CN112275255A - Treating agent for ordnance explosive wastewater containing HMX and preparation method thereof - Google Patents
Treating agent for ordnance explosive wastewater containing HMX and preparation method thereof Download PDFInfo
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- CN112275255A CN112275255A CN202011097371.8A CN202011097371A CN112275255A CN 112275255 A CN112275255 A CN 112275255A CN 202011097371 A CN202011097371 A CN 202011097371A CN 112275255 A CN112275255 A CN 112275255A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- 239000002360 explosive Substances 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 21
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940080314 sodium bentonite Drugs 0.000 claims abstract description 13
- 229910000280 sodium bentonite Inorganic materials 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 45
- 239000012065 filter cake Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002023 wood Substances 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 16
- 229940092782 bentonite Drugs 0.000 claims description 16
- 229910000278 bentonite Inorganic materials 0.000 claims description 16
- 239000000440 bentonite Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 7
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- -1 glyceryl octadecyl ester Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000000028 HMX Substances 0.000 abstract description 20
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 238000003911 water pollution Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000004898 kneading Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to the field of ordnance explosive wastewater treatment, and provides a treatment agent for ordnance explosive wastewater containing octogen and a preparation method thereof, wherein the treatment agent is prepared from the following components in parts by mass: 1 part of sodium bentonite, 0.01-0.12 part of alkali, 0.03-0.1 part of nonionic surfactant, 0.1-0.3 part of mesoporous activated carbon and 0.005-0.04 part of adhesive, wherein the removal rate of the chemical oxygen demand of the treating agent provided by the invention can reach more than 90%, so that the water pollution is greatly reduced, and the preparation method provided by the invention is simple and efficient and is suitable for popularization.
Description
Technical Field
The invention relates to the field of ordnance waste water treatment, in particular to a treatment agent for ordnance explosive waste water containing octogen and a preparation method thereof.
Background
In each link of explosive production, transportation, charging, storage, destruction and the like, a large amount of nitrobenzene compounds and byproducts thereof enter the environment, and a series of explosive wastewater containing various organic pollutants is formed. The explosive waste water has high biological toxicity and strong chemical stability, poses serious threat to the ecological environment and living organisms and has attracted high attention of all countries. In the wastewater discharged by explosive industry, HMX is one of the main components to be removed, and if proper control measures are not taken, serious pollution is caused to the environment.
At present, the main method for treating the organic wastewater containing HMX is based on hydroxyl free radical (. OH) and sulfate free radical (SO)4-The biological technology of the microorganism metabolism, but the conventional biochemical treatment is difficult to work due to the biological toxicity and the chemical stability of the explosive wastewater, and the conventional treatment methods have the defects of long treatment period, large scale, high capital investment and the like, and can cause secondary pollution to the environment, so the effect is not ideal and the individual application is difficult. Accordingly, there is a need to provide a simple, efficient, and high chemical oxygen demand removal process for treating explosive waste water.
Disclosure of Invention
The invention aims to provide a treatment agent for ordnance explosive wastewater containing HMX and a preparation method thereof, aiming at solving the problems in the prior art, the invention is realized by adopting the following technical scheme:
the treatment agent for ordnance explosive wastewater containing HMX is prepared from the following components in parts by mass: 1 part of sodium bentonite, 0.01-0.12 part of alkali, 0.03-0.1 part of nonionic surfactant, 0.1-0.3 part of mesoporous activated carbon and 0.005-0.04 part of adhesive.
Further, the alkali comprises an aqueous solution of potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or/and potassium bicarbonate;
the nonionic surfactant includes: polyacrylamide, polyethylene glycol ether or/and glyceryl octadecyl ester.
Further, the adhesive includes: a cyanoacrylate.
The preparation method of the treatment agent for the war industry explosive wastewater comprises the following steps:
1) preparing alkaline sodium bentonite;
2) preparing mesoporous activated carbon;
3) preparing the treatment agent for the war explosive wastewater by using the product obtained in the step 1) 2).
Further, the step 1) comprises:
1.1) mixing and soaking the sodium bentonite powder and alkali for 1-2 days;
1.2) centrifugally washing the material obtained in the step 1.1) with distilled water until the pH value is 8-9, and then carrying out suction filtration;
1.3) drying the filter cake after suction filtration, and calcining for 1-3 h at 400-600 ℃ in a protective atmosphere;
1.4) crushing and screening to obtain the alkalinized bentonite.
Furthermore, the particle size of the alkalized bentonite is 30-50 μm.
Further, the step 2) comprises:
2.1) crushing the wood into powder with the particle size of 50-70 mu m;
2.2) dipping the powder in an activating agent solution for 1-2 days and then drying;
2.3) heating to 600-800 ℃ at the speed of 8-15 ℃/min under the protective atmosphere, and carbonizing the dried powder for 1-3 h to obtain the mesoporous activated carbon.
Further, the protective atmosphere comprises nitrogen or argon;
the activating agent comprises saturated potassium hydroxide, sodium hydroxide, nitric acid, phosphoric acid solution or/and zinc chloride.
Further, the mass ratio of the activating agent in the step 2.2) to the wood powder is 0.5-3: 1.
Further, the step 3) comprises:
3.1) heating the alkalized bentonite to 40-60 ℃, sequentially adding a nonionic surfactant and water, and stirring for 12 hours;
3.2) centrifuging and washing the product obtained in the step 3.1), mixing with the mesoporous activated carbon and the adhesive, extruding and drying to obtain the wastewater treatment agent.
The invention discloses the following technical effects:
1) the pretreatment agent for the orderine-containing orderine-contained war explosive wastewater has a remarkable treatment effect on orderine-contained orderine explosive wastewater, and the removal rate of Chemical Oxygen Demand (COD) can reach more than 90%.
2) The modified bentonite of the invention takes sodium bentonite as raw material, the raw material source is wide, the modification step is simple, the cost is lower, the montmorillonite content of the modified bentonite is more than 89%, the adsorptivity and cation exchange performance are excellent, and the modified bentonite has high stability, high safety and high environmental compatibility, and further improves the wastewater treatment capacity.
3) The treatment agent for the ordor-containing ordor explosive wastewater is simple in use method and convenient to transport, effectively purifies ordor-containing ordor explosive wastewater, reduces pollution to the environment, and leaves more available resources for offspring.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only. As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
1) Preparation of alkalized Bentonite
Mixing and soaking 1 part of sodium bentonite powder and 0.12 part of aqueous solution of potassium hydroxide and sodium bicarbonate for 1 day, then centrifugally washing with distilled water until the pH value is 8, and then carrying out suction filtration; and drying the filter cake after suction filtration at 40 ℃, placing the filter cake in a nitrogen protective atmosphere, calcining the filter cake at the high temperature of 400 ℃ for 1 hour, crushing the filter cake, and screening the crushed filter cake with a 200-mesh sieve to obtain the alkalized bentonite powder.
2) Preparation of mesoporous activated carbon
The wood is crushed into powder with the particle size of 50-70 mu m. Then, soaking the wood powder in a potassium hydroxide solution for 1 day according to the mass ratio of the potassium hydroxide to the wood powder of 3:1, and drying. Finally, heating the dried wood powder to 600 ℃ at the speed of 8 ℃/min for carbonization for 3h under the nitrogen protection atmosphere to prepare mesoporous activated carbon;
3) preparation of ordor (HMX) -containing war explosive wastewater treatment agent
Heating the alkalized modified bentonite powder to 40 ℃, adding 0.1 part of polyethanol ether, mixing with water, stirring for 12 hours, centrifuging and washing to obtain paste for later use;
and (b) adding 0.3 part of mesoporous activated carbon and 0.04 part of cyanoacrylate into the paste obtained in the step (a), mixing and kneading to obtain a wet mixture, and finally extruding and drying to obtain the octogen (HMX) -containing war explosive wastewater treatment agent.
After the treatment agent provided by the embodiment is used for treating the war explosive wastewater, the removal rate of Chemical Oxygen Demand (COD) is 90.8%.
Example 2
1) Preparation of alkalized Bentonite
Mixing and soaking 1 part of sodium bentonite powder and 0.05 part of aqueous solution of calcium hydroxide, sodium hydroxide and potassium bicarbonate for 2 days, centrifuging and washing the mixture for multiple times by using distilled water until the pH value is 8.5, and performing suction filtration; and drying the filter cake after suction filtration at 40 ℃, placing the filter cake in a nitrogen protective atmosphere, calcining the filter cake at 450 ℃ for 2 hours, crushing the filter cake, and sieving the filter cake with a 200-mesh sieve to obtain the alkalized bentonite powder.
2) Preparation of mesoporous activated carbon
Pulverizing the wood into powder with the particle size of 50-70 mu m. Then, soaking the wood powder in a zinc chloride solution for 2 days according to the mass ratio of the potassium hydroxide to the sodium hydroxide to the wood powder of 1:1, and drying. Finally, the dried wood powder is heated to 700 ℃ at the speed of 10 ℃/min and carbonized for 1h under the nitrogen protection atmosphere to obtain mesoporous activated carbon;
3) preparation of ordor (HMX) -containing war explosive wastewater treatment agent
Heating the alkalized modified bentonite powder to 40 ℃, adding 0.08 part of polyethanol ether, mixing with water, stirring for 12 hours, centrifuging and washing to obtain paste for later use;
and (b) adding 0.25 part of mesoporous activated carbon and 0.035 part of cyanoacrylate into the paste obtained in the step (a), mixing and kneading to obtain a wet mixture, and finally extruding and drying to obtain the ordetor (HMX) -containing war explosive wastewater treatment agent.
After the treatment agent provided by the embodiment is used for treating the war explosive wastewater, the removal rate of Chemical Oxygen Demand (COD) is 91.3%.
Example 3
1) Preparation of alkalized Bentonite
Mixing and soaking 1 part of sodium bentonite powder and 0.08 part of aqueous solution of sodium bicarbonate and potassium carbonate for 2 days, centrifuging and washing the mixture for multiple times by using distilled water until the pH value is 9, and performing suction filtration; and drying the filter cake after suction filtration at 40 ℃, calcining the filter cake for 2 hours at 450 ℃ under the nitrogen protection atmosphere, crushing the filter cake, and screening the crushed filter cake with a 200-mesh sieve to obtain the alkalized bentonite powder.
2) Preparation of mesoporous activated carbon
Firstly, wood is crushed into powder with the particle size of 50-70 mu m. Then, soaking the wood powder in a zinc chloride solution for 2 days according to the mass ratio of the zinc chloride to the wood powder of 3:1, and drying. Finally, heating the dried wood powder to 700 ℃ at the speed of 10 ℃/min under the nitrogen protection atmosphere, and carbonizing for 2h to obtain mesoporous activated carbon;
3) preparation of ordor (HMX) -containing war explosive wastewater treatment agent
Heating the alkalized modified bentonite powder to 50 ℃, adding 0.05 part of octadecyl glyceride, mixing with water, stirring for 12 hours, centrifuging, and washing to obtain paste for later use;
and (b) adding 0.25 part of mesoporous activated carbon and 0.03 part of cyanoacrylate into the paste obtained in the step (a), mixing and kneading to obtain a wet mixture, and finally extruding and drying to obtain the ordetor (HMX) -containing war explosive wastewater treatment agent.
After the treatment agent provided by the embodiment is used for treating the war explosive wastewater, the removal rate of Chemical Oxygen Demand (COD) is 90.2%.
Example 4
1) Preparation of alkalized Bentonite
Mixing and soaking 1 part of sodium bentonite powder and 0.11 part of aqueous solution of calcium hydroxide and potassium carbonate for 2 days, centrifuging and washing the mixture for many times by using distilled water until the pH value is 9, and performing suction filtration; and drying the filter cake after suction filtration at 40 ℃, placing the filter cake in a nitrogen protective atmosphere, calcining the filter cake at a high temperature of 500 ℃ for 2 hours, crushing the filter cake, and screening the crushed filter cake with a 200-mesh sieve to obtain the alkalized bentonite powder.
2) Preparation of mesoporous activated carbon
Pulverizing the wood into powder with the particle size of 50-70 mu m. Then, the wood powder is soaked in phosphoric acid solution for 2 days according to the mass ratio of the phosphoric acid to the wood powder of 0.5:1, and then dried. Finally, the dried wood powder is heated to 800 ℃ at the speed of 10 ℃/min and carbonized for 1h under the nitrogen protection atmosphere to obtain mesoporous activated carbon;
3) preparation of ordor (HMX) -containing war explosive wastewater treatment agent
Heating the alkalized modified bentonite powder to 50 ℃, adding 0.05 part of polyacrylamide, polyethylene glycol ether and octadecyl glyceride, mixing with water, stirring for 12 hours, centrifuging, and washing to obtain paste for later use;
and (b) adding 0.2 part of mesoporous activated carbon and 0.02 part of cyanoacrylate into the paste obtained in the step (a), mixing and kneading to obtain a wet mixture, and finally extruding and drying to obtain the octogen (HMX) -containing war explosive wastewater treatment agent.
After the treatment agent provided by the embodiment is used for treating the war explosive wastewater, the removal rate of Chemical Oxygen Demand (COD) is 91.5%.
Example 5
1) Preparation of alkalized Bentonite
Mixing and soaking 1 part of sodium bentonite powder and 0.01 part of aqueous solution of potassium hydroxide and sodium bicarbonate for 2 days, centrifuging and washing the mixture for many times by using distilled water until the pH value is 8, and performing suction filtration; and drying the filter cake after suction filtration at 40 ℃, placing the filter cake in a nitrogen protective atmosphere, calcining the filter cake at 600 ℃ for 3 hours, crushing the filter cake, and screening the filter cake with a 200-mesh sieve to obtain the alkalized bentonite powder.
2) Preparation of mesoporous activated carbon
Pulverizing the wood into powder with the particle size of 50-70 mu m. Then, soaking the wood powder in a zinc chloride solution for 2 days according to the mass ratio of the zinc chloride to the wood powder of 0.5:1, and drying. Finally, the dried wood powder is heated to 800 ℃ at the speed of 15 ℃/min and carbonized for 1h under the nitrogen protection atmosphere to obtain mesoporous activated carbon;
3) preparation of ordor (HMX) -containing war explosive wastewater treatment agent
Heating the alkalized modified bentonite powder to 60 ℃, adding 0.03 part of polyacrylamide and octadecyl glyceride, mixing and stirring with water for 12 hours, centrifuging, and washing to obtain paste for later use;
and (b) adding 0.1 part of mesoporous activated carbon and 0.005 part of cyanoacrylate into the paste obtained in the step (a), mixing and kneading to obtain a wet mixture, and finally extruding and drying to obtain the octogen (HMX) -containing war explosive wastewater treatment agent.
After the treatment agent provided by the embodiment is used for treating the war explosive wastewater, the removal rate of Chemical Oxygen Demand (COD) is 93.2%.
The chemical oxygen demand reflects the degree of pollution of reducing substances in water, the substances comprise organic matters, nitrite, ferrite, sulfide and the like, the removal rate of COD provided by the embodiment of the invention can reach more than 90 percent, and the COD is taken as a comprehensive index of the relative content of organic substances, which shows that the invention can effectively improve the waste water of the military explosive and greatly reduce the water body pollution.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The treatment agent for ordnance explosive wastewater containing HMX is characterized by being prepared from the following components in parts by mass: 1 part of sodium bentonite, 0.01-0.12 part of alkali, 0.03-0.1 part of nonionic surfactant, 0.1-0.3 part of mesoporous activated carbon and 0.005-0.04 part of adhesive.
2. The agent for treating waste water of military industry explosives in accordance with claim 1, wherein the alkali comprises an aqueous solution of potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or/and potassium bicarbonate;
the nonionic surfactant includes: polyacrylamide, polyethylene glycol ether or/and glyceryl octadecyl ester.
3. The agent for treating weapons explosive wastewater as claimed in claim 1, wherein said adhesive agent comprises: a cyanoacrylate.
4. The method for preparing a treatment agent for waste water of weapons explosives according to any one of claims 1 to 3, characterized in that the method comprises the following steps:
1) preparing alkaline sodium bentonite;
2) preparing mesoporous activated carbon;
3) preparing the treatment agent for the war explosive wastewater by using the product obtained in the step 1) 2).
5. The method for preparing the ordnance explosive wastewater treatment agent according to claim 4, wherein the step 1) comprises:
1.1) mixing and soaking the sodium bentonite powder and alkali for 1-2 days;
1.2) centrifugally washing the material obtained in the step 1.1) with distilled water until the pH value is 8-9, and then carrying out suction filtration;
1.3) drying the filter cake after suction filtration, and calcining for 1-3 h at 400-600 ℃ in a protective atmosphere;
1.4) crushing and screening to obtain the alkalinized bentonite.
6. The method for preparing a ordnance explosive wastewater treatment agent as claimed in claim 5, wherein the particle size of the alkalinized bentonite is 30-50 μm.
7. The method for preparing a ordnance explosive wastewater treatment agent as claimed in claim 4, wherein the step 2) comprises:
2.1) crushing the wood into powder with the particle size of 50-70 mu m;
2.2) dipping the powder in an activating agent solution for 1-2 days and then drying;
2.3) heating to 600-800 ℃ at the speed of 8-15 ℃/min under the protective atmosphere, and carbonizing the dried powder for 1-3 h to obtain the mesoporous activated carbon.
8. The method for preparing a ordnance explosive wastewater treatment agent as claimed in claim 7, wherein the protective atmosphere comprises nitrogen or argon;
the activating agent comprises saturated potassium hydroxide, sodium hydroxide, nitric acid, phosphoric acid solution or/and zinc chloride.
9. The preparation method of the ordnance explosive wastewater treatment agent as claimed in claim 7, wherein the mass ratio of the activating agent in the step 2.2) to the wood powder is 0.5-3: 1.
10. The method for preparing a ordnance explosive wastewater treatment agent as claimed in claim 4, wherein the step 3) comprises:
3.1) heating the alkalized bentonite to 40-60 ℃, sequentially adding a nonionic surfactant and water, and stirring for 12 hours;
3.2) centrifuging and washing the product obtained in the step 3.1), mixing with the mesoporous activated carbon and the adhesive, extruding and drying to obtain the wastewater treatment agent.
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