CN114100669B - Pretreatment agent for silicon-containing VOCs, and preparation method and application thereof - Google Patents
Pretreatment agent for silicon-containing VOCs, and preparation method and application thereof Download PDFInfo
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- CN114100669B CN114100669B CN202111415513.5A CN202111415513A CN114100669B CN 114100669 B CN114100669 B CN 114100669B CN 202111415513 A CN202111415513 A CN 202111415513A CN 114100669 B CN114100669 B CN 114100669B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 67
- 239000010703 silicon Substances 0.000 title claims abstract description 67
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000011149 active material Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims description 26
- 210000001161 mammalian embryo Anatomy 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 9
- 229910052761 rare earth metal Chemical class 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- -1 transition metal salt Chemical class 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 229910001570 bauxite Inorganic materials 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910001648 diaspore Inorganic materials 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003754 zirconium Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 238000007602 hot air drying Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000003111 delayed effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to the technical field of VOCs treatment, in particular to a pretreatment agent for silicon-containing VOCs, and a preparation method and application thereof. Meanwhile, the invention also relates to a treatment method of the silicon-containing VOCs. The pretreatment agent provided by the invention comprises an aluminum-containing substrate and an active material. When the silicon-containing organic waste gas is treated, the silicon-containing component can be treated in advance, so that the contact between the subsequent noble metal VOCs catalyst and silicon is reduced, the activity reduction speed of the noble metal VOCs catalyst is delayed, and the service life of the noble metal VOCs catalyst is prolonged.
Description
Technical Field
The invention relates to the technical field of VOCs treatment, in particular to a pretreatment agent for silicon-containing VOCs, and a preparation method and application thereof.
Meanwhile, the invention also relates to a treatment method of the silicon-containing VOCs.
Background
At present, the VOCs treatment method is various, the most efficient and low-energy-consumption mode is a catalytic combustion method, and the adopted catalyst is a noble metal catalyst, but when VOCs waste gas contains organic silicon components, after catalytic combustion, silicon element can generate SiO 2 And cover on the surface of the catalyst, cover the active site of noble metal, cause the catalyst to deactivate, reduce the service life of the catalyst, and generate SiO 2 Difficult to clean, resulting in a failure of the catalyst to regenerate, resulting in increased operating costs.
Therefore, there is a need to develop a low-cost pretreatment agent for treating silicon element in a pretreatment agent layer and for producing SiO 2 The catalyst is fixed on the treating agent layer to protect the subsequent noble metal VOCs catalyst, prolong the service life of the catalyst and reduce the cost.
Disclosure of Invention
The invention aims to provide a pretreatment agent for silicon-containing VOCs and a preparation method thereof, which can treat silicon-containing components in advance when treating silicon-containing organic waste gas, reduce the contact between a subsequent noble metal VOCs catalyst and silicon, protect the activity of noble metals and prolong the service life of the noble metal VOCs catalyst.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a pretreatment agent for silicon-containing VOCs comprises an aluminum-containing substrate with the mass ratio of 70-90%, an active material with the mass ratio of 8-20%, and the balance of auxiliary agents and binders.
The aluminum-containing substrate comprises one or more of alumina, aluminum hydroxide, diaspore, pseudo-boehmite, soft bauxite, surge bauxite or zeolite molecular sieves; the active material includes one or more of strong acids, transition metal salts, rare earth element salts, and dispersible nano-oxide particles;
preferably, the strong acid comprises one or more of hydrochloric acid, nitric acid and sulfuric acid;
preferably, the transition metal salt comprises one or more of manganese salt, zirconium salt, iron salt and copper salt;
preferably, the rare earth element salt includes a cerium salt.
When VOCs are catalytically combusted by the aluminum-containing substrate in the pretreatment agent, B acid sites can be generated in the water-gas environment, the silicon element has stronger adsorptivity, electrons on the outermost layer of the transition metal element in the active material are more active, the catalytic oxidation of organic matters is facilitated, the rare earth element has better oxygen storage performance, the decomposition rate of silicon-containing organic matters can be improved, the silicon-containing macromolecules are decomposed, and the silicon element is adsorbed on the aluminum-containing substrate in the form of silicon dioxide. Meanwhile, the pretreatment agent can also catalyze and decompose part of organic matters, so that the efficiency of the subsequent VOCs catalyst is improved.
The invention also provides a preparation method of the pretreatment agent for the silicon-containing VOCs, which comprises the following steps:
s1: preparing an aqueous solution of an active material, adding an aluminum-containing substrate, and stirring and activating for 20min-4h to prepare an active slurry with the solid content of 30-70%;
the active material includes one or more of strong acids, transition metal salts, rare earth element salts, and dispersible nano-oxide particles;
preferably, the strong acid comprises one or more of hydrochloric acid, nitric acid and sulfuric acid;
preferably, the transition metal salt comprises one or more of manganese salt, zirconium salt, iron salt and copper salt;
preferably, the rare earth element salt includes cerium salt;
the acid is used as an active material, so that the acidity of the aluminum-containing substrate can be improved, and the adsorption of silicon element is facilitated;
the transition metal salt is used, so that the catalysis of organic matters is facilitated;
the use of rare earth elements is beneficial to improving the oxygen storage performance and the catalytic efficiency.
The aluminum-containing substrate comprises one or more of alumina, aluminum hydroxide, diaspore, pseudo-boehmite, soft bauxite, surge bauxite or zeolite molecular sieves;
the active material content in the prepared active slurry is 0.1-20%;
s2: adding an auxiliary agent and a binder into the active slurry in the step S1, pugging, extruding and cutting into blanks with the length of 50-800 mm;
the auxiliary agent comprises one or more of cellulose, glass fiber, ethanolamine, resin, glycol, polyethylene glycol, glycerol, butanol, isobutanol, alkynes, ethers, organic silicon, mineral oil, polyethers, polycarboxylate or polyacrylic acid;
the content of the auxiliary agent in the prepared embryo body is 0.1-10%;
the binder comprises one or more of silica sol, alumina sol, zirconium sol, titanium sol, fumed silica or pseudo-boehmite;
the content of the binder in the prepared embryo body is 0.5-10%;
the hole type of the extruder used for extrusion can be one or more of round, square, triangle, trapezoid, hexagon or quadrilateral, the section of the extruder can be square or round, and the mesh number is 20-400.
S3: and (3) pre-drying the embryo body in the step (S2) through drying in the shade or drying in the air at room temperature, drying through drying in the shade, drying in the hot air or drying in the microwave, and roasting for 2-24 hours at 300-500 ℃ to obtain the pretreatment agent of the silicon-containing VOCs.
The invention also provides application of the pretreatment agent of the silicon-containing VOCs in treating waste gas containing organic silicon.
Meanwhile, another object of the present invention is to provide a treatment method of silicon-containing VOCs by installing a pretreatment agent of silicon-containing VOCs at or upstream of the front end of the VOCs catalyst.
The aluminum-containing substrate in the pretreatment agent reacts with the organic silicon in the VOCs and adsorbs the generated SiO under the catalysis of the active material 2 Preventing elemental silicon from contacting subsequent VOCs catalysts.
Compared with the prior art, the invention has the following advantages:
(1) The pretreatment agent provided by the invention can remove silicon element in organic silicon VOCs, and is arranged at the front end of the VOCs catalyst, so that the silicon element can be prevented from contacting with the VOCs catalyst, the VOCs catalyst containing noble metal is protected, the service life of the VOCs catalyst is prolonged, and the treatment cost is reduced; meanwhile, the pretreatment agent can catalyze part of organic matters, which is beneficial to improving the catalytic efficiency of the subsequent VOCs.
(2) Compared with the conventional coating process, the preparation method provided by the invention can reduce the density of the pretreatment agent and improve the adsorption capacity of the pretreatment agent, and the pretreatment agent prepared by the molding process has the advantages of low production cost and long service life.
(3) The pretreatment agent provided by the invention is prepared from rare earth elements, is environment-friendly, and has no secondary pollution in the production process.
Drawings
FIG. 1 is a schematic illustration of a method of using a pretreatment agent;
FIG. 2 is a graph of activity of the VOSs catalyst of test example 5 over time;
fig. 3 is a graph of activity of the VOSs catalyst of test comparative example 1 over time.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The technical solution of the present invention will be described in detail with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a pretreatment agent for silicon-containing VOCs comprises the following steps:
s1: preparing 20kg of ferric nitrate nonahydrate into an aqueous solution of an active material by using deionized water, adding 100kg of zeolite molecular sieve, and stirring and activating for 20min to obtain an active slurry with 30% of solid content;
s2: adding 3kg of hydroxymethyl cellulose, 5kg of glass fiber, 1kg of ethanolamine, 1kg of polyethylene glycol, 3kg of mineral oil as an auxiliary agent and 3kg of pseudo-boehmite as a binder into the active slurry in the step S1, uniformly stirring, adding a pugging machine for pugging for 4 hours, extruding by using a 200-mesh section extruder with square holes, and cutting into blanks of 50 mm;
s3: and (3) drying the embryo body obtained in the step (S2) in the shade for 72h, drying the embryo body with hot air at 100 ℃ for 2h, and roasting the embryo body at 300 ℃ for 24h to obtain the pretreatment agent of the silicon-containing VOCs.
The pretreatment agent for the silicon-containing VOCs comprises 73.5% by mass of aluminum-containing base material, 14.7% by mass of active material, and the balance of auxiliary agent and binder.
Example 2
A preparation method of a pretreatment agent for silicon-containing VOCs comprises the following steps:
s1: preparing 15kg of copper acetate monohydrate into an aqueous solution of an active material by using deionized water, adding 100kg of aluminum oxide, and stirring and activating for 1h to prepare an active slurry with a solid content of 40%;
s2: adding 0.5kg of resin, 1kg of ethanolamine, 2kg of glycerol, 1kg of organic silicon as an auxiliary agent and 1.5kg of silica sol as a binder into the active slurry in the step S1, uniformly stirring, adding a pugging machine for pugging for 4 hours, extruding by using a 240-mesh section extruder with square holes, and cutting into blanks with 200 mm;
s3: and (3) drying the embryo body obtained in the step (S2) for 24 hours at room temperature in a blowing way, drying in the shade for 24 hours, and roasting at 350 ℃ for 18 hours to obtain the pretreatment agent of the silicon-containing VOCs.
The pretreatment agent for the silicon-containing VOCs comprises 86.2% of aluminum-containing base material by mass and 8.6% of active material by mass, and the balance of auxiliary agent and binder.
Example 3
A preparation method of a pretreatment agent for silicon-containing VOCs comprises the following steps:
s1: preparing 10kg of manganese acetate into an active material aqueous solution by using deionized water, adding 100kg of soft aluminum stone, and stirring and activating for 90min to obtain an active slurry with the solid content of 50%;
s2: adding 3kg of polyethylene glycol, 3kg of diethyl ether, 3kg of butanol as an auxiliary agent and 8kg of aluminum sol as a binder into the active slurry in the step S1, uniformly stirring, adding a pugging machine for pugging for 4 hours, extruding by using a 300-mesh section extruder with a trapezoid hole pattern, and cutting into a 300mm blank;
s3: and (3) drying the embryo body in the step (S2) in shade for 72h, drying by microwaves for 5h, and roasting at 400 ℃ for 12h to obtain the pretreatment agent of the silicon-containing VOCs.
The pretreatment agent for the silicon-containing VOCs comprises an aluminum-containing substrate with the mass ratio of 74 percent, an active material with the mass ratio of 11.5 percent, and the balance of an auxiliary agent and a binder.
Example 4
A preparation method of a pretreatment agent for silicon-containing VOCs comprises the following steps:
s1: preparing 7kg of zirconium nitrate into an active material aqueous solution by using deionized water, adding 100kg of aluminum hydroxide, and stirring and activating for 2 hours to prepare an active slurry with a solid content of 60%;
s2: adding 1kg of isobutanol, 1kg of acetylene, 1kg of organic silicon, 1kg of polyacrylic acid, 1kg of polycarboxylic acid copper as an auxiliary agent and 3kg of zirconium sol as a binder into the active slurry in the step S1, uniformly stirring, adding into a pugging machine for pugging for 4 hours, extruding by using a 360-mesh section extruder with a triangular hole pattern, and cutting into blanks of 500 mm;
s3: drying the embryo body in the step S2 in shade for 72h, drying the embryo body with hot air at 100 ℃ for 5h, and roasting the embryo body at 450 ℃ for 6h to obtain the pretreatment agent of the silicon-containing VOCs.
The pretreatment agent for the silicon-containing VOCs comprises 83.6% of aluminum-containing base material by mass and 9.2% of active material by mass, and the balance of auxiliary agent and binder.
Example 5
A preparation method of a pretreatment agent for silicon-containing VOCs comprises the following steps:
s1: preparing 10kg of cerium nitrate into an active material aqueous solution by using deionized water, adding 100kg of active alumina, and stirring and activating for 4 hours to prepare an active slurry with 70% of solid content;
s2: adding 1kg of glycerol, 2kg of glass fiber, 1kg of mineral oil as an auxiliary agent and 1kg of fumed silica as a binder into the active slurry in the step S1, uniformly stirring, adding into a pugging machine for pugging for 4 hours, extruding by using a 400-mesh cross-section extruder with square holes, and cutting into blanks of 800 mm;
s3: and (3) drying the embryo body obtained in the step (S2) in the shade for 72h, drying the embryo body with hot air at 100 ℃ for 6h, and roasting the embryo body at 500 ℃ for 2h to obtain the pretreatment agent of the silicon-containing VOCs.
The pretreatment agent for the silicon-containing VOCs comprises 87% by mass of aluminum-containing substrate, 8.7% by mass of active material, and the balance of auxiliary agent and binder.
Comparative example 1
S1: adding 100kg of activated alumina into deionized water, and stirring for 20min to obtain slurry with the solid content of 60%;
s2: adding 1kg of glycerol, 2kg of glass fiber, 1kg of mineral oil as an auxiliary agent and 1kg of fumed silica as a binder into the slurry in the step S1, uniformly stirring, adding into a pugging machine for pugging for 4 hours, extruding by using a 200-mesh cross-section extruder with square holes, and cutting into blanks with the diameter of 100 mm;
s3: drying the embryo body in the step S2 in the shade for 72h, drying the embryo body with hot air at 100 ℃ for 6h, and roasting the embryo body at 500 ℃ for 4h to obtain the pretreatment agent.
Test example 1
The pretreatment agents prepared in examples 1 to 5 and comparative example 1 were tested. Pretreatment sample size: v=79.5 mL, the pretreatment agent was placed at the front end of the VOCs catalyst and connected in series with the front end (fig. 1), and the activity of the VOSs catalyst was examined with time after the pretreatment agent was added by using the inlet and outlet concentrations of the catalyst before and after the gas chromatography reaction (fig. 2).
Test conditions: tetraethoxysilane=780 mg/m 3 Reaction temperature t=300 ℃, reaction space velocity sv=10000 h -1 。
Surface element analysis: and (3) carrying out surface element analysis on the pretreatment agent samples before and after the reaction to determine the change of the silicon element.
Test comparative example 1
VOCs catalyst without pretreatment in series were tested, sample size: v=79.5 mL, and the activity of the VOSs catalyst was examined as a function of time using the catalyst inlet and outlet concentrations before and after the gas chromatography reaction (see fig. 3).
Test conditions: tetraethoxysilane=780 mg/m 3 Reaction temperature t=300 ℃, reaction space velocity sv=10000 h -1 。
Surface element analysis: surface elemental analysis was performed on the VOSs catalyst samples to determine elemental silicon changes.
The results of test example 1 and test comparative example 1 are shown in table 1,
TABLE 1 results for VOCs catalysts under test conditions
As can be seen from Table 1, the pretreatment agent provided by the invention can catalyze silicon element in waste gas containing organic silicon, and adsorb generated silicon-containing oxide, so that the silicon-containing oxide is effectively reduced from precipitating on the surface of the subsequent VOCs catalyst containing noble metal, the activity reduction speed of the VOCs catalyst is reduced, and the VOCs catalyst can be effectively protected.
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 same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (7)
1. The preparation method of the pretreatment agent for the silicon-containing VOCs is characterized by comprising the following steps:
s1: preparing an aqueous solution of an active material, adding an aluminum-containing substrate, and activating for T1 time to prepare an active slurry;
s2: adding an auxiliary agent and a binder into the active slurry in the step S1, pugging, extruding and cutting to obtain a blank;
s3: pre-drying, drying and roasting the embryo body in the step S2 to obtain the pretreatment agent of the silicon-containing VOCs;
the active material comprises one or two of transition metal salt and rare earth element salt;
the aluminum-containing substrate comprises one or more of alumina, aluminum hydroxide, diaspore, pseudo-boehmite, soft bauxite, surge bauxite or zeolite molecular sieves;
the auxiliary agent comprises one or more of cellulose, glass fiber, ethanolamine, resin, glycol, polyethylene glycol, glycerol, butanol, isobutanol, acetylenes, ethers, organic silicon, mineral oil, polyethers, polycarboxylate or polyacrylic acid.
2. The method of claim 1, wherein step S1 satisfies one or more of the following conditions:
a. the transition metal salt comprises one or more of manganese salt, zirconium salt, ferric salt and cupric salt;
b. the rare earth element salt comprises cerium salt;
c. the mass content of the active material in the active slurry is 0.1-20%;
d. the time of T1 is 20min-4h;
e. the activation is a reaction under stirring;
f. the solid content in the active slurry is 30-70%.
3. The method of claim 1, wherein step S2 satisfies one or more of the following conditions:
g. the mass content of the auxiliary agent in the embryo body is 0.1-10%;
h. the binder comprises one or more of silica sol, alumina sol, zirconium sol, titanium sol, fumed silica or pseudo-boehmite;
i. the mass content of the binder in the embryo body is 0.5-10%;
j. the number of cross section meshes of the extruder used for extrusion is between 20 and 400 meshes;
k. the cutting is to cut into blanks with the length of 50-800 mm.
4. The method of claim 1, wherein step S3 satisfies one or more of the following conditions:
the pre-drying is drying in the shade or drying in the air at room temperature;
m, drying in the shade, hot air drying or microwave drying;
and n, roasting for 2-24h at 300-500 ℃.
5. Use of the pretreatment agent for silicon-containing VOCs obtained by the method for producing a pretreatment agent for silicon-containing VOCs according to any one of claims 1 to 4 for treating exhaust gas containing organic silicon.
6. A method of treating silicon-containing VOCs obtained by the process of any one of claims 1 to 4, wherein the method is a pretreatment agent for installing silicon-containing VOCs at or upstream of the front end of the VOCs catalyst.
7. The method according to claim 6, wherein the aluminum-containing substrate in the pretreatment agent reacts with the organic silicon in the VOCs and adsorbs the generated SiO under the catalysis of the active material 2 Preventing elemental silicon from contacting subsequent VOCs catalysts.
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| CN104884164A (en) * | 2012-12-25 | 2015-09-02 | 日挥通用株式会社 | Exhaust gas purifying catalyst having excellent silicon tolerance |
| CN112973785A (en) * | 2021-02-25 | 2021-06-18 | 华电光大(宜昌)环保技术有限公司 | Catalyst for synergistically removing VOCs and NOx and preparation method thereof |
| CN113262581A (en) * | 2021-05-11 | 2021-08-17 | 江苏优冠汽车配件有限公司 | Wall-flow type honeycomb formaldehyde-removing air conditioner filter element |
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| JPH0259020A (en) * | 1988-08-26 | 1990-02-28 | Nippon Shokubai Kagaku Kogyo Co Ltd | Pretreatment of waste gas |
| US5102634A (en) * | 1990-01-17 | 1992-04-07 | Nippon Shokubai Kagaky Kogyo Co., Ltd. | Method for purifying exhaust gas and apparatus |
| JPH0985087A (en) * | 1995-09-20 | 1997-03-31 | Nikki Universal Co Ltd | Poisoning-resistant pretreatment agent and treatment of exhaust gas of factory |
| JPH10309459A (en) * | 1997-05-12 | 1998-11-24 | Nikki Universal Co Ltd | Poisoning-proof pretreatment agent having catalytic activity |
| CN104884164A (en) * | 2012-12-25 | 2015-09-02 | 日挥通用株式会社 | Exhaust gas purifying catalyst having excellent silicon tolerance |
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