CN103657729A - Hydrocarbon oil catalytic cracking sulfur transfer cocatalyst and preparation method thereof - Google Patents
Hydrocarbon oil catalytic cracking sulfur transfer cocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocarbon oil catalytic cracking sulfur transfer cocatalyst and a preparation method thereof, belonging to a catalyst additive containing metal or metal oxide or hydroxide. The hydrocarbon oil catalytic cracking sulfur transfer cocatalyst is prepared form the following raw materials in parts by weight: 2-5 parts of IIA-family metal oxide, 10-20 parts of stibium oxide, 5-8 parts of lanthanide series metal compound, 25-45 parts of organic acid, 6-12 parts of surface active component and 20-40 parts of deionized water. The invention provides the hydrocarbon oil catalytic cracking sulfur transfer cocatalyst which is capable of well removing SOX in regeneration flue gas, better in heavy metal passivation effect, flexible and convenient to add and use and excellent in dispersing property, and the preparation method thereof. 50-200ppm of liquid sulfur transfer agent is added in a catalytic cracking raw material, the SO2 removal rate in smoke is capable of reaching 55-87 percent, the H2/CH4 in the obtained cracking gas is remarkably reduced, and the passivation effect is better. The hydrocarbon oil catalytic cracking sulfur transfer cocatalyst enters a catalytic cracking device together with hydrocarbon oil along with a catalytic cracking raw material, and cooperates with a catalytic cracking catalyst to jointly realize a catalysis function.
Description
Technical field
The present invention is that a kind of hydrocarbon oil catalytic cracking sulphur shifts co-catalyst and preparation method thereof.Belong to the catalyst promoter that comprises metal or metal oxide or hydroxide.
Background technology
Hydrocarbon oil catalytic cracking is one of main secondary operations device of producing by the contour use value light oil of petrol and diesel oil.Along with the ratio of residual oil and mink cell focus in the raising of sour crude processing capacity and catalytic cracking unit charging constantly increases, make SO in regeneration fume from catalytic cracking
xcontent increases, and causes corrosion of equipment serious, simultaneously contaminated environment, harm humans health.Reduce the SO in catalytic cracking regenerator
xthe main method of discharge has: the washing of flue gas; FCC feedstock oil hydrodesulfurization pretreatment; Catalysis method takes off SO
x(sulfur transfer additive).Due to the de-SO of catalysis method
xdo not need device for modifying and equipment investment, and easy and simple to handle, therefore become the optimal selection of oil plant.
The mechanism of action of sulfur transfer additive is that sulfur transfer additive is mixed with catalytic cracking catalyst, and in regenerator, sulfur transfer additive active component is reacted with SOx and generated metal sulfate, and in riser reactor, at H
2, under the reducing atmosphere such as hydrocarbon gas, sulfate is reduced, and discharges that hydrogen sulfide enters gas sweetening and Crouse's sulfur recovery system is recycled.
Reduction facilitation that sulfur transfer additive active component is in the regeneration of catalytic cracking process---having played respectively oxidation in reaction continuous process---.
The preparation of sulfur transfer additive is to take metal oxide as basis at first, as adopted oxide, aluminium oxide and their mixture of alkali metal, alkaline-earth metal as sulfur transfer additive, is that accelerating oxidation ability is by CeO afterwards
2introduce, for improving reducing degree, the transition metal elements such as V, Fe, Co, Cr, Cu are introduced.
Chinese patent CN1883794A discloses a kind of regeneration fume from catalytic cracking high-performance sulfur transfer agent and preparation method thereof, take iron, magnesium and aluminium as active component, take copper as auxiliary agent, by coprecipitation, make iron magnesia-alumina hydrotalcite, adopt infusion process to make copper-iron magnesia-alumina hydrotalcite again, through roasting, be prepared into sulfur transfer additive.
Chinese patent CN101905168A discloses a kind of catalytic cracking promoter for more propylene with sulfur transfer additive function, belongs to the improvement of PETROLEUM PROCESSING field catalyst promoter.This auxiliary agent not only has the function of propylene enhancing, and the effect that can also simultaneously play sulfur transfer additive removes the SOx in flue gas, and its addition is identical with the addition of independent promoter for more propylene, can reduce the dilution to major catalyst.
Above sulfur transferring assistant is all solid granular, requires to have the distribution of particles harmonious with catalytic cracking catalyst, mechanical strength and sphericity, and therefore this solid particle adds after system, and its ratio shared in system reserve can not be carried out flexible modulation.In actual applications, solid sulfur transferring assistant progressively exposes some shortcomings: FCC catalyst is had to diluting effect, affect the activity and selectivity of system balancing catalyst, affect product and distribute; Solid additive complicated process of preparation, cost is higher, and also inconvenient on using.
Chinese patent CN1258713 discloses a kind of sulfur transferring assistant for catalytic cracking of hydrocarbon and using method, solution, emulsion or the suspension of the oil-soluble that this auxiliary agent is comprised of metallic compound, solvent and helper component or water miscible molecule or colloid.This sulfur transferring assistant can be injected in reactor with catalytic cracking charging or water vapour, also can be injected into separately in reactor or regenerator.The weak point of this liquid phase sulfur transfer additive is that desulfurization degree is low, and addition is large, adds 2000ppm～14000ppm in catalytically cracked stock, can make flue gas SOx reduce 40%～70%, and there is no heavy metal-passivated function.
In catalytic cracking process, in feedstock oil, the heavy metal such as contained nickel, vanadium, copper, iron can be deposited on catalyst surface, causes catalyst poisoning inactivation and selective decline, thereby yield of light oil is declined, and hydrogen and coke yield rise.Industrial except raw material is carried out pretreatment demetalization, the means of generally taking to add passivator are carried out the character of equilibrium catalyst in improvement system, to adapt to the variation of the character of raw material.
Chinese patent CN1245198A discloses a kind of preparation method of catalytic cracking metal passivant of antimony containing compounds, in the method, with antimony oxide, organic acid, aliphatic amide and hydration, has become water-soluble metal passivator.Its shortcoming is that decomposition temperature is low, and poorly soluble in feedstock oil is dispersed bad.
In sum, hydrocarbon oil catalytic cracking sulphur of the prior art shifts co-catalyst and preparation thereof, exists following not enough:
1. sulfur transferring assistant is all solid granular, and requiring has the distribution of particles harmonious with catalytic cracking catalyst, mechanical strength and sphericity, and shared ratio can not be carried out flexible modulation in catalytic cracking catalyst.
2. solid granular sulfur transfer additive has diluting effect to FCC catalyst, affects the activity and selectivity of system balancing catalyst, affects product and distributes; Solid additive complicated process of preparation, cost is higher, and also inconvenient on using.
3. desulfurization degree is low, and addition is large, and there is no heavy metal-passivated function.
4. water-soluble metal passivator decomposition temperature is low, poorly soluble in feedstock oil, and dispersiveness is good not.
Summary of the invention
The object of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of, not only can remove preferably SO in regenerated flue gas
x, there is good heavy metal-passivated effect simultaneously; Add use flexibly, conveniently, dispersed superior hydrocarbon oil catalytic cracking sulphur transfer liquid co-catalyst.
The present invention also aims to provide the preparation method of the hydrocarbon oil catalytic cracking sulphur transfer liquid co-catalyst that a kind of preparation technology is simple, manufacturing cost is lower.
Object of the present invention can reach by following measure:
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, it is characterized in that by making according to the raw material of mass fraction meter as follows:
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, not only plays the function that regeneration flue gas sulphur shifts, and also has heavy metal-passivated, to improve product distribution effect.This agent can be annotated with catalytically cracked stock, contacts decomposition under FCC reaction condition with catalyst, and its active principle evenly adsorbs and is deposited on catalyst surface.Active principle can equally with the active principle of solid sulfur transfer agent play sulphur transferance like this, usings FCC catalyst as the carrier of liquid sulfur transferring assistant active principle simultaneously, thereby avoids the diluting effect of inert carrier to system catalyst.Solve the technical problem existing in prior art, completed task of the present invention.
Object of the present invention can also reach by following measure:
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, it is characterized in that by making according to the raw material of mass fraction meter as follows:
It is preferred technical scheme.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, and described IIA family metal is any one in Mg, Ca or Sr.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, and the oxide of described antimony is selected from antimony oxide, antimony pentoxide or their mixture.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, and described lanthanide metal compound is that lanthanide series metal is the inorganic salts of La or Ce.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, and described organic acid is selected from citric acid, acetic acid or the mixture of the two.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, and described surface active composition is selected from diethanol amine or triethanolamine..
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst, and described IIA family metal oxide is magnesia, and lanthanide metal compound is the carbonate of Ce, and surface active composition is triethanolamine.It is preferred technical scheme.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts the preparation method of co-catalyst, it is characterized in that comprising the steps:
1. the preparation of intermediate product A
According to drafting formula, the organic acid of part formula ratio and deionized water are dropped in reactor, be stirred to after dissolving completely, drop into the IIA family metal oxide of formula ratio, stirring reaction 0.5～3h at 50～90 ℃ of temperature, obtains supernatant liquid; Be down to after room temperature sedimentation completely, add lanthanide metal compound, control reactor temperature stirring reaction 0.5～2h at 50～90 ℃; After dissolving completely, add surface active composition again, mix, obtaining transparency liquid is intermediate product A.
2. the preparation of intermediate product B
The surface active composition of another part organic acid, deionized water and formula ratio after 1. step being fed intake according to formula drops in stirred tank, is heated with stirring to after dissolving completely, then adds the oxide of antimony to dissolving completely, and obtaining transparency liquid is intermediate product B.
3. mix
The mass mixings such as intermediate product B that 2. the intermediate product A that 1. step is prepared and step are prepared, obtain transparency liquid and are target product-hydrocarbon oil catalytic cracking sulphur transfer co-catalyst.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts the preparation method of co-catalyst, it is characterized in that described step 2. 3. the reaction temperature in be 5. 60 ℃.It is preferred technical scheme.
The preparation method of liquid sulfur transfer agent of the present invention is simple, does not produce the three wastes in preparation process, is a kind of environmental friendliness, efficient preparation method.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts the using method of co-catalyst, it is characterized in that hydrocarbon oil catalytic cracking sulphur shifts co-catalyst and enters catalytic cracking unit with catalytically cracked material hydrocarbon ils, collaborative with catalytic cracking catalyst, jointly brings into play catalytic action.
Hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst and preparation method thereof, can produce following good effect compared to existing technology:
1. provide a kind of and not only can remove preferably SO in regenerated flue gas
x, there is good heavy metal-passivated effect simultaneously; Add use flexibly, conveniently, dispersed superior hydrocarbon oil catalytic cracking sulphur transfer liquid co-catalyst.
2. provide a kind of preparation technology simple, in preparation process, do not produced the three wastes, the preparation method of the hydrocarbon oil catalytic cracking sulphur transfer liquid co-catalyst that manufacturing cost is lower.
3. in catalytically cracked material, add liquid sulfur transfer agent of the present invention 50～200ppm, can make SO in flue gas
2removal efficiency reaches 55%～87%,
4. can obviously improve product and distribute, yield of light oil increases more than 1 percentage point, the H in gained cracked gas
2/ CH
4significantly reduce, passivation effect is good.
Accompanying drawing explanation
Fig. 1 is that hydrocarbon oil catalytic cracking sulphur of the present invention shifts co-catalyst preparation technology schematic flow sheet
In figure:
1-deionized water 2-organic acid 3-IIA family metal oxide 4-lanthanide metal compound 5-surface active composition 6-organic acid 7-sb oxide
The specific embodiment
The present invention will now be further detailed embodiment:
(1) 100g acetic acid and 75g deionized water are put into reactor, be stirred to completely and add 25g magnesia stirring reaction 0.5h at 60 ℃ after dissolving, progressively dissolve, after complete reaction, obtain supernatant liquid; After cooling sedimentation, add 37.5g cerous carbonate, control reactor temperature stirring reaction 1h at 60 ℃, after dissolving completely, add again 12.5g triethanolamine, mix, obtain intermediate product A1.
(2) 70g deionized water and 75g citric acid and 30g triethanolamine are put into reactor heating and be stirred to completely and dissolve, then add 75g antimony oxide, continue to add thermal response to dissolving completely, obtain intermediate product B.A1 and B are mixed to get to S1.
(1) 112.5g acetic acid and 75g deionized water are put into reactor, be stirred to completely and add 12.5g magnesia stirring reaction 0.5h at 60 ℃ of temperature after dissolving, progressively dissolve, after complete reaction, obtain supernatant liquid; After cooling sedimentation, add 37.5g cerous carbonate, control reactor temperature stirring reaction 1h at 60 ℃, after dissolving completely, add again 12.5g triethanolamine, mix, obtain intermediate product A2.
(2) with embodiment 1(2) obtain S2.
(1) 112.5g acetic acid and 75g deionized water are put into reactor, be stirred to completely and add 25g magnesia stirring reaction 0.5h at 60 ℃ of temperature after dissolving, progressively dissolve, after complete reaction, obtain supernatant liquid; After cooling sedimentation, add 25g cerous carbonate, control reactor temperature stirring reaction 1h at 60 ℃, after dissolving completely, add again 12.5g triethanolamine, mix, obtain intermediate product A3.
(2) with embodiment 1(2) obtain S3.
(1) 125g acetic acid and 75g deionized water are put into reactor, be stirred to completely and add 12.5g magnesia stirring reaction 0.5h at 60 ℃ of temperature after dissolving, progressively dissolve, after complete reaction, obtain supernatant liquid; After cooling sedimentation, add 25g cerous carbonate, control reactor temperature stirring reaction 1h at 60 ℃, after dissolving completely, add again 12.5g triethanolamine, mix, obtain intermediate product A4.
(2) with embodiment 1(2) obtain S4.
(1) 112.5g acetic acid and 75g deionized water are put into reactor, be stirred to completely and add 15.5g magnesia stirring reaction 0.5h at 60 ℃ of temperature after dissolving, progressively dissolve, after complete reaction, obtain supernatant liquid; After cooling sedimentation, add 34.5g cerous carbonate, control reactor temperature stirring reaction 1h at 60 ℃, after dissolving completely, add again 12.5g triethanolamine, mix, obtain intermediate product A5.
(2) with embodiment 1(2) obtain S5.
The effect assessment of embodiment 1～5
On riser catalytic cracking evaluating apparatus, the liquid sulfur transfer agent S1～S5 of embodiment 1 to embodiment 5 preparation is carried out to flue gas desulfurization evaluation test and passivation test, investigate desulfurized effect and the passivation effect of liquid sulfur transfer agent.The sulfur content of fcc raw material is 1.5%, and oil ratio is 5.0, and catalyst inventory is 8Kg, and the dosage that adds of liquid sulfur transfer agent is respectively 50ppm, 100ppm, 150ppm and 200ppm(to fcc raw material).Wherein the SO2 content in flue gas adopts the on-line analysis of flue gas analyzer.Sulfur transfer additive represents with following formula the removal efficiency of smoke SO 2:
The character of fcc raw material is listed in table 1.
Table 1 fcc raw material character
The desulfurized effect of the sulfur transfer additive that embodiment 1～5 makes is listed in table 2～table 5.
Desulfurized effect when table 2 liquid sulfur transfer agent addition is 50ppm
| Sulfur transfer additive | Add dosage | SO
2Removal efficiency, |
| Embodiment | ||
| 1 | 50ppm | 61 |
| |
50ppm | 59 |
| |
50ppm | 56 |
| |
50ppm | 55 |
| |
50ppm | 63 |
Desulfurized effect when table 3 liquid sulfur transfer agent addition is 100ppm
| Sulfur transfer additive | Add dosage | SO
2Removal efficiency, |
| Embodiment | ||
| 1 | 100ppm | 69 |
| |
100ppm | 67 |
| |
100ppm | 64 |
| |
100ppm | 63 |
| |
100ppm | 71 |
Desulfurized effect when table 4 liquid sulfur transfer agent addition is 150ppm
| Sulfur transfer additive | Add dosage | SO
2Removal efficiency, |
| Embodiment | ||
| 1 | 150ppm | 75 |
| |
150ppm | 73 |
| |
150ppm | 70 |
| |
150ppm | 69 |
| |
150ppm | 79 |
Desulfurized effect when table 5 liquid sulfur transfer agent addition is 200ppm
| Sulfur transfer additive | Add dosage | SO
2Removal efficiency, |
| Embodiment | ||
| 1 | 200ppm | 82 |
| |
200ppm | 80 |
| |
200ppm | 77 |
| |
200ppm | 76 |
| |
200ppm | 85 |
By table 2～table 5, can be found out, the desulfurized effect of sulfur transfer additive is good.
Table 6 adds to be tested products obtained therefrom and distributes when dosage is 100ppm
| Project | Blank | S1 | S2 | S3 | S4 | S5 |
| Dry gas | 4.37 | 4.11 | 4.13 | 4.19 | 4.17 | 4.10 |
| Liquefied gas | 15.12 | 15.53 | 15.51 | 15.45 | 15.43 | 15.55 |
| Gasoline | 39.32 | 39.92 | 39.89 | 39.76 | 39.79 | 39.96 |
| Diesel oil | 25.16 | 25.57 | 25.61 | 25.51 | 25.49 | 25.58 |
| Heavy oil | 7.72 | 7.08 | 7.11 | 7.23 | 7.25 | 7.05 |
| Coke | 8.31 | 7.79 | 7.75 | 7.86 | 7.87 | 7.76 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Light oil | 64.48 | 65.49 | 65.50 | 65.27 | 65.28 | 65.54 |
| Total liquid is received | 79.60 | 81.02 | 81.01 | 80.72 | 80.71 | 81.09 |
| Conversion ratio | 92.28 | 92.92 | 92.89 | 92.77 | 92.75 | 92.95 |
Table 7 adds tests gained Composition of cracking gases when dosage is 100ppm
| | Blank | Embodiment | 1 | |
|
|
|
| H2 | 25.09 | 21.14 | 21.12 | 21.55 | 21.54 | 21.01 | |
| H2S | 1.57 | 2.01 | 2.03 | 1.99 | 2.01 | 2.04 | |
| Methane | 10.83 | 13.12 | 13.11 | 12.86 | 12.88 | 13.17 | |
| Ethane | 4.67 | 4.01 | 3.98 | 4.12 | 4.11 | 4.02 | |
| Ethene | 4.13 | 4.30 | 4.27 | 4.25 | 4.28 | 4.33 | |
| Propane | 6.87 | 6.75 | 6.73 | 6.77 | 6.79 | 6.65 | |
| Propylene | 20.85 | 22.27 | 22.31 | 22.18 | 22.16 | 22.35 | |
| Normal butane | 3.29 | 3.34 | 3.35 | 3.32 | 3.33 | 3.38 | |
| Iso-butane | 10.33 | 10.24 | 10.22 | 10.25 | 10.24 | 10.11 | |
| Butene-1+isobutene | 5.59 | 5.77 | 5.81 | 5.76 | 5.75 | 5.82 | |
| Anti-butylene | 2.68 | 2.83 | 2.81 | 2.79 | 2.78 | 2.81 |
| Maleic | 4.10 | 4.22 | 4.26 | 4.16 | 4.13 | 4.31 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 |
| H2/CH4 | 2.32 | 1.61 | 1.61 | 1.68 | 1.67 | 1.60 |
| C3＝/∑C3 | 0.75 | 0.77 | 0.77 | 0.77 | 0.77 | 0.77 |
| C4＝/∑C4 | 0.48 | 0.49 | 0.49 | 0.48 | 0.48 | 0.49 |
By table 6, table 7 can be found out, adds after the auxiliary agent of embodiment 1～5, and during product distributes, dry gas yield reduces, and liquefied gas, gasoline and diesel yield raise, and yield of light oil and total liquid are received and increased, and heavy oil yield and coke yield reduce; Gained gas composition hydrogen content reduces, and hydrogen methane, than reducing, illustrates that the auxiliary agent of embodiment 1～5 has heavy metal-passivated effect, and respond well.
Claims (11)
1. hydrocarbon oil catalytic cracking sulphur shifts a co-catalyst, it is characterized in that by making according to the raw material of mass fraction meter as follows:
2. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that by making according to the raw material of mass fraction meter as follows:
3. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that described IIA family metal is any one in Mg, Ca or Sr.
4. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that the oxide of described antimony is selected from antimony oxide, antimony pentoxide or their mixture.
5. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that described lanthanide metal compound is that lanthanide series metal is the inorganic salts of La or Ce.
6. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that described organic acid is selected from citric acid, acetic acid or the mixture of the two.
7. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that described surface active composition is selected from diethanol amine or triethanolamine..
8. according to the hydrocarbon oil catalytic cracking sulphur of claim 1, shift co-catalyst, it is characterized in that described IIA family metal oxide is magnesia, lanthanide metal compound is the carbonate of Ce, and surface active composition is triethanolamine.
9. the hydrocarbon oil catalytic cracking sulphur of claim 1 shifts the preparation method of co-catalyst, it is characterized in that comprising the steps:
1. the preparation of intermediate product A
According to drafting formula, the organic acid of part formula ratio and deionized water are dropped in reactor, be stirred to after dissolving completely, drop into the IIA family metal oxide of formula ratio, stirring reaction 0.5～3h at 50～90 ℃ of temperature, obtains supernatant liquid; Be down to after room temperature sedimentation completely, add lanthanide metal compound, control reactor temperature stirring reaction 0.5～2h at 50～90 ℃; After dissolving completely, add surface active composition again, mix, obtaining transparency liquid is intermediate product A.
2. the preparation of intermediate product B
The surface active composition of another part organic acid, deionized water and formula ratio after 1. step being fed intake according to formula drops in stirred tank, is heated with stirring to after dissolving completely, then adds the oxide of antimony to dissolving completely, and obtaining transparency liquid is intermediate product B.
3. mix
The mass mixings such as intermediate product B that 2. the intermediate product A that 1. step is prepared and step are prepared, obtain transparency liquid and are target product-hydrocarbon oil catalytic cracking sulphur transfer co-catalyst.
10. according to the hydrocarbon oil catalytic cracking sulphur of claim 9, shift the preparation method of co-catalyst, it is characterized in that described step 2. 3. the reaction temperature in be 5. 60 ℃.
The hydrocarbon oil catalytic cracking sulphur of 11. claims 1 shifts the using method of co-catalyst, it is characterized in that hydrocarbon oil catalytic cracking sulphur shifts co-catalyst and enters catalytic cracking unit with catalytically cracked material hydrocarbon ils, collaborative with catalytic cracking catalyst, jointly bring into play catalytic action.
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| CN105498831A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same |
| CN105582943A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN105582944A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105498831A (en) * | 2014-10-20 | 2016-04-20 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same |
| CN105582943A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN105582944A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method thereof as well as hydrocarbon oil desulfurizing method |
| CN105582943B (en) * | 2014-10-20 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105498831B (en) * | 2014-10-20 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN105582944B (en) * | 2014-10-20 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
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| CN103657729B (en) | 2015-10-21 |
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