CN1488721A - Selective hydrogenation catalyst for gasoline and process - Google Patents
Selective hydrogenation catalyst for gasoline and process Download PDFInfo
- Publication number
- CN1488721A CN1488721A CNA021331367A CN02133136A CN1488721A CN 1488721 A CN1488721 A CN 1488721A CN A021331367 A CNA021331367 A CN A021331367A CN 02133136 A CN02133136 A CN 02133136A CN 1488721 A CN1488721 A CN 1488721A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- beds
- potassium
- catalyst
- atomic ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a selective hydro-desulfurization catalyst of gasoline and process for using said catalyst. Said invented catayst uses alumina as carrier, uses molybdenum and cobalt as active component, at the same time contains adjuvant potassium and phosphorus, and the optimized atomic ratio of phosphorus and potassium is 1-2. Said invented catalyst has good selectivity and stability, and at the same time has proper activity, and is mainly used for selective hydro-desulfurization of catalytic cracked gasoline.
Description
1, technical field
The present invention relates to a kind of catalyst for selective hydrodesulfurizationof of gasoline and use this catalyzer to carry out two sections processing sulfur removal technologies, especially for catalytic gasoline selective desulfurization catalyst and two sections selective hydrogenation desulfurization process.
2, background technology
In recent years, in order to protect environment, countries in the world government makes great efforts to reduce emission of harmful substances in the exhaust gases of internal combustion engines, and the specification of quality of automotive fuel is strict day by day, and special requirement reduce the sulphur content in the motor spirit.The products of combustion SO of sulfide in petrol
xBe vehicle exhaust mainly contain one of harmful substances, also be one of vehicle exhaust conversion system catalyzer poison.Therefore, make laws one after another in countries in the world, and the sulphur content in the gasoline has been proposed more and more stricter restriction.
As everyone knows, the straight-run spirit sulphur content is main relevant with sulfur content in crude oil, even sulphur content is higher, but because of its olefin(e) centent seldom, when adopting the processing of conventional H DS method, do not have tangible loss of octane number.And FCC gasoline sulfur, olefin(e) centent height, can effectively deviate from wherein sulfide though adopt traditional HDS method, 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 value.
United States Patent (USP) 5441630 discloses a kind of class-water talcite (Hydrotalcite-likeHTIC) of using and has added r-Al as carrier component
2O
3In, having high surface area, alkalescence through the HTIC of roasting, the catalyzer behind the carrier impregnation Co-Mo demonstrate the characteristics that the HDS activity is high, the alkene saturation percentage is low, but the octane value of gasoline still has loss to a certain degree.On the basis of United States Patent (USP) 5459118 above-mentioned catalyst components, propose to increase the alkali-metal raw catalyst of IA family, it is selected catalyst surface hydrogenation lattice degree of intoxication much larger than the desulfurization lattice, though this catalyzer HDS activity is lower than the HDS catalyzer that those do not add this denaturant slightly, but it stops the saturated characteristic of alkene is prior, the subject matter of this patent is that the poor stability of catalyzer, particularly selectivity of catalyst descend fast with the increase of runtime.It is carrier that United States Patent (USP) 5423976,5538930 proposes with the gac, think that activated carbon surface is long-pending big, help supporting of metal component, often contain K in addition in the gac, help selectivity of catalyst, when the C carrier that uses does not contain above-mentioned metal, can add at the Preparation of Catalyst arbitrary steps.The shortcoming of absorbent charcoal carrier is that the metal component of load and auxiliary agent are easy to run off.United States Patent (USP) 5985136 has proposed a kind of two-stage hydrogenation sweetening process, one section catalyzer adopted have the selective hydrodesulfurization characteristic than the low-metal content catalyzer, two sections catalyzer adopt traditional Hydrobon catalysts.Mention that in this patent first section catalyzer contains the carrier annexing ingredient, annexation is selected from phosphorus family and IA family metal, but failed call phosphorus family and IA family whisker are present in the catalyzer simultaneously, more phosphorus family and alkali-metal concrete ratio are not provided clear and definite numerical value, the selectivity of this technology can further improve in addition.
3, summary of the invention
At the deficiencies in the prior art, the invention provides two sections gasoline hydrodesulfurizationmethod methods that a kind of activity and selectivity all improve, another object of the present invention is to provide the catalyzer of employed highly selective of gasoline two-stage hydrogenation sulfur removal technology and high stability.
A kind of catalyst for selective hydrodesulfurizationof of gasoline of the present invention, reaching the bigger aluminum oxide of pore volume more greatly with specific surface area is carrier, catalyzer contains MoO
31.0-18.0w%, CoO0.1-6.0w%, Co/Mo atomic ratio 0.1-1.0, catalyzer contains potassium and phosphorus component simultaneously, contains potassium 0.2-10.2w%, P/K atomic ratio 0.1-10.0, catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g.
Two sections gasoline hydrodesulfurizationmethod methods of the present invention are as follows: the beds that stock oil increases by active metallic content under the hydrodesulfurization condition successively gradually, the catalyzer that the above beds of one of them or uses contains auxiliary agent potassium and phosphorus simultaneously, contain potassium 0.2-10.2w%, P/K atomic ratio 0.5-10.0, catalyzer pore volume 0.4-1.3ml/g, specific surface area 150-300m
2/ g.Generally speaking, can adopt two beds, have at least a bed to use the catalyzer that contains potassium and phosphorus simultaneously in two beds, another bed uses conventional catalyst, and preferred two beds all use the catalyzer that contains potassium and phosphorus simultaneously.First bed uses the catalyzer of low-metal content, and catalyzer is a carrier with the aluminum oxide, contains MoO
31.0-10.0w%, CoO0.1-5.0w%, Co/Mo atomic ratio 0.1-1.0.Second bed uses the catalyzer of high metal content, is carrier with the aluminum oxide, and catalyzer contains MoO
310.0-18.0w%, CoO0.1-6.0w%, Co/Mo atomic ratio 0.1-1.0.One, two sections catalyst volumes are than being 2/8-8/2.
Catalyzer of the present invention contains potassium and phosphorus simultaneously, and has determined best potassium content and phosphorus potassium atom ratio, two kinds of auxiliary agent coordinative roles, phosphorus plays alkali-metal constraint effect, reach the effect that prevents that basic metal runs off, catalyzer is had well optionally simultaneously, also have ideal stability.And catalyzer of the present invention strengthens for the adaptability of raw material, and the moisture impurity level that waits of stock oil is had stronger adaptability.Selectivity is good, stability is strong, the different activities catalyzer makes up owing to use two kinds for technology of the present invention, makes this technology have hydrodesulfurization activity, selectivity height, and the steady running time is long, improves the economy of device.
4, embodiment
Gasoline hydrodesulfurizationmethod catalyzer of the present invention can be determined best metal content according to the different positions at reactor.Use the lower catalyzer of metal content at first beds, contain MoO
31.0-10.0w% is preferably 2.0-8.0w%, is preferably 4.0-6.0w%, and CoO0.1-5.0w% is preferably 0.5-4.0w%, is preferably 1.0-3.0w%.Use the higher catalyzer of metal content at second beds, contain MoO
310.0-18.0w% is preferably 10.0-16.0w%, is preferably 10.0-15.0w%, and CoO1.0-6.0w% is preferably 2.0-5.0w%, is preferably 2.0-4.0w%.One, two two-stage catalytic agent pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g, Co/Mo atomic ratio 0.1-1.0 is preferably 0.2-0.8, is preferably 0.25-0.72, contains potassium 0.2-10.2w%, is preferably 0.5-5.0w%, is preferably 1.0-3.0w%, and P/K atomic ratio 0.1-10.0 is preferably 0.8-5.0, is preferably 1.0-2.0.
Catalyzer of the present invention can adopt the ordinary method preparation, and detailed process is as follows:
1. taking by weighing a certain amount of specific surface area reaches pore volume bigger siliceous, phosphorated alumina supporter more greatly and places to spray and roll pot, under the rotation condition, alumina supporter in rolling pot sprays into the potassium salt soln that contains of carrier saturated water adsorptive value with atomizing type, after solution has sprayed, in rolling pot, be rotated further 10-60 minute, placed then 1-24 hour, 100-120 ℃ dry 1-5 hour down, rise to 400-600 ℃ of roasting 1-5 hour with 150-250 ℃/hour heat-up rate again.Take by weighing to place again after the weight 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 minute, placed then 1-24 hour, 100-120 ℃ dry 1-5 hour down, rise to 450-650 ℃ of roasting 1-5 hour with 150-250 ℃/hour heat-up rate again, make finished catalyst.
2. take by weighing a certain amount of carrier with the bigger dried glue aluminum oxide extruded moulding of specific surface area, place to spray and roll pot, under the rotation condition, alumina supporter in rolling pot sprays into the phosphorated potassium salt soln of carrier saturated water adsorptive value with atomizing type, after solution has sprayed, in rolling pot, be rotated further 10-60 minute, placed then 1-24 hour, 100-120 ℃ dry 1-5 hour down, rise to 400-600 ℃ of roasting 1-5 hour with 150-250 ℃/hour heat-up rate again.Take by weighing to place again after the weight 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 minute, placed then 1-24 hour, 100-120 ℃ dry 1-5 hour down, rise to 400-650 ℃ of roasting 1-5 hour with 150-250 ℃/hour heat-up rate again, make finished catalyst.
In above-mentioned preparation method, the concentration of steeping fluid is formed (content) by water-intake rate and desired catalyzer and is determined.
Gasoline selective hydrodesulfurizationmodification technological process of the present invention is: under hydrodesulfurizationconditions conditions, raw material at first contacts with one section catalyzer with hydrogen, enters two sections by one section reactor product, contacts with two sections catalyzer.One, the filling ratio of two sections catalyzer in reactor is 2/8-8/2, is preferably 3/7-8/2, is preferably 4/6-8/2.Temperature of reaction is 230-320 ℃, more preferably 250-300 ℃; Reaction pressure is 1.0-4.0Mpa, more preferably 1.6-3.2Mpa; Hydrogen to oil volume ratio is 100-1000Nm
3/ m
3, 200-800Nm more preferably
3/ m
3Air speed is 1.0-10.0h
-1, 2.0-6.0h more preferably
-1
According to the inventive method, in order further to improve the overall performance of reactive system, can be along the Flow of Goods and Materials direction, the two or more Hydrobon catalyst that uses in order that increases gradually according to catalyst activity (active metallic content), as the catalyzer of 3～5 kinds of different activities, other composition of catalyzer preferably provides by the present invention program.
Below specify with embodiment and to adopt two sections selective hydrodesulfurization processes of catalyzer of the present invention and employed catalyzer.
Embodiment 1
With the 200g specific surface area is 362m
2/ g, pore volume are that the alumina supporter of 0.76ml/g siliceous, phosphorous (phosphorus content is 1.9%) places to spray and rolls pot, under the rotation condition, alumina supporter in rolling pot sprays into the aqueous solution that 190ml contains 12.5g saltpetre with atomizing type, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour heat-up rate again.Take by weighing to place again after the weight and roll pot.The 7.6g citric acid is dissolved in the 170ml water purification, adds the 5.2g cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 11.5g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 193ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour heat-up rate again, make finished catalyst A.
Embodiment 2
The carrier of the dried glue aluminum oxide extruded moulding that the 200g specific surface area is bigger, specific surface area is 266m
2/ g, pore volume are 0.61ml/g, place to spray and roll pot, under the rotation condition, alumina supporter in rolling pot sprays into the aqueous solution that 154ml contains the 16.6g potassium primary phosphate with atomizing type, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour heat-up 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 cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 29.4g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 153ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour heat-up rate again, make finished catalyst B.
Embodiment 3
Potassium primary phosphate among the embodiment 2 changed into 154ml contain the phosphoric acid mixed aqueous solution that 2.3g saltpetre and 24.0g contain 53w%, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour heat-up 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 cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 8.4g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour heat-up rate again, make finished catalyst C.
Embodiment 4
Change the saltpetre amount among the embodiment 3 into 37.4g, phosphoric acid amount changes 11.1g into, after solution has sprayed, is rotated further 30 minutes in rolling pot, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour heat-up 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 cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 14.6g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour heat-up rate again, make finished catalyst D.
Embodiment 5
Change potassium primary phosphate amount among the embodiment 2 into 17.6g, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour heat-up 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 cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 46.5g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour heat-up rate again, make finished catalyst E.
Embodiment 6
Change potassium primary phosphate amount among the embodiment 2 into 18.5g, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour heat-up rate again.Take by weighing to place again after the weight and roll pot.The 37.4g citric acid is dissolved in the 40ml water purification, adds the 25.6g cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 61.0g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 155ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour heat-up rate again, make finished catalyst F.
Embodiment 7
On 200ml fixed bed small hydrogenation device, one section is adopted A, B, C, D catalyzer respectively, two sections are adopted catalyzer E, E, F, E respectively, and the filling ratio of one, two section catalyzer is respectively 5/5,7/3,3/7,5/5, at reaction pressure 1.6Mpa, volume space velocity 3.0h
-1, hydrogen to oil volume ratio is 300Nm
3/ m
3, under 280 ℃ of conditions of temperature of reaction, to sulphur content be 2850 μ g/g, olefin(e) centent be 40.9v%, RON be 92.0＞90 ℃ of feedstock fraction carry out selective hydrodesulfurization.
Embodiment 8
Evaluation method is with embodiment 7, and just one section catalyzer adopts the preparation method with embodiment 1, does not just add the potassium component, molybdenum, the catalyzer G that the cobalt metal content is identical with catalyst A, and two sections are adopted catalyzer E, and the filling ratio of one, two section catalyzer is 5/5.
Comparative example 1
Evaluation method is with embodiment 7, just one section catalyzer adopts the preparation method with embodiment 4, just do not add phosphorus and potassium component, molybdenum, the catalyzer H that the cobalt metal content is identical with catalyzer D, two sections catalyzer adopt the preparation method with embodiment 5, just do not add phosphorus and potassium component, molybdenum, the catalyst I that the cobalt metal content is identical with catalyzer E, the filling ratio of one, two section catalyzer is 5/5.
Comparative example 2
Evaluation method is a loading catalyst H in the reactor with embodiment 7, and temperature of reaction is 320 ℃.
Comparative example 3
Evaluation method is a loading catalyst I in the reactor with embodiment 7, and temperature of reaction is 270 ℃.
Embodiment 9
This example is the comparing result that above each routine institute controlling catalyst physico-chemical property and above each example turned round 600 hours on small hydrogenation device.
Table 1 catalyzer main character
Project A B C D E F G H I
MoO
3，w％??????4.2???8.1????2.5????4.3????11.9???15.8???4.2????4.1???11.8
CoO，w％????????1.4???2.5????1.0????1.4????3.2????4.0????1.4????1.3???3.2
Co/Mo atomic ratio 0.64 0.59 0.77 0.63 0.52 0.49 0.64 0.61 0.52
P，w％??????????1.9???1.7????1.9????0.8????1.6????1.8????1.9????-?????-
K
2O，w％???????2.7???2.6????0.5????7.5????2.5????2.7????-??????-?????-
P/K atomic ratio 1.1 1.0 5.8 0.2 1.0 1.0---
Pore volume, ml/g 0.65 0.49 0.55 0.54 0.47 0.45 0.66 0.55 0.48
Specific surface area, m
2/ g 259 205 226 228 200 199 260 225 203
Tap density, g/ml 0.66 0.68 0.66 0.67 0.74 0.75 0.65 0.66 0.73
Intensity, N/ unit 62 120 119 121 130 125 63 121 125
Table 2 catalyst activity and selectivity
| Project | Raw material | Product | ||||||||
| Two sections | Single hop | |||||||||
| One section catalyzer | ??A | ??B | ??C | ??D | ??G | ??H | ??H | ??I | ||
| Two sections catalyzer | ??E | ??E | ??F | ??E | ??E | ??I | ??/ | ??/ | ||
| One section, the long-pending ratio of bis body | ??5/5 | ??7/3 | ??3/7 | ??5/5 | ??5/5 | ??5/5 | ??/ | ??/ | ||
| T，℃ | ??280 | ??320 | ??270 | |||||||
| ＞90 ℃ of cuts | Sulphur, μ g/g | ??2850 | ??212 | ??205 | ??208 | ??203 | ??199 | ??190 | ??207 | ??209 |
| Alkene, v% | ??40.9 | ??25.2 | ??25.4 | ??25.4 | ??26.2 | ??26.0 | ??28.2 | ??28.6 | ??27.8 | |
| ??RON | ??92.0 | ??85.9 | ??85.8 | ??85.8 | ??85.5 | ??85.4 | ??84.4 | ??84.6 | ??84.2 | |
| The RON loss | ??6.1 | ??6.2 | ??6.2 | ??6.5 | ??6.6 | ??7.6 | ??7.4 | ??7.8 | ||
Reaction conditions: P=1.6MPa; LHSV=3.0h
-1H
2/ Oil=300Nm
3/ m
3
Table 1,2 results show, the present invention adopts two sections selective hydrodesulfurization processes, one and/or two section is adopted catalyst for selectively hydrodesulfurizing, potassium and phosphorus component have been introduced in the catalyzer simultaneously, under the situation of equal desulfurization degree, loss of octane number is little, through after certain runtime, use activity, the selectivity of the two-stage process that contains potassium and phosphorus catalyst simultaneously good, the selective hydrodesulfurization stable performance.
Claims (10)
1, a kind of catalyst for selective hydrodesulfurizationof of gasoline is a carrier with the aluminum oxide, is active ingredient with Mo and Co, and catalyzer contains MoO
31.0-18.0w%, CoO 0.1-6.0w%, Co/Mo atomic ratio 0.1-1.0, catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g is characterized in that catalyzer contains potassium and phosphorus component simultaneously, contains potassium 0.2-10.2w%, P/K atomic ratio 0.1-10.0.
2, according to the described catalyzer of claim 1, it is characterized in that described MoO
3Content is 1.0-10.0w%.
3, according to the described catalyzer of claim 1, it is characterized in that described MoO
3Content is 10.0-18.0w%.
4, a kind of gasoline selective hydrodesulfurizationmodification method, the beds that stock oil increases by active metallic content under the hydrodesulfurization condition successively gradually, one or more that it is characterized in that the beds that contacts with raw material contain potassium and phosphorus component simultaneously, contain potassium 0.2-10.2w%, P/K atomic ratio 0.1-10.0, catalyzer pore volume 0.4-1.3ml/g, specific surface area 150-300m
2/ g.
5, in accordance with the method for claim 4, it is characterized in that the beds that described active metallic content increases gradually is two beds, the catalyzer that first beds uses is carrier with aluminum oxide, and catalyzer contains MoO
31.0-10.0w%, CoO0.1-5.0w%, Co/Mo atomic ratio 0.1-1.0.
6, according to claim 4 or 5 described methods, it is characterized in that the beds that described active metallic content increases gradually is two beds, the catalyzer that second beds uses is carrier with aluminum oxide, catalyzer contains MoO
310.0-18.0w%, CoO0.1-6.0w%, Co/Mo atomic ratio 0.1-1.0.
7, in accordance with the method for claim 6, it is characterized in that the catalyzer that described two beds use all contains potassium and phosphorus simultaneously.
8, in accordance with the method for claim 5, it is characterized in that described first and second section catalyst volume than being 2/8-8/2.
9, in accordance with the method for claim 4, it is characterized in that described P/K atomic ratio 1.0-2.0.
10,, it is characterized in that described potassium content is 1.0-3.0w% according to claim 4 or 9 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133136 CN1252222C (en) | 2002-10-10 | 2002-10-10 | Selective hydrogenation catalyst for gasoline and process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133136 CN1252222C (en) | 2002-10-10 | 2002-10-10 | Selective hydrogenation catalyst for gasoline and process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488721A true CN1488721A (en) | 2004-04-14 |
| CN1252222C CN1252222C (en) | 2006-04-19 |
Family
ID=34145470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02133136 Expired - Lifetime CN1252222C (en) | 2002-10-10 | 2002-10-10 | Selective hydrogenation catalyst for gasoline and process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1252222C (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331991C (en) * | 2004-10-29 | 2007-08-15 | 中国石油化工股份有限公司 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
| CN101619234A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using light weight gasoline |
| CN101089129B (en) * | 2006-06-16 | 2010-05-12 | 中国石油化工股份有限公司 | Process of selectively hydrogenating and desulfurizing inferior gasoline |
| CN1988952B (en) * | 2004-06-23 | 2010-05-26 | 环球油品公司 | Selective naphtha desulfurization process and catalyst |
| CN101306378B (en) * | 2007-05-16 | 2010-07-21 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and its preparation method |
| CN101439291B (en) * | 2007-11-19 | 2010-08-18 | 中国石油大学(北京) | Multiple-addition agent modified selective hydrodesulfurization catalyst and preparation method thereof |
| CN101307255B (en) * | 2007-05-18 | 2011-12-21 | 中国石油化工股份有限公司 | Process for producing sweet gas for poor-quality gasoline distillate |
| CN101376835B (en) * | 2007-08-27 | 2012-05-09 | 中国石油化工股份有限公司 | Gasoline hydrofining method and gasoline hydrofining start-up method |
| CN101314734B (en) * | 2007-05-31 | 2012-05-30 | 中国石油化工股份有限公司 | Selective hydrodesulfurization method for gasoline |
| CN101418234B (en) * | 2007-10-26 | 2012-09-12 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline from catalytically cracked gasoline |
| CN102049271B (en) * | 2009-10-27 | 2012-09-12 | 中国石油化工股份有限公司 | Gasoline selective hydrogenation catalyst and preparation method and application thereof |
| CN102049270B (en) * | 2009-10-27 | 2013-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and preparation method thereof |
| CN101173184B (en) * | 2006-11-01 | 2013-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurization method for bastard gasoline |
| CN102041066B (en) * | 2009-10-21 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrodesulfurization method of benzine |
| CN105521791A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing sulfuration-type gasoline selective hydro-desulfurization catalyst |
| CN105985799A (en) * | 2015-02-12 | 2016-10-05 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst system, sulfided hydrodesulfurization catalyst system, and hydrodesulfurization method for diesel oil |
| CN108795488A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of method of isomerization production clean gasoline |
| CN111111701A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN112705224A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940936B (en) * | 2010-08-20 | 2013-04-24 | 陕西煤业化工集团(上海)胜帮化工技术有限公司 | Coal tar hydrogenation protective agent and preparation method thereof |
-
2002
- 2002-10-10 CN CN 02133136 patent/CN1252222C/en not_active Expired - Lifetime
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988952B (en) * | 2004-06-23 | 2010-05-26 | 环球油品公司 | Selective naphtha desulfurization process and catalyst |
| CN1331991C (en) * | 2004-10-29 | 2007-08-15 | 中国石油化工股份有限公司 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
| CN101089129B (en) * | 2006-06-16 | 2010-05-12 | 中国石油化工股份有限公司 | Process of selectively hydrogenating and desulfurizing inferior gasoline |
| CN101173184B (en) * | 2006-11-01 | 2013-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurization method for bastard gasoline |
| CN101306378B (en) * | 2007-05-16 | 2010-07-21 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and its preparation method |
| CN101307255B (en) * | 2007-05-18 | 2011-12-21 | 中国石油化工股份有限公司 | Process for producing sweet gas for poor-quality gasoline distillate |
| CN101314734B (en) * | 2007-05-31 | 2012-05-30 | 中国石油化工股份有限公司 | Selective hydrodesulfurization method for gasoline |
| CN101376835B (en) * | 2007-08-27 | 2012-05-09 | 中国石油化工股份有限公司 | Gasoline hydrofining method and gasoline hydrofining start-up method |
| CN101418234B (en) * | 2007-10-26 | 2012-09-12 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline from catalytically cracked gasoline |
| CN101439291B (en) * | 2007-11-19 | 2010-08-18 | 中国石油大学(北京) | Multiple-addition agent modified selective hydrodesulfurization catalyst and preparation method thereof |
| CN101619234B (en) * | 2008-07-04 | 2012-09-12 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using light weight gasoline |
| CN101619234A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using light weight gasoline |
| CN102041066B (en) * | 2009-10-21 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrodesulfurization method of benzine |
| CN102049270B (en) * | 2009-10-27 | 2013-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and preparation method thereof |
| CN102049271B (en) * | 2009-10-27 | 2012-09-12 | 中国石油化工股份有限公司 | Gasoline selective hydrogenation catalyst and preparation method and application thereof |
| CN105521791A (en) * | 2014-10-22 | 2016-04-27 | 中国石油化工股份有限公司 | Method for preparing sulfuration-type gasoline selective hydro-desulfurization catalyst |
| 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 |
| CN105985799A (en) * | 2015-02-12 | 2016-10-05 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst system, sulfided hydrodesulfurization catalyst system, and hydrodesulfurization method for diesel oil |
| CN105985799B (en) * | 2015-02-12 | 2017-11-03 | 中国石油化工股份有限公司 | The hydrodesulfurizationprocess process of Hydrobon catalyst system and sulphided state Hydrobon catalyst system and diesel oil |
| CN108795488A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of method of isomerization production clean gasoline |
| CN108795488B (en) * | 2017-05-05 | 2020-04-14 | 中国石油化工股份有限公司 | Method for producing clean gasoline by isomerization |
| CN111111701A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| 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 |
| CN112705224A (en) * | 2019-10-25 | 2021-04-27 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1252222C (en) | 2006-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1252222C (en) | Selective hydrogenation catalyst for gasoline and process | |
| CN101374931B (en) | Selective catalysts for naphtha hydrodesulfurization | |
| CN101439293B (en) | Selective hydrodesulfurization catalyst containing mesoporous molecular screen and preparation method thereof | |
| KR20080114686A (en) | Selective catalysts for naphtha hydrodesulfurization | |
| CN112725014B (en) | Grading method of hydrotreating catalyst | |
| US7938955B2 (en) | Method for producing super-low sulfur gas oil blending component or super-low sulfur gas oil composition, and super-low sulfur gas oil composition | |
| CN102049270B (en) | Selective hydrogenation catalyst for gasoline and preparation method thereof | |
| EP1702682A1 (en) | Hydrogenation desulfurization catalyst for petroleum hydrocarbon and method of hydrogenation desulfurization using the same | |
| CN1668723A (en) | A process for the hydroprocessing of heavy hydrocarbon feeds using at least two reactors | |
| CN102451694A (en) | Hydrogenation sweetening catalyst and preparation method and application thereof | |
| CN109772368B (en) | High-activity hydrodesulfurization catalyst and preparation method thereof | |
| CN1597859A (en) | Catalyst for hyrogenating deoxidating and olefine saturating of Feather synthesizing oil and its mfg. process and application | |
| CN103240117A (en) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method | |
| CN102049271B (en) | Gasoline selective hydrogenation catalyst and preparation method and application thereof | |
| CN102049269B (en) | Selective hydrogenation catalyst for gasoline and preparation method thereof | |
| CN1583962A (en) | Absorbing desulfurizing catalyst for catalytic cracking petroleum and preparing method thereof | |
| CN1506163A (en) | Aluminia carrier and hydrogenating catalyst with the carrier | |
| CN103773435B (en) | A kind of vulcanization process of FCC gasoline catalyst for selectively hydrodesulfurizing | |
| CN108855115A (en) | A kind of coated catalysts and preparation method and application | |
| CN1136296C (en) | Catalyst for selectively hydrodesulfurizing gasoline and its preparing process | |
| CN102451693A (en) | Hydrogenation sweetening catalyst and preparation method and application thereof | |
| CN107961771B (en) | Alumina carrier and preparation method thereof, and hydrofining catalyst and preparation method thereof | |
| CN113797938B (en) | Catalyst for selective hydrodesulfurization and olefin reduction of gasoline, and preparation method and application thereof | |
| CN1088093C (en) | Process for preparing hydrorefining catalyst | |
| CN1163573C (en) | Selectively mercaptan-eliminating catalyst for aviation fuel and its prepn |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060419 |
|
| CX01 | Expiry of patent term |