CN1173011C - Desulfurizing catalyst for reducing content of sulfure in both gasoline and coke on catalyst - Google Patents
Desulfurizing catalyst for reducing content of sulfure in both gasoline and coke on catalyst Download PDFInfo
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- CN1173011C CN1173011C CNB011369701A CN01136970A CN1173011C CN 1173011 C CN1173011 C CN 1173011C CN B011369701 A CNB011369701 A CN B011369701A CN 01136970 A CN01136970 A CN 01136970A CN 1173011 C CN1173011 C CN 1173011C
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- gasoline
- coke
- sulphur content
- catalyzer
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Abstract
The present invention relates to a desulfurizing additive for simultaneously decreasing the sulfur content of gasoline and coke on catalysts. Zeolite materials are used as cracking and hydrogen transfer reaction active ingredients, composite or complex oxides formed from a plurality of kinds of metal oxides having the function for selectively absorbing sulfide are used as carriers for selectively absorbing the sulfide, and oxides of alkali metal or alkali earth metal are used as adjuvant for suppressing the condensation and the coke generation of the sulfide. The desulfurizing additive can selectively crack the sulfide in the gasoline and transform the sulfide into hydrocarbon and H2S, and can decreases the sulfur content of the coke deposited on the catalysts when simultaneously greatly decreasing the sulfur content of the gasoline by catalysis and cracking. Therefore, the sulfur emission of the tail gas of vehicles and smoke gas catalyzed and cracked by smelting plants is decreased, and the living environment of people is protected.
Description
The present invention relates to a kind of sweetening additive of sulphur content in the coke that can reduce simultaneously on gasoline and the catalyzer, it is a kind of novel sweetening additive that belongs to newly developed on refining of petroleum field and oil purification technology.This catalyzer is the sulfide in the pressure gasoline optionally, converts it into hydro carbons and H
2S, and can when reducing sulfur content of catalytic cracking gasoline significantly, reduce the sulphur content in the coke that is deposited on the catalyzer.
As everyone knows, gasoline is one of main products in the petroleum refining process.People have often taked the complete processing of many raising light-end products yields in order to obtain more light-end products from crude oil in the process in refining of petroleum, catalytic cracking is exactly one of main processing means, and catalytically cracked gasoline is exactly its main product.And the sulphur 90% in the gasoline (quality percentage composition, down together) is above from the catalytically cracked gasoline component, thereby the sulphur content of reduction catalytically cracked gasoline is to reduce the key of content of sulfur in gasoline.Though it is a kind of very effective sulfur method that catalytically cracked gasoline is carried out hydrogenation, the cost height of hydrogenation, the octane value of gasoline also can decrease because of alkene is saturated.Wormsbecher and Kim (U.S.Pat.No.5,525,210 and U.S.Pat.No.5,376,608) Fa Ming catalytically cracked gasoline sweetening additive can add in the catalytic cracking reaction process at any time, also can be prepared in the catalytic cracking catalyst, can play the effect of desulfurization.Though this additive can play the effect of desulfurization, absolute desulfurization amount is lower, and generally less than 300 μ g/g, and the sulphur content in the catalyst coke has increase to a certain degree.The hydrogenation ability of China refinery is lower, and most catalytically cracked materials are without hydrotreatment, and sulphur content is higher, the sulphur content height in the catalytically cracked gasoline of production, and the sulphur content of the catalytically cracked gasoline that has can be up to more than the 1500 μ g/g.The sulphur content that wants to close the high gasoline of sulphur drops to below China's new gasoline standard 800 μ g/g, and don't want the hydrogenation means that adopt cost high, a kind of novel sweetening additive of just essential searching, make it when reducing sulfur content of catalytic cracking gasoline, also to reduce the sulphur content in the coke that is deposited on the catalyzer.
Purpose of the present invention provides a kind of sweetening additive of sulphur content in the coke that can reduce simultaneously on gasoline and the catalyzer with regard to being to avoid above-mentioned the deficiencies in the prior art part.This additive is that the sulfide that fully takes into account in the catalytically cracked gasoline has mercaptan, thioether and thiophene-based material etc. in design, and it is in the majority with the thiophene-based material, and mercaptan, thioether can be on an acidic catalyst remove wherein sulphur through hydrogen transference, cracking reaction, its thiophene-based material is first cracking open loop on the B acid site of an acidic catalyst earlier then, generate the middle species of thio-alcohol, species pass through hydrogen transference, cracking reaction again in the middle of the thio-alcohol, and sulphur wherein changes into H
2S removes.So,, when design, at first must contain acid stronger component in the additive, as SAPO series zeolite, MCM series zeolite, ZSM-5, β zeolite, HY and USY etc. according to this principle.Additive also must have the function of selective absorption sulphide having certain acidity and hydrogen transfer activity simultaneously, so just can help the absorption and the conversion of sulfide, improves the desulfuration selectivity of additive.The stronger material of sulfide adsorptive power is comprised the oxide compound of Cu, Zn, Fe, Al, As, Hg, Ni, Zr, Sn, Ga and Ti etc. or the compound or complex oxide of being made up of these metal oxides.In addition, the condensation green coke for the sulfide that suppresses absorption promotes its cracking desulfurization, should add an amount of basic metal or alkaline earth metal oxide in additive.Method by comprehensive employing dipping and co-precipitation can make the sweetening additive of sulphur content in the coke that can reduce simultaneously on gasoline and the catalyzer of the present invention, and its concrete operation steps is:
(1) (quality) rare earth behind 60～200 ℃ of drying 5～10h, again at 200～700 ℃ of roasting 0.5～10h, makes rare earth be dispersed on the zeolite with the form of oxide compound down together to flood 0.1～30% on acid zeolite.
(2) one or more are had the soluble salt of metal of strong adsorptive power and the soluble salt of rare earth to sulfide and be dissolved in the distilled water, be mixed with concentration at 0.5～30% solution, the KOH with 0.1～15%, NaOH or NH
3H
20 the aqueous solution is made precipitation agent, in whipping process, be added drop-wise in the metal salt solution, to pH value be 7～9, metal-salt is changed into fully the precipitation of hydroxide of metal.
(3) zeolite that will flood rare earth fully stirs by 2～50% joining in the precipitation of being prepared into finished catalyst, and zeolite and throw out are mixed, and leaves standstill 5～10h then.
(4) after the throw out that will be mixed with zeolite stirs 10～60min once more, carry out suction filtration, and with an amount of distilled water wash 3～5 times.The gained filter cake is at 50～200 ℃ of drying 10～24h, and roasting 1～24h in 300～900 ℃ retort furnace pulverizes and sieves then.
(5) adopt the just wet method that is dipped into, in the salts solution that floods basic metal or alkaline-earth metal on the additive again (the amount on the additive of being impregnated in its oxide compound between 1～30%), again at 50～200 ℃ of drying 10～24h, roasting 1～24h in 300～900 ℃ retort furnace then.
(6) fine powder is removed in screening.Promptly prepared specific surface having selective adsorption, cracking sulfide, can reduce on the catalyzer gasoline catalyzing cracking sweetening additive of sulphur content in the coke simultaneously again at 50～400m2/g.
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail.
In actual design and preparation, the inventor adopts above-mentioned operation steps and method, makes the additive of function of the present invention:
1. take by weighing USY zeolite 19.6g, fully grind to form behind the fine powder standby.
2. get each 300mL of nitrate solution that salic, zirconium white and zinc oxide are respectively 0.1g/mL, 0.05g/mL and 0.1g/mL respectively, after admixed together, USY is joined in this mixed solution, then under continuous stirring condition, the ammonia soln of dropping 15% changes into precipitation of hydroxide with each metal in the solution.Leave standstill 6h.
3. use 100mL distilled water wash 5 times in the filtration procedure, to remove the NH in the precipitation as far as possible
4 +And NO
3 -Filter cake is dry 20h in 150 ℃ baking oven, again roasting 10h in 750 ℃ retort furnace.The particle of 0.078～0.18mm is pulverized, sieved out to the additive that obtains.
4. adopt the just wet method that is dipped into, dipping contains the Ca (NO that CaO is 0.1g/mL repeatedly
3)
2Solution, to the content of CaO be 8%, then will 100 ℃ of dried additives in retort furnace at 750 ℃ of roasting 6h.Sieve removes fine powder, has promptly obtained the additive that will prepare.
Use the sweetening additive of sulphur content in the coke that to reduce simultaneously on gasoline and the catalyzer of the present invention, experimental result on fixed fluidized bed catalytic cracking evaluating apparatus shows, the additive of preparation has the effect of excellent reduction content of sulfur in gasoline, can significantly reduce the sulphur content on the carbon deposited catalyst simultaneously again.Under temperature of reaction and agent-oil ratio are respectively 500 ℃ and 5 condition, use pure catalytic cracking poiser, the sulphur content of the gasoline of generation is 1300 μ g/g, the sulphur content on the catalyzer is 120 μ g/g; And other condition is constant, and behind the additive of interpolation 10% preparation, catalytic cracking production distributes constant, and the sulphur content of the gasoline of generation and the sulphur content on the catalyzer have been reduced to 890 μ g/g and 88 μ g/g respectively, have reduced by 32% and 27% respectively.The absolute range of decrease of content of sulfur in gasoline has surpassed 400 μ g/g.As seen, the additive sweetening effectiveness of preparation is very remarkable.
Institute of the present invention development of new catalytically cracked gasoline sweetening additive, it is the sulfide in the pressure gasoline optionally both, converts it into hydro carbons and H
2S can reduce the sulphur content in the coke that is deposited on the catalyzer again, thereby reduce the quantity discharged of vehicle exhaust and plant catalytic cracking flue gas sulphur when reducing sulfur content of catalytic cracking gasoline significantly, protect our living environment.
Claims (3)
1. can reduce on gasoline and the catalyzer sweetening additive of sulphur content in the coke simultaneously, it mainly is by having more highly acid zeolitic material, basic metal or alkaline earth metal oxide and metal oxide composition with function of selective absorption sulphide, it is characterized in that zeolite with β, the zeolitic material of HY or USY is as cracking and hydrogen transfer reaction activity component, Cu with function with selective absorption sulphide, Zn, Fe, the carrier that the metal of Al or As or one or more the formed complex oxides in the nonmetal oxide are selective absorption sulphide, with Mg, Ca, the basic metal of Sr or Ba or alkaline earth metal oxide are for suppressing the auxiliary agent of sulfide condensation green coke, and the mass percent of its each component is:
Zeolitic material: 19.06%
Metal or nonmetal oxide: 72.93%
Basic metal or alkaline earth metal oxide: 8.01%
2. according to claim 1ly can reduce on gasoline and the catalyzer sweetening additive of sulphur content in the coke simultaneously, it is characterized in that described zeolitic material is SAPO zeolite, MCM zeolite or ZSM-5 molecular sieve.
3. one kind prepares and can reduce on gasoline and the catalyzer processing method of the sweetening additive of sulphur content in the coke simultaneously, the method that it is characterized in that its preparation is comprehensively to have adopted pickling process and coprecipitation method, its measure unit is mass percent, and its concrete preparation process is:
(1) on acid zeolite, floods 0.1～30% rare earth, 60～200 ℃ of dryings 5～10
After hour, 200～700 ℃ of roastings 0.5～10 hour, make rare earth again with oxide compound
Form be dispersed on the zeolite;
(2) one or more had Cu, Zn, Fe, the Al of the function of selective absorption sulphide
Or the soluble salt of the soluble salt of the metal of As or nonmetal oxide and rare earth is dissolved in
Can reduce on gasoline and the catalyzer sweetening additive of sulphur content in the coke simultaneously
The present invention relates to a kind of sweetening additive of sulphur content in the coke that can reduce simultaneously on gasoline and the catalyzer, it is a kind of novel sweetening additive that belongs to newly developed on refining of petroleum field and oil purification technology.This catalyzer is the sulfide in the pressure gasoline optionally, converts it into hydro carbons and H
2S, and can when reducing sulfur content of catalytic cracking gasoline significantly, reduce the sulphur content in the coke that is deposited on the catalyzer.
As everyone knows, gasoline is one of main products in the petroleum refining process.People have often taked the complete processing of many raising light-end products yields in order to obtain more light-end products from crude oil in the process in refining of petroleum, catalytic cracking is exactly one of main processing means, and catalytically cracked gasoline is exactly its main product.And the sulphur 90% in the gasoline (quality percentage composition, down together) is above from the catalytically cracked gasoline component, thereby the sulphur content of reduction catalytically cracked gasoline is to reduce the key of content of sulfur in gasoline.Though it is a kind of very effective sulfur method that catalytically cracked gasoline is carried out hydrogenation, the cost height of hydrogenation, the octane value of gasoline also can decrease because of alkene is saturated.Wormsbecher and Kim (U.S.Pat.No.5,525,210 and U.S.Pat.No.5,376,608) Fa Ming catalytically cracked gasoline sweetening additive can add in the catalytic cracking reaction process at any time, also can be prepared in the catalytic cracking catalyst, can play the effect of desulfurization.Though this additive can play the effect of desulfurization, absolute desulfurization amount is lower, and generally less than 300 μ g/g, and the sulphur content in the catalyst coke has increase to a certain degree.The hydrogenation ability of China refinery is lower, and most catalytically cracked materials are without hydrotreatment, and sulphur content is higher, the sulphur content height in the catalytically cracked gasoline of production, and the sulphur content of the catalytically cracked gasoline that has can be up to more than the 1500 μ g/g.The sulphur content that wants the gasoline that sulfur-bearing is high drops to below China's new gasoline standard 800 μ g/g, and don't wants the hydrogenation means that adopt cost high, just essentially seeks a kind of novel sweetening additive, makes it
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011369701A CN1173011C (en) | 2001-12-27 | 2001-12-27 | Desulfurizing catalyst for reducing content of sulfure in both gasoline and coke on catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011369701A CN1173011C (en) | 2001-12-27 | 2001-12-27 | Desulfurizing catalyst for reducing content of sulfure in both gasoline and coke on catalyst |
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|---|---|
| CN1356379A CN1356379A (en) | 2002-07-03 |
| CN1173011C true CN1173011C (en) | 2004-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011369701A Expired - Fee Related CN1173011C (en) | 2001-12-27 | 2001-12-27 | Desulfurizing catalyst for reducing content of sulfure in both gasoline and coke on catalyst |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433820B (en) * | 2007-11-15 | 2011-11-30 | 中国石油化工股份有限公司 | Sorbent for reducing sulfide in hydrocarbon oils |
| CN101434855B (en) * | 2007-11-15 | 2013-06-05 | 中国石油化工股份有限公司 | Sorbent for reducing sulfide in light hydrocarbon oil |
| CN101433817B (en) * | 2007-11-15 | 2012-05-09 | 中国石油化工股份有限公司 | Desulphurization sorbent |
| CN101966470B (en) * | 2010-09-25 | 2012-06-13 | 东华大学 | Rare-earth desulfurization catalyst and preparation method thereof |
| CN104129774B (en) * | 2014-05-29 | 2016-08-24 | 山东宇佳新材料有限公司 | Behavior of High-sulfur Petroleum Coke chemical desulfurization calcining comprehensive utilization process |
| CN108212168A (en) * | 2016-12-22 | 2018-06-29 | 中国石油天然气股份有限公司 | A kind of Hydrobon catalyst of modification and preparation method and application |
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2001
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Granted publication date: 20041027 Termination date: 20201227 |