CN101954287B - Rare earth catalyst for treating hydrocarbon and preparation method thereof - Google Patents
Rare earth catalyst for treating hydrocarbon and preparation method thereof Download PDFInfo
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- CN101954287B CN101954287B CN201010289794XA CN201010289794A CN101954287B CN 101954287 B CN101954287 B CN 101954287B CN 201010289794X A CN201010289794X A CN 201010289794XA CN 201010289794 A CN201010289794 A CN 201010289794A CN 101954287 B CN101954287 B CN 101954287B
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Abstract
The invention provides a rare earth catalyst for treating hydrocarbon and a preparation method thereof. The rare earth catalyst for treating the hydrocarbon consists of a mixture of rare earth, a binder and metallic oxide. The preparation method comprises the following steps of: mixing the rare earth and the binder according to a proportion, and impregnating the obtained mixture in active metal salt or alkali mixed solution which is mixed solution of copper salt, nickel salt, manganese salt, cobalt salt, zinc salt and nickel hydroxide; and filtering, washing, drying and roasting to obtain the rare earth catalyst finished product for treating the hydrocarbon. The invention has the advantages of high efficiency of treating the hydrocarbon and simple preparation process.
Description
Technical field
The present invention relates to a kind of rare earth catalyst of handling hydrocarbon and preparation method thereof, belong to new material technology field.
Background technology
Along with the high speed development of urban economy, the urban automobile degree is increasingly high, and the discharging of tail gas is also more and more serious to the influence of atmospheric environment, the environmental pollution that causes thus and serious day by day to the harm of human body.Hydrocarbon is one of main harmful components in the vehicle exhaust.At present the improvement of hydrocarbon-containiproducts is mainly adopted the method for conversion, but problems such as the disposal ability removal efficient limited, hydrocarbon that conversion method exists is low, expense height.
It is carrier that Chinese patent CN01127915.X disclosed " a kind of macromolecular hydrocarbon hydrofining catalyst and preparation method thereof " adopts with nickeliferous aluminium oxide, is that the catalyst of active component carries out hydrotreatment to hydrocarbon with family's metallic element.This catalyst is complicated to the removal process of hydrocarbon, and catalyst is non-renewable.
Summary of the invention
The purpose of this invention is to provide a kind of Catalysts and its preparation method that process is simple, the hydrocarbon removal effect is good for preparing.
In order to achieve the above object, the invention provides a kind of rare earth catalyst of handling hydrocarbon, it is characterized in that forming by rare earth 40-90 weight portion, adhesive 5-12 weight portion and metal oxide mixture 5-48 weight portion.
Said rare earth is cerium oxide and zirconic mixture.
Said adhesive is that molecular weight is the polyvinyl alcohol of 20000-2000000.
Said metal oxide mixture is made up of cupric oxide 2-9 weight portion, nickel oxide 1-8 weight portion, manganese oxide 2-8 weight portion, cobalt oxide 1-8 weight portion and zinc oxide 1-8 weight portion.
The present invention also provides the preparation method of the rare earth catalyst of above-mentioned processing hydrocarbon, it is characterized in that, concrete steps are:
The first step, rare earth and adhesive are mixed in proportion; The gained mixture was flooded 2-20 hour in active metal salt or aqueous slkali; Described active metal salt or alkali mixed solution are the mixed solution of mantoquita, nickel salt, manganese salt, cobalt salt and zinc salt, and the metal ion total concentration is 5-50% in the mixed solution;
Second step, the maceration extract of the first step is filtered, washing, the gained solid was at 80-200 ℃ of dry 2-20 hour; Dried solid was obtained the rare earth catalyst finished product at 200-800 ℃ of roasting 2-10 hour.
Described mantoquita is one or more the mixture in Schweinfurt green, copper sulphate and the copper nitrate.
Described nickel salt is one or more the mixture in nickel acetate, nickel nitrate, nickelous sulfate and the nickel hydroxide.
Described manganese salt is one or more the mixture in manganese nitrate, manganese sulfate and the manganese acetate.
Described cobalt salt is one or more the mixture in cobalt acetate, cobalt nitrate and the cobaltous sulfate.
Described zinc salt is one or more the mixture in zinc acetate, zinc nitrate and the zinc sulfate.
The specific area of said rare earth catalyst is 0.1-300 m
2/ g.
The present invention compared with prior art, advantage is following:
(1) preparation process is pollution-free, and productive rate has the 50-250 ℃ of reproducible advantage of heating up to 90-95%, reaches 10 years service life.
(2) catalyst according to the invention clearance to hydrocarbon under 300 ℃ reaches 100 %, and product is water and carbon dioxide.
(3) catalyst according to the invention have that technology is simple, raw material is extensive, cheap, pollution-free, remove the efficient advantages of higher, can be used for fields such as vehicle exhaust processing, petrochemical plant, oil plant.
The specific embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1
A kind of rare earth catalyst of handling hydrocarbon is made up of rare earth 14g, adhesive 9 g and metal oxide mixture 16.4g.Said rare earth is cerium oxide and zirconic mixture.Adhesive is the polyvinyl alcohol of molecular weight 20000.Said metal oxide mixture is made up of 1.8g cupric oxide, 5.8g nickel oxide, 4.7g manganese oxide, 2.4g cobalt oxide and 1.7g zinc oxide.
Its preparation method is: the polyvinyl alcohol of 6g cerium oxide, 8g zirconia, 9g molecular weight 20000 is mixed evenly; Joined in the aqueous solution of 200mL 2wt% copper sulphate, 7wt% nickel acetate, 5wt% manganese nitrate, 3wt% cobalt acetate and 2wt% zinc acetate dipping 2 hours; Filter then; Washing, the solid that obtains was 200 ℃ of dryings 2 hours, and the mixture after will drying then obtained specific area 300 m in 2 hours 800 ℃ of roastings
2The catalyst finished product of/g.0.7g this catalyst methane gas clearance to the 20mL/min flow velocity in the time of 300 ℃ reaches 100%.
Embodiment 2
A kind of rare earth catalyst of handling hydrocarbon is made up of rare earth 18g, adhesive 7g and metal oxide mixture 34.3g.Said rare earth is cerium oxide and zirconic mixture.Adhesive is the polyvinyl alcohol of molecular weight 2000000.Said metal oxide mixture is made up of 6.4g cupric oxide, 8g nickel oxide, 10.2g manganese oxide, 3.5g cobalt oxide and 6.2g zinc oxide.
Its preparation method is: the polyvinyl alcohol of 12g cerium oxide, 6g zirconia, 7g molecular weight 2000000 is mixed evenly; Joined in the aqueous solution of 300mL 5wt% Schweinfurt green, 7wt% nickel nitrate, 6wt% manganese sulfate, 3wt% cobalt nitrate and 5wt% zinc nitrate dipping 2 hours; Filter then; Washing, the solid that obtains was 80 ℃ of dryings 20 hours, and the mixture after will drying then obtained specific area 50 m in 3 hours 500 ℃ of roastings
2The catalyst finished product of/g.This catalyst of 1g propane gas clearance to the 50mL/min flow velocity in the time of 300 ℃ reaches 100%.
Embodiment 3
A kind of rare earth catalyst of handling hydrocarbon is made up of rare earth 13g, adhesive 9g and metal oxide mixture 31.6g.Said rare earth is cerium oxide and zirconic mixture.Adhesive is the polyvinyl alcohol of molecular weight 30000.Said metal oxide mixture is made up of 2g cupric oxide, 8g nickel oxide, 11.3g manganese oxide, 2g cobalt oxide and 8.3g zinc oxide.
Its preparation method is: the polyvinyl alcohol of 10g cerium oxide, 3g zirconia, 9g molecular weight 30000 is mixed evenly; Joined in the aqueous solution of 250mL 2wt% Schweinfurt green, 8wt% nickel acetate, 8wt% manganese sulfate, 2wt% cobalt nitrate and 8wt% zinc nitrate dipping 10 hours; Filter then; Washing, the solid that obtains was 80 ℃ of dryings 10 hours, and the mixture after will drying then obtained specific area 200 m in 4 hours 200 ℃ of roastings
2The catalyst finished product of/g.0.5g this catalyst methane gas clearance to the 40mL/min flow velocity in the time of 300 ℃ reaches 100%.
Embodiment 4
A kind of rare earth catalyst of handling hydrocarbon is made up of rare earth 22g, adhesive 9g and metal oxide mixture 31g.Said rare earth is cerium oxide and zirconic mixture.Adhesive is the polyvinyl alcohol of molecular weight 1000000.Said metal oxide mixture is made up of 5.7g cupric oxide, 8.6g nickel oxide, 7g manganese oxide, 4.7g cobalt oxide and 5g zinc oxide.
Its preparation method is: the polyvinyl alcohol of 10g cerium oxide, 12g zirconia, 9g molecular weight 1000000 is mixed evenly; Joined in the aqueous solution of 200mL 7wt% copper nitrate, 8wt% nickelous sulfate, 7wt% manganese acetate, 5wt% cobaltous sulfate and 5wt% zinc sulfate dipping 5 hours; Filter then; Washing, the solid that obtains was 80 ℃ of dryings 5 hours, and the mixture after will drying then obtained specific area 180 m in 10 hours 400 ℃ of roastings
2The catalyst finished product of/g.This catalyst of 2g propane gas clearance to the 100mL/min flow velocity in the time of 300 ℃ reaches 100%.
Embodiment 5
A kind of rare earth catalyst of handling hydrocarbon is made up of rare earth 20g, adhesive 10g and metal oxide mixture 29g.Said rare earth is cerium oxide and zirconic mixture.Adhesive is the polyvinyl alcohol of molecular weight 60000.Said metal oxide mixture is made up of 1.6g cupric oxide, 11.5g nickel oxide, 6g manganese oxide, 3.8g cobalt oxide and 6.1g zinc oxide.
Its preparation method is: the polyvinyl alcohol of 11g cerium oxide, 9g zirconia, 10g molecular weight 60000 is mixed evenly; Joined in the aqueous solution of 180mL 2wt% copper sulphate, 8wt% nickel hydroxide, 7wt% manganese nitrate, 5wt% cobalt acetate and 8wt% zinc acetate dipping 8 hours; Filter then; Washing, the solid that obtains was 100 ℃ of dryings 6 hours, and the mixture after will drying then obtained specific area 145 m in 8 hours 800 ℃ of roastings
2The catalyst finished product of/g.This catalyst of 1g propane gas clearance to the 80mL/min flow velocity in the time of 300 ℃ reaches 100%.
Claims (5)
1. rare earth catalyst of handling hydrocarbon; It is characterized in that; Form by rare earth 40-90 weight portion, adhesive 5-12 weight portion and metal oxide mixture 5-48 weight portion; Said rare earth is cerium oxide and zirconic mixture, and said metal oxide mixture is made up of cupric oxide, nickel oxide, manganese oxide, cobalt oxide and zinc oxide; Its preparation method is:
The first step, rare earth and adhesive are mixed in proportion; The gained mixture was flooded 2-20 hour in the reactive metal salting liquid; Described reactive metal mixed salt solution is the mixed solution of mantoquita, nickel salt, manganese salt, cobalt salt and zinc salt, and the metal ion total concentration is 5-50% in the mixed solution;
Second step, the maceration extract of the first step is filtered, washing, the gained solid was at 80-200 ℃ of dry 2-20 hour; Dried solid was obtained the rare earth catalyst finished product at 200-800 ℃ of roasting 2-10 hour.
2. the rare earth catalyst of processing hydrocarbon as claimed in claim 1 is characterized in that, said adhesive is that molecular weight is the polyvinyl alcohol of 20000-2000000.
3. the rare earth catalyst of processing hydrocarbon as claimed in claim 1; It is characterized in that said metal oxide mixture is made up of cupric oxide 2-9 weight portion, nickel oxide 1-8 weight portion, manganese oxide 2-8 weight portion, cobalt oxide 1-8 weight portion and zinc oxide 1-8 weight portion.
4. the rare earth catalyst of processing hydrocarbon as claimed in claim 1 is characterized in that, the mantoquita in the said first step is one or more the mixture in Schweinfurt green, copper sulphate and the copper nitrate; Nickel salt is one or more the mixture in nickel acetate, nickel nitrate and the nickelous sulfate; Manganese salt is one or more the mixture in manganese nitrate, manganese sulfate and the manganese acetate; Cobalt salt is one or more the mixture in cobalt acetate, cobalt nitrate and the cobaltous sulfate; Zinc salt is one or more the mixture in zinc acetate, zinc nitrate and the zinc sulfate.
5. the rare earth catalyst of processing hydrocarbon as claimed in claim 1 is characterized in that, gained rare earth catalyst specific area is 0.1-300 m
2/ g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010289794XA CN101954287B (en) | 2010-09-25 | 2010-09-25 | Rare earth catalyst for treating hydrocarbon and preparation method thereof |
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| CN201010289794XA CN101954287B (en) | 2010-09-25 | 2010-09-25 | Rare earth catalyst for treating hydrocarbon and preparation method thereof |
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| CN101954287A CN101954287A (en) | 2011-01-26 |
| CN101954287B true CN101954287B (en) | 2012-06-13 |
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| CN201010289794XA Expired - Fee Related CN101954287B (en) | 2010-09-25 | 2010-09-25 | Rare earth catalyst for treating hydrocarbon and preparation method thereof |
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| CN109647429B (en) * | 2017-10-11 | 2022-01-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and preparation method of tetrahydrofurfuryl alcohol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4034060A (en) * | 1972-10-13 | 1977-07-05 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Exhaust gas purifying catalyst and process of making and using same |
| CN1394936A (en) * | 2001-07-09 | 2003-02-05 | 中国石油化工股份有限公司 | Macromolecular hydrocarbon hydrofining catalyst and its preparation method |
| CN100998941A (en) * | 2007-01-04 | 2007-07-18 | 华东理工大学 | Precatalyst and its preparation method |
| CN101528325A (en) * | 2006-10-20 | 2009-09-09 | 罗地亚管理公司 | Highly acidic composition containing zirconium and silicon oxides and an oxide of at least one element selected from titanium, aluminium, tungsten, molybdenum, cerium, iron, tin, zinc, and manganese |
| CN101623629A (en) * | 2008-07-09 | 2010-01-13 | W.C.贺利氏有限公司 | Oxidation catalyst |
-
2010
- 2010-09-25 CN CN201010289794XA patent/CN101954287B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4034060A (en) * | 1972-10-13 | 1977-07-05 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Exhaust gas purifying catalyst and process of making and using same |
| CN1394936A (en) * | 2001-07-09 | 2003-02-05 | 中国石油化工股份有限公司 | Macromolecular hydrocarbon hydrofining catalyst and its preparation method |
| CN101528325A (en) * | 2006-10-20 | 2009-09-09 | 罗地亚管理公司 | Highly acidic composition containing zirconium and silicon oxides and an oxide of at least one element selected from titanium, aluminium, tungsten, molybdenum, cerium, iron, tin, zinc, and manganese |
| CN100998941A (en) * | 2007-01-04 | 2007-07-18 | 华东理工大学 | Precatalyst and its preparation method |
| CN101623629A (en) * | 2008-07-09 | 2010-01-13 | W.C.贺利氏有限公司 | Oxidation catalyst |
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