CN111498947A - Treating agent for halogen-containing compound sewage and preparation method thereof - Google Patents
Treating agent for halogen-containing compound sewage and preparation method thereof Download PDFInfo
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- CN111498947A CN111498947A CN202010323685.9A CN202010323685A CN111498947A CN 111498947 A CN111498947 A CN 111498947A CN 202010323685 A CN202010323685 A CN 202010323685A CN 111498947 A CN111498947 A CN 111498947A
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- exchange resin
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- ion exchange
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- 239000010865 sewage Substances 0.000 title claims abstract description 38
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 31
- 150000002367 halogens Chemical class 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 43
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 18
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 18
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 17
- 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 claims abstract description 16
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 16
- 239000010455 vermiculite Substances 0.000 claims abstract description 16
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 16
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 239000010881 fly ash Substances 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 32
- 238000002791 soaking Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 23
- 238000007789 sealing Methods 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 16
- 239000003595 mist Substances 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims 4
- 238000011282 treatment Methods 0.000 abstract description 15
- -1 halogen ions Chemical class 0.000 abstract description 7
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/135—Combustion residues, e.g. fly ash, incineration waste
- C04B33/1352—Fuel ashes, e.g. fly ash
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a treating agent for halogen-containing compound sewage and a preparation method thereof, wherein the treating agent for halogen-containing compound sewage comprises the following components in parts by weight: 5-18 parts of clay, 16-20 parts of fly ash, 3-7 parts of vermiculite, 8-12 parts of montmorillonite, 7-13 parts of silicon carbide, 2-5 parts of zeolite, 1-3 parts of ammonium carbonate, 11-23 parts of deionized water, 5-10 parts of kieselguhr and 26-48 parts of ion exchange resin. The invention generates the ceramsite with high strength, low density and porous hydrophobicity by various raw materials and processes, the ceramsite is used as an attachment matrix of the ion exchange resin, the ceramsite and the ion exchange resin jointly act on impurities in sewage, halogen ions are absorbed by diatomite and the anion exchange resin in the ceramsite to complete the treatment of halogen-containing compounds, and the alkaline conditions of the ceramsite and the ion exchange resin enable organic compounds to remove the halogen ions, so that the treatment efficiency of the treating agent on the sewage containing the halogen compounds is improved, and meanwhile, the treating agent can also absorb other impurities and can be recycled after treatment and regeneration.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a treating agent for halogen-containing compound sewage and a preparation method thereof.
Background
Sewage is effluent from life and production which is polluted to a certain extent, the original use function of the sewage is lost, and in the production, impurities in the sewage are treated by using a sewage treatment agent so as to enable the sewage to reach the discharge standard. The existing treating agent for the halogen-containing compound sewage is fixed and single in property, low in halogen compound content or low in treatment efficiency of small-batch sewage. Therefore, we propose a treating agent for halogen-containing compound sewage and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a treating agent for halogen-containing compound sewage and a preparation method thereof, which solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a treating agent for halogen-containing compound sewage comprises the following components in parts by weight: 5-18 parts of clay, 16-20 parts of fly ash, 3-7 parts of vermiculite, 8-12 parts of montmorillonite, 7-13 parts of silicon carbide, 2-5 parts of zeolite, 1-3 parts of ammonium carbonate, 11-23 parts of deionized water, 5-10 parts of kieselguhr and 26-48 parts of ion exchange resin.
In a preferred embodiment of the present invention, the clay has a particle size of 2 to 5mm, and the fly ash has a particle size of 1 to 5 mm.
In a preferred embodiment of the present invention, the montmorillonite has a particle size of 3 to 6mm, the silicon carbide has a particle size of 1 to 5mm, and the ammonium carbonate has a particle size of 2 to 5 mm.
In a preferred embodiment of the present invention, the particle size of the vermiculite is 6-12mm, the particle size of the zeolite is 6-12mm, and the particle size of the diatomaceous earth is 6-12 mm.
As a preferred embodiment of the present invention, the ion exchange resin is a strongly basic anion exchange resin, and the particle size of the ion exchange resin is 0.4 to 0.6 mm.
In the technical scheme, the ceramsite is prepared by clay, fly ash, vermiculite, montmorillonite, silicon carbide, zeolite, ammonium carbonate and diatomite, matrix support is provided for ion exchange resin, ammonium carbonate is used for promoting the formation of pores in the ceramsite, meanwhile ammonium carbonate solution dissolves the separator in the middle of the silicon carbide, influence is eliminated, the purity of the silicon carbide is improved, and the reinforcement of the silicon carbide on the ceramsite matrix is promoted, the montmorillonite, the vermiculite and the diatomite are used for improving the adsorption capacity of the ceramsite, the pores in the ceramsite are expanded under the action of the montmorillonite and the ammonium carbonate solution, the pores are further expanded under the combined action of the vermiculite and the zeolite, the clay is used as a bonding agent to bond other viscous raw materials together, the combination of various raw materials is prepared into the ceramsite with small density and porosity, the attachment of the ion exchange resin on the ceramsite is facilitated, the treating agent is suspended in sewage, and the contact between the treating agent and halogen-containing compounds in the sewage is, is favorable for adsorbing suspended impurities in water.
A preparation method of a treating agent for halogen-containing compound sewage comprises the following steps:
1) pre-treating;
2) granulating;
3) roasting;
4) and (4) combining.
As a preferred embodiment of the present invention, the step 1) includes the steps of:
1.1) treating ion exchange resin:
soaking the resin in 10% sodium chloride solution for 20-48 hours, washing the resin with deionized water, soaking the resin in 3-10% sodium hydroxide solution for 20-50 minutes, and washing the resin with deionized water until the pH value of a washing solution is 7.0-8.0 to obtain ion exchange resin A;
1.2) processing other raw materials:
a) and (3) processing other raw materials: respectively placing clay, fly ash, vermiculite, montmorillonite, silicon carbide, zeolite, ammonium carbonate and diatomite in a crusher for crushing to prepare smaller particles and removing impurities;
b) treating the diatomite: soaking the diatomite in the previous step in 3-10% sodium hydroxide solution for 2-5 hours, stirring to disperse the diatomite, filtering and washing, and drying to obtain diatomite A;
c) grinding: and grinding the raw materials in a grinder respectively to obtain the raw material A with the required particle size.
In the technical scheme, the raw materials are pretreated to ensure that the activation of the ion exchange resin is convenient for subsequent operation, the treatment of the diatomite provides a foundation for the improvement of the subsequent adsorption capacity of the diatomite, the combined action of the two after treatment can effectively improve the treatment efficiency of the treating agent on halogen-containing compounds in the sewage, and the grinding of the raw materials ensures that the raw materials can reach the optimal mixed particle size and can be uniformly distributed in subsequent mixing, so that the prepared ceramsite reaches the optimal state, and meanwhile, the surface property of the raw materials is improved, and further, the adsorption capacity of the ceramsite is improved.
As a preferred embodiment of the present invention, the step 2) includes the steps of:
a) dissolving ammonium carbonate in deionized water in the components to obtain a solution A, placing the 16-25% of the component in the raw material A in the step 1) in a stirrer, sealing, spraying water mist into the stirring chamber by using the 16-25% of the solution A, pumping out gas in the stirring chamber, and then filling the gas into the stirring chamber to achieve gas circulation, and stirring for 1-2 hours;
b) adding 22-35% of the raw material A into the stirrer again, sealing, spraying 22-35% of the solution A into the stirring chamber, pumping out the gas in the stirring chamber, charging the gas into the stirring chamber to achieve gas circulation, and stirring for 1-2 hours;
c) and finally, adding the raw material A of the rest components into the stirrer, sealing, spraying water mist into the stirring chamber by using the rest solution A, pumping out the gas in the stirring chamber, filling the gas into the stirring chamber to achieve gas circulation, and stirring for 1-2 hours to obtain the raw material B.
In the technical scheme, ammonium carbonate is dissolved in deionized water and is contacted with raw materials in a water mist mode, so that the solution is uniformly mixed with the raw materials, the viscosity among the raw materials is increased, impurities in silicon carbide can be dissolved, meanwhile, as the raw materials are alkaline, the ammonium carbonate solution reacts to generate gas and the gas is dissipated in a stirring chamber, gas circulation formed by external machinery is utilized to consolidate the formation of pores, the raw materials are added for three times, so that the internal and external textures of the ceramsite are uniform, the influence of the aggregation of single raw materials on the distribution of the pores in the ceramsite is avoided, the pores in the inner cavity of the ceramsite are uniform, the montmorillonite expands with water to promote the loose distribution among the raw materials, and the porous state.
As a preferred embodiment of the present invention, the step 3) includes the steps of:
a) firing: preheating the rotary kiln at 100 ℃, placing the raw material B obtained in the step 2) into the rotary kiln, gradually heating to 150-;
b) and (3) cooling: cooling the substrate A in a cooling machine, cooling the substrate A to 300-500 ℃ at the speed of 5-10 ℃/min, and cooling to room temperature at the speed of 10-20 ℃ to obtain a substrate B;
c) cleaning: and putting the matrix B into deionized water for repeated cleaning to obtain a matrix C.
In the technical scheme, the process enables the raw material green bodies to be made into the ceramic particles, generates a ceramic particle substrate, forms an internal framework of the ceramic particles, increases the internal pore diameter of the ceramic particles, increases the strength of the ceramic particles, simultaneously completes the change of the tissue form of the diatomite, improves the adsorption capacity of the ceramic particles on halogen ions, increases the number of pores due to the thermal expansion of zeolite and vermiculite, enables deionized water in the previous step to evaporate and ammonium carbonate to decompose and overflow in the previous low-temperature roasting step, leaves the pores, and then cleans and removes impurities to ensure the cleanness of the ceramic particles.
As a preferred embodiment of the present invention, the step 4) includes the steps of:
a) mixing: putting the matrix C and the ion exchange resin into a stirrer, slowly stirring for 3-5 hours, allowing the ion exchange resin to enter pores in the matrix C, heating to 25-55 ℃, stirring for 20-30 minutes, cooling to room temperature, and continuously stirring for 1-2 hours to obtain a mixture A;
b) infiltrating: soaking the mixture in deionized water for 45-60 min, sealing and aging for 24-48 hr, soaking in 3-10% sodium hydroxide solution for 20-50 min, and repeatedly cleaning to obtain the final product.
In the technical scheme, the ion exchange resin enters the inner pores of the ceramsite matrix under the stirring effect, the ion exchange resin is enabled to be more attached to the pores of the inner cavity of the ceramsite through heating and stirring, the ion exchange resin is enabled to expand and be more tightly combined with the ceramsite through subsequent soaking in deionized water, the ion exchange resin is prevented from being separated from the ceramsite, the ion exchange resin and the ceramsite are more convenient to combine and play a role together, and the performance of the ceramsite is stabilized and reaches the optimal treatment state through aging and soaking.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention relates to a treating agent for halogen-containing sewage and a preparation method thereof, which generate high-strength, low-density, porous and hydrophobic ceramsite through the combination of various raw materials and subsequent process operation, wherein the ceramsite suspended in the sewage is used as an attachment matrix of ion exchange resin, so that the ceramsite and the ion exchange resin cooperate to act on impurities in the sewage together, halogen ions are adsorbed by diatomite and the anion exchange resin in the ceramsite, the treatment of halogen-containing compounds in the sewage is completed, the ceramsite provides a basic environment, and the strong basicity of the ion exchange resin can promote the halogen ions to be removed when the halogen-containing compounds are organic compounds, so that the treatment efficiency of the treating agent on the halogen-containing sewage is improved, meanwhile, the treating agent can also adsorb other impurities in the sewage, and the treating agent can be recycled through treatment and regeneration.
2. According to the treating agent for the sewage containing the halogen compounds and the preparation method thereof, the weight components of the raw materials are changed within the range, so that the ceramsite can improve the density per se according to the density of the sewage, the ceramsite can be controlled to suspend at any position in the sewage, the treating agent is convenient to treat in the sewage and adsorb the halogen compounds, and the treatment efficiency of the treating agent on the sewage containing the halogen compounds is improved.
3. According to the treating agent for the halogen-containing compound sewage and the preparation method thereof, the ceramsite with uniformly distributed raw materials and pores can be formed by the components, the granulating and roasting modes of the ceramsite in the treating agent, so that the porous and low-density state of the ceramsite is favorably formed, the specific surface area of the ceramsite is increased, the large amount of ion exchange resin can be conveniently attached to the ceramsite, and the preparation tamping foundation of the treating agent is provided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Soaking 26 parts of ion exchange resin in a 10% sodium chloride solution for 20 hours, washing with deionized water, soaking in a 3% sodium hydroxide solution for 20 minutes, washing with deionized water until the pH of a washing solution is 7.0, respectively placing 5 parts of clay, 16 parts of fly ash, 3 parts of vermiculite, 8 parts of montmorillonite, 7 parts of silicon carbide, 2 parts of zeolite and 5 parts of diatomite in a crusher for crushing to prepare smaller particles and remove impurities, taking the diatomite, soaking in a 3% sodium hydroxide solution for 2 hours, stirring to disperse the diatomite, filtering, washing and drying, and finally respectively placing the raw materials in a grinder for grinding to obtain the raw materials with the required particle size;
dissolving 1 part of ammonium carbonate in 11 parts of deionized water to obtain a solution A for later use, placing 16% of raw materials in a stirrer and sealing, spraying water mist into the stirrer chamber by using the 16% solution A, pumping out and filling gas in the stirrer chamber to achieve gas circulation, stirring for 1 hour, adding 22 parts of raw materials into the stirrer again and sealing, spraying water mist into the stirrer chamber by using the 22 part of solution A, pumping out and filling gas in the stirrer chamber to achieve gas circulation, stirring for 1 hour, finally adding the rest of raw materials into the stirrer and sealing, spraying water mist into the stirrer chamber by using the rest of solution A, pumping out and filling gas in the stirrer chamber to achieve gas circulation, and stirring for 1 hour to obtain raw material balls;
preheating a rotary kiln at 100 ℃, placing the obtained raw material balls into the rotary kiln, gradually heating to 150 ℃, roasting for 20 minutes, controlling the rotating speed of the rotary kiln to be 2 revolutions per minute, then heating to 450 ℃, roasting for 2 hours, placing the raw material balls into a cooling machine for cooling, cooling to 300 ℃ at the speed of 5 ℃/minute, cooling to room temperature at the speed of 10 ℃/minute, and finally placing the raw material balls into deionized water for repeated cleaning;
and (3) putting the raw material ball and the ion exchange resin into a stirrer, slowly stirring for 3 hours, allowing the ion exchange resin to enter pores in the raw material ball, heating to 25 ℃, stirring for 20 minutes, cooling to room temperature, continuously stirring for 1 hour, soaking for 45 minutes by using deionized water, taking out, sealing, aging for 24 hours, soaking for 20 minutes by using a 3% sodium hydroxide solution, and finally repeatedly cleaning to obtain a finished product.
Example 2
Firstly, soaking 37 parts of ion exchange resin in a 10% sodium chloride solution for 34 hours, washing with deionized water, then soaking in a 7% sodium hydroxide solution for 35 minutes, then washing with deionized water until the pH of a washing solution is 7.5, respectively placing 12 parts of clay, 18 parts of fly ash, 5 parts of vermiculite, 10 parts of montmorillonite, 10 parts of silicon carbide, 3 parts of zeolite and 7 parts of diatomite in a crusher for crushing to prepare smaller particles and remove impurities, taking the diatomite, soaking in a 7% sodium hydroxide solution for 4 hours, stirring to disperse the diatomite, then filtering, washing and drying, and finally respectively placing the raw materials in a grinder for grinding to obtain the raw materials with required particle size;
dissolving 2 parts of ammonium carbonate in 17 parts of deionized water to obtain a solution A for later use, placing 21% of the raw materials in a stirrer and sealing, spraying water mist into the stirrer chamber by using the 41% solution A, pumping out and refilling the gas in the stirrer chamber to achieve gas circulation, stirring for 1.5 hours, adding 29% of the raw materials into the stirrer again and sealing, spraying water mist into the stirrer chamber by using the 29% solution A, pumping out and refilling the gas in the stirrer chamber to achieve gas circulation, stirring for 1.5 hours, finally adding the raw materials of the rest components into the stirrer and sealing, spraying water mist into the stirrer chamber by using the rest solution A, pumping out and refilling the gas in the stirrer chamber to achieve gas circulation, and stirring for 1.5 hours to obtain raw material balls;
preheating a rotary kiln at 100 ℃, placing the obtained raw material balls into the rotary kiln, gradually heating to 180 ℃, roasting for 25 minutes, setting the rotating speed of the rotary kiln to 4 revolutions per minute, then heating to 650 ℃, roasting for 3 hours, placing the raw material balls into a cooling machine for cooling, cooling to 400 ℃ at the speed of 8 ℃/minute, cooling to room temperature at the speed of 15 ℃/minute, and finally placing the raw material balls into deionized water for repeated cleaning;
and (3) putting the raw material ball and the ion exchange resin into a stirrer, slowly stirring for 4 hours, allowing the ion exchange resin to enter pores in the raw material ball, heating to 35 ℃, stirring for 25 minutes, cooling to room temperature, continuously stirring for 1.5 hours, soaking with deionized water for 52 minutes, taking out, sealing, aging for 36 hours, soaking with 7% sodium hydroxide solution for 35 minutes, and finally repeatedly cleaning to obtain a finished product.
Example 3
Soaking 48 parts of ion exchange resin in 10% sodium chloride solution for 48 hours, washing with deionized water, soaking in 10% sodium hydroxide solution for 50 minutes, washing with deionized water until the pH value of a washing solution is 8.0, respectively placing 18 parts of clay, 20 parts of fly ash, 7 parts of vermiculite, 12 parts of montmorillonite, 13 parts of silicon carbide, 5 parts of zeolite and 10 parts of diatomite in a crusher for crushing to prepare smaller particles and remove impurities, taking the diatomite, soaking in 10% sodium hydroxide solution for 5 hours, stirring to disperse the diatomite, filtering, washing and drying, and finally respectively placing the raw materials in a grinder for grinding to obtain the raw materials with the required particle size;
dissolving 3 parts of ammonium carbonate in 23 parts of deionized water to obtain a solution A for later use, placing 25% of raw materials in a stirrer and sealing, spraying water mist into the stirrer chamber by using the 25% solution A, pumping out and filling gas in the stirrer chamber to achieve gas circulation, stirring for 2 hours, adding 35% of raw materials into the stirrer again and sealing, spraying water mist into the stirrer chamber by using the 35% solution A, pumping out and filling gas in the stirrer chamber to achieve gas circulation, stirring for 2 hours, finally adding the raw materials of the rest components into the stirrer and sealing, spraying water mist into the stirrer chamber by using the rest solution A, pumping out and filling gas in the stirrer chamber to achieve gas circulation, and stirring for 2 hours to obtain raw material balls;
preheating a rotary kiln at 100 ℃, placing the obtained raw material balls into the rotary kiln, gradually heating to 210 ℃, roasting for 30 minutes, controlling the rotating speed of the rotary kiln to be 5 revolutions per minute, then heating to 850 ℃, roasting for 5 hours, placing the raw material balls into a cooling machine for cooling, cooling to 500 ℃ at the speed of 10 ℃/minute, cooling to room temperature at the speed of 20 ℃/minute, and finally placing the raw material balls into deionized water for repeated cleaning;
and (3) putting the raw material ball and the ion exchange resin into a stirrer, slowly stirring for 5 hours, allowing the ion exchange resin to enter pores in the raw material ball, heating to 55 ℃, stirring for 30 minutes, cooling to room temperature, continuously stirring for 2 hours, soaking with deionized water for 60 minutes, taking out, sealing, aging for 48 hours, soaking with 10% sodium hydroxide solution for 50 minutes, and finally repeatedly cleaning to obtain a finished product.
Example 4
Firstly, soaking 37 parts of ion exchange resin in 10% sodium chloride solution for 34 hours, washing with deionized water, then soaking in 7% sodium hydroxide solution for 35 minutes, then washing with deionized water until the pH value of a washing solution is 7.5, respectively placing 12 parts of clay, 18 parts of fly ash, 5 parts of vermiculite, 10 parts of montmorillonite, 10 parts of silicon carbide, 3 parts of zeolite and 7 parts of diatomite in a crusher for crushing to prepare smaller particles and remove impurities, and then respectively placing the raw materials in a grinder for grinding to obtain the raw materials with the required particle size;
taking 17 parts of deionized water in the components for standby, putting the fly ash, the montmorillonite, the silicon carbide, the zeolite and the diatomite in the raw materials into a stirring chamber for stirring, spraying water mist into the stirring chamber by using the deionized water, gradually adding the clay and the vermiculite into the stirring chamber, and stirring for 3 hours to obtain a raw material ball;
preheating a rotary kiln at 210 ℃, placing the obtained raw material balls into the rotary kiln, gradually heating to 450 ℃, roasting for 25 minutes, controlling the rotating speed of the rotary kiln to be 4 revolutions per minute, then heating to 1000 ℃, roasting for 3 hours, placing the raw material balls into a cooling machine for cooling, cooling to 400 ℃ at the speed of 8 ℃/minute, cooling to room temperature at the speed of 15 ℃/minute, and finally placing the raw material balls into deionized water for repeated cleaning;
and (3) putting the raw material ball and the ion exchange resin into a stirrer, slowly stirring for 4 hours, allowing the ion exchange resin to enter pores in the raw material ball, heating to 35 ℃, stirring for 25 minutes, cooling to room temperature, continuously stirring for 1.5 hours, soaking with deionized water for 52 minutes, taking out, sealing, aging for 36 hours, soaking with 7% sodium hydroxide solution for 35 minutes, and finally repeatedly cleaning to obtain a finished product.
Experiment:
taking the treating agent and the common ion exchange resin prepared in the examples 1-4, taking sewage from the same source, carrying out an experiment under the same condition, measuring the adsorption capacity of the treating agent to halogen ions, recording the detection result, and obtaining the following data:
from the data in the table above, it is clear that the following conclusions can be drawn:
the examples 1-3 and the common ion exchange resin form a contrast experiment, and the detection result shows that the treatment agent in the examples 1-3 has obviously improved halogen ion adsorption capacity, which fully shows that the treatment efficiency of the invention for halogen-containing compound sewage is effectively improved, and the adsorption capacity is stable and has higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The treating agent for the sewage containing the halogen compounds is characterized by comprising the following components in parts by weight: 5-18 parts of clay, 16-20 parts of fly ash, 3-7 parts of vermiculite, 8-12 parts of montmorillonite, 7-13 parts of silicon carbide, 2-5 parts of zeolite, 1-3 parts of ammonium carbonate, 11-23 parts of deionized water, 5-10 parts of kieselguhr and 26-48 parts of ion exchange resin.
2. The agent according to claim 1, wherein the agent is selected from the group consisting of: the particle size of the clay is 2-5mm, and the particle size of the fly ash is 1-5 mm.
3. The agent according to claim 1, wherein the agent is selected from the group consisting of: the particle size of the montmorillonite is 3-6mm, the particle size of the silicon carbide is 1-5mm, and the particle size of the ammonium carbonate is 2-5 mm.
4. The agent according to claim 1, wherein the agent is selected from the group consisting of: the particle size of the vermiculite is 6-12mm, the particle size of the zeolite is 6-12mm, and the particle size of the diatomite is 6-12 mm.
5. The agent according to claim 1, wherein the agent is selected from the group consisting of: the ion exchange resin is strong-base anion exchange resin, and the particle size of the ion exchange resin is 0.4-0.6 mm.
6. A preparation method of a treating agent for halogen-containing compound sewage is characterized by comprising the following steps:
1) pre-treating;
2) granulating;
3) roasting;
4) and (4) combining.
7. The method for preparing the treating agent for the halogen-containing compound wastewater according to claim 6, wherein the step 1) comprises the steps of:
1.1) treating ion exchange resin:
soaking the resin in 10% sodium chloride solution for 20-48 hours, washing the resin with deionized water, soaking the resin in 3-10% sodium hydroxide solution for 20-50 minutes, and washing the resin with deionized water until the pH value of a washing solution is 7.0-8.0 to obtain ion exchange resin A;
1.2) processing other raw materials:
a) and (3) processing other raw materials: respectively placing clay, fly ash, vermiculite, montmorillonite, silicon carbide, zeolite and diatomite in a crusher for crushing to prepare smaller particles and removing impurities;
b) treating the diatomite: soaking the diatomite in the previous step in 3-10% sodium hydroxide solution for 2-5 hours, stirring to disperse the diatomite, filtering and washing, and drying to obtain diatomite A;
c) grinding: and grinding the raw materials in a grinder respectively to obtain the raw material A with the required particle size.
8. The method for preparing the treating agent for the halogen-containing compound wastewater according to claim 6, wherein the step 2) comprises the steps of:
a) dissolving ammonium carbonate in deionized water in the components to obtain a solution A, placing the 16-25% of the component in the raw material A in the step 1) in a stirrer, sealing, spraying water mist into the stirring chamber by using the 16-25% of the solution A, pumping out gas in the stirring chamber, and then filling the gas into the stirring chamber to achieve gas circulation, and stirring for 1-2 hours;
b) adding 22-35% of the raw material A into the stirrer again, sealing, spraying 22-35% of the solution A into the stirring chamber, pumping out the gas in the stirring chamber, charging the gas into the stirring chamber to achieve gas circulation, and stirring for 1-2 hours;
c) and finally, adding the raw material A of the rest components into the stirrer, sealing, spraying water mist into the stirring chamber by using the rest solution A, pumping out the gas in the stirring chamber, filling the gas into the stirring chamber to achieve gas circulation, and stirring for 1-2 hours to obtain the raw material B.
9. The method for preparing the treating agent for the halogen-containing compound wastewater according to claim 6, wherein the step 3) comprises the steps of:
a) firing: preheating the rotary kiln at 100 ℃, placing the raw material B obtained in the step 2) into the rotary kiln, gradually heating to 150-;
b) and (3) cooling: cooling the substrate A in a cooling machine, cooling the substrate A to 300-500 ℃ at the speed of 5-10 ℃/min, and cooling to room temperature at the speed of 10-20 ℃/min to obtain a substrate B;
c) cleaning: and putting the matrix B into deionized water for repeated cleaning to obtain a matrix C.
10. The method for preparing the treating agent for the halogen-containing compound wastewater according to claim 6, wherein the step 4) comprises the steps of:
a) mixing: putting the matrix C and the ion exchange resin into a stirrer, slowly stirring for 3-5 hours, allowing the ion exchange resin to enter pores in the matrix C, heating to 25-55 ℃, stirring for 20-30 minutes, cooling to room temperature, and continuously stirring for 1-2 hours to obtain a mixture A;
b) infiltrating: soaking the mixture in deionized water for 45-60 min, sealing and aging for 24-48 hr, soaking in 3-10% sodium hydroxide solution for 20-50 min, and repeatedly cleaning to obtain the final product.
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