CN114082401B - Adsorptive dephosphorization bacteria particles, preparation method thereof and method for treating waste gas of organophosphorus pesticide - Google Patents
Adsorptive dephosphorization bacteria particles, preparation method thereof and method for treating waste gas of organophosphorus pesticide Download PDFInfo
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- CN114082401B CN114082401B CN202111372932.5A CN202111372932A CN114082401B CN 114082401 B CN114082401 B CN 114082401B CN 202111372932 A CN202111372932 A CN 202111372932A CN 114082401 B CN114082401 B CN 114082401B
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- 241000894006 Bacteria Species 0.000 title claims abstract description 115
- 230000000274 adsorptive effect Effects 0.000 title claims abstract description 44
- 239000002245 particle Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002912 waste gas Substances 0.000 title claims abstract description 31
- 239000003987 organophosphate pesticide Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 70
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 67
- 239000011574 phosphorus Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 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 66
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- 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
- 238000003483 aging Methods 0.000 claims description 3
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- 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
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- 239000007789 gas Substances 0.000 abstract description 6
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- 235000011121 sodium hydroxide Nutrition 0.000 description 34
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
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- 229910052799 carbon Inorganic materials 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
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- 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
- 235000009319 Terminalia catappa Nutrition 0.000 description 2
- 244000277583 Terminalia catappa Species 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
- 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
- 208000009043 Chemical Burns Diseases 0.000 description 1
- 208000018380 Chemical injury Diseases 0.000 description 1
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- 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect 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
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 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
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 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
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J20/02—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)
- Engineering & Computer Science (AREA)
- 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)
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- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides adsorptive phosphorus removal bacteria particles and a preparation method thereof, and an organophosphorus pesticide waste gas treatment method, wherein the adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and auxiliary materials, and the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the auxiliary materials is 1:0.5-1. The invention combines the adsorbent and the dephosphorization bacteria, fully combines the advantages of the adsorbent on the capturing capability of organic pollutants in waste gas and the advantages of the dephosphorization bacteria on degrading organic matters, and has certain capturing capability on the dephosphorization bacteria, so that the dephosphorization bacteria can be intensively distributed in the adsorbent, and after the adsorbent captures the organic pollutants, the dephosphorization bacteria can fully and quickly contact the organic pollutants, thereby greatly improving the overall efficiency of removing the organic phosphorus pesticide waste gas.
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 removal bacteria particles and an organophosphorus pesticide waste gas treatment method.
Background
In recent years, researchers have conducted a great deal of research on the removal of organophosphorus pesticide waste gas, and chemical methods commonly used in industry such as ozone, hydrogen peroxide, peracetic acid, hypochlorite oxidation and the like have the defects of high cost, easiness in secondary pollution and the like.
At present, biological methods are also 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 larger biotoxicity, has toxic effect on most insects, people and livestock and microorganisms, and is difficult to effectively remove common microorganisms in the traditional aerobic biological spray tower device, thereby endangering the environment.
The phosphorus removal bacteria have better effect on degradation of organophosphorus pesticide waste gas than other microorganisms due to the characteristic phosphorus removal property. Most organophosphorus pesticides belong to hydrophobic compounds, microorganisms are difficult to capture pollutants in pesticide waste gas in a spray tower device, and phosphorus removal bacteria are insufficient in contact with the pollutants, so that the degradation efficiency is low.
Therefore, a safe and effective method for degrading organophosphorus pesticide waste gas is needed to be continuously sought.
Disclosure of Invention
The invention aims to provide adsorptive dephosphorization bacteria particles, a preparation method thereof and an organophosphorus pesticide waste gas treatment method. The dephosphorization bacteria disclosed by the invention have the advantages of taking adsorption and dephosphorization properties into account, capturing organic matters in waste gas better, enabling the dephosphorization bacteria to be in full contact with pollutants, and achieving higher degradation rate.
In order to achieve the above purpose, the first aspect of the present invention provides an adsorptive phosphorus removal bacteria particle, which comprises phosphorus removal bacteria, zr-loaded biochar adsorbent and auxiliary materials, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the auxiliary materials is 1:0.5-1.
The adsorptive phosphorus removal bacteria particles of the invention combine the adsorbent and the phosphorus removal bacteria together, and can simultaneously take account of adsorption and phosphorus removal. The method can solve the problem of secondary pollution caused by overflowing of organic matters in the adsorption and regeneration processes when a single adsorbent is adopted for waste gas treatment, and can also solve the problems of poor solubility and capturing capacity of strain nutrient solution to organic matters, insufficient contact of the phosphorus removal bacteria with pollutants and low degradation efficiency when the phosphorus removal bacteria are singly adopted for waste gas treatment. The invention combines the adsorbent and the dephosphorization bacteria, fully combines the advantages of the adsorbent on the capturing capability of organic pollutants in waste gas and the advantages of the dephosphorization bacteria on degrading organic matters, and has certain capturing capability on the dephosphorization bacteria, so that the dephosphorization bacteria can be intensively distributed in the adsorbent, and after the adsorbent captures the organic pollutants, the dephosphorization bacteria can fully and quickly contact the organic pollutants, thereby greatly improving the overall efficiency of removing the organic phosphorus pesticide waste gas.
As a preferred 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 method for preparing adsorptive phosphorus removal bacteria particles, comprising the steps of:
(1) Preparation of biochar
Pulverizing shell, sieving, cleaning, and carbonizing at high temperature to obtain biochar;
(2) Zr preloaded biochar
Adding the biochar into a sodium hydroxide solution for reflux, filtering, 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, filtering, washing the solid phase, and drying to obtain Zr preloaded biochar;
(3) Preparation of adsorbents
Slowly adding the sodium hydroxide stock solution 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 ageing, filtering, washing and drying to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
And adding a drying protective agent into the fermented dephosphorization bacteria to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the auxiliary materials, and carrying out vacuum drying to obtain the adsorptive dephosphorization bacteria.
In the preparation of the adsorptive phosphorus removal bacteria particles, the adsorbent loaded with Zr is prepared firstly, the adsorbent has stronger adsorption capacity, and then the phosphorus removal bacteria particles which have both adsorption performance and phosphorus removal function can be obtained by adopting the auxiliary material composite phosphorus removal bacteria, so that the phosphorus removal bacteria can be intensively distributed in the adsorbent, and after the adsorbent captures organic pollutants, the phosphorus removal bacteria can fully and quickly contact with the organic pollutants, thereby greatly improving the overall efficiency of removing the organic phosphorus pesticide waste gas.
As a preferred technical scheme, the shell is a nut shell, and the nut shell is any one of pistachio nut shell, hawaii nut shell, badam nut shell and pecan nut shell.
As a preferred technical scheme, the preparation of the biochar comprises the steps of crushing the shells, sieving with a 100-mesh sieve, cleaning with water for 3-7 times, placing in a tube furnace, introducing nitrogen, heating to 500 ℃ at a speed of 4-8 ℃, preserving heat for 3-5 h, carbonizing, and cooling to room temperature.
As a preferred technical scheme, in the step (2), zirconium ions in the zirconium nitrate solution and OH on the solid phase surface - The molar ratio of (2) is 1:4-6.
As a preferred technical scheme, the reflux condition in the step (2) is that the reflux is carried out for 10-14 h at 80 ℃, and the drying conditions in the step (2) and the step (3) are respectively and independently 75-85 ℃ for 24-30 h.
As a preferred technical scheme, the alcohol solution in the step (2) is n-propanol or isopropanol.
As a preferred embodiment, 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.
As a preferable technical scheme, the molar mass of zirconium ions in the zirconium nitrate solution in the step (3) accounting for the Zr preloaded biochar is 1.5-2.5 mmol/g.
As a preferred technical scheme, the drying protective agent is at least one of raffinose, dimethyl sulfoxide, trehalose, lactose, glycerol and gelatin.
As a preferred 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 third aspect of the invention provides a method for treating organophosphorus pesticide waste gas, which comprises the following steps in sequence:
(1) Adopting strong alkaline electrolyzed water with pH value of 11-13 to perform primary absorption decomposition on the organophosphorus pesticide waste gas;
(2) The adsorptive phosphorus removal bacteria particles prepared by the adsorptive phosphorus removal bacteria particles or the preparation method of the adsorptive phosphorus removal bacteria particles are used for adsorbing and degrading organic pollutants in the organophosphorus pesticide waste gas.
The invention firstly adopts the strong alkaline electrolyzed water with the pH value of 11-13 to carry out preliminary 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 is absorbed 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 particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and auxiliary materials, wherein the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the auxiliary materials is 1:0.5-1. The mass ratio of the phosphorus removal bacteria, the Zr loaded biochar adsorbent and 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, 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 removal bacteria particles can comprise the following steps:
(1) Preparation of biochar
Pulverizing shell, sieving, cleaning, and carbonizing at high temperature to obtain biochar;
(2) Zr preloaded biochar
Adding biochar into a sodium hydroxide solution for reflux, filtering, storing filtrate as a sodium hydroxide stock solution, drying a solid phase, adding into an alcohol solution, adding a zirconium nitrate solution, stirring and aging at room temperature, filtering, washing the solid phase, and drying to obtain Zr preloaded biochar;
(3) Preparation of adsorbents
Slowly adding the sodium hydroxide stock solution 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 ageing, filtering, washing and drying to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
Adding a drying protective agent into the fermented dephosphorization bacteria to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and auxiliary materials, and carrying out vacuum drying to obtain the adsorptive dephosphorization bacteria.
Wherein, in the step (1), the shell is a nut shell, and the nut shell is any one of pistachio shell, hawaii shell, badam shell and pecan shell, preferably pistachio shell. The step (1) is specifically that the shells are crushed, sieved by a 100-mesh sieve, washed by water for 3 to 7 times, placed in a tube furnace, filled with nitrogen, heated to 500 ℃ at a speed of 4 to 8 ℃, kept for 3 to 5 hours for carbonization, and cooled to room temperature.
In the step (2), zirconium ions in the zirconium nitrate solution and OH on the solid phase surface - The molar ratio of (2) is 1:4-6, preferably 1:5, the reflux condition is that the reflux is performed for 10-14 h at 80 ℃, the drying condition is that the drying is performed for 24-30 h at 75-85 ℃, and the alcohol solution is n-propanol or isopropanol.
In step (3), OH in sodium hydroxide stock solution - And the molar ratio of zirconium ions in the zirconium nitrate solution is 4-6:1. The zirconium ion in the zirconium nitrate solution accounts for 1.5-2.5 mmol/g of the molar mass of the Zr preloaded biochar.
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 h, and the water content of the adsorptive dephosphorization bacteria is less than or equal to 5%.
The method for treating the organophosphorus pesticide waste gas comprises the following steps in sequence:
(1) Adopting strong alkaline electrolyzed water with pH value of 11-13 to perform primary absorption decomposition on organophosphorus pesticide waste gas;
(2) And adsorbing and degrading organic pollutants in the organophosphorus pesticide waste gas by adopting adsorptive phosphorus removing bacteria particles.
The waste gas of organophosphorus pesticides is mostly phosphate or thiophosphate substances, has strong volatility, is slightly soluble in water and is more acidic, and the waste gas is easily decomposed into organic matters with low toxicity and easier degradation under the strong alkaline electrolyte with the pH value of 11-13. The active ingredient of the strong alkaline electrolyzed water is usually NaOH or KOH, contains active hydrogen, and can effectively remove dirt such as lipid, protein and the like through saponification and emulsification dispersion. Unlike other alkaline water formed by caustic soda, the strong alkaline electrolyzed water does not cause skin irritation or chemical burn, has obvious effect of decomposing oily substances, and has the characteristics of safety, no secondary pollution, low cost, easy obtainment and the like. Using MoS 2 /NiSe 2 The composite material is added as a catalyst to a working electrode to perform electrolysis to obtain strongly alkaline electrolyzed water.
For a better description of the objects, technical solutions and advantageous effects 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 limiting the present invention.
Example 1
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and diatomite, and 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 pistachio nuts, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tube 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 biochar
5g of charcoal was added to 60mL of 1 mol.L -1 Reflux for 12h at 80 ℃, filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 ℃ for 24h, determining the amount of NaOH on the surface of the biochar, adding the NaOH into n-propanol solution, and adding zirconium ions and OH on the surface of the solid phase according to the zirconium nitrate solution - Slowly dropwise adding 0.1 mol.L in a molar ratio of 1:5 -1 Adding zirconium nitrate solution, stirring for 2 hours and aging for 6 hours at room temperature, filtering, washing and drying a solid phase to obtain Zr pre-loaded biochar;
(3) Preparation of adsorbents
The sodium hydroxide stock solution in the step (2) is treated according to OH therein - And zirconium ions in the zirconium nitrate solution were slowly added to 50ml of 0.1 mol.L at a molar ratio of 5:1 -1 Adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution accounting for 2mmol/g of the Zr pre-loaded biochar, stirring for 2 hours, aging for 6 hours, filtering, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
Adding glycerol (the solid content is controlled to be 60%) into the fermented dephosphorization bacteria (the content is 1.5% of the weight of the dephosphorization bacteria) to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the diatomite according to the mass ratio of 1:0.8:1, and vacuum drying for 8 hours at 40 ℃ to obtain the adsorptive dephosphorization bacteria with the water content of 4.1%.
Example 2
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and diatomite, and the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the diatomite is 1:0.75:0.5.
The preparation method comprises the following steps:
(1) Preparation of biochar
Crushing pistachio nuts, sieving with a 100-mesh sieve, cleaning with deionized water for 5 times, placing in a tube furnace, introducing nitrogen, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 4 hours, carbonizing, and cooling to room temperature;
(2) Zr preloaded biochar
5g of charcoal was added to 60mL of 1 mol.L -1 Reflux for 14h at 80 ℃, filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 85 ℃ for 30h, determining the amount of NaOH on the surface of the biochar, adding the NaOH into n-propanol solution, and adding zirconium ions and OH on the surface of the solid phase into zirconium nitrate solution - Slowly dropwise adding 0.1 mol.L in a molar ratio of 1:4 -1 Adding zirconium nitrate solution, stirring for 2 hours and aging for 6 hours at room temperature, filtering, washing and drying a solid phase to obtain Zr pre-loaded biochar;
(3) Preparation of adsorbents
The sodium hydroxide stock solution in the step (2) is treated according to OH therein - And zirconium ions in the zirconium nitrate solution were slowly added to 50ml of 0.1 mol.L at a molar ratio of 4:1 -1 Adding Zr pre-loaded biochar into the precursor mixed solution, wherein zirconium ions in the precursor mixed solution account for 1.5mmol/g of the Zr pre-loaded biochar, stirring for 2 hours, aging for 6 hours, filtering, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
Adding glycerol (the solid content is controlled to be 60%) into the fermented dephosphorization bacteria (the content is 1% of the weight of the dephosphorization bacteria) to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the diatomite according to the mass ratio of 1:0.75:0.5, and vacuum drying at 45 ℃ for 10 hours to obtain the adsorptive dephosphorization bacteria with the water content of 4%.
Example 3
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and diatomite, and the mass ratio of the phosphorus removal bacteria to the Zr-loaded biochar adsorbent to the diatomite is 1:1:1.
The preparation method comprises the following steps:
(1) Preparation of biochar
Crushing pistachio nuts, sieving with a 100-mesh sieve, cleaning with deionized water for 7 times, placing in a tube furnace, introducing nitrogen, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 4 hours, carbonizing, and cooling to room temperature;
(2) Zr preloaded biochar
5g of charcoal was added to 60mL of 1 mol.L -1 Reflux for 10h at 80 ℃, filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 85 ℃ for 30h, determining the amount of NaOH on the surface of the biochar, adding the NaOH into n-propanol solution, and adding zirconium ions and OH on the surface of the solid phase into zirconium nitrate solution - Slowly adding 0.1 mol.L dropwise in a molar ratio of 1:6 -1 Adding zirconium nitrate solution, stirring for 2 hours and aging for 6 hours at room temperature, filtering, washing and drying a solid phase to obtain Zr pre-loaded biochar;
(3) Preparation of adsorbents
The sodium hydroxide stock solution in the step (2) is treated according to OH therein - And zirconium ions in the zirconium nitrate solution were slowly added to 50ml of 0.1 mol.L at a molar ratio of 6:1 -1 Adding Zr pre-loaded biochar into the precursor mixed solution, wherein zirconium ions in the precursor mixed solution account for 2.5mmol/g of the Zr pre-loaded biochar, stirring for 2 hours, aging for 6 hours, filtering, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
Adding glycerol (the solid content is controlled to be 60%) into the fermented dephosphorization bacteria (the content is 1% of the weight of the dephosphorization bacteria) to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the diatomite according to the mass ratio of 1:1:1, and vacuum drying for 8 hours at 40 ℃ to obtain the adsorptive dephosphorization bacteria with the water content of 4.1%.
Example 4
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and kaolin, and 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
Pulverizing macadamia nut shells, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tube furnace, introducing nitrogen, heating to 500 ℃ at a speed of 5 ℃, preserving heat for 3h, carbonizing, and cooling to room temperature;
(2) Zr preloaded biochar
5g of charcoal was added to 60mL of 1 mol.L -1 Reflux for 12h at 80 ℃, filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 ℃ for 24h, determining the amount of NaOH on the surface of the biochar, adding the NaOH into n-propanol solution, and adding zirconium ions and OH on the surface of the solid phase according to the zirconium nitrate solution - Slowly dropwise adding 0.1 mol.L in a molar ratio of 1:5 -1 Adding zirconium nitrate solution, stirring for 2 hours and aging for 6 hours at room temperature, filtering, washing and drying a solid phase to obtain Zr pre-loaded biochar;
(3) Preparation of adsorbents
The sodium hydroxide stock solution in the step (2) is treated according to OH therein - And zirconium ions in the zirconium nitrate solution were slowly added to 50ml of 0.1 mol.L at a molar ratio of 5:1 -1 Adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution accounting for 2mmol/g of the Zr pre-loaded biochar, stirring for 2 hours, aging for 6 hours, filtering, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
Adding glycerol (the solid content is controlled to be 60%) into the fermented dephosphorization bacteria (the content is 1.5% of the weight of the dephosphorization bacteria) to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the kaolin according to the mass ratio of 1:0.8:1, and vacuum drying for 8 hours at 40 ℃ to obtain the adsorptive dephosphorization bacteria with the water content of 4.1%.
Example 5
The adsorptive phosphorus removal bacteria particles comprise phosphorus removal bacteria, zr-loaded biochar adsorbent and diatomite, and 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 the pecan shells, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tube 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 biochar
5g of charcoal was added to 60mL of 1 mol.L -1 Reflux for 12h at 80 ℃, filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 ℃ for 24h, determining the amount of NaOH on the surface of the biochar, adding the NaOH into n-propanol solution, and adding zirconium ions and OH on the surface of the solid phase according to the zirconium nitrate solution - Slowly dropwise adding 0.1 mol.L in a molar ratio of 1:5 -1 Adding zirconium nitrate solution, stirring for 2 hours and aging for 6 hours at room temperature, filtering, washing and drying a solid phase to obtain Zr pre-loaded biochar;
(3) Preparation of adsorbents
The sodium hydroxide stock solution in the step (2) is treated according to OH therein - And zirconium ions in the zirconium nitrate solution were slowly added to 50ml of 0.1 mol.L at a molar ratio of 5:1 -1 Adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution accounting for 2mmol/g of the Zr pre-loaded biochar, stirring for 2 hours, aging for 6 hours, filtering, washing, and drying at 80 ℃ for 24 hours to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
Adding trehalose (the solid content is controlled to be 60%) into the fermented dephosphorization bacteria (the content is 1.5% of the weight of the dephosphorization bacteria) to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the diatomite according to the mass ratio of 1:0.8:1, and vacuum drying at 40 ℃ for 8 hours to obtain the adsorptive dephosphorization bacteria with the water content of 4.1%.
Comparative example 1
The adsorptive particles are Zr-loaded biochar adsorbent, and the preparation method comprises the following steps:
(1) Preparation of biochar
Crushing pistachio nuts, sieving with a 100-mesh sieve, cleaning with deionized water for 3 times, placing in a tube 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 biochar
Adding 5g of biochar intoTo 60mL 1 mol.L -1 Reflux for 12h at 80 ℃, filtering, storing the filtrate as sodium hydroxide stock solution, drying the solid phase at 80 ℃ for 24h, determining the amount of NaOH on the surface of the biochar, adding the NaOH into n-propanol solution, and adding zirconium ions and OH on the surface of the solid phase according to the zirconium nitrate solution - Slowly dropwise adding 0.1 mol.L in a molar ratio of 1:5 -1 Adding zirconium nitrate solution, stirring for 2 hours and aging for 6 hours at room temperature, filtering, washing and drying a solid phase to obtain Zr pre-loaded biochar;
(3) Preparation of adsorbents
The sodium hydroxide stock solution in the step (2) is treated according to OH therein - And zirconium ions in the zirconium nitrate solution were slowly added to 50ml of 0.1 mol.L at a molar ratio of 5:1 -1 Adding Zr pre-loaded biochar into the precursor mixed solution, wherein the molar mass of zirconium ions in the precursor mixed solution accounting for 2mmol/g of the Zr pre-loaded biochar, stirring for 2 hours, aging for 6 hours, filtering, washing, and drying at 80 ℃ for 24 hours to obtain the adsorbent.
The waste gas of a certain organophosphorus pesticide is subjected to preliminary absorption and decomposition by adopting an absorption and decomposition tower filled with strong alkaline electrolyzed water with pH value of 13, and then is subjected to biodegradation by standing for 20s in a biological tower, the adsorptive phosphorus removing bacteria particles of examples 1-5, the adsorptive particles of comparative example 1 and the phosphorus removing bacteria mixture same as that of example 1 are respectively contained in the filler in the biological tower, and are subjected to biodegradation treatment to be respectively used as experiments one to seven, and the change of the total organophosphorus pesticide content before and after the treatment of the experiments one to seven is tested, and the results are shown in table 1.
TABLE 1 variation of total organophosphorus pesticide content for experiments one to seven
| Concentration of inlet air (mg/m) 3 ) | Concentration of outgas (mg/m) 3 ) | Removal rate of | |
| 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 shown in Table 1, the total organic phosphorus pesticide removal rate after biological treatment of the adsorptive phosphorus removal bacteria particles can reach more than 98.8%, and in experiments six and seven, the total organic phosphorus content is higher, because the biological tower in experiment six only contains Zr-loaded biological carbon adsorbent, although the biological tower has better adsorption capacity, the biological tower can capture organic pollutants in waste gas, but the biological tower is a physical effect, and the degradation problem can not be fundamentally solved. In the experiment seven, although the Zr-loaded biological carbon adsorbent and the dephosphorization bacteria are simultaneously provided, the Zr-loaded biological carbon adsorbent and the dephosphorization bacteria are simply and physically mixed, and the Zr-loaded biological carbon adsorbent is only combined with the physical adsorption effect and the degradation effect of the dephosphorization bacteria, and can not cause the dephosphorization bacteria to be intensively distributed in the adsorbent like the method, so that the dephosphorization bacteria can fully and quickly contact with the organic pollutants after the organic pollutants are captured by the adsorbent, the overall efficiency of removing the organic phosphorus pesticide waste gas is greatly improved, and the removal effect of the adsorbent dephosphorization bacteria is still inferior to that of the adsorbent dephosphorization bacteria particles of the invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The adsorption dephosphorization bacteria particle is characterized by comprising dephosphorization bacteria, zr-loaded biochar adsorbent and auxiliary materials, wherein the mass ratio of the dephosphorization bacteria to the Zr-loaded biochar adsorbent to the auxiliary materials is 1:0.5-1, and the preparation method of the adsorption dephosphorization bacteria particle comprises the following steps:
(1) Preparation of biochar
Pulverizing shell, sieving, cleaning, and carbonizing at high temperature to obtain biochar;
(2) Zr preloaded biochar
Adding the biochar into a sodium hydroxide solution for reflux, filtering, 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, filtering, washing the solid phase, and drying to obtain Zr preloaded biochar;
(3) Preparation of adsorbents
Slowly adding the sodium hydroxide stock solution 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 ageing, filtering, washing and drying to obtain an adsorbent;
(4) Adsorption dephosphorization bacteria granulation
And adding a drying protective agent into the fermented dephosphorization bacteria to obtain bacterial slurry, mixing and granulating the bacterial slurry, the adsorbent and the auxiliary materials, and carrying out vacuum drying to obtain the adsorptive dephosphorization bacteria.
2. The adsorptive phosphorus removal bacteria granule of claim 1, 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, heating to 500 ℃ at a speed of 4-8 ℃, preserving heat for 3-5 h, carbonizing, and cooling to room temperature.
3. The adsorptive phosphorus removal bacteria particle of claim 1, wherein zirconium ions in said zirconium nitrate solution and OH on said solid phase surface in said step (2) - The molar ratio of (2) is 1:4-6.
4. The adsorptive phosphorus removal bacteria particle of claim 1, wherein the reflux condition in step (2) is 80 ℃ reflux for 10-14 h, and the drying conditions in step (2) and step (3) are each independently 75-85 ℃ drying for 24-30 h.
5. The adsorptive phosphorus removal bacteria particle of claim 1, wherein OH in said sodium hydroxide stock solution in step (3) - And the molar ratio of zirconium ions in the zirconium nitrate solution is 4-6:1.
6. The adsorptive phosphorus removal bacteria particle according to claim 1, wherein the ratio of zirconium ions in the zirconium nitrate solution in the step (3) to the Zr preloaded biochar is 1.5-2.5 mmol/g.
7. The adsorptive phosphorus removal bacteria granule of claim 1, wherein the dryness protectant is at least one of raffinose, dimethyl sulfoxide, trehalose, lactose, glycerol and gelatin.
8. The adsorptive phosphorus removal bacteria particle according to claim 1, wherein in the step (4), the temperature of vacuum drying 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%.
9. The method for treating the organophosphorus pesticide waste gas is characterized by comprising the following steps in sequence:
(1) Performing preliminary absorption and decomposition on the organophosphorus pesticide waste gas by using strong alkaline electrolyzed water with pH value of 11-13;
(2) The adsorption and degradation of organic pollutants in the organophosphorus pesticide waste gas by adopting the adsorption and dephosphorization bacteria particles according to any one of claims 1-8.
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| CN111992194A (en) * | 2020-08-04 | 2020-11-27 | 四川轻化工大学 | Preparation method of nano hydrous zirconia loaded biochar for removing phosphorus |
| CN112520860A (en) * | 2020-10-20 | 2021-03-19 | 广州振清环保技术有限公司 | Natural adsorption material microorganism-loaded ecological restoration agent and preparation method thereof |
| CN112940732A (en) * | 2021-02-18 | 2021-06-11 | 陕西省微生物研究所 | Soil organic phosphorus pesticide degradation catalyst and preparation method thereof |
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