CN1542087A - Method for reducing sulfur content of catalytic cracking product - Google Patents

Abstract

The method of reducing sulfur content in catalytically cracked product includes the contact of sulfur containing petroleum material with one kind of cracking catalyst comprising vanadium containing component, molecular sieve and alkali metal component with molar ratio between vanadium and alkali earth metal of 1/60 to 10, or the contact of sulfur containing petroleum material with the mixture of the said catalyst and catalytically cracking catalyst under the condition of cracking. Compared with available technology, the method of the present invention has even higher desulfurizing capacity and heavy oil converting capacity.

Description

A kind of method that reduces sulphur content of catalytic cracking production

Technical field

The invention relates to a kind of cracking method of hydrocarbon ils, more particularly, is the method that reduces sulphur content of catalytic cracking production about a kind of.

Background technology

In recent years, for the consideration of environmental protection, worldwide, the requirement of oil fuel standard is improved constantly.With China is example, and State Quality Supervision Bureau had formulated " motor spirit objectionable impurities control criterion " in 1999, and according to the requirement of this standard, the sulphur content of gasoline product should be less than 800ppm.In fact, the sulphur of gasoline product more than 90% comes from FCC gasoline, and on the other hand, the proportion of middle-eastern crude in the shared crude oil in Chinese refinery with higher sulfur content is increasing, and therefore, the sulphur content that reduces in the FCC gasoline is most important to producing clean gasoline.

At present, can be by stock oil be carried out the hydrogenation pre-treatment, or FCC gasoline carried out making with extra care behind the hydrogenation reach the purpose that reduces the FCC sulfur in gasoline.Yet these two kinds of method investments are big, and the process cost height also can cause the loss of gasoline octane rating.

In the FCC riser tube, by the method for catalytic cracking, it is the most attractive technological approaches economically that the sulphur original position is removed.For reaching this purpose, need in catalytic cracking process, add promotor with desulfurizing function, perhaps use the cracking catalyst that has desulfurizing function, contains the desulfurization component.

US6,036,847 and patent families EP0,798,362A2 discloses a kind of fluidized catalytic cracking of hydrocarbons method, wherein, and under the condition of described hydrocarbon feed hydrogenation outside not existing, a zone of cracking by cracking, and all particles that comprise granules of catalyst wherein, contain another particle constantly in cracking hydrocarbon district and a catalyst regeneration zones circulation in all particles, this particle has the activity of the cracking hydrocarbon ils lower than granules of catalyst, and described activity is benchmark with the fresh granules.This particle is made up of the inorganic oxide of titanium oxide and a kind of non-oxide titanium basically.The inorganic oxide of described non-oxide titanium contains a kind of Lewis acid, this Lewis acid is selected from following element and compound composition thereof one group: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and germanium, described Lewis acid loads on the aluminum oxide.Because use this auxiliary agent that contains titanium oxide, crackate FCC sulfur in gasoline content is reduced.

US5,376,608 disclose a kind of cracking catalyst composition with desulfidation, said composition contains (A) and is dispersed in zeolite/molecular sieve in a kind of inorganic oxide matrix, (b) contain the alumina component of Lewis acid, this alumina component contains the Lewis acid of 1-50 weight %, and described Lewis acid is selected to load on and contains nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and the element of gallium and a group of oxide compound on the aluminum oxide.

WO 99/49001A1 discloses a kind of composition that reduces sulphur content in the hydrocarbon component, and said composition contains a kind of houghite (hydrotalcite) material, and this material can also contain a kind of FCC catalyzer with a kind of Lewis acid dipping in the said composition.Described Lewis acid comprises transition metal, particularly the element of zinc, copper, nickel, cobalt, iron and manganese and compound.

WO 01/21733A1 discloses a kind of in the presence of heat regeneration cracking catalyst, contains the catalyst cracking method of organosulfur compound hydrocarbon raw material, and described catalyzer contains a kind of component that reduces The product sulfur, this component contains a kind of oxidation state greater than zero metal component, and described metal component comprises the 3rd cycle of the periodic table of elements, VB family, VIIB family, VIII family, IIB family, the metallic compound of IVA family or complex compound, as vanadium, zinc, iron, cobalt, the metallic compound of manganese and gallium or complex compound.The component of described reduction The product sulfur comprises that pore structure contains the molecular sieve of above-mentioned metal component, also comprises being dispersed in the support of the catalyst optional position, as the above-mentioned metal component in the porous oxide carrier.

WO 01/21732A1 discloses a kind of method that reduces sulphur content in the cracking petroleum fraction, this method is included in the temperature of raising and a kind of cracking catalyst and a kind of catalyzer that reduces the product sulphur content and exists down, with the petroleum fractions catalytic cracking, obtain having liquid crackate than low sulfur content.Wherein, the catalyzer of described reduction product sulphur content contains a kind of non-molecular sieve carrier of vanadium that contains, and described non-molecular sieve carrier can be the organic or inorganic carrier, preferred carrier is amorphous or the para-crystal inorganic oxide, as aluminum oxide, silicon oxide, clay or their mixture.

CN1281887A discloses a kind of method that reduces catalytic cracking gasoline cut sulphur content, and this method is included in high temperature and the product desulfurization catalyst exists down, catalytic cracking gasoline feedstock fraction, the liquid cracked product of preparation low sulfur content.This desulfurization catalyst contains the porous molecular screen that metal ingredient is contained in a kind of cavernous structure inside.Described porous molecular screen can be a large pore zeolite, and promptly orifice diameter is at least the zeolite of 0.7 nanometer, as y-type zeolite, rare earth Y type zeolite (REY), ultrastable Y (USY), L zeolite, Beta zeolite, mordenite, ZSM-18 zeolite.Described molecular sieve also can be a mesopore zeolite, be orifice diameter for greater than 0.56 zeolite, as Pentasil zeolite, ZSM-5 zeolite, ZSM-22, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite less than 0.7 nanometer.Described molecular sieve can also be a non-zeolite molecular sieve, as the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate.Titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), gallium germanate (gallogermanates) and their combination.

CN1261618A discloses a kind of sulfur method of catalytic cracking gasoline cut, this method is included under the existence of high temperature, cracking catalyst and product desulfurization catalyst, to contain the petroleum cut catalytic cracking of organosulfur compound, produce the liquid crackate of low sulfur content.Described product desulfurization catalyst contains a kind of porous molecular screen, this molecular sieve contains first metal component and second metal component, first metal component is positioned at Molecular Sieve Pore inside and oxidation state greater than zero, and second metal component comprises at least a rare earth element that is positioned at Molecular Sieve Pore inside.Described first kind of metal component is selected from periodic table of elements period 4 and IIB, VB, IIIA, the metal, particularly vanadium of VIII family, zinc, iron, gallium.

In the prior art, be one of the best way with the method that contains vanadium cracking catalyst reduction sulphur content of catalytic cracking production.Yet, in the aging and regenerative process of catalyzer, need under high temperature and moisture vapor condition, handle the catalyst mixture that contains the vanadium cracking catalyst or contain vanadium cracking catalyst and catalytic cracking catalyst.Under this condition, contain vanadium compound contained in the vanadium cracking catalyst and easily form the liquid vanadic acid, on the one hand, liquid vanadic acid meeting outflow catalyst or catalyst mixture, cause the loss of vanadium, make the desulphurizing activated reduction of catalyzer or catalyst mixture, on the other hand, the liquid vanadic acid can be moved to catalytic cracking catalyst and/or be contained in the duct of the contained molecular sieve of vanadium cracking catalyst, corrode the skeleton of molecular sieve, make the skeleton avalanche of molecular sieve, thereby the desulphurizing activated and cracking activity of catalyzer is reduced.Therefore, use the sweetening power and the heavy oil conversion performance of method of the reduction crackate sulphur content of this catalyzer all to have much room for improvement.

Summary of the invention

The objective of the invention is to overcome prior art sweetening power and the not high shortcoming of heavy oil conversion performance, a kind of method of the reduction sulphur content of catalytic cracking production with higher sweetening power and heavy oil conversion performance newly is provided, particularly reduces the method for sulfur content of catalytic cracking gasoline.

As previously mentioned, to containing the vanadium cracking catalyst or containing in the aging and regenerative process of catalyst mixture of vanadium cracking catalyst, contain vanadium component contained in the vanadium cracking catalyst and easily form the liquid vanadic acid.Thereby the desulfurization and the cracking activity of the catalyst mixture that contains the vanadium cracking catalyst or contain the vanadium cracking catalyst have been reduced.If in containing the vanadium cracking catalyst, add a kind of component that vanadium forms the liquid vanadic acid that suppresses, can obviously improve the desulphurizing activated and cracking activity of catalyzer and/or catalyst mixture.The present inventor finds, the component that alkaline-earth metal comes to this.

Method provided by the invention is included under the cracking conditions, the sulfur-bearing oil raw material is contacted with a kind of catalyzer, reclaim the catalytic cracking production that sulphur content reduces, wherein, described catalyzer is a kind of cracking catalyst that contains vanadium and molecular sieve, or contain this and contain the cracking catalyst of vanadium and molecular sieve and the catalyst mixture of catalytic cracking catalyst, the described cracking catalyst that contains vanadium and molecular sieve contains vanadium component and molecular sieve and a kind of alkaline earth metal component, and the mol ratio of vanadium and alkaline earth metal component is 10: 1-1: 60.

Compared with prior art, method provided by the invention has higher sweetening power and heavy oil cracking ability.

For example, adopt method provided by the invention, with containing rare earth exchanged Y zeolite 30 weight %, al binder (in aluminum oxide) 28 weight %, inorganic oxide (kaolin+Al ₂O ₃) 37.68 weight %, the vanadium component is (with V ₂O ₅Meter) 3 weight %, magnesium component (in MgO) 1.32 weight % through 800 ℃, the aging catalyzer that contains vanadium and molecular sieve of the present invention after 8 hours of 100% water vapour is 500 ℃ in temperature of reaction, liquid hourly space velocity is 20 hours ^-1, agent-oil ratio is under 3.0 the condition, to be 1.39 weight % to sulphur content, boiling range is that 294-572 ℃ the residual oil and the mixing oil of decompressed wax oil carry out catalytic cracking, sulphur content in the gasoline product that obtains has only 231ppm, and transformation efficiency is up to 68.8 weight %, and yield of gasoline is up to 49.7 weight %.And adopt rare earth exchanged Y zeolite, content of vanadium identical, the not magniferous existing cracking catalyst that contains vanadium and molecular sieve, under similarity condition, same stock oil is carried out catalytic cracking, sulphur content in the gasoline product that obtains is up to 825ppm, transformation efficiency has only 43.6 weight %, and yield of gasoline has only 32.8 weight %.

Embodiment

According to method provided by the invention, in the described cracking catalyst that contains vanadium and molecular sieve, described vanadium components contents is with existing to contain vanadium cracking catalyst content of vanadium scope identical.In general, with V ₂O ₅Meter, the vanadium components contents is 0.1-25 weight %, is preferably 0.2-10 weight %.Vanadium and alkali-metal mol ratio are 10: 1-1: 60, be preferably 4: 1-1: 40.

Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, preferably magnesium and/or calcium.The content of described molecular sieve is 10-99.6 weight %, is preferably 10-80 weight %.

The molecular sieve that contains in the cracking catalyst of vanadium and molecular sieve can be a large pore zeolite, and mesopore zeolite and/or non-zeolite molecular sieve, these molecular sieves have been done to describe in detail in CN1281887A.As, described large pore zeolite refers to that its pore structure ring opening is at least the zeolite of 0.7 nanometer, it can be selected from y-type zeolite, rare earth Y type zeolite (REY), baked rare earth Y type zeolite CREY, ultrastable Y (USY), the L zeolite, Beta zeolite, mordenite, in the ZSM-18 zeolite one or more, be preferably y-type zeolite, rare earth Y type zeolite, baked rare earth Y type zeolite, ultrastable Y, one or more in the Beta zeolite.Described mesopore zeolite refers to the zeolite of its cavernous structure opening in the 0.56-0.70 nanometer, it can be selected from ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more, preferred ZSM-5 zeolite.Described non-zeolite molecular sieve be selected from have the Different Silicon aluminum ratio silicate (as metal silicate metallosilicate, titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integratedsilicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more are preferably the SAPO-11 molecular sieve.

The cracking catalyst that contains vanadium and molecular sieve in the method provided by the invention can only contain molecular sieve, and vanadium component and alkaline earth metal component also can contain any component that does not influence or improve catalyst desulfurizing activity provided by the invention and/or cracking activity.In addition, the cracking catalyst that contains vanadium and molecular sieve can also optionally contain following component: (1) al binder, its content is the conventional content of al binder in the cracking catalyst, in general, total amount with the cracking catalyst that contains vanadium and molecular sieve is a benchmark, in aluminum oxide, the content of al binder is 0-80 weight %, is preferably 5-60 weight %; (2) inorganic oxide matrix is a benchmark with the cracking catalyst total amount that contains vanadium and molecular sieve, and the content of inorganic oxide matrix is 0-80 weight %, is preferably 10-70 weight %; This inorganic oxide matrix is selected from cracking catalyst inorganic oxide matrix commonly used, preferred aluminum oxide, silicon oxide, amorphous aluminum silicide, one or more in the clay; Described clay is selected from cracking catalyst clay commonly used, as being selected from kaolin, halloysite, polynite, diatomite, tired in the soil one or more, the preferred kaolin of taking off; (3) additional metals component, this additional metals component is selected from one or more in IIIA family metal in the periodic table of elements, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except that vanadium, as in gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal one or more.Wherein, lanthanide series metal is selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more, the norium of preferred lanthanum, cerium, lanthanum rich norium or rich cerium.With the cracking catalyst total amount that contains vanadium and molecular sieve is benchmark, and in oxide compound, described additional metals components contents is 0-20 weight %, is preferably 0-10 weight %.

In the described cracking catalyst that contains vanadium and molecular sieve, vanadium, alkaline-earth metal, IIIA family metal, IVA family metal, IIB family metal, IVB family metal, the VB family metal components such as metal, group vib metal, VIII family metal and rare earth metal except that vanadium, can be with its all cpds separately, as the state existence of oxide compound, salt.Also can form the compound that contains above-mentioned metal component more than two kinds between each metal component, as by inference, may form vanadic acid magnesium between vanadium and the alkaline-earth metal, vanadic acid magnesium not only can make vanadium fill part its desulfidation of performance but also can make the vanadium component can not form the liquid vanadic acid, avoided the erosion of vanadic acid, the cracking activity of catalyzer is improved and has kept framework of molecular sieve.

In the described cracking catalyst that contains vanadium and molecular sieve, vanadium, alkaline-earth metal, IIIA family metal, IVA family metal, IIB family metal, IVB family metal, the VB family metal components such as metal, group vib metal, VIII family metal and rare earth metal except that vanadium may reside in the pore passage structure inside of molecular sieve, the outside surface of molecular sieve, also can there be inorganic oxide matrix, in aluminum oxide, silicon oxide, amorphous aluminum silicide and/or clay, can also be present in simultaneously in the outside surface and inorganic oxide matrix of molecular sieve structure inside, molecular sieve.Under the preferable case, above-mentioned metal component is present in the inorganic oxide matrix of the described cracking catalyst that contains vanadium and molecular sieve.In the present invention, contain if described additional metals component is a zeolite itself, its content does not calculate separately, count in the lump in the content of zeolite, in example of the present invention, contained rare earth in the rare earth exchanged Y zeolite, do not calculate separately, calculate in the lump in the mode of rare earth exchanged Y zeolite.

According to first embodiment preferred of the present invention, the described cracking catalyst that contains vanadium and molecular sieve contains molecular sieve and vanadium component, wherein, also contain alkaline earth metal component, contain or do not contain al binder, contain or do not contain inorganic oxide matrix, with the cracking catalyst total amount that contains vanadium and molecular sieve is benchmark, and the content of molecular sieve is 10-99.6 weight %, is preferably 10-80 weight %, in aluminum oxide, the content of al binder is 0-80 weight %, is preferably 5-60 weight %, and the content of inorganic oxide matrix is 0-80 weight %, be preferably 10-70 weight %, with V ₂O ₅Meter, the vanadium components contents is 0.1-25 weight %, is preferably 0.2-10 weight %, and in oxide compound, the content of alkaline-earth metal is 0.05-65 weight %, is preferably 0.1-50 weight %, and the mol ratio of vanadium and alkaline-earth metal is 10: 1-1: 60, preferred 4: 1-1: 40.Under the preferable case, affiliated alkaline-earth metal is magnesium and/or calcium, and affiliated inorganic oxide matrix is selected from aluminum oxide, silicon oxide, one or more in amorphous aluminum silicide and the clay.In described vanadium component and alkaline earth metal component existence and the inorganic oxide matrix.

According to second embodiment preferred of the present invention, the described cracking catalyst of vanadium and molecular sieve that contains is except that the component that contains above-mentioned first preferred version, also contain a kind of additional metals component, this additional metals component is selected from IIIA family metal in the periodic table of elements, IVA family metal, IIB family metal, IVB family metal, the metal of VB family except that vanadium, the group vib metal, in VIII family metal and the rare earth metal one or more are as gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, in the lanthanide rare metal one or more.Wherein, lanthanide series metal is selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more, the norium of preferred lanthanum, cerium, lanthanum rich norium or rich cerium.With the described cracking catalyst total amount that contains vanadium and molecular sieve is benchmark, and in oxide compound, described additional metals components contents is 0-20 weight %, is preferably 0-10 weight %.These metal components preferably are present in the inorganic oxide matrix.

The described cracking catalyst that contains vanadium and molecular sieve can adopt following method preparation: introduce vanadium component and alkaline earth metal component in the precursor of molecular sieve and/or inorganic oxide matrix and/or inorganic oxide matrix, the product that dry also roasting obtains.The molecular sieve that contains vanadium component and alkaline earth metal component that obtains can directly be used as the described cracking catalyst that contains vanadium and molecular sieve.Also the molecular sieve that contains vanadium component and alkaline earth metal component that obtains can be mixed making beating with the precursor and the deionized water of al binder, drying obtains the described cracking catalyst that contains vanadium and molecular sieve.The molecular sieve that contains vanadium component and alkaline earth metal component that perhaps will obtain mixes making beating with the precursor of the precursor of al binder and inorganic oxide matrix and/or inorganic oxide matrix, and drying obtains the described cracking catalyst that contains vanadium and molecular sieve.The inorganic oxide matrix that contains vanadium component and alkaline earth metal component that perhaps will obtain and/or its precursor are mixed making beating with molecular sieve, al binder and deionized water, and drying obtains the described cracking catalyst that contains vanadium and molecular sieve.The molecular sieve that contains vanadium component and alkaline earth metal component that perhaps will obtain mixes making beating with the precursor and the deionized water of the precursor of al binder, the inorganic oxide matrix that contains vanadium component and alkaline earth metal component and/or inorganic oxide matrix, drying obtains the described cracking catalyst that contains vanadium and molecular sieve.

The precursor of described al binder is selected from pseudo-boehmite and/or aluminium colloidal sol.Described inorganic oxide matrix has been made detailed description in front, its precursor refers in containing the cracking catalyst preparation process of vanadium and molecular sieve, the material of described inorganic oxide matrix can be formed, pseudo-boehmite and/or aluminium colloidal sol can be selected from as the precursor of aluminum oxide; The precursor of silicon oxide can be selected from silicon sol, one or more in silicon gel and the water glass, and the precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of silicon sol and aluminium colloidal sol, one or more in the silica-alumina gel.

In the preparation method of the described cracking catalyst that contains vanadium and molecular sieve, molecular sieve and/or inorganic oxide matrix and/or and precursor in introduce the method for vanadium component, can adopt existing the whole bag of tricks, as adopting the method that the vanadium compound aqueous solution and molecular sieve are carried out ion-exchange, can adopt method with vanadium compound impregnated zeolite and/or inorganic oxide matrix, can adopt the vanadium-containing compound and/or the vanadium-containing compound aqueous solution are mixed with molecular sieve and/or heat-resistant inorganic oxide matrix, grind or abrasive method not, can adopt sedimentary method that the vanadium in the vanadium compound aqueous solution is deposited to method on molecular sieve and/or the inorganic oxide matrix, also can adopt the vanadium compound aqueous solution is mixed with molecular sieve and/or inorganic oxide, make the method for colloidal sol then.

The method of introducing alkaline earth metal component in molecular sieve and/or inorganic oxide matrix and/or its precursor is identical with the method for introducing the vanadium component, and alkaline earth metal component can be before the vanadium introducing, carry out afterwards, also can carry out simultaneously.Introduce drying temperature after vanadium component and/or the alkaline earth metal component and can be room temperature to 400 ℃, be preferably 100-200 ℃, the temperature of roasting is 400-1200 ℃, is preferably 600-900 ℃, and roasting time is 0.5-100 hour, preferred 1-10 hour.

The solid content of the slurries that making beating forms is generally 10-50 weight %, is preferably 15-30 weight %.Drying conditions after the making beating is a drying conditions commonly used in the catalytic cracking catalyst preparation process.In general, drying temperature is 100-350 ℃, is preferably 200-300 ℃.Described drying can be used oven dry, forced air drying or spray-dired method, the method for preferably spray drying.

If contain one or more the additional metals component that also contains in the cracking catalyst of vanadium and molecular sieve in IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except that vanadium, can any step in above-mentioned preparation process introduce above-mentioned additional metals component, preferably before introducing vanadium component and alkaline earth metal component, simultaneously or after introducing vanadium component and alkaline earth metal component, before the making beating, introduce above-mentioned additional metals component, dry and roasting.The method of introducing is identical with the introducing alkaline earth metal component with introducing vanadium component, just replaces vanadium component and alkaline earth metal component to get final product with described additional metals component composition, and drying is also identical with the condition of roasting.

When introducing metal except that vanadium of vanadium, alkaline-earth metal, IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family, group vib metal, VIII family metal and rare earth metal, employed compound is selected from one or more in above-mentioned the metal component water-soluble and/or water-insoluble compound separately.For example, the compound of vanadium can be selected from the soluble salt of vanadium, the vitriol of vanadium (Vanadosulfuric acid particularly, vanadylic sulfate), the water-soluble organic compounds (as vanadium oxalate, alkanoic acid vanadium, naphthenic acid vanadium) of halogenide, vanadium, one or more in the vanadate (as ammonium vanadate) of the metavanadate of basic metal or ammonium (as ammonium meta-vanadate), basic metal or ammonium.Alkaline earth metal compound can be selected from the water-soluble cpds of alkaline-earth metal, as the nitrate (particularly magnesium nitrate, nitrocalcite) of alkaline-earth metal, in the halogenide (particularly magnesium chloride, calcium chloride) one or more.Alkaline earth metal compound also can be selected from the water-insoluble compound of alkaline-earth metal, as the oxide compound of alkaline-earth metal, the oxyhydroxide of alkaline-earth metal, in the carbonate of alkaline-earth metal one or more, the water-insoluble compound of alkaline-earth metal use when using sol method to introduce alkaline-earth metal usually.The compound of IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except that vanadium can be selected from its water-soluble cpds separately, as in the nitrate of gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, rare earth metal and muriate, water-soluble molybdate, water-soluble tungstate, the water-soluble metatungstate one or more.The compound of IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except that vanadium also can be selected from its water-insoluble compound, as the oxide compound of gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, rare earth metal and in the oxyhydroxide one or more.

Described catalytic cracking catalyst comprises existing various cracking catalyst, these cracking catalyst are conventionally known to one of skill in the art, as contain y-type zeolite, overstable gamma zeolite, rare earth exchanged Y zeolite, ZSM-5 zeolite, the Beta zeolite, in the mordenite one or more contain or do not contain al binder, contain or do not contain the cracking catalyst of inorganic oxide matrix, do not give unnecessary details one by one here.

In the mixture of described cracking catalyst that contains vanadium and molecular sieve and cracking catalyst, the described content of cracking catalyst in catalyst mixture that contains vanadium and molecular sieve is arbitrarily.The described cracking catalyst that contains vanadium and molecular sieve is high more, and under same reaction conditions, the effect that reduces sulphur content in the crackate is good more.Sulphur content in the stock oil is high more, and the content of cracking catalyst that contains vanadium and molecular sieve in the described catalyzer is high more.Under the preferable case, in the described catalyst mixture, contain the content at least 0.1 weight % of the cracking catalyst of vanadium and molecular sieve, be preferably at least 1 weight %, more preferably at least 3 weight %, preferably at least 5 weight %.

Can also contain the auxiliary agent that contains usually in other cracking methods in the mixture of described cracking catalyst that contains vanadium and molecular sieve and existing cracking catalyst, as ignition dope, sulfur transfer additive, in the octane enhancing additive one or more, the composition of these auxiliary agents, character and add-on are conventionally known to one of skill in the art, do not repeat them here.

Described cracking conditions is conventionally known to one of skill in the art, comprises that in general temperature of reaction is 400-600 ℃, is preferably 450-550 ℃, weight hourly space velocity 5-30 hour ^-1, be preferably 8-25 hour ^-1, agent-oil ratio 1-10, preferred 2-7.Agent-oil ratio refers to the weight ratio of catalyzer and stock oil.

The described sulfur-bearing oil raw material of method provided by the invention refers to contain the various catalytically cracked stock of organic and/or inorganic sulfur, as the long residuum of sulfur-bearing, vacuum residuum, decompressed wax oil, normal pressure wax oil, straight-run gas oil, propane light/heavy one or more in de-oiling and the wax tailings.Sulphur content in the described sulfur-bearing oil raw material in elementary sulfur, is 0.3-2.2 weight %, and wherein sulphur content is that the sulfur-bearing oil raw material of 0.5-2.0 weight % is the most common.

The following examples will the invention will be further described.

Example 1

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

(lattice constant is 24.6 dusts with 529.4 rare earth exchanged Y zeolites that restrain, sodium oxide content 1.5 weight %, rare earth oxide content 18.9 weight %, lanthanum trioxide content 7.0 weight % wherein, cerium oxide content 10.4 weight %, other rare earth oxide contents 1.5 weight %, solid content 85 weight %, the Zhou village catalyst plant is produced), 64.3 gram ammonium meta-vanadate (NH ₄VO ₃, chemical pure, the Beijing Chemical Plant produces), 1850 gram anhydrous nitric acid magnesium (Mg (NO ₃) ₂, chemical pure, the Beijing Chemical Plant produces) and 834.2 restrain deionized waters and mix, under 150 ℃ temperature, dry, again 750 ℃ of roastings 1 hour, only contained the cracking catalyst C1 that contains vanadium and molecular sieve of molecular sieve, vanadium component and alkaline earth metal component.The composition of C1 is listed among the table 2-1.The cracking catalyst that contains vanadium and molecular sieve is formed and to be got by calculating, and is benchmark with the gross weight of the cracking catalyst that contains vanadium and molecular sieve all.

Example 2

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

(1) (solid content is 61 weight % with 5 kilograms of pseudo-boehmites, Shandong Aluminum Plant produces), 1.1 kilogram ammonium meta-vanadate (specification is with example 1), 1.39 kilogram anhydrous nitric acid magnesium (specification is with example 1) and deionized water mix for 15 kilograms, obtain the slurries that solid content is 15 weight %, the aqueous hydrochloric acid that under agitation to add 0.549 kilogram of concentration be 31 volume %, continue to stir, up to forming uniform sol, with the colloidal sol spraying drying under 280 ℃ temperature that obtains, 800 ℃ of roastings 1 hour, obtain containing the inorganic oxide matrix VA1 of vanadium component and alkaline earth metal component, inorganic oxide matrix described here is an aluminum oxide.The composition of VA1 is listed among the table 1-1.

(2) the inorganic oxide matrix VA1 that contains vanadium component and alkaline earth metal component that (1) is obtained, rare earth exchanged Y zeolite (specification is with example 1), pseudo-boehmite (specification is with (1) in this example) mix by 15: 30: 55 butt weight ratio, adding deionized water mixes, the solid content that makes slurries is 15 weight %, spraying drying under 280 ℃ temperature obtains average particulate diameter and is 68 microns the cracking catalyst C2 that contains vanadium and molecular sieve.Table 2-1 has provided the composition of C2.

Example 3

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

The inorganic oxide matrix VA1 that contains vanadium component and alkaline earth metal component that (1) in the example 2 is obtained, rare earth exchanged Y zeolite (specification is with example 1), pseudo-boehmite (specification is with example 2), (solid content is 76 weight % to kaolin, Suzhou kaolin company produces) by 15: 30: 28: 27 butt weight ratio is mixed, adding deionized water mixes, the solid content that makes slurries is 25 weight %, spraying drying under 280 ℃ temperature obtains average particulate diameter and is 70 microns the cracking catalyst C3 that contains vanadium and molecular sieve.Table 2-1 has provided the composition of C3.

Comparative Examples 1

The existing vanadium containing catalysts of this Comparative Examples explanation.

(1) 5 kilograms of pseudo-boehmites (specification is with example 2) and 0.98 kilogram of ammonium meta-vanadate and deionized water are mixed for 15 kilograms, the aqueous hydrochloric acid that under agitation to add 0.549 kilogram of concentration be 31 volume % continues to stir until making mixture form uniform colloid.The colloid that obtains 280 ℃ of following spraying dryings, 800 ℃ of following roastings 1 hour, is obtained containing vanadium component inorganic oxide matrix VAB1, and inorganic oxide matrix described here is an aluminum oxide, and the composition of VAB1 is listed among the table 1-1.

(2) method by example 3 prepares catalyzer, different just contain the inorganic oxide matrix VA1 that contains vanadium component and alkaline components that (1) obtains in the vanadium component inorganic oxide matrix VAB1 replacement example 2, obtain average particulate diameter and be 70 microns reference catalyst CB1 with what (1) in this Comparative Examples obtained.The composition of CB1 is listed among the table 2-1.

Example 4

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

(1) method by (1) in the example 2 prepares the inorganic oxide matrix that contains vanadium component and alkaline earth metal component, different is with silicon sol (solid content 25 weight %, produce in upright sail chemical plant, Qingdao) the replacement pseudo-boehmite, the consumption of silicon sol is 12.2 kilograms, the consumption of ammonium meta-vanadate is 1.1 kilograms, the consumption of anhydrous nitric acid magnesium is 1.39 kilograms, 0.25 kilogram of aqueous nitric acid with concentration 69 weight % replaces aqueous hydrochloric acid, obtain containing the inorganic oxide matrix VA2 of vanadium component and alkaline components, inorganic oxide matrix described here is a silicon oxide.The composition of VA2 is listed among the table 1-1.

(2) method by example 3 prepares catalyzer, different is to replace VA1 with VA2, VA2, rare earth exchanged Y zeolite, pseudo-boehmite and kaolinic butt weight ratio are 15: 30: 28: 27, obtain average particulate diameter and be 71 microns the cracking catalyst C4 that contains vanadium and molecular sieve.The composition of C4 is listed among the table 2-1.

Example 5-6

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

(1) method by (1) in the example 2 prepares the inorganic oxide matrix that contains vanadium component and alkaline earth metal component, different is replaces anhydrous nitric acid magnesium with 2.32 kilograms of anhydrous nitric acid calcium or with the mixture of 1.39 kilograms of anhydrous nitric acid magnesium and 0.78 kilogram of anhydrous nitric acid calcium respectively, pseudo-boehmite (specification is with example 1) consumption is used 4.31 kilograms and 4.56 kilograms respectively simultaneously, must contain the inorganic oxide matrix VA3 and the VA4 of vanadium component and alkaline earth metal component, inorganic oxide matrix described here is aluminum oxide.The composition of VA3 and VA4 is listed among the table 1-1.

(2) method by example 3 prepares catalyzer, different is to replace VA1 with VA3 and VA4 respectively, (lattice constant is 24.35 dusts to use overstable gamma zeolite respectively, sodium oxide is 0.5 weight %, the Zhou village catalyst plant is produced) or the mixture of above-mentioned overstable gamma zeolite and ZSM-5 zeolite (weight ratio of overstable gamma zeolite and ZSM-5 zeolite is 8: 1, the sodium oxide content of ZSM-5 zeolite is weight 0.1 weight %, and silica alumina ratio is 30, and the Zhou village catalyst plant is produced) the replacement rare earth exchanged Y zeolite; VA3, overstable gamma zeolite, pseudo-boehmite and kaolinic butt weight ratio are 10: 25: 15: 50; VA4, overstable gamma zeolite, ZSM-5 zeolite, pseudo-boehmite and kaolinic butt weight ratio are 7.5: 40: 5: 32.5: 15.Obtain average particulate diameter provided by the invention and be the catalyzer C5 and the C6 of 72 microns and 69 microns.The composition of C5 and C6 is listed among the table 2-1.Obtain average particulate diameter and be the cracking catalyst C5 that contains vanadium and molecular sieve and the C6 of 72 microns and 69 microns.The composition of C5 and C6 is listed among the table 2-1.

Example 7

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof

Method by example 3 prepares catalyzer, different is to replace VA1 with VA3, and (lattice constant is 24.56 dusts with the hydrogen Y zeolite, sodium oxide is 0.5 weight %, Zhou village catalyst plant product) mixture (weight ratio of hydrogen Y zeolite and rare earth exchanged Y zeolite is 1: 1 in the mixture) with rare earth exchanged Y zeolite (specification is with example 1) replaces rare earth exchanged Y zeolite, VA3, rare earth exchanged Y zeolite, hydrogen Y zeolite, pseudo-boehmite, kaolinic butt weight ratio are 5: 20: 20: 20: 35, obtain average particulate diameter and be 71 microns the cracking catalyst C7 that contains vanadium and molecular sieve.The composition of C7 is listed among the table 2-1.

Example 8

This example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

Method by example 3 prepares catalyzer, be not both and replace VA1 with VA4, and (sodium oxide is 0.05 weight % with rare earth exchanged Y zeolite (specification is with example 1) and Beta zeolite, silica alumina ratio is 25, Beijing Research Institute of Petro-Chemical Engineering product) mixture replaces rare earth exchanged Y zeolite, VA4, rare earth exchanged Y zeolite, Beta zeolite, pseudo-boehmite, kaolinic butt weight ratio are 12.5: 15: 5: 35: 32.5, obtain average particulate diameter and be 68 microns the cracking catalyst C8 that contains vanadium and molecular sieve.The composition of C8 is listed among the table 2-1.

Example 9-14

Following example illustrates used cracking catalyst that contains vanadium and molecular sieve of method provided by the invention and preparation method thereof.

(1) method by (1) in the example 2 prepares the inorganic oxide matrix that contains vanadium and alkaline earth metal component, and difference is respectively:

1), in the mixture of pseudo-boehmite, ammonium meta-vanadate, anhydrous nitric acid magnesium and deionized water, also added 0.59 kilogram anhydrous nitric acid zinc (chemical pure, Beijing Chemical Plant produce), pseudo-boehmite (specification is with example 1) consumption is 4.58 kilograms.

2), in the mixture of pseudo-boehmite, ammonium meta-vanadate, anhydrous nitric acid magnesium and deionized water, 6.27 kilograms of suspension liquids that also added rare-earth hydroxide, contain rare earth oxide 25 weight % in this suspension liquid, wherein lanthanum trioxide accounts for 23 weight % of rare earth oxide, cerium oxide accounts for 67 weight % of rare earth oxide, and other rare earth oxides account for 10 weight % of rare earth oxide.This suspension liquid is in oxide compound, contains rare earth chloride (RECl ₃, RE ₂O ₃Content is greater than 45 weight %, and Gansu Rare Earth Co. produces) add 2.1 kilograms of strong aquas, the suspension liquid that the rare earth ion precipitation is formed in the 4.26 kg of water solution of 36.73 weight %; Ammonium meta-vanadate (specification is with example 1) consumption is 1.53 kilograms, and anhydrous nitric acid magnesium (specification is with example 1) consumption is 0.48 kilogram.

3), in the mixture of pseudo-boehmite, ammonium meta-vanadate, anhydrous nitric acid magnesium and deionized water, also having added concentration is the zirconium oxychloride (ZrO of 2.0 mol ₂Content is greater than 35 weight %, and brilliant Anhua, Jiangxi worker company limited produces) 2.82 liters and 0.314 kilogram Calcium Chloride Powder Anhydrous of the aqueous solution; Pseudo-boehmite (specification is with example 1) consumption is 3.60 kilograms.

4) in the mixture of pseudo-boehmite, ammonium meta-vanadate, anhydrous nitric acid magnesium and deionized water, also added concentration and be 3.44 liters of iron(ic) chloride (chemical pure, the Beijing Chemical Plant produces) aqueous solution of 2.0 mol; Ammonium meta-vanadate (specification is with example 1) consumption is 1.46 kilograms, and anhydrous nitric acid magnesium (specification is with example 1) consumption is 2.78 kilograms.

5), in the mixture of pseudo-boehmite, ammonium meta-vanadate, anhydrous nitric acid magnesium and deionized water, also added concentration and be 3.13 liters of gallium chloride (chemical pure is produced) aqueous solution of 2 mol; Pseudo-boehmite (specification is with example 1) consumption is 4.03 kilograms.

6), in the mixture of pseudo-boehmite, ammonium meta-vanadate, anhydrous nitric acid magnesium and deionized water, also added 0.48 kilogram of kaolin; Pseudo-boehmite (specification is with example 1) consumption is 4.40 kilograms, obtains containing the inorganic oxide matrix VA5 of vanadium component and alkaline earth metal component, VA6, VA7, VA8, VA9, VA10.The composition of VA5-VA10 is listed among the table 1-2.

(2) method by example 3 prepares catalyzer, and different is to use VA5 respectively, VA6, and VA7, VA8, VA9, VA10 replaces VA1, obtains containing the cracking catalyst C9-C14 of vanadium and molecular sieve.The average particulate diameter of catalyzer C9-C14 is respectively 70,69,72,74,68,70 microns.The composition of catalyzer C9-C14 is listed among the table 2-2.

Table 1-1

Example number	????2	Comparative Examples 1	??4	??5	??6
						Contain vanadium component inorganic oxide matrix numbering	????VA1	??VAB1	??VA2	??VA3	??VA4
The vanadium component concentration, weight % is (with V 2O 5) meter	????20	??20	??20	??20	??20
						The magnesium component concentration, weight % (in MgO)	????8.8	??-	??8.8	??-	??8.8
The calcium component concentration, weight % (in CaO)	????-	??-	??-	??18.5	??6.2
						The kind of inorganic oxide matrix	????Al 2O 3	??Al 2O 3	??SiO 2	??Al 2O 3	??Al 2O 3
The content of inorganic oxide matrix, weight %	????71.2	??80	??71.2	??61.5	??65.0
						The mol ratio of vanadium and alkaline-earth metal	????1∶1	??1∶1	??1∶1	??2∶3	??2∶3

</entry></row></tbody></tgroup></table></tables>

Table 2-1

Example number	1	??2	??3	Comparative Examples 1	??4	??5	??6	??7	??8
										The catalyzer numbering	C1	??C2	??C3	??CB1	??C4	??C5	??C6	??C7	??C8
The molecular sieve kind	Rare Earth Y	Rare Earth Y	Rare Earth Y	Rare Earth Y	Rare Earth Y	Super steady Y	Super steady Y+ZSM-5	Rare Earth Y+hydrogen Y	Rare Earth Y+Beta
										Molecular sieve content, weight %	45	??30	??30	??30	??30	??25	??45	??40	??20
The content of al binder, weight % is (with Al 2O 3Meter)	-	??55	??28	??55	??28	??15	??32.5	??20	??35
										The inorganic oxide matrix kind		??Al 2O 3	??Al 2O 3+ kaolin	??Al 2O 3+ kaolin	??Al 2O 3+ kaolin	??Al 2O 3+ kaolin	??Al 2O 3+ kaolin	??Al 2O 3+ kaolin	??Al 2O 3+ kaolin
Inorganic oxide matrix content, weight %		??10.68	??37.68	??12	??37.68	??56.15	??19.88	??38.07	??40.62
										The vanadium component concentration, weight % is (with V 2O 5Meter)	5	??3	??3	??3	??3	??2	??1.5	??1.0	??2.5
The alkaline earth metal component kind	Mg	??Mg	??Mg	??-	??Mg	??Ca	??Mg+Ca	??Ca	??Mg+Ca
										Alkaline earth metal component content, weight % (in oxide compound)	50	??1.32	??1.32	??0	??1.32	??1.85	??1.12	??0.93	??1.88
The mol ratio of vanadium and alkaline-earth metal	1∶23	??1∶1	??1∶1	??-	??1∶1	??2∶3	??2∶3	??2∶3	??2∶3

</entry></row></tbody></tgroup></table></tables>

Example 15-28

Following example illustrates method provided by the invention.

On small fixed flowing bed-tion reacting device, employing contains the cracking catalyst C1-C14 of vanadium and molecular sieve, his-and-hers watches 3 listed boiling ranges are that 294-572 ℃ the sulfur containing atmospheric and the mixing oil of decompressed wax oil carry out catalytic cracking, and temperature of reaction is 500 ℃, and weight hourly space velocity is 20 hours ^-1Agent-oil ratio was 3.0 (agent-oil ratio refers to the weight ratio of catalyzer and described mixing oil here), and the catalyzer loading amount is 120 grams, and reaction result is listed in table 4 and 5.The sulphur content determination method is referring to " petrochemical complex analytical procedure (RIPP experimental technique) ", volumes such as Yang Cuiding, P157-159, Science Press, 1990 in the crackate.

Comparative Examples 2

The method of reference catalyst is adopted in the explanation of this Comparative Examples.

Method by example 17 is carried out catalytic cracking to same raw material, and different is that the results are shown in Table 4 with reference catalyst CB1 replaced C 3.

Table 3

The oil product title	The mixing oil of long residuum and decompressed wax oil
		Density, grams per cubic centimter	????0.9057
Viscosity, millimeter 2/ second	????11.60
		Carbon residue content, weight %	????＜0.02
Saturated hydrocarbon content, weight %	????66.3
		Aromaticity content, weight %	????27.2
Gum level, weight %	????6.5
		Asphalt content, weight %	????0
Sulphur content, weight %	????1.39
		Nitrogen content	????0.10
Boiling range, ℃
		Initial boiling point	????294
30％	????419
		50％	????444
70％	????470
		90％	????522
Do	????572

Table 4

Example number	????15	????16	????17	Comparative Examples 2	????18	????19	????20
								The catalyzer numbering	????C	????C2	????C3	????CB1	????C4	????C5	????C6
Transformation efficiency, weight %	????78.9	????71.3	????68.8	????43.6	????70.5	????63.0	????73.4
								The crackate yield, weight %
Dry gas	????2.6	????1.8	????2.0	????1.1	????1.9	????1.6	????2.4
								Liquefied gas	????13.5	????13.1	????12.9	????6.2	????13.1	????12.5	????13.8
Gasoline	????57.0	????52.3	????49.7	????31.8	????51.2	????45.1	????53.5
								Diesel oil	????15.9	????23.1	????25.5	????18.0	????23.3	????31.3	????20.6
Heavy oil	????5.2	????5.6	????5.7	????38.4	????6.2	????5.7	????6.0
								Coke	????5.8	????4.1	????4.2	????4.5	????4.3	????3.8	????3.7
Content of sulfur in gasoline, ppm	????173	????224	????231	????825	????229	????289	????236

Table 5

Example number	??21	????22	????23	????24	????25	????26	????27	????28
									The catalyzer numbering	??C7	????C8	????C9	????C10	????C11	????C12	????C13	????C14
Transformation efficiency, weight %	??72.2	????64.8	????63.4	????66.3	????70.1	????73.5	????75.0	????81.7
									The crackate yield, weight %
Dry gas	??2.4	????1.8	????2.0	????1.8	????2.2	????2.1	????2.3	????2.1
									Liquefied gas	??13.6	????10.8	????12.5	????12.5	????13.1	????13.2	????12.9	????13.5
Gasoline	??50.6	????46.8	????44.7	????48.2	????50.2	????53.2	????54.0	????59.7
									Diesel oil	??22.4	????29.6	????30.8	????28.0	????24.7	????21.7	????20.0	????13.5
Heavy oil	??5.4	????5.6	????5.8	????5.7	????5.2	????4.8	????5.0	????4.8
									Coke	??5.6	????5.4	????4.2	????3.8	????4.6	????5.0	????5.8	????6.4
Content of sulfur in gasoline, ppm	??260	????295	????272	????254	????253	????248	????279	????306

Example 29-32

Following example illustrates method provided by the invention.

Method by example 17 is carried out catalytic cracking to same stock oil, and different is reaction conditions difference and/or catalyzer difference, reaction conditions, and catalyst system therefor and reaction result are listed in the table 6.

Comparative Examples 3

The method of reference catalyst is used in the explanation of this Comparative Examples.

Method by example 17 is carried out catalytic cracking to same raw material, and different is that catalyst system therefor is reference catalyst CB1, and reaction result is listed in the table 6.

Table 6

Example number	????29	Comparative Examples 3	????30	????31	????32
						The catalyzer numbering	????C3	????CB1	????C3	????C4	????C10
Temperature of reaction, ℃	????520	????520	????520	????460	????460
						Weight hourly space velocity, hour -1	????15	????15	????10	????20	????20
Agent-oil ratio	????3.0	????3.0	????2.0	????3.5	????4.0
						Transformation efficiency, weight %	????72.5	????47.9	????65.2	????73.0	????74.8
The crackate yield, weight %
						Dry gas	????3.0	????1.4	????1.1	????2.1	????2.2
Liquefied gas	????14.4	????7.2	????11.4	????13.3	????12.8
						Gasoline	????50.4	????35.5	????48.9	????53.0	????55.0
Diesel oil	????22.8	????14.6	????28.5	????21.2	????19.6
						Heavy oil	????4.7	????37.5	????6.3	????5.8	????5.6
Coke	????4.7	????3.8	????3.8	????4.6	????4.8
						Content of sulfur in gasoline, ppm	????198	????754	????276	????185	????210

Result in contrast table 4 and the table 6 as can be seen, adopt method provided by the invention, use and reference catalyst vanadium component, when identical of the present invention of molecular sieve content contains the cracking catalyst C3 of vanadium and molecular sieve, sulphur content in the pressure gasoline reduces greatly, transformation efficiency improves greatly, and yield of gasoline also improves greatly.

Example 33-34

Following example illustrates method provided by the invention.

Method by example 17 is carried out catalytic cracking to sulfur-bearing stock oil, and different is that raw materials used oil is respectively the mixing oil of wax tailings shown in the table 7 and vacuum residuum and the mixing oil of vacuum residuum shown in the table 8 and decompressed wax oil.Reaction conditions is also different.Reaction conditions and reaction result are listed in the table 9.

Table 7

The oil product title	The mixing oil of wax tailings and vacuum residuum
		Density, gram per centimeter 3	????0.9356
Viscosity (100 ℃), millimeter 2/ second	????13.31
		Carbon residue content, weight %	????4.89
Saturated hydrocarbon content, weight %	????58.6
		Aromaticity content, weight %	????31.4
Gum level, weight %	????8.3
		Asphalt content, weight %	????1.0
Sulphur content, weight %	????0.7892
		Nitrogen content, weight %	????0.57
Boiling range, ℃
		Initial boiling point	????205
30％	????409
		50％	????453
70％	????520
		95％	????572
Do	????630

Table 8

The oil product title	The mixing oil of vacuum residuum and decompressed wax oil
		Density, grams per cubic centimter	????0.9166
Viscosity (100 ℃), millimeter 2/ second	????12.04
		Carbon residue content, weight %	????1.23
Saturated hydrocarbon content, weight %	????65.2
		Aromaticity content, weight %	????27.5
Gum level, weight %	????7.0
		Asphalt content, weight %	????0.3
Sulphur content, weight %	????1.15
		Nitrogen content, weight %	????0.39
Boiling range, ℃
		Initial boiling point	????＜305
??30％	????430
		??50％	????456
??70％	????481
		??95％	????538
Do	????595

Table 9

Example number	????33	????34
			The catalyzer numbering	????C3	????C3
Stock oil	The mixing oil of wax tailings shown in the table 7 and vacuum residuum	The mixing oil of vacuum residuum shown in the table 8 and decompressed wax oil
			Temperature of reaction, ℃	????520	????520
Weight hourly space velocity, hour -1	????20	????20
			Agent-oil ratio	????3	????3
Transformation efficiency, weight %	????61.4	????65.9
			The crackate yield, weight %
Dry gas	????1.3	????1.5
			Liquefied gas	????11.4	????12.1
Gasoline	????44.0	????47.9
			Diesel oil	????29.4	????28.0
Heavy oil	????9.2	????6.1
			Coke	????4.7	????4.4
Content of sulfur in gasoline, ppm	????187	????226

Example 35-36

This example illustrates method provided by the invention.

Method by example 17 is carried out catalytic cracking to same stock oil, different is that catalyst system therefor is respectively: containing 5 weight %C3 and the 95 weight % industry trade mark and be the catalyst mixture of MLC500 commercial catalysts (Zhou village catalyst plant products) and 40 weight %C3 and the industrial trade mark of 60 weight % is the catalyst mixture of MLC500 commercial catalysts, and the results are shown in Table 10.

Table 10

Example number	????35	????36
			The catalyzer numbering	5 weight %C3+95 weight %MLC500	40 weight %C3+60 weight %MLC500
Transformation efficiency, weight %	????71.3	????70.2
			The crackate yield, weight %
Dry gas	????2.0	????1.8
			Liquefied gas	????13.2	????12.9
Gasoline	????51.5	????51.1
			Diesel oil	????23.8	????24.2
Heavy oil	????4.9	????5.6
			Coke	????4.6	????4.4
Content of sulfur in gasoline, ppm	????612	????459

Claims (31)

1. method that reduces sulphur content of catalytic cracking production, this method is included under the cracking conditions, the sulfur-bearing oil raw material is contacted with a kind of catalyzer, reclaim the catalytic cracking production that sulphur content reduces, it is characterized in that, described catalyzer is a kind of cracking catalyst that contains vanadium and molecular sieve, or contain this and contain the cracking catalyst of vanadium and molecular sieve and the catalyst mixture of catalytic cracking catalyst, the described cracking catalyst that contains vanadium and molecular sieve contains vanadium component and molecular sieve and a kind of alkaline earth metal component, and the mol ratio of vanadium and alkaline earth metal component is 10: 1-1: 60.

2. method according to claim 1 is characterized in that described catalytic cracking production refers to gasoline.

3. method according to claim 1 is characterized in that, is benchmark with the described cracking catalyst total amount that contains vanadium and molecular sieve, with V ₂O ₅Meter, the vanadium components contents is 0.1-25 weight %.

4. method according to claim 3 is characterized in that, described vanadium components contents is 0.2-10 weight %

5. method according to claim 1 is characterized in that, the mol ratio of described vanadium and alkaline-earth metal is 4: 1-1: 40.

6. method according to claim 1 or 5 is characterized in that described alkaline-earth metal is meant magnesium and/or calcium.

7. method according to claim 1 is characterized in that, is benchmark with the cracking catalyst total amount that contains vanadium and molecular sieve, and the content of described molecular sieve is 10-99.6 weight %

8. method according to claim 7 is characterized in that, the content of described molecular sieve is 10-80 weight %.

9. according to the described method of claim 1,7 or 8, it is characterized in that described molecular screening is from the macropore zeolite, mesopore zeolite and/or non-zeolite molecular sieve.

10. method according to claim 9 is characterized in that, described molecular screening is from y-type zeolite, rare earth Y type zeolite, baked rare earth Y type zeolite, ultrastable Y, Beta zeolite, one or more in the ZSM-5 zeolite.

11. method according to claim 1, it is characterized in that the described cracking catalyst that contains vanadium and molecular sieve also contains al binder, is benchmark with the described cracking catalyst total amount that contains vanadium and molecular sieve, in aluminum oxide, the content of described al binder is 0-80 weight %.

12. method according to claim 11 is characterized in that, the content of described al binder is 5-60 weight %.

13. method according to claim 1, it is characterized in that, the described cracking catalyst that contains vanadium and molecular sieve also contains inorganic oxide matrix, is benchmark with the described cracking catalyst that contains vanadium and molecular sieve, and the content of described inorganic oxide matrix is 0-80 weight %.

14. method according to claim 13 is characterized in that, the content of described inorganic oxide matrix is 10-70 weight %.

15., it is characterized in that described inorganic oxide matrix is selected from one or more in aluminum oxide, silicon oxide, amorphous aluminum silicide, the clay according to claim 13 or 14 described methods.

16. method according to claim 15 is characterized in that, described clay is selected from kaolin, halloysite, polynite, diatomite, tiredly takes off in the soil one or more.

17. method according to claim 1, it is characterized in that, the described cracking catalyst that contains vanadium and molecular sieve also contains a kind of additional metals component, and this additional metals component is selected from one or more in IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except that vanadium.

18. method according to claim 17 is characterized in that, described additional metals component is selected from one or more in gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal.

19., it is characterized in that according to claim 17 or 18 described methods, be benchmark with the described cracking catalyst total amount that contains vanadium and molecular sieve, in oxide compound, described additional metals components contents is 0-20 weight %.

20. method according to claim 19 is characterized in that, described additional metals components contents is 0-10 weight %.

21. method according to claim 1, it is characterized in that, the described catalyzer that contains vanadium and molecular sieve contains vanadium component and molecular sieve, also contains alkaline earth metal component, contains or do not contain al binder, contain or do not contain inorganic oxide matrix, with the cracking catalyst total amount that contains vanadium and molecular sieve is benchmark, the content of molecular sieve is 10-99.6 weight %, and in aluminum oxide, the content of al binder is 0-80 weight %, the content of inorganic oxide matrix is 0-80 weight %, with V ₂O ₅Meter, the vanadium components contents is 0.1-25 weight %, and in oxide compound, the content of alkaline earth metal component is 0.05-65 weight %, and the mol ratio of vanadium and alkaline-earth metal is 10: 1-1: 60.

22. method according to claim 21, it is characterized in that, the content of described molecular sieve is 10-80 weight %, the content of al binder is 5-60 weight %, the content of inorganic oxide matrix is 10-70 weight %, the vanadium components contents is 0.2-10 weight %, and the content of alkaline earth metal component is 0.1-50 weight %, and the mol ratio of vanadium and alkaline-earth metal is 4: 1-1: 40.

23., it is characterized in that described vanadium component and alkaline earth metal component are present among the inorganic oxide matrix according to claim 21 or 22 described methods.

24., it is characterized in that described inorganic oxide matrix is selected from one or more in aluminum oxide, silicon oxide, amorphous aluminum silicide, the clay according to claim 21 or 22 described methods.

25. according to claim 21 or 22 described methods, it is characterized in that, the described catalyzer that contains vanadium and molecular sieve also contains a kind of metal component, this metal component is selected from one or more in periodic table of elements IIIA family metal, IVA family metal, IIB family metal, IVB family metal, VB family metal, group vib metal, VIII family metal and the rare earth metal except that vanadium, with the cracking catalyst total amount that contains vanadium and molecular sieve is benchmark, in oxide compound, described additional metals components contents is 0-20 weight %.

26. method according to claim 25 is characterized in that, described additional metals components contents is 0-10 weight %

27. method according to claim 25 is characterized in that, described additional metals component is selected from one or more in gallium, indium, thallium, germanium, tin, zinc, cadmium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal.

28. method according to claim 1 is characterized in that, in the mixture of described cracking catalyst that contains vanadium and molecular sieve and catalytic cracking catalyst, the content that contains the cracking catalyst of vanadium and molecular sieve is not less than 0.1 weight %.

29. method according to claim 28 is characterized in that, the described content that contains the cracking catalyst of vanadium and molecular sieve is not less than 1 weight %.

30. method according to claim 1 is characterized in that, described cracking conditions comprises that described temperature of reaction is 400-600 ℃, and weight hourly space velocity is 5-30 hour ^-1, agent-oil ratio is 1-10.

31. method according to claim 1 is characterized in that, the long residuum, vacuum residuum, decompressed wax oil, normal pressure wax oil, straight-run gas oil, propane that described sulfur-bearing oil raw material is selected from sulfur-bearing be light/and heavy one or more in de-oiling and the wax tailings.