CN1169337A - Catalyst treated by distillate added with hydrogen and preparation method thereof - Google Patents
Catalyst treated by distillate added with hydrogen and preparation method thereof Download PDFInfo
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Abstract
The catalyst comprises gamma-Al2O3 to carry on Ni, W and Co active components and any one of Mg, Zn, Fe and Ca as assistant component. Said active components comprise 10-30% of Wo3, 1.0-7.0% of NiOand 0.01-1.0% of CoO, and the assistant component comprises respectively 0.1-5.0% of MgO, 0.1-2.0% of ZnO, 0.1-3.0% of Fe2O3 and 2-10% of Cao2. Said catalyst has high hydrogen sweetening and hydrogen denitrogenation activity, and can be used for raw-material refinishing, gasoline fractional distillation and hydrogen processing for intermadiate distillate.
Description
The present invention relates to hydrocarbon hydrogenizing treamtent catalyst, more particularly.Be a kind of about the particularly hydrodesulfurization, hydrodenitrogenation catalyst and preparation method thereof of light ends oil and intermediate oil of distillate.
Hydrofinishing is petroleum refining industry method commonly used, and its main purpose is sulphur, nitrogen, oxygen compound or the metal of removing in the petroleum hydrocarbon etc.For example the raw material naphtha used of reformer generally must carry out pre-hydrogenation before entering the reforming reaction system, to remove wherein the catalyst harmful substance, comprises sulphur, nitrogen and other impurity.For other distillate such as kerosene, diesel oil distillate, for guaranteeing product quality, often need hydrofinishing, remove wherein sulphur, nitrogen and aromatic hydrocarbons etc., to improve smoke point and diesel index etc.The used catalyst of hydrogenation process plays an important role to hydrogenation.It is main catalyst component that the catalyst that above-mentioned fraction oil hydrogenation refining is commonly used adopts Mo or W more, and Ni or Co are co-catalyst component, and carrier adopts γ-Al
2O
3, also sneak into SiO sometimes
2Representative catalyst for hydrorefining distillate oil is that trade names are the catalyst of S-12, and it is a kind of Co-Mo/Al
2O
3The type catalyst, be used for the pre-hydrogenation of reforming raw oil, have higher desulphurizing activated, but reaction temperature and pressure are higher, at least 310 ℃ of reaction temperatures, the minimum 2.5MPa of pressure (China Petrochemical Corporation's production and operation coordination portion is compiled, " oil refining process units basic data compilation; fuel oil part ", 1994).
In the petroleum hydrocarbon hydrotreating method that USP4880524 proposes, adopt a kind of highly active hydrogenation catalyst that has.This catalyst belongs to Ni-Mo/Al
2O
3Type, forming content is: Ni1～6%, Mo or W8～40%, its preparation method adopts gelling process promptly to use the water-soluble acid aluminium salt of water-soluble alkali aluminide titration, formation hydrogel precipitation, aging under certain conditions, washing precipitate mix the Ni-Mo salting liquid then with this sediment, promptly make required catalyst through moulding, drying, roasting again.This specific surface area of catalyst is greater than 300m
2/ g.Less than the aperture of 70 greater than 70%, provide in the example＜aperture of 50 accounts for 88.9%.Because the aperture is less than normal, this catalyst can only be used for the hydrodesulfurization of light-end products, in addition also more complicated of this Preparation of catalysts process.
USP4464481 introduces a kind of hydrocracking catalyst, and its composition comprises: 0.5～2%Ni, 0.5～14%W, 1～3%F, carrier are SiO
2-ThO
2Or SiO
2-ThO
2-Al
2O
3, its preparation method is that activated metal component is impregnated into the SiO that makes with the oil column method with coprecipitation method
2-ThO
2On the spherical colloid, drying, roasting again.This catalyst is used to contain 3% sulphur and 0.12% nitrogen, boiling range are the hydrocracking process of 245～515 ℃ VGO raw material, and 149～343 ℃ of product yields that obtain are 94%, but this patent does not provide the hydrodesulfurization and the hydrodenitrogenationactivity activity horizontal data of catalyst.
The CN85104438 patent proposes a kind of fraction oil of petroleum Hydrobon catalyst, belongs to Ni-W-F/Al
2O
3, its carrier is a high purity aluminium oxide.This catalyst is mainly used in the intermediate oil hydrodenitrogeneration.
As can be known above-mentioned, general hydrotreating catalyst is difficult to have high hydrodesulfurization and hydrodenitrogenationactivity activity simultaneously.
The purpose of this invention is to provide a kind ofly have simultaneously that high alkene is saturated, the catalyst for hydrogenation of fraction oil of hydrodesulfurization and hydrodenitrogeneration.
Another object of the present invention provides a kind of simple and can obtain high-intensity Preparation of catalysts method.
The objective of the invention is to realize by following technology contents.
Catalyst is formed
Activity of such catalysts component of the present invention is W, Ni, Co, can also add therein to be selected from Mg, Zn, Ca, Fe element as co-catalyst component.The composition content of following catalyst is that the weight with catalyst is benchmark, and metallic element is in oxide form, and concrete content is as follows:
1. catalyst one, γ-Al
2O
3Load W, Ni, Co active component, its content: WO
310-30%, preferably 16～27%; NiO1.0～7.0%, preferably 1.5～4.0%; CoO0.01～1.0%, preferably 0.02～0.3%.
2. catalyst two, and active component is W, Ni, Co, and co-catalyst component is selected from Mg, Zn, the arbitrary element of Fe, Ca, its content: WO
310～30%, NiO1.0～7.0%, CoO0.01～1.0%, co-catalyst component MgO0.1～5.0%, ZnO0.1～2.0%, Fe
2O
30.1～3.0%, CaO2～10%, all the other are γ-Al
2O
3Optimum content: active component WO
316～27%, NiO1.5～4.0%, CoO0.02～0.3%, co-catalyst component MgO0.5～4.0%, ZnO0.5～1.5%, Fe
2O
30.5～2.0%, CaO3.0～8.0%, all the other are γ-Al
2O
3
Described γ-Al
2O
3Precursor is selected from one or both mixtures in amorphous hydroted alumina, vacation-diaspore, boehmite, gibbsite, the surge aluminium stone, preferably vacation-diaspore and boehmite.When adopting single aluminium oxide, its aperture 40～80 account for more than 90%; When adopting composite alumina, its aperture 30～100 account for more than 90%, and carrier adopts special-shaped bar, preferably cloverleaf pattern.
Described catalyst routinely method before use carries out presulfurization.
Preparation of catalysts
1. the preparation process of catalyst one
(1) γ-Al
2O
3Precursor through moulding, drying, have following 500～700 ℃ of roastings 1～6 hour in air or water vapour again, make γ-Al
2O
3Carrier;
(2) carrier that (1) step is obtained floods in the compound water solution that contains W, Ni, Co, and filtration, drying 400～600 ℃ of following roastings 2～5 hours, promptly obtain catalyst prod then.
2. the preparation process of catalyst two
(1) γ-Al
2O
3Precursor through moulding, drying, have following 500～700 ℃ of roastings 1～6 hour in air or water vapour again, make γ-Al
2O
3Carrier;
(2) with γ-Al
2O
3Soak in the compound water solution that is selected from Mg, Zn, Fe, the arbitrary element of Ca that immersion prepares, filtration, drying 400～700 ℃ of following roastings 2～8 hours, obtain containing the γ-Al of co-catalyst component then
2O
3Carrier;
(3) carrier that (2) step is obtained floods in the compound water solution that contains W, Ni, Co, and filtration, drying 400～600 ℃ of following roastings 2～5 hours, promptly obtain catalyst prod then.
Active component Co in the preparation process of described catalyst two can add in (2) step, makes the γ-Al that contains Co and co-catalyst component
2O
3Carrier.
The preparation process (2) of described catalyst two, (3) step can also be adopted the saturated dipping method in hole.
The compound water solution of described Mg, Zn, Fe, Ca makes according to a conventional method, and their compound is a nitrate.
The compound water solution of the described Ni of containing, W, Co makes according to a conventional method, and wherein the compound of Ni, Co element is nitrate, acetate, carbonate, subcarbonate, preferably nitrate, subcarbonate.
Catalyst of the present invention can be used for reforming that the alkene of prerefining feedstock oil, gasoline fraction and intermediate oil is saturated, hydrodesulfurization, hydrodenitrogeneration process, and its operating condition can be adjusted in following ranges according to the raw material oil properties with to the requirement of oil quality: 200～400 ℃ of reaction temperatures, volume space velocity 3～15h
-1, hydrogen dividing potential drop 0.8～6.0MPa, hydrogen/oil 50～800: 1 (body).
The major advantage of catalyst of the present invention: owing to adopt Ni-W and micro-Co as main active component, and obtain best proportioning.Can also add among Mg, Zn, Fe, the Ca arbitrary element as co-catalyst component, adjust the performance of catalyst, therefore catalyst of the present invention is used for the distillate hydrogenation processing, can have high desulphurizing activated and denitrification activity simultaneously, this catalyst for hydrogenation of fraction oil in prior art is inaccessible.Mix the blend gasoline of 5～30% secondary processing of gasoline as direct steaming gasoline, wherein contain＜sulphur of 400ppm, the nitrogen of 20ppm and＜arsenic of 1000ppb, under the reaction condition that relaxes, use catalyst hydrogenation of the present invention to handle, can obtain qualified reforming raw oil.Catalyst of the present invention is used for the distillate hydrogenation processing procedure, can not only improve the character of oil product effectively, and has the saturated performance of less aromatic hydrocarbons.Preparation of catalysts method of the present invention is simple, and used raw material all is commercially available prod, and the carrier hole that makes distributes more concentrated, and adopts special-shaped bar, has increased specific surface and bulk density, and the intensity of catalyst is also than higher, and crushing strength is up to nearly 29N/mm.
Further specify characteristics of the present invention with example below.
Example 1
This example is the carrier of preparation catalyst.
With adding sesbania powder 30g in the 1000gSB aluminium hydrate powder, mix; With 40g citric acid and the dense HNO of 9ml
3Add in the 700ml water and dissolve, this solution is added in the compound that contains SB aluminium hydroxide, mix then pinch, extrusion, making D is the wet bar of 1.6mm cloverleaf pattern, again in 140 ℃ dry 2 hours down, 600 ℃ of following roastings 4 hours make carrier a.
Carrier a performance: specific surface 255m
2/ g, pore volume 0.5ml/g, can a few bore dia 66A and 40～80A account for more than 90% crushing strength 19.5N/mm.
Example 2
This example is that the high purity aluminium oxide (abbreviation HP-1) that obtains with the low-carbon alkoxy aluminium hydrolysis that adopts that boehmite and CN85100218.8 patent propose is produced γ-Al
2O
3Carrier.
Adding 35g sesbania powder in 500g boehmite powder and 500gHP-1 aluminium hydrate powder mixes; With 40g citric acid and 13ml HNO
3Be added in the 750ml water and dissolve, this solution is added in the mixture that contains boehmite and HP-1 aluminium hydroxide, pinch through mixing then, extrusion, making diameter is the wet bar of 1.6mm cloverleaf pattern, and again in 120 ℃ of dryings 3 hours, 600 ℃ of roastings 4 hours make carrier b.
The performance of carrier b: specific surface 235m
2/ g, pore volume 0.48ml/g can several holes be a double-pore structure, can several apertures be 38A and 88A, the hole of 30～100A accounts for total pore volume 90% above crushing strength 22.0N/mm.
Example 3
This example is the γ-Al that adopts false boehmite to make
2O
3
Adding 35g sesbania powder in (Shandong Aluminum Plant's production) in the false boehmite powder of 1000g mixes; With 35g citric acid and 10ml HNO
3Be added in the 650ml water and dissolve, the solution that will contain nitric acid and citric acid is added in the mixed powder that contains false boehmite, pinch through mixing then, extrusion makes D=1.6mm cloverleaf pattern bar, after under 120 ℃ dry 4 hours, put into the steam treatment stove again, in 550 ℃, water/agent is to handle 6 hours for 1: 1 time, makes carrier c.
The performance of carrier c: specific surface 202m
2/ g, pore volume 0.39ml/g, can a few bore dia 66A and 40A～80A account for more than 90% crushing strength 20.2N/mm.
Example 4
This example is preparation Ni-W-Co/Al
2O
3Catalyst.
(call AMT in the following text, concentration is 77.6 gram WO to get nickel nitrate 64.5g, ammonium metatungstate solution
3/ 100ml) 34ml, cobalt nitrate 1.1g is made into Ni-W-Co co-impregnated solution 120ml, and with this co-impregnated solution dipping 60g carrier a4 hour, then after filtration, drying, 450 ℃ of following roastings promptly made catalyst A in 4 hours, and its performance sees Table 1.
Example 5
This example is preparation Ni-W-Co/Al
2O
3-Ca catalyst.
1. preparation contains the Ca carrier and gets calcium nitrate 25.8g, is made into the 120ml maceration extract, with this maceration extract dipping 60g carrier a4 hour, then after filtration, dry, 580 ℃ of following roastings 4 hours, makes the Al that contains Ca
2O
3Carrier d;
2. preparation catalyst: get cobalt nitrate 0.3g, nickel nitrate 26.0g and AMT solution 55ml, be made into Co-Ni-W co-impregnated solution 120ml.Get carrier d59.8g, immerse co-impregnated solution under room temperature, kept 4 hours, then after filtration, drying, 500 ℃ of following roastings made catalyst B in 4 hours, and its performance sees Table 1.
Example 6
This examples preparation Ni-W-Co/Al
2O
3-Zn catalyst.
1. preparation contains the Zn carrier and gets zinc nitrate 7.1g, is made into 60ml solution, and with this solution impregnation 30g carrier a3 hour, then after filtration, drying, 550 ℃ of following roastings 4 hours made and contain Zn carrier e;
2. preparation catalyst: get cobalt nitrate 0.15g, nickel nitrate 13.0g, AMT solution 27.5ml, be made into the 60ml co-impregnated solution, 30g carrier e was immersed in the co-impregnated solution 3 hours, then after filtration, drying, 550 ℃ of roastings 3 hours make catalyst C, and its performance sees Table 1.
Example 7
This example is to adopt the hole saturation to prepare Ni-W-Co/Al
2O
3-Mg catalyst.
1. get magnesium nitrate 14.8g, cobalt nitrate 0.45g, be made into the 130ml maceration extract, this maceration extract is sprayed on the 173g support C equably, in 140 ℃ of dry down 2 hours, 550 ℃ following roastings 4 hours, make the Al that contains Mg, Co then
2O
3Carrier f;
2. get nickel nitrate 21.3g, AMT solution 673ml, be made into the 130ml co-impregnated solution, and place sprayer, get 173g carrier f then, constantly stir down co-impregnated solution is sprayed into, in dipping under the room temperature after 3 hours, drying, 500 ℃ of following roastings 3 hours make catalyst D, and its performance sees Table 1.
Example 8
This example is preparation Ni-W-Co/Al
2O
3-Mg catalyst.
1. get magnesium nitrate 7.3g, be made into 61ml solution, with the hole saturation of example 7, b floods to carrier, and drying, roasting make the Al that contains Mg again
2O
3Carrier g;
2. get cobalt nitrate 0.18g, nickel nitrate 8.85g, concentration is 86.3g WO
3The ammonium metatungstate solution 23.5ml of/100ml is made into the 60ml co-impregnated solution, by the method for example 7 73g carrier g is carried out the saturated dipping in hole, through 2 hours, 400 ℃ following roastings of 120 ℃ of dryings 5 hours, makes catalyst E then, and its performance sees Table 1.
Example 9
This example is preparation Ni-W-Co/Al
2O
3-Mg catalyst.
Adopt the method for example 5, a floods to carrier, makes the Al that contains Mg
2O
3Carrier h uses Co-Ni-W co-impregnated solution impregnated carrier h then, makes catalyst F, and its performance sees Table 1.
Example 10
This example adopts the same quadrat method of example 4, makes Ni-W-Co/Al
2O
3Catalyst G, its performance sees Table 1.
Below example 11～13rd, in the small stationary bed bioreactor, catalyst activity of the present invention is estimated, and is compared with the catalyst of prior art.All carrying out presulfurization by existent method before the evaluating catalyst handles.The presulfurization condition that the present invention adopts: at hydrogen dividing potential drop 1.6MPa, volume space velocity 2.0
-1, hydrogen/oil 300: 1 (body) condition under, advance to contain 2%CS in 150 ℃
2Direct steaming gasoline, 230 ℃ of constant temperature 3 hours rises to 290 ℃ again, constant temperature sulfuration 3 hours.
Example 11
This example is mixed 25% coker gasoline with direct steaming gasoline and direct steaming gasoline catalyst A, B, C, D, E is carried out activity rating, and compares with contrast 1 catalyst and contrast 2 catalyst (their performance sees Table 1).Reaction condition when adopting direct steaming gasoline is: 260 ℃ of temperature, hydrogen dividing potential drop 1.6MPa, volume space velocity 10
-1, hydrogen/oil 70: 1 (body); Reaction condition when adopting direct steaming gasoline to mix 25% coker gasoline is: 280 ℃ of temperature, hydrogen dividing potential drop 3.2MPa, volume space velocity 10
-1, hydrogen/oil 200: 1 (body).Feedstock oil character sees Table 2.Result of the test sees Table 3.
As shown in Table 3, catalyst of the present invention has high hydrodesulfurization and hydrodenitrogenationactivity activity simultaneously
Example 12
This example is that the activated feedstock oil nature with the heavy aromatics feedstock oil evaluate catalysts F after the catalytic cracking diesel oil extracting sees Table 2.Operating condition and result of the test see Table 4.
Find out that by table 4 catalyst of the present invention not only has high hydrodesulfurization and hydrodenitrogenationactivity activity simultaneously but also has the saturated performance of less aromatic hydrocarbons.
Example 13
This example is that catalyst E of the present invention is compared test with contrast 3 catalyst (composition and performance see Table 1).The raw material of test usefulness is that direct steaming gasoline is mixed 25% coker gasoline, and its character sees Table 2.Operating condition and result of the test see Table 5.
Being found out by table 5, is 209 ℃ blend gasoline for doing, and has equally that good alkene is saturated, hydrodesulfurization and a hydrodenitrogenationactivity activity.
The composition of table 1 catalyst and performance
Annotating 1. contrasts, 1 catalyst is that the trade mark of being produced by Uop Inc. is the catalyst of S-12, belongs to Co-Mo-/Al
2O
3Type is mainly used in distillate hydrogenation and takes off S
Take off N with hydrogenation; 2 contrasts, 2 catalyst are that the trade mark of being produced by Procatalys company is the catalyst of HR-306, belong to Co-Mo-/Al
2O
3Type, main
Be used for distillate hydrogenation and take off S; 3. contrasting 3 catalyst is CN8510443.8 patents, is mainly used in the intermediate oil hydrogenation and takes off N, and hydrogenation takes off S; 4. right
Character than catalyst is measured result.
Table 2 feedstock oil character
| Project | Example 11 feedstock oils | Example 12 feedstock oils | Example 13 feedstock oils | |
| Direct steaming gasoline | Direct steaming gasoline+25% coker gasoline | |||
| Density (20 ℃), g/cm 3Total S, the total N of ppm, ppm bromine valency, the gBr/100g saturated hydrocarbons, % aromatic hydrocarbons, % is mononuclear aromatics % alkene wherein, the % boiling range, ℃ initial boiling point 10% 50% 90% 95% is done | ????0.7229 ????239 ????1.0 ????2.8 ????63 ????81 ????99 ????119 ????129 ????158 | ????0.7266 ????393 ????20 ????9.6 ????62 ????83 ????102 ????135 ????158 ????198 | ??0.9063 ??769 ??125 ??8.8 ??11.0 ??85.5 ??0.51 ??3.5 ??184 ??209 ??224 ??272 ??323 ??337 | ??0.7388 ??286 ??70 ??14.5 ??75 ??90 ??135 ??182 ??209 |
Table 3 catalyst A, B, C, D, E activity rating result
Table 4 catalyst F activity rating result
| Reaction condition hydrogen dividing potential drop, MPa 4.0 4.8 temperature, ℃ 300 340 volume space velocities, h -11.85 2.0 hydrogen/oil (v) 500: 1 500: 1 result of the test S, ppm 33 4.3 takes off S and leads, % 95.7 99.4 N, ppm 23 1.0 takes off N and leads, % 81.6 99.2 bromine valencys, gBr/100g 1.0 0.4 saturated hydrocarbons, % 14.0 aromatic hydrocarbons, % 85.8 is mononuclear aromatics wherein, %0.70 alkene, % 0.17 boiling range, ℃ initial boiling point 182 10% 207 50% 220 90% 260 95% 314 does 335 |
Table 5 catalyst E and contrast 3 catalyst comparative test result
Claims (9)
1. a hydrocarbon hydrogenizing treamtent catalyst comprises active component Ni, W and carrier γ-Al
2O
3, it is characterized in that γ-Al
2O
3Load comprises Ni, W and Co active component, forms content (in metal oxide, catalyst weight is a benchmark): WO
310～30%, NiO1.0～7.0%, CoO0.01～1.0%, all the other are γ-Al
2O
3
2. according to the described catalyst of claim 1, it is characterized in that adding and be selected among Mg, Zn, Fe, the Ca arbitrary element as co-catalyst component, its content (weight with catalyst is benchmark): MgO0.1～5.0%, ZnO0.1～2.0%, Fe
2O
30.1 CaO2～10%～3.0%.
3. according to claim 1 or 2 described catalyst, it is characterized in that active component content: WO
316～27%, NiO1.5～4.0%, CoO0.02～0.3%.
4. according to the described catalyst of claim 2, it is characterized in that co-catalyst component content MgO0.5～4.0%, ZnO0.5～1.5%, Fe
2O
30.5 CaO3.0～8.0%～2.0%.
5. the described Preparation of catalysts method of claim 1 comprises pre-forming carrier dipping active component, and dry again, roasting is characterized in that concrete preparation process and condition comprise: (1) γ-Al
2O
3The moulding of precursor elder generation, drying, again under the existence of air or water vapour, 500～700 ℃ of roastings 1～6 hour make γ-Al
2O
3In the compound water solution that contains Ni, W, Co, more after filtration, drying, 400～600 ℃ of following roastings 2～5 hours promptly make catalyst to carrier (2) with the carrier impregnation that makes of (1) step.
6. it is characterized in that in accordance with the method for claim 5, γ-Al
2O
3Put into the compound water solution dipping that is selected from Mg, Zn, Fe, the arbitrary element of Ca for preparing, filter then, drying, 400～700 ℃ of roastings 2～8 hours make the γ-Al that contains co-catalyst component
2O
3Carrier.
7. in accordance with the method for claim 5, it is characterized in that described γ-Al
2O
3Precursor comprises one or both mixtures in amorphous alumina, false boehmite, boehmite, gibbsite, the surge aluminium stone, single γ-Al
2O
3Aperture 40～80 account for more than 90% of total pore volume, compound γ-Al
2O
3Aperture 30～100 account for more than 90% of total pore volume.
8. according to claim 5 or 6 described methods, it is characterized in that active component Co and arbitrary co-catalyst component are mixed with the aqueous solution, flood γ-Al again
2O
3
9. the described catalyst of claim 1 is characterized in that can be used for the hydrotreatment process of reforming prerefining feedstock oil, gasoline fraction and intermediate oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106586A CN1056784C (en) | 1996-06-28 | 1996-06-28 | Catalyst treated by distillate added with hydrogen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106586A CN1056784C (en) | 1996-06-28 | 1996-06-28 | Catalyst treated by distillate added with hydrogen and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1169337A true CN1169337A (en) | 1998-01-07 |
| CN1056784C CN1056784C (en) | 2000-09-27 |
Family
ID=5119292
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|---|---|---|---|
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| US6037306A (en) * | 1998-03-20 | 2000-03-14 | China Petrochemical Corporation | Catalyst containing molybdenum and/or tungsten for hydrotreating light oil distillates and preparation method thereof |
| CN1073616C (en) * | 1998-11-13 | 2001-10-24 | 中国石油化工集团公司 | Preparation method of hydrogenation catalyst |
| CN1083476C (en) * | 1999-09-29 | 2002-04-24 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
| CN100364668C (en) * | 2004-10-29 | 2008-01-30 | 中国石油化工股份有限公司 | Method for preparing surface modified IIB metal oxide hydrogenation catalyst |
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| US4314901A (en) * | 1980-07-15 | 1982-02-09 | Phillips Petroleum Company | Catalytic hydrodesulfurization of an organic sulfur compound contained in gasoline |
| US4464481A (en) * | 1983-08-25 | 1984-08-07 | Uop Inc. | Hydrocracking catalyst |
| US4572778A (en) * | 1984-01-19 | 1986-02-25 | Union Oil Company Of California | Hydroprocessing with a large pore catalyst |
| US4880524A (en) * | 1987-11-20 | 1989-11-14 | Shell Oil Company | Process for hydrotreating hydrocarbon feeds |
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- 1996-06-28 CN CN96106586A patent/CN1056784C/en not_active Expired - Lifetime
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