CN103611578A - Phase transfer catalyst for oxidative desulfurization of activated carbon supported heteropolyacid quaternary ammonium salt diesel and preparation method of phase transfer catalyst - Google Patents
Phase transfer catalyst for oxidative desulfurization of activated carbon supported heteropolyacid quaternary ammonium salt diesel and preparation method of phase transfer catalyst Download PDFInfo
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- CN103611578A CN103611578A CN201310585721.9A CN201310585721A CN103611578A CN 103611578 A CN103611578 A CN 103611578A CN 201310585721 A CN201310585721 A CN 201310585721A CN 103611578 A CN103611578 A CN 103611578A
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Abstract
The invention discloses a phase transfer catalyst for oxidative desulfurization of activated carbon supported heteropolyacid quaternary ammonium salt diesel and a preparation method of the phase transfer catalyst. The catalyst is prepared from an activated carbon carrier and a heteropolyacid quaternary ammonium salt active component, wherein the content of the heteropolyacid quaternary ammonium salt is 20-40% of the content of the activated carbon; the aperture of the catalyst is 1-2nm; the specific surface area of the catalyst is 500-700 m<2>/g. According to the invention, the activated carbon is taken as a support, and the heteropolyacid quaternary ammonium salt is taken as an active component, so as to prepare the phase transfer catalyst for oxidative desulfurization for the diesel, so that the defects that a non-supported phase transfer catalyst is fine in particles, low in specific surface area, and not easy to recycle are overcome. The heteropolyacid quaternary ammonium salt is supported on the activated carbon by adopting a two-step impregnation method. Firstly, heteropolyacid is supported to the activated carbon, and then reacts with the quaternary ammonium salt, so as to prepare the supported heteropolyacid quaternary ammonium salt phase transfer catalyst. The obtained catalyst is high in specific surface area; the active components are high in dispersity on the support, easy to separate and recycle, and less in oil loss. Thus, the diesel efficiency and the desulphurization rate are improved.
Description
One, technical field
The invention belongs to catalyst technical field, be specifically related to a kind of activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst and preparation method thereof.
Two, background technology
Although catalytic oxidation desulfurization is typical non-hydrodesulfurizationprocess process, because oxidizer system and oil product system are not dissolved each other mutually, make effective degree of mixing of aqueous phase oxidation agent and sulfur-containing compound poor, oxidation reaction only occurs in the interface place of water-organic phase, not only affects the yield that desulfurization degree also affects diesel oil.
Heteropoly acid quaternary ammonium salt has hydrophily and lipophile, also has highly acid and strong oxidizing property simultaneously, can effectively address the above problem.But heteropoly acid quaternary ammonium salt phase transfer catalyst particle is thin, separation difficulty, cost are high, therefore considers to be carried out load, and active carbon has high specific area, cheap and easy to get, is good catalyst carrier.Therefore can select active carbon is that carrier is prepared heteropoly acid quaternary ammonium salt catalyst, and correlative study at present has no report.
Heteropoly acid quaternary ammonium salt phase transfer catalyst is solid, cannot directly be carried on active carbon, therefore first by loaded by heteropoly acid to active carbon, then by reacting with quaternary ammonium salt, prepare carried heteropoly acid quaternary ammonium salt phase transfer catalyst, the correlative study that current two-step method is prepared activated carbon supported heteropoly acid quaternary ammonium salt phase transfer catalyst also has no report.
Three, summary of the invention
The object of this invention is to provide a kind of catalytic activity high, easily separated, oil product loss is few, activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst that diesel yield and desulfurization degree are high and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: this catalyst is comprised of absorbent charcoal carrier and heteropoly acid quaternary ammonium salt active component, the 20-40% that wherein mass content of heteropoly acid quaternary ammonium salt is active carbon; The aperture of this catalyst is 1-2nm, and specific area is 500-700m
2/ g.
The preparation method of catalyst of the present invention comprises the steps:
1. the pretreatment of active carbon: take active carbon, the salpeter solution that is 10% with percentage by weight is in equal-volume ratio dipping 12-24 hour, heating water bath 2-3 hour, suction filtration, is washed to neutrality, puts into baking oven, at 100-120 ℃ of temperature, dries and get final product;
2. the preparation of Catalyzed by Heteropolyacid Supported on Actived Carbon agent: get in proportion heteropoly acid and be fully dissolved in ethanolic solution, in above-mentioned solution, add pretreated active carbon, first under constant temperature, stir, then heat up and make solution evaporate to dryness, continue to be drying to obtain the 14-30% that wherein mass content of heteropoly acid is active carbon;
3. the preparation of activated carbon supported heteropoly acid quaternary ammonium salt phase transfer catalyst: quaternary ammonium salt is fully dissolved in ethanolic solution, the Catalyzed by Heteropolyacid Supported on Actived Carbon agent making is joined in above-mentioned solution, under constant temperature reaction, suction filtration, be washed to neutrality, continue to be drying to obtain the 20-40% that wherein mass content of heteropoly acid quaternary ammonium salt is active carbon; The mol ratio of above-mentioned heteropoly acid and quaternary ammonium salt is 0.8-1:1-2.
Above-mentioned steps 2. in heteropoly acid used be phosphotungstic acid or phosphomolybdic acid.
Above-mentioned steps 3. in quaternary ammonium salt used be softex kw or TBAB.
Above-mentioned steps 2., 3. in the mass concentration of ethanolic solution used be 30-50%.
Above-mentioned steps 2. middle preparation condition is: first at 50-70 ℃, stir 2-4 hour, be then warming up to 80-90 ℃ and make solution evaporate to dryness.
Above-mentioned steps 2. middle continuation baking temperature is 100-120 ℃, and be 24-48 hour drying time.
Above-mentioned steps 3. middle reaction temperature is 60-80 ℃, and the reaction time is 2-4 hour,
Above-mentioned steps 3. middle baking temperature is 100-140 ℃, and be 24-48 hour drying time.
The present invention be take active carbon as carrier, and heteropoly acid quaternary ammonium salt is that active component is prepared diesel oxidation desulfurizing phase transfer catalyst, has overcome that non-loading type phase transfer catalyst particle is thin, specific area is low, has been difficult for the shortcoming that reclaims.Adopt two step infusion processes that heteropoly acid quaternary ammonium salt is carried on active carbon, first by loaded by heteropoly acid to active carbon, then, by reacting with quaternary ammonium salt, prepare carried heteropoly acid quaternary ammonium salt phase transfer catalyst, gained specific surface area of catalyst is high, the decentralization on carrier of active component is high, is easy to separated recovery, and oil product loss is few, diesel yield and desulfurization degree have been improved, can reach respectively more than 99% and more than 50%, and catalyst reuses 5 times, actively do not decline.
Four, the specific embodiment
Embodiment 1:
1. take active carbon, the salpeter solution that is 10% with percentage by weight is in equal-volume ratio Immesion active carbon 24 hours, and heating water bath 2-3 hour, is washed to neutrality at suction filtration, puts into baking oven, 120 ℃ of oven dry;
2. take in 30% the ethanolic solution that phosphomolybdic acid 0.3g is fully dissolved in 40ml, in above-mentioned solution, add the pretreated active carbon of 1g, first at 60 ℃, stir 2 hours, then will be warming up to 85 ℃ and make solution evaporate to dryness, at 110 ℃, be dried 24 hours, obtain activated carbon supported phosphomolybdic acid catalyst;
3. taking softex kw 0.08g is fully dissolved in 30% 40ml ethanolic solution, the activated carbon supported phosphomolybdic acid catalyst making is joined in above-mentioned solution, at 70 ℃, stir 2 hours, then suction filtration, be washed to neutrality, at 100 ℃, freeze-day with constant temperature is 24 hours, obtains activated carbon supported phosphomolybdic acid softex kw salt phase transfer catalyst.
Embodiment 2:
1. take active carbon, the salpeter solution that is 10% with percentage by weight is in equal-volume ratio Immesion active carbon 24 hours, and heating water bath 2-3 hour, is washed to neutrality at suction filtration, puts into baking oven, 120 ℃ of oven dry;
2. take in 30% the ethanolic solution that phosphotungstic acid 0.3g is fully dissolved in 40ml, in above-mentioned solution, add the pretreated active carbon of 1g, first at 70 ℃, stir 2 hours, then will be warming up to 85 ℃ and make solution evaporate to dryness, at 110 ℃, be dried 24 hours, obtain Phosphotungstic Acid Supported by Activated Carbon agent;
3. taking TBAB 0.004g is fully dissolved in 30% 40ml ethanolic solution, the Phosphotungstic Acid Supported by Activated Carbon agent making is joined in above-mentioned solution, at 75 ℃, stir 2 hours, then suction filtration, be washed to neutrality, freeze-day with constant temperature 24h at 100 ℃, obtains activated carbon supported phosphotungstic acid TBAB salt phase transfer catalyst.
Embodiment 3:
1. take active carbon, the salpeter solution that is 10% with percentage by weight is in equal-volume ratio Immesion active carbon 24 hours, and heating water bath 2-3 hour, is washed to neutrality at suction filtration, puts into baking oven, 120 ℃ of oven dry;
2. take in 30% the ethanolic solution that phosphomolybdic acid 0.2g is fully dissolved in 40ml, in above-mentioned solution, add the pretreated active carbon of 1g, first at 65 ℃, stir 2 hours, then will be warming up to 80 ℃ and make solution evaporate to dryness, at 110 ℃, be dried 24 hours, obtain activated carbon supported phosphomolybdic acid catalyst;
3. take TBAB 0.04g fully solution in 30% 40ml ethanolic solution, the activated carbon supported phosphomolybdic acid catalyst making is joined in above-mentioned solution, at 70 ℃, stir 2 hours, then suction filtration, be washed to neutrality, at 100 ℃, freeze-day with constant temperature is 24 hours, obtains activated carbon supported phosphomolybdic acid TBAB salt phase transfer catalyst.
Embodiment 4:
1. take active carbon, the salpeter solution that is 10% with percentage by weight is in equal-volume ratio Immesion active carbon 24 hours, and heating water bath 2-3 hour, is washed to neutrality at suction filtration, puts into baking oven, 120 ℃ of oven dry;
2. take in 30% the ethanolic solution that phosphotungstic acid 0.3g is fully dissolved in 40ml, in above-mentioned solution, add the pretreated active carbon of 1g, first at 70 ℃, stir 2 hours, then will be warming up to 85 ℃ and make solution evaporate to dryness, at 110 ℃, be dried 24 hours, obtain Phosphotungstic Acid Supported by Activated Carbon agent;
3. taking softex kw 0.04g is dissolved in 30% 40ml ethanolic solution, the Phosphotungstic Acid Supported by Activated Carbon agent making joins in above-mentioned solution, at 75 ℃, stir 2 h, then suction filtration, be washed to neutrality, freeze-day with constant temperature 24h at 100 ℃, obtains activated carbon supported phosphotungstic acid softex kw salt phase transfer catalyst.
The using method of catalyst of the present invention is: get proper catalyst and add round-bottomed flask, consumption is the 1-3% of diesel quality, then adds in proportion successively diesel oil, 30% hydrogen peroxide, O/S mol ratio is 10-12, finally reaction system is put into 60-70 ℃ of water bath with thermostatic control and reacted, the time is 1-2 h, after reaction finishes, first that reaction system is standing to room temperature, then with the DMF of volume fraction 75 %, extract oil ratio 0.5-1::0.8-1(v/v), reaction time 0.5-1.0h.
Claims (10)
1. an activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst, this catalyst is comprised of absorbent charcoal carrier and heteropoly acid quaternary ammonium salt active component, the 20-40% that wherein mass content of heteropoly acid quaternary ammonium salt is active carbon; The aperture of this catalyst is 1-2nm, and specific area is 500-700m
2/ g.
2. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst according to claim 1, it is characterized in that: the using method of this catalyst is: get proper catalyst and add round-bottomed flask, consumption is the 1-3% of diesel quality, then add in proportion successively diesel oil, 30% hydrogen peroxide, O/S mol ratio is 10-12, finally reaction system being put into 60-70 ℃ of water bath with thermostatic control reacts, time is 1-2 h, after reaction finishes, first that reaction system is standing to room temperature, then with the DMF of volume fraction 75 %, extract, oil ratio 0.5-1::0.8-1(v/v), reaction time 0.5-1.0h.
3. an activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method, comprises the steps:
1. the pretreatment of active carbon: take active carbon, the salpeter solution that is 10% with percentage by weight is in equal-volume ratio dipping 12-24 hour, heating water bath 2-3 hour, suction filtration, is washed to neutrality, puts into baking oven, at 100-120 ℃ of temperature, dries and get final product;
2. the preparation of Catalyzed by Heteropolyacid Supported on Actived Carbon agent: get in proportion heteropoly acid and be fully dissolved in ethanolic solution, in above-mentioned solution, add pretreated active carbon, first under constant temperature, stir, then heat up and make solution evaporate to dryness, continue to be drying to obtain the 14-30% that wherein mass content of heteropoly acid is active carbon;
3. the preparation of activated carbon supported heteropoly acid quaternary ammonium salt phase transfer catalyst: quaternary ammonium salt is fully dissolved in ethanolic solution, the Catalyzed by Heteropolyacid Supported on Actived Carbon agent making is joined in above-mentioned solution, under constant temperature reaction, suction filtration, be washed to neutrality, continue to be drying to obtain the 20-40% that wherein mass content of heteropoly acid quaternary ammonium salt is active carbon; The mol ratio of above-mentioned heteropoly acid and quaternary ammonium salt is 0.8-1:1-2.
4. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, is characterized in that: described step 2. in heteropoly acid used be phosphotungstic acid or phosphomolybdic acid.
5. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, is characterized in that: described step 3. in quaternary ammonium salt used be softex kw or TBAB.
6. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, is characterized in that: described step 2., 3. in the mass concentration of ethanolic solution used be 30-50%.
7. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, it is characterized in that: described step 2. middle preparation condition is: first at 50-70 ℃, stir 2-4 hour, be then warming up to 80-90 ℃ and make solution evaporate to dryness.
8. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, is characterized in that: described step 2. middle continuation baking temperature is 100-120 ℃, and be 24-48 hour drying time.
9. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, is characterized in that: described step 3. middle reaction temperature is 60-80 ℃, and the reaction time is 2-4 hour.
10. activated carbon supported heteropoly acid quaternary ammonium salt diesel oxidation desulfurizing phase transfer catalyst preparation method according to claim 3, is characterized in that: described step 3. middle baking temperature is 100-140 ℃, and be 24-48 hour drying time.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475155A (en) * | 2014-12-03 | 2015-04-01 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation desulfurization of fuel oil and preparation method and application thereof |
| CN105618138A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Immobilized tungstophosphoric heteropoly acid catalyst and use thereof |
| CN108795484A (en) * | 2018-07-11 | 2018-11-13 | 济南开发区星火科学技术研究院 | A kind of dioxygen oxidation diesel oil desulfurization method |
| CN108855232A (en) * | 2018-07-02 | 2018-11-23 | 东北师范大学 | A kind of composite nano fiber and its preparation method and application |
| CN110252413A (en) * | 2019-06-27 | 2019-09-20 | 石河子开发区汇智元科技有限责任公司 | One kind being used for C9 resin raw material oil oxidation desulfurization catalyst |
| CN113617397A (en) * | 2021-07-30 | 2021-11-09 | 江苏大学 | Preparation of porous carbon loaded NHPI catalyst and application of porous carbon loaded NHPI catalyst in oxidative desulfurization of fuel oil |
| CN114588938A (en) * | 2022-03-17 | 2022-06-07 | 浙江肯特催化材料科技有限公司 | Preparation method of silicon dioxide loaded quaternary ammonium salt phase transfer catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101116824A (en) * | 2007-08-31 | 2008-02-06 | 聊城大学 | Activated charcoal laden heteropoly phosphorus molybdenum tungstic acid argentic salt catalyzer and method for preparing the same and application thereof |
-
2013
- 2013-11-21 CN CN201310585721.9A patent/CN103611578A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101116824A (en) * | 2007-08-31 | 2008-02-06 | 聊城大学 | Activated charcoal laden heteropoly phosphorus molybdenum tungstic acid argentic salt catalyzer and method for preparing the same and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘淑芝等人: "杂多酸（盐）用于油品氧化脱硫的研究进展", 《化学工业与工程技术》, vol. 34, no. 5, 31 October 2013 (2013-10-31), pages 2 - 3 * |
| 孙波等人: "杂多酸催化氧化脱除柴油中硫化物的研究", 《吉林化工学院学报》, vol. 27, no. 1, 28 February 2010 (2010-02-28) * |
Cited By (10)
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| CN105618138A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Immobilized tungstophosphoric heteropoly acid catalyst and use thereof |
| CN105618138B (en) * | 2014-10-29 | 2018-01-09 | 中国科学院大连化学物理研究所 | Solid-carrying type phosphorus heteropoly tungstic acid catalyzer and its application |
| CN104475155A (en) * | 2014-12-03 | 2015-04-01 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation desulfurization of fuel oil and preparation method and application thereof |
| CN108855232A (en) * | 2018-07-02 | 2018-11-23 | 东北师范大学 | A kind of composite nano fiber and its preparation method and application |
| CN108855232B (en) * | 2018-07-02 | 2021-03-19 | 东北师范大学 | Composite nanofiber and preparation method and application thereof |
| CN108795484A (en) * | 2018-07-11 | 2018-11-13 | 济南开发区星火科学技术研究院 | A kind of dioxygen oxidation diesel oil desulfurization method |
| CN110252413A (en) * | 2019-06-27 | 2019-09-20 | 石河子开发区汇智元科技有限责任公司 | One kind being used for C9 resin raw material oil oxidation desulfurization catalyst |
| CN113617397A (en) * | 2021-07-30 | 2021-11-09 | 江苏大学 | Preparation of porous carbon loaded NHPI catalyst and application of porous carbon loaded NHPI catalyst in oxidative desulfurization of fuel oil |
| CN113617397B (en) * | 2021-07-30 | 2023-04-25 | 江苏大学 | Preparation of porous carbon-supported NHPI catalyst and application of catalyst in fuel oil oxidative desulfurization |
| CN114588938A (en) * | 2022-03-17 | 2022-06-07 | 浙江肯特催化材料科技有限公司 | Preparation method of silicon dioxide loaded quaternary ammonium salt phase transfer catalyst |
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Application publication date: 20140305 |