CN114082401A - Adsorptive phosphorus-removing bacterium particle, preparation method thereof and organophosphorus pesticide waste gas treatment method - Google Patents
Adsorptive phosphorus-removing bacterium particle, preparation method thereof and organophosphorus pesticide waste gas treatment method Download PDFInfo
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- CN114082401A CN114082401A CN202111372932.5A CN202111372932A CN114082401A CN 114082401 A CN114082401 A CN 114082401A CN 202111372932 A CN202111372932 A CN 202111372932A CN 114082401 A CN114082401 A CN 114082401A
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- phosphorus
- adsorptive
- bacteria
- adsorbent
- removing bacteria
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- 241000894006 Bacteria Species 0.000 title claims abstract description 131
- 230000000274 adsorptive effect Effects 0.000 title claims abstract description 49
- 239000002245 particle Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002912 waste gas Substances 0.000 title claims abstract description 29
- 239000003987 organophosphate pesticide Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 87
- 239000011574 phosphorus Substances 0.000 claims abstract description 87
- 239000003463 adsorbent Substances 0.000 claims abstract description 70
- 239000003610 charcoal Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 108
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 65
- 238000001035 drying Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 229910052726 zirconium Inorganic materials 0.000 claims description 25
- -1 zirconium ions Chemical class 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
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- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 4
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims description 4
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 claims description 3
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000008101 lactose Substances 0.000 claims description 3
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 claims description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims 2
- 239000008187 granular material Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 8
- 239000010914 pesticide waste Substances 0.000 abstract description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 32
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 235000003447 Pistacia vera Nutrition 0.000 description 7
- 240000006711 Pistacia vera Species 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000014571 nuts Nutrition 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
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- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 235000009025 Carya illinoensis Nutrition 0.000 description 3
- 244000068645 Carya illinoensis Species 0.000 description 3
- 235000018330 Macadamia integrifolia Nutrition 0.000 description 3
- 240000000912 Macadamia tetraphylla Species 0.000 description 3
- 235000003800 Macadamia tetraphylla Nutrition 0.000 description 3
- 244000144725 Amygdalus communis Species 0.000 description 2
- 235000011437 Amygdalus communis Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 235000020224 almond Nutrition 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 206010057941 Chemical burn of skin Diseases 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides an adsorptive phosphorus removal bacterium particle and a preparation method thereof, and an organophosphorus pesticide waste gas treatment method, wherein the adsorptive phosphorus removal bacterium particle comprises phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and an auxiliary material, and the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the auxiliary material is 1: 0.5-1. The adsorbent and the phosphorus removing bacteria are compounded, so that the advantage of the capacity of the adsorbent for capturing organic pollutants in the waste gas and the advantage of the phosphorus removing bacteria for degrading organic matters are fully combined, in addition, the adsorbent has certain capturing capacity for the phosphorus removing bacteria, the phosphorus removing bacteria can be intensively distributed in the adsorbent, and therefore after the adsorbent captures the organic pollutants, the phosphorus removing bacteria can be fully and quickly contacted with the organic pollutants, and the overall removal efficiency of the organic phosphorus pesticide waste gas is greatly improved.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a waste gas treatment method, and more particularly relates to a preparation method of adsorptive phosphorus-removing bacteria particles and an organophosphorus pesticide waste gas treatment method.
Background
In recent years, researchers have conducted a lot of research on the removal of organic phosphorus pesticide waste gas, and chemical methods such as ozone, hydrogen peroxide, peracetic acid, hypochlorite oxidation and the like are commonly used in industry, but the chemical methods have the defects of high cost, easy secondary pollution and the like.
At present, biological methods are adopted for treatment, and a biological spray tower device is generally adopted for waste gas treatment in China. When the gas passes through the biological layer of the biological spray tower device, pollutants in the waste gas are captured and degraded by microorganisms in an aerobic environment to generate substances such as nontoxic and odorless carbon dioxide, water and the like so as to achieve the aim of purification. The organophosphorus pesticide has high biotoxicity, has toxic action on most insects, people and livestock and microorganisms, and is difficult to effectively remove common microorganisms in the traditional aerobic biological spray tower device, so that the common microorganisms are harmful to the environment.
The phosphorus removing bacteria have better effect on degrading the organophosphorus pesticide waste gas than other microorganisms due to the specific phosphorus removing characteristic. Most organophosphorus pesticides belong to hydrophobic compounds, and microorganisms are difficult to capture pollutants in pesticide waste gas in a spray tower device, so that phosphorus removal bacteria are not in full contact with the pollutants, and the degradation efficiency is low.
Therefore, there is a continuing need to find a safe and effective method for degrading organophosphorus pesticide waste gases.
Disclosure of Invention
The invention aims to provide adsorptive phosphorus-removing bacteria particles, a preparation method thereof and an organophosphorus pesticide waste gas treatment method. The phosphorus removing bacteria provided by the invention has both adsorption and phosphorus removal performances, can better capture organic matters in waste gas, and enables the phosphorus removing bacteria to be fully contacted with pollutants, thereby achieving higher degradation rate.
In order to achieve the purpose, the invention provides an adsorptive phosphorus removal bacterium particle, which comprises phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and an auxiliary material, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the auxiliary material is 1: 0.5-1.
The adsorptive phosphorus removal bacteria particle combines the adsorbent and phosphorus removal bacteria together, and can simultaneously realize adsorption and phosphorus removal. The problem that secondary pollution is caused by overflow of organic matters in the adsorption and regeneration processes when a single adsorbent is used for waste gas treatment can be solved, and the problems that the solubility and the capture capacity of strain nutrient solution to the organic matters are poor, the contact of phosphorus removing bacteria with pollutants is insufficient, and the degradation efficiency is low when phosphorus removing bacteria are used alone for waste gas treatment can be solved. The adsorbent and the phosphorus removing bacteria are compounded, so that the advantage of the capacity of the adsorbent for capturing organic pollutants in the waste gas and the advantage of the phosphorus removing bacteria for degrading organic matters are fully combined, in addition, the adsorbent has certain capturing capacity for the phosphorus removing bacteria, the phosphorus removing bacteria can be intensively distributed in the adsorbent, and therefore after the adsorbent captures the organic pollutants, the phosphorus removing bacteria can be fully and quickly contacted with the organic pollutants, and the overall removal efficiency of the organic phosphorus pesticide waste gas is greatly improved.
As a better technical scheme, the auxiliary material is at least one of diatomite, clay, kaolin, plant ash and vermiculite powder.
The second aspect of the invention provides a preparation method of adsorptive phosphorus-removing bacteria particles, which comprises the following steps:
(1) preparation of biochar
Crushing the fruit shells, sieving, cleaning, and carbonizing at high temperature to obtain charcoal;
(2) zr-preloaded biocarbon
Adding the biochar into a sodium hydroxide solution for refluxing and suction filtration, storing filtrate as a sodium hydroxide stock solution, drying a solid phase, adding the solid phase into an alcohol solution, adding a zirconium nitrate solution, stirring and aging at room temperature, and washing and drying the solid phase after suction filtration to obtain Zr-preloaded biochar;
(3) preparation of the adsorbent
Slowly adding the sodium hydroxide stock solution obtained in the step (2) into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding the Zr pre-loaded biochar into the precursor mixed solution, stirring and aging, and washing and drying after suction filtration to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
And adding a drying protective agent into the fermented phosphorus removing bacteria to obtain bacteria slurry, mixing and granulating the bacteria slurry, the adsorbent and the auxiliary materials, and performing vacuum drying to obtain the adsorptive phosphorus removing bacteria.
In the preparation of the adsorptive phosphorus removing bacteria particles, the Zr-loaded adsorbent is prepared, the adsorbent has strong adsorption capacity, the auxiliary material composite phosphorus removing bacteria is adopted to obtain the phosphorus removing bacteria particles which have both adsorption performance and phosphorus removal performance, and the adsorbent can enable the phosphorus removing bacteria to be distributed in the adsorbent in a concentrated manner, so that after the adsorbent captures organic pollutants, the phosphorus removing bacteria can be in full and rapid contact with the organic pollutants, and the overall removal efficiency of organophosphorus pesticide waste gas is greatly improved.
As a preferred technical scheme, the nut shell is nut shell, and the nut shell is any one of pistachio nut shell, macadamia nut shell, almond shell and pecan shell.
As a better technical scheme, the preparation of the biochar comprises the steps of crushing the shells, sieving the crushed shells through a 100-mesh sieve, cleaning the crushed shells for 3-7 times by using water, introducing nitrogen into a tubular furnace, heating the mixture to 500 ℃ at the speed of 4-8 ℃, preserving the heat for 3-5 hours, carbonizing the mixture, and cooling the carbonized mixture to room temperature.
As a preferred technical scheme, in the step (2), zirconium ions in the zirconium nitrate solution and the solid phase tableOH on the surface-The molar ratio of (A) to (B) is 1: 4-6.
As a better technical scheme, the refluxing condition in the step (2) is 80 ℃ refluxing for 10-14 h, and the drying conditions in the step (2) and the step (3) are respectively independent of drying for 24-30 h at 75-85 ℃.
As a preferred technical scheme, the alcohol solution in the step (2) is n-propanol or isopropanol.
As a preferred technical solution, OH in the sodium hydroxide stock solution in the step (3) is-And the molar ratio of zirconium ions in the zirconium nitrate solution is 4-6: 1.
As a better technical scheme, the molar mass of zirconium ions in the zirconium nitrate solution in the step (3) in the Zr-loaded biochar is 1.5-2.5 mmol/g.
As a better technical scheme, the drying protective agent is at least one of raffinose, dimethyl sulfoxide, trehalose, lactose, glycerol and gelatin.
As a better technical scheme, in the step (4), the temperature of vacuum drying is 30-50 ℃, the time is 1-10 h, and the water content of the adsorptive phosphorus removal bacteria is less than or equal to 5%.
The invention provides a method for treating organophosphorus pesticide waste gas, which comprises the following steps in sequence:
(1) preliminarily absorbing and decomposing the organophosphorus pesticide waste gas by using strongly alkaline electrolyzed water with the pH value of 11-13;
(2) the adsorptive phosphorus-removing bacteria particles or the adsorptive phosphorus-removing bacteria particles prepared by the preparation method can be used for adsorbing and degrading organic pollutants in the organophosphorus pesticide waste gas.
According to the invention, the strongly alkaline electrolyzed water with the pH value of 11-13 is firstly adopted to carry out primary absorption and decomposition on the organophosphorus pesticide waste gas, and the toxicity of the organophosphorus pesticide waste gas is obviously reduced and becomes a pollutant which is easier to degrade after absorption and decomposition. Then the phosphorus is adsorbed by the adsorbent in the adsorptive phosphorus removing bacteria particles and is contacted and degraded by the phosphorus removing bacteria compounded with the adsorbent so as to be removed.
Detailed Description
The adsorptive phosphorus removal bacteria particle comprises phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and an auxiliary material, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the auxiliary material is 1: 0.5-1. The mass ratio of the phosphorus-removing bacteria to the Zr-loaded charcoal adsorbent to the auxiliary materials can be but is not limited to 1:0.5:0.5, 1:1:1, 1:0.5:1, 1:1:0.5, 1:0.75:0.75, 1:0.75:1, 1:0.75:0.5 and 1:0.8: 1. The auxiliary material is at least one of diatomite, clay, kaolin, plant ash and vermiculite powder.
The preparation method of the adsorptive phosphorus removing bacteria particle can comprise the following steps:
(1) preparation of biochar
Crushing the fruit shells, sieving, cleaning, and carbonizing at high temperature to obtain charcoal;
(2) zr-preloaded biocarbon
Adding the biochar into a sodium hydroxide solution for refluxing and suction filtration, storing filtrate as a sodium hydroxide stock solution, drying a solid phase, adding the solid phase into an alcohol solution, adding a zirconium nitrate solution, stirring and aging at room temperature, and washing and drying the solid phase after suction filtration to obtain Zr-preloaded biochar;
(3) preparation of the adsorbent
Slowly adding the sodium hydroxide stock solution obtained in the step (2) into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, stirring and aging, performing suction filtration, washing, and drying to obtain an adsorbent;
(4) adsorption phosphorus-removing bacterium granulation
Adding the fermented phosphorus-removing bacteria into a drying protective agent to obtain bacteria slurry, mixing and granulating the bacteria slurry, an adsorbent and auxiliary materials, and carrying out vacuum drying to obtain the adsorptive phosphorus-removing bacteria.
In the step (1), the nut shell is nut shell, and the nut shell is any one of pistachio nut shell, macadamia nut shell, almond shell and pecan shell, preferably pistachio nut shell. The step (1) specifically comprises the steps of crushing the shells, sieving the crushed shells through a 100-mesh sieve, cleaning the crushed shells for 3-7 times by using water, introducing nitrogen into the crushed shells in a tubular furnace, heating the crushed shells to 500 ℃ at the speed of 4-8 ℃, preserving the temperature for 3-5 hours, carbonizing the crushed shells, and cooling the carbonized shells to room temperature.
In the step (2), zirconium ions in the zirconium nitrate solution and OH on the surface of the solid phase-The molar ratio of (1: 4) - (6), preferably 1:5, refluxing for 10-14 h at 80 ℃, drying for 24-30 h at 75-85 ℃, and the alcohol solution is n-propanol or isopropanol.
In the step (3), OH in the sodium hydroxide stock solution-And the molar ratio of zirconium ions in the zirconium nitrate solution is 4-6: 1. The molar mass of zirconium ions in the zirconium nitrate solution in the Zr pre-loaded biochar is 1.5-2.5 mmol/g.
In the step (4), the drying protective agent is at least one of raffinose, dimethyl sulfoxide, trehalose, lactose, glycerol and gelatin, the vacuum drying temperature is 30-50 ℃, the time is 1-10 hours, and the water content of the adsorptive phosphorus removal bacteria is less than or equal to 5%.
The method for treating the organophosphorus pesticide waste gas comprises the following steps in sequence:
(1) carrying out primary absorption and decomposition on the organophosphorus pesticide waste gas by using strongly alkaline electrolyzed water with the pH value of 11-13;
(2) the organic pollutants in the organophosphorus pesticide waste gas are adsorbed and degraded by adopting the adsorptive phosphorus removing bacteria particles.
The organophosphorus pesticide waste gas is mostly phosphate or thiophosphate substances, has strong volatility, is slightly soluble in water, shows acidity, and is easily decomposed into organic matters with low toxicity and easier degradation under strong alkaline electrolyte with the pH value of 11-13. The strongly alkaline electrolyzed water contains active hydrogen as effective component usually NaOH or KOH, and can effectively remove dirt such as lipid and protein by saponification and emulsification dispersion. Unlike other alkaline water formed by caustic soda, the strong alkaline electrolyzed water does not cause irritation or chemical burn of skin, has obvious effect on decomposing oily substances, and has the characteristics of safety, no secondary pollution, low cost, easy obtainment and the like. Using MoS2/NiSe2The composite material is added as a catalyst to the working electrode to perform electrolysis to obtain strongly alkaline electrolyzed water.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and diatomite, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the diatomite is 1:0.8: 1.
The preparation method comprises the following steps:
(1) preparation of biochar
Crushing pistachio nut shells, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tubular furnace, introducing nitrogen, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 3 hours, carbonizing, and cooling to room temperature;
(2) zr-preloaded biocarbon
5g of biochar was added to 60mL of 1 mol. L-1Refluxing at 80 deg.C for 12 hr, vacuum filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 deg.C for 24 hr, measuring the amount of NaOH on the surface of charcoal, adding into n-propanol solution, and adding zirconium ions in zirconium nitrate solution and OH on the surface of solid phase-Slowly dropwise adding 0.1 mol.L with the molar ratio of 1:5-1Adding the zirconium nitrate solution into the zirconium nitrate solution, stirring for 2 hours at room temperature, aging for 6 hours, filtering, washing a solid phase, and drying to obtain Zr pre-loaded biochar;
(3) preparation of the adsorbent
According to OH in the sodium hydroxide stock solution in the step (2)-And zirconium ions in the zirconium nitrate solution at a molar ratio of 5:1 were slowly added to 50ml of 0.1 mol. L-1Adding Zr pre-loaded biochar into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution, which accounts for the Zr pre-loaded biochar, is 2mmol/g, stirring for 2h, aging for 6h, performing suction filtration, washing, and drying at 80 ℃ for 24h to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
Adding 60% of fermented phosphorus-removing bacteria into glycerol (the content is 1.5% of the weight of the phosphorus-removing bacteria) to obtain bacteria slurry, mixing and granulating the bacteria slurry, adsorbent and diatomite according to the mass ratio of 1:0.8:1, and vacuum drying at 40 ℃ for 8 hours to obtain the adsorptive phosphorus-removing bacteria with the water content of 4.1%.
Example 2
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and diatomite, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the diatomite is 1:0.75: 0.5.
The preparation method comprises the following steps:
(1) preparation of biochar
Crushing pistachio nut shells, sieving with a 100-mesh sieve, cleaning with deionized water for 5 times, placing in a tubular furnace, introducing nitrogen, heating to 500 ℃ at the speed of 5 ℃, preserving heat for 4h, carbonizing, and cooling to room temperature;
(2) zr-preloaded biocarbon
5g of biochar was added to 60mL of 1 mol. L-1Refluxing at 80 deg.C for 14 hr, vacuum filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 85 deg.C for 30 hr, measuring the amount of NaOH on the surface of biochar, adding into n-propanol solution, and adding zirconium ions in zirconium nitrate solution and OH on the surface of solid phase-Slowly dropwise adding 0.1 mol.L with the molar ratio of 1:4-1Adding the zirconium nitrate solution into the zirconium nitrate solution, stirring for 2 hours at room temperature, aging for 6 hours, filtering, washing a solid phase, and drying to obtain Zr pre-loaded biochar;
(3) preparation of the adsorbent
The sodium hydroxide stock solution in the step (2) is treated according to OH in the sodium hydroxide stock solution-And zirconium ions in the zirconium nitrate solution at a molar ratio of 4:1 were slowly added to 50ml of 0.1 mol. L-1Adding Zr pre-loaded biochar into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution, which accounts for the Zr pre-loaded biochar, is 1.5mmol/g, stirring for 2 hours, aging for 6 hours, performing suction filtration, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
Adding 60% of fermented phosphorus-removing bacteria into 1% of glycerol to obtain bacteria slurry, mixing and granulating the bacteria slurry, adsorbent and diatomite according to the mass ratio of 1:0.75:0.5, and vacuum drying at 45 deg.C for 10 hr to obtain adsorptive phosphorus-removing bacteria with water content of 4%.
Example 3
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and diatomite, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the diatomite is 1:1: 1.
The preparation method comprises the following steps:
(1) preparation of biochar
Crushing pistachio nut shells, sieving with a 100-mesh sieve, cleaning with deionized water for 7 times, placing in a tubular furnace, introducing nitrogen, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 4h, carbonizing, and cooling to room temperature;
(2) zr-preloaded biocarbon
5g of biochar was added to 60mL of 1 mol. L-1Refluxing at 80 deg.C for 10 hr, vacuum filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 85 deg.C for 30 hr, measuring the amount of NaOH on the surface of biochar, adding into n-propanol solution, and adding zirconium ions in zirconium nitrate solution and OH on the surface of solid phase-Is slowly dropped with 0.1 mol.L according to the molar ratio of 1:6-1Adding the zirconium nitrate solution into the zirconium nitrate solution, stirring for 2 hours at room temperature, aging for 6 hours, filtering, washing a solid phase, and drying to obtain Zr pre-loaded biochar;
(3) preparation of the adsorbent
The sodium hydroxide stock solution in the step (2) is treated according to OH in the sodium hydroxide stock solution-And zirconium ions in the zirconium nitrate solution at a molar ratio of 6:1 were slowly added to 50ml of 0.1 mol. L-1Adding Zr pre-loaded biochar into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution, which accounts for the Zr pre-loaded biochar, is 2.5mmol/g, stirring for 2 hours, aging for 6 hours, performing suction filtration, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
Adding 60% of fermented phosphorus-removing bacteria into 1% of glycerol to obtain bacteria slurry, mixing the bacteria slurry, adsorbent and diatomite at a mass ratio of 1:1:1, granulating, and vacuum drying at 40 deg.C for 8 hr to obtain adsorptive phosphorus-removing bacteria with water content of 4.1%.
Example 4
The adsorptive phosphorus removal bacteria particle comprises phosphorus removal bacteria, a Zr-loaded charcoal adsorbent and kaolin, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded charcoal adsorbent to the diatomite is 1:0.8: 1.
The preparation method comprises the following steps:
(1) preparation of biochar
Crushing macadamia nut shells, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tubular furnace, introducing nitrogen, heating to 500 ℃ at the speed of 5 ℃, preserving heat for 3 hours, carbonizing, and cooling to room temperature;
(2) zr-preloaded biocarbon
5g of biochar was added to 60mL of 1 mol. L-1Refluxing at 80 deg.C for 12 hr, vacuum filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 deg.C for 24 hr, measuring the amount of NaOH on the surface of charcoal, adding into n-propanol solution, and adding zirconium ions in zirconium nitrate solution and OH on the surface of solid phase-Slowly dropwise adding 0.1 mol.L with the molar ratio of 1:5-1Adding the zirconium nitrate solution into the zirconium nitrate solution, stirring for 2 hours at room temperature, aging for 6 hours, filtering, washing a solid phase, and drying to obtain Zr pre-loaded biochar;
(3) preparation of the adsorbent
The sodium hydroxide stock solution in the step (2) is treated according to OH in the sodium hydroxide stock solution-And zirconium ions in the zirconium nitrate solution at a molar ratio of 5:1 were slowly added to 50ml of 0.1 mol. L-1Adding Zr pre-loaded biochar into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution, which accounts for the Zr pre-loaded biochar, is 2mmol/g, stirring for 2h, aging for 6h, performing suction filtration, washing, and drying at 80 ℃ for 24h to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
Adding 60% of fermented phosphorus-removing bacteria into glycerol (the content is 1.5% of the weight of the phosphorus-removing bacteria) to obtain bacteria slurry, mixing and granulating the bacteria slurry, an adsorbent and kaolin according to the mass ratio of 1:0.8:1, and drying in vacuum at 40 ℃ for 8 hours to obtain the adsorptive phosphorus-removing bacteria with the water content of 4.1%.
Example 5
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, a Zr-loaded biochar adsorbent and diatomite, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the diatomite is 1:0.8: 1.
The preparation method comprises the following steps:
(1) preparation of biochar
Crushing pecan shells, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, introducing nitrogen into a tubular furnace, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 3 hours, carbonizing, and cooling to room temperature;
(2) zr-preloaded biocarbon
5g of biochar was added to 60mL of 1 mol. L-1Refluxing at 80 deg.C for 12 hr, vacuum filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 deg.C for 24 hr, measuring the amount of NaOH on the surface of biochar, adding into n-propanol solution, and adding zirconium ions in zirconium nitrate solution and OH on the surface of solid phase-Slowly dropwise adding 0.1 mol.L with the molar ratio of 1:5-1Adding the zirconium nitrate solution into the zirconium nitrate solution, stirring for 2 hours at room temperature, aging for 6 hours, filtering, washing a solid phase, and drying to obtain Zr pre-loaded biochar;
(3) preparation of the adsorbent
The sodium hydroxide stock solution in the step (2) is treated according to OH in the sodium hydroxide stock solution-And zirconium ions in the zirconium nitrate solution at a molar ratio of 5:1 were slowly added to 50ml of 0.1 mol. L-1Adding Zr pre-loaded biochar into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution, which accounts for the Zr pre-loaded biochar, is 2mmol/g, stirring for 2h, aging for 6h, performing suction filtration, washing, and drying at 80 ℃ for 24h to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
Adding trehalose (the content is 1.5 percent of the weight of the phosphorus removing bacteria) into the fermented phosphorus removing bacteria (the solid content is controlled to be 60 percent) to obtain bacteria slurry, mixing and granulating the bacteria slurry, the adsorbent and the diatomite according to the mass ratio of 1:0.8:1, and drying in vacuum at 40 ℃ for 8 hours to obtain the adsorptive phosphorus removing bacteria with the water content of 4.1 percent.
Comparative example 1
The adsorptive particles are Zr loaded charcoal adsorbent, and the preparation method comprises the following steps:
(1) preparation of biochar
Crushing pistachio nut shells, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tubular furnace, introducing nitrogen, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 3 hours, carbonizing, and cooling to room temperature;
(2) zr-preloaded biocarbon
5g of biochar was added to 60mL of 1 mol. L-1Refluxing at 80 deg.C for 12 hr, vacuum filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 deg.C for 24 hr, measuring the amount of NaOH on the surface of biochar, adding into n-propanol solution, and adding zirconium ions in zirconium nitrate solution and OH on the surface of solid phase-Slowly dropwise adding 0.1 mol.L with the molar ratio of 1:5-1Adding the zirconium nitrate solution into the zirconium nitrate solution, stirring for 2 hours at room temperature, aging for 6 hours, filtering, washing a solid phase, and drying to obtain Zr pre-loaded biochar;
(3) preparation of the adsorbent
According to OH in the sodium hydroxide stock solution in the step (2)-And zirconium ions in the zirconium nitrate solution at a molar ratio of 5:1 were slowly added to 50ml of 0.1 mol. L-1Adding Zr pre-loaded biochar into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution, which accounts for the Zr pre-loaded biochar, is 2mmol/g, stirring for 2h, aging for 6h, performing suction filtration, washing, and drying at 80 ℃ for 24h to obtain the adsorbent.
The method comprises the steps of carrying out primary absorption decomposition on organic phosphorus pesticide waste gas by using an absorption decomposition tower filled with strong alkaline electrolyzed water with the pH value of 13, then dividing the organic phosphorus pesticide waste gas into 7 parts, staying the 7 parts in a biological tower for 20s for biodegradation, respectively filling the filler in the biological tower with the adsorptive phosphorus removal bacteria particles of examples 1-5, the adsorptive particles of comparative example 1 and the phosphorus removal bacteria mixture which is the same as the phosphorus removal bacteria mixture of example 1, carrying out biodegradation treatment on the mixture to respectively serve as experiments one to seven, and testing the change of the total organic phosphorus pesticide content before and after the treatment of the experiments one to seven, wherein the results are shown in Table 1.
Table 1 variation of total organophosphorus pesticide content from experiment one to seven
| Intake air concentration (mg/m)3) | Concentration of outgas (mg/m)3) | Removal rate | |
| Experiment one | 68 | 0.51 | 99.3％ |
| Experiment two | 68 | 0.78 | 98.8％ |
| Experiment three | 68 | 0.16 | 99.8％ |
| Experiment four | 68 | 0.27 | 99.6％ |
| Experiment five | 68 | 0.19 | 99.7％ |
| Experiment six | 68 | 23.47 | 65.5％ |
| Experiment seven | 68 | 12.31 | 81.9％ |
As can be seen from table 1, the removal rate of the total organophosphorus pesticide after the biological treatment by the adsorptive phosphorus removing bacteria particles of the present invention can reach more than 98.8%, while in the sixth experiment and the seventh experiment, the total organophosphorus content is higher, because the biological tower of the sixth experiment only contains Zr-loaded charcoal adsorbent, which has a good adsorption capacity and can capture the organic pollutants in the exhaust gas, but is a physical action and cannot fundamentally solve the degradation problem. Although the experiment seven simultaneously has the Zr-loaded charcoal adsorbent and the phosphorus removing bacteria, the Zr-loaded charcoal adsorbent and the phosphorus removing bacteria are simply physically mixed, and only the combination of the physical adsorption effect and the degradation effect of the phosphorus removing bacteria is realized, so that the phosphorus removing bacteria can not be intensively distributed in the adsorbent like the phosphorus removing bacteria, and after the adsorbent captures organic pollutants, the phosphorus removing bacteria can be fully and quickly contacted with the organic pollutants, the overall removal efficiency of the organophosphorus pesticide waste gas is greatly improved, and the removal effect is still inferior to that of the adsorptive phosphorus removing bacteria particles.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The adsorptive phosphorus removal bacterium particle is characterized by comprising phosphorus removal bacteria, a Zr-loaded biochar adsorbent and an auxiliary material, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the auxiliary material is 1: 0.5-1.
2. A preparation method of adsorptive phosphorus removal bacteria particles is characterized by comprising the following steps:
(1) preparation of biochar
Crushing the fruit shells, sieving, cleaning, and carbonizing at high temperature to obtain charcoal;
(2) zr-preloaded biocarbon
Adding the biochar into a sodium hydroxide solution for refluxing and suction filtration, storing filtrate as a sodium hydroxide stock solution, drying a solid phase, adding the solid phase into an alcohol solution, adding a zirconium nitrate solution, stirring and aging at room temperature, and washing and drying the solid phase after suction filtration to obtain Zr-preloaded biochar;
(3) preparation of the adsorbent
Slowly adding the sodium hydroxide stock solution obtained in the step (2) into a zirconium nitrate solution, stirring to obtain a precursor mixed solution, adding the Zr pre-loaded biochar into the precursor mixed solution, stirring and aging, and washing and drying after suction filtration to obtain an adsorbent;
(4) granulation by adsorbing phosphorus-removing bacteria
And adding a drying protective agent into the fermented phosphorus removing bacteria to obtain bacteria slurry, mixing and granulating the bacteria slurry, the adsorbent and the auxiliary materials, and performing vacuum drying to obtain the adsorptive phosphorus removing bacteria.
3. The preparation method of the adsorptive phosphorus-removing bacteria particle as claimed in claim 2, wherein the preparation of the biochar comprises crushing the fruit shell, sieving with a 100-mesh sieve, washing with water for 3-7 times, placing in a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at a speed of 4-8 ℃, preserving the temperature for 3-5 h, carbonizing, and cooling to room temperature.
4. The method for preparing the adsorptive phosphorus-removing bacteria particle as claimed in claim 2, wherein the zirconium ion in the zirconium nitrate solution and the OH on the solid phase surface in the step (2)-The molar ratio of (A) to (B) is 1: 4-6.
5. The method for preparing the adsorptive phosphorus-removing bacteria particle as claimed in claim 2, wherein the refluxing condition in the step (2) is 80 ℃ refluxing for 10-14 h, and the drying conditions in the step (2) and the step (3) are respectively 75-85 ℃ drying for 24-30 h.
6. The method for preparing the adsorptive phosphorus-removing bacteria particle as claimed in claim 2, wherein OH in the sodium hydroxide stock solution in the step (3)-And the molar ratio of zirconium ions in the zirconium nitrate solution is 4-6: 1.
7. The method for preparing the adsorptive phosphorus-removing bacteria particle as claimed in claim 2, wherein the molar mass of the zirconium ion in the zirconium nitrate solution in the step (3) in the Zr-pre-loaded biochar is 1.5-2.5 mmol/g.
8. The method for preparing adsorptive phosphorus-removing bacteria granule according to claim 2, wherein the drying protective agent is at least one of raffinose, dimethyl sulfoxide, trehalose, lactose, glycerol and gelatin.
9. The method for preparing the adsorptive phosphorus-removing bacteria particle according to claim 2, wherein in the step (4), the temperature of vacuum drying is 30-50 ℃ and the time is 1-10 h, and the water content of the adsorptive phosphorus-removing bacteria is less than or equal to 5%.
10. The method for treating the organophosphorus pesticide waste gas is characterized by comprising the following steps in sequence:
(1) preliminarily absorbing and decomposing the organophosphorus pesticide waste gas by using strongly alkaline electrolyzed water with the pH value of 11-13;
(2) the adsorptive phosphorus-removing bacteria particle of claim 1 or the adsorptive phosphorus-removing bacteria particle prepared by the preparation method of the adsorptive phosphorus-removing bacteria particle of any one of claims 2 to 9 is used for adsorbing and degrading organic pollutants in the organophosphorus pesticide waste gas.
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