CN1173010C - Method and Catalyst for Selective Hydrofining of Cracked Gasoline - Google Patents
Method and Catalyst for Selective Hydrofining of Cracked Gasoline Download PDFInfo
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- CN1173010C CN1173010C CNB011314540A CN01131454A CN1173010C CN 1173010 C CN1173010 C CN 1173010C CN B011314540 A CNB011314540 A CN B011314540A CN 01131454 A CN01131454 A CN 01131454A CN 1173010 C CN1173010 C CN 1173010C
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nitrogenous compound Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The hydrofining process and the catalyst have stronger hydrodesulfurization capability (75-95% HDS) than the traditional hydrofining catalyst, and the desulfurized gasoline has smaller octane number loss (the RON is reduced by 3-4 units). The catalyst does not contain any harmful substance, and has excellent catalytic activity and good stability. The method adopts a catalyst and a gas phase hydrogenation process, wherein the reaction pressure of the process is 1-4 MPa, the reaction temperature is 240-350 ℃, and the liquid phase space velocity LHSV is 1-10 h-1The volume ratio of hydrogen to oil is 100-500.
Description
The present invention relates to the method and the Preparation of catalysts method of a kind of pressure gasoline (petroleum naphtha) selective hydrogenation refining, it is to belong in the petroleum chemical industry the improvement and the innovation of light-end products process for refining, exactly is the selective hydrogenation refining technology of pressure gasoline in the presence of catalyzer (petroleum naphtha).
As everyone knows, pressure gasoline (petroleum naphtha) contains a large amount of sulfocompounds.The method that reduces sulphur content has: 1) to cracking or the unitary full feedstock hydrofining of coking, 2) these unitary products are carried out hydrofining.First kind of selection is because need huge hydrogen treatment unit and a large amount of hydrogen consumptions, and be costly.Second kind of selection be shortcut but can cause alkene (account for usually raw material 20～60v%) saturated, this anti-knock index ((RON+MON)/2) that also can reduce the sweet gasoline product reaches 10～20 units simultaneously.The loss of octane number relevant with desulfurization is a very big impact to the octane value of refinery's gasoline product.For reaching the octane value that the sulphur that can remove effectively in the pressure gasoline can farthest keep sweet gasoline again, approach one is to improve catalyzer; The 2nd, adopt suitable process conditions.
(and Cherry Hill has described a kind of FCC gasoline low temperature hydrogenation desulfurization in NJ) and has reduced the gasoline octane rating technology for Shih, Stuart S at U.S.Pat.No.6042719.The patent catalyst system therefor is a dual-function catalyst, and just the metal with group vib and VIII family is supported on by ZSM-5 and Al
2O
3On the carrier of forming, ZSM-5/Al
2O
3=80/20.More more specifically, the group vib metal is Mo, and VIII family metal is Co.In the hydrogenating desulfurization degree is 80～95% o'clock, loss of octane number: MON＜5%, RON＜10%.Under the condition of lesser temps, especially desulfurization degree was less than 95% o'clock, and process has less alkene saturation exponent.
Purpose of the present invention provides a kind of method and Preparation of catalysts method that is used for pressure gasoline (petroleum naphtha) selective hydrodesulfurization with regard to being to avoid above-mentioned the deficiencies in the prior art part.Its major technology characteristics are exactly by the special-purpose Hydrobon catalyst of purchasing in advance, again will pending stock oil get final product in the reactor by catalyzer formation bed thus.
Its major ingredient of this catalyzer is that its major ingredient is CoO+MoO, shape-selective molecular sieve ZSM-5 and/or super stable molecular sieve USY, Al
2O
3And/or TiO
2/ Al
2O
3:, it is characterized in that the weight ratio of each component is: CoO+MoO:6～20%; ZSM-5 and/or USY:0～40%; Al
2O
3And/or TiO
2/ Al
2O
3: 0～80%.
The gas phase hydrogenation process is then adopted in the selective hydrodesulfurization of pressure gasoline, promptly adopts above-mentioned special-purpose catalyst, and the reaction pressure of its process is 1～4MPa, and temperature of reaction is 240～350 ℃, and the liquid phase air speed is 1～10h
-1, hydrogen to oil volume ratio is 100～500.Use fluidized-bed or ebullated bed as much as possible, preferably fixed bed.
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail:
(1) on the Preparation of catalysts, its main step is as follows:
1. prepare carrier: with shape-selective molecular sieve ZSM-5 and/or super stable molecular sieve USY, aluminium oxide Al
2O
3, water and acid, behind the mixed grinding, its mixture is forged or is pushed bar to form by the size of design requirements, 80～150 ℃ dry 10～30 hours down, then at 400～600 ℃ of following roasting 2～8h;
2. adopt the metal salt solution immersion process for preparing, used metal-salt is nitrate or carbonate, and dipping time is 6～12 hours
3. calcination process: maturing temperature is that 300～600 ℃, time are 2～8 hours; Preferably maturing temperature is that 400～500 ℃, time are 4～6 hours.
4. sulfidizing: curing temperature is 240～350 ℃, and curing time is 8～48 hours, and hydrogen to oil volume ratio is 100～500.
(2) in the selection of material oil, mainly be pressure gasoline (petroleum naphtha), can be pressure gasoline or petroleum naphtha, catalytically cracked gasoline or petroleum naphtha, coker gasoline or petroleum naphtha, the gasoline of ethylene production steam cracking or petroleum naphtha, the full range pressure gasoline (petroleum naphtha) that normally from cracking and coking unit operation, gets.Can contain 3～80% alkane, 1～80% alkene, 3～80% naphthenic hydrocarbon, 3～80% aromatic hydrocarbons and a small amount of sulfur-bearing and nitrogenous compound, its cut scope can be 25～225 ℃, also can be any cut that cuts in above scope.Wherein, sulphur content can be 100～20000ppm, and nitrogen content can be 20～2000ppm.
(3) in the use of reactor, possible use fluidized-bed or ebullated bed, preferably fixed bed although mainly be.
According to three above principles, the present invention is carried out implementation and operation, obtain following result:
Embodiment 1
Take by weighing SB powder (the German Condea product γ-Al of company of 30g
2O
3) and a certain proportion of ZSM-5 (30%), with the HNO of 30ml water and 0.9g
3Mix, on the catalyzer extrusion shaping machine, be extruded into the bar of diameter 1.6mm, under infrared lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 120 ℃, roasting 5h in muffle furnace, last porphyrize sieves out 20～40 purpose catalyst carrier particles.
Embodiment 2
Take by weighing SB powder and a certain proportion of USY (30%) of 30g, with the HNO of 30ml water and 0.9g
3Mix, with the bar that is extruded into diameter 1.6mm on the catalyzer extrusion shaping machine, under infrared lamp, behind the dry 5h, put in the baking oven following dry 10 hours at 120 ℃, in 550 ℃ of following roasting 5h, last porphyrize sieves out 20～40 purpose catalyst carrier particles in muffle furnace.
Embodiment 3
Taking by weighing a certain amount of tetrabutyl titanate is dissolved in and makes it form the ethanolic soln of tetrabutyl titanate in the ethanol of certain volume; Take by weighing a certain amount of SB powder and place the ethanolic soln of tetrabutyl titanate, stir 2～12hr, boil off etoh solvent then, place 5～24hr, then at 550 ℃ of following roasting 5hr, TiO
2-Al
2O
3
Embodiment 4
Take by weighing the TiO of 30g embodiment 3 preparations
2-Al
2O
3With a certain proportion of ZSM-5 (30%w), with the HNO of 30ml water and 0.9g
3Mix, with the bar that is extruded into diameter 1.6mm on the catalyzer extrusion shaping machine, under infrared lamp, behind the dry 5h, put in the baking oven following dry 10 hours at 120 ℃, in 550 ℃ of following roasting 5h, last porphyrize sieves out 20～40 purpose catalyst carrier particles in muffle furnace.
Embodiment 5
Take by weighing the TiO of 30g embodiment 3 preparations
2-Al
2O
3With a certain proportion of HUSY (30%w), with the HNO of 30ml water and 0.9g
3Mix, with the bar that is extruded into diameter 1.6mm on the catalyzer extrusion shaping machine, under infrared lamp, behind the dry 5h, put in the baking oven following dry 10 hours at 120 ℃, in 550 ℃ of following roasting 5h, last porphyrize sieves out 20～40 purpose catalyst carrier particles in muffle furnace.
Embodiment 6
Take by weighing carrier 12 g, take by weighing the Co (NO of 1.2g with the method preparation of embodiment 1
3)
2.7H
2O pours carrier in the solution into the deionized water dissolving of 8g, dipping 12h, and drying is 10 hours under 120 ℃, then at 550 ℃ of roasting 5h.With 12% MoO in the ammonium molybdate load, make catalyst I according to above-mentioned steps.
Embodiment 7
Take by weighing carrier 12 g, prepare catalyst I I by embodiment 6 methods with the method preparation of embodiment 2.
Embodiment 8
Take by weighing carrier 12 g, prepare catalyst I II by embodiment 6 methods with the method preparation of embodiment 4.
Embodiment 9
Take by weighing carrier 12 g, prepare catalyst I V by embodiment 6 methods with the method preparation of embodiment 4.
Embodiment 10
Take by weighing γ-Al by the preparation of embodiment 1 method
2O
3Carrier 12 g prepares catalyst V by embodiment 6 methods, and this catalyzer as a reference.
The typical catalyst composition is as described in Table 1:
The composition situation of table 1 catalyzer
| Numbering | Carrier | Active ingredient | Charge capacity |
| I | ZSM-5/γ-Al 2O 3 | Co，Mo | CoO+MoO＝16％ Co∶Mo＝1∶3 |
| II | USY/γ-Al 2O 3 | Co，Mo | |
| III | ZSM-5/TiO 2-γ-Al 2O 3 | Co，Mo | |
| IV | USY/TiO 2-γ-Al 2O 3 | Co，Mo | |
| V | γ-Al 2O 3 | Co，Mo |
Typical pressure gasoline (petroleum naphtha) raw material properties of being handled by hydrofining sees Table the description in 2:
The character of table 2 raw material FCC gasoline
| Sample | The FCC raw material |
| Normal paraffin (%) | 4.3 |
| Isoparaffin (%) | 20.3 |
| Alkene (%) | 39.7 |
| Naphthenic hydrocarbon (%) | 6.7 |
| Aromatic hydrocarbons (%) | 22.4 |
| RON | 94.2 |
| MON | 87.5 |
| (RON+MON)/2 | 90.9 |
| Sulphur content (ppm) | 1203.2 |
Each catalyst system of embodiment 6～10 all carries out the hydrogenating desulfurization test on anti-in that high pressure is little.Catalyzer is 20～40 order sizes, with the 16ml catalyzer reactor of packing into, 260 ℃, 280 ℃, 300 ℃ following times with containing 3v%CS
2Straight-run spirit prevulcanized 12h.Under test conditions, feed FCC gasoline.Sampling analysis after 10 hours is carried out in reaction.The type reaction condition is: 260～300 ℃ of temperature, pressure 2.0Mpa, liquid air speed 3.75h
-1, hydrogen to oil volume ratio 180.
In each example, indicated 1) hydrogenating desulfurization percentage (this with feed sulfur to remove quality percentage relevant); 2) loss of anti-knock index (RON+MON)/2 and octane value, its result is as shown in table 4:
Table 4 FCC gasoline hydrodesulfurizationmethod test-results table
| Numbering | Temperature of reaction ℃ | HDS％ | (RON+MON)/2 | (RON+MON)/2 loss |
| I | 260 | 63.3 | 82.0 | 8.1 |
| II | 260 | 62.2 | 84.9 | 6.1 |
| III | 260 | 78.5 | 87.9 | 3.0 |
| IV | 260 | 73.0 | 88.4 | 2.5 |
| V | 260 | 75.1 | 75.7 | 15.2 |
The character of hydrofining gained typical products FCC gasoline is as described in Table 5:
The composition and property of table 5 product F CC gasoline
| Sample | Product 1 | Product 2 |
| Normal paraffin (%) | 6.31 | 7.70 |
| Isoparaffin (%) | 23.30 | 24.82 |
| Alkene (%) | 36.81 | 33.21 |
| Naphthenic hydrocarbon (%) | 7.67 | 8.62 |
| Aromatic hydrocarbons (%) | 22.63 | 22.28 |
| RON | 90.33 | 89.55 |
| MON | 84.03 | 83.34 |
| (RON+MON)/2 | 87.18 | 86.45 |
| Sulphur content (ppm) | 431.2 | 339.8 |
In sum, can draw as drawing a conclusion:
1. in the temperature and pressure scope of being tested, the technology of the present invention shows higher hydrodesulfurization activity by physical causes.
2. operation in the scope of conventional liquid phase air speed (LHSV), the technology of the present invention is promised to undertake the target that reaches hydrogenating desulfurization 〉=80%.
3. add ZSM-5 and/or USY molecular sieve and can improve the HDS selectivity of catalyst.
4. with TiO
2-Al
2O
3Composite oxides are that the catalyzer of carrier has the active and less loss of octane number of higher H DS;
In the hydrogenating desulfurization rate greater than 80% o'clock, loss of octane number is 3.9 units only.
Claims (4)
1, a kind of catalyzer that is used for selective hydrogenation refining of cracked gasoline, its major ingredient is CoO+MoO
3, ZSM-5 or USY, Al
2O
3Or TiO
2/ Al
2O
3, it is characterized in that the weight ratio of each component is:
CoO+MoO： 6～20％；
ZSM-5 or USY:0～40%;
Al
2O
3Or TiO
2/ Al
2O
3: 0～80%;
Each component sum of above-mentioned catalyzer should be 100%.
2, Hydrobon catalyst according to claim 1 is characterized in that should adopting in preparation as follows
Step realizes:
1. prepare carrier: with shape-selective molecular sieve ZSM-5 or super stable molecular sieve USY, aluminium oxide Al
2O
3, water and acid,
Behind the mixed grinding, its mixture is forged or is pushed bar to form by the size of design requirements,
Drying is 10～30 hours under 80～150 ℃, then 400～600 ℃ of following roastings 2～8 hours;
2. adopt the metal salt solution immersion process for preparing, used metal-salt is nitrate or carbonate, and dipping time is
6～12 hours;
3. calcination process: maturing temperature is that 300～600 ℃, time are 2～8 hours;
4. sulfidizing: curing temperature is 240～350 ℃, and curing time is 8～48 hours, hydrogen to oil volume ratio
Be 100～500.
3, a kind of pressure gasoline hydrogen process for purification that adopts the selective hydrogenation refining catalyzer, it is characterized in that adopting the described catalyzer of claim 1, and adopt the gas phase hydrogenation process, the reaction pressure of its process is 1～4MPa, temperature of reaction is 240～350 ℃, and the liquid phase air speed is 1～10h
-1, hydrogen to oil volume ratio is 100～500.
4, the method for selective hydrogenation refining of cracked gasoline according to claim 3 is characterized in that described employing gas phase hydrogenation process should use fluidized-bed, ebullated bed or fixed bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011314540A CN1173010C (en) | 2001-09-11 | 2001-09-11 | Method and Catalyst for Selective Hydrofining of Cracked Gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011314540A CN1173010C (en) | 2001-09-11 | 2001-09-11 | Method and Catalyst for Selective Hydrofining of Cracked Gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1335360A CN1335360A (en) | 2002-02-13 |
| CN1173010C true CN1173010C (en) | 2004-10-27 |
Family
ID=4670591
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011314540A Expired - Fee Related CN1173010C (en) | 2001-09-11 | 2001-09-11 | Method and Catalyst for Selective Hydrofining of Cracked Gasoline |
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|---|---|
| CN (1) | CN1173010C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465020B (en) * | 2010-11-05 | 2014-08-20 | 中国石油化工股份有限公司 | Combined hydrofining method |
| CN104624227A (en) * | 2013-11-15 | 2015-05-20 | 中国石油天然气股份有限公司 | Mesoporous-microporous molecular sieve hydrocracking catalyst |
| CN105312078B (en) * | 2014-08-01 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105312084B (en) * | 2014-08-01 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105289706B (en) * | 2014-08-01 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105289682B (en) * | 2014-08-01 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105289705B (en) * | 2014-08-01 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
-
2001
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| Publication number | Publication date |
|---|---|
| CN1335360A (en) | 2002-02-13 |
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