CN109939677B - Third main group element modified ruthenium-titanium composite oxide and preparation method and application thereof - Google Patents
Third main group element modified ruthenium-titanium composite oxide and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical class [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003608 titanium Chemical class 0.000 claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims abstract description 10
- 150000002258 gallium Chemical class 0.000 claims abstract description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002471 indium Chemical class 0.000 claims abstract description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001638 boron Chemical class 0.000 claims description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000003303 ruthenium Chemical class 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical group [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical group N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical group [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 65
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 239000010936 titanium Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 229910052733 gallium Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 206010002091 Anaesthesia Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DQQFNNITATXZEB-UHFFFAOYSA-N [Ru].[Zr].[Ti] Chemical compound [Ru].[Zr].[Ti] DQQFNNITATXZEB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- -1 aromatic hydrocarbon chlorides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 231100000025 genetic toxicology Toxicity 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a ruthenium-titanium composite oxide modified by a third main group element, a preparation method and application thereof, belonging to the technical field of catalytic materials. Firstly, preparing titanium oxide catalyst carriers modified by different molar contents of third main group elements by adopting a sol-gel method, and then loading ruthenium by adopting an impregnation method to prepare the composite oxide. The titanium salt used by the sol-gel method is titanium sulfate, tetraisopropyl titanate or tetrabutyl titanate, and the third main group element salt is boron salt, aluminum salt, gallium salt or indium salt. When the catalyst prepared by the invention is used for catalytic combustion of chlorohydrocarbon, the ignition temperature is low, and the complete combustion temperature is low. At space velocity of 60000ml g‑1·h‑1The chlorinated hydrocarbon can be completely combusted at the temperature of less than 350 ℃ under the condition that the concentration of the chlorinated hydrocarbon is 1000 ppm. Meanwhile, the catalyst has high stability, and can be kept for 100 hours at 305 ℃ without inactivation when dichloromethane is catalytically combusted. The preparation method of the catalyst is simple and easy to operate, and the prepared catalyst has both activity and stability.
Description
Technical Field
The invention relates to a ruthenium-titanium composite oxide modified by a third main group element, a preparation method and application thereof, belonging to the technical field of catalytic materials.
Background
In recent years, environmental problems are more prominent, and the ecological environment is continuously destroyed, which seriously endangers the health of human beings and the sustainable development of society. Environmental protection problems, especially air pollution problems, have become the most interesting problem. The promotion of green development, the solution of outstanding environmental problems, and the winning of the guard war in blue days are important problems faced by our country. In view of the fact that the pharmaceutical industry, the petrochemical industry, the chemical industry, the textile printing and dyeing industry and the like can not eliminate pollutants from the source in China at present, in particular to various chlorine-containing organic compounds (CVOCs). In the international treaty of environmental projects of the united nations, 12 first-ranked persistent organic pollutants are chlorine-containing organic compounds, and the substances almost have the effects of anesthesia and three-induced effects of genetic toxicology (mutation-carcinogenesis-teratogenesis), thereby seriously harming the environment and human health. The pollution caused by the compounds is required to be eliminated by adopting a proper means, and the catalytic combustion method is used as an elimination technology with low energy consumption and wide application range and has wide application prospect. The chlorine-containing organic compounds can be roughly classified into aromatic hydrocarbon chlorides such as chlorobenzene and dichlorobenzene; examples of the chlorinated aliphatic hydrocarbon compounds include unsaturated chlorinated aliphatic hydrocarbons such as vinyl chloride and trichloroethylene, and unsaturated chlorinated aliphatic hydrocarbons such as methylene chloride and ethylene dichloride, and representative examples thereof include chlorobenzene, methylene chloride and trichloroethylene.
At present, the catalysts for catalytic combustion of chlorinated hydrocarbons are supported noble metals (active components are noble metals such as Pt, Pd, Rh, Ru, and the like), proton type molecular sieve catalysts, and transition metal oxide type catalysts. The supported noble metal catalyst is known as the 'vitamin' of an industrial catalyst, has good catalytic performance for catalytic combustion of dichloromethane, but due to the defects of high price, low abundance and the like of noble metals, how to reduce the content of catalytic noble metals is the key point of research, and meanwhile, ruthenium (Ru) used by the method is low in price and has been industrially used for Deacon reaction. The proton type molecular sieve catalyst has good thermal stability, but has low reaction activity and is easy to be deactivated by carbon deposition and limited in use. The transition metal type catalyst is a catalyst which is widely researched due to good activity and low price, but is difficult to be applied to industrialization at present. The vanadium-titanium catalyst adopted in the prior art is used for catalytic combustion of chlorohydrocarbon and has certain activity, but is limited due to the toxicity of vanadium.
Disclosure of Invention
The invention solves the technical problems of limited activity, low stability and toxicity of catalysts for catalytic combustion of chlorohydrocarbons in the prior art, and provides a high-efficiency ruthenium-gallium-titanium composite oxide catalyst, a preparation method thereof and application thereof in catalytic combustion of chlorohydrocarbons.
According to a first aspect of the present invention, there is provided a method for preparing a ruthenium-titanium composite oxide modified with a group iii element, comprising the steps of:
(1) dissolving titanium salt in an organic solvent which can be mutually dissolved with water to obtain a solution A; dissolving a third main group element salt in water or a mixed solution of an organic solvent and water which can be mutually dissolved with water to obtain a solution B;
(2) pouring the solution B in the step (1) into the solution A to hydrolyze the titanium salt to obtain gel;
(3) drying the gel obtained in the step (2), and roasting at the temperature of 400-550 ℃ for 3-6 h to obtain TiO modified by the third main group element2A composite oxide of (a); the third main group element modified TiO2In the composite oxide of (1), the TiO modified with the third main group element2The amount of the substance of the third main group element atom in the composite oxide of (1) is 10% or less of the total amount of the substance of the third main group element atom and the titanium atom;
(4) TiO modified with the third main group element in the step (3)2Adding ruthenium salt into the composite oxide, fully and uniformly mixing, drying and then roasting again to obtain ruthenium-titanium composite oxide modified by the third main group element; the mass of ruthenium in the third main group element modified ruthenium-titanium composite oxide accounts for 0.2-1.0%; the temperature of the secondary roasting is 400-550 ℃, and the time of the secondary roasting is 3-6 h.
Preferably, the titanium salt in step (1) is titanium sulfate, tetraisopropyl titanate or tetrabutyl titanate.
Preferably, the third main group element salt in step (1) is a gallium salt, an aluminum salt, a boron salt or an indium salt;
preferably, the gallium salt is gallium acetylacetonate or gallium nitrate hydrate; the aluminum salt is aluminum nitrate or aluminum isopropoxide; the boron salt is ammonium borate; the indium salt is indium nitrate or indium chloride.
Preferably, the ruthenium salt in step (4) is ruthenium chloride or ruthenium oxynitrate.
Preferably, the water-miscible organic solvent in step (1) is ethanol, methanol, or ethylene glycol.
According to another aspect of the present invention, there is provided a group iii element-modified ruthenium-titanium composite oxide prepared by any one of the methods.
According to another aspect of the present invention, there is provided the use of the third main group element-modified ruthenium titanium composite oxide for catalytic combustion of exhaust gas containing chlorinated hydrocarbons.
Preferably, the chlorinated hydrocarbon is chlorinated saturated hydrocarbon, chlorinated unsaturated hydrocarbon or chlorinated aromatic hydrocarbon;
preferably, the chlorinated saturated hydrocarbon is dichloromethane; the chlorinated unsaturated hydrocarbon is trichloroethylene; the chlorinated aromatic hydrocarbon is chlorobenzene.
Preferably, the volume of the chlorohydrocarbon in the waste gas containing chlorohydrocarbon accounts for 0.05-5%, and each gram of the composite oxide catalyzes the waste gas containing chlorohydrocarbon for 5L-60L per hour.
Preferably, the reaction pressure during the catalytic combustion is 0.1MPa-0.5MPa, and the temperature is 100-400 ℃.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the invention adopts third main group element to modify TiO2The catalyst has high catalytic activity and stability on catalytic combustion of chlorohydrocarbon, and when the catalyst is used in catalytic combustion of chlorohydrocarbon, especially dichloromethane, the catalyst has low igniting temperature and low complete converting temperature.
(2) The method can stably convert the chlorine-containing volatile organic compounds in the exhaust gas into carbon dioxide, water and hydrogen chloride for a long time in the presence of the catalyst in the air at a relatively low reaction temperature without reducing the activity of the catalyst.
(3) The catalyst provided by the invention has the characteristics of simple preparation process, low price, high catalytic activity, strong chlorine poisoning resistance, long service life and the like; the technical route is convenient and practical, and can be widely used for catalytic combustion elimination of chlorine-containing organic pollutants in papermaking, pharmacy, tanning and washing.
(4) In the presence of the catalyst, air as an oxidant is taken into the reactor, so that the chlorine-containing volatile organic compound is completely combusted under the action of the catalyst, and the chlorine-containing volatile organic compound is converted into carbon dioxide, water, hydrogen chloride and chlorine. The tail gas of complete combustion can be absorbed by dilute alkali solution (acidic gases such as hydrogen chloride, chlorine and the like are absorbed) and then is discharged, and the discharged gases are all products meeting the environmental requirements.
(5) When the catalyst prepared by the invention is used for catalytic combustion of chlorohydrocarbons, especially dichloromethane, air is used as an oxidant, so that the ignition temperature is low, and the complete combustion temperature is low. At space velocity of 60000ml g-1h-1At a methylene chloride concentration of 1000ppm, methylene chloride can be completely combusted at 305 ℃. Meanwhile, the catalyst has high stability and can be kept for 100 hours at 305 ℃ without deactivation. The preparation method of the catalyst is simple and easy to operate, and the prepared catalyst has both activity and stability.
(6) The ruthenium-titanium composite oxide catalyst modified by the third main group element, which is prepared by the invention, takes water in a third main group element salt solution as an initiator, the titanium salt is quickly hydrolyzed to form gel, and the gel is dried and calcined to obtain TiO modified by the third main group element2The composite oxide of (3).
(7) The catalyst prepared by the invention takes ruthenium as a catalytic active component, takes a third main group element as an auxiliary agent and takes titanium oxide as a carrier, and the modification of the third main group can increase the specific surface area of the titanium oxide and improve the dispersion degree of the active component ruthenium; and the acid-base property of the carrier can be changed, so that the carrier is beneficial to the breaking of a C-Cl bond, and the reaction activity of catalyzing chlorohydrocarbon is improved.
(8) The modified ruthenium-titanium composite oxide catalyst of the third main group element prepared by the invention has a carrier with larger specific surface area and proper acidity. The mass of ruthenium in the ruthenium-titanium composite oxide modified by the third main group element is 0.2-1.0%, and the loaded low-content active metal Ru is highly dispersed, so that more active sites can be exposed, the number of active sites for catalytic combustion of chlorine-containing waste gas can be provided, and a better catalytic effect can be achieved.
Drawings
FIG. 1 is a graph showing the effect of the catalytic stability of the catalyst of the present invention to methylene chloride.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
14.2g of (CH) are weighed3CH3CHO)4Dissolving Ti in 30ml of ethanol, stirring for 1 hour, quickly dropwise adding 20ml of ethanol-water mixed solution to obtain gel, drying at 110 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain a catalyst carrier; 2g of TiO are weighed2Carrier, measuring 1ml RuCl3The solution (10 g/L) was added to a crucible, about 1ml of deionized water was added dropwise, and the mixture was repeatedly stirred with a glass rod until uniform mixing. Naturally evaporating to dryness, putting into a 110 ℃ oven for drying overnight, and roasting at 400 ℃ for 4 hours to obtain Ru/TiO2The catalyst was tested for its catalytic effect on methylene chloride.
Example 2
14.07g of (CH) are weighed3CH3CHO)4Ti and 0.14g Ga (NO)3)3·xH2Dissolving O in a mixed solution of 30ml of ethanol and 30ml of ethanol water respectively, stirring for 1 hour, quickly pouring a gallium salt solution into a titanium salt solution to obtain gel, drying the obtained gel at 110 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain a catalyst carrier; 2g of xGa-TiO are weighed2Carrier, measuring 1ml RuCl3Solutions of(the concentration is 10g/L) is added into a crucible, about 1ml of deionized water is dripped, the mixture is repeatedly stirred by a glass rod until the mixture is uniformly mixed, the mixture is naturally evaporated to dryness and then is put into a 110 ℃ oven for overnight drying, and the mixture is roasted for 4 hours at 400 ℃ to prepare Ru/1% Ga-TiO2A catalyst. The amount of the substance of the third main group element Ga was 1% in the total amount of the substances of Ga and Ti, and the mass of ruthenium in the third main group element-modified ruthenium-titanium composite oxide was 0.5%. The catalyst was tested for its catalytic effect on methylene chloride.
Example 3
Ru/3% Ga-TiO was prepared by adjusting the ratio of titanium salt to gallium salt in the same manner as in example 22A catalyst. The amount of the substance of the third main group element Ga accounted for 3% of the total amount of the substances of Ga and Ti, and the catalytic effect of the catalyst on methylene chloride was tested.
Example 4
Ru/5% Ga-TiO was prepared by adjusting the ratio of titanium salt to gallium salt in the same manner as in example 22A catalyst. The amount of the substance of the third main group element Ga accounted for 5% of the total amount of the substances of Ga and Ti, and the catalytic effect of the catalyst on methylene chloride was tested.
Example 5
Ru/7% Ga-TiO was prepared by adjusting the ratio of titanium salt to gallium salt in the same manner as in example 22A catalyst. The amount of the substance of the third main group element Ga accounted for 7% of the total amount of the substances of Ga and Ti, and the catalytic effect of the catalyst on methylene chloride was tested.
Example 6
Ru/10% Ga-TiO was prepared by adjusting the ratio of titanium salt to gallium salt in the same manner as in example 22A catalyst. The amount of the substance of the third main group element Ga accounted for 10% of the total amount of the substances of Ga and Ti, and the catalytic effect of the catalyst on methylene chloride was tested.
Example 7
Ru/5% B-TiO was prepared by adjusting the ratio of titanium salt to boron salt in the same manner as in example 22A catalyst. The amount of the substance of the third main group element B accounting for the sum of the amounts of the substances of B and Ti is 5%, and the catalytic combustion performance of the material on methylene chloride is tested。
Example 8
Ru/5% Al-TiO compound was prepared by adjusting the ratio of titanium salt to aluminum salt in the same manner as in example 22A catalyst. The catalytic combustion performance of methylene chloride was tested with the amount of the third main group element Al substance accounting for 5% of the sum of the amounts of the Al and Ti substances.
Example 9
Ru/5% In-TiO was prepared by adjusting the ratio of titanium salt to indium salt In the same manner as In example 22A catalyst. The catalytic combustion performance for methylene chloride was tested with the amount of the species of the third main group element In accounting for 5% of the total amount of the species of In and Ti.
Example 10
The catalyst prepared in example 4 was Ru/5% Ga-TiO2And testing the catalytic combustion effect of the catalyst on trichloroethylene.
Example 11
The catalyst prepared in example 4 was Ru/5% Ga-TiO2And testing the catalytic combustion effect of the catalyst on chlorobenzene.
Example 12
2g of 5% Ga-TiO are weighed2Carrier, 0.6ml RuCl measured3Adding the solution (with concentration of 10g/L) into a crucible, dropwise adding about 1ml of deionized water, repeatedly stirring with a glass rod until the mixture is uniformly mixed, naturally drying, putting into a 110 ℃ oven for overnight drying, and roasting at 400 ℃ for 4 hours to obtain the 0.3% Ru/5% Ga-TiO2And the mass of ruthenium in the ruthenium-titanium composite oxide modified by the third main group element is 0.3%. The catalytic combustion performance of the catalyst on dichloromethane is tested.
Example 13
2g of 5% Ga-TiO are weighed2Carrier, 2ml of RuCl measured3Adding the solution (with the concentration of 10g/L) into a crucible, repeatedly stirring by using a glass rod until the solution is uniformly mixed, naturally drying, putting the mixture into a 110 ℃ oven for overnight drying, and roasting at 400 ℃ for 4 hours to prepare the 1% Ru/5% Ga-TiO2And the mass of ruthenium in the ruthenium-titanium composite oxide modified by the third main group element is 1%. The catalytic combustion performance of the catalyst on dichloromethane is tested.
And (4) analyzing results:
evaluation of catalytic combustion activity of chlorinated organic pollutants for all the catalysts of the examples was carried out in a fixed-bed microreactor (quartz with an internal diameter of 4 mm), the amount of catalyst used was 100mg and the temperature was automatically controlled using a type K thermocouple. The chlorinated organic pollutants are injected into a vaporization chamber by a 100 series KDS100 micro-injection pump of Stoelting company in the United states, and then are mixed with air to enter a reactor for combustion. The total flow is controlled by a mass flow meter, and the concentration of the chlorine-containing organic pollutants is controlled at 1000 ppm. The reaction pressure is 0.1MPa, the relationship between the conversion rate of the chlorinated organic pollutants and the reaction temperature is shown in the following table, wherein T in the table10％、T50％、T90％The reaction temperatures required for the conversions to 10%, 50% and 90%, respectively. The main reaction products are carbon dioxide, water, hydrogen chloride and chlorine.
Example 14
The catalyst prepared in example 4 was used in the form of Ru/5% Ga-TiO, the catalyst prepared in example 4 was used in an amount of 60L per hour of exhaust gas treatment per gram of catalyst, a reaction pressure of 0.1MPa, a reaction temperature of 305 ℃ was maintained, a concentration of dichloromethane was 1000ppm, air was used as an oxidizing gas, and air was used as dry air2In the above, the conversion of methylene chloride was maintained at 90% or more in 100 hours, and no catalyst deactivation was observed, as shown in FIG. 1.
Comparative example
The ruthenium titanium zirconium catalyst of the 201510166386.8 patent with the best catalyst being Ru/T5Z5 treated 10L of methylene chloride waste gas per gram of catalyst at 290 deg.C per hour, while the catalyst of the present invention can treat 60L of methylene chloride waste gas under similar conditions, the catalytic reaction rate of the catalyst of the present application is 6 times that of the prior art.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (12)
1. A preparation method of ruthenium-titanium composite oxide modified by third main group elements is characterized by comprising the following steps:
(1) dissolving titanium salt in an organic solvent which can be mutually dissolved with water to obtain a solution A; dissolving a third main group element salt in water or a mixed solution of an organic solvent and water which can be mutually dissolved with water to obtain a solution B;
(2) pouring the solution B in the step (1) into the solution A to hydrolyze the titanium salt to obtain gel;
(3) drying the gel obtained in the step (2), and roasting at the temperature of 400-550 ℃ for 3-6 h to obtain TiO modified by the third main group element2A composite oxide of (a); the third main group element modified TiO2The amount of the substance of the third main group element atom in the composite oxide of (1) is 10% or less of the total amount of the substance of the third main group element atom and the titanium atom;
(4) TiO modified with the third main group element in the step (3)2Adding ruthenium salt into the composite oxide, fully and uniformly mixing, drying and then roasting again to obtain ruthenium-titanium composite oxide modified by the third main group element; the mass of ruthenium in the third main group element modified ruthenium-titanium composite oxide accounts for 0.2-1.0%; the temperature of the secondary roasting is 400-550 ℃, and the time of the secondary roasting is 3-6 h.
2. The method for preparing a ruthenium-titanium composite oxide modified with a group III element according to claim 1, wherein the titanium salt in the step (1) is titanium sulfate, tetraisopropyl titanate or tetrabutyl titanate.
3. The method for preparing a ruthenium-titanium composite oxide modified with a group iii element according to claim 1, wherein the group iii element salt in the step (1) is a gallium salt, an aluminum salt, a boron salt or an indium salt.
4. The method for producing a ruthenium-titanium composite oxide modified with a third main group element according to claim 3, wherein the gallium salt is gallium acetylacetonate or gallium nitrate hydrate; the aluminum salt is aluminum nitrate or aluminum isopropoxide; the boron salt is ammonium borate; the indium salt is indium nitrate or indium chloride.
5. The method for preparing a ruthenium-titanium composite oxide modified with a group III element according to claim 1, wherein the ruthenium salt in the step (4) is ruthenium chloride or ruthenium oxynitrate.
6. The method for preparing a group iii element-modified ruthenium-titanium composite oxide according to claim 1, wherein the water-miscible organic solvent in step (1) is ethanol, methanol, or ethylene glycol.
7. A group III element-modified ruthenium-titanium composite oxide produced by the method according to any one of claims 1 to 6.
8. Use of the group III element-modified ruthenium titanium composite oxide according to claim 7 for catalytic combustion of exhaust gases containing chlorinated hydrocarbons.
9. Use according to claim 8, wherein the chlorinated hydrocarbon is a chlorinated saturated hydrocarbon, a chlorinated unsaturated hydrocarbon or a chlorinated aromatic hydrocarbon.
10. Use according to claim 9, wherein the chlorinated saturated hydrocarbon is dichloromethane; the chlorinated unsaturated hydrocarbon is trichloroethylene; the chlorinated aromatic hydrocarbon is chlorobenzene.
11. The use according to claim 8, wherein the volume of chlorinated hydrocarbons in the waste gas containing chlorinated hydrocarbons is 0.05-5%, and the waste gas containing chlorinated hydrocarbons is catalyzed by the composite oxide in an amount of 5-60L per hour.
12. The use according to claim 8, wherein the catalytic combustion is carried out at a reaction pressure of 0.1MPa to 0.5MPa and a temperature of 100 ℃ to 400 ℃.
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| CN104826624A (en) * | 2015-04-10 | 2015-08-12 | 华东理工大学 | Ruthenium titanium zirconium catalyst obtained by catalytic combustion of dichloromethane and preparation method thereof |
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| CN104826624A (en) * | 2015-04-10 | 2015-08-12 | 华东理工大学 | Ruthenium titanium zirconium catalyst obtained by catalytic combustion of dichloromethane and preparation method thereof |
| CN107202333A (en) * | 2017-06-15 | 2017-09-26 | 华南理工大学 | A kind of sulfur-bearing VOC method for innocent treatment |
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