater discharge standard requirements, and to freshwater resources consumption limitation, how
Processing citric acid wastewater has great significance to citric acid industry healthy development.
Country's citric acid wastewater mainly uses " anaerobism+aerobic sigestion " treatment process at present.Anaerobic digestion in the method
The Organic substance in water that citric acid fermentation can be given up is converted into clean energy resource-biogas, and obtains preferable economic benefit.However aerobic disappear
Changing treatment process, that there are power consumptions is big, and processing cost is high, the problems such as taking up a large area, and the water outlet after aerobic sigestion
Still it is unable to qualified discharge, it is also necessary to which further advanced treating, this cost for wastewater treatment not only improved are also meagre profit citric acid row
Industry brings heavy financial burden, directly constrains citric acid industry development.
Patent application (CN102690003A) propose using for aerobic sigestion water outlet using flocculation, ultrafiltration and reverse osmosis
System processing method, is used for reverse osmosis water outlet as cooling water or process water in production.But this processing method does not have not only
The high aerobic sigestion process of processing cost is eliminated, flocculation operation program and the high reverse osmosis process of operating pressure, water are also increased
The rate of recovery is lower, and total operating cost increases significantly, hardly results in the use of enterprise.Patent application (CN104109697A) proposes
Citric acid wastewater is directly flowed back the method for production citric acid, however is studied in discovery citric acid wastewater and contained higher black song
The metal ion of by-product and raw material the institute band of mould metabolism, and appearance accumulation is carried out with circulating and recovering, these ingredients are equal
It can inhibit Citric Acid Production bacterial strain-aspergillus niger growth and metabolism, to influence the fermentation of citric acid.Patent application
(CN102503019A) propose a kind of method that biogas slurry recycling is realized in biogas slurry reuse, by biogas slurry by low-level oxidation, decoloration and
Solid acid adsorption treatment, the method that circulating and recovering produces citric acid, has saved a large amount of fresh waters while eliminating contaminated wastewater
Resource.But the invention Shortcomings are: for the mortifier in absorption biogas slurry, a large amount of activity is added in recycling means
The substances such as charcoal, activated alumina and silica gel, resin, cause recycling cost to greatly improve, in addition for parse these substances and
New pollutant effluents is generated, while can also generate solid waste such as active carbon and adsorbate, resin etc., there are pollution transportations can
Energy.It can thus be anticipated that these factors will limit the promotion and implementation of the invention.
Summary of the invention
It is an object of the present invention to overcome the above deficiencies, proposes that a kind of utilization recycling anaerobic digestion solution produces lemon
The method of acid realizes the pollution for reducing waste water and saves the consumption of fresh water resource, and eliminates traditional aerobic process, reduces fortune
Row cost.
The present invention provides a kind of annular production methods of citric acid, it may be assumed that use during Citric Acid Production ultrafiltration membrane and
Anaerobic digestion solution after nanofiltration membrane treatment is as industrial water, conductivity≤1800 μ s/cm of the industrial water；The anaerobism
Digestive juice is that spent liqour of citric acid fermentation is obtained through Anaerobic Digestion.
In one embodiment of the invention, the ultrafiltration membrane is tubular ultra-filtration membrane, rolling ultrafiltration membrane, Ceramic excessive filtration
One of film is a variety of, operating parameter: 10~500kDa of molecular cut off, and operation temperature is 15~45 DEG C, and operating pressure is
0.1~0.6MPa, crossflow velocity are 1~6m/s.
In one embodiment of the invention, the pH for the anaerobic digestion solution that biogas fermentation obtains is 6.0~8.2, total COD
For 800~2500mg/L.
In one embodiment of the invention, the mode of the Anaerobic Digestion and condition are unlimited.
In one embodiment of the invention, preferred anaerobic digestion mode are as follows: single-stage intermediate temperature anaerobic fermentation, temperature 32~
42 DEG C, hydraulic detention time 1-5 days.
In one embodiment of the invention, the operating parameter of the nanofiltration membrane treatment is: molecular cut off 100~
600Da, operation temperature are 15~45 DEG C, and operating pressure is 0.8~1.4MPa.
In one embodiment of the invention, industrial water water rate be anaerobic digestion solution 40~80%.
In one embodiment of the invention, it the described method comprises the following steps: citric acid fermentation, citric acid fermentation broth
Extraction, fermented waste fluid anaerobic digestion, ultrafiltration membrane treatment, nanofiltration membrane treatment, ingredient liquefaction, new round citric acid fermentation.
In one embodiment of the invention, the method specifically includes the following steps:
(1) fermentation liquid obtains fermented waste fluid and crude product by separation of solid and liquid, extraction process；
(2) fermented waste fluid enters anaerobic digester system, obtains biogas and anaerobic digestion solution；
(3) anaerobic digestion solution obtains filtrate by separation of solid and liquid；
(4) filtrate obtains that liquid and ultrafiltration clear liquid is concentrated by ultrafiltration by ultrafiltration membrane, and ultrafiltration clear liquid passes through nanofiltration membrane, obtains nanofiltration
The stillness of night and nanofiltration concentrate, nanofiltration clear liquid are used as next group ingredient water；
(5) smashed starchy material is mixed with nanofiltration clear liquid, nanofiltration clear liquid insufficient section can be used deionized water or
Other process water supplements；Then enzyme liquefaction, sterilizing, inoculation enter next group citric acid fermentation, then press the step of (1)~(5)
Suddenly it circuits sequentially.
In one embodiment of the invention, described be separated by solid-liquid separation is plate-frame filtering, centrifuge separation, band filter, micro-filtration
One of UF membrane or various ways tandem compound；The extraction process is calcium salt method, hydrogen calcium method, chromatographic any.
In one embodiment of the invention, concentrate obtained in step (4) is recycled to anaerobic digester system, to increase
Add biogas output, can choose whether to recycle according to actual needs.
In one embodiment of the invention, the starchy material refers to potato, corn, paddy, molasses, starch water
Solve one or more of sugar.
In one embodiment of the invention, water is expected when the smashed starchy material is mixed with electrodialysis fresh water
Mass volume ratio Kg/L is 1:2.5~5.
In one embodiment of the invention, the liquefier that the enzyme liquefaction generates can completely or partially pass through solid-liquid
Separation, obtains clear liquid and enters next group citric acid fermentation.
In one embodiment of the invention, when starchy material is single corn, above-mentioned liquefier whole or portion
The operation that lease making crosses separation of solid and liquid can not omit.
The advantageous effects that the present invention obtains:
1, the present invention does not add other materials, and Citric Acid Production cost per ton reduces by 46.5 yuan, while also not generating new
Pollution；
2, the present invention in anaerobic digestion solution after double film recycling treatments on citric acid fermentation level without influence, lemon
Acid concentration is that the concentration of ingredient water is suitable with deionization, real circulating and recovering purpose；
3, recycling treatment is carried out to anaerobic digestion solution in the present invention, really eliminates anaerobic digestion solution circulating and recovering and produced
The composition that may be accumulated in journey, realizes the zero-emission of waste water and recycling for water resource, and eliminate traditional aerobic device, drops
Low operating cost and occupied area.
4, ultrafiltration membrane, nanofiltration membrane concentrate cycle back in anaerobic digester system in present invention implementation, and biogas production can be improved
Amount promotes economic benefit.
Detailed description of the invention
Fig. 1 is the overall procedure schematic diagram for the method that the present invention produces citric acid using recycling anaerobic digestion solution.
Specific embodiment
COD content assaying method: using National Standard Method, i.e. potassium dichromate method is measured.
The detection method of conductivity: it is measured using thunder magnetic DDSJ-308A conductivity meter.
The present invention will be further described technical solution of the present invention in the form of embodiment in conjunction with Fig. 1 below:
Embodiment 1
(1) tapioca starch is mixed with corn flour 4:1 in mass ratio, mixed raw material and nanofiltration clear liquid is then pressed into quality
Volume ratio 1:3.5 (Kg/L) mixing, adjusts pH to 5.9 with sodium hydroxide solution, adds high temperature alphalise starch by 20U/g raw material
Enzyme heats after mixing evenly, and 110 DEG C of heat preservations liquefaction 60min, liquefier is cooled to rapidly 36 DEG C after sterilizing, accesses black song
Mould 106A spore/mL, into citric acid fermentation.
(2) after fermentation, after fermentation liquid first passes through plate-frame filtering removal thallus and other solid contents, using hydrogen calcium method
It extracts and obtains fermented waste fluid and citric acid crude product, waste liquid will be extracted and entered in anaeration in normal temperature UASB reactor, temperature is maintained to exist
33 DEG C, hydraulic detention time (HRT) 4.5d, pH 6.8~7.2, obtains biogas and anaerobic digestion solution, obtained anaerobic digestion solution
COD be 1000mg/L, conductivity be 3850 μ s/cm.
(3) anaerobic digestion solution is after centrifuge separates, and liquid enters 10kDa tubular ultra-filtration membrane, in operating pressure
0.2MPa, under the conditions of crossflow velocity is 5m/s, obtains 10% ultrafiltration concentration liquid and conductivity is 3280 μ by 25 DEG C of operation temperature
The ultrafiltration clear liquid of the 90% of s/cm is concentrated by ultrafiltration liquid and is back to biogas fermentation.Ultrafiltration clear liquid enters 150Da nanofiltration membrane, presses in operation
Power 0.8MPa, under the conditions of 25 DEG C of operation temperature, the nanofiltration concentrate and conductivity for obtaining 35% (volume fraction) are 650 μ s/cm
65% nanofiltration clear liquid, nanofiltration concentrate is back to biogas fermentation.The nanofiltration clear liquid handled well is recycled back to as ingredient water
For next group citric acid fermentation, with this continuous circulation 12 batches.The fermentation period average out to 69h of 12 batches of citric acid fermentations, lemon
Lemon acid mean concentration 16.25% (w/v, Kg/L, similarly hereinafter), with use deionized water for the citric acid fermentation of ingredient water fermentation week
Phase 69h, citric acid mean concentration 16.23% (w/v) maintain an equal level, it is seen that the present embodiment is constructed to be detested using combination membrane technology resource
Oxygen digestive juice is come the technique that produces citric acid.
Embodiment 2
(1) corn flour and nanofiltration clear liquid are pressed into mass volume ratio 1:4 mixing, sodium hydroxide solution is used in enzyme liquefaction
PH to 5.8 is adjusted, high-temperatureα-amylase is added by 20U/g raw material, heats after mixing evenly, 105 DEG C of heat preservations liquefaction 70min take
30% liquefier passes through plate-frame filtering, will cross cleaner liquid and mix with 70% former liquefier, liquefier is rapid after sterilizing
36 DEG C are cooled to, aspergillus niger 10 is accessed6A spore/mL, into citric acid fermentation.
(2) after fermentation, after fermentation liquid first passes through centrifugal filtration removal thallus and other solid contents, using salt calcium method
It extracts and obtains fermented waste fluid and citric acid crude product, waste liquid will be extracted and entered in anaeration in normal temperature UASB reactor, temperature is maintained to exist
37.5 DEG C, hydraulic detention time (HRT) 2.5d, pH 7.0~7.3, obtains biogas and anaerobic digestion solution, obtained anaerobic digestion
The COD of liquid is 1200mg/L, and conductivity is 3660 μ s/cm.
(3) anaerobic digestion solution is after sheet frame separates, and liquid enters 100kDa tubular ultra-filtration membrane, in operating pressure
0.4MPa, under the conditions of crossflow velocity is 4m/s, obtains 8% ultrafiltration concentration liquid and conductivity is 3040 μ s/ by 35 DEG C of operation temperature
The ultrafiltration clear liquid of the 92% of cm.Ultrafiltration clear liquid enters 300Da nanofiltration membrane, under the conditions of operating pressure 1.0MPa, 35 DEG C of operation temperature,
30% nanofiltration concentrate and conductivity is obtained as the 70% nanofiltration clear liquid of 980 μ s/cm.Using the nanofiltration clear liquid handled well as matching
Material water is recycled to be used in next group citric acid fermentation, with this continuous circulation 10 batches.The fermentation period of 10 batches of citric acid fermentations is flat
It is 67h, citric acid mean concentration 15.28% (w/v) and uses deionized water same for the fermentation of the citric acid fermentation of ingredient water
Phase is 67h, and citric acid mean concentration 15.21% (w/v) maintains an equal level, it is seen that the present embodiment, which constructs, utilizes combination membrane technology resource
Anaerobic digestion solution is come the technique that produces citric acid.
Embodiment 3
(1) rice flour and nanofiltration clear liquid are pressed into mass volume ratio 1:4.5 mixing, with sodium hydroxide solution adjust pH to
5.6, high-temperatureα-amylase is added by 25U/g raw material, is heated after mixing evenly, 115 DEG C of heat preservations liquefaction 55min, liquefier passes through
37 DEG C are cooled to after sterilizing rapidly, accesses aspergillus niger 106A spore/mL, into citric acid fermentation.
(2) after fermentation, it after fermentation liquid first passes through band filter removal thallus and other solid contents, is mentioned using chromatography
It takes and obtains fermented waste fluid and citric acid crude product, waste liquid will be extracted and entered in anaeration in normal temperature UASB reactor, maintain temperature 35
DEG C, hydraulic detention time (HRT) 4d, pH 6.8~7.1, obtains biogas and anaerobic digestion solution, obtained anaerobic digestion solution
COD is 1850mg/L, and conductivity is 3470 μ s/cm.
(3) anaerobic digestion solution is after micro-filtration UF membrane, and liquid enters 200kDa ceramic super-filtering film, in operating pressure
0.6MPa, under the conditions of crossflow velocity is 3m/s, obtains 5% ultrafiltration concentration liquid and conductivity is 2950 μ s/ by 45 DEG C of operation temperature
The ultrafiltration clear liquid of the 95% of cm is concentrated by ultrafiltration liquid and is back to biogas fermentation.Ultrafiltration clear liquid enters 600Da nanofiltration membrane, in operating pressure
1.2MPa under the conditions of 45 DEG C of operation temperature, obtains 24% nanofiltration concentrate and 76% nanofiltration that conductivity is 1280 μ s/cm
Clear liquid, nanofiltration concentrate are back to biogas fermentation.The nanofiltration clear liquid handled well is recycled to be used in next group lemon as ingredient water
Lemon acid fermentation, with this continuous circulation 15 batches.The fermentation period average out to 64h of 15 batches of citric acid fermentations, citric acid mean concentration
14.08% (w/v), and uses deionized water for the fermentation same period of the citric acid fermentation of ingredient water to be 64h, citric acid mean concentration
14.13% (w/v) maintains an equal level, it is seen that the present embodiment constructs using combination membrane technology resource anaerobic digestion solution and produces citric acid
Technique.
Comparative example 1
The molecule interception 800Da of the nanofiltration membrane of selection is obtained under the conditions of operating pressure 1.2MPa, 40 DEG C of operation temperature
The 82% nanofiltration clear liquid of 2580 μ s/cm of conductivity and 18% nanofiltration concentrate, remaining condition and step and 1 phase of embodiment
Together, next group citric acid fermentation, fermentation period 71h, citric acid are recycled to be used in using the nanofiltration clear liquid handled well as ingredient water
Concentration is 14.04% (w/v), less than the citric acid concentration for using deionized water to obtain for the citric acid fermentation of ingredient water
16.25% (w/v), and 5 batches are recycled, production citric acid concentration is far below control group, can not constitute annular technique.
Comparative example 2
The molecule interception 1000Da of the nanofiltration membrane of selection is obtained under the conditions of operating pressure 1.0MPa, 45 DEG C of operation temperature
The 85% nanofiltration clear liquid of 2520 μ s/cm of conductivity and 15% nanofiltration concentrate, remaining condition and step and 1 phase of embodiment
Together, next group citric acid fermentation, fermentation period 71h, citric acid are recycled to be used in using the nanofiltration clear liquid handled well as ingredient water
Concentration is 13.66% (w/v), less than the citric acid concentration for using deionized water to obtain for the citric acid fermentation of ingredient water
16.25% (w/v), and 5 batches are recycled, production citric acid concentration is below control group, can not enough circularize technique.
Comparative example 3
Anaerobic digestion solution is after centrifuge separates, and liquid enters 1000kDa tubular ultra-filtration membrane, in operating pressure
0.3MPa, under the conditions of crossflow velocity is 4m/s, obtains the ultrafiltration concentration liquid of 93% ultrafiltration clear liquid and 7%, surpasses by 25 DEG C of operation temperature
Filter concentration liquid is back to biogas fermentation.Ultrafiltration clear liquid enters 150Da nanofiltration membrane, in operating pressure 0.8MPa, 25 DEG C of items of operation temperature
Under part, the nanofiltration concentrate of 40% nanofiltration clear liquid that conductivity is 1250 μ s/cm and 60% is obtained, nanofiltration concentrate is back to natural pond
Gas fermentation, remaining condition and step are same as Example 1, and fermentation is normal.The selection of ultrafiltration retaining molecular weight influences nanofiltration
Clear liquid obtains water rate, the increase of operating cost when eventually leading to circulating and recovering.
Comparative example 4
For anaerobic digestion solution after centrifuge separates, liquid enters 300kDa tubular ultra-filtration membrane, in operating pressure 0.3MPa,
10 DEG C of operation temperature, under the conditions of crossflow velocity is 0.2m/s, the ultrafiltration concentration liquid of 61% ultrafiltration clear liquid and 39% is obtained, ultrafiltration is dense
Contracting liquid is back to biogas fermentation.Ultrafiltration clear liquid enters 150Da nanofiltration membrane, under the conditions of operating pressure 0.8MPa, 25 DEG C of operation temperature,
Obtain conductivity be 760 μ s/cm 36% nanofiltration clear liquid and 64% nanofiltration concentrate, nanofiltration concentrate be back to biogas hair
Ferment, remaining condition and step are same as Example 1, and fermentation is normal.Ultrafiltration membrane abnormal operation influences whether that nanofiltration clear liquid obtains water rate,
The increase of operating cost when eventually leading to circulating and recovering.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (10)
1. a kind of annular production method of citric acid, which is characterized in that use by ultrafiltration membrane and receive during Citric Acid Production
Filter membrane treated anaerobic digestion solution is as industrial water, conductivity≤1800 μ s/cm of the industrial water；The anaerobism disappears
Changing liquid is that spent liqour of citric acid fermentation is obtained through Anaerobic Digestion.
2. a kind of annular production method of citric acid according to claim 1, which is characterized in that the anaerobic digestion solution
PH is 6.0~8.2, total COD is 800~2500mg/L.
3. a kind of annular production method of citric acid according to claim 1 or 2, which is characterized in that the ultrafiltration membrane is
One or both of tubular ultra-filtration membrane, rolling ultrafiltration membrane or ceramic super-filtering film, operating parameter are as follows: molecular cut off 10~
500kDa, operation temperature are 15~45 DEG C, and operating pressure is 0.1~0.6MPa, and crossflow velocity is 1~6m/s.
4. a kind of annular production method of citric acid according to claim 1 to 3, which is characterized in that the nanofiltration membrane
Operating parameter are as follows: 100~600Da of molecular cut off, operation temperature be 15~45 DEG C, operating pressure be 0.8~1.4MPa.
5. a kind of annular production method of citric acid according to claim 1 to 4, which is characterized in that the production is used
Water obtains water rate as the 40~80% of anaerobic digestion solution.
6. the annular production method of -5 any a kind of citric acids according to claim 1, which is characterized in that the method packet
Include following steps: citric acid fermentation, citric acid fermentation broth extraction, fermented waste fluid anaerobic digestion, ultrafiltration membrane treatment, at nanofiltration membrane
Reason, ingredient liquefaction, new round citric acid fermentation.
7. -6 any a kind of annular production method of citric acid according to claim 1, which is characterized in that the method is specific
The following steps are included:
(1) fermentation liquid obtains fermented waste fluid and crude product by separation of solid and liquid, extraction process；
(2) fermented waste fluid enters anaerobic digester system, obtains biogas and anaerobic digestion solution；
(3) anaerobic digestion solution obtains filtrate by separation of solid and liquid；
(4) filtrate obtains that liquid and ultrafiltration clear liquid is concentrated by ultrafiltration by ultrafiltration membrane, and ultrafiltration clear liquid passes through nanofiltration membrane, obtains nanofiltration clear liquid
And nanofiltration concentrate, nanofiltration clear liquid are used as next group ingredient water；
(5) smashed starchy material is mixed with nanofiltration clear liquid, and deionized water or other can be used in nanofiltration clear liquid insufficient section
Process water supplement；Then it is enzyme liquefaction, sterilizing, inoculation enter next group citric acid fermentation, then press (1)~(5) the step of according to
Secondary circulation.
8. a kind of annular production method of citric acid according to claim 7, which is characterized in that described be separated by solid-liquid separation is plate
Frame filtering, centrifuge separation, band one of filter, micro-filtration UF membrane or various ways tandem compound；The extraction process is calcium
It is salt method, hydrogen calcium method, chromatographic any.
9. a kind of annular production method of citric acid according to claim 7 or 8, which is characterized in that the starchiness is former
Material refers at least one of potato, corn, paddy, molasses, amylum hydrolysate of the sugar.
10. according to a kind of annular production method of any citric acid of claim 7-9, which is characterized in that the starch
The mass volume ratio Kg/L of matter raw material and nanofiltration clear liquid is 1:(2.5~5).
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| 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 |
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