CN104131039A - Method for producing organic acid by anaerobic fermentation of aquatic plant - Google Patents
Method for producing organic acid by anaerobic fermentation of aquatic plant Download PDFInfo
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- CN104131039A CN104131039A CN201410385178.2A CN201410385178A CN104131039A CN 104131039 A CN104131039 A CN 104131039A CN 201410385178 A CN201410385178 A CN 201410385178A CN 104131039 A CN104131039 A CN 104131039A
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- fermentation
- waterplant
- acid
- organic acid
- fermented liquid
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- 238000000855 fermentation Methods 0.000 title claims abstract description 97
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 230000004151 fermentation Effects 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 58
- 239000010802 sludge Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 103
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 54
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 50
- 240000001085 Trapa natans Species 0.000 claims description 48
- 235000009165 saligot Nutrition 0.000 claims description 44
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 42
- 235000011054 acetic acid Nutrition 0.000 claims description 35
- 235000019260 propionic acid Nutrition 0.000 claims description 27
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 21
- 235000019253 formic acid Nutrition 0.000 claims description 21
- 241001123263 Zostera Species 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000012258 culturing Methods 0.000 claims description 2
- 240000001398 Typha domingensis Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000010298 pulverizing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 33
- 229910052799 carbon Inorganic materials 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 241000196324 Embryophyta Species 0.000 description 30
- 239000000243 solution Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 241000233948 Typha Species 0.000 description 14
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002203 pretreatment Methods 0.000 description 12
- 239000010865 sewage Substances 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 244000005700 microbiome Species 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 150000002632 lipids Chemical class 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical group CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- ZSLZBFCDCINBPY-ZSJPKINUSA-N acetyl-CoA Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCSC(=O)C)O[C@H]1N1C2=NC=NC(N)=C2N=C1 ZSLZBFCDCINBPY-ZSJPKINUSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
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- 150000007513 acids Chemical class 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
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- 229920002488 Hemicellulose Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
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- 239000004310 lactic acid Substances 0.000 description 2
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- 239000002953 phosphate buffered saline Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229940107700 pyruvic acid Drugs 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
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- 235000000346 sugar Nutrition 0.000 description 2
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000003462 zymogenic effect Effects 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- YUVLVONHNMXKBW-UHFFFAOYSA-L [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O YUVLVONHNMXKBW-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
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- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for producing an organic acid by anaerobic fermentation of an aquatic plant. The method comprises the steps of cleaning the aquatic plant, drying to constant weight, pulverizing, then putting the treated aquatic plant into a fermentation tank, adding acclimated fermentation sludge, adding water, and performing constant temperature fermentation to obtain fermentation liquid containing the organic acid. The method has the advantages of simplicity in operation, wide raw material source, low price, good fermentation effect and the like, so that the method is the one for producing the organic acid by fermentation with important industrial application potential.
Description
Technical field
The invention belongs to abandoned biomass Application Areas, be specifically related to a kind of waterplant fermentation and produce organic acid method.
Background technology
Recent study is found, in the anaerobically fermenting product of city organic waste water (as brewing wastewater, molasses containing waste water, starch wastewater etc.) and municipal effluent plant excess sludge, contain a large amount of short chain volatile lipid acid, as acetic acid, propionic acid etc., can preferentially be utilized by denitrifying microorganism.
Anaerobically fermenting refer to the isolated condition of air under, rely on the biochemical action of facultative anaerobe and obligatory anaerobic bacteria, organism is carried out to biodegradable process, also claiming Anaerobic biotreatment method or anaerobic digestion, is mainly mud, plant and animal residues and ight soil etc. for processing high-concentration organic industrial waste water, town sewage.Complicated organic anaerobic digestion process will experience several stages, has been taken over by different bacterial flora.States of matter transitivity according to complicated organism in this process changes, and anaerobically fermenting can be divided 4 stages: hydrolysis, acidifying, product hydrogen produce acetic acid, produce methane phase, have worked in coordination with whole process by three quasi-microorganisms.
First stage, outside born of the same parents, under lytic enzyme and zymogenic combined action, the insoluble state organism of macromole (as total reducing sugar, protein, lipid etc.) is converted into small molecules dissolved organic matter (monose, amino acid, glycerine and longer chain fatty acid etc.).Total reducing sugar is decomposed into polysaccharide under the effect of the lytic enzymes such as cellulase, then is decomposed into oligosaccharides, is finally hydrolyzed to various monose.Macro-molecular protein is decomposed into polypeptide under the effect of proteolytic ferment, then is decomposed into dipeptides, finally under the effect of peptase, is hydrolyzed to each seed amino acid.Lipid is hydrolyzed to glycerine and longer chain fatty acid under the effect of lipase.
Subordinate phase, under zymogenic effect, the solubility small organic molecule that hydrolysis stage produces is converted into various short chain volatile lipid acid (VFAs) as acetic acid, propionic acid, isopropylformic acid, butyric acid, valeric acid and isovaleric acid and alcohols and letones etc.Monose is pyruvic acid by EMP, HMP or the glycolysis of ED approach, under acetyl-CoA effect, forms butyric acid, propionic acid, acetic acid, H
2and CO
2deng small organic molecule.Amino acid forms VFAs, H in deamination, depickling reaction
2s, NH
3deng.Transformation of glycerol is phosphoglyceraldehyde, then is converted into pyruvic acid and then forms VFAs, and longer chain fatty acid forms acetyl-CoA and acetic acid by β-oxidation.
Phase III, under the effect of hydrogen-producing acetogens, the end products of souring stage (VFAs, alcohols, lactic acid etc.) is converted into H
2, CO
2and acetic acid.
Fourth stage, methanogen utilizes acetic acid production CH
4or at CO
2while existence, utilize H
2generate CH
4, react as follows:
CH
3COOH→CH
4+CO
2
4H
2+CO
2→CH
4+2H
2O
It is to utilize methanogen to suppress to produce methane process by means such as soda acid regulation and control to the weakness of the environmental factors sensitivities such as pH, ORP, DO that urban waste biomass anaerobic fermentation produces acid, and the VFAs that fermentation is produced is accumulated.
At present, urban waste biomass anaerobic fermentation is produced the anaerobic acid-production of the excess sludge of town sewage plant of sour most study.
The process that the acid of biomass ferment product is is VFAs by complicated larger molecular organics Degradation and Transformation under numerous microorganisms synergies.Therefore, many environmental factorss (as temperature, pH, redox potential, pretreatment mode, hydraulic detention time, sludge retention time, nutritive element etc.) can be by affecting structure of community, dominant population, Metabolic activity, the hydrolysis rate of biomass etc. of microorganism and then affecting fermentation and acid type, produce sour efficiency etc.
Temperature has very big impact to fermentation and acid efficiency, and this is mainly because temperature can affect: the hydrolysis rate of (1) biomass; (2) height that enzyme is lived; (3) microbial growth speed; (4) population structure of microorganism; (5) speed of biochemical reaction.Hydrolysed ferment bacterium is wider to the subject range of temperature, all energy metabolism growths under low temperature (10～30 DEG C), middle temperature (30～50 DEG C) and high temperature (50～60 DEG C) condition.Anaerobically fermenting can be divided three classes according to the difference of leavening temperature: low temperature fermentation (10～20 DEG C), mesophilic digestion (30～35 DEG C) and thermophilic fermentation (50～60 DEG C).
High temperature is conducive to the stripping of labile organic compound in substrate, thereby significantly improves rate of producing acid, can also increase the ratio of acetic acid in total acid simultaneously.Mose etc. find under study for action, the hydrolytic rate constant K of mixing sludge 20 DEG C time
hwhile being 10 DEG C 2～3 times; Substrate hydrolysis rate constant K when the discovery temperature such as Ferreiro are 10 DEG C, 20 DEG C and 35 DEG C
hbe respectively 0.038,0.095 and 0.169d
-1, rising temperature is conducive to the carrying out of acid process.But thermophilic fermentation big energy-consuming, and fermenting process is unstable.
Mesophilic digestion speed of response is very fast, and the fermentation of fermentation time lower temperature is short, and does not have the above-mentioned shortcoming of thermophilic fermentation, therefore mostly adopts at present mesophilic digestion.Banerjee etc. utilize primary sludge and starch wastewater mixture (1:1) to carry out fermentation and acid, investigate 22～35 DEG C within the scope of the impact of temperature on substrate hydrolysis and acidifying.Result shows, VFAs and SCOD output raise and increase with temperature within the scope of 22～30 DEG C.Emine etc. utilize primary sludge to carry out fermentation and acid research, find that VFAs output is increased to 2950mg/L from 610mg/L, has improved nearly 5 times in the time that temperature rises to 24 DEG C from 10 DEG C.
PH is one of most important influence factor in anaerobic fermentation and acid production process.Both at home and abroad a large amount of results of study shows, the speed of pH on fermentation and acid, kind and the content of acidizing product all have impact.Horiuchi etc. utilize glucose to make substrate research pH to producing the impact of acids type, find that in the time of pH=6 product is taking butyric acid as main, and in the time of pH=8, product is taking acetic acid and propionic acid as main.Ren Nanqi etc. (1997) produce acid taking molasses containing waste water as fermenting substrate, find that the contents increased of ethanol in product, finally forms with ethanol, acetic acid, H when pH is lower than 5 time
2/ CO
2for the ethanol-type fermentation of primary product.Li Yuxiang etc. (2010) adopt batch test to study VFA productive rate and the organic matter degradation rate in the blue-green algae anaerobic fermentation and acid production process of Taihu Lake under acid (pH 5), neutral (pH 7) and alkalescence (pH 9) condition.Result shows, alkaline condition is more conducive to blue algae fermentation and produces acid, pH is that 9 o'clock VFAs productive rates are the highest, for 0.274gVFAs/g VS, acetic acid productive rate is 0.144g acetic acid/g VS, VS degradation rate reaches 51.91%, and while pH is that the degradation rate of 9 o'clock organic matters is also the highest, and the degradation rate of protein, carbohydrate and lipid reaches respectively 53.2%, 30% and 40.6%.Xiao Benyi etc. have also drawn the conclusion consistent with Li Yuxiang etc. by experiment, produce acid taking residual active sludge as fermenting substrate, fermentation 8d, pH be 9 and 10 o'clock VFAs productive rates be significantly higher than acidity and neutrallty condition, they think that reason has following two aspects: solubility rate organic under (1) alkaline condition is significantly higher than acidity and neutrallty condition; (2) under alkaline condition, produce methane process and be blocked, VFAs consumption still less.
It is generally acknowledged, the growth of obligate anaerobes requires ORP between-200～-250mV.The discovery ORP such as Zhou Hongbo directly affect fermentation and acid type, and when ORP is during at-550～-300mV, tunning is taking acetic acid and lactic acid as main, and along with the rising butyric acid density of ORP reduces gradually, the concentration of propionic acid and formic acid raises gradually.The people's such as Ren Nanqi result of study shows, ORP, in the time of-400～-200mV, ferments as main taking ethanol-type and butyric acid type, and ORP is in the time of-250～100mV, taking propionic acid type fermentation as main.
Many investigators have carried out large quantity research to the preconditioning technique in biomass anaerobic fermentation process, to improve solubility rate and dissolution rate organic in biomass by pre-treatment, to improve and forced fermentation effect, shorten fermentation period.The preconditioning technique that investigators adopt mainly contains chemical treatment, Mechanical Crushing, thermal treatment, destruction lignin structure, also destroys the structure of the nitrogenous thing such as amino acid, nucleic acid, after 5%NaOH Treating straw 48h, and COD, TN, NH
3-N and NO
3 --N respectively from 2311.11,175.40,117.82 and 5.02mg/L increase to 10488.89,417.84,141.44 and 248.64mg/L.Pre-treatment is suitable with aftertreatment gas production rate, is respectively 382.32ml/g TS and 375.84ml/g TS, and the alkali consumption of aftertreatment is only for 50% of pre-treatment, has reduced alkali consumption.Mechanical Crushing is to be sprayed, stirred the modes such as pulverizing, ball mill pulverizing to destroy microorganism wall in mud by high-pressure machinery, makes insoluble intracellular matter become soluble substance, is directly used in follow-up fermentation and acid aerogenesis.Other preconditioning technique research overviews are as shown in table 1.
Table 1 sludge anaerobic fermentation preconditioning technique research overview
In city organic waste water (as brewing wastewater, molasses containing waste water, starch wastewater etc.) and municipal effluent plant excess sludge, contain a large amount of readily biodegradable materials, after anaerobically fermenting, can produce a large amount of short chain volatile lipid acid, as acetic acid, propionic acid etc., be the denitrification additional carbon of high-quality, can be preferentially utilized by denitrifying microorganism.Table 2 has been summed up the denitrification effect while studying more city organic waste anaerobic acid-production fermented liquid as denitrification supplementary carbon source.
Table 2 abandoned biomass anaerobic acid-production fermented liquid is as denitrifying carbon source research overview
What Chinese scholars research was at present more is the denitrification effect while utilizing excess sludge of town sewage plant anaerobically fermenting acidizing product as additional carbon.Using excess sludge as fermentation substrate, both reduced sludge quantity, reduce the processing cost of mud, for sewage denitrification and dephosphorization provides high-quality carbon source, reduce carbon source cost again.The fermented liquid that Tong Juan (2008) obtains under alkaline condition with excess sludge as a supplement carbon source is processed the sanitary sewage of low COD, and carry out comparative study using actual sewage as carbon source, result shows to add the Nitrogen/Phosphorus Removal of SBR after fermented liquid and is greatly promoted, the clearance of COD, TN and SOP reaches respectively 93%, 80.9% and 97.2%, and add actual sewage while making carbon source the clearance of COD, TN and SOP only have respectively 85%, 63.5% and 43.9%.Liu Dao extensively adopts tensio-active agent to promote sludge fermentation to produce acid, the carbon source using fermented liquid as denitrification dephosphorization system, TP, NH
3the clearance of-N and TN reaches respectively 97%, 95% and 81%, and the order that in fermented liquid, VFAs is utilized is butyric acid, propionic acid, acetic acid.Nitrogen/Phosphorus Removal when some scholars have also studied product after the organic waste water anaerobic fermentation of high density city as carbon source.As the employing SBR techniques such as Quan are processed common municipal effluent using hydrolysis honey as additional carbon, nitric efficiency can reach (91.6 ± 1.6) %, (85.3 ± 2.0) % while making carbon source higher than methyl alcohol, but carbon source cost is lower by 20% than methyl alcohol.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and utilizes waterplant anaerobically fermenting to produce organic acid method.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of waterplant anaerobically fermenting produces organic acid method, and it comprises the steps:
(1) preparation of waterplant: waterplant is dried to constant weight, pulverize;
(2) fermentation condition: step (1) waterplant after treatment is placed in to fermentor tank, adds the fermented sludge of taming, ferment at constant temperature, obtains containing organic acid fermented liquid.
Wherein, described waterplant is cattail, the combination of any one or a few in power flower, eel grass and water caltrop again.
Wherein, described fermented sludge prepares by following acclimation method:
Active sludge after dehydration is mixed according to 1.5～2.5kg:4L with fermented liquid, regulating pH value is 7～8,28 DEG C of constant temperature culture 7 days, and in culturing process, system is regulated to pH value is 7～8 to every 24h, the fermented sludge of the domestication finally obtaining, fermented sludge concentration MLSS is 10000～15000%.
Wherein, the active sludge after described dehydration, its water-content is 85%.
Wherein, described fermented liquid, the weight ratio of its C:N:P is 200:5:1～300:5:1.
Wherein, waterplant and fermented sludge are thrown according to following ratio: waterplant dry weight and fermented sludge ratio are 0.3kg::1L:1L～0.5kg:1L:1L.
Wherein, the fermentation condition that step (2) is described, temperature range is 10 DEG C～37 DEG C, is preferably 25 DEG C～37 DEG C; The time range of fermentation is 4～14 days, is preferably 5-10 days; It is 7～8 that the pH of fermentation controls, and is preferably 7～7.5.
Wherein, in the fermented liquid finally obtaining, organic acid comprises formic acid, acetic acid, propionic acid and butyric acid etc.
Beneficial effect:
The present invention has following distinguishing feature and effect:
1, utilize waterplant to produce organic acid raw material as anaerobically fermenting, solved the problem of the processing difficulty after aquatic plant harvesting, prevent that it from producing secondary pollution to environment, there are important ecological benefits.
2, it is simple that this anaerobically fermenting produces organic acid method, and all kinds of organic acid contents that fermentation produces are high, are suitable as carbon source and add in the reaction system of sewage disposal.
3, utilize waterplant fermentation to produce organic acid, in the fermented liquid finally obtaining, the content of TN and TP is low, if add in sewage disposal system and can not bring new processing pressure to sewage disposal system as carbon source, has important industrial application potentiality.
Brief description of the drawings
The variation of fermented liquid TN in the dissimilar wetland plant fermenting process of Fig. 1;
Fermented liquid NH in the dissimilar wetland plant fermenting process of Fig. 2
3the variation of-N;
Fermented liquid COD in the dissimilar wetland plant fermenting process of Fig. 3
crvariation;
In the dissimilar wetland plant fermenting process of Fig. 4, fermented liquid formic acid content changes;
In the dissimilar wetland plant fermenting process of Fig. 5, fermented liquid acetic acid content changes;
In the dissimilar wetland plant fermenting process of Fig. 6, fermented liquid propionic acid content changes;
Fermented liquid butyric acid content in the dissimilar wetland plant fermenting process of Fig. 7;
Fig. 8 each volatile acid content in 6th～14 days fermented liquids that ferments;
At Fig. 9 different fermentations temperature, water caltrop fermented liquid TN is with the variation of fermentation time;
At Figure 10 different fermentations temperature, water caltrop fermented liquid TP is with the variation of fermentation time;
Water caltrop fermented liquid COD under Figure 11 different pretreatments
crwith the variation of fermentation time;
At Figure 12 different fermentations temperature, water caltrop fermented liquid formic acid is with the variation of fermentation time;
At Figure 13 different fermentations temperature, water caltrop fermented liquid acetic acid is with the variation of fermentation time;
At Figure 14 different fermentations temperature, water caltrop fermented liquid propionic acid is with the variation of fermentation time;
At Figure 15 different fermentations temperature, water caltrop fermented liquid butyric acid is with the variation of fermentation time;
Under Figure 16 different pretreatments, water caltrop fermented liquid TN is with the variation of fermentation time;
Under Figure 17 different pretreatments, water caltrop fermented liquid TP is with the variation of fermentation time;
Water caltrop fermented liquid COD under Figure 18 different pretreatments
crwith the variation of fermentation time;
Under Figure 19 different pretreatments, water caltrop fermented liquid formic acid content is with the variation of fermentation time;
Under Figure 20 different pretreatments, water caltrop fermented liquid acetic acid content is with the variation of fermentation time;
Under Figure 21 different pretreatments, water caltrop fermented liquid propionic acid content is with the variation of fermentation time;
Under Figure 22 different pretreatments, water caltrop fermented liquid butyric acid content is with the variation of fermentation time.
Embodiment
According to following embodiment, the present invention may be better understood.But, those skilled in the art will readily understand, the described content of embodiment is only for the present invention is described, and should also can not limit the present invention described in detail in claims.
The experimental plant adopting in embodiment: cattail stalk, power chopped straw stalk, eel grass, water caltrop again, all pick up from sounds of nature river, the celestial woods school district of Nanjing University.After draining, respectively get 10g above-mentioned materials and dry to constant weight, measure plant psychrometric ratio.
Instrument in embodiment comprises: Agilent liquid chromatograph, Eclipse XDB-C18 (4.6 × 100mm) chromatographic column, KH3200-DB numerical control ultrasonic cleaner, plant pulverizer, constant incubator, 500ml Erlenmeyer flask, ultraviolet-visible spectrophotometer UV2450, D-1 type automatic steam sterilization pan, electronic balance, 25mL tool plug glass ground joint colorimetric cylinder, quartz colorimetric utensil, ultrapure water system (Milli-Q, Millipore), 0.22 μ m water system filter membrane.
The detection method adopting in embodiment is as follows:
(1) survey total nitrogen reagent: adopt potassium persulfate oxidation-ultraviolet spectrophotometry.
Nitrate standardized solution, ultrapure water (without ammoniacal liquor), 20% sodium hydroxide solution, (1+9) hydrochloric acid (top grade is pure)
Alkalescence potassium persulfate solution: claim 40g Potassium Persulphate (K
2s
2o
3), 15g sodium hydroxide, is dissolved in ultrapure water, demarcates to 1000ml, is kept in polyethylene bottle.
(2) survey nitric nitrogen reagent: adopt ultraviolet spectrophotometry, detection line is at 0.08-4mg/L.
(1+9) hydrochloric acid (top grade is pure), 0.8% thionamic acid solution, nitrate standardized solution (standard stock solution, standard solution).
(3) survey nitrite nitrogen reagent: adopt N-(1-naphthyl)-quadrol light-intensity method to detect, detectability is at 0.003-0.2mg/L.
Without nitrous acid salt solution, developer, phosphoric acid, nitrite standardized solution (standard stock solution, standard intermediate liquid, standard solution).
Developer: add 250mL water and 50mL phosphoric acid in 500mL beaker, add 20.0g sulfanilic amide, by 1.00g N-(1-naphthyl)-quadrol dihydrochloride (C
10h
7nHC
2h
4nH
22HCl) be dissolved in above-mentioned solution, be transferred in 500mL volumetric flask, water is settled to graticule, mixes brown bottle refrigeration.
(4) survey ammonia-state nitrogen reagent: adopt nessler reagent light-intensity method, monitoring is limited to 0.025～2mg/L.
Nessler reagent, potassium sodium tartrate solution, ammonium standardized solution liquid (standard reserving solution, standard solution), without ammoniacal liquor.
(5) survey total phosphorus reagent: adopt alkaline potassium per-sulfate digestion-molybdenum-antimony anti-spectrophotometric method, monitoring is limited to 0.01～0.6mg/L.
5% potassium persulfate solution, (1+1) sulfuric acid, 10% ascorbic acid solution, molybdate solution, turbidity-colourity compensation liquid, phosphoric acid salt reference liquid (standard reserving solution, standard solution).
(6) survey COD
crreagent: adopt potassium dichromate process.
Potassium bichromate standardized solution (0.25mol/L, 0.025mol/L), phenanthroline ion indicating liquid, ferrous ammonium sulphate standardized solution, sulfuric acid-silver sulfate solution, Mercury bisulfate.
(7) DO measures and adopts the portable dissolved oxygen meter of Hash HQ30d.
(8) pH measures and adopts the portable pH meter of Hash HQ30d.
(9) survey short chain volatile lipid acid (VFAs) reagent: formic acid, acetic acid, propionic acid, butyric acid standard substance (purchased from Town in Shanghai spectrum), methyl alcohol, acetonitrile (chromatographically pure), phosphate buffered saline buffer (10mmol/L sodium dihydrogen phosphate, regulate pH=2.43 with phosphoric acid), ultrapure water.
Chromatographic condition: chromatographic column is Eclipse XDB-C18 (4.6 × 100mm) chromatographic column, mobile phase A: 3% methyl alcohol, Mobile phase B: 97% phosphate buffered saline buffer (10mmol/L sodium dihydrogen phosphate), pH=2.43, flow velocity 0.5ml/min, 30 DEG C of column temperatures, ultraviolet detection wavelength 210nm, sample size 10 μ L.
VFAs determination step: four kinds of organic acid list marks of first, second, third, fourth that first accurately compound concentration is 100mg/L, upper machine testing, determines each sour appearance time.Accurately prepare again that organic acid concentration is respectively 1000,500,200,100,50, (the mixed sample nail of 1000mg/L, second, third, four kinds of organic acid concentrations of fourth are 1000mg/L to the mixed sample of 20mg/L, other are same), upper machine testing, drawing standard curve, determines linearity range and relation conefficient.Taking organic acid mass concentration as X-coordinate, peak area is ordinate zou drawing standard curve, obtains equation of linear regression as shown in table 3.Finally measure pretreated fermentation broth sample, bring peak area into regression equation calculation VFAs content.
The regression equation of table 3 formic acid, acetic acid, propionic acid, butyric acid
Embodiment 1: the preparation of fermented sludge.
Test fermented sludge used and take from the excess sludge after certain sewage work's dehydration.
Following component preparation domestication substratum: glucose 15g/L, NaNO
33.04g/L, KH
2pO
40.44g/L, MgSO
47H
2o 0.96g/L, CaCl
20.72g/L, NaHCO
30.96g/L, MnCl
20.11g/L.The excess sludge after the dehydration of 2.5kg sewage work is packed in the fermentor tank of 5L again, add 4L domestication substratum, regulating pH is 7.4,28 DEG C of domestications one week, monitoring regulation and control every day pH.
Active sludge in following examples is preparation according to the method described above all.
Embodiment 2: the impact of wetland plant type on ferment effect.
Take respectively a certain amount of (by 30g dry weight basis) fresh cattail stalk, power chopped straw stalk, eel grass, water caltrop again, after pulverizing, pack in 500ml Erlenmeyer flask, add the fermented sludge 300ml (sludge concentration MLSS10000mg/L) after domestication, add water 200ml, regulating pH value is 7-8, is placed in 37 DEG C of thermostat containers and ferments.Test duration 2 weeks, the the the 0th, 1,2,4 ..., within 14 days, get fermented liquid 15ml, centrifugal 5 minutes of 12000rmp, gets supernatant liquor, a part is surveyed TN, NH
3-N, TP, COD
cr, pH, separately get after 4ml crosses 0.22 μ m water system filter membrane and survey voltaile fatty acid (VFAs).
Cattail, again power flower, eel grass and four kinds of constructed wetland plants of water caltrop during the fermentation nitrogenous source and carbon source release conditions as shown in FIG. 1 to 3, VFAs maximum production is as shown in Figure 4 to 7.
As shown in Figure 1, in anaerobic fermentation process, then power flower, eel grass, water caltrop fermented liquid TN content all present first to increase and reduce afterwards last stable rule gradually, and maximum value all appears at 4th～6 days.The clean burst size maximum of nitrogen be again power flower, its TN initial value is 592.3mg/L, ferments and within the 4th day, reaches maximum value 1270.8mg/L; Next is water caltrop and eel grass, respectively by initial value 241.4,137.1mg/L be increased to 686.3,594.3mg/L.And the clean burst size of the nitrogen of cattail is negative value, fermented liquid TN content initial value is 188.6mg/L, ferment and within one day, be reduced to rapidly afterwards minimum value 58.4mg/L, then gradually raise, reached 154.4mg/L at the 4th day, after reduce gradually again and tend towards stability.
As shown in Figure 2, the dispose procedure of ammonia nitrogen presents the rule similar to TN, and fermented liquid NH
3the ratio that-N content accounts for TN increases along with the prolongation of fermentation time, and ρ (NH after 4 days ferments
3-N)/ρ (TN) reaches 65.8%～97.6%, and the variation that TN content in fermenting process is described is mainly by NH
3-N content causes.
Fig. 3 reflects the different wetland plants releasing rule of carbon source during the fermentation.The initial COD of 4 kind of plant fermented liquid
crall, at 10296～12980mg/L, except cattail, other 3 kind of plant present the rule similar to nitrogen dispose procedure.Water caltrop, eel grass fermented liquid COD
crwithin the 8th day, reach respectively maximum value 30480,24560mg/L in fermentation, increased respectively 1.7,0.9 times compared with initial value; Power flower fermented liquid COD again
crwithin the 4th day, reach maximum value 16100mg/L in fermentation, increased by 0.3 times compared with initial value; The clean burst size of carbon element of cattail is negative value, fermented liquid COD
cralong with fermentation time extends and reduces, illustrate that the carbon element that in fermenting process, Cattail Plant body discharges is less than the carbon element that mud growth metabolism consumes.The descending order of the clean burst size of carbon element is: water caltrop > eel grass > is power flower > cattail again, and the carbon element burst size of submerged plant water caltrop, eel grass is obviously greater than emergent power flower, cattail again.The carbon element that plant materials discharges is during the fermentation mainly derived from the hydrolysis of Mierocrystalline cellulose and hemicellulose, submerged plant Mierocrystalline cellulose and hemicellulose level are higher than emergent, and the difficult content of lignin decomposing of microorganism is far below emergent, and submerged plant body structure is loose more easily to be decomposed by microorganism, this is to cause in fermenting process two types of waterplant in carbon element burst size, to show the major cause of the significance difference opposite sex.
From Fig. 4～Fig. 7, the formic acid output of Four Plants presents relatively consistent variation tendency, after primary fermentation starts first 4 days, fermented liquid formic acid content rises gradually, within the 4th day, reaches maximum value in fermentation, within 4th～8 days, decline gradually, after tend towards stability.Wherein water caltrop formic acid output maximum, ferment the 4th day be 1854.2mg/L, be secondly eel grass and power flower again, be respectively 1209.4,1034.7mg/L, cattail formic acid output is minimum, maximum value only has 501.6mg/L.
Acetic acid in fermented liquid, butyric acid content trend are similar to formic acid, and single acid content maximum value all appears at the 2nd or the 4th day.Acetic acid, butyric acid output maximum are all water caltrops, maximum value reaches respectively 7684.0,9428.5mg/L; Next is eel grass, and maximum value is respectively 5053.1,4216.3mg/L; Be again power flower again, maximum value is respectively 3605.8,2730.1mg/L; Cattail fermented liquid acetic acid, butyric acid content are minimum, and maximum value is respectively 1606.5,1428.0mg/L.
Propionic acid output maximum be eel grass, maximum value is the 3720.4mg/L of the 4th day; Next is again power flower, ferments and within the 4th day, reaches maximum value 2550.7mg/L; In water caltrop fermenting process, there are two peak values in fermented liquid propionic acid content, is respectively the 1652.0mg/L of the 2nd day and the 2128.3mg/L of the 4th day; Cattail propionic acid output is lower, ferments and reaches maximum value 953.6mg/L on the 2nd day, and then content declines always, and during to the 14th day, content is lower than detectability (20mg/L).
What Fig. 8 reflected is that fermentation enters relatively stable after date (6th～14 days), each single acid content mean value in Four Plants fermented liquid.Can find out, vegetation type has remarkably influenced to each single acid and total acid yield, and except propionic acid, in water caltrop fermented liquid, formic acid, acetic acid, butyric acid content are all the highest in Four Plants fermented liquid; Next is eel grass and power flower again, and that cattail produces acid amount is minimum.Vegetation type is little on producing the impact of acids type, and in Four Plants fermented liquid, acetic acid is all main acidizing products, be secondly butyric acid and propionic acid, and formic acid output is relatively low.
Embodiment 3: the impact of temperature on water caltrop ferment effect.
Experimental technique is with reference to embodiment 2, and difference is that according to dissimilar wetland plant fermentation test result, selecting the best submerged plant water caltrop of ferment effect is object, investigates the impact of differing temps (10 DEG C, 25 DEG C, 37 DEG C) on ferment effect.
Under 10 DEG C, 25 DEG C, 37 DEG C these 3 kinds of leavening temperatures, water caltrop fermented liquid TN, TP, COD
crwith VFAs content with the variation of fermentation time as Figure 6-9.
As shown in Figure 9, leavening temperature all has remarkably influenced to water caltrop release rate of nitrogen and burst size.Under 3 kinds of leavening temperatures, water caltrop release rate of nitrogen and the descending order of burst size are: 37 DEG C of >25 DEG C of >10 DEG C.37 DEG C time, nitrogen discharges the fastest, and in fermentation, the 6th day TN reaches maximum value 686.5mg/L, then reduces gradually; 25 DEG C time, nitrogen dispose procedure is more slow, and the first 10 days TN that ferment, all in ascent stage, reach maximum value 561.0mg/L on the 10th day, then reduces gradually; 10 DEG C time, nitrogen discharges the slowest, and TN rising always in whole fermentation period, reaches maximum value 429.8mg/L on the 14th day.
As shown in Figure 10, under 3 kinds of leavening temperatures, the rate of release of water caltrop phosphorus is all very fast, and temperature is also less on the impact of phosphorus burst size.Under 37 DEG C and 25 DEG C of conditions, after fermentation starts first 2 days, the phosphoric in water caltrop plant materials is discharged in fermented liquid fast, fermented liquid TP content by 62.8,58.9mg/L rises to 109.4,103.5mg/L, then all slightly rise and tend towards stability.10 DEG C time, the rate of release of water caltrop phosphorus wants slow during compared with 25 DEG C and 37 DEG C, after fermentation starts first 8 days, in fermented liquid, TP content is rising always, within the 8th day, reaches 113.8mg/L, the 14th day time, is 117.4mg/L, concentration with 25 DEG C and 37 DEG C of conditions under suitable.At contrast different fermentations temperature, fermented liquid TN content is known with the change procedure of fermentation time, and rate of release and the burst size impact of leavening temperature on water caltrop phosphorus is less.
As shown in Figure 11,37 DEG C time, water caltrop carbon source rate of release is the fastest, and first 8 days fermented liquid COD content after fermentation starts increase continuously and healthily, reach maximum value 30480mg/L the 8th day time, within the 10th day, be down to 24360mg/L and tend towards stability, within first 8 days, carbon source average rate of release is 2534.4mgCODkg
-1d
-1(the COD amount that every day, every kilogram of water caltrop discharged); 25 DEG C time, water caltrop carbon source rate of release is very fast, and the front 10 days COD content sustainable growth of fermenting reaches 25350mg/L on the 10th day, and within first 10 days, carbon source average rate of release is 1628.5mgCODkg
-1d
-1; 10 DEG C time carbon source discharge the slowest, within the 10th day, reach maximum value 16550mg/L, within first 10 days, carbon source average rate of release is 595.2mgCODkg
-1d
-1.
From Figure 12～Figure 15, temperature affects main manifestations both ways to water caltrop fermentation product volatile acid: (1) temperature affects the output of volatile acid and produces speed.37 DEG C time fermented liquid formic acid, acetic acid, propionic acid, butyric acid maximum level be respectively 1854,7684,2128,9428mg/L, acid process mainly occurs in 2nd～6 days; 25 DEG C time fermented liquid formic acid, acetic acid, propionic acid, butyric acid maximum level be down to respectively 1120,2884,1840,1480mg/L, acid process extends to fermentation after starting first 10 days; 10 DEG C time fermented liquid formic acid, acetic acid maximum level only have respectively 168,240mg/L, propionic acid, butyric acid do not detect, substantially do not produce acid.(2) acids type is produced in temperature impact.37 DEG C time, to produce the main component of volatile acid be acetic acid and butyric acid in fermentation, and main component 25 DEG C time is acetic acid and propionic acid, does not substantially produce acid 10 DEG C time.
Embodiment 4: the impact of pretreatment mode on water caltrop ferment effect.
Experimental procedure is with reference to embodiment 2, and difference is that the best submerged plant water caltrop of selection ferment effect is object, and whether the water caltrop that pretreated water caltrop and pulverizing are not carried out in investigation has impact to ferment effect.
Ferment as raw material not carry out pre-treatment and pulverized water caltrop respectively, TN, TP, COD in fermented liquid
crwith VFAs content with the variation of fermentation time as shown in Figure 16～22.
Can find out, rate of release and the burst size of pretreatment mode on nitrogen, phosphorus, carbon in water caltrop fermenting process all has utmost point remarkably influenced (p<0.01).Under pulverization conditions, 2nd～6 day fast rise of water caltrop fermented liquid TN content after fermentation starts, reach maximum value 686.5mg/L on the 6th day; The dispose procedure of plant materials phosphorus is faster, and the 4th day TP content that ferments rises to 116.0mg/L by initial value 62.8mg/L; The release of carbon wants slow compared with nitrogen, phosphorus, COD
crcontent reached maximum value 30480mg/L at the 8th day.
Degree of grinding also has utmost point remarkably influenced (p<0.01) to rate of producing acid and product acid amount.Under pulverization conditions, after starting first 4 days of fermentation, in fermented liquid, the content of formic acid, acetic acid, propionic acid, butyric acid all rises rapidly, what rate of producing acid was the fastest is acetic acid and butyric acid, within the 2nd day, reach 7684.5mg/L and 9428.0mg/L in fermentation respectively, formic acid and propionic acid reach maximum value 1854.0mg/L and 2128.0mg/L for the 4th day and the 6th day in fermentation respectively.And not under treatment condition, 4 kinds of sour rate of producing acid are all slower, (14 days) fermented liquid formic acid, acetic acid, propionic acid, butyric acid content rising in whole experimental period, all reached maximum value at the 14th day, be followed successively by 828.4,4150.8,709.5,2280.6mg/L, significantly lower than pulverizing group.
Claims (8)
1. waterplant anaerobically fermenting produces an organic acid method, it is characterized in that, it comprises the steps:
(1) preparation of waterplant: waterplant is cleaned, dried to constant weight, pulverize;
(2) fermentation condition: step (1) waterplant after treatment is placed in to fermentor tank, adds the fermented sludge of taming, then add water, ferment at constant temperature, obtains containing organic acid fermented liquid.
2. waterplant anaerobically fermenting according to claim 1 produces organic acid method, it is characterized in that, described waterplant is cattail, the combination of any one or a few in power flower, eel grass and water caltrop again.
3. waterplant anaerobically fermenting according to claim 1 produces organic acid method, it is characterized in that, described fermented sludge prepares by following acclimation method:
Active sludge after dehydration is mixed according to 1.5～2.5kg:4L with fermented liquid, regulating pH value is 7～8,28 DEG C of constant temperature culture 5～7 days, in culturing process, system is regulated to pH value is 7～8 to every 24h, the fermented sludge of the domestication finally obtaining, fermented sludge concentration MLSS is 10000～15000mg/L.
4. waterplant anaerobically fermenting according to claim 3 produces organic acid method, it is characterized in that, and the active sludge after described dehydration, its water-content is 80～85%.
5. waterplant anaerobically fermenting according to claim 3 produces organic acid method, it is characterized in that, and described fermented liquid, the weight ratio of its C:N:P is 200:5:1～300:5:1.
6. waterplant anaerobically fermenting according to claim 1 produces organic acid method, it is characterized in that, waterplant, fermented sludge and water are thrown according to following ratio: waterplant dry weight and fermented sludge ratio are 0.3kg::1L:1L～0.5kg:1L:1L.
7. waterplant anaerobically fermenting according to claim 1 produces organic acid method, it is characterized in that, and the fermentation condition that step (2) is described, temperature range is 10 DEG C～37 DEG C; The time range of fermentation is 5～14 days; It is 7～8 that the pH of fermentation controls.
8. waterplant anaerobically fermenting according to claim 1 produces organic acid method, it is characterized in that, described organic acid comprises formic acid, acetic acid, propionic acid and butyric acid.
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