CN103657729B - hydrocarbon oil catalytic cracking sulphur transfer co-catalyst and preparation method thereof - Google Patents
hydrocarbon oil catalytic cracking sulphur transfer co-catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention is a kind of hydrocarbon oil catalytic cracking sulphur transfer co-catalyst and preparation method thereof.Belong to the catalyst promoter comprising metal or metal oxide or hydroxide.Be made up of the following raw material according to mass fraction meter: IIA family metal oxide 2 ~ 5, the oxide 10 ~ 20 of antimony, lanthanide metal compound 5 ~ 8, organic acid 25 ~ 45, surface active composition 6 ~ 12, deionized water 20 ~ 40.Provide one and not only can remove SO in regenerated flue gas preferably
x, there is good heavy metal-passivated effect simultaneously; Add use flexibly, conveniently, dispersed superior hydrocarbon oil catalytic cracking sulphur transfer liquid co-catalyst and preparation method thereof.In catalytically cracked material, add liquid sulfur transfer agent of the present invention 50 ~ 200ppm, SO in flue gas can be made
2removal efficiency reaches 55% ~ 87%, the H in gained cracked gas
2/ CH
4remarkable reduction, passivation effect is good.Enter catalytic cracking unit with catalytically cracked material hydrocarbon ils, work in coordination with catalytic cracking catalyst, jointly play catalytic action.
Description
Technical field
The present invention is a kind of hydrocarbon oil catalytic cracking sulphur transfer co-catalyst and preparation method thereof.Belong to the catalyst promoter comprising metal or metal oxide or hydroxide.
Background technology
Hydrocarbon oil catalytic cracking is one of main secondary operations device producing petrol and diesel oil contour use value light oil.Along with in the raising of high sulfur bauxite amount and catalytic cracking unit charging, the ratio of residual oil and mink cell focus constantly increases, and makes 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).Because catalysis method takes off SO
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 mixed with catalytic cracking catalyst by sulfur transfer additive, and in regenerator, sulfur transfer additive active component and SOx react and generate metal sulfate, and in riser reactor, at H
2, under the reducing atmosphere such as hydrocarbon gas, sulfate is reduced, discharge hydrogen sulfide and enter 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---playing oxidation respectively in reaction continuous process---.
The preparation of sulfur transfer additive is based on metal oxide at first, as adopted alkali metal, the oxide of alkaline-earth metal, aluminium oxide and their mixture as sulfur transfer additive, is that accelerating oxidation ability is by CeO afterwards
2introducing, for improving reducing degree, the transition metals such as V, Fe, Co, Cr, Cu being introduced.
Chinese patent CN1883794A discloses a kind of regeneration fume from catalytic cracking high-performance sulfur transfer agent and preparation method thereof, with iron, magnesium and aluminium for active component, take copper as auxiliary agent, obtain iron magnesia-alumina hydrotalcite by coprecipitation, adopt infusion process to obtain copper-iron magnesia-alumina hydrotalcite again, be prepared into sulfur transfer additive through roasting.
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 simultaneously can also playing 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 the distribution of particles harmonious with catalytic cracking catalyst, mechanical strength and sphericity, and after therefore this solid particle adds system, its ratio shared in system reserve can not carry out flexible modulation.In actual applications, solid sulfur transferring assistant progressively exposes some shortcomings: have diluting effect to FCC catalyst, and the activity and selectivity of influential system equilibrium catalyst, affects product slates; 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, the solution of the oil-soluble that this auxiliary agent is made up of metallic compound, solvent and helper component or water miscible molecule or colloid, emulsion or suspension.This sulfur transferring assistant can be injected in reactor with catalytic cracking feeds 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, in catalytically cracked stock, add 2000ppm ~ 14000ppm, flue gas SOx can be made to reduce 40% ~ 70%, and do not have heavy metal-passivated function.
In catalytic cracking process, the heavy metal such as nickel, vanadium, copper, iron contained in feedstock oil can be deposited on catalyst surface, causes catalyst poisoning inactivation and selective decline, thus yield of light oil is declined, and hydrogen and coke yield rise.Industrial except carrying out except pretreatment demetalization to raw material, generally take the means adding passivator to carry out the character of equilibrium catalyst in improvement system, to adapt to the change of the character of raw material.
Chinese patent CN1245198A discloses a kind of preparation method of catalytic cracking metal passivant of antimony containing compounds, has become water-soluble metal passivator in the method with antimony oxide, organic acid, aliphatic amide and hydration.Its shortcoming is that decomposition temperature is low, poorly soluble in feedstock oil, dispersed bad.
In sum, hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the prior art and preparation thereof, exist following not enough:
1. sulfur transferring assistant is all solid granular, requires the distribution of particles harmonious with catalytic cracking catalyst, mechanical strength and sphericity, and ratio shared in catalytic cracking catalyst can not carry out flexible modulation.
2. solid granular sulfur transfer additive has diluting effect to FCC catalyst, and the activity and selectivity of influential system equilibrium catalyst, affects product slates; Solid additive complicated process of preparation, cost is higher, and also inconvenient on using.
3. desulfurization degree is low, and addition is large, and does not have 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 one not only can remove SO in regenerated flue gas preferably
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 be reached by following measure:
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, is characterized in that being made up of the following raw material according to mass fraction meter:
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, not only plays the function of regeneration flue gas sulphur transfer, also has effect that is heavy metal-passivated, that improve product slates.This agent can be annotated with catalytically cracked stock, decomposes under FCC reaction condition with catalyst exposure, and its active principle uniform adsorption is also deposited on catalyst surface.Such active principle equally with the active principle of solid sulfur transfer agent can play sulphur transferance, the carrier simultaneously using FCC catalyst as liquid sulfur transferring assistant active principle, thus avoids inert carrier to the diluting effect of system catalyst.Solve the technical problem existed in prior art, complete task of the present invention.
Object of the present invention can also be reached by following measure:
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, is characterized in that being made up of the following raw material according to mass fraction meter:
It is preferred technical scheme.
Hydrocarbon oil catalytic cracking sulphur of the present invention transfer co-catalyst, described IIA race metal is any one in Mg, Ca or Sr.
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, the oxide of described antimony is selected from antimony oxide, antimony pentoxide or their mixture.
Hydrocarbon oil catalytic cracking sulphur of the present invention transfer co-catalyst, the inorganic salts of described lanthanide metal compound to be lanthanide series metal be La or Ce.
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, described organic acid is selected from citric acid, acetic acid or the mixture of the two.
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, described surface active composition is selected from diethanol amine or triethanolamine..
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, 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.
The preparation method of hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, is characterized in that comprising the steps:
1. the preparation of intermediate product A
The organic acid of part formulation amount and deionized water are dropped in reactor according to drafting formula, be stirred to after dissolving completely, drop into the IIA family metal oxide of formula ratio, at 50 ~ 90 DEG C of temperature, stirring reaction 0.5 ~ 3h, obtains supernatant liquid; Be down to room temperature and after sedimentation completely, add lanthanide metal compound, controlling reactor temperature stirring reaction 0.5 ~ 2h at 50 ~ 90 DEG C; Add surface active composition again after dissolving completely, 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 step 1. being fed intake according to formula drops in stirred tank, is heated with stirring to after dissolving completely, then the oxide adding antimony extremely dissolves completely, and obtaining transparency liquid is intermediate product B.
3. mix
The mass mixings such as the intermediate product B that 2. intermediate product A step 1. prepared and step are prepared, obtain transparency liquid and are target product-hydrocarbon oil catalytic cracking sulphur transfer co-catalyst.
The preparation method of hydrocarbon oil catalytic cracking sulphur of the present invention transfer co-catalyst, it is characterized in that described step 2. 3. 5. in reaction temperature be 60 DEG C.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, efficiently preparation method.
The using method of hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention, is characterized in that hydrocarbon oil catalytic cracking sulphur transfer co-catalyst enters catalytic cracking unit with catalytically cracked material hydrocarbon ils, works in coordination with, jointly play catalytic action with catalytic cracking catalyst.
Hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of the present invention and preparation method thereof, can produce following good effect compared to existing technology:
1. provide one and not only can remove SO in regenerated flue gas preferably
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, do not produce the three wastes in preparation process, 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, SO in flue gas can be made
2removal efficiency reaches 55% ~ 87%,
4. obviously can improve product slates, yield of light oil increases by more than 1 percentage point, the H in gained cracked gas
2/ CH
4remarkable reduction, passivation effect is good.
Accompanying drawing explanation
Fig. 1 is hydrocarbon oil catalytic cracking sulphur of the present invention transfer 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
Detailed description of the invention
The present invention will now be further detailed embodiment:
Embodiment 1
(1) 100g acetic acid and 75g deionized water are put into reactor, be stirred to after dissolving completely and add 25g magnesia stirring reaction 0.5h at 60 DEG C, progressively dissolve, after complete reaction, obtain supernatant liquid; Add 37.5g cerous carbonate after cooling sedimentation, control reactor temperature stirring reaction 1h at 60 DEG C, after dissolving completely, add 12.5g triethanolamine again, mix, obtain intermediate product A1.
(2) 70g deionized water and 75g citric acid and 30g triethanolamine are put into reactor to heat to be stirred to and dissolve completely, then add 75g antimony oxide, continuing to add thermal response to dissolving completely, obtaining intermediate product B.A1 and B is mixed to get S1.
Embodiment 2
(1) 112.5g acetic acid and 75g deionized water are put into reactor, be stirred to after dissolving completely and add 12.5g magnesia stirring reaction 0.5h at 60 DEG C of temperature, progressively dissolve, after complete reaction, obtain supernatant liquid; Add 37.5g cerous carbonate after cooling sedimentation, control reactor temperature stirring reaction 1h at 60 DEG C, after dissolving completely, add 12.5g triethanolamine again, mix, obtain intermediate product A2.
(2) with embodiment 1(2) obtain S2.
Embodiment 3
(1) 112.5g acetic acid and 75g deionized water are put into reactor, be stirred to after dissolving completely and add 25g magnesia stirring reaction 0.5h at 60 DEG C of temperature, progressively dissolve, after complete reaction, obtain supernatant liquid; Add 25g cerous carbonate after cooling sedimentation, control reactor temperature stirring reaction 1h at 60 DEG C, after dissolving completely, add 12.5g triethanolamine again, mix, obtain intermediate product A3.
(2) with embodiment 1(2) obtain S3.
Embodiment 4
(1) 125g acetic acid and 75g deionized water are put into reactor, be stirred to after dissolving completely and add 12.5g magnesia stirring reaction 0.5h at 60 DEG C of temperature, progressively dissolve, after complete reaction, obtain supernatant liquid; Add 25g cerous carbonate after cooling sedimentation, control reactor temperature stirring reaction 1h at 60 DEG C, after dissolving completely, add 12.5g triethanolamine again, mix, obtain intermediate product A4.
(2) with embodiment 1(2) obtain S4.
Embodiment 5
(1) 112.5g acetic acid and 75g deionized water are put into reactor, be stirred to after dissolving completely and add 15.5g magnesia stirring reaction 0.5h at 60 DEG C of temperature, progressively dissolve, after complete reaction, obtain supernatant liquid; Add 34.5g cerous carbonate after cooling sedimentation, control reactor temperature stirring reaction 1h at 60 DEG C, after dissolving completely, add 12.5g triethanolamine again, mix, obtain intermediate product A5.
(2) with embodiment 1(2) obtain S5.
The effect assessment of embodiment 1 ~ 5
Liquid sulfur transfer agent S1 ~ S5 that riser catalytic cracking evaluating apparatus is prepared embodiment 1 to embodiment 5 carries out flue gas desulfurization evaluation test and passivation test, investigates 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).SO2 content wherein in flue gas adopts the on-line analysis of flue gas analyzer.The removal efficiency of sulfur transfer additive to smoke SO 2 represents with following formula:
The character of fcc raw material lists in table 1.
Table 1 fcc raw material character
The desulfurized effect of the sulfur transfer additive that embodiment 1 ~ 5 is obtained lists 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 |
| Embodiment 2 | 50ppm | 59 |
| Embodiment 3 | 50ppm | 56 |
| Embodiment 4 | 50ppm | 55 |
| Embodiment 5 | 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 |
| Embodiment 2 | 100ppm | 67 |
| Embodiment 3 | 100ppm | 64 |
| Embodiment 4 | 100ppm | 63 |
| Embodiment 5 | 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 |
| Embodiment 2 | 150ppm | 73 |
| Embodiment 3 | 150ppm | 70 |
| Embodiment 4 | 150ppm | 69 |
| Embodiment 5 | 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 |
| Embodiment 2 | 200ppm | 80 |
| Embodiment 3 | 200ppm | 77 |
| Embodiment 4 | 200ppm | 76 |
| Embodiment 5 | 200ppm | 85 |
As can be seen from table 2 ~ table 5, the desulfurized effect of sulfur transfer additive is good.
Table 6 adds when dosage is 100ppm tests products obtained therefrom distribution
| 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 yield | 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 when dosage is 100ppm tests gained cracked gas composition
| Project | Blank | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| 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, after adding the auxiliary agent of embodiment 1 ~ 5, in product slates, dry gas yield reduces, and liquefied gas, gasoline and diesel yield raise, and yield of light oil and total liquid yield increase, 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 (5)
1. a hydrocarbon oil catalytic cracking sulphur transfer co-catalyst, is characterized in that being made up of the following raw material according to mass fraction meter:
Wherein:
1.. described II A race metal is any one in Mg, Ca or Sr;
2.. the oxide of described antimony is selected from antimony oxide, antimony pentoxide or their mixture;
3.. described lanthanide metal compound is the inorganic salts of lanthanide series metal La or Ce;
4.. described organic acid is selected from citric acid, acetic acid or the mixture of the two;
5.. described surface active composition is selected from diethanol amine or triethanolamine;
The preparation method of described hydrocarbon oil catalytic cracking sulphur transfer co-catalyst, comprises the steps:
1. the preparation of intermediate product A
The organic acid of part formulation amount and deionized water are dropped in reactor according to drafting formula, be stirred to after dissolving completely, drop into II A family metal oxide of formula ratio, at 50 ~ 90 DEG C of temperature, stirring reaction 0.5 ~ 3h, obtains supernatant liquid; Be down to room temperature and after sedimentation completely, add lanthanide metal compound, controlling reactor temperature stirring reaction 0.5 ~ 2h at 50 ~ 90 DEG C; Add surface active composition again after dissolving completely, 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 step 1. being fed intake according to formula drops in stirred tank, is heated with stirring to after dissolving completely, then the oxide adding antimony extremely dissolves completely, and obtaining transparency liquid is intermediate product B;
3. mix
The mass mixings such as the intermediate product B that 2. intermediate product A step 1. prepared and step are prepared, obtain transparency liquid and are target product-hydrocarbon oil catalytic cracking sulphur transfer co-catalyst.
2. hydrocarbon oil catalytic cracking sulphur transfer co-catalyst according to claim 1, is characterized in that being made up of the following raw material according to mass fraction meter:
3. hydrocarbon oil catalytic cracking sulphur transfer co-catalyst according to claim 1, it is characterized in that described II A family metal oxide is magnesia, lanthanide metal compound is the carbonate of Ce, and surface active composition is triethanolamine.
4. hydrocarbon oil catalytic cracking sulphur transfer co-catalyst according to claim 1, is characterized in that the preparation method of described hydrocarbon oil catalytic cracking sulphur transfer co-catalyst, comprises the steps:
1. the preparation of intermediate product A
The organic acid of part formulation amount and deionized water are dropped in reactor according to drafting formula, be stirred to after dissolving completely, drop into II A family metal oxide of formula ratio, at 60 DEG C of temperature, stirring reaction 0.5 ~ 3h, obtains supernatant liquid; Be down to room temperature and after sedimentation completely, add lanthanide metal compound, controlling reactor temperature stirring reaction 0.5 ~ 2h at 60 DEG C; Add surface active composition again after dissolving completely, 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 step 1. being fed intake according to formula drops in stirred tank, is heated with stirring to after dissolving completely, then the oxide adding antimony extremely dissolves completely, and obtaining transparency liquid is intermediate product B;
3. mix
The mass mixings such as the intermediate product B that 2. intermediate product A step 1. prepared and step are prepared, obtain transparency liquid and are target product-hydrocarbon oil catalytic cracking sulphur transfer co-catalyst.
5. the using method of the hydrocarbon oil catalytic cracking sulphur transfer co-catalyst of claim 1, it is characterized in that hydrocarbon oil catalytic cracking sulphur transfer co-catalyst enters catalytic cracking unit with catalytically cracked material hydrocarbon ils, work in coordination with catalytic cracking catalyst, jointly play catalytic action.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245198A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for preparing metallic passivator containing antimony compound for catalytic cracking |
| CN1258713A (en) * | 1998-12-29 | 2000-07-05 | 中国石油化工集团公司 | Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage |
| CN1383909A (en) * | 2001-04-27 | 2002-12-11 | 中国石化集团齐鲁石油化工公司 | Catalytically cracking fume purifying agent |
| CN1485132A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and and the preparation thereof |
| WO2005097817A2 (en) * | 2004-04-05 | 2005-10-20 | Alnylam Pharmaceuticals, Inc. | Process and reagents for oligonucleotide synthesis and purification |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245198A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for preparing metallic passivator containing antimony compound for catalytic cracking |
| CN1258713A (en) * | 1998-12-29 | 2000-07-05 | 中国石油化工集团公司 | Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage |
| CN1383909A (en) * | 2001-04-27 | 2002-12-11 | 中国石化集团齐鲁石油化工公司 | Catalytically cracking fume purifying agent |
| CN1485132A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and and the preparation thereof |
| WO2005097817A2 (en) * | 2004-04-05 | 2005-10-20 | Alnylam Pharmaceuticals, Inc. | Process and reagents for oligonucleotide synthesis and purification |
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