CN102049270B - Selective hydrogenation catalyst for gasoline and preparation method thereof - Google Patents
Selective hydrogenation catalyst for gasoline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a selective hydrogenation catalyst for gasoline and a preparation method thereof. A carrier of the catalyst is alumina modified by carbon and silicon oxide in a specific ratio; the silicon oxide is added to regulate the acid distribution of the carrier, particularly greatly improve the L acid; and the carbon is added to inhibit the hydrogenation activity of olefin through selective interaction with an olefin hydrogenation activity center, so that the selective hydrodesulfurization capacity of the catalyst is improved, the effect of the carrier on an aid of potassium is enhanced, the carrier is coordinate with an aid of phosphorus, the loss of the potassium is prevented and the stability of the catalyst is improved. The catalyst is mainly used for selective hydrodesulfurization of the gasoline, particularly hydrodesulfurization of catalytically cracked gasoline.
Description
Technical field
The present invention relates to a kind of catalyst for selective hydrodesulfurizationof of gasoline and preparation method thereof, especially for two sections selective hydrogenation desulfurization process of catalytically cracked gasoline.
Background technology
In recent years, for protection of the environment, countries in the world government makes great efforts to reduce the discharging of harmful substance in the exhaust gases of internal combustion engines, and the specification of quality of automotive fuel is increasingly strict, and special requirement reduce the sulfur content in the motor petrol.The combustion product SO of Removal of Sulfur Compounds from Gasoline
xBe vehicle exhaust mainly contain one of harmful substances, also be one of vehicle exhaust reforming unit catalyst poison.Therefore, make laws one after another in countries in the world, and the sulfur content in the gasoline has been proposed more and more stricter restriction.
As everyone knows, the direct steaming gasoline sulfur content is main relevant with sulfur content in crude oil, even sulfur content is higher, but because of its olefin(e) centent seldom, when adopting conventional H DS method to process, without obvious loss of octane number.And FCC gasoline sulfur and olefin(e) centent are all higher, although adopt traditional HDS method can effectively remove wherein sulfur-containing compound, but because the lower alkene of the collateralization degree low-octane alkane of the saturated generation of hydrogenation very easily in the FCC gasoline, so, adopt traditional HDS method, along with the reduction of FCC content of sulfur in gasoline, must follow the rapid decline of octane number.
US 5441630 discloses a kind of class-water talcite (Hydrotalcite-like HTIC) of using and has added γ-Al as carrier component
2O
3In, having high surface area, alkalescence through the HTIC of roasting, the catalyst behind the carrier impregnation Co-Mo demonstrate the characteristics that the HDS activity is high, the olefin saturated percentage is low, but the loss of octane number of gasoline is still larger.US 5459118 is on the basis of above-mentioned catalytic component, propose to increase the alkali-metal raw catelyst of IA family, it is selected catalyst surface hydrogenation lattice degree of intoxication much larger than the desulfurization lattice, although this catalyst HDS activity slightly is lower than the HDS catalyst that those do not add this denaturant, but it stops the characteristic of olefin saturated is prior, the subject matter of this patent is the selectively fast-descending with the increase of the duration of runs of the poor stability of catalyst, particularly catalyst.US 5423976, US 5538930 propose take active carbon as carrier, think that activated carbon surface is long-pending large, be conducive to supporting of metal component, often contain in addition K in the active carbon, be conducive to the selective of catalyst, when the C carrier that uses does not contain above-mentioned metal, can prepare arbitrary steps at catalyst and add.The shortcoming of absorbent charcoal carrier is that the metal component of load and auxiliary agent are easy to run off.
CN1488721A discloses a kind of catalyst for selective hydrodesulfurizationof of gasoline and two sections selective hydrogenation desulfurization process.This catalyst adopts alumina support, P and K are adjuvant component, Co and Mo are active metal component, but the acidity of carrier is also larger on the impact of catalyst selectivity hydrodesulfurization, and alumina support is the faintly acid carrier, and the catalyst hydrodesulfurization active take it as carrier is lower, introduce again auxiliary agent P and K, inhibitory action to the olefin saturated activity is limited, and therefore, the hydrodesulfurization of this catalyst selectively awaits further to improve.
Summary of the invention
For the deficiencies in the prior art, the invention provides high selectivity that a kind of activity and selectivity all improves and catalyst for selective hydrodesulfurizationof of gasoline of high stability and preparation method thereof.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention, take Co and Mo as active metal component, take potassium and phosphorus as auxiliary agent, carrier is comprised of silica, carbon and aluminium oxide, wherein carbon content is 1.0%～30.0%, be preferably 3.0%～15.0%, silica content is 1.0%～30.0%, be preferably 3.0%～15.0%, the atomic ratio of carbon and silicon is 1.0～10.0, is preferably 2.0～8.0, carrier meleic acid total acid content is 0.32～0.72mmol/g, L acid acid amount is 0.30～0.70mmol/g, take the weight of catalyst as benchmark, and MoO
3Content is 1.0%～18.0%, and being preferably 1.0%～16.0%, CoO content is 0.1%～6.0%, is preferably 0.1%～5.0%, Co/Mo atomic ratio 0.1～1.0, preferably 0.2～0.8, and K
2O content is 0.2%～10.2%, preferably 0.5%～5.0%, and P/K atomic ratio 0.1～10.0, preferably 0.8～5.0, be preferably 1.0～2.0, surplus is carrier.
The pore volume of catalyst of the present invention is 0.3～1.3ml/g, and specific area is 150～400m
2/ g.
The preparation method of catalyst of the present invention comprises following content:
(1) aluminum oxide dry glue powder, carbon black powder, Ludox and peptizing agent and extrusion aid are mixed, mix afterwards extruded moulding on band extrusion molding machine, after drying and the roasting, obtain catalyst carrier;
(2) adopt infusion process load auxiliary agent potassium and phosphorus, after drying and the roasting, obtain containing the catalyst carrier of potassium and phosphorus again;
(3) adopt infusion process supported active metal Co and Mo, drying and roasting obtain catalyst of the present invention.
Described aluminum oxide dry glue powder can adopt conventional method to synthesize, and such as Alchlor process, aluminum nitrate method or aluminum sulfate method, can adopt a kind of aluminum oxide dry glue powder, also can adopt simultaneously multiple aluminum oxide dry glue powder.Described aluminum oxide dry glue powder was through 400～550 ℃ of roastings 1～5 hour, and the character of gained gama-alumina is as follows: specific area is 150～400m
2/ g, pore volume are 0.3～1.0ml/g.
The present invention is in the process of catalyst preparation, extrusion aid commonly used can be: one or more in sesbania powder, citric acid, oxalic acid, cellulose, starch, the high molecular surfactant etc., and consumption accounts for 0.1%～20.0% of step (1) article shaped weight; Used peptizing agent can be: one or more in aluminum sulfate, citric acid, nitric acid, acetic acid, the oxalic acid etc., consumption accounts for 0.1%～20.0% of step (1) article shaped weight.
The described drying of step (1) and roasting condition are as follows: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
The described drying of step (2) and roasting condition are as follows: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
The described drying of step (3) and roasting condition are as follows: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
Catalyst carrier of the present invention is comprised of aluminium oxide, carbon and silica, by an amount of carbon and silica modified aluminium oxide, adds the total acid content that silica can improve carrier, particularly increases substantially L acid acid amount.The acidity of carrier is larger on the selective hydrodesulfurization impact, the content of sulphur accounts for more than 60% of total sulfur-containing compound in the thiophene-type sulfide, thiophenes is L alkali, be easy to adsorb in the L acid site, thereby the close sulfur materials of selecting to form the L acid site can improve the desulphurizing ability of catalyst as carrier, but the olefin saturated ability also can improve simultaneously, suppress the hydrogenation activity of alkene by the carbon that adds proper proportion by optionally interacting with the hydrogenation of olefins activated centre, the amplitude of this inhibition is greater than the amplitude that desulphurizing activated center is suppressed, thereby has improved the selective of catalyst.Simultaneously, in carrier, introduce potassium and phosphorus component, and best potassium content and phosphorus potassium atom ratio have been determined, two kinds of auxiliary agent coordinative roles of potassium and phosphorus, carrier and auxiliary agent coordinative role have improved alkali-metal constraint effect, reach the effect that prevents that alkali metal runs off, and alkali metal to the inhibitory action of olefin saturated activity greater than the inhibitory action to hydrodesulfurization activity, resulting catalyst has better selective, better stability.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention can be used in the gasoline selective hydrodesulfurizationmodification technique, especially in two sections gasoline selective hydrodesulfurizationmodification technique, general process is as follows: under hydrodesulfurizationconditions conditions, raw material at first contacts with one section catalyst with hydrogen, enter two sections by one section reactor product, contact with two sections catalyst; Wherein the active metallic content in the catalyst system therefor increases gradually along the liquid phase stream direction increases successively, and one of them or an above beds use catalyst for selective hydrodesulfurizationof of gasoline of the present invention.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention adopts the different activities catalyst to make up, can make this technique not only the steady running time long, and keep high hydrodesulfurization activity and selective, the economy of raising device always.
The specific embodiment
Among the present invention, specific area and pore volume employing low temperature liquid nitrogen determination of adsorption method, it is the infrared absorption spectrographic determination of employing pyridine that meleic acid total acid content, B acid amount and L acid are measured.Wt% represents mass percent among the present invention.
The concrete preparation process of catalyst of the present invention is as follows:
Aluminum oxide dry glue powder, carbon black powder, Ludox and peptizing agent and extrusion aid are mixed, mix afterwards extruded moulding on band extrusion molding machine, then lower dry 1～5 hour at 100～120 ℃, rise to 400～550 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again, obtain catalyst carrier.Place afterwards and roll pot, under the rotation condition, to the phosphorous potassium salt soln that rolls alumina support in the pot and spray into atomizing type the carrier saturated water adsorptive value, after solution has sprayed, in rolling pot, be rotated further 10～60 minutes, then placed 1～24 hour, lower dry 1～5 hour at 100～120 ℃, rise to 400～550 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again, obtain phosphorous and catalyst carrier potassium.Again phosphorous and catalyst carrier potassium are placed and roll pot, spray into Mo, the Co ammonia solution of saturated water adsorptive value, after solution has sprayed, in rolling pot, be rotated further 10～60 minutes, then placed 1～24 hour, 100～120 ℃ lower dry 1～5 hour, rise to 400～550 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again, make finished catalyst.
In above-mentioned preparation method, the concentration of maceration extract forms (content) by water absorption rate and desired catalyst and determines.
Below specify catalyst used in the present invention with embodiment.
Macroporous aluminium oxide dry glue powder used in the embodiment of the invention was 500 ℃ of roastings 3 hours, and the specific area of gained is 400m
2/ g, pore volume are 0.91ml/g.Used aperture aluminum oxide dry glue powder (SB powder) was 500 ℃ of roastings 3 hours, and the specific area of gained is 240m
2/ g, pore volume are 0.51ml/g.Used carbon black powder is to be produced by the Fushun safe chemical industry of gold Co., Ltd.
Embodiment 1
With 186g macroporous aluminium oxide dry glue powder, 36gSB powder, 54g Ludox (SiO
2Weight content is 30%), 14g carbon black powder and 136ml water, 23ml nitric acid mixes, extruded moulding on band extrusion molding machine was placed 18 hours, and is lower dry 3 hours at 110 ℃, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, obtain catalyst carrier A.Take by weighing to place again after the weight and roll pot, under the rotation condition, spray into the aqueous solution that 158ml contains the 16.6g potassium dihydrogen phosphate to the alumina support A that rolls in the pot with atomizing type, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 21.1g citric acid is dissolved in the 122ml water purification, adds the 14.6g cobalt carbonate, boil dissolving, after the cooling, add again 25% (weight) ammoniacal liquor to 170ml, add the 29.4g ammonium molybdate in mentioned solution, with 25% ammoniacal liquor liquor capacity is transferred to 200ml, airtight preservation after the dissolving.Spray with molybdenum that 153ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst A.
Embodiment 2
With 222g macroporous aluminium oxide dry glue powder, 61g Ludox (SiO
2Weight content is 30%), 24g carbon black powder and 136ml water, 23ml nitric acid mixes, extruded moulding on band extrusion molding machine, placed 18 hours, 110 ℃ lower dry 3 hours, rise to 3 hours catalyst carrier B of 500 ℃ of roastings with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot, under the rotation condition, spray into the aqueous solution that 158ml contains the 16.6g potassium dihydrogen phosphate to the alumina support B that rolls in the pot with atomizing type, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 9.6g citric acid is dissolved in the 134ml water purification, adds the 6.6g cobalt carbonate, boil dissolving, after the cooling, add again 25% ammoniacal liquor to 170ml, add the 14.6g ammonium molybdate in mentioned solution, with 25% ammoniacal liquor liquor capacity is transferred to 200ml, airtight preservation after the dissolving.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst B.
Embodiment 3
With 186g macroporous aluminium oxide dry glue powder, 36gSB powder, 76g Ludox (SiO
2Weight content is 30%), 23g carbon black powder and 136ml water, 23ml nitric acid mixes, extruded moulding on band extrusion molding machine was placed 18 hours, and is lower dry 3 hours at 110 ℃, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, obtain catalyst carrier C.Take by weighing to place again after the weight and roll pot, under the rotation condition, spray into the aqueous solution that 158ml contains the 17.6g potassium dihydrogen phosphate to the alumina support C that rolls in the pot with atomizing type, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 26.7g citric acid is dissolved in the 94ml water purification, adds the 18.3g cobalt carbonate, boil dissolving, after the cooling, add again 25% ammoniacal liquor to 170ml, add the 46.5g ammonium molybdate in mentioned solution, with 25% ammoniacal liquor liquor capacity is transferred to 200ml, airtight preservation after the dissolving.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst C.
Embodiment 4
With 186g macroporous aluminium oxide dry glue powder, 36gSB powder, 54g Ludox (SiO
2Weight content is 30%), 16g carbon black powder and 136ml water, 23ml nitric acid mixes, extruded moulding on band extrusion molding machine was placed 18 hours, and is lower dry 3 hours at 110 ℃, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, obtain catalyst carrier D.Take by weighing to place again after the weight and roll pot, under the rotation condition, spray into 154ml with atomizing type and contain the phosphoric acid mixed aqueous solution that 9.3g potassium nitrate and 24.0g contain 53wt% to rolling alumina support D in the pot, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 7.8g citric acid is dissolved in the 172ml water purification, adds the 5.4g cobalt carbonate, boil dissolving, after the cooling, add again 25% ammoniacal liquor to 170ml, add the 8.4g ammonium molybdate in mentioned solution, with 25% ammoniacal liquor liquor capacity is transferred to 200ml, airtight preservation after the dissolving.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, then placed 18 hours, 110 ℃ lower dry 3 hours, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst D.
Embodiment 5
On 200ml fixed bed small hydrogenation device, adopt respectively A, B, C, D catalyst, volume space velocity 3.0h when reaction pressure 1.6MPa, liquid
-1, hydrogen to oil volume ratio is 300Nm
3/ m
3, reaction temperature is respectively under 270,310,260,250 ℃ of conditions, is that 664 μ g/g, RON are that 93.0 raw material carries out selective hydrodesulfurization to sulfur content.
Comparative example 1
The preparation method does not just add carbon black powder and Ludox in the carrier with embodiment 3, obtains catalyst E.
Comparative example 2
The preparation method does not just add Ludox in the carrier with embodiment 3, obtains catalyst F.
Comparative example 3
The preparation method does not just add carbon black powder in the carrier with embodiment 3, obtains catalyst G.
Comparative example 4
The preparation method does not just phosphorate and the potassium component in the carrier with embodiment 3, obtains catalyst H.
Comparative example 5
Difference evaluate catalysts E, F, G and H, evaluation method is with embodiment 5.
Embodiment 6
This example is that above each routine institute controlling catalyst physico-chemical property and above each example see Table 1,2 at 600 hours comparing result of small hydrogenation device running.
Table 1 catalyst main character
| The catalyst numbering | A | B | C | D | E | F | G | H |
| Support | ||||||||
| C，wt％ | 7.03 | 12.1 | 12.0 | 8.13 | - | 12.0 | - | 12.0 |
| SiO 2，wt％ | 8.04 | 9.07 | 11.9 | 8.07 | - | - | 11.9 | 11.9 |
| The C/Si atomic ratio | 4.3 | 6.6 | 5.0 | 5.1 | - | - | - | 5.0 |
| Infrared total acid content, mmol/g | 0.576 | 0.388 | 0.379 | 0.567 | 0.226 | 0.220 | 0.569 | 0.379 |
| B acid acid amount, mmol/g | 0.081 | 0.071 | 0.074 | 0.083 | 0.023 | 0.019 | 0.086 | 0.074 |
| L acid acid amount, mmol/g | 0.495 | 0.317 | 0.305 | 0.484 | 0.203 | 0.201 | 0.483 | 0.305 |
| Catalyst property | ||||||||
| MoO 3，wt％ | 8.1 | 4.2 | 11.9 | 15.8 | 11.8 | 11.8 | 12.0 | 12.1 |
| CoO，wt％ | 2.5 | 1.4 | 3.2 | 4.0 | 3.2 | 3.2 | 3.3 | 3.4 |
| The Co/Mo atomic ratio | 0.59 | 0.64 | 0.52 | 0.49 | 0.52 | 0.52 | 0.52 | 0.53 |
| P，wt％ | 1.7 | 1.9 | 1.6 | 1.8 | 1.6 | 1.6 | 1.6 | - |
| K 2O，wt％ | 2.6 | 2.7 | 2.5 | 2.0 | 2.5 | 2.5 | 2.5 | - |
| The P/K atomic ratio | 1.0 | 1.1 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | - |
| Pore volume, ml/g | 0.43 | 0.48 | 0.47 | 0.42 | 0.48 | 0.49 | 0.46 | 0.49 |
| Specific area, m 2/g | 245 | 249 | 224 | 208 | 221 | 226 | 225 | 230 |
| Bulk density, g/ml | 0.74 | 0.71 | 0.77 | 0.79 | 0.73 | 0.72 | 0.78 | 0.76 |
| Intensity, N/ unit | 125 | 150 | 120 | 125 | 124 | 123 | 121 | 133 |
Table 2 catalyst activity and selective
Reaction condition: P=1.6MPa; LHSV=3.0h
-1H
2/ Oil=300Nm
3/ m
3
Table 2 is the result show, it is selective that catalyst of the present invention has better hydrodesulfurization, and in the situation of equal desulfurization degree, loss of octane number is less.Through after certain duration of runs, the selective hydrodesulfurization performance of catalyst of the present invention is stable than the comparative catalyst.
Claims (11)
1. catalyst for selective hydrodesulfurizationof of gasoline, take Co and Mo as active metal component, take potassium and phosphorus as auxiliary agent, carrier is comprised of silica, carbon and aluminium oxide, and wherein the carbon weight content is 1.0%～30.0%, silica content is 1.0%～30.0%, the atomic ratio of carbon and silicon is 1～10, and carrier meleic acid total acid content is 0.32～0.72mmol/g, and L acid acid amount is 0.30～0.70mmol/g, take the weight of catalyst as benchmark, MoO
3Content is that 1.0%～18.0%, CoO content is 0.1%～6.0%, Co/Mo atomic ratio 0.1～1.0, K
2O content is 0.2%～10.2%, P/K atomic ratio 0.1～10.0, and surplus is carrier.
2. according to catalyst claimed in claim 1, it is characterized in that weight take catalyst carrier as benchmark, carbon content is 3.0%～15.0%, and silica content is 3.0%～15.0%, and the atomic ratio of carbon and silicon is 2～8.
3. according to claim 1 or 2 described catalyst, it is characterized in that weight take catalyst as benchmark, MoO
3Content is that 1.0%～16.0%, CoO content is that 0.1%～5.0%, Co/Mo atomic ratio is 0.2～0.8, K
2O content is that 0.5%～5.0%, P/K atomic ratio is 0.8～5.0, and surplus is carrier.
4. according to claim 1 or 2 described catalyst, it is characterized in that in the described catalyst that the P/K atomic ratio is 1.0～2.0.
5. according to catalyst claimed in claim 1, the pore volume that it is characterized in that described catalyst is 0.3～1.3ml/g, and specific area is 150～400m
2/ g.
6. the preparation method of the arbitrary described catalyst of claim 1～5 comprises following content:
(1) aluminum oxide dry glue powder, carbon black powder, Ludox and peptizing agent and extrusion aid are mixed, mix afterwards extruded moulding on band extrusion molding machine, after drying and the roasting, obtain catalyst carrier;
(2) adopt infusion process load auxiliary agent potassium and phosphorus, after drying and the roasting, obtain containing the catalyst carrier of potassium and phosphorus again;
(3) adopt infusion process supported active metal Co and Mo, drying and roasting obtain the catalyst finished product.
7. in accordance with the method for claim 6, it is characterized in that what described aluminum oxide dry glue powder was synthesized by Alchlor process, aluminum nitrate method or aluminum sulfate method, described aluminum oxide dry glue powder was through 400～550 ℃ of roastings 1～5 hour, and the character of gained gama-alumina is as follows: specific area is 150～400m
2/ g, pore volume are 0.3～1.0ml/g.
8. in accordance with the method for claim 6, it is characterized in that the described drying of step (1) and roasting condition are as follows: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
9. in accordance with the method for claim 6, it is characterized in that the described drying of step (2) and roasting condition are as follows: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
10. in accordance with the method for claim 6, it is characterized in that the described drying of step (3) and roasting condition are as follows: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
11. a method for selective hydrodesulfurizationof of gasoline is characterized in that adopting the arbitrary described catalyst of claim 1～5.
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| CN105521791B (en) * | 2014-10-22 | 2017-10-27 | 中国石油化工股份有限公司 | The preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline |
| CN106902892B (en) * | 2017-02-28 | 2019-09-10 | 山西大学 | A kind of SiO2- C Modification on Al2O3Carrier and preparation method and application |
| CN106902800B (en) * | 2017-02-28 | 2019-09-10 | 山西大学 | A kind of SiO2-C-Al2O3Carrier and preparation method and application |
| CN109647453B (en) * | 2017-10-10 | 2022-02-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst for producing cyclohexylamine |
| CN111117693B (en) * | 2018-10-30 | 2021-08-31 | 中国石油化工股份有限公司 | Gasoline selective hydrodesulfurization method |
| CN111111701B (en) * | 2018-10-30 | 2022-08-12 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN112705224B (en) * | 2019-10-25 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
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| CN1184844A (en) * | 1996-12-10 | 1998-06-17 | 中国石油化工总公司 | Catalyst for hydrodesulfurization fraction oil |
| CN1488721A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and process |
| CN1648214A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Refined catalyst for fraction oil hydrogenation and its preparing method |
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|---|---|---|---|---|
| CN1184844A (en) * | 1996-12-10 | 1998-06-17 | 中国石油化工总公司 | Catalyst for hydrodesulfurization fraction oil |
| CN1488721A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and process |
| CN1648214A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Refined catalyst for fraction oil hydrogenation and its preparing method |
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