CN116282622A - Method for synchronously recycling nitrogen and phosphorus in cultivation biogas slurry by combining farmland high-salt drainage with modified carbon - Google Patents
Method for synchronously recycling nitrogen and phosphorus in cultivation biogas slurry by combining farmland high-salt drainage with modified carbon Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000001721 carbon Chemical class 0.000 title claims abstract description 43
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 39
- 239000011574 phosphorus Substances 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 32
- 239000002002 slurry Substances 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 210000003608 fece Anatomy 0.000 claims abstract description 14
- 239000010871 livestock manure Substances 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000009360 aquaculture Methods 0.000 claims abstract description 11
- 244000144974 aquaculture Species 0.000 claims abstract description 11
- 239000002910 solid waste Substances 0.000 claims abstract description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010306 acid treatment Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000007605 air drying Methods 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 229910052567 struvite Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005859 coupling reaction Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 16
- 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 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003337 fertilizer Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000012271 agricultural production Methods 0.000 claims description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000003973 irrigation Methods 0.000 claims description 7
- 230000002262 irrigation Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005457 optimization Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 244000144972 livestock Species 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 244000144977 poultry Species 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 125000003277 amino group Chemical group 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
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 238000009374 poultry farming Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F2001/007—Processes including a sedimentation step
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- 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
- C02F2101/105—Phosphorus compounds
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a method for synchronously recycling nitrogen and phosphorus in aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon, and relates to the technical field of agriculture. When nitrogen and phosphorus in the culture biogas slurry are synchronously recovered by combining farmland high-salt drainage with modified carbon, separating culture waste of a pig farm to obtain solid waste and culture waste liquid, air-drying, dehydrating and crushing the solid waste to obtain pig manure particles, carbonizing the pig manure particles, performing acid treatment, reacting and depositing the acid-treated biochar, a metal-organic framework material and ethylenediamine, granulating to obtain modified carbon, and finally carrying out a mixed reaction of the modified carbon, farmland high-salt drainage and the culture waste liquid to recover nitrogen and phosphorus. The process flow has good recovery effect and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of agriculture, in particular to a method for synchronously recycling nitrogen and phosphorus in cultivation biogas slurry by combining farmland high-salt drainage with modified carbon.
Background
Along with the rapid development of animal husbandry, a batch of large-scale livestock farms, livestock and poultry professional breeding areas, professional villages and special households are built around large and medium cities, a large amount of generated livestock and poultry wastes cannot be fully utilized and discharged at will, huge pressure is formed on the environment of the large and medium cities and the rural ecological environment, and pollution to the livestock and poultry breeding industry is increasingly serious. Therefore, strengthening pollution control and environmental management in livestock and poultry farming has become a significant and urgent task for rural environmental protection at present.
The technology solves the problems of nitrogen and phosphorus pollution caused by the discharge of the treated and cultivated waste, combines the current situations of nitrogen and phosphorus pollution and salinization of the cultivation industry, solves the problems of nitrogen and phosphorus pollution and resource recovery of cultivation waste water by utilizing high-salt drainage and biochar of salinization farmlands, combines the treatment of salinization and the recovery of nitrogen and phosphorus, develops a waste resource recycling mode combining nitrogen and phosphorus recovery and pollution control, and has important significance for improving the current cultivation waste water treatment technology level and realizing the unification of social benefit, economic benefit and environmental benefit.
Disclosure of Invention
The invention aims to provide a method for synchronously recycling nitrogen and phosphorus in aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon, so as to solve the problems in the prior art.
The method for synchronously recycling nitrogen and phosphorus in the cultivation biogas slurry by combining farmland high-salt drainage with modified carbon is characterized in that the farmland high-salt drainage is obtained by collecting farmland drainage through ditches and realizing ion enrichment by adopting methods such as distillation or membrane separation.
As optimization, the modified carbon is prepared by carbonizing pig manure particles, performing acid treatment, reacting and depositing the acid-treated biochar, a metal organic framework material and ethylenediamine, and granulating.
Preferably, the metal organic framework material is prepared by hydrothermal reaction of zinc nitrate and terephthalic acid.
As optimization, the method for synchronously recycling nitrogen and phosphorus in the culture biogas slurry by combining farmland high-salt drainage with modified carbon comprises the following process steps:
(1) Compacting pig manure particles in a crucible, calcining for 2-3 hours at 600-700 ℃ in a nitrogen atmosphere, grinding for 30-40 min in a pulverizer, and sieving with a 60-80 mesh sieve to obtain biochar; the acid-treated biochar, metal organic framework material, ethylenediamine and 30% hydrochloric acid are mixed according to the mass ratio of 3:1:1: 20-5: 2:1:30, uniformly mixing, reacting at 60-70 ℃ under 30-40 kHz ultrasonic oscillation until the deposition thickness is 3-5 mm, washing 3-5 times by absolute ethyl alcohol, drying at-10 to-1 ℃ under 5-10 Pa for 6-8 hours to obtain a deposition film, and preparing modified carbon with the diameter of 1-3 mm by a granulator;
(2) Collecting farmland drainage through a ditch, realizing ion enrichment by adopting methods such as distillation or membrane separation and the like, and obtaining farmland high-salt drainage;
(3) The coupling reaction process comprises the following steps: the modified carbon, farmland high-salt drainage and culture waste liquid are mixed according to the mass ratio of 1:300: 1000-11: 1300:1000, reacting for 20-30 min at the reaction temperature of 20-30 ℃ and the stirring speed of 100-300 r/min at the pH of 9, and collecting a reaction product after the reaction is finished;
(4) After the coupling reaction is finished, solid-liquid separation is realized on the reaction product by adopting a sedimentation or centrifugation method, so as to obtain reaction tail water 1 and a solid product;
(5) The reaction tail water 1 is further purified by a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation.
As optimization, the pig manure particles in the step (1) are obtained by separating the culture waste of a pig farm to obtain solid waste and culture waste liquid, and air-drying and dehydrating the solid waste and grinding the solid waste until the particle size is smaller than 1 mm.
As an optimization, the acid treatment method in the step (1) comprises the following steps: the method comprises the following steps of (1) mixing biochar and 40-50% of nitric acid according to a mass ratio of 1:10 to 1:15 are evenly mixed, stirred and reacted for 20 to 30 minutes at the temperature of 80 to 90 ℃ and the speed of 1000 to 1500r/min, filtered after being cooled to the room temperature, washed for 3 to 5 times by pure water and dried for 8 to 10 hours at the temperature of 40 to 50 ℃ and the speed of 1 to 2 kPa.
As optimization, the preparation method of the metal organic framework material in the step (1) comprises the following steps: zinc nitrate, terephthalic acid and pure water are mixed according to the mass ratio of 2:1: 20-3: 1:30, reacting for 6-8 h in a reaction kettle with polytetrafluoroethylene as a substrate at 130-150 ℃, then placing the mixture into a centrifuge, centrifugally separating the mixture at the rotating speed of 8000r/min to obtain a product, washing the product with deionized water and absolute ethyl alcohol for 3-5 times respectively, and drying the product at 90 ℃ for 5-6 h to prepare the product.
And (3) optimally, the magnesium content of the farmland high-salt drainage water in the step (2) is 0.5g/L.
As optimization, the ammonia nitrogen content of the culture waste liquid in the step (3) is 400mg/L, and the total phosphorus content is 200mg/L.
As an optimization, the solid product in the step (4) has three forms, namely, unreacted complete dry biochar, struvite and biochar-struvite mixture; the unreacted dry biochar can be reused for coupling reaction after being desorbed; struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for synchronously recycling nitrogen and phosphorus in the culture biogas slurry by combining farmland high-salt drainage with modified carbon, disclosed by the invention, the culture waste of a pig farm is separated to obtain solid waste and culture waste liquid, the solid waste is subjected to air drying and dehydration and crushed to obtain pig manure particles, the pig manure particles are carbonized and then subjected to acid treatment, the acid-treated biochar, a metal organic framework material and ethylenediamine react and are deposited and then are granulated to obtain modified carbon, and finally, the modified carbon, the farmland high-salt drainage and the culture waste liquid are subjected to mixed reaction to recycle nitrogen and phosphorus.
Firstly, solid waste in the culture waste is used for preparing modified carbon, the culture waste water is used as a reaction raw material, the effective utilization of the culture waste is realized, the modified biochar contains rich oxygen-containing groups, amino groups, imino groups and metal organic framework materials, and has good adsorption effect on ammonia nitrogen and phosphorus, so that the recovery rate is improved; the farmland drainage magnesium source is used as a magnesium source for struvite reaction, so that the magnesium source is easy to obtain and low in cost, and compared with the conventional magnesium source, the magnesium source has the advantages that the reaction cost is greatly reduced, and the economic benefit is effectively improved.
Secondly, the magnesium modified carbon can be used as an adsorption base point for the generation of struvite and has a certain adsorption effect on other substances in the culture wastewater; the reaction tail water 1 is further purified through a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation, so that the recycling of resources is realized; the unreacted dry biochar can be reused for coupling reaction through simple treatment (resolution); struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production.
Drawings
FIG. 1 is a general process flow diagram of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method for synchronously recycling nitrogen and phosphorus in the culture biogas slurry by combining farmland high-salt drainage with modified carbon mainly comprises the following preparation steps:
(1) Compacting pig manure particles in a crucible, calcining for 3 hours at 600 ℃ in a nitrogen atmosphere, grinding for 30min in a pulverizer, and sieving with a 60-mesh sieve to obtain biochar; the method comprises the following steps of (1) mixing biochar and 40% nitric acid by mass: 10, uniformly mixing, stirring at 80 ℃ for reaction for 20min at 1000r/min, cooling to room temperature, filtering, washing with pure water for 3 times, and drying at 40 ℃ for 8h at 1kPa to obtain acid-treated biochar; zinc nitrate, terephthalic acid and pure water are mixed according to the mass ratio of 2:1:20, reacting for 8 hours in a reaction kettle taking polytetrafluoroethylene as a substrate at 130 ℃, then putting the mixture into a centrifuge, centrifugally separating the mixture at the rotating speed of 8000r/min to obtain a product, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the product at 90 ℃ for 6 hours to obtain a metal organic framework material; the acid-treated biochar, metal organic framework material, ethylenediamine and 30% hydrochloric acid are mixed according to the mass ratio of 3:1:1:20, uniformly mixing, reacting under ultrasonic oscillation at 60 ℃ and 30kHz until the deposition thickness is 3mm, washing with absolute ethyl alcohol for 3 times, drying at-10 ℃ and 5Pa for 8 hours to obtain a deposition film, and preparing modified carbon with the diameter of 2mm by a granulator;
(2) Collecting farmland drainage through a ditch, realizing ion enrichment by adopting methods such as distillation or membrane separation and the like, and obtaining farmland high-salt drainage;
(3) The coupling reaction process comprises the following steps: the modified carbon, farmland high-salt drainage and culture waste liquid are mixed according to the mass ratio of 1:300:1000, reacting for 30min at a reaction temperature of 20 ℃ and a stirring speed of 100r/min at a pH=9, and collecting a reaction product after the reaction is finished;
(4) After the coupling reaction is finished, solid-liquid separation is realized on the reaction product by adopting a sedimentation or centrifugation method, so as to obtain reaction tail water 1 and a solid product; the solid product has three forms, namely, unreacted complete dry biochar, struvite and biochar-struvite mixture; the unreacted dry biochar can be reused for coupling reaction after being desorbed; struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production;
(5) The reaction tail water 1 is further purified by a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation.
Example 2
The method for synchronously recycling nitrogen and phosphorus in the culture biogas slurry by combining farmland high-salt drainage with modified carbon mainly comprises the following preparation steps:
(1) Compacting pig manure particles in a crucible, calcining for 2.5 hours at 650 ℃ in a nitrogen atmosphere, grinding for 35min in a pulverizer, and sieving with a 70-mesh sieve to obtain biochar; the method comprises the following steps of (1) mixing biochar and 45% nitric acid in mass ratio: 12, uniformly mixing, stirring at 85 ℃ and 1200r/min for reaction for 25min, cooling to room temperature, filtering, washing with pure water for 4 times, and drying at 45 ℃ and 1.5kPa for 9h to obtain the biochar after acid treatment; zinc nitrate, terephthalic acid and pure water are mixed according to the mass ratio of 2.5:1:25, reacting for 6-8 h in a reaction kettle taking polytetrafluoroethylene as a substrate at 130-150 ℃, then putting the mixture into a centrifuge, centrifugally separating the mixture at the rotating speed of 8000r/min to obtain a product, washing the product with deionized water and absolute ethyl alcohol for 4 times respectively, and drying the product at 90 ℃ for 5.5h to obtain the metal-organic framework material; the acid-treated biochar, metal organic framework material, ethylenediamine and 30% hydrochloric acid are mixed according to the mass ratio of 4:1.5:1:25, reacting under ultrasonic oscillation at 65 ℃ and 35kHz until the deposition thickness is 4mm, washing with absolute ethyl alcohol for 4 times, drying at-5 ℃ and 8Pa for 7h to obtain a deposition film, and preparing modified carbon with the diameter of 2mm by a granulator;
(2) Collecting farmland drainage through a ditch, realizing ion enrichment by adopting methods such as distillation or membrane separation and the like, and obtaining farmland high-salt drainage;
(3) The coupling reaction process comprises the following steps: the modified carbon, farmland high-salt drainage and culture waste liquid are mixed according to the mass ratio of 8:700:1000, reacting for 25min at a reaction temperature of 25 ℃ and a stirring speed of 200r/min at a pH=9, and collecting a reaction product after the reaction is finished;
(4) After the coupling reaction is finished, solid-liquid separation is realized on the reaction product by adopting a sedimentation or centrifugation method, so as to obtain reaction tail water 1 and a solid product; the solid product has three forms, namely, unreacted complete dry biochar, struvite and biochar-struvite mixture; the unreacted dry biochar can be reused for coupling reaction after being desorbed; struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production;
(5) The reaction tail water 1 is further purified by a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation.
Example 3
The method for synchronously recycling nitrogen and phosphorus in the culture biogas slurry by combining farmland high-salt drainage with modified carbon mainly comprises the following preparation steps:
(1) Compacting pig manure particles in a crucible, calcining for 2 hours at 700 ℃ in a nitrogen atmosphere, grinding for 40min in a pulverizer, and sieving with a 60-mesh sieve to obtain biochar; the method comprises the following steps of (1) mixing biochar and 50% by mass of nitric acid: 15, stirring at 90 ℃ for reaction for 20min at 1500r/min, cooling to room temperature, filtering, washing with pure water for 5 times, and drying at 50 ℃ for 8h at 2kPa to obtain acid-treated biochar; zinc nitrate, terephthalic acid and pure water are mixed according to the mass ratio of 3:1:30, mixing, reacting for 8 hours in a reaction kettle taking polytetrafluoroethylene as a substrate at 150 ℃, putting into a centrifuge, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product with deionized water and absolute ethyl alcohol for 5 times respectively, and drying at 90 ℃ for 5 hours to obtain a metal organic framework material; the acid-treated biochar, metal organic framework material, ethylenediamine and 30% hydrochloric acid are mixed according to the mass ratio of 5:2:1:30, uniformly mixing, reacting under ultrasonic oscillation at 70 ℃ and 40kHz until the deposition thickness is 3mm, washing with absolute ethyl alcohol for 5 times, drying at-1 ℃ and 10Pa for 6 hours to obtain a deposition film, and preparing modified carbon with the diameter of 2mm by a granulator;
(2) Collecting farmland drainage through a ditch, realizing ion enrichment by adopting methods such as distillation or membrane separation and the like, and obtaining farmland high-salt drainage;
(3) The coupling reaction process comprises the following steps: the modified carbon, farmland high-salt drainage and culture waste liquid are mixed according to the mass ratio of 11:1300:1000, and mixing uniformly. Reacting for 20min at a reaction temperature of 30 ℃ and a stirring speed of pH=9 and 300r/min, and collecting a reaction product after the reaction is finished;
(4) After the coupling reaction is finished, solid-liquid separation is realized on the reaction product by adopting a sedimentation or centrifugation method, so as to obtain reaction tail water 1 and a solid product; the solid product has three forms, namely, unreacted complete dry biochar, struvite and biochar-struvite mixture; the unreacted dry biochar can be reused for coupling reaction after being desorbed; struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production;
(5) The reaction tail water 1 is further purified by a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation.
Comparative example
The method for synchronously recycling nitrogen and phosphorus in the culture biogas slurry by combining farmland high-salt drainage with modified carbon mainly comprises the following preparation steps:
(1) Compacting pig manure particles in a crucible, calcining for 2.5 hours at 650 ℃ in a nitrogen atmosphere, grinding for 35min in a pulverizer, and sieving with a 70-mesh sieve to obtain biochar;
(2) Collecting farmland drainage through a ditch, realizing ion enrichment by adopting methods such as distillation or membrane separation and the like, and obtaining farmland high-salt drainage;
(3) The coupling reaction process comprises the following steps: the modified carbon, farmland high-salt drainage and culture waste liquid are mixed according to the mass ratio of 8:700:1000, reacting for 25min at a reaction temperature of 25 ℃ and a stirring speed of 200r/min at a pH=9, and collecting a reaction product after the reaction is finished;
(4) After the coupling reaction is finished, solid-liquid separation is realized on the reaction product by adopting a sedimentation or centrifugation method, so as to obtain reaction tail water 1 and a solid product; the solid product has three forms, namely, unreacted complete dry biochar, struvite and biochar-struvite mixture; the unreacted dry biochar can be reused for coupling reaction after being desorbed; struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production;
(5) The reaction tail water 1 is further purified by a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation.
Effect example
Table 1 below shows the results of nitrogen and phosphorus recovery analysis obtained by taking example 2 as a standard, wherein the ammonia nitrogen content of the culture waste liquid is 400mg/L, the total phosphorus content is 200mg/L, the volume is 1L, the magnesium content of farmland high-salt drainage is 0.5g/L, and the addition amounts are different.
TABLE 1
From the experimental data in Table 1, it was found that the highest ammonia nitrogen recovery rate and total phosphorus recovery rate were achieved by adding 8.828g of modified carbon and 765.6mL of farmland high salt drainage to 1L of the culture waste liquid in each of the above-mentioned addition amounts.
Table 2 below the nitrogen and phosphorus recovery rates of examples 1 to 3 and comparative examples were analyzed with an addition amount of 8.828g of modified carbon or biochar and 765.6mL of farmland high salt drainage:
TABLE 2
From the experimental data in table 2, it can be found that the ammonia nitrogen recovery rate and the total phosphorus recovery rate of the comparative examples 1-3 are high, which indicates that the modified biochar contains rich oxygen-containing groups, amino groups, imino groups and metal organic framework materials after the biochar is modified, and has good adsorption effect on ammonia nitrogen and phosphorus, thereby improving the recovery rate.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The method for synchronously recycling nitrogen and phosphorus in the cultivation biogas slurry by combining farmland high-salt drainage with modified carbon is characterized in that the farmland high-salt drainage is obtained by collecting farmland drainage through ditches and realizing ion enrichment by adopting methods such as distillation or membrane separation.
2. The method for synchronously recycling nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 1, wherein the modified carbon is prepared by carbonizing pig manure particles, performing acid treatment, reacting and depositing the acid-treated biochar, a metal-organic framework material and ethylenediamine, and granulating.
3. The method for synchronously recycling nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 2, wherein the metal-organic framework material is prepared by a hydrothermal reaction of zinc nitrate and terephthalic acid.
4. The method for synchronously recovering nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage and modified carbon as claimed in claim 1, which is characterized by comprising the following steps:
(1) Compacting pig manure particles in a crucible, calcining for 2-3 hours at 600-700 ℃ in a nitrogen atmosphere, grinding for 30-40 min in a pulverizer, and sieving with a 60-80 mesh sieve to obtain biochar; the acid-treated biochar, metal organic framework material, ethylenediamine and 30% hydrochloric acid are mixed according to the mass ratio of 3:1:1: 20-5: 2:1:30, uniformly mixing, reacting at 60-70 ℃ under 30-40 kHz ultrasonic oscillation until the deposition thickness is 3-5 mm, washing 3-5 times by absolute ethyl alcohol, drying at-10 to-1 ℃ under 5-10 Pa for 6-8 hours to obtain a deposition film, and preparing modified carbon with the diameter of 1-3 mm by a granulator;
(2) Collecting farmland drainage through a ditch, realizing ion enrichment by adopting methods such as distillation or membrane separation and the like, and obtaining farmland high-salt drainage;
(3) The coupling reaction process comprises the following steps: the modified carbon, farmland high-salt drainage and culture waste liquid are mixed according to the mass ratio of 1:300: 1000-11: 1300:1000, reacting for 20-30 min at the reaction temperature of 20-30 ℃ and the stirring speed of 100-300 r/min at the pH of 9, and collecting a reaction product after the reaction is finished;
(4) After the coupling reaction is finished, solid-liquid separation is realized on the reaction product by adopting a sedimentation or centrifugation method, so as to obtain reaction tail water 1 and a solid product;
(5) The reaction tail water 1 is further purified by a graded biological filter, and the obtained reaction tail water 2 reaching the discharge standard can be directly used for irrigation.
5. The method for synchronously recycling nitrogen and phosphorus in the biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 3, wherein in the step (1), pig manure particles are obtained by separating pig farm cultivation waste to obtain solid waste and cultivation waste liquid, and air-drying and dehydrating the solid waste and grinding the solid waste to a particle size of less than 1 mm.
6. The method for synchronously recovering nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 3, wherein the acid treatment method in the step (1) is as follows: the method comprises the following steps of (1) mixing biochar and 40-50% of nitric acid according to a mass ratio of 1:10 to 1:15 are evenly mixed, stirred and reacted for 20 to 30 minutes at the temperature of 80 to 90 ℃ and the speed of 1000 to 1500r/min, filtered after being cooled to the room temperature, washed for 3 to 5 times by pure water and dried for 8 to 10 hours at the temperature of 40 to 50 ℃ and the speed of 1 to 2 kPa.
7. The method for synchronously recycling nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 3, wherein the preparation method of the metal-organic framework material in the step (1) is as follows: zinc nitrate, terephthalic acid and pure water are mixed according to the mass ratio of 2:1: 20-3: 1:30, reacting for 6-8 h in a reaction kettle with polytetrafluoroethylene as a substrate at 130-150 ℃, then placing the mixture into a centrifuge, centrifugally separating the mixture at the rotating speed of 8000r/min to obtain a product, washing the product with deionized water and absolute ethyl alcohol for 3-5 times respectively, and drying the product at 90 ℃ for 5-6 h to prepare the product.
8. The method for synchronously recycling nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 3, wherein the magnesium content of the farmland high-salt drainage in the step (2) is 0.5g/L.
9. The method for synchronously recycling nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 3, wherein the ammonia nitrogen content of the aquaculture waste liquid in the step (3) is 400mg/L, and the total phosphorus content is 200mg/L.
10. The method for synchronously recovering nitrogen and phosphorus in the aquaculture biogas slurry by combining farmland high-salt drainage with modified carbon according to claim 3, wherein the solid product in the step (4) has three forms, namely, unreacted complete dry biochar, struvite and biochar-struvite mixture; the unreacted dry biochar can be reused for coupling reaction after being desorbed; struvite can be used as fertilizer for farmland production; the biochar-struvite mixture can be used as a novel carbon-based fertilizer for agricultural production.
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