CN104437486A - Catalytic combustion catalyst for hydrochloric ether and preparation method of catalytic combustion catalyst - Google Patents
Catalytic combustion catalyst for hydrochloric ether and preparation method of catalytic combustion catalyst Download PDFInfo
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- CN104437486A CN104437486A CN201410605598.7A CN201410605598A CN104437486A CN 104437486 A CN104437486 A CN 104437486A CN 201410605598 A CN201410605598 A CN 201410605598A CN 104437486 A CN104437486 A CN 104437486A
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Abstract
The invention relates to a catalytic combustion catalyst for hydrochloric ether and a preparation method of the catalytic combustion catalyst. The catalytic combustion catalyst for the hydrochloric ether is a composite material consisting of platinum atoms doped Al2O3, SnO2 and BaO. The preparation method comprises the following steps of dissolving aluminum salt, tin salt and barium salt together in a hydrochloric acid aqueous solution, adding a proper amount of malic acid and isobutanol, stirring at a constant temperature, adding glucose and chloroplatinic acid, carrying out heating reflux, carrying out rotary evaporation, controlling the temperature to room temperature, dropwise adding ammonia hydroxide to regulate the pH value to 5.5-6.5, stirring further, standing, seasoning, filtering, drying and grinding filtered substances, roasting the grinded substances in a box type resistance furnace, naturally cooling down to obtain the composite material consisting of platinum atoms doped Al2O3, SnO2 and BaO. When the composite material provided by the invention is taken as the catalytic combustion catalyst for hydrochloric ether, the conversion rate of chlorobenzene at 200 DEG C is over 55%, and the T90 is about 250 DEG C.
Description
Technical field
The present invention relates to catalyst for catalytic combustion of a kind of chlorohydrocarbon and preparation method thereof, the Al particularly adulterated by pt atom
2o
3, SnO
2composite with BaO composition, belongs to environmental protection technical field.
Background technology
Catalytic combustion be combustible under the effect of catalyst, the combustion reaction carried out under certain temperature conditions.Compared with directly burning, catalytic combustion temperature is lower, and ratio of combustion is more complete.Chlorinatedorganic, as a kind of important organic solvent and product intermediate, is widely used in a lot of industry, but is often carcinogenic, teratogenesis, mutagenic matter.Chloride organic exhaust gas (CVOCs) is extensively present in the production processes such as machinery, petrochemical industry, pharmacy, coatings decoration industry, and its discharge can cause serious harm to atmospheric environment and human health.Common CVOCs processing method has direct combustion method, photocatalytic method, solvent absorption, Production by Catalytic Combustion Process etc., wherein, Production by Catalytic Combustion Process have when processing CVOCs initiation temperature compared with low, energy consumption is little, the advantage being convenient to industrial applications and effectively avoiding second-class extremely toxic substance to produce, is considered to one of effective ways of improvement CVOCs.There is bibliographical information V
2o
5/ TiO
2catalyst shows good catalytic activity and anti-fluorine poisoning ability when processing the aromatic hydrocarbons CVOCs such as chlorobenzene, dichloro-benzenes, but to CO
2selective not high, in catalyticing combustion process, easily produce a large amount of CO; In addition, V
2o
5/ TiO
2be difficult under cryogenic alkanes chloride more stable to carrene, dichloroethanes etc. be transformed completely, and in combustion process, easily generate harmful intermediate product such as monochloro methane, formaldehyde, cause secondary pollution.In the catalytic combustion of chloride organic exhaust gas, not only require that catalyst has greater activity and stability, also need a large amount of generations avoiding harmful intermediate material such as CO, monochloro methane.
Summary of the invention
The object of the invention is the deficiency overcoming conventional art, a kind of Catalysts and its preparation method chlorohydrocarbon being had to greater catalytic oxidation activity is provided.The catalyst for catalytic combustion of chlorohydrocarbon of the present invention is the Al adulterated by pt atom
2o
3, SnO
2with the composite of BaO composition, its preparation method is:
The aluminium salt of acidic aqueous solution will be soluble in, it is in the aqueous hydrochloric acid solution of 10-20% that pink salt and barium salt are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 2-3 hour, then appropriate glucose and chloroplatinic acid is added, add hot reflux 3-5 hour, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 5.5-6.5, continue to stir still aging 5-6 hour after 1-2 hour, filter and much filtrate is dried, after grinding, 220-240 DEG C is warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 4-5 hour, continue to be warming up to 480-495 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 2-3 hour, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
Wherein, aluminium salt is aluminum nitrate, aluminum sulfate, aluminum perchlorate, aluminum phosphate, aluminium chloride and the anhydride of aluminum acetate or the mixture of one or more of hydrate, pink salt is stannic chloride, stannous chloride, the sub-tin of nitric acid and the anhydride of stannous sulfate or the mixture of one or more of hydrate, and barium salt is the anhydride of barium chloride and barium nitrate or one or both mixture of hydrate.
When the obtained each constituent mass mark of composite meets Pt (3-5%), Al
2o
3(28-35%), SnO
2(32-40%), time with BaO (25-30%), can be used as the efficient catalytic combustion catalyst of chlorohydrocarbon.
Detailed description of the invention
Embodiment 1
Nine water aluminum nitrates of acidic aqueous solution will be soluble in, it is in the aqueous hydrochloric acid solution of 15% that five water stannic chlorides and barium chloride are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 2 hours, then appropriate glucose and chloroplatinic acid is added, add hot reflux 4 hours, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 6, continue stirring after 1 hour still aging 5 hours, filter and much filtrate is dried, after grinding, 230 DEG C are warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 4 hours, continue to be warming up to 490 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 2 hours, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
Analyze: carry out constituent analysis to composite, recording mass percent is 4.1%Pt, 28.7%Al
2o
3, 37.2%SnO
2and 30.0%BaO.
Application: using this composite as the catalyst for catalytic combustion of chlorohydrocarbon, when the conversion ratio of chlorobenzene is 56.7%, 250 DEG C when 200 DEG C, the conversion ratio of chlorobenzene is 89.8%.
Embodiment 2
The aluminum sulfate octadecahydrate of acidic aqueous solution will be soluble in, it is in the aqueous hydrochloric acid solution of 17% that stannous chloride dihydrate and barium nitrate are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 3 hours, then appropriate glucose and chloroplatinic acid is added, add hot reflux 3 hours, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 5.6, continue stirring after 1.5 hours still aging 6 hours, filter and much filtrate is dried, after grinding, 224 DEG C are warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 5 hours, continue to be warming up to 484 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 3 hours, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
Analyze: carry out constituent analysis to composite, recording mass percent is 3.6%Pt, 31.4%Al
2o
3, 35.5%SnO
2and 29.5%BaO.
Application: using this composite as the catalyst for catalytic combustion of chlorohydrocarbon, when the conversion ratio of chlorobenzene is 58.2%, 250 DEG C when 200 DEG C, the conversion ratio of chlorobenzene is 90.7%.
Embodiment 3
Nine water aluminum perchlorates of acidic aqueous solution will be soluble in, it is in the aqueous hydrochloric acid solution of 19% that the sub-tin of nitric acid and barium chloride are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 3 hours, then appropriate glucose and chloroplatinic acid is added, add hot reflux 5 hours, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 5.8, continue stirring after 2 hours still aging 5 hours, filter and much filtrate is dried, after grinding, 228 DEG C are warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 4 hours, continue to be warming up to 487 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 2 hours, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
Analyze: carry out constituent analysis to composite, recording mass percent is 3.3%Pt, 33.6%Al
2o
3, 39.2%SnO
2and 23.9%BaO.
Application: using this composite as the catalyst for catalytic combustion of chlorohydrocarbon, when the conversion ratio of chlorobenzene is 54.8%, 250 DEG C when 200 DEG C, the conversion ratio of chlorobenzene is 89.5%.
Embodiment 4
The aluminum phosphate of acidic aqueous solution will be soluble in, Aluminum Chloride Hexahydrate, it is in the aqueous hydrochloric acid solution of 11% that stannous sulfate and nitric hydrate barium are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 2.5 hours, then appropriate glucose and chloroplatinic acid is added, add hot reflux 3 hours, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 6.2, continue stirring after 2 hours still aging 6 hours, filter and much filtrate is dried, after grinding, 237 DEG C are warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 5 hours, continue to be warming up to 491 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 3 hours, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
Analyze: carry out constituent analysis to composite, recording mass percent is 4.8%Pt, 32.8%Al
2o
3, 33.7%SnO
2and 28.7%BaO.
Application: using this composite as the catalyst for catalytic combustion of chlorohydrocarbon, when the conversion ratio of chlorobenzene is 60.4%, 250 DEG C when 200 DEG C, the conversion ratio of chlorobenzene is 91.3%.
Embodiment 5
The acetate dihydrate aluminium of acidic aqueous solution will be soluble in, stannous chloride, it is in the aqueous hydrochloric acid solution of 13% that the sub-tin of nitric acid and barium nitrate are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 2 hours, then appropriate glucose and chloroplatinic acid is added, add hot reflux 4 hours, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 6.4, continue stirring after 1 hour still aging 5 hours, filter and much filtrate is dried, after grinding, 232 DEG C are warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 4 hours, continue to be warming up to 494 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 2 hours, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
Analyze: carry out constituent analysis to composite, recording mass percent is 4.5%Pt, 34.5%Al
2o
3, 34.1%SnO
2and 26.9%BaO.
Application: using this composite as the catalyst for catalytic combustion of chlorohydrocarbon, when the conversion ratio of chlorobenzene is 58.5%, 250 DEG C when 200 DEG C, the conversion ratio of chlorobenzene is 89.9%.
Claims (2)
1. the catalyst for catalytic combustion and preparation method thereof of chlorohydrocarbon, is characterized in that the Al adulterated by pt atom
2o
3, SnO
2with the composite of BaO composition, wherein the mass percent of each component is 3-5%Pt, 28-35%Al
2o
3, 32-40%SnO
2and 25-30%BaO, its preparation method is: will be soluble in the aluminium salt of acidic aqueous solution, it is in the aqueous hydrochloric acid solution of 10-20% that pink salt and barium salt are dissolved in mass fraction altogether, add appropriate malic acid and isobutanol, at 40 DEG C of temperature, constant temperature stirs 2-3 hour, then appropriate glucose and chloroplatinic acid is added, add hot reflux 3-5 hour, rotary evaporation falls 1/3rd moisture, ammoniacal liquor to the pH value dripping mass fraction 20% after being down to room temperature is 5.5-6.5, continue to stir still aging 5-6 hour after 1-2 hour, filter and much filtrate is dried, after grinding, 220-240 DEG C is warming up to the speed being no more than 3 DEG C per minute in chamber type electric resistance furnace, keep this temperature 4-5 hour, continue to be warming up to 480-495 DEG C with the speed being no more than 3 DEG C per minute, keep this temperature 2-3 hour, naturally the Al obtaining being adulterated by pt atom is cooled
2o
3, SnO
2with the composite of BaO composition.
2. the catalyst for catalytic combustion and preparation method thereof of chlorohydrocarbon according to claim 1, it is characterized in that described aluminium salt is aluminum nitrate, aluminum sulfate, aluminum perchlorate, aluminum phosphate, aluminium chloride and the anhydride of aluminum acetate or the mixture of one or more of hydrate, pink salt is stannic chloride, stannous chloride, the sub-tin of nitric acid and the anhydride of stannous sulfate or the mixture of one or more of hydrate, and barium salt is the anhydride of barium chloride and barium nitrate or one or both mixture of hydrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038549A (en) * | 2019-05-22 | 2019-07-23 | 中国科学院上海高等研究院 | A kind of monatomic catalyst of oxide carried noble metal and its preparation method and application |
Citations (5)
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|---|---|---|---|---|
| JPS58139742A (en) * | 1982-02-16 | 1983-08-19 | Matsushita Electric Ind Co Ltd | Catalytic body for combustion |
| US6087295A (en) * | 1992-12-14 | 2000-07-11 | Asec Manufacturing | Reduction of NOx in the exhaust gases from internal combustion engines containing excess oxygen |
| US20120071700A1 (en) * | 2010-09-21 | 2012-03-22 | Long Huang | Catalysts for hydrogenation of unsaturated hydrocarbons and preparations and uses thereof |
| CN103969249A (en) * | 2014-04-14 | 2014-08-06 | 北京联合大学生物化学工程学院 | Composite oxide sensitive material used for monitoring formaldehyde and ammonia simultaneously |
| CN104109080A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid |
-
2014
- 2014-11-03 CN CN201410605598.7A patent/CN104437486B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58139742A (en) * | 1982-02-16 | 1983-08-19 | Matsushita Electric Ind Co Ltd | Catalytic body for combustion |
| US6087295A (en) * | 1992-12-14 | 2000-07-11 | Asec Manufacturing | Reduction of NOx in the exhaust gases from internal combustion engines containing excess oxygen |
| US20120071700A1 (en) * | 2010-09-21 | 2012-03-22 | Long Huang | Catalysts for hydrogenation of unsaturated hydrocarbons and preparations and uses thereof |
| CN104109080A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid |
| CN103969249A (en) * | 2014-04-14 | 2014-08-06 | 北京联合大学生物化学工程学院 | Composite oxide sensitive material used for monitoring formaldehyde and ammonia simultaneously |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038549A (en) * | 2019-05-22 | 2019-07-23 | 中国科学院上海高等研究院 | A kind of monatomic catalyst of oxide carried noble metal and its preparation method and application |
| CN110038549B (en) * | 2019-05-22 | 2022-01-21 | 中国科学院上海高等研究院 | Oxide-supported noble metal monatomic catalyst and preparation method and application thereof |
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| CN104437486B (en) | 2017-04-12 |
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