CN110563259A - Pig farm wastewater anaerobic hydrogen production and recycling treatment method - Google Patents
Pig farm wastewater anaerobic hydrogen production and recycling treatment method Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000001257 hydrogen Substances 0.000 title claims abstract description 128
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 99
- 239000002351 wastewater Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000004062 sedimentation Methods 0.000 claims abstract description 54
- 239000010802 sludge Substances 0.000 claims abstract description 53
- 238000010521 absorption reaction Methods 0.000 claims abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 24
- 241000894006 Bacteria Species 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 238000000855 fermentation Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 136
- 238000004659 sterilization and disinfection Methods 0.000 claims description 36
- 239000006228 supernatant Substances 0.000 claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 24
- 239000012047 saturated solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 159000000003 magnesium salts Chemical class 0.000 claims description 21
- 150000003017 phosphorus Chemical class 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 230000014759 maintenance of location Effects 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003814 drug Substances 0.000 claims description 11
- 230000001954 sterilising effect Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 239000001963 growth medium Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007836 KH2PO4 Substances 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000004151 fermentation Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 239000002028 Biomass Substances 0.000 abstract description 5
- 238000011010 flushing procedure Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 238000009826 distribution Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- 239000003513 alkali Substances 0.000 description 12
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052567 struvite Inorganic materials 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YREOLPGEVLLKMB-UHFFFAOYSA-N 3-methylpyridin-1-ium-2-amine bromide hydrate Chemical compound O.[Br-].Cc1ccc[nH+]c1N YREOLPGEVLLKMB-UHFFFAOYSA-N 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a pig farm wastewater anaerobic hydrogen production and recycling treatment method, which comprises the steps of passing pig farm flushing wastewater through a grating, then entering an MAP sedimentation tank for pretreatment, sending supernate into a wastewater adjusting tank, adjusting the pH value of the supernate, then sending the supernate into an anaerobic hydrogen production reactor, operating for a certain time, then carrying out hydrogen-producing bacteria separation and enrichment culture on activated sludge in the anaerobic hydrogen production reactor, then adding enrichment culture solution into the anaerobic hydrogen production reactor again to mix with anaerobic sludge, sending hydrogen and carbon dioxide gas generated by the anaerobic hydrogen production reactor into an absorption tower, injecting carbon dioxide absorption liquid at the bottom back into an aerobic biochemical tank, and sending purified hydrogen into an air collecting bag. The method provided by the invention realizes the purpose of producing hydrogen by anaerobic fermentation of the pig farm wastewater, remarkably improves the efficiency of producing hydrogen by anaerobic fermentation and the volume load of a hydrogen production reactor, obtains hydrogen with purity higher than 90%, can reduce carbon emission of a large-scale pig farm by more than 80%, and realizes the purpose of converting the pig farm wastewater into biomass clean energy.
Description
Technical Field
the invention relates to a method for treating wastewater in a pig farm by anaerobic hydrogen production and recycling, belongs to the field of agricultural breeding wastewater treatment, and achieves the aim of producing clean energy hydrogen in the anaerobic treatment process of the wastewater in the pig farm and recycling the wastewater after treatment.
Background
The pig farm waste water belongs to high-concentration organic waste water, and is one of the main 'abominant' causing rural water environment pollution due to the high-concentration ammonia nitrogen, soluble phosphorus and COD substances. Anaerobic fermentation is a necessary and preferred process in the course of its treatment, and only methane gas is obtained in the current anaerobic process. Methane is the main component of natural gas and methane, a large amount of methane in a pig farm is directly discharged into the atmosphere, and the greenhouse effect generated by methane is more than 20 times larger than that of carbon dioxide. With the progress of science and technology, the phenomenon of hydrogen production in the anaerobic process is more and more emphasized, the product of hydrogen combustion is water, the greenhouse effect is not generated, the hydrogen is the cleanest and most efficient energy, the heat value of the hydrogen is 143.35 kJ/g, which is 2.6 times of methane, so that the hydrogen production has great superiority compared with the methane production during the pig farm wastewater treatment, and the hydrogen production has very important practical significance for solving the problems of carbon emission and environmental pollution caused by the breeding industry.
But the current piggery wastewater anaerobic process only produces methane. The utility model discloses a "a wastewater treatment system of raising pigs" (application number 2012206386350) has explored the anaerobism/good oxygen processing technology after waste water nitrogen phosphorus retrieves, but has not explored the hydrogen technique of anaerobism, more does not have to waste water further cyclic recycling, so about the pig farm waste water hydrogen and the technique and the technology research and development of handling the back retrieval and utilization lack very much. In addition, the invention patent 'a method for culturing high-temperature anaerobic hydrogen-producing granular sludge' (application number 200410088598.0) applies a mode of heating sludge to carry out anaerobic hydrogen production, but does not explore hydrogen production efficiency, a gas purification technology and a subsequent treatment process, does not purify the produced hydrogen, and cannot obtain high-quality hydrogen. In the process of anaerobic hydrogen production, about 30-50% CO is produced2And also small amounts of H2S、NO2And the like, so the purification of the gas after anaerobic hydrogen production is very important, and the purification mode has great influence on the treatment cost. After the high-purity hydrogen is obtained by the method, the carbon dioxide absorption liquid is designed and utilized, and the carbon emission is reduced by more than 80%.
The process design reduces the hydraulic retention time of the aerobic biochemical pool from more than 8-12 hours to less than 4-6 hours, obviously improves the treatment efficiency and reduces the aerobic treatment cost by about more than 30%. In addition, a chemical feeding pipe is arranged at the water inlet of the mixing sedimentation tank, the medicament is uniformly mixed by utilizing the action of hydraulic turbulence to remove soluble phosphorus in water, and then the wastewater is recycled by further adopting a disinfection technology, so that 90% of water is saved in a pig farm. Has very important significance for the wastewater treatment of the large-scale pig farm. Therefore, the method finally realizes the pig farm wastewater anaerobic hydrogen production treatment mode, and provides a new way for the development of biomass clean energy in the pig industry.
Disclosure of Invention
the invention aims to provide a method for treating wastewater in a pig farm by anaerobic hydrogen production and recycling, which has high hydrogen production efficiency and can realize the purpose of converting the wastewater in the pig farm into biomass clean energy.
The invention provides a method for treating wastewater in a pig farm by anaerobic hydrogen production and recycling, which comprises the following steps:
(1) The pig farm washing wastewater enters an MAP sedimentation tank for pretreatment after passing through a grating, sediment after sedimentation is discharged and recovered from the bottom of the MAP sedimentation tank, and supernatant after sedimentation is sent to a wastewater adjusting tank;
(2) Adjusting the pH value of the supernatant in the wastewater adjusting tank to 3.5-4.0, then feeding the supernatant into an anaerobic hydrogen production reactor, wherein the anaerobic hydrogen production reactor takes residual activated sludge of a sewage plant as a filler and VSS (VSS) 6-8g/L, adding the supernatant into the anaerobic hydrogen production reactor after heating pretreatment for 0.5h at 70 ℃, the volume ratio of mud to water is 1:2.5-4.5, stirring for 20min every 1 hour after water enters, and when the hydraulic retention time is 12h, the operation period comprises: feeding water for 0.5h, reacting for 10h, precipitating for 1h and discharging water for 0.5h, and feeding water again after discharging water, wherein the operation is carried out for 30 days in the way;
(3) Taking the sterilized pig farm wastewater as a culture medium, performing hydrogen production dominant bacteria separation on anaerobic activated sludge in an anaerobic hydrogen production reactor under strict anaerobic conditions to obtain hydrogen production dominant bacteria MH-1 and MH-2, performing enrichment culture on the MH-1 and MH-2 at the pH value of 5.0 by using the sterilized pig farm wastewater containing 0.5 percent of glycerol under the strict anaerobic conditions, and when each milliliter of enrichment culture solution contains 1 multiplied by 10 respectively17-1025After MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor are added into the anaerobic hydrogen production reactor again according to the volume ratio of 1:1 of muddy water; after mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating for 4-6 times, and increasing the water inlet volume ratio to 1: 2.5;
(4) Hydrogen and carbon dioxide gas generated by the anaerobic hydrogen generating reactor are sent into an absorption tower, and after being absorbed by alkaline absorption liquid, the purified hydrogen enters an air collecting bag; sending carbon dioxide absorption liquid at the bottom of the absorption tower into an aerobic biochemical tank;
(5) Feeding fermentation liquor discharged by an anaerobic hydrogen production reactor into an aerobic biochemical pool, feeding effluent in the aerobic biochemical pool into a mixed sedimentation pool, adding a phosphorus removing agent into water in the mixed sedimentation pool to remove soluble phosphorus in the water, then feeding the water into a disinfection pool, and performing disinfection and sterilization treatment to obtain reuse water, wherein precipitated sludge at the bottom of the mixed sedimentation pool respectively flows back into the aerobic biochemical pool and the anaerobic hydrogen production reactor;
Wherein, in the step (1), the pretreatment is carried out by adopting the following method: after the water feeding amount reaches half of the volume of the MAP sedimentation tank, stirring, controlling the rotating speed to be 150-350rpm, adding magnesium salt and phosphorus salt, after water feeding and medicine feeding are finished, continuing stirring for 10-15min, and adjusting the rotating speed to be two thirds of the original rotating speed; the magnesium salt is MgCl which is chemically pure, analytically pure or used industrially2、MgSO4And MgO, which is prepared into a saturated solution or a solution with any concentration before being added, wherein the phosphorus salt is NaH which is chemically pure, analytically pure or industrially used2PO4、Na2HPO4、Na3PO4、KH2PO4 、K2HPO4And H3PO4The one of the two solutions is prepared into a saturated solution or a solution with any concentration before adding, the adding amount of the magnesium salt solution and the phosphorus salt solution is controlled to be 1.0-1.3:1 in terms of the molar ratio of the magnesium salt to the phosphorus salt, and the amount of the phosphorus salt is controlled to be equal to NH in the pig farm wastewater4 +The molar ratio of-N is 0.6-0.8: 1. The solvent water for dissolving the medicament comes from the top water of the disinfection tank, so that the consumption of fresh water can be saved, and the total discharge amount of wastewater is reduced.
In the step (2), industrial sulfuric acid or hydrochloric acid is used for adjusting the pH of the supernatant.
In the step (3), the pH of the alkaline absorbent is 8.5 or more.
In the step (5), activated sludge MLSS in the aerobic biochemical pool is 3000-7000mg/L, and the hydraulic retention time is 4-6 h.
in the step (5), the phosphorus removing agent adopts saturated solution of common phosphorus removing agents such as aluminum sulfate, aluminum trichloride or ferric trichloride, and the like, and the hydraulic retention time of the mixing sedimentation tank is 2-3 h.
In the step (5), O is adopted for disinfection and sterilization in the disinfection tank3And ultraviolet rays.
Due to the adoption of the method, the invention has the following positive effects:
1. The invention provides a process technology for generating clean energy hydrogen by pig farm wastewater anaerobic reaction. After active sludge in an anaerobic hydrogen production reactor is subjected to strain separation to obtain hydrogen production dominant strains MH-1 and MH-2, the MH-1 and MH-2 are subjected to enrichment culture at the pH value of 5.0 by using sterilized pig farm wastewater containing 0.5% of glycerin under strict anaerobic conditions, then a culture solution is inoculated to an original hydrogen production reactor, and the pH value of inlet water is adjusted to 3.5-4.0, so that the hydrogen production efficiency of the reactor is improved by more than 90%. The anaerobic process of the wastewater is controlled to be four stages of hydrolysis, acidification, acid production and hydrogen production, the traditional anaerobic methane production mode is changed, the aim of converting the wastewater of a pig farm into biomass clean energy is achieved, and a new way is provided for the development of biomass energy in the pig industry.
2. Part of circulating water is added into alkali liquor and then is used as absorption liquid in an absorption tower for removing CO generated by a hydrogen production reactor2、H2S and the like, high-quality hydrogen is obtained, the purity of the hydrogen is about 90 percent, and therefore the hydrogen can be used as an industrial raw material or a fuel, and the wastewater treatment cost is reduced. In addition, the absorption liquid is discharged into the aerobic biochemical pool for treatment, so that on one hand, carbon dioxide generated in the anaerobic process of the wastewater is utilized as a carbon source by autotrophic bacteria such as nitrifying bacteria and the like in the aerobic treatment process, and on the other hand, the alkalinity required by the nitrification reaction of ammonia nitrogen in the aerobic biochemical pool is supplemented, and the method can effectively reduce the carbon emission of the large-scale pig farm by more than 80 percent and has very important significance on the carbon emission reduction of the aquaculture.
3. The anaerobic hydrogen production can degrade COD to a small molecular organic acid stage, provide a high-quality carbon source for aerobic heterotrophic bacteria treatment, and greatly improve the C/N ratio of the aerobic treatment, so that the hydraulic retention time of an aerobic section is reduced from 8-12h to below 4-6h, the treatment efficiency is obviously improved, and the aerobic treatment cost is reduced by about 30 percent. The invention realizes the anaerobic hydrogen production and NH of the wastewater of the pig farm4 +-N、PO4 3+the technical goals of recycling and wastewater recycling are realized, and the clean production concept of 'carbon emission reduction' and the recycling economy of the pig industry are realized.
Drawings
FIG. 1 is a process flow diagram of the present invention.
in the figure, 1-grid channel, 2-grid, 3-MAP sedimentation tank, 4-magnesium salt pipe, 5-first stirrer, 6-phosphate salt pipe, 7-first valve, 8-sedimentation recovery device, 9-fourth valve, 10-first water outlet pump, 11-wastewater adjusting tank, 12-first pH value monitoring probe, 13-second stirrer, 14-acidification pipe, 15-second water outlet pump, 16-anaerobic hydrogen production reactor, 17-first pipeline, 18-gas booster pump, 19-third stirrer, 20-absorption tower, 21-gas distribution pipe, 22-filler, 23-second pH value monitoring probe, 24-alkali adding pipe, 25-alkali liquid valve, 26-second pipeline, 27-gas collecting bag, 28-a third water outlet pump, 29-a discharge pipe, 30-an aerobic biochemical tank, 31-a water distribution pipe, 32-a fourth water outlet pump, 33-a fourth pipeline, 34-a fifth water outlet pump, 35-a mixed sedimentation tank, 36-a medicine feeding pipe, 37-a mud valve, 38-a third pipeline, 39-a second valve, 40-a third valve, 41-a sixth water outlet pump, 42-a disinfection tank, 43-O3Valve, 44-UV sterilizing lamp.
Detailed Description
As shown in figure 1, the device adopted by the invention comprises a grid ditch 1, an MAP sedimentation tank 3, a wastewater adjusting tank 11, an anaerobic hydrogen production reactor 16, an absorption tower 20, an aerobic biochemical tank 30, a mixed sedimentation tank 35 and a disinfection tank 42,
Install grid 2 in grid canal 1, the delivery port of grid canal 1 connects the water inlet of MAP sedimentation tank 3, is provided with in the MAP sedimentation tank 3 with magnesium salt pipe 4, with phosphonium salt pipe 6 and first agitator 5, 3 bottom sedimentation outlets of MAP sedimentation tank connect through first valve 7 and deposit recovery unit 8, the delivery port on 3 upper portions of MAP sedimentation tank connects the water inlet of waste water equalizing basin 11 through first play water pump 10.
A first pH value monitoring probe 12, a second stirrer 13 and an acidification pipe 14 are installed in a wastewater adjusting tank 11, a water outlet of the wastewater adjusting tank 11 is connected with a water inlet of an anaerobic hydrogen production reactor 16 through a second water outlet pump 15, the anaerobic hydrogen production reactor 16 is provided with a third stirrer 19, and a gas outlet at the top end of the anaerobic hydrogen production reactor 16 is connected with an absorption tower 20 through a first pipeline 17 and a gas booster pump 18.
The absorption tower 20 is internally provided with a filler 22, an air distribution pipe 21, a second pH value monitoring probe 23 and a water distribution pipe 31, the top of the absorption tower 20 is provided with an alkali adding pipe 24, wherein the air distribution pipe 21 is positioned below the filler 22, the water distribution pipe 31 is positioned above the filler 22, the air distribution pipe 21 is connected with a first pipeline 17 behind a gas booster pump 18, the alkali adding pipe 24 is provided with an alkali liquor valve 25, and a hydrogen outlet at the top of the absorption tower 20 is connected with an air inlet of an air collecting bag 27 through a second pipeline 26.
The water outlet at the upper part of the anaerobic hydrogen production reactor 16 is connected with an aerobic biochemical pool 30 through a third water outlet pump 28, the water outlet at the bottom of the absorption tower 20 is connected with the aerobic biochemical pool 30 through a fourth water outlet pump 32, the water outlet of the aerobic biochemical pool 30 is connected with the water inlet of a mixed sedimentation pool 35 through a fifth water outlet pump 34, and a chemical feeding pipe 36 is arranged at the water inlet of the mixed sedimentation pool 35.
One path of a precipitated sludge outlet at the bottom of the mixed sedimentation tank 35 is connected with the aerobic biochemical tank 30 through a third pipeline 38 and then respectively through a second valve 39, is connected with the anaerobic hydrogen production reactor 16 through a third valve 40, the other path is connected with a discharge pipe through a sludge discharge valve 37, and a water outlet of the mixed sedimentation tank 35 is connected with a water inlet of a disinfection tank 42 through a sixth water outlet pump 41.
the bottom of the disinfection tank 42 is provided with an O3A valve 43, a UV disinfection lamp 44 is arranged in the tank, one path of the water outlet at the top of the disinfection tank 42 is connected with the water distribution pipe 31 in the absorption tower 20 through a fourth valve 9 and a fourth pipeline 33, and the other path is connected with the discharge pipe 29.
As shown in figure 1, after the pigsty is washed, the wastewater is collected to a grid channel 1 through a drainage ditch and a sewage pipeline, the wastewater is subjected to flow into an MAP sedimentation tank 3 automatically after granular impurities such as floating or large feed and excrement are removed through a grid 2, and the pigsty is subjected to a dry excrement cleaning mode.
After the wastewater enters the MAP sedimentation tank 3, after the water inlet amount reaches half of the tank volume, the first stirrer 5 is started, and the rotating speed is controlled to be 150-350 rpm. According to the total amount of the wastewater, medicament magnesium salt and phosphorus salt are respectively added through a magnesium salt adding pipe 4 and a phosphorus salt adding pipe 6, the rotating speed of the first stirrer 5 is adjusted to be two thirds of the original rotating speed after water inlet and medicament adding are finished, and stirring is continued for 10-15 min. The magnesium salt is chemically pure, analytically pure or industrially useful MgCl2、MgSO4And MgO, which is prepared into a saturated solution before being added, and the phosphorus salt is chemically pure, analytically pure or industrially usedNaH2PO4、Na2HPO4、Na3PO4、KH2PO4 、K2HPO4And H3PO4One of the two is prepared into saturated solution before adding, the adding amount of the magnesium salt solution and the phosphorus salt solution is controlled to be 1.0-1.3:1 in molar ratio of magnesium salt to phosphorus salt, and the amount of the phosphorus salt is controlled to be equal to NH in the pig farm wastewater4 +The molar ratio of-N is 0.6-0.8: 1. The solvent water for preparing the saturated solution of magnesium salt and phosphorus salt comes from the top of the disinfection tank 42, so that the consumption of fresh water is saved, and the total amount of discharged wastewater is reduced.
And (3) enabling precipitates generated after the chemical reaction in the MAP sedimentation tank 3 to enter a sedimentation recovery device 8 through a first valve 7 at the bottom to obtain nitrogen and phosphorus sediments, and utilizing the nitrogen and phosphorus sediments as slow release fertilizers. The MAP recovery device 8 can adopt Chinese patent 'a device for recycling struvite from wastewater nitrogen and phosphorus' (application number 201420458242.0), the sediment generated by the MAP reaction sedimentation tank 3 is white, after dehydration and drying by the MAP recovery device 8, the content of magnesium ammonium phosphate is higher than 85 percent, and the magnesium ammonium phosphate can be recovered as high-quality chemical raw materials or agricultural slow-release fertilizers, thereby realizing the circular economy concept of the aquaculture industry.
The supernatant of the MAP sedimentation tank 3 enters a wastewater adjusting tank 11 through a first water outlet pump 10, the pH value of the wastewater is adjusted to 3.5-4.0 through an acid adding pipe 14 under the stirring of a second stirrer 13, the acid used for adjusting the pH value of the wastewater is hydrochloric acid, and the acid enters an anaerobic hydrogen production reactor 16 through a second water outlet pump 15.
The anaerobic hydrogen production reactor 16 takes residual activated sludge of a sewage plant as a filler, and is firstly heated at 70 ℃ for 0.5h and then added into the anaerobic hydrogen production reactor 16, so that methane bacteria are killed, the sludge VSS is 6-8g/L, and the volume ratio of mud to water is 1: 2.5-4.5. Stirring for 20min by a third stirrer 19 every 1 hour after water inflow, wherein when the hydraulic retention time is 12 hours, the operation period comprises: water is fed for 0.5h, reaction is carried out for 10h, precipitation is carried out for 1h, water is discharged for 0.5h, and water is fed again after water discharge. After the operation is carried out for 30 days in the way, the sterilized pig farm wastewater is used as a culture medium, and hydrogen production dominant bacteria species are separated from the anaerobic activated sludge in the anaerobic hydrogen production reactor 16 under strict anaerobic conditions to obtain hydrogen production dominant bacteria species MH-1 and MH-2. Using under strict anaerobic conditionPerforming enrichment culture on MH-1 and MH-2 at pH 5.0 with the waste water of pig farm containing 0.5% glycerol after bacteria cultivation, wherein each milliliter of enrichment culture solution contains 1 × 1017-1025After MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor 16 are added into the anaerobic hydrogen production reactor 16 again according to the volume ratio of 1:1 of muddy water. After mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating for 4-6 times, and increasing the water inlet volume ratio to 1: 2.5; the process mode improves the hydrogen production efficiency of the reactor by more than 40 percent.
the conical part at the top end of the anaerobic hydrogen production reactor 16 is a gas collection chamber, hydrogen and carbon dioxide gas generated by the anaerobic hydrogen production reactor 16 uniformly enter the absorption tower 20 from a gas distribution pipe 21 at the bottom of the absorption tower 20 through a first pipeline 17 and a gas booster pump 18, the pH value of liquid entering the absorption tower from a water distribution pipe 31 is adjusted to be more than 8.5 through an alkali adding pipe 24 and an alkali liquor valve 25 so as to absorb the carbon dioxide in the gas, and effluent at the bottom of the absorption tower 20 is sent to an aerobic biochemical pool 30 through a fourth water outlet pump 32. Carbon dioxide generated in the anaerobic process is used as a carbon source of nitrifying bacteria in the aerobic treatment stage, and simultaneously, the alkalinity required by the ammonia nitrogen nitration reaction in the aerobic tank 30 is supplemented, so that the carbon emission of the large-scale pig farm can be effectively reduced by more than 80%. The purified hydrogen gas enters a gas collecting bag 27 through a second pipe 26 at the top of the absorption tower 20.
The effluent of the anaerobic hydrogen production reactor 16 enters an aerobic biochemical pool 30 through a third effluent pump 28, the activated sludge MLSS in the aerobic biochemical pool 30 is 3000-7000mg/L, and the hydraulic retention time is 4-6 h. The effluent of the aerobic biochemical tank 30 enters a mixing sedimentation tank 35 through a fifth effluent pump 34, a phosphorus removing agent is added through a dosing pipe 36, and the phosphorus removing agent is uniformly mixed by utilizing the hydraulic self-turbulence effect to remove soluble phosphorus in the water. The dephosphorizing agent adopts saturated solution of aluminum sulfate, aluminum trichloride or ferric trichloride, and the hydraulic retention time of the mixed settling tank is 2-3 h.
The sludge settled at the bottom of the mixed sedimentation tank 35 returns to the aerobic biochemical tank 30 through a sludge discharge valve 37, a third pipeline 38 and a second valve 39, and passes through the sludge discharge valve 37The third pipeline 38 and the third valve 40 are returned to the anaerobic hydrogen production reactor 16, so that the discharge amount of residual activated sludge can be reduced. The effluent of the mixing sedimentation tank 35 enters a disinfection tank 42 through a sixth effluent pump 41, and the bottom of the disinfection tank 42 is provided with O3Valve 43, UV disinfection lamp 44 arranged in the tank, with O3And sterilizing by cooperating with ultraviolet rays, wherein a part of the effluent at the top of the sterilizing tank 42 is discharged for later use through the discharge pipe 29, and a part of the effluent enters the water distribution pipe 31 through the fourth valve 9 and the fourth pipeline 33 for recycling.
The first embodiment is as follows:
3000 large-scale piggery wastewater in a certain city in Guangdong province is taken as an implementation object, a piggery is implemented in a dry manure cleaning mode, and the COD (chemical oxygen demand) of the wastewater for flushing the piggery is 1470mg/L and the ammonia nitrogen is 270 mg/L. The wastewater is gathered to a grid channel 1 through a drainage ditch and a sewage pipeline, the floating feed, excrement and other granular impurities are removed through a grid 2, the wastewater enters an MAP sedimentation tank 3, after the water inlet amount reaches half of the tank volume, a first stirrer 5 is started, and the rotating speed is controlled to be 210 rpm.
In the MAP precipitation tank 3, industrial MgCl is respectively added through a magnesium salt adding pipe 4 and a phosphate salt adding pipe 62And Na3PO4The saturated solution, the solvent water for preparing the saturated solution of magnesium salt and phosphorus salt comes from the top of the disinfection tank 42 to discharge water, thus saving the consumption of fresh water and reducing the total amount of discharged wastewater. According to the total amount of the wastewater, NH in the medicament and the wastewater of the pig farm is controlled4 +The molar ratio of N to P to Mg is 1:0.8:0.8, the rotation speed of the first stirrer 5 is adjusted to 140rpm after water feeding and medicine adding are finished, and stirring is continued for 15 min. The MAP reaction settling tank 3 is operated intermittently. The precipitate that produces after the chemical reaction is white, gets into sediment recovery unit 8 through bottom first valve 7, and MAP recovery unit 8 adopts the chinese patent "a device that carries out guanite resource recovery to waste water nitrogen phosphorus" (application number 201420458242.0), obtains the MAP precipitate after the dehydration drying, and magnesium ammonium phosphate content is higher than 85%.
The supernatant of the MAP sedimentation tank 3 enters a wastewater adjusting tank 11 through a first water outlet pump 10, and enters an anaerobic hydrogen production reactor 16 through a second water outlet pump 15 after the pH value of the wastewater is adjusted to 4.0 by adding hydrochloric acid through an acid adding pipe 14 under the stirring of a second stirrer 13. Anaerobic productThe hydrogen reactor 16 takes residual activated sludge of a sewage plant of a certain petrochemical enterprise as a filler, the residual activated sludge is heated at 70 ℃ for 0.5h and then is added into an anaerobic hydrogen production reactor 16, the inoculated sludge VSS is 6.3g/L, the volume ratio of the sludge to the water is 1:2.9, the anaerobic hydrogen production reactor 16 is stirred for 20min by a third stirrer 19 every 1 hour after water enters, the hydraulic retention time is 12h, and the operation period comprises: water is fed for 0.5h, reaction is carried out for 10h, precipitation is carried out for 1h, water is discharged for 0.5h, and water is fed again after water discharge. After the operation is carried out for 30 days in the way, the sterilized pig farm wastewater is used as a culture medium, and hydrogen production dominant bacteria species are separated from the anaerobic activated sludge in the anaerobic hydrogen production reactor 16 under strict anaerobic conditions to obtain hydrogen production dominant bacteria species MH-1 and MH-2. Performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1025After MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor 16 are added into the anaerobic hydrogen production reactor 16 again according to the volume ratio of 1:1 of muddy water. After mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating the steps for 4 times, increasing the volume ratio of the water inlet to be 1:2, stirring every 1 hour, standing the reactor after 48 hours, and discharging the supernatant. Repeating the steps for 4 times, increasing the volume ratio of the water inlet to be 1:2.5, stirring every 1 hour, standing the reactor after 48 hours, and discharging the supernatant. Gas generated by the anaerobic hydrogen generating reactor 16 enters the absorption tower 20 through the first pipeline 17, the gas booster pump 18 and the gas distribution pipe 21, and then NaOH saturated solution is added through the alkali adding pipe 24 and the alkali liquor valve 25 to adjust the pH value of liquid entering the tower from the water distribution pipe 31 to 9, so that the hydrogen concentration is 93%. The quality of anaerobic effluent water is COD 620.3mg/L, ammonia nitrogen 131 mg/L and soluble phosphorus 23.1 mg/L.
The effluent of the anaerobic hydrogen production reactor 16 enters an aerobic biochemical pool 30 through a third effluent pump 28 and a carbon dioxide absorption liquid at the bottom of the absorption tower 20 through a fourth effluent pump 32, the activated sludge MLSS is 3400mg/L, and the hydraulic retention time is 4 hours. The pH value of the effluent is 6.5, the COD52.3mg/L, the ammonia nitrogen is 7.1 mg/L, and the soluble phosphorus is 16.3 mg/L. The effluent of the aerobic biochemical tank 30 passes through a fifth water outletAnd the effluent pump 34 enters a mixed sedimentation tank 35, industrial aluminum sulfate saturated solution is added through a dosing pipe 36 to remove soluble phosphorus in water, and the hydraulic retention time of the mixed sedimentation tank 35 is 2.5 hours. The sludge settled at the bottom of the mixed settling tank 35 returns to the aerobic biochemical tank 30 through a sludge discharge valve 37, a third pipeline 38 and a second valve 39, and returns to the anaerobic hydrogen production reactor 16 through the sludge discharge valve 37, the third pipeline 38 and a third valve 40. The effluent of the mixing sedimentation tank 35 enters a disinfection tank 42 through a sixth effluent pump 41, and O arranged at the bottom of the disinfection tank 42 is utilized3Valve 43 and in-tank UV sterilizing lamp 44 to produce O3and ultraviolet rays are matched for disinfection and sterilization, part of effluent at the top of the disinfection tank 42 is recycled for standby through a discharge pipe 45 and another valve and is used as solvent water for preparing saturated solution of magnesium salt and phosphorus salt and solvent water for preparing saturated solution of aluminum sulfate, and part of effluent is directly recycled as absorption liquid through a fourth valve 9, a fourth pipeline 33 and a water distribution pipe 31. The effluent quality is COD33.0mg/L, ammonia nitrogen 3.5 mg/L, and soluble phosphorus 0.6 mg/L.
Example two:
1000 large-scale piggery wastewater in a certain city in Guangdong province is taken as an implementation object, a piggery is implemented in a dry manure cleaning mode, the wastewater for washing the piggery is collected to a grating channel 1 through a drainage ditch and a sewage pipeline, granular impurities such as floating or large feed, excrement and the like are removed through a grating 2, the wastewater enters an MAP sedimentation tank 3, after the water inlet amount reaches half of the tank volume, a first stirrer 5 is started, the rotating speed is controlled to be 300rpm, and the wastewater quality is COD1501mg/L, ammonia nitrogen 243 mg/L and soluble phosphorus 63 mg/L.
In the MAP precipitation tank 3, industrial MgCl is respectively added through a magnesium salt adding pipe 4 and a phosphate salt adding pipe 62And Na3PO4The saturated solution, the solvent water for preparing the saturated solution of magnesium salt and phosphorus salt comes from the top of the disinfection tank 42 to discharge water, thus saving the consumption of fresh water and reducing the total amount of discharged wastewater. According to the total amount of the wastewater, NH in the medicament and the wastewater of the pig farm is controlled4 +The molar ratio of N to P to Mg is 1:0.8:0.8, the rotation speed of the first stirrer 5 is adjusted to 200rpm after water feeding and medicine adding are finished, and stirring is continued for 10 min. The MAP reaction settling tank 3 is operated intermittently. The precipitate produced after the chemical reaction is white and enters through the first valve 7 at the bottomThe precipitation recovery device 8 and the MAP recovery device 8 adopt Chinese patent 'a device for recycling struvite from wastewater nitrogen and phosphorus' (application number 201420458242.0), and MAP precipitates 9 are obtained after dehydration and drying, and the content of magnesium ammonium phosphate is higher than 87%.
And the supernatant of the MAP sedimentation tank 3 enters a wastewater adjusting tank 11 through a first water outlet pump 10, and enters an anaerobic hydrogen production reactor 16 through a second water outlet pump 15 after the pH value of the wastewater is adjusted to 3.5 by adding hydrochloric acid through an acid adding pipe 14 under the stirring of a second stirrer 13. The anaerobic hydrogen production reactor 16 takes residual activated sludge of a sewage plant of a petrochemical enterprise as a filler, the residual activated sludge is heated for 0.5h at 70 ℃, then the residual activated sludge is added into the reactor, methane bacteria are killed, hydrogen production microorganisms are obtained, the sludge VSS is inoculated to be 6.51g/L, the volume ratio of sludge to water is 1:2.8-3.0, the anaerobic hydrogen production reactor 16 is stirred for 20min by a third stirrer 19 every 1 hour after water enters, the hydraulic retention time is 12h, and the operation period comprises the following steps: water is fed for 0.5h, reaction is carried out for 10h, precipitation is carried out for 1h, water is discharged for 0.5h, and water is fed again after water discharge. After the operation is carried out for 30 days in the way, the sterilized pig farm wastewater is used as a culture medium, and hydrogen production dominant bacteria species are separated from the anaerobic activated sludge in the anaerobic hydrogen production reactor 16 under strict anaerobic conditions to obtain hydrogen production dominant bacteria species MH-1 and MH-2. Performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1020After MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor 16 are added into the reactor 16 again according to the volume ratio of 1:1 of muddy water. After mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating the steps for 4 times, increasing the volume ratio of the water inlet to be 1:2, stirring every 1 hour, standing the reactor after 48 hours, and discharging the supernatant. Repeating the steps for 4 times, increasing the volume ratio of the water inlet to be 1:2.5, stirring every 1 hour, standing the reactor after 48 hours, and discharging the supernatant. Gas generated by the anaerobic hydrogen generating reactor 16 enters an absorption tower 20 through a first pipeline 17, a gas booster pump 18 and a gas distribution pipe 21, and then is added through an alkali adding pipe 24 and an alkali liquor valve 25and adding NaOH saturated solution to adjust the pH value of liquid entering the tower from the water distribution pipe 31 to 9 to obtain the hydrogen with the concentration of 90%. The water quality of the effluent of the anaerobic hydrogen production reactor 16 is COD770mg/L, ammonia nitrogen 125 mg/L and soluble phosphorus 27 mg/L.
The effluent of the anaerobic hydrogen production reactor 16 enters an aerobic biochemical pool 30 through a third effluent pump 28 and the effluent at the bottom of the absorption tower 20 through a fourth effluent pump 32, the MLSS of the activated sludge is 3400mg/L, and the hydraulic retention time is 4 hours. The pH value of effluent is 6.3, the COD43.8mg/L, the ammonia nitrogen is 5.2 mg/L, and the soluble phosphorus is 18.3 mg/L. The effluent of the aerobic biochemical tank 30 enters a mixed sedimentation tank 35 through a fifth effluent pump 34, and industrial aluminum sulfate saturated solution is added through a dosing pipe 36 on the mixed sedimentation tank 35 to remove soluble phosphorus in the water. The hydraulic retention time of the mixed sedimentation tank 35 is 2.5h, the settled sludge at the bottom of the mixed sedimentation tank 35 flows back to the aerobic biochemical tank 30 through a sludge discharge valve 37, a third pipeline 38 and a second valve 39, and flows back to the anaerobic hydrogen production reactor 16 through the sludge discharge valve 37, the third pipeline 38 and a third valve 40. The effluent of the mixing sedimentation tank 35 enters a disinfection tank 42 through a sixth effluent pump 41, and O arranged at the bottom of the disinfection tank 42 is utilized3Valve 43 and in-tank UV sterilizing lamp 44 to produce O3and ultraviolet rays are matched for disinfection and sterilization, part of effluent at the top of the disinfection tank 42 is recycled for standby through a discharge pipe 45 and another valve and is used as solvent water for preparing saturated solution of magnesium salt and phosphorus salt and solvent water for preparing saturated solution of aluminum sulfate, and part of effluent is directly recycled as absorption liquid through a fourth valve 9, a fourth pipeline 33 and a water distribution pipe 31. The effluent quality is COD28.2mg/L, ammonia nitrogen 3.1 mg/L, and soluble phosphorus 0.7 mg/L.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. a method for treating wastewater in a pig farm by anaerobic hydrogen production and recycling is characterized by comprising the following steps:
(1) The pig farm washing wastewater enters an MAP sedimentation tank for pretreatment after passing through a grating, sediment after sedimentation is discharged and recovered from the bottom of the MAP sedimentation tank, and supernatant after sedimentation is sent to a wastewater adjusting tank;
(2) adjusting the pH value of the supernatant in the wastewater adjusting tank to 3.5-4.0, then feeding the supernatant into an anaerobic hydrogen production reactor, wherein the anaerobic hydrogen production reactor takes residual activated sludge of a sewage plant as a filler and VSS (VSS) 6-8g/L, adding the supernatant into the anaerobic hydrogen production reactor after heating pretreatment for 0.5h at 70 ℃, the volume ratio of mud to water is 1:2.5-4.5, stirring for 20min every 1 hour after water enters, and when the hydraulic retention time is 12h, the operation period comprises: feeding water for 0.5h, reacting for 10h, precipitating for 1h and discharging water for 0.5h, and feeding water again after discharging water, wherein the operation is carried out for 30 days in the way;
(3) Taking the sterilized pig farm wastewater as a culture medium, performing hydrogen production dominant bacteria separation on anaerobic activated sludge in an anaerobic hydrogen production reactor under strict anaerobic conditions to obtain hydrogen production dominant bacteria MH-1 and MH-2, performing enrichment culture on the MH-1 and MH-2 at the pH value of 5.0 by using the sterilized pig farm wastewater containing 0.5 percent of glycerol under the strict anaerobic conditions, and when each milliliter of enrichment culture solution contains 1 multiplied by 10 respectively17-1025After MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor are added into the anaerobic hydrogen production reactor again according to the volume ratio of 1:1 of muddy water; mixing with anaerobic sludge, stirring at intervals of 1 hour within 48 hours without water, standing the reactor after 48 hours, discharging supernatant, feeding wastewater into a pig farm according to the volume ratio of 1:1.5 of sludge to water, repeating the operation, and discharging supernatant after 48 hours; repeating for 4-6 times, and increasing the water inlet volume ratio to 1: 2.5;
(4) hydrogen and carbon dioxide gas generated by the anaerobic hydrogen generating reactor are sent into an absorption tower, and after being absorbed by alkaline absorption liquid, the purified hydrogen enters an air collecting bag;
(5) Feeding fermentation liquor discharged by an anaerobic hydrogen production reactor into an aerobic biochemical pool, feeding effluent from the bottom of an absorption tower into the aerobic biochemical pool, feeding effluent from the aerobic biochemical pool into a mixed sedimentation pool, adding a phosphorus removing agent into the water in the mixed sedimentation pool to remove soluble phosphorus in the water, feeding the water into a disinfection pool, performing disinfection and sterilization treatment to obtain recycled water, and respectively refluxing precipitated sludge at the bottom of the mixed sedimentation pool into the aerobic biochemical pool and the anaerobic hydrogen production reactor;
Wherein, in the step (1), the pretreatment is carried out by adopting the following method: after the water feeding amount reaches half of the volume of the MAP sedimentation tank, stirring, controlling the rotating speed to be 150-350rpm, adding magnesium salt and phosphorus salt, after water feeding and medicine feeding are finished, continuing stirring for 10-15min, and adjusting the rotating speed to be two thirds of the original rotating speed; the magnesium salt is MgCl which is chemically pure, analytically pure or used industrially2、MgSO4And MgO, which is prepared into a saturated solution or a solution with any concentration before being added, wherein the phosphorus salt is NaH which is chemically pure, analytically pure or industrially used2PO4、Na2HPO4、Na3PO4、KH2PO4 、K2HPO4And H3PO4The one of the two solutions is prepared into a saturated solution or a solution with any concentration before adding, the adding amount of the magnesium salt solution and the phosphorus salt solution is controlled to be 1.0-1.3:1 in terms of the molar ratio of the magnesium salt to the phosphorus salt, and the amount of the phosphorus salt is controlled to be equal to NH in the pig farm wastewater4 +The molar ratio of-N is 0.6-0.8: 1.
2. The method for treating the wastewater in the pig farm by the anaerobic hydrogen production and the recycling according to claim 1, wherein in the step (2), industrial sulfuric acid or hydrochloric acid is used for adjusting the pH of the supernatant.
3. The method for treating the wastewater in the pig farm by the anaerobic hydrogen production and the recycling according to claim 1, wherein in the step (4), the pH value of the alkaline absorption solution is more than 8.5.
4. The method for the treatment of the wastewater in the pig farm for the anaerobic hydrogen production and the recycling according to claim 1, wherein in the step (5), the activated sludge MLSS in the aerobic biochemical tank is 3000-7000mg/L, and the hydraulic retention time is 4-6 h.
5. The method for the treatment of the pig farm wastewater through the anaerobic hydrogen production and the recycling of the wastewater as claimed in claim 1, wherein in the step (5), the dephosphorizing agent adopts saturated solution of aluminum sulfate, aluminum trichloride or ferric trichloride, and the hydraulic retention time of the mixing and settling tank is 2-3 h.
6. The method for the treatment of the wastewater in the pig farm for the anaerobic hydrogen production and the recycling according to claim 1, wherein in the step (5), O is adopted for the disinfection and sterilization in the disinfection tank3And ultraviolet rays.
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| CN203007087U (en) * | 2012-11-28 | 2013-06-19 | 广东石油化工学院 | Pig-raising wastewater treatment system |
| CN105000766A (en) * | 2015-08-12 | 2015-10-28 | 广东石油化工学院 | Cleaner production method for increasing nitrogen and phosphorus recovery rate of residual activated sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN203007087U (en) * | 2012-11-28 | 2013-06-19 | 广东石油化工学院 | Pig-raising wastewater treatment system |
| CN105000766A (en) * | 2015-08-12 | 2015-10-28 | 广东石油化工学院 | Cleaner production method for increasing nitrogen and phosphorus recovery rate of residual activated sludge |
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Application publication date: 20191213 |
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