CN102335621A - Heteropolyacid-containing aromatics hydrogenation catalyst and preparation method thereof - Google Patents
Heteropolyacid-containing aromatics hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102335621A CN102335621A CN2011101986372A CN201110198637A CN102335621A CN 102335621 A CN102335621 A CN 102335621A CN 2011101986372 A CN2011101986372 A CN 2011101986372A CN 201110198637 A CN201110198637 A CN 201110198637A CN 102335621 A CN102335621 A CN 102335621A
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Abstract
The invention discloses a heteropolyacid-containing aromatics hydrogenation catalyst and a preparation method thereof, relating to a catalyst. The invention provides the heteropolyacid-containing aromatics hydrogenation with high sulphur resistance and high activity and the preparation method thereof. The catalyst comprises caesium heteropolyacid salts, hydrogenated components and a carrier, wherein the heteropolyacid caesium salts are caesium phosphotungstate or caesium silicotungstate, and the like; the hydrogenated components comprise Ni transition metal element, and the like; the carrier is a porous heat-resisting inorganic material; and the contents of all the components of the catalyst in percentage by mass are that: 5-40 percent of heteropolyacid, 0.2-0.5 percent of caesium, 5-20 percent of hydrogenated component and the balance of carrier. The preparation method comprises the following steps of: adding an water-soluble nickel salt solution and water-soluble heteropolyacid caesium salts into the carrier and impregnating; drying solid matters obtained through liquid-solid separation, and then roasting; preparing an aqueous caesium heteropolyacid salt solution, adding the aqueous caesium heteropolyacid salt solution to the obtained solid matters; impregnating and drying; and tabletting and forming to obtain the heteropolyacid-containing aromatics hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid and preparation method thereof.
Background technology
In petroleum refining industry, the aromatic hydrogenation technology is more and more paid attention to, and this mainly is the problem that causes aspects such as environment owing to too high arene content in the oil product.As the diesel oil that derives from mink cell focus contains too much aromatic hydrocarbons in slip dividing, and this will increase the particle emission in the diesel combustion waste gas, so that the weighting ring environment pollution.Therefore and owing to all have a certain amount of sulfide in the oil product, catalyst will receive the influence of sulfur poisoning inevitably in hydrogenation process, and exploitation has high anti-sulphur property and highly active aromatic hydrocarbon hydrogenation catalyst is one of present research focus.
Also the aromatic hydrocarbon hydrogenation catalyst of ortho states mainly comprises noble metal and non-precious metal catalysts such as Ni, Co such as Pt, Pd; It has the high advantage of aromatic hydrogenation activity; But poisoned by sulfur-containing compound easily; In addition, go back the existence of ortho states noble metal catalyst and cost an arm and a leg, be unfavorable for the problem of large-scale industrial production.Therefore, development has high anti-sulphur property highly active to go back ortho states base metal aromatic hydrocarbon hydrogenation catalyst significant.
U.S. Pat 5258346 has been reported the arenes catalytic agent of a kind of metal Ni as active component, can be applicable to multiple oil product especially than the hydrogenation aromatics-removing of heavy-hydrocarbon oil.This patent thinks that the sulfur poisoning-resistant ability key of Ni/ supported catalyst is to improve the distribution in hole.
Summary of the invention
The object of the invention is intended to going back ortho states base metal aromatic hydrocarbon hydrogenation catalyst easily by problems such as sulfur poisonings a kind of have high anti-sulphur property and highly active aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid and preparation method thereof are provided.
The said aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid consist of heteropoly acid caesium, hydrogenation component and carrier, said heteropoly acid caesium is Tricesium dodecatungstophosphate or silicotungstic acid cesium etc., preferred Tricesium dodecatungstophosphate; Said hydrogenation component is a Ni transition metal etc.; Said carrier is the heat-resisting inorganic material of porous, preferred silica; Each components contents of catalyst is a heteropoly acid 5%～40% by mass percentage, and is preferred 5%～30%, and caesium content is 0.2%～0.5%, and hydrogenation component (in oxide) is 5%～20%, preferred 8%～15%, and surplus is a carrier.
Tricesium dodecatungstophosphate that said heteropoly acid caesium adopts or silicotungstic acid cesium etc. all have higher heat endurance.
The said preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid may further comprise the steps:
1) water-soluble nickel salt solution and water-soluble acidic cs salts of heteropolyacid are added in the carrier successively flood, after the oven dry of the solids after the liquid-solid separation, roasting;
In step 1), the time of said dipping can be 4～12h; The time of said oven dry can be 3～8h, and the temperature of said roasting can be 350～450 ℃, and the time of said roasting can be 3～5h.
2) according to the constituent content preparation heteropoly acid caesium aqueous solution of catalyst, join again in the solids of step 1) gained, dipping, oven dry, compression molding promptly gets the aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid.
In step 2) in, the time of said dipping can be 4～12h, and the temperature of said oven dry can be 100～120 ℃, and the time of said oven dry can be 3～8h.
Differential reactor---the gas phase chromatographic device that flows is adopted in evaluation to the aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid.In reaction pressure is 1.0MPa, and temperature is 200 ℃, and the liquid air speed is 2.0h
-1, hydrogen to oil volume ratio is under 1500 the condition, to be reaction raw materials with the ethylbenzene that contains 300ppm sulphur.
The present invention selects that composition is comparatively simple, structure is clear and definite for use, and has the heteropoly acid caesium of good thermal stability, to improve the acid of catalyst and to form the hydrogen overflow.This catalyst is applicable to the aromatic hydrogenation course of reaction, has the active and stronger sulfur poisoning-resistant ability of higher hydrogenation reaction.Can be drawn by experimental data, the particle of this catalyst is less, and the activity of such catalysts component is at the carrier good dispersion, and this has higher activity with it is consistent.
Description of drawings
Fig. 1 is the Ni-based aromatic hydrocarbon hydrogenation catalyst typical X x ray diffraction spectrogram that contains heteropoly acid.In Fig. 1, abscissa is angle of diffraction 2Theta/degree, and ordinate is diffracted intensity Intensity (a.u.); Can know that from Fig. 1 heteropoly acid has loaded on the carrier silica.
Fig. 2 is the Ni-based aromatic hydrocarbon hydrogenation catalyst exemplary scanning Electronic Speculum figure that contains heteropoly acid.In Fig. 2, scale is 100nm; Can know that from Fig. 2 the particle of this catalyst is less, and the activity of such catalysts component is at the carrier good dispersion, this has higher activity with it is consistent.
The specific embodiment
Through embodiment the present invention is described further below.
Embodiment 1
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 106mL concentration is that nickel nitrate solution and the 5.6mL concentration of 1mol/L is 3.0 * 10
-4The cesium carbonate solution of mol/L joins the above-mentioned carrier S iO of 82g respectively
2In, leave standstill 12h, then dry 6h down in 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Baked solids impregnated in the phosphotungstic acid aqueous solution that contains 10g, leave standstill behind the 8h, dried material compression molding is promptly got catalyst at 120 ℃ of oven dry 6h down.The chemical composition and the heteropoly acid thing of institute's controlling catalyst are listed in table 1 mutually.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 106mL concentration is that nickel nitrate solution and the 11.4mL concentration of 1mol/L is 3.0 * 10
-4The cesium carbonate solution of mol/L joins the above-mentioned carrier S iO of 72g respectively
2In, leave standstill 12h, then dry 6h down in 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Baked solids impregnated in the phosphotungstic acid aqueous solution that contains 20g, leave standstill behind the 8h, dried material compression molding is promptly got catalyst at 120 ℃ of oven dry 6h down.The chemical composition and the heteropoly acid thing of institute's controlling catalyst are listed in table 1 mutually.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
Embodiment 3
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 200mL concentration is that nickel nitrate solution and the 5.6mL concentration of 1mol/L is 3.0 * 10
-4The cesium carbonate solution of mol/L joins the above-mentioned carrier S iO of 75g respectively
2In, leave standstill 12h, then dry 6h down in 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Baked solids impregnated in the phosphotungstic acid aqueous solution that contains 10g, leave standstill behind the 8h, dried material compression molding is promptly got catalyst at 120 ℃ of oven dry 6h down.The chemical composition and the heteropoly acid thing of institute's controlling catalyst are listed in table 1 mutually.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
Embodiment 4
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 106mL concentration is that nickel nitrate solution and the 11.4mL concentration of 1mol/L is 3.0 * 10
-4The cesium carbonate solution of mol/Lmol/L joins the above-mentioned carrier S iO of 65g respectively
2In, leave standstill 12h, then dry 6h down in 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Baked solids impregnated in the phosphotungstic acid aqueous solution that contains 20g, leave standstill behind the 8h, dried material compression molding is promptly got catalyst at 120 ℃ of oven dry 6h down.The chemical composition and the heteropoly acid thing of institute's controlling catalyst are listed in table 1 mutually.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
Embodiment 5
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 106mL concentration is that nickel nitrate solution and the 5.6mL concentration of 1mol/L is 3.0 * 10
-4The cesium carbonate solution of mol/L joins the above-mentioned carrier S iO of 82g respectively
2In, leave standstill 12h, then dry 6h down in 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Baked solids impregnated in the silicon tungsten acid solution that contains 10g, leave standstill behind the 8h, dried material compression molding is promptly got catalyst at 120 ℃ of oven dry 6h down.The chemical composition and the heteropoly acid thing of institute's controlling catalyst are listed in table 1 mutually.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
Embodiment 6
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 106mL concentration is that nickel nitrate solution and the 11.4mL concentration of 1mol/L is 3.0 * 10
-4The cesium carbonate solution of mol/L joins the above-mentioned carrier S iO of 72g respectively
2In, leave standstill 12h, then dry 6h down in 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Baked solids impregnated in the silicon tungsten acid solution that contains 20g, leave standstill behind the 8h, dried material compression molding is promptly got catalyst at 120 ℃ of oven dry 6h down.The chemical composition and the heteropoly acid thing of institute's controlling catalyst are listed in table 1 mutually.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
Comparative example 1
1) select carrier: carrier is that 40～60 order specific surfaces are 380m
2The SiO of/g
2Particle.
2) Preparation of Catalyst: with 106mL concentration is that the nickel nitrate solution of 1mol/L joins the above-mentioned carrier S iO of 92g
2In, leave standstill 12h, then dry 6h down with 110 ℃.Solids speed with 10 ℃/min in muffle furnace after the oven dry is risen to 400 ℃, constant temperature 4h.Solids compression molding after the roasting is promptly got catalyst.
3) appreciation condition: the catalyst for preparing is descended reduction 4h in 400 ℃ in hydrogen atmosphere.After reduction finished, incision contained the ethylbenzene reaction raw materials of 300ppm sulphur, and reaction process condition is seen table 2.The aromatic hydrogenation activity of evaluate catalysts under this reaction condition, the result sees table 3.
The chemical composition of each embodiment catalyst of table 1
Table 2 feedstock property and reaction process condition thereof
Each embodiment of table 3/comparative example catalyst activity evaluation result
Claims (10)
1. an aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid is characterized in that it consists of heteropoly acid caesium, hydrogenation component and carrier, and said heteropoly acid caesium is Tricesium dodecatungstophosphate or silicotungstic acid cesium; Said hydrogenation component is the Ni transition metal; Said carrier is the heat-resisting inorganic material of porous; Each components contents of catalyst is a heteropoly acid 5%～40% by mass percentage, and caesium content is 0.2%～0.5%, is 5%～20% in the oxide hydrogenation component, and surplus is a carrier.
2. a kind of aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid as claimed in claim 1 is characterized in that said heteropoly acid caesium is a Tricesium dodecatungstophosphate.
3. a kind of aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid as claimed in claim 1 is characterized in that said carrier is a silica.
4. a kind of aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid as claimed in claim 1; It is characterized in that each components contents of catalyst is a heteropoly acid 5%～30% by mass percentage; Caesium content is 0.2%～0.5%, is 8%～15% in the oxide hydrogenation component, and surplus is a carrier.
5. a kind of preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid as claimed in claim 1 is characterized in that may further comprise the steps:
1) water-soluble nickel salt solution and water-soluble acidic cs salts of heteropolyacid are added in the carrier successively flood, after the oven dry of the solids after the liquid-solid separation, roasting;
2) according to the constituent content preparation heteropoly acid caesium aqueous solution of catalyst, join again in the solids of step 1) gained, dipping, oven dry, compression molding promptly gets the aromatic hydrocarbon hydrogenation catalyst that contains heteropoly acid.
6. a kind of preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid as claimed in claim 5 is characterized in that in step 1) the time of said dipping is 4～12h.
7. a kind of preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid as claimed in claim 5 is characterized in that in step 1) the time of said oven dry is 3～8h.
8. a kind of preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid as claimed in claim 5 is characterized in that in step 1) the temperature of said roasting is 350～450 ℃, and the time of said roasting is 3～5h.
9. a kind of preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid as claimed in claim 5 is characterized in that in step 2) in, the time of said dipping is 4～12h.
10. a kind of preparation method who contains the aromatic hydrocarbon hydrogenation catalyst of heteropoly acid as claimed in claim 5 is characterized in that in step 2) in, the temperature of said oven dry is 100～120 ℃, the time of said oven dry is 3～8h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101472498B1 (en) * | 2013-04-04 | 2014-12-15 | 고려대학교 산학협력단 | A method for preparing light oil from extra heavy oil using cesium substituted heteropolyacid catalyst and method for regenerating the catalyst |
| CN104646059A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Heteropolyacid cesium salt containing hydrocracking catalyst, preparation and application thereof |
| CN105749972A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | Petroleum resin hydrogenation catalyst and preparation method and application thereof |
| CN107008504A (en) * | 2016-01-27 | 2017-08-04 | 中国石油化工股份有限公司 | A kind of catalyst, its preparation method and the method for preparing cyclohexyl benzene |
| CN108348899A (en) * | 2015-11-19 | 2018-07-31 | 国际壳牌研究有限公司 | Antigravity system for manufacturing glycol and method |
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| US5536687A (en) * | 1990-05-22 | 1996-07-16 | Uop | Catalyst containing zeolite Beta |
| CN1927461A (en) * | 2006-09-30 | 2007-03-14 | 厦门大学 | Heteropoly acid containing hydrocracking catalyst and its preparation method |
| CN101670300A (en) * | 2009-10-01 | 2010-03-17 | 厦门大学 | Sulphur-nitrogen resistant hydrocracking catalyst and preparation method thereof |
| CN101797512A (en) * | 2010-03-15 | 2010-08-11 | 厦门大学 | High-activity hydrocracking catalyst and preparation method thereof |
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2011
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| US5536687A (en) * | 1990-05-22 | 1996-07-16 | Uop | Catalyst containing zeolite Beta |
| US5258346A (en) * | 1992-07-13 | 1993-11-02 | United Catalysts Inc. | Nickel hydrogenation catalyst |
| CN1927461A (en) * | 2006-09-30 | 2007-03-14 | 厦门大学 | Heteropoly acid containing hydrocracking catalyst and its preparation method |
| CN101670300A (en) * | 2009-10-01 | 2010-03-17 | 厦门大学 | Sulphur-nitrogen resistant hydrocracking catalyst and preparation method thereof |
| CN101797512A (en) * | 2010-03-15 | 2010-08-11 | 厦门大学 | High-activity hydrocracking catalyst and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101472498B1 (en) * | 2013-04-04 | 2014-12-15 | 고려대학교 산학협력단 | A method for preparing light oil from extra heavy oil using cesium substituted heteropolyacid catalyst and method for regenerating the catalyst |
| CN104646059A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Heteropolyacid cesium salt containing hydrocracking catalyst, preparation and application thereof |
| CN105749972A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | Petroleum resin hydrogenation catalyst and preparation method and application thereof |
| CN105749972B (en) * | 2014-12-17 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
| CN108348899A (en) * | 2015-11-19 | 2018-07-31 | 国际壳牌研究有限公司 | Antigravity system for manufacturing glycol and method |
| CN108348899B (en) * | 2015-11-19 | 2021-06-04 | 国际壳牌研究有限公司 | Catalyst system and process for the manufacture of diols |
| CN107008504A (en) * | 2016-01-27 | 2017-08-04 | 中国石油化工股份有限公司 | A kind of catalyst, its preparation method and the method for preparing cyclohexyl benzene |
| CN107008504B (en) * | 2016-01-27 | 2020-03-24 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for preparing cyclohexylbenzene |
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Application publication date: 20120201 |