CN105755059B - Method for improving synthetic concentration of carbon chain biological extension product - Google Patents
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Abstract
The invention relates to a method for improving the synthetic concentration of a carbon chain biological extension product, which converts low-carbon chain organic acid into medium-long carbon chain organic acid and comprises the following steps: filling an anaerobic reactor with an electric conductive carbon-based material; introducing anaerobic sludge generated by sewage treatment, biogas residues generated by anaerobic digestion of garbage, water body bottom mud, petroleum-polluted soil or brewing residues into an anaerobic reactor as a starter microbial agent for carbon chain biological extension; and continuously introducing a low-carbon chain organic acid raw material and an electron donor reactant into the anaerobic reactor, converting the low-carbon chain organic acid into medium-long carbon chain organic acid under the action of a microbial inoculum, and continuously discharging. Compared with the prior art, the conductive carbon-based material capable of promoting the enrichment of the carbon chain organism extension microorganisms is introduced into the anaerobic reaction system, so that the capability of the carbon chain extension microorganisms for resisting short carbon chain and medium and long carbon chain organic acids can be improved, and the synthetic concentration of the medium and long carbon chain organic acids is further improved.
Description
Technical Field
The invention belongs to the field of environmental protection and comprehensive utilization of resources, and particularly relates to a method for improving the synthetic concentration of a carbon chain biological extension product.
Background
The final fermentation products of natural fermentation of biomass wastes are mainly low carbon chain organic acids, because of the high degree of mixing of the biomass wastes, the mixed growth of microorganisms leads to low concentration of the low carbon chain organic acids, high content of impurities introduced by waste sources, mixing of non-target intermediate metabolites, and poor separability due to the high hydrophilicity of the short chain organic acids, high cost of separation by filtration, evaporation or distillation, and unfavorable conversion to ethanol and butanol (energy density 20.9 and 29.2 MJ/L, respectively) by high temperature or catalytic hydrogenation, therefore, these liquid fermentation products can only be applied to occasions requiring low purity of the feed, such as carbon sources for denitrification and dephosphorization as wastewater treatment [ L WS, Chua ASM, Yeoh HK, Ngoh GC.2014.
In order to solve The above problems, The carbon chain of organic substances can be extended by repolymerization technology, and The resource level of waste fermentation products can be further improved by reasonable cost, namely, low-carbon chain organic acid is converted into medium-carbon chain organic acid and long-carbon chain organic acid with higher carbon atom number, and The medium-carbon chain organic acid and The long-carbon chain organic acid are used as precursor raw materials of fuels or solvents such as mixed alcohol, alkane, ester and The like.
However, the isolation cost of the medium-long carbon chain products synthesized by the carbon chain biological extension Technology is greatly reduced if the concentration of the organic acid reaches 30 g/L or more according to measurement, but the highest concentration of caproic acid in the currently known mixed bacteria carbon chain biological extension system can only be 8.27-12.8 g/L [ Steinbushch KJJ, Hamers HVM, Pluge CM, Buisman CJN.2011.biological formation of caproate and caproate from acetate: Fuel and chemical product biology science 4: 216. microorganism. origin. Environment & Environment science 4: 2011. Isolato, chromatography, and enrichment of carbon chain synthesis medium PJ. Stevenson DM.2011. medium of organic acid, and carbon chain biological extension medium could also increase the concentration of the product of carbon chain biological extension medium 94. the mixed bacteria carbon chain biological extension medium could also increase the concentration of the product of carbon chain biological extension medium 94. 2014. the carbon chain biological extension medium could increase the concentration of the product of carbon chain biological extension medium.
The Chinese invention patent 'electrically-promoted carbon chain biological extension method and device' (application number CN201510019239.8) adopts an external current mode to promote the carbon chain biological extension reaction.
The Application of biochar to anaerobic digestion of glucose for methane production finds that biochar can promote glucose fermentation to produce short-chain organic acids (acetic acid, butyric acid and propionic acid) and the rate of degradation of the short-chain organic acids to methane is also accelerated.
Technical article [ Andersen, s.j., Candry, p., basal, t., Khor, w.c., Roume, h., Hernandez-Sanabria, e., Coma, m.and Rabaey, k. (2015) Electrolytic extraction solvent failure acid reaction of crude fatty acid and reproduction chemical pH control in reaction of biological enzyme conversion, biotechnology for Biofuels8(1),1-14 ] uses membrane electroextraction to separate the produced carbon chain extension products in real time to reduce their concentration in the reactor and avoid causing organic acid inhibition.
Scientific articles [ Agler, M.T., Spirito, C.M., Upack, J.G., Werner, J.J.and antigen, L. T. (2012) Chain interaction with microorganisms: upper gradient solvent medium-Chain carboxylic acids. energy & Environmental Science 5(8), 8189. 8192 ] drive liquid-liquid extraction and separation of the produced carbon Chain extension products by pH gradient to reduce the concentration thereof in the reactor and avoid causing organic acid inhibition.
Disclosure of Invention
Based on the technical background, the invention provides a method for improving the synthetic concentration of a carbon chain biological extension product. The key point of the method is that an auxiliary substrate capable of promoting electron transfer is introduced into a reaction system, so that the method is helpful for improving the inhibition resistance of the microorganism, namely improving the reactivity of the microorganism.
The purpose of the invention can be realized by the following technical scheme:
a method for improving the synthetic concentration of carbon chain biological extension products is used for converting low-carbon chain organic acid into medium-long carbon chain organic acid, and comprises the following steps:
(1) filling an anaerobic reactor with an electric conductive carbon-based material;
(2) introducing anaerobic sludge generated by sewage treatment, biogas residues generated by anaerobic digestion of garbage, water body bottom mud, petroleum-polluted soil or brewing residues into an anaerobic reactor as a starter microbial agent for carbon chain biological extension;
(3) and continuously introducing a low-carbon chain organic acid raw material and an electron donor reactant into the anaerobic reactor, converting the low-carbon chain organic acid into medium-long carbon chain organic acid under the action of a microbial inoculum, and continuously discharging.
Preferably, the conductive carbon-based material comprises activated carbon, biochar, graphite, or modified materials of the carbon-based materials which are modified to have conductivity.
Preferably, the particle size of the conductive carbon-based material is less than 100 microns.
Preferably, the volume filling rate of the conductive carbon-based material in the anaerobic reactor is more than or equal to 5%.
Preferably, the parameters of the anaerobic reactor are: the reaction temperature is 25-60 ℃, the pH value is 6-7, and the hydraulic retention time is more than or equal to 5 days.
Preferably, the low-carbon chain organic acid raw material is clear liquid obtained by hydrolyzing and acidifying biomass waste and performing solid-liquid separation, and the mass total fraction of acetic acid, propionic acid and butyric acid in the liquid is more than or equal to 80% of the total amount of organic matters in the liquid.
Preferably, the biomass waste comprises kitchen waste, fruit and vegetable waste, sludge, livestock and poultry manure or food processing residues.
Preferably, the electron donor reactant is selected from ethanol, lactic acid or hydrogen.
Preferably, the concentration of the electron donor reactant in the feed of the low carbon chain organic acid starting material and the electron donor reactant is greater than or equal to 25 mmol/L.
The conductive carbon-based material is added in the carbon chain biological extension reaction as an auxiliary base material, so that the capability of the carbon chain extension microorganism for resisting short carbon chain and medium-long carbon chain organic acid can be improved, and the synthetic concentration of the medium-long carbon chain organic acid is further improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the introduction of the conductive carbon-based material can promote the inter-species electron transfer of microorganisms with carbon chain biological extension function in the microbial inoculum, so that a microorganism reticular accumulation area with the radius range of hundreds of microns is formed in an area taking the carbon-based material as a core, the high-abundance enrichment of carbon chain biological extension microorganisms is realized, and the tolerance capability to molecular state organic acid inhibition is improved.
2. Therefore, the synthetic concentration of the organic acid with the medium and long carbon chains in the reactor filled with the conductive carbon-based material is greatly improved, and the product value of the carbon chain biological extension product is improved.
Drawings
FIG. 1 is a schematic structural diagram of a carbon chain biological extension reactor according to the present invention.
The reference numbers in the figures are as follows: 1-carbon chain organism extension microorganism; 2-low carbon chain organic acid raw material; 3-an electron donor reactant; 4-a feed inlet; 5-an anaerobic reactor; 6-lower perforated plate; 7-lower geotextile; 8-conductive activated carbon; 9-filling the reaction zone; 10-upper geotextile; 11-upper perforated plate; 12-an upper buffer; 13-a discharge hole; 14-discharging water; 15-side road; 16-delivery pump.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Referring to figure 1, firstly, brewing residues are used as a starter microbial inoculum, the residues are rich in carbon chain biological extension microorganisms 1 such as clostridium kluyveri, fermentation liquor obtained by hydrolyzing, acidifying and centrifuging kitchen waste is used as a low-carbon chain organic acid raw material 2, the n-butyric acid content of the fermentation liquor accounts for 80% of the total organic matters, the n-butyric acid concentration is 250 mmol/L, and an ethanol aqueous solution is used as an electron donor reactant 3, and the ethanol concentration is 250 mmol/L.
The low-carbon chain organic acid raw material 2 and the electron donor reactant 3 enter an anaerobic reactor 5 from a feed inlet 4, pass through a lower porous plate 6 and an overlying lower geotextile 7, and then enter a filling reaction zone 9 filled with conductive activated carbon 8 with the particle size of 50 mu m; the carbon chain biological extension microorganism 1 can be enriched around the conductive active carbon 8 to convert n-butyric acid and ethanol into n-caproic acid; the volume filling rate of the conductive activated carbon 8 in the filling reaction zone 9 is 15 percent, and the effective volume of the reaction zone can ensure that the hydraulic retention time of the reaction liquid in the zone is 15 days; the solution rich in n-caproic acid flows through the upper geotextile 10 and the upper porous plate 11 from the upper part of the filling reaction zone 9, enters the upper buffer zone 12, and flows out through the discharge port 13, and the effluent is the effluent 14.
The anaerobic reactor 5 adopts temperature control equipment to maintain the temperature in the reactor at 30 ℃ and adopts a pH control system to maintain the pH in the reactor at 7. In order to promote the flow of the solution in the reactor and to further increase the conversion, the reactor is provided with a side line 15, a transfer pump 16 is provided on the side line 15, and the internal circulation between the upper buffer zone 12 and the packed reaction zone 9 is realized by the transfer pump 16.
The concentration of the n-hexanoic acid in the effluent 14 can reach 23 g/L (in an alcohol-water solution system) at most, and the conversion rate of the n-hexanoic acid reaches 90%.
Example 2
Referring to fig. 1, the difference from embodiment 1 is:
in this embodiment, biochar is used as the conductive carbon-based material instead of conductive activated carbon. The particle size of the biochar is 80 microns.
In this embodiment, anaerobic sludge generated by sewage treatment is introduced into the anaerobic reactor as a starter inoculum for carbon chain biological extension.
The volume filling rate of the conductive carbon-based material in the anaerobic reactor in this example was 5%.
In this example, the parameters of the anaerobic reactor were: the reaction temperature was 25 ℃, pH 6, and hydraulic retention time was 5 days.
In the embodiment, the low-carbon chain organic acid raw material is clear liquid obtained by hydrolyzing and acidifying fruit and vegetable garbage and performing solid-liquid separation, and the mass total fraction of acetic acid, propionic acid and butyric acid in the clear liquid is equal to 80% of the total amount of organic matters in the clear liquid.
In this example, the electron donor reactant was lactic acid and the concentration of the electron donor reactant in the feed of the low carbon chain organic acid feed and the electron donor reactant was equal to 25 mmol/L.
In the method of this embodiment, carbon chain organism extension microorganisms in the microbial inoculum are activated to convert acetic acid, propionic acid and butyric acid into n-hexanoic acid; and the conversion rate of the acetic acid, the propionic acid and the butyric acid reaches more than 90 percent.
Example 3
Referring to fig. 1, the difference from embodiment 1 is:
in this embodiment, graphite is used as the conductive carbon-based material instead of conductive activated carbon. The particle size of the graphite is less than 100 microns.
In the embodiment, biogas residues generated by anaerobic digestion of garbage are introduced into the anaerobic reactor as a starter microbial inoculum for carbon chain biological extension.
The volume filling rate of the conductive carbon-based material in the anaerobic reactor in this example was 10%.
In this example, the parameters of the anaerobic reactor were: the reaction temperature was 40 ℃, pH 7, and the hydraulic retention time was 8 days.
In the embodiment, the low-carbon chain organic acid raw material is clear liquid obtained by hydrolyzing and acidifying sludge and performing solid-liquid separation, and the total mass fraction of acetic acid, propionic acid and butyric acid in the liquid is 85% of the total mass fraction of organic matters in the liquid.
In this example, the electron donor reactant was hydrogen and the concentration of the electron donor reactant in the feed of the low carbon chain organic acid feedstock and electron donor reactant was 55 mmol/L.
In the method of this embodiment, carbon chain organism extension microorganisms in the microbial inoculum are activated to convert acetic acid, propionic acid and butyric acid into n-hexanoic acid; and the conversion rate of the acetic acid, the propionic acid and the butyric acid reaches more than 90 percent.
Example 4
Referring to fig. 1, the difference from embodiment 1 is:
in this embodiment, modified biochar, which is modified to have conductivity, is used as a conductive carbon-based material instead of conductive activated carbon. The particle size of the modified biochar is 50 microns.
In this embodiment, the oil-contaminated soil is introduced into the anaerobic reactor as a starter inoculum for carbon chain biological extension.
The volume filling rate of the conductive carbon-based material in the anaerobic reactor in this example was 25%.
In this example, the parameters of the anaerobic reactor were: the reaction temperature was 60 ℃, the pH 6, and the hydraulic retention time was 10 days.
In the embodiment, the low-carbon chain organic acid raw material is clear liquid obtained by hydrolyzing and acidifying livestock and poultry manure and performing solid-liquid separation, and the mass total fraction of acetic acid, propionic acid and butyric acid in the clear liquid is 83% of the total amount of organic matters in the clear liquid.
In this example, the electron donor reactant was lactic acid, and the concentration of the electron donor reactant in the feed of the low carbon chain organic acid feedstock and the electron donor reactant was 125 mmol/L.
In the method of this embodiment, carbon chain organism extension microorganisms in the microbial inoculum are activated to convert acetic acid, propionic acid and butyric acid into n-hexanoic acid; and the conversion rate of the acetic acid, the propionic acid and the butyric acid reaches more than 90 percent.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. A method for improving the synthetic concentration of carbon chain biological extension products is used for converting low-carbon chain organic acid into medium-long carbon chain organic acid, and is characterized by comprising the following steps:
(1) filling an anaerobic reactor with an electric conductive carbon-based material;
(2) introducing anaerobic sludge generated by sewage treatment, biogas residues generated by anaerobic digestion of garbage, water body bottom mud, petroleum-polluted soil or brewing residues into an anaerobic reactor as a starter microbial agent for carbon chain biological extension;
(3) continuously introducing a low-carbon chain organic acid raw material and an electron donor reactant into the anaerobic reactor, converting the low-carbon chain organic acid into medium-long carbon chain organic acid under the action of a microbial inoculum, and continuously discharging;
the conductive carbon-based material is selected from activated carbon, biochar, modified activated carbon still having conductivity after modification or modified biochar still having conductivity after modification;
the particle size of the conductive carbon-based material is less than 100 microns, and the volume filling rate of the conductive carbon-based material in the anaerobic reactor is more than or equal to 5 percent;
the introduction of the conductive carbon-based material can promote the inter-species electron transfer of microorganisms with the carbon chain biological extension function in the microbial inoculum, so that a microorganism reticular accumulation area with the radius range of hundreds of microns is formed in an area taking the carbon-based material as a core, and the high-abundance enrichment of the carbon chain biological extension microorganisms is realized.
2. The method for increasing the synthesis concentration of carbon chain biological extension products according to claim 1, wherein the parameters of the anaerobic reactor are as follows: the reaction temperature is 25-60 ℃, the pH value is 6-7, and the hydraulic retention time is more than or equal to 5 days.
3. The method of claim 1, wherein the electron donor reactant is selected from the group consisting of ethanol, lactic acid, and hydrogen.
4. The method for increasing the synthesis concentration of carbon chain biological extension products as claimed in claim 1, wherein the concentration of the electron donor reactant in the feed of the low carbon chain organic acid raw material and the electron donor reactant is greater than or equal to 25 mmol/L.
5. The method for improving the synthesis concentration of carbon chain biological extension products according to claim 1, wherein the low-carbon chain organic acid raw material is a clarified liquid obtained by hydrolyzing and acidifying biomass waste and performing solid-liquid separation, and the mass total fraction of acetic acid, propionic acid and butyric acid in the clarified liquid is greater than or equal to 80% of the total organic matter content in the clarified liquid.
6. The method for increasing the synthesis concentration of carbon chain biological extension products according to claim 5, wherein the biomass waste comprises kitchen waste, fruit and vegetable waste, sludge, livestock and poultry manure or food processing residues.
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| 生物质炭对模拟淹水土壤CO2排放和CH4释放潜力的影响;唐志刚;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20141231;全文 * |
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