CN105289713A - Triphase composite catalyst used for gasoline desulfurization - Google Patents
Triphase composite catalyst used for gasoline desulfurization Download PDFInfo
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- CN105289713A CN105289713A CN201510927501.9A CN201510927501A CN105289713A CN 105289713 A CN105289713 A CN 105289713A CN 201510927501 A CN201510927501 A CN 201510927501A CN 105289713 A CN105289713 A CN 105289713A
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Abstract
The invention discloses a triphase composite catalyst used for gasoline desulfurization. The triphase composite catalyst comprises an acidified carrier and triphase composite metal oxides, wherein the carrier is HSZM-5; and the triphase composite metal oxides are nickel oxide, copper oxide, chromium oxide and aluminium oxide. The triphase composite catalyst has appropriate pore structure distribution and reactive metal dispersity and has the advantages of simple preparation process, high activity, incapability of causing saturation of unsaturated olefin, and the like.
Description
Technical field
The invention belongs to gasoline processing technique field, be specifically related to a kind of three-phase composite catalyst for gasoline desulfur.
Background technology
Along with the enhancing of people's environmental consciousness, the index of gasoline, diesel oil sulfur content is tending towards strict, and gasoline, diesel fuel desulfurization seem more and more important.According to statistics, in China's motor petrol, the sulphur of 90% carrys out catalytic cracking.And the sulfide existence form in catalytically cracked gasoline is based on mercaptan, thioether, disulphide and thiophene-type sulfide, wherein the content of thiophene sulphur accounts for more than 60% of total sulfur content, and the content of thioether sulphur and thiophenic sulfur accounts for more than 85% of total sulfur content.Therefore, how to promote in catalytic gasoline sweetening process that the conversion of thiophene-based and thio-ether type compounds is the key reducing catalytic gasoline sulfur content.Relevant desulfur technology can be divided into two classes at present: hydrodesulfurization and non-hydrodesulfurization.Hydrodesulfurization technology mainly comprises catalytic cracking hydrodesulfurization technology, selective hydrodesulfurization technology, non-selective hydrodesulfurization technology and catalytic distillation hydrogenation desulfur technology; Non-hydrodesulfurization mainly comprises adsorption desulfurize, biological desulphurization and additive technology and oxidation sweetening etc.The basic reason that hydrogenation technique develops rapidly is the development of catalyst, routine techniques makes olefin saturated while desulfurization, octane number is caused to decline, general MON decline 3-4 unit, RON decline 7-8 unit, and consumption hydrogen, therefore develop a series of not only desulfurization but also the hydrodesulfurization technology that loss of octane number is reduced.
Summary of the invention
The object of this invention is to provide a kind of three-phase composite catalyst for gasoline desulfur, there is suitable pore size distribution$ and active metal decentralization, there is preparation technology simple, active high, can not cause unsaturated olefin that the advantages such as saturated occur.。
For a three-phase composite catalyst for gasoline desulfur, comprise the carrier for acidifying and three-phase composite metal oxide, described carrier is HSZM-5, and described three-phase composite catalyst is nickel oxide, cupric oxide, chromium oxide and aluminium oxide.
The preparation method of this catalyst is:
1) HSZM-5 selecting suitable construction is carrier, and be immersed in by carrier in phosphotungstic acid, soak time is 3h, removes nature and dries, then put into Muffle furnace 400 DEG C of high temperature sinterings 2 hours;
2) configure nickel nitrate solution, concentration is 0.1mol/L; HSZM-5 after acidifying is soaked in the solution, then dries at 200 DEG C;
3) configure copper chromite solution, concentration is 0.05mol/L; By step 2) carrier carry out plated film with the method for Best-Effort request, then at 150-180 DEG C dry;
4) configure acidic hydrogen alumina solution, concentration is 0.1mol/L, pH is 6-7; Solution is slowly added drop-wise on the carrier of step 3), then 200 DEG C of oven dry;
5), after carrier cooling step 4) obtained, rejoin Muffle furnace, the mode of gradient increased temperature carries out high temperature sintering, then Isothermal sinter 3h at 800 DEG C.
Wherein, the concentration of the phosphotungstic acid of step 1) is 0.5mol/L.
Wherein, step 2) soak time is 20min.
Wherein, the impregnating speed of step 3) is 200mm/min, and pull rate is 400mm/min, and coating times is 2-4 time, and interval time is 1min, and the time of staying is 5s.
Wherein, the rate of addition of step 4) is 5mL/min.
Wherein, the gradient increased temperature of step 5) is 20 DEG C/min.
Compared with prior art, the present invention has following beneficial effect: the present invention has suitable pore size distribution$ and active metal decentralization, has preparation technology simple, active high, can not cause unsaturated olefin that the advantages such as saturated occur.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further:
Embodiment 1
For a three-phase composite catalyst for gasoline desulfur, comprise the carrier for acidifying and three-phase composite metal oxide, described carrier is HSZM-5, and described three-phase composite catalyst is nickel oxide, cupric oxide, chromium oxide and aluminium oxide.
Embodiment 2
A kind of preparation method of the three-phase composite catalyst for gasoline desulfur is:
1) HSZM-5 selecting suitable construction is carrier, and be immersed in by carrier in phosphotungstic acid, soak time is 3h, removes nature and dries, then put into Muffle furnace 400 DEG C of high temperature sinterings 2 hours;
2) configure nickel nitrate solution, concentration is 0.1mol/L; HSZM-5 after acidifying is soaked in the solution, then dries at 200 DEG C;
3) configure copper chromite solution, concentration is 0.05mol/L; By step 2) carrier carry out plated film with the method for Best-Effort request, then at 150-180 DEG C dry;
4) configure acidic hydrogen alumina solution, concentration is 0.1mol/L, pH is 6-7; Solution is slowly added drop-wise on the carrier of step 3), then 200 DEG C of oven dry.
5), after carrier cooling step 4) obtained, rejoin Muffle furnace, the mode of gradient increased temperature carries out high temperature sintering, then Isothermal sinter 3h at 800 DEG C.
Wherein, the concentration of the phosphotungstic acid of step 1) is 0.5mol/L.
Wherein, step 2) soak time is 20min.
Wherein, the impregnating speed of step 3) is 200mm/min, and pull rate is 400mm/min, and coating times is 2-4 time, and interval time is 1min, and the time of staying is 5s.
Wherein, the rate of addition of step 4) is 5mL/min.
Wherein, the gradient increased temperature of step 5) is 20 DEG C/min.
Etherificate is tested:
With Jinxi refinery heavy oil catalytically cracked gasoline for raw material, carry out hydrodesulfurization performance and the evaluation of olefin saturated performance of catalyst.Catalytic reaction temperature is 280 DEG C, reaction pressure 3.0MPa, liquid hourly space velocity (LHSV) 2h
-1, hydrogen-oil ratio 600(volume ratio) under hydrodesulfurization and olefin saturated performance result as follows.
Find through application example, it is selective that invention catalyst has good hydrodesulfurization.With the Al of routine
2o
3catalyst is compared, and absorption and the hydrotreated lube base oil of catalyst supression alkene of the present invention react, and improve the desulfuration selectivity of catalyst to gasoline.
The foregoing is only one embodiment of the invention, do not limit the present invention, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, all drop in protection scope of the present invention.
Claims (7)
1. for a three-phase composite catalyst for gasoline desulfur, it is characterized in that: it comprises carrier for acidifying and three-phase composite metal oxide, and described carrier is HSZM-5, and described three-phase composite catalyst is nickel oxide, cupric oxide, chromium oxide and aluminium oxide.
2. a kind of three-phase composite catalyst for gasoline desulfur according to claims 1, it is characterized in that, the preparation method of this catalyst is:
1) HSZM-5 selecting suitable construction is carrier, and be immersed in by carrier in phosphotungstic acid, soak time is 3h, removes nature and dries, then put into Muffle furnace 400 DEG C of high temperature sinterings 2 hours;
2) configure nickel nitrate solution, concentration is 0.1mol/L; HSZM-5 after acidifying is soaked in the solution, then dries at 200 DEG C;
3) configure copper chromite solution, concentration is 0.05mol/L; By step 2) carrier carry out plated film with the method for Best-Effort request, then at 150-180 DEG C dry;
4) configure acidic hydrogen alumina solution, concentration is 0.1mol/L, pH is 6-7; Solution is slowly added drop-wise on the carrier of step 3), then 200 DEG C of oven dry;
5), after carrier cooling step 4) obtained, rejoin Muffle furnace, the mode of gradient increased temperature carries out high temperature sintering, then Isothermal sinter 3h at 800 DEG C.
3. a kind of three-phase composite catalyst for gasoline desulfur according to claims 1, is characterized in that, the concentration of the phosphotungstic acid of step 1) is 0.5mol/L.
4. a kind of three-phase composite catalyst for gasoline desulfur according to claims 1, is characterized in that, step 2) soak time is 20min.
5. a kind of three-phase composite catalyst for gasoline desulfur according to claims 1, is characterized in that, the impregnating speed of step 3) is 200mm/min, pull rate is 400mm/min, coating times is 2-4 time, and interval time is 1min, and the time of staying is 5s.
6. a kind of three-phase composite catalyst for gasoline desulfur according to claims 1, is characterized in that, the rate of addition of step 4) is 5mL/min.
7. a kind of three-phase composite catalyst for gasoline desulfur according to claims 1, is characterized in that, the gradient increased temperature of step 5) is 20 DEG C/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114682264A (en) * | 2022-04-11 | 2022-07-01 | 福州大学 | Catalyst for preparing 4-terpineol by epoxidizing terpinolene through hydrogenation, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214451A (en) * | 2007-12-29 | 2008-07-09 | 大连理工大学 | Novel composite solid acid catalyst and application |
| CN101270299A (en) * | 2008-04-30 | 2008-09-24 | 武汉科技大学 | Method for oxidation sweetening of light-end products |
| CN101455966A (en) * | 2007-12-11 | 2009-06-17 | 南化集团研究院 | Methanol synthesis gas desulfurizer and preparation method thereof |
| CN102188954A (en) * | 2010-03-03 | 2011-09-21 | 中国石油天然气股份有限公司 | Activated carbon for adsorbing and removing sulfide in gasoline and preparation method thereof |
| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN103285923A (en) * | 2013-04-24 | 2013-09-11 | 中科院广州化学有限公司 | Oxidative desulfurization amphiphilic catalyst, and preparation method and applications thereof |
| JP2013199534A (en) * | 2012-03-23 | 2013-10-03 | Idemitsu Kosan Co Ltd | Method for producing desulfurized gaseous fuel |
-
2015
- 2015-12-14 CN CN201510927501.9A patent/CN105289713A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101455966A (en) * | 2007-12-11 | 2009-06-17 | 南化集团研究院 | Methanol synthesis gas desulfurizer and preparation method thereof |
| CN101214451A (en) * | 2007-12-29 | 2008-07-09 | 大连理工大学 | Novel composite solid acid catalyst and application |
| CN101270299A (en) * | 2008-04-30 | 2008-09-24 | 武汉科技大学 | Method for oxidation sweetening of light-end products |
| CN102188954A (en) * | 2010-03-03 | 2011-09-21 | 中国石油天然气股份有限公司 | Activated carbon for adsorbing and removing sulfide in gasoline and preparation method thereof |
| JP2013199534A (en) * | 2012-03-23 | 2013-10-03 | Idemitsu Kosan Co Ltd | Method for producing desulfurized gaseous fuel |
| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN103285923A (en) * | 2013-04-24 | 2013-09-11 | 中科院广州化学有限公司 | Oxidative desulfurization amphiphilic catalyst, and preparation method and applications thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114682264A (en) * | 2022-04-11 | 2022-07-01 | 福州大学 | Catalyst for preparing 4-terpineol by epoxidizing terpinolene through hydrogenation, and preparation method and application thereof |
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