CN112830652B - Method for preparing water-soluble fertilizer by comprehensively treating excrement, urine and sewage of large-scale livestock and poultry farm - Google Patents
Method for preparing water-soluble fertilizer by comprehensively treating excrement, urine and sewage of large-scale livestock and poultry farm Download PDFInfo
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- CN112830652B CN112830652B CN202011633673.2A CN202011633673A CN112830652B CN 112830652 B CN112830652 B CN 112830652B CN 202011633673 A CN202011633673 A CN 202011633673A CN 112830652 B CN112830652 B CN 112830652B
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 51
- 244000144972 livestock Species 0.000 title claims abstract description 50
- 244000144977 poultry Species 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 46
- 210000002700 urine Anatomy 0.000 title claims abstract description 28
- 239000010865 sewage Substances 0.000 title claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 46
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 45
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000005189 flocculation Methods 0.000 claims abstract description 38
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- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 29
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- 238000000855 fermentation Methods 0.000 claims abstract description 23
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004021 humic acid Substances 0.000 claims abstract description 21
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- 231100000719 pollutant Toxicity 0.000 claims description 7
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- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005728 strengthening Methods 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- 125000000101 thioether group Chemical group 0.000 claims 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- -1 arsenic acid compound Chemical class 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 description 1
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Images
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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
-
- 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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F3/00—Fertilisers from human or animal excrements, e.g. manure
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
-
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Abstract
The invention relates to a method for preparing a water soluble fertilizer by comprehensively treating feces and urine sewage of a large-scale livestock and poultry farm, which comprises the steps of carrying out anaerobic fermentation on the feces and urine of the livestock and poultry farm and flushing water, then filtering fermentation biogas slurry, drying filter residues to obtain a solid organic fertilizer, adding a chemical precipitator to remove heavy metals in filtrate, adding a flocculating agent into suspension for flocculation and sedimentation after complete reaction, carrying out centrifugal filtration on a flocculating body, combining the filtrate with supernatant of the flocculation and sedimentation, adding a composite adsorbent to remove organic arsenic, filtering feed liquid, carrying out microfiltration on the filtrate by using a ceramic membrane to remove colloidal particles and proteins, carrying out reverse osmosis concentration on microfiltration permeate liquid, taking the obtained concentrated liquid as a raw material for preparing a liquid fertilizer, adding a large amount of elements and humic acid into the reverse osmosis concentrated liquid, and preparing the liquid water soluble fertilizer meeting the national standard, wherein the reverse osmosis effluent reaches the discharge standard specified by the country. The process realizes the comprehensive treatment and recycling of the excrement and urine sewage of the livestock and poultry farm, and does not cause environmental pollution.
Description
Technical Field
The invention belongs to the field of treatment of excrement and urine sewage of livestock and poultry farms and production of liquid fertilizers, and particularly relates to a method for preparing a water-soluble fertilizer by comprehensively treating the excrement and urine sewage of the large-scale livestock and poultry farms.
Background
In order to solve the problem of environmental pollution caused by waste water and solid waste in livestock farms, researchers have been exploring methods for treating feces and urine in livestock farms. At present, the biogas engineering technology plays a core role in the ecological treatment, reduction treatment, energy regeneration and resource utilization of excrement in large-scale livestock and poultry farms, and is a main process for treating livestock and poultry breeding wastewater in China, but the method has the problem that a large amount of sewage and excrement residues generated after fermenting excrement and urine cannot be treated and utilized. In order to solve the problem of biogas slurry wastewater generated by anaerobic fermentation which does not reach the national discharge standard, the current common method is to concentrate and enrich anaerobic fermentation liquid by using a membrane separation technology. Such as a biogas slurry precise filtering device and a filtering method (CN 102258900A), a method for recycling a biogas slurry multi-component whole process (CN 102795725A), a method for separating the effective components of biological medical fertilizers from biogas slurry (CN 101269999A), a method for treating and recycling biogas slurry (CN 105692962A), a device and a method for ecologically treating biogas slurry as a livestock and poultry breeding pollutant (CN 101343134A), a method for recycling nutrients from wastewater of a multi-stage filtering pig farm (CN 103708678A), a multi-stage filtering device for recycling nutrients from wastewater of a livestock and poultry farm (CN 103723846A) and the like. The method is basically characterized in that anaerobic fermentation biogas slurry is concentrated by membrane separation technologies such as precise filtration, ultrafiltration, nanofiltration and reverse osmosis, and the obtained concentrated solution and waste residues can be used as organic fertilizers or biological medicine fertilizers. From the existing report of 'livestock and poultry anaerobic fermentation biogas slurry treatment method', the biogas slurry can be concentrated by adopting a membrane separation method, but due to the reasons of feeding environment and feed, the heavy metal content in domestic livestock and poultry anaerobic fermentation biogas slurry is high, most of the ecological risk indexes of mercury content in biogas slurry in different areas reach medium or strong ecological hazards, and most of the heavy metal content of arsenic, copper, chromium, lead and the like reach slight or medium ecological hazards (the biogas slurry component analysis and risk evaluation of household biogas slurry of biogas tanks from different sources, the chemical industry report, vol 65, no. 5 in 2014). The existing 'livestock and poultry anaerobic fermentation biogas slurry treatment method' concentrates biogas slurry through membrane separation, heavy metal elements, inorganic arsenic and organic arsenic cannot be removed, the content of heavy metal and arsenic in concentrated solution is higher, serious environmental problems exist when the concentrated solution is used as an organic fertilizer or a biological medicine fertilizer, and the limit indexes specified in 'limit requirements of NY 1110-2010 water-soluble fertilizers of mercury, arsenic, cadmium, lead and chromium' are difficult to achieve. In addition, colloidal particles and proteins contained in the anaerobic fermentation biogas slurry for livestock and poultry can be separated out from the biogas slurry in the concentration process of membrane separation to block membrane pores of an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, and the membrane pores are difficult to dredge thoroughly by water backwashing, so that the service life of the membrane and the stable operation of the device are seriously influenced.
Chinese patent CN105692962A discloses a method for biogas slurry treatment and resource utilization, the whole process route is: the effluent of the biogas slurry after secondary anaerobic digestion sequentially passes through: flocculation precipitation (removing residual solid matters in secondary anaerobic biogas slurry and further reducing COD concentration), fine filtration treatment (quartz sand, activated carbon, diatomite or fiber filter material, further removing residual solid matters in biogas slurry and avoiding or lightening subsequent ultrafiltration membrane blockage), ultrafiltration treatment (intercepting colloid, protein, microorganism and macromolecular organic matters with the particle size of more than 0.002-0.1 micrometer), reverse osmosis treatment (intercepting small molecular substances and soluble salts, namely ammonia nitrogen, phosphorus, potassium and the like contained in biogas slurry).
The processing sequence of patent CN105692962A is as follows: removing residual solid matters in the secondary anaerobic biogas slurry, (2) further removing the residual solid matters in the biogas slurry, (3) intercepting colloid, protein, microorganism and macromolecular organic matters with the particle size of more than 0.002-0.1 micron, and (4) intercepting small molecular substances and soluble salts. Because the patent treatment object is waste water obtained after the kitchen waste is smashed, pulped and filtered, common kitchen waste does not relate to heavy metals, so the patent does not relate to heavy metals, and does not relate to the problem of how to avoid the enrichment of heavy metals in the ultrafiltration and reverse osmosis treatment processes.
The heavy metal content of the livestock and poultry farm manure biogas slurry is high, and the problem of removing heavy metal elements needs to be considered in the treatment process.
Chinese patent CN107311702A discloses a method for preparing liquid fertilizer by comprehensively treating and recycling feces, urine and biogas slurry of livestock and poultry farms, which comprises anaerobic fermentation of feces, urine and washing water of livestock and poultry farms, filtering the fermented biogas slurry, drying filter residues to obtain solid organic fertilizer, subjecting the filtrate to flocculation and sedimentation, subjecting the flocculent to centrifugal filtration, combining the filtrate with the supernatant of the flocculation and sedimentation, removing macromolecular proteins and colloidal particles by ceramic membrane microfiltration, subjecting the microfiltration filtrate to ultrafiltration to remove middle and small molecular weight proteins, subjecting the ultrafiltration filtrate to reverse osmosis filtration, and adding a large amount of elements and humic acid into the reverse osmosis concentrated solution to obtain liquid fertilizer meeting national standards, wherein the reverse osmosis effluent meets the discharge standards specified by the country.
The technical proposal of patent CN107311702A removes most heavy metals, colloidal particles and macromolecular proteins in the original biogas slurry through flocculation and ceramic membrane filtration, and then enrichment in the ultrafiltration and reverse osmosis treatment process is avoided.
However, in the patent CN107311702A, flocculation sedimentation is used to remove heavy metal ions and organic arsenic, but the flocculation sedimentation has limited ability to remove heavy metal ions and organic arsenic, and in addition, in the patent CN107311702A, ultrafiltration is used to remove proteins with small and medium molecular weight before reverse osmosis.
Disclosure of Invention
The invention aims to provide a method for preparing a water-soluble fertilizer by comprehensively treating excrement, urine and sewage of a large-scale livestock and poultry farm so as to overcome the defects of the conventional livestock and poultry anaerobic fermentation biogas slurry treatment method.
The invention utilizes the process of combining chemical precipitation, flocculation, adsorption and solid-film separation to treat the excrement and urine sewage of the livestock and poultry farm and prepares the water-soluble fertilizer.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for preparing a water-soluble fertilizer by comprehensively treating excrement, urine and sewage of a large-scale livestock and poultry farm: anaerobic fermentation is carried out on excrement and urine and flushing water of a livestock and poultry farm, then fermentation biogas slurry is filtered, filter residues are dried to serve as solid organic fertilizers, chemical precipitator is added into filtrate to remove heavy metals, flocculating agent is added into suspension after complete reaction to carry out flocculating settling, flocculating agent is centrifugally filtered, the filtrate is combined with supernatant after flocculating settling, composite adsorbent is added to remove organic arsenic, after feed liquid is filtered, colloidal particles and protein are removed from the filtrate through microfiltration of a ceramic membrane, microfiltration permeate liquid is finally subjected to reverse osmosis concentration, obtained concentrated solution is used as raw materials for preparing liquid fertilizers, a proper amount of macroelements and humic acid are added into the reverse osmosis concentrated solution, liquid water-soluble fertilizers meeting national standards are prepared, and reverse osmosis effluent reaches the discharge standards specified by the state.
In one embodiment of the invention, the method for preparing the water soluble fertilizer by comprehensively treating the excrement, urine and sewage of the large-scale livestock and poultry farm comprises the following steps:
(1) Anaerobic fermentation treatment of a large-scale livestock and poultry farm: mixing excrement and urine of a large-scale livestock and poultry farm and flushing water, feeding the mixture into an anaerobic fermentation tank, filtering fermented biogas slurry, and removing heavy metals from filtrate through chemical sedimentation;
(2) Settling heavy metal removal treatment: adding a chemical precipitator into the biogas slurry filtrate obtained in the step (1) under the stirring condition, stirring for a certain time to ensure that the precipitation reaction is complete, and then performing flocculation treatment;
(3) Flocculation treatment: adding a composite flocculant into the reaction suspension obtained in the step (2) under the condition of stirring, stopping stirring after stirring for a certain time for flocculation and sedimentation, and combining the filtrate and flocculation supernatant after filtering a flocculating body to remove the organic arsenic by adsorption;
(4) And (3) adsorption organic arsenic removal treatment: adding a composite adsorbent into the filtrate obtained in the step (3) and the flocculated supernatant under the stirring condition, stirring for a certain time, stopping stirring, filtering, and removing the filtrate by ceramic membrane microfiltration;
(5) Microfiltration by a ceramic membrane: microfiltering the flocculated and settled filtrate and supernatant through a ceramic membrane to remove colloidal particles and proteins;
(6) Reverse osmosis: performing reverse osmosis concentration on the filtrate obtained by ceramic membrane treatment, wherein the concentrated solution is used as a liquid fertilizer raw material, and the reverse osmosis effluent reaches the discharge standard of livestock and poultry breeding pollutant of the people's republic of China (GB 18596-2001) and can be used as flushing water of membrane device equipment and flushing water of livestock and poultry farms;
(7) Preparing a liquid fertilizer: adding macroelements and humic acid into the reverse osmosis concentrated solution to prepare a water-soluble fertilizer with the standard NY1106-2010 humic acid-containing water-soluble fertilizer.
In one embodiment of the invention, the filtering equipment for filtering the fermented biogas slurry is a centrifugal filter or a plate and frame filter.
In one embodiment of the invention, the chemical precipitator used is sulfide, and the addition amount is 3 to 5 times of the total molar weight of heavy metals in the raw material liquid; the sulfide is selected from water-soluble sulfur salt or phosphorus pentasulfide. Because the effect of removing heavy metals by flocculation or adsorption is not good, the heavy metals are removed by adding sulfides, and the sulfides can form insoluble sulfide precipitates with heavy metal ions such as mercury, cadmium, lead, chromium and the like so as to deeply remove the heavy metals in the feed liquid.
In one embodiment of the invention, the reaction conditions for removing heavy metals by adding the chemical precipitator into the filtrate are as follows: stirring and reacting for 15-30 minutes at normal temperature.
In one embodiment of the invention, the flocculant added in the flocculation sedimentation process is a composite flocculant, the composite flocculant comprises a main flocculant and a coagulant aid, the main flocculant is a polyferric flocculant, the coagulant aid is polyacrylamide or a derivative thereof, the addition amount of the main flocculant is 0.05-0.5% of the mass of the raw material liquid, and the addition amount of the coagulant aid is 0.003-0.01% of the mass of the raw material liquid. The flocculant adopts a compounding and combining mode of the polyferric flocculant and polyacrylamide or derivatives thereof, iron atoms in the polyferric flocculant can form a complex with organic arsenic acid compounds with larger polarity such as arsanilic acid and the like, the organic arsenic acid compounds can be removed while colloid particles, heavy metal sulfide precipitate particles and macromolecular protein are removed by flocculation, and the polyamide coagulant aid has flocculation and flocculating constituent sedimentation strengthening effects. Therefore, the polyferric flocculant and the polyacrylamide or the derivative thereof have better composite use effect.
In one embodiment of the invention, the polyferric flocculant is selected from the group consisting of polymeric ferric sulfate, polymeric ferric phosphate or polymeric ferric chloride.
In one embodiment of the invention, the conditions for adding the flocculant to perform flocculation and sedimentation are as follows: and after the flocculant is added, continuously stirring for 3-5 minutes, and standing the feed liquid for 3-8 hours after stopping stirring. Then discharging the supernatant, centrifugally filtering the settled floccule, combining the filtrate and the supernatant, and removing the organic arsenic by adsorption.
In one embodiment of the invention, the filtration apparatus used for the flocculent centrifugal filtration is a tubular centrifuge, a disk centrifuge or a horizontal screw centrifuge.
In one embodiment of the invention, the composite adsorbent is a mixture of activated carbon and activated clay, the mass ratio of the activated carbon to the activated clay is 1. In the invention, the composite adsorbent is mainly used for adsorbing the low-polarity organic arsenic compound and the small molecular protein.
In one embodiment of the present invention, after the composite adsorbent is added, the stirring is continued for 30 to 60 minutes, and the filtration is performed after the stirring is stopped.
In one embodiment of the invention, after the composite adsorbent is added, the equipment used for filtering the feed liquid is a centrifugal filter or a plate and frame filter.
In one embodiment of the invention, the average pore diameter of the ceramic membrane is 50-200 nm, and the microfiltration pressure of the ceramic membrane is 0.1-1.0 MPa.
In one embodiment of the invention, in the reverse osmosis filtration process, the reverse osmosis operation pressure is 1.0MPa to 6.5MPa, the volume of the concentrated solution is 10 percent to 30 percent of that of the reverse osmosis feeding material, and the reverse osmosis effluent reaches the discharge standard of pollutants for livestock and poultry breeding industry specified in GB18596-2001 and can be used as membrane device flushing water and farm flushing water.
In one embodiment of the invention, the major elements added into the reverse osmosis concentrated solution are inorganic salts containing nitrogen, phosphorus and potassium, the added humic acid is water-soluble humic acid, the addition amount of the major elements and the humic acid is determined according to the content of the major elements and the humic acid in the reverse osmosis concentrated solution, and the finally obtained liquid water-soluble fertilizer meets the standard of 'NY 1106-2010 humic acid-containing water-soluble fertilizer'.
The invention adopts the anaerobic fermentation biogas slurry treatment process combining chemical precipitation, flocculation, adsorption and membrane separation technologies. After the fermented biogas slurry is filtered, the clear filtrate is subjected to chemical precipitation, flocculation, adsorption and ceramic membrane filtration, most heavy metals, organic arsenic, colloidal particles and protein in the original biogas slurry are removed, the filtrate after the ceramic membrane filtration is subjected to reverse osmosis concentration, the reverse osmosis effluent reaches the requirements specified in the livestock and poultry breeding pollutant discharge Standard (GB 18596-2001), the concentrated solution is used for preparing a water-soluble fertilizer, and the content of heavy metals in the concentrated solution can also meet the limit indexes specified in the limit requirements of mercury, arsenic, cadmium, lead and chromium of the NY 1110-2010 water-soluble fertilizer. Therefore, the process of the invention realizes the comprehensive treatment and recycling of the livestock and poultry farm excrement and urine sewage, does not cause environmental pollution, and the prepared water-soluble fertilizer meets the requirements of national relevant standards on products.
Compared with the prior art, the improvement and the technical effect of the invention are mainly reflected in that:
1. the method is used for researching the characteristics and components of the anaerobic biogas slurry of the large-scale livestock and poultry farm, and finds that the existing forms of arsenic in the anaerobic biogas slurry of the large-scale livestock and poultry farm mainly comprise organic arsenic acid compounds with larger polarity and organic arsenic compounds with weak polarity, and the existing forms of arsenic are generally not distinguished in the prior art for arsenic removal.
2. In the prior art, colloidal particles, macromolecular proteins, heavy metals and organic arsenic are generally removed by single flocculation sedimentation, and a single flocculant mainly removes impurities in feed liquid by utilizing the electrostatic action of a flocculating constituent, so that the single flocculant has a good effect of removing the colloidal particles and the macromolecular proteins, and has a limited effect of removing the heavy metals, particularly the organic arsenic. The composite flocculant for the application forms a complex by using iron atoms in the polyferric flocculant and an organic arsenic acid compound with larger polarity, and can remove the organic arsenic acid compound while removing colloidal particles, heavy metal sulfide precipitate particles and macromolecular protein by flocculation, the polyamide coagulant aid has flocculation and flocculating constituent sedimentation strengthening effects, and the polyamide coagulant aid are used in a compounding manner, so that the effect is far better than that of a single polyamide flocculant in the prior art.
3. The technical scheme of the patent CN107311702A is that heavy metal ions and organic arsenic are removed by flocculation precipitation, and then ceramic membrane filtration, ultrafiltration and reverse osmosis are carried out; and it gets rid of the heavy metal to be chemical precipitation in this application, recycles flocculation and precipitation and adsorbs the edulcoration dearsenification, then ceramic membrane micro-filtration, reverse osmosis, compares with it, and chemical precipitation desorption heavy metal effect is better, and because different raising environment and fodder difference, the heavy metal content difference of each district birds poultry farm fermentation is huge, and chemical precipitation desorption heavy metal has stronger adaptability to the heavy metal concentration of feed liquid. This patent adopts the flocculation and precipitation and adsorbs can effectively get rid of organic arsenic, and compound adsorbent when the organic arsenic compound of desorption weak polarity, adsorbs the organic matter of the micromolecular protein in the desorption feed liquid, can save the step that the micromolecular protein was taken off in the ultrafiltration, has better economic nature.
Drawings
FIG. 1 is a schematic diagram of a process flow of a method for preparing a water-soluble fertilizer by comprehensively treating excrement and urine sewage of a large-scale livestock and poultry farm.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
Example 1
A method for preparing a water-soluble fertilizer by comprehensively treating excrement, urine and sewage of a large-scale livestock and poultry farm comprises the following steps:
(1) Anaerobic fermentation treatment of large-scale livestock and poultry farms: mixing excrement and urine and flushing water of a large-scale livestock and poultry farm, feeding the mixture into an anaerobic fermentation tank, filtering fermented biogas slurry by using a plate-and-frame filter after fermentation is finished, drying filter residues, returning organic fertilizers to fields, removing sediments and heavy metal from filter liquor, and forming a typical batch of filter liquor: COD7830mg/L, ammonia nitrogen concentration 3520mg/L, total phosphorus 1052mg/L, total potassium 857mg/L, total mercury 0.56mg/L, total arsenic 0.89mg/L, total cadmium 0.67mg/L, total lead 0.06mg/L and total chromium 0.07mg/L;
(2) Settling heavy metal removal treatment: adding phosphorus pentasulfide into the biogas slurry filtrate obtained in the step (1) under the stirring condition, wherein the addition amount of the phosphorus pentasulfide is 5 times of the total molar amount of heavy metals in the filtrate, stirring for 20 minutes to complete the precipitation reaction, and then performing flocculation treatment;
(3) Flocculation treatment: adding polymeric ferric sulfate and polyacrylamide into the heavy metal removal reaction liquid obtained in the step (2) under the condition of stirring, wherein the addition amount of the polymeric ferric sulfate is 0.12% of the amount of the filter liquid, the addition amount of the polyacrylamide is 0.005% of the amount of the filter liquid, stirring for 3 minutes, stopping stirring for flocculation and sedimentation, settling for 5 hours, discharging supernatant, filtering the flocculating agent at the bottom of a sedimentation tank by using a disk centrifuge, and combining the filtrate and the flocculation supernatant for adsorption treatment;
(4) And (3) adsorption treatment: adding a composite adsorbent into the filtrate obtained in the step (3) and the flocculation supernatant under the stirring condition, wherein the addition amount is 0.35 percent of the mass of the feed liquid, the mass ratio of active carbon to activated clay in the composite adsorbent is 2, stirring is continued for 60 minutes after the adsorbent is added, the stirring is stopped, and the filtering is carried out by using a plate-and-frame filter, and the contents of heavy metal and arsenic in the filtrate are as follows: 0.014mg/L of total mercury, 0.039mg/L of total arsenic, 0.023mg/L of total cadmium, 0.016mg/L of total lead and 0.032mg/L of total chromium, and removing ceramic membrane microfiltration from the filtrate;
(5) Microfiltration by using a ceramic membrane: filtering the organic arsenic and the supernatant in the filtrate obtained in the step (4) by a ceramic membrane with the average pore diameter of 50 nanometers, wherein the filtering operation pressure of the ceramic membrane is 0.1Mp a ～1.0Mp a . In the operating pressure range, when the filtration flux is sharply reduced, the ceramic membrane needs to be cleaned.
(6) Reverse osmosis: the filtrate obtained in the step (5) is at 0.6Mp a ～6.5Mp a And performing reverse osmosis concentration under the operating pressure until the concentration is 15% of the feeding amount, wherein the reverse osmosis effluent meets the requirements of the national people's republic of China' discharge Standard of pollutants for livestock and poultry Breeding (GB 18596-2001), and can be used as membrane device flushing water and farm flushing water.
(7) Preparing a liquid fertilizer: indexes of the reverse osmosis concentrated solution are as follows: 56.8g/L of ammonia nitrogen, 13.5g/L of total phosphorus, 11.5g/L of total potassium, 22.6mg/L of humic acid, 0.2mg/L of total mercury, 0.56mg/L of total arsenic, 0.3mg/L of total cadmium, 0.18mg/L of total lead and 0.5mg/L of total chromium. Heavy metal elements in the reverse osmosis concentrated solution reach the indexes specified in the limit requirements of mercury, arsenic, cadmium, lead and chromium of the NY 1110-2010 water-soluble fertilizer. And supplementing macroelements and water-soluble humic acid into the concentrated solution, and preparing the water-soluble fertilizer with the macroelement content of more than 200g/L and the humic acid content of more than 30g/L, so that the requirements specified in NY1106-2010 humic acid-containing water-soluble fertilizer are met.
The anaerobic fermentation biogas slurry treatment process combines chemical precipitation, flocculation and adsorption with a membrane separation technology. After the livestock and poultry fermented biogas slurry is filtered, the filtrate is subjected to chemical precipitation, flocculation, adsorption and ceramic membrane filtration, most heavy metals, proteins and colloidal particles in the original biogas slurry are removed, the filtrate after the ceramic membrane filtration is subjected to reverse osmosis concentration, the reverse osmosis effluent reaches the discharge standard of pollutants for livestock and poultry breeding in the people's republic of China, the concentrated solution is used for preparing an aqueous liquid fertilizer, and the content of heavy metals in the aqueous liquid fertilizer can meet the limit indexes specified in the limit requirements of mercury, arsenic, cadmium, lead and chromium of the NY 1110-2010 water soluble fertilizer. The process provided by the embodiment realizes comprehensive treatment and recycling of the excrement and urine sewage of the livestock and poultry farm, does not cause environmental pollution, and the prepared liquid fertilizer meets the requirements of 'NY 1106-2010 humic acid-containing water-soluble fertilizer' on products.
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 (5)
1. A method for preparing water soluble fertilizer by comprehensively treating excrement and urine sewage of a large-scale livestock and poultry farm,
firstly, carrying out anaerobic fermentation on feces and urine and flushing water of a livestock and poultry farm, then filtering fermented biogas slurry, drying filter residues to obtain a solid organic fertilizer, adding a chemical precipitator into filtrate to remove heavy metals, adding a flocculating agent into suspension after complete reaction to carry out flocculation and sedimentation, centrifugally filtering a flocculating agent, combining the filtrate with supernatant of the flocculation and sedimentation, adding a composite adsorbent to remove organic arsenic, filtering feed liquid, carrying out microfiltration on the filtrate by using a ceramic membrane to remove colloidal particles and protein, carrying out reverse osmosis concentration on microfiltration permeate, taking the obtained concentrate as a raw material for preparing liquid fertilizer, adding a proper amount of elements and humic acid into the reverse osmosis concentrate to prepare a liquid water-soluble fertilizer meeting national standards, wherein reverse osmosis effluent reaches the discharge standard specified by the state;
the used chemical precipitator is sulfide, and the addition amount of the chemical precipitator is 3 to 5 times of the total molar weight of heavy metals in the raw material liquid; the sulfide is selected from water-soluble sulfur salt or phosphorus pentasulfide;
the flocculant added in the flocculation and sedimentation process is a composite flocculant, the composite flocculant comprises a main flocculant and a coagulant aid, the main flocculant is a polyferric flocculant, the coagulant aid is polyacrylamide or derivatives thereof, the addition amount of the main flocculant is 0.05-0.5% of the mass of a raw material liquid, the addition amount of the coagulant aid is 0.003-0.01% of the mass of the raw material liquid, and the polyferric flocculant is selected from polymeric ferric sulfate, polymeric ferric phosphate or polymeric ferric chloride; by adopting a compounding and combining mode of the polyferric flocculant and polyacrylamide or derivatives thereof, iron atoms in the polyferric flocculant can form a complex with the organic arsenic acid compounds, the organic arsenic acid compounds can be removed while colloid particles, heavy metal sulfide precipitate particles and macromolecular proteins are removed by flocculation, and the polyamide coagulant aid has flocculation and flocculating constituent sedimentation strengthening effects;
the composite adsorbent is a mixture of activated carbon and activated clay, the mass ratio of the activated carbon to the activated clay is 1 to 2.5; the composite adsorbent is mainly used for adsorbing a weak-polarity organic arsenic compound and micromolecular protein;
the elements added into the reverse osmosis concentrated solution are inorganic salts containing nitrogen, phosphorus and potassium, the added humic acid is water-soluble humic acid, the adding amount of the elements and the humic acid is determined according to the content of the elements and the humic acid in the reverse osmosis concentrated solution, and the finally obtained liquid water-soluble fertilizer meets the standard of 'NY 1106-2010 humic acid-containing water-soluble fertilizer'.
2. The method for preparing the water soluble fertilizer by comprehensively treating the excrement, urine and sewage of the large-scale livestock and poultry farm according to claim 1, wherein the filtering equipment for filtering the fermentation biogas slurry is a centrifugal filter or a plate and frame filter.
3. The method for preparing the water soluble fertilizer by comprehensively treating the excrement and urine sewage of the large-scale livestock and poultry farm according to claim 1, wherein the filtering equipment used for flocculating constituent centrifugal filtration is a tubular centrifuge, a disk centrifuge or a horizontal screw centrifuge.
4. The method for preparing the water soluble fertilizer by comprehensively treating the excrement, urine and sewage of the large-scale livestock and poultry farm according to claim 1, wherein the average pore diameter of the ceramic membrane is 50-200 nanometers, and the microfiltration operating pressure of the ceramic membrane is 0.1Mpa-1.0 Mpa.
5. The method for preparing the water-soluble fertilizer through comprehensive treatment of the excrement, urine and sewage of the large-scale livestock and poultry farm according to claim 1, wherein in the reverse osmosis filtration process, the reverse osmosis operating pressure is 1.0MPa to 6.5MPa, the volume of the concentrated solution is 10% to 30% of that of the reverse osmosis feed, and the reverse osmosis effluent reaches the livestock and poultry breeding pollutant discharge standard specified in GB 18596-2001.
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