CN109628507A - A kind of method that papermaking wastewater prepares lactic acid - Google Patents
A kind of method that papermaking wastewater prepares lactic acid Download PDFInfo
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Abstract
The invention discloses a kind of methods that papermaking wastewater prepares lactic acid, its efficiently extracting and developing lignin from waste liquid by using sieve, phosphoric acid and organic solvent, obtained waste liquid handles laggard one-step fermentation through hyperfiltration membrane assembly and obtains lactic acid, then retains reuse strain.The method that papermaking wastewater of the present invention prepares lactic acid, mild condition, stability is good, can sufficiently recycle hemicellulose, lignin and cellulose spent in waste liquid；Not only the recycling for having improved waste liquid recycles, but also significantly reduces the content as pollutant such as hemicellulose, lignin；And embody the feature of resource utilization and environmental protection.
Description
Technical field
The present invention relates to the sides that pulping and paper-making and biological material field more particularly to a kind of papermaking wastewater prepare lactic acid
Method.
Background technique
Paper industry is the important conventional column industry in China, meanwhile, paper industry or China's industrial energy, resource consumption are big, dirty
Contaminate serious industry.According to the data of Chinese environmental department in 2007: the displacement of paper industry is 31.8 billion cubic meters, accounts for national industry
The 18.4% of total displacement；152.6 ten thousand tons of COD discharge amount, the 29.8% of Zhan Quanguo total release.Wherein, the half fiber in waste liquid
Dimension element and lignin are one of the principal elements polluted.
On the other hand, lactic acid is a kind of important organic acid, is widely used in food, medicine, chemical industry, brewing and weaving etc.
Field contains an asymmetric carbon atom in molecular structure, there is two kinds of optical isomers of D and L.It in recent years, is single with lactic acid
The polylactic acid plastic of body synthesis is because having biodegradability properties, it is considered to be one of the best substitute of petrochemical industry plastics.
The existing preparation method about lactic acid, chemical method equipment investment is high, and solvent-oil ratio is high, with high costs, fermentation method
Stringent aseptic condition and cumbersome operating procedure are needed, feedstock processing is more difficult, and contains fermentation inhibitor after handling, and drops
Low fermentation efficiency.Wherein, lactic acid is mainly produced by fermentation method, and fermentation method is Batch fermentation, i.e., fermentation requires each time
The even multistage seed of level-one is cultivated, seed culture not only extends fermentation period, also adds the throwing of the Zymolysis Equipment such as seeding tank
Enter.And during large scale fermentation, single batch fermentation volume is increasing, and seed culture volume also increases accordingly, seed culture
Energy consumption in the process can not be ignored.It, can be by Batch fermentation in order to avoid the multistage seed culture that each batch will carry out
The seed that obtained somatic cells ferment as next batch, also referred to as cell recycle circulating fermentation.Chinese patent
CN201010148026.2 carries out cell separation using centrifugal process and realizes that cell recycles circulating fermentation glucose production lactic acid, still
Centrifugal process recycles cell and there is the disadvantages of operating discontinuously, cannot retaining the nutrition compositions such as protein in fermentation liquid.And membrane technology
Have the characteristics that high efficiency, low energy consumption, process simple, mild condition, easy to operate, and is easy to integrated, just with other technologies
Amplify in industry, and pigment, protein can be retained, is conducive to the later separation purifying of product, is separated with tradition such as centrifugations
It compares, application of membrane is fermented more competitive in cell cycle.And Chinese patent CN200910272524.5 reports one
Kind " method of intermittent reflux cell high production rate fermentation production of organic acid ", but it is fermented using mesophile, is entirely produced
Journey needs stringent sterile working, increases production cost, is unfavorable for industrial amplification.
To reduce production cost, become research hotspot using papermaking wastewater resource production lactic acid.Waste liquid contains more half
Cellulose and cellulose.Wherein, the hemi-cellulose components rich in pentose (based on xylose, arabinose) account for raw material dry weight
20-50%, therefore pentose utilizes different ignorance.Bacillus acidi lactici (Lactobacillus) is the lactic-acid-producing strain of industrial application,
However, it is extremely limited to the Utilization ability of pentose.Bacillus coagulans (Bacillus coagulans) are a kind of lactic acid hairs
Ferment novel bacterial, which not only has glucose fermentation production lactic acid ability, and pentose fermentation ability is also very prominent.Condensation
Bacillus passes through phosphopentose (Pentose-PhosphatePathway, PP) approach fermenting xylose, and lactic acid theoretical yield is
100%.Bacillus coagulans have high temperature (45~60 DEG C) fermentation character, equipment and culture medium without sterilizing, and production process is
It is open, greatly reduce production cost.Compared with medium temperature production of lactic acid strain, bacillus coagulans are recycled more suitable for cell
Circulating fermentation, because hot fermentation microbiological contamination probability is low, it is ensured that the technique is run steadily in the long term, is easy to industrial amplification.However, solidifying
When tying bacillus with the fermentation of hexose pentose mixed liquor, there are carbon catabolite repression (carbon catabolite
Repression, CCR) phenomenon that is, first with glucose recycles pentose after metabolism.Therefore, thallus cannot synchronize utilization
Glucose present in ligno-cellulose hydrolysate, xylose and arabinose, cause fermentation period to extend, and lactic acid yield is not high.
It has been reported that cell concentration can be improved using multistage reactor cascade fermentation, mixed sugar can be improved using effect
Rate.Therefore, the cell for being applied to fermentation UF membrane coupling with the bacillus coagulans of thermophilic characteristic is recycled into circulating fermentation, led to
It crosses the method for improving biomass and improves thallus to mixed sugar utilization efficiency；Meanwhile equipment is not required to sterilize during hot fermentation, pole
Operating procedure is simplified greatly, reduces production cost, this is of great significance for the industry amplification of cell cycle fermentation technique.
It researches and develops a kind of method that papermaking wastewater prepares lactic acid so comprehensive and has very for entire paper industry and biological material field
Big meaning.
Summary of the invention
The present invention is to solve the problems, such as that the existing pollution of current papermaking wastewater is big, resource utilization is low, while solving lactic acid
Production technology low efficiency, problem at high cost provide a kind of method that papermaking wastewater prepares lactic acid.
Papermaking wastewater main component includes hemicellulose, lignin, cellulose spent, organic acid and salt.Wherein hemicellulose
Element and lignin are main pollutants.The method of the present invention is added by carrying out sieve and sedimentation impurity and purification to papermaking wastewater
Organic solvent extraction and separation lignin is added in phosphoric acid hydrolysis hemicellulose, and it is waste liquid that water phase, which recycles Phosphoric Acid Concentration,.Waste liquid is certain
Under the conditions of ferment, and recycle somatic cells, recycling reduces cost.
To achieve the above object, the invention adopts the following technical scheme:
The present invention provides a kind of method that papermaking wastewater prepares lactic acid, comprising the following steps:
(1) waste liquid is placed in separation vessel, removes undissolved suspended matter with sieve, is settled 3~5 hours after stirring,
Discharge lower layer's fiber fines and silt；
(2) phosphoric acid is added into step (1) purified waste liquid waste liquid is hydrolyzed；
(3) organic solvent is added into step (2) reaction system and extracts lignin；
(4) by step (3) reaction system stratification, the organic phase after layering is through being distilled to recover organic solvent, organic phase
It is divided into lignin for remaining group after middle distillation, is recycled, the water phase after layering recycles phosphoric acid therein, then through nanofiltration membrane
Concentration；
(5) the waste liquid concentrate after step (4) concentration is transferred in fermentor, is accessed under certain fermentation condition solidifying
Bacillus, fermenting lactic acid are tied, culture medium is also not required to sterile working without sterilizing, process；
(6) after fermentation, fermentation liquid obtains the permeate containing lactic acid through Ultra filtration membrane to first batch, retention
Somatic cells return in fermentor, and finally fermentating liquid volume is concentrated；
(7) Fermented Condensed liquid is re-used as in inoculum access next batch fermentation medium, with complete with last batch
Exactly the same fermentation condition continues to ferment；
(8) repeat the above steps (1)-(7), realizes the successive batches fermenting lactic acid of papermaking wastewater.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (1), the waste liquid includes various
Pulping wood waste liquid and draft pulping waste liquor, waste liquid main component include hemicellulose, lignin, cellulose spent, organic acid
And salt.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (1), the waste liquid contains admittedly for 5~
50% (25 DEG C), pH are 3.5~6.5.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (1), the mesh number of the sieve is
50~500 mesh.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (2), phosphorus described in reaction system
The mass concentration of acid is 50~90%, and hydrolysis pH is 1.5~5.5, and hydrolysis temperature is 30~80 DEG C, and hydrolysis time is 30~120
Minute.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (3), the organic solvent is ester
Class compound, the ester type compound are one kind of ethyl acetate, propyl acetate, butyl acetate or Ethyl formate；It is described organic
Solvent usage and waste liquid ratio are 5~50% (w/w), are extracted under stirring condition.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (4), the side of the phosphoric acid recycling
Method are as follows: calcium hydroxide or calcium carbonate are added in water phase, forms calcium phosphate precipitation, is filtered and separate calcium phosphate with waste liquid, phosphorus
The sulfuric acid that sour calcium precipitate is added 50~98% is acidified, and is separated by filtration recycling phosphoric acid, and obtain byproduct calcium sulfate.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (4), the phosphoric acid of recycling is back to
Step (2), recovered solvent are back to step (3).
Further, in the method that the papermaking wastewater prepares lactic acid, in step (4), the nanofiltration membrane be rolling,
Tubular type is flat；Nanofiltration membrane material is that cellulose acetate, sulfonated polysulfone, polyamide, polyether sulfone, sulfonation are poly- in the nanofiltration membrane
Ether sulfone, poly- piperazine or polyvinyl alcohol；The molecular cut off of the nanofiltration membrane component is between 90 to 400 dalton.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (5), (6) and (7), the condensation
The inoculum concentration of bacillus is 5~15%.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (5), the fermentation condition are as follows: temperature
35~55 DEG C of degree, 20~40h of Batch fermentation time, 100~250rpm of speed of agitator use sodium hydroxide, ammonium hydroxide or carbonic acid
Sodium controls pH value between 6.0~6.5.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (6) and (7), the ultrafiltration membrane group
Ultrafiltration membrane material is polysulfones, polysulfonamides, polyamide, sulfonated polysulfone, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, gathers in part
Ether sulfone or polyether-ketone or inorganic ceramic membrane；The hyperfiltration membrane assembly is flat, tubular type, wide runner rolling or the hollow fibre of external-compression type
Dimension formula；The molecular cut off of the hyperfiltration membrane assembly is between 10,000 to 100,000 dalton.
Further, in the method that the papermaking wastewater prepares lactic acid, in step (6), using the ultrafiltration membrane group
It is the 5%~50% of initial volume that fermentation liquid is concentrated part.
Further, in the method that the papermaking wastewater prepares lactic acid, continuously ferment in step (5), (6) (7) and criticize
It is secondary to be at least 5 times.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
(1) lignin is extracted from waste liquid, yield generally 93% or more, reaches as high as 95%；
(2) hydrolysis of hemicellulose is hemicellulose waste liquid by phosphoric acid, and corrosivity is small, and mild condition, side reaction is less, is free of
Fermentation inhibitor, the rate of recovery is 93% or more；
(3) fermenting microbe condition is wider, and recycling improves efficiency；
(4) resource utilization is higher, lower cost；
Specific embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
Embodiment 1
The paper mill 10kg provide poplar alkaline process waste liquid (admittedly contain 5%, pH3.5, hemicellulose level 1.65%, lignin
Content 1.75%, cellulose spent total reducing sugar 0.1kg) it is placed in separation vessel, undissolved suspended matter is removed with 50 mesh screens, is stirred
It is settled 1 hour after mixing, discharges lower layer's fiber fines and silt；
90% phosphoric acid is added to pH1.5,30 DEG C of temperature, hydrolyzes 120 minutes, ethyl acetate 5kg is added, is stirred after being stirred
Layering after mixing uniformly.Organic phase vacuum distillation recycling ethyl acetate 4.75kg, the rate of recovery 95% obtain lignin 0.163kg, obtain
Rate 93%.
Water phase adds calcium carbonate to be reacted, and is separated by filtration, and isolated waste liquid total reducing sugar is 0.248kg, hydrolysis of hemicellulose rate
It is 89.7%.Fermentation inhibitor furfural, phenols, acetic acid is not detected.The acidification of 98% sulfuric acid is added in calcium phosphate, recycling phosphoric acid contains
Amount is 78%, the rate of recovery 96%.
It is concentrated into the 20% of volume using the flat polyamide nanofiltration membrane module that molecular cut off is about 90 dalton, is obtained
To the waste liquid concentrate (wherein glucose 64.34g/L, xylose 49.38g/L, arabinose 10.28g/L) containing 124g/L.
MRS culture medium (peptone 10g/L, powdered beef 10g/L, yeast powder 0.5g/L, anhydrous sodium acetate 0.5g/L, lemon
Sour diammonium hydrogen 0.2g/L, dipotassium hydrogen phosphate 0.2g/L).It is seed culture medium that 10g/L glucose is added in MRS culture medium.
0.0124kg bacillus coagulans (Bacillus coagulans) CGMCC No.7635 is inoculated in seed culture
Base, shaking table shaken cultivation (100rpm) 12 hours, 50 DEG C of cultivation temperature.
When fermentation, 20g/L yeast powder is added into mixed sugar liquid and obtains fermentation medium, fermentation medium does not have to sterilizing.
Seed culture medium is inoculated in 2L fermentation medium with the inoculum concentration of 5% (v/v), fermentor automatic control fermentation condition: 35
~55 DEG C, 100~250rpm of speed of agitator, 20~40h of incubation time, terminate fermentation.Incubation uses 40% sodium hydroxide
PH value 6.0 is automatically adjusted, fermentation process does not need sterile working.
Repeated-batch: the 1st fermentation ends start the hyperfiltration membrane assembly coupled with fermentor, and hyperfiltration membrane assembly makes
With polyacrylonitrile (PAN) material ultrafiltration membrane, molecular cut off is 10,000 dalton.When fermentation liquid is concentrated into original volume 5%,
That is ultrafiltration terminates when 0.1L.Liquid will be concentrated by ultrafiltration as inoculum, fermentation medium is added again in fermentor and arrives
2L continues to start in next batch fermentation medium, carries out fermented and cultured, culture knot with condition identical with fermenting for the first time
It is again started up membrane module after beam, 6 batch of common fermentation, as shown in table 1.
The continuous 6 Batch fermentation papermaking wastewater of 1 UF membrane of table
Embodiment 2
(admittedly containing 12.5%, pH4.8, hemicellulose level 4.13% is wooden for the Wheat Straw Alkaline waste liquid that the paper mill 8kg provides
Cellulose content 3.75%, cellulose spent total reducing sugar 0.24kg) it is placed in separation vessel, undissolved suspension is removed with 200 mesh screens
Object settles 1 hour after stirring, discharges lower layer's fiber fines and silt.
70% phosphoric acid is added to pH3.5, temperature 50 C hydrolyzes 60 minutes, and propyl acetate 2kg is added, stirs after being stirred
Layering after mixing uniformly.Organic phase vacuum distillation recycling propyl acetate 1.92kg, the rate of recovery 96% obtain lignin 0.285kg, obtain
Rate 95%.
Water phase adds calcium carbonate to be reacted, and is separated by filtration, and isolated waste liquid total reducing sugar is 0.58kg, and hydrolysis of hemicellulose rate is
91.9%.Fermentation inhibitor furfural, phenols, acetic acid is not detected.The acidification of 82% sulfuric acid is added in calcium phosphate, recycles phosphorus acid content
It is 70%, the rate of recovery 95%.
Volume is concentrated into using the rolling cellulose acetate nano filter-membrane component that molecular cut off is about 150 dalton
50%, obtain waste liquid concentrate (wherein glucose 64.34g/L, xylose 49.38g/L, the arabinose containing 145g/L
31.28g/L)。
Seed culture based formulas used in the present embodiment is same as Example 1.
0.8kg bacillus coagulans (Bacillus coagulans) CGMCC No.7635 is inoculated in seed culture medium,
Shaking table shaken cultivation (100rpm) 12 hours, 50 DEG C of cultivation temperature.
When fermentation, 20g/L yeast powder is added into mixed sugar liquid and obtains fermentation medium, fermentation medium does not have to sterilizing.
Seed culture medium is inoculated in 8L fermentation medium with the inoculum concentration of 5% (v/v), fermentor automatic control fermentation condition: 35
~55 DEG C, 100~250rpm of speed of agitator, 20~40h of incubation time, terminate fermentation.Incubation is automatic using 40% ammonium hydroxide
PH value 6.0 is adjusted, fermentation process does not need sterile working.
Repeated-batch: the 1st fermentation ends start the hyperfiltration membrane assembly coupled with fermentor, and hyperfiltration membrane assembly makes
With sulfonated polyether sulfone material ultrafiltration membrane, molecular cut off is 50,000 dalton.When fermentation liquid is concentrated into original volume 20%, i.e.,
Ultrafiltration terminates when 1.6L.Liquid will be concentrated by ultrafiltration as inoculum, fermentation medium is added in fermentor again to 8L,
Continue to start in next batch fermentation medium, fermented and cultured is carried out with condition identical with fermenting for the first time, culture terminates
After be again started up membrane module, 8 batch of common fermentation.Fermentation results show that lactic acid yield improves after 8 batches are continuously fermented
2.85 times, each batch rotational rate of lactic acid illustrates that this process stabilizing is efficient all in 0.95g/g or more.
Embodiment 3
The paper mill 4kg provide Wheat Straw Alkaline waste liquid (admittedly contain 50%, pH6.5, hemicellulose level 16.54%, lignin
Content 10%, cellulose spent total reducing sugar 0.40kg) it is placed in separation vessel, undissolved suspended matter is removed with 500 mesh screens, is stirred
It is settled 1 hour after mixing, discharges lower layer's fiber fines and silt.
50% phosphoric acid is added to pH5.5,80 DEG C of temperature, hydrolyzes 30 minutes, Ethyl formate 0.2kg is added, after being stirred
It is layered after mixing evenly.Organic phase vacuum distillation recycling propyl acetate 0.188kg, the rate of recovery 94% obtain lignin
0.384kg, yield 96%.
Water phase adds calcium carbonate to be reacted, and is separated by filtration, and isolated waste liquid total reducing sugar is 0.995kg, hydrolysis of hemicellulose rate
It is 89.93%.Fermentation inhibitor furfural, phenols, acetic acid is not detected.The acidification of 50% sulfuric acid is added in calcium phosphate, recycles phosphoric acid
Content is 50%, the rate of recovery 93%.
It is concentrated into the 50% of volume using the flat polyether-ketone nanofiltration membrane component that molecular cut off is about 400 dalton,
Obtain the waste liquid concentrate (wherein glucose 257.7g/L, sugared 197.5g/L, arabinose 42.3g/L) containing 497.5g/L.
Seed culture based formulas used in the present embodiment is same as Example 1.
0.6kg bacillus coagulans (Bacillus coagulans) CGMCC No.7635 is inoculated in seed culture medium,
Shaking table shaken cultivation (100rpm) 12 hours, 50 DEG C of cultivation temperature.
When fermentation, 20g/L yeast powder is added into mixed sugar liquid and obtains fermentation medium, fermentation medium does not have to sterilizing.
Seed culture medium is inoculated in 2L fermentation medium with the inoculum concentration of 5% (v/v), fermentor automatic control fermentation condition: 35
~55 DEG C, 100~250rpm of speed of agitator, 20~40h of incubation time, terminate fermentation.Incubation uses 40% sodium carbonate certainly
Dynamic to adjust pH value 6.5, fermentation process does not need sterile working.
Repeated-batch: the 1st fermentation ends start the hyperfiltration membrane assembly coupled with fermentor, and hyperfiltration membrane assembly makes
With sulfonated polyether sulfone material ultrafiltration membrane, molecular cut off is 100,000 dalton.When fermentation liquid is concentrated into original volume 50%, i.e.,
Ultrafiltration terminates when 1L.Liquid will be concentrated by ultrafiltration as inoculum, fermentation medium is added in fermentor again to 2L, after
It is continuous to start in next batch fermentation medium, fermented and cultured is carried out with condition identical with fermenting for the first time, after culture
It is again started up membrane module, 8 batch of common fermentation.Fermentation results show that lactic acid yield improves 2.89 after 9 batches are continuously fermented
Times, each batch rotational rate of lactic acid illustrates that this process stabilizing is efficient all in 0.96g/g or more, before having wide industrial application
Scape.
The method that papermaking wastewater provided by the invention prepares lactic acid, by using sieve, phosphoric acid and organic solvent from waste liquid
In efficiently extracting and developing lignin, obtained waste liquid obtains lactic acid through the laggard one-step fermentation of ultrafiltration membrane treatment, then retains reuse
Strain.Preparation method mild condition, stability is good, can sufficiently recycle hemicellulose, lignin and fiber in waste liquid
Plain waste liquid；Not only the recycling for having improved waste liquid recycles, but also significantly reduces the containing as pollutant such as hemicellulose, lignin
Amount；And embody the feature of resource utilization and environmental protection.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (14)
1. a kind of method that papermaking wastewater prepares lactic acid, which comprises the following steps:
(1) waste liquid is placed in separation vessel, removes undissolved suspended matter with sieve, settled 3~5 hours after stirring, is discharged
Lower layer's fiber fines and silt；
(2) phosphoric acid is added into step (1) purified waste liquid waste liquid is hydrolyzed；
(3) organic solvent is added into step (2) reaction system and extracts lignin；
(4) by step (3) reaction system stratification, the organic phase after layering is distilled to recover organic solvent, is steamed in organic phase
It evaporates latter remaining group and is divided into lignin, recycled, phosphoric acid therein is recycled, then is concentrated through nanofiltration membrane by the water phase after layering；
(5) the waste liquid concentrate after step (4) concentration is transferred in fermentor, the access condensation bud under certain fermentation condition
Spore bacillus；
(6) after fermentation, fermentation liquid obtains the permeate containing lactic acid, the thallus of retention through Ultra filtration membrane to first batch
Cell returns in fermentor, and finally fermentating liquid volume is concentrated；
(7) Fermented Condensed liquid be re-used as inoculum access next batch fermentation medium in, with the complete phase of last batch
Same fermentation condition continues to ferment；
(8) repeat the above steps (1)-(7), realizes the successive batches fermenting lactic acid of papermaking wastewater.
2. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (1), the waste liquid
Including various pulping wood waste liquids and draft pulping waste liquor, waste liquid main component includes that hemicellulose, lignin, cellulose are useless
Liquid, organic acid and salt.
3. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (1), the waste liquid
Gu pH is 3.5~6.5 containing being 5~50% (25 DEG C).
4. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (1), the sieve
Mesh number be 50~500 mesh.
5. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (2), the phosphoric acid
Mass concentration be 50~90%, hydrolysis pH be 1.5~5.5, hydrolysis temperature be 30~80 DEG C, hydrolysis time be 30~120 points
Clock.
6. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that described organic in step (3)
Solvent is ester type compound, and the ester type compound is one kind of ethyl acetate, propyl acetate, butyl acetate or Ethyl formate；
The consumption of organic solvent and waste liquid ratio are 5~50% (w/w), are extracted under stirring condition.
7. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (4), the phosphoric acid
The method of recycling are as follows: calcium hydroxide or calcium carbonate are added in water phase, forms calcium phosphate precipitation, is filtered calcium phosphate and waste liquid
Separation, the sulfuric acid that calcium phosphate precipitation is added 50~98% are acidified, and are separated by filtration recycling phosphoric acid, and obtain byproduct sulfuric acid
Calcium.
8. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (4), the phosphorus of recycling
Acid is back to step (2), and recovered solvent is back to step (3).
9. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (4), the nanofiltration
Membrane module is rolling, tubular type or flat；Nanofiltration membrane material is cellulose acetate, sulfonated polysulfone, gathers in the nanofiltration membrane component
Amide, polyether sulfone, sulfonated polyether sulfone, poly- piperazine or polyvinyl alcohol；The molecular cut off of the nanofiltration membrane component is 90 to 400 roads
Between you pause.
10. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that step (5), (6) and (7)
In, the inoculum concentration of the bacillus coagulans is 5~15%.
11. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (5), the hair
Ferment condition are as follows: 35~55 DEG C of temperature, 20~40h of Batch fermentation time, 100~250rpm of speed of agitator use sodium hydroxide, ammonia
Water or sodium carbonate control pH value are between 6.0~6.5.
12. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (6) and (7), institute
Stating in hyperfiltration membrane assembly ultrafiltration membrane material is polysulfones, polysulfonamides, polyamide, sulfonated polysulfone, polyacrylonitrile, polyvinyl chloride, partially
Polyvinyl chloride, polyether sulfone or polyether-ketone or inorganic ceramic membrane；The hyperfiltration membrane assembly be flat, tubular type, wide runner rolling or
External-compression type hollow fiber form；The molecular cut off of the hyperfiltration membrane assembly is between 10,000 to 100,000 dalton.
13. the method that papermaking wastewater according to claim 1 prepares lactic acid, which is characterized in that in step (6), using institute
Stating hyperfiltration membrane assembly and fermentation liquid is concentrated is the 5%~50% of initial volume.
14. the method for requiring shown papermaking wastewater to prepare lactic acid according to right 1, which is characterized in that connect in step (5), (6) (7)
Continuous batch fermentation is at least 5 times.
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