CN1323132C - Method for cracking hydrocarbon oil containing surphur - Google Patents

Abstract

The present invention relates to a cracking method of sulfur-containing hydrocarbon oil, which comprises: the sulfur-containing hydrocarbon oil contacts a catalyst mixture containing a cracking catalyst and a sulfur transfer catalyst under hydrocarbon oil cracking conditions; cracked products are recovered. The sulfur transfer catalyst contains a spinel composition and oxides of additional metallic components, wherein the spinel composition contains alkaline earth metals and aluminium; the spinel composition containing alkaline earth metals and aluminium contains the alkaline earth metals, the aluminum, contains or does not contain rare earth metals except for cerium and contains or does not contain vanadium; the oxides of additional metallic components comprise cerium oxide and zinc oxide; the catalyst is used as the reference, the content of the spinel composition containing alkaline earth metals and aluminium is from 50 to 90 wt%, and the total content of the cerium oxide and the zinc oxide is from 10 to 50 wt%; the average particle diameter of the cerium oxide, which is measured with an XRD method, is smaller than 130 angstroms, and the average particle diameter of the zinc oxide is smaller than 300 angstroms. The method which can be used for simultaneously reducing the SOx discharge of FCC regenerated smoke gas and the content of sulfur in an FCC gasoline product has high capability of reducing the SOx discharge of the FCC regenerated smoke gas.

Description

A kind of cracking method of hydrocarbon oil containing surphur

Technical field

The invention relates to a kind of cracking method of hydrocarbon ils, more specifically say so about a kind of cracking method of hydrocarbon oil containing surphur.

Background technology

Fluid catalytic cracking (FCC) is a main method of being obtained gasoline, the contour use value light-end products of diesel oil by heavy raw oil.FCC apparatus is made up of a riser reactor and a revivifier usually, in operating process, cracking catalyst microballoon and hydrocarbon oil crude material with cracking activity carry out the pyrolytic cracking reaction in riser reactor, generate lightweight oil and gas products, meanwhile, cracking catalyst also loses cracking activity because of coking.The cracking catalyst of inactivation need enter in the revivifier, carries out high temperature and burn in the presence of air, makes catalyst regeneration.If described hydrocarbon ils is a hydrocarbon oil containing surphur, can contain a large amount of sulphur compounds in the catalyst surface coke, therefore, in burning process, can generate a large amount of sulfur oxide SO _x(SO ₂And SO ₃), SO _xCan corrode regenerator device on the one hand, on the other hand, can enter atmosphere, cause serious pollution, therefore, must adopt otherwise effective technique, control flue gas SO with regenerator flue gas _xDischarging.

At present, control SO _xA kind of effective means of discharging is to add a small amount of fluidizing performance SO close with cracking catalyst in cracking catalyst _xSorbing material (sulfur transfer catalyst), sulfur transfer catalyst can promote SO in the FCC catalyst regeneration process ₂Be oxidized to SO ₃, and with SO ₃Be adsorbed on the surface and form metal sulfate, be adsorbed with SO ₃Sulfur transfer catalyst with regeneration after catalyzer enter riser reactor, under the reductive condition in reactor, the metal sulfate that is adsorbed on the sulfur transfer catalyst is reduced into H ₂S, H ₂S enters the FCC gaseous product, reclaims by sulfur recovery facility, thereby, make the SO that enters in the atmosphere _xReduce.Metal sulfate is reduced into H ₂In the time of S, described sulfur transfer catalyst obtains regeneration simultaneously, and is circulated to revivifier again with decaying catalyst, performance absorption SO _xEffect.

US4,472,532 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that (1) mix a kind of acidic aqueous solution of at least a alkaline earth metal component and aluminium wherein of containing with the basic solution that contains at least a al composition that anionic form exists, form a kind of mixture that contains liquid phase and alkaline including earth metal and aluminum precipitation, wherein, the pH value of liquid phase remains on the scope of 7.0-8.5 in mixing process, (2) the described precipitation of roasting obtains the spinel composition of alkaline including earth metal and aluminium.This method can also comprise with at least a additional metal component dipping said composition or sedimentary process.Described additional metal component is selected from IB in the periodic table of elements, IIB, IVB, VIA, VIB, VIIA and VII family metal, rare earth metal, vanadium, iron, tin, antimony and their mixture.

US4,476,245 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, this method comprises 1) a kind of acidic solution and a kind of wherein aluminium are mixed with the basic solution that contains at least a al composition that anionic form exists, (2) with the product and the aqueous solution that contains at least a alkaline earth metal component, the precipitation that (3) roasting obtains that obtain.Can also further described precipitation or spinel composition be contacted with at least a additional metal component in this method, in said composition in the load significant quantity can under oxidizing condition, promote SO ₂Be oxidized to SO ₃The additional metal component, described additional metal component also is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.

US4,492,677 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, this method comprise (1) with a kind of acidic medium that contains at least a alkaline earth metal component, at least aly have the organic compound of inherent alkalescence and aluminium wherein mixes with the aluminium basic solution that contains that anionic form exists, obtain a kind of sedimentary material that contains liquid phase and alkaline-earth metal and aluminium, in the mixing process, the pH value is maintained at about 8.0 or higher, (2) the described precipitation of roasting obtains the spinel composition of alkali metal containing and aluminium.Can also contain in the described composition and a kind ofly can promote SO ₂Oxidation or SO ₃The additional metal component, described additional metal component is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.

US4,522,937 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that (1) mix a kind of acidic solution that contains at least a alkaline earth metal component and at least a wherein aluminium with the alkaline aqueous solution that contains at least a al composition that anionic form exists, obtain containing the sedimentary material of a kind of liquid phase and a kind of alkaline including earth metal and al composition, wherein, at least a in described acidic solution and the basic solution contains at least a additional metal component, and the consumption of described additional metal component is enough to make contain in the composition of described alkaline including earth metal and al composition and can effectively promotes SO ₂Oxidation or SO ₃At least a additional metal component of amount, and, remain on the scope of 7.O-10.5, the precipitation that (2) roasting obtains in the pH of liquid phase described in mixing process value.Described additional metal component is selected from IB, IIB, IVB, VIA, VIB, VIIA and VIII family metal component, rare earth metal, vanadium, iron, tin, antimony and their mixture.

US4,497,902 disclose a kind of SO that removes from gas _xComposition, said composition contains a kind of inorganic oxide compositions and at least a free or bonded rare earth metal, described rare earth metal is selected from one group that is made up of lanthanum, cerium, praseodymium, samarium, dysprosium, and described inorganic oxide compositions is selected from by magnesium-aluminium spinel (MgAl ₂O ₄), a group of forming of the mixture of aluminum oxide and magnesian mixture and magnesium oxide and spinel.Do not provide the character and the preparation method of spinel in the specification sheets of this patent, find from the example, with calcium oxide, a water Alpha-alumina and magnesium oxide mix, and adding nitric acid mixes to be pinched, and obtains a kind of magnesium oxide, Ca of containing after the roasting ₃Al ₁₀O ₁₈And magnesium-aluminium spinel (MgAl ₂O ₄) mixture, roasting, and dipping goes up cerium, can obtain the described SO of taking off _xComposition.

US4,728,635 disclose the preparation method of the spinel composition of a kind of alkaline including earth metal and aluminium, comprise that the acidic composition that there is a kind of aluminium wherein with positively charged group form in (1) and a kind of alkaline compositions of alkaline including earth metal mix, (2) mixture that obtains of roasting obtains the spinel composition of alkaline including earth metal and aluminium.

CN1334316A discloses a kind of sulfur transfer catalyst, this catalyzer contains the composition that contains magnesium-aluminium spinel and the cerium of 2-30 weight % and/or the oxide compound of vanadium of 70-98 weight %, the described composition that contains magnesium-aluminium spinel contains the magnesium oxide of 25-30 weight %, the rare-earth oxide except that cerium of the aluminum oxide of 60-70 weight % and 5-15 weight %, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than the described 5 weight % that contain the total composition of magnesium-aluminium spinel, and the described most probable bore dia that contains the composition of magnesium-aluminium spinel is not less than 100 dusts.

Hydrocarbon oil containing surphur is being carried out in the process of catalytic cracking, not only can generate sulfur oxide SO in the flue gas _x, also can generate a large amount of organosulfur compounds in the FCC gasoline product.The existence of organosulfur compound can aggravate the discharging of dusty gas in the vehicle exhaust in the gasoline, simultaneously its products of combustion SO _xAlso can cause the poisoning and the inactivation of cleaning catalyst for tail gases of automobiles.Disclosed composition of above-mentioned patent (application) and catalyzer are used for the FCC process, though can reduce SO in the FCC flue gas effectively _xDischarging, and can not reduce sulphur content in the FCC gasoline product.In addition, the ability of the sulphur content in the cracking method reduction FCC regenerated flue gas of the disclosed sulfur transfer catalyst of use prior art also has much room for improvement.

Summary of the invention

The purpose of this invention is to provide and a kind ofly can reduce FCC regenerated flue gas SO simultaneously _xSulphur content in discharging and the FCC gasoline product, and have the cracking method of the hydrocarbon oil containing surphur of the ability of sulphur content in the higher reduction FCC regenerated flue gas.

The present inventor finds that the lower reason of sulfur transfer catalyst activity of prior art is that its contained additional metal component oxide is present in the sulfur transfer catalyst with bigger crystal grain, and for example, the average particulate diameter of cerium oxide is greater than 130 dusts.If introduce the less additional metal component oxide of particle in sulfur transfer catalyst, and described additional metal component oxide is limited in a kind of specific combination, the sulfur transfer catalyst that then obtains can not only reduce FCC regenerated flue gas SO simultaneously _xSulphur content in discharging and the FCC gasoline product, and reduce FCC regenerated flue gas SO _xThe activity of discharging is also higher.

Method provided by the present invention is included under the cracking hydrocarbon oil condition, hydrocarbon oil containing surphur is contacted with a kind of catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, reclaim crackate, wherein, described sulfur transfer catalyst contains the spinel composition of alkaline including earth metal, aluminium and the oxide compound of additional metal component, and the spinel composition of described alkaline including earth metal, aluminium contains alkaline-earth metal, aluminium, contains or do not contain rare earth metal except that cerium, contains or do not contain vanadium; Described additional metal component oxide is cerium oxide and zinc oxide, with the sulfur transfer catalyst is benchmark, the content of the spinel composition of alkaline including earth metal, aluminium is 50-90 weight %, the content of cerium oxide and zinc oxide is 10-50 weight %, the content of cerium oxide wherein is 5-25 weight %, and the content of zinc oxide is 5-25 weight %; The average particulate diameter of the cerium oxide that records with XRD method is less than 130 dusts, and the average particulate diameter of zinc oxide is less than 300 dusts.

Because the particle of additional metal component is less in the described sulfur transfer catalyst of method provided by the invention, the average particulate diameter of the cerium oxide that records with XRD method is less than 130 dusts, the average particulate diameter of zinc oxide is less than 300 dusts, be significantly less than the average particulate diameter (being respectively greater than 130 dusts with greater than 500 dusts) of cerium oxide and zinc oxide in the sulfur transfer catalyst of prior art, the active centre number of unit surface is significantly improved in the sulfur transfer catalyst.Therefore, method provided by the invention has higher reduction FCC regenerated flue gas SO _xThe ability of discharging because the present invention has adopted and contained small-particle cerium and this specific combination sulfur transfer catalyst of zinc, can also significantly reduce the content of sulphur in the FCC gasoline product.

Embodiment

According to method provided by the invention, described hydrocarbon ils can carry out in any one reactor with contacting of described catalyst mixture.For example, described reactor can be riser reactor, fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor.Described reactor is a riser reactor under the preferable case.

Described cracking hydrocarbon oil condition is conventional cracking hydrocarbon oil condition, and these conditions are conventionally known to one of skill in the art.In general, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-650 ℃, is preferably 420-600 ℃, and agent-oil ratio (weight ratio of catalyzer and hydrocarbon ils) is 1-25, is preferably 3-20.

For fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor, described cracking hydrocarbon oil condition comprises that also weight hourly space velocity is 10-120 hour ^-1, be preferably 15-80 hour ^-1For riser reactor, described cracking hydrocarbon oil condition comprises that also the reaction times is 0.5-15 second, is preferably O.5-10 second.

According to method provided by the invention, described catalyst mixture can disposablely use, still, and under the preferable case, with the regeneration of described catalyst mixture and recycle.The regeneration of described catalyst mixture is exactly in oxygen-containing atmosphere, and with the process that the coke in the catalyst mixture is burnt, this process is to well known to a person skilled in the art general knowledge.For example, in general, described regeneration temperature is 600-770 ℃, preferred 650-730 ℃.When described hydrocarbon ils carries out in fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor with contacting of catalyst mixture, can feed oxygen-containing atmosphere regeneration in position.When described hydrocarbon ils carries out in riser reactor with contacting of catalyst mixture, can directly utilize existing reaction-regeneration system to finish." residual oil complete processing ", 282-338 page or leaf (Li Chunnian writes, and Sinopec press published in 2002) is summarized existing catalytic cracking reaction-regeneration system rapidly and revivifier.Described oxygen-containing atmosphere is selected from any one can make coke incendiary gas in the catalyzer, and oxygen-containing atmosphere commonly used is an air.

In the described catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, cracking catalyst and sulfur transfer catalyst content separately is conventionally known to one of skill in the art.In general, in this catalyst mixture, the content of cracking catalyst is 75-99.5 weight %, is preferably 80-98 weight %, and the content of sulfur transfer catalyst is weight % O.5-25, is preferably 2-20 weight %.

Described cracking catalyst can be various cracking catalyst, as the various cracking catalyst that contain molecular sieve.The kind of described cracking catalyst and consist of conventionally known to one of skill in the art.

According to method provided by the invention, the average particulate diameter of the cerium oxide in the described sulfur transfer catalyst that records with XRD method is not more than 130 dusts, is preferably and is not more than 100 dusts, more preferably the 20-100 dust.The average particulate diameter of zinc oxide is not more than 300 dusts, preferably is not more than 200 dusts, more preferably the 120-200 dust.

Zinc oxide in the sulfur transfer catalyst (ZnO) and cerium oxide (CeO ₂) the average particulate diameter measuring method referring to JohnWiley ﹠amp; The Sons work, flourishing age hero etc. is translated " X-ray diffraction technology (polycrystal and non-quality material) ", metallurgical industry press, 1986, p442.This method comprises with X-ray diffractometer at CuK _α, voltage 40kV, electric current 40mA, slit 2mm/2mm/0.2mm, 0.02 ° of step-length, step time 1s experiment condition under, catalyst sample is carried out thing phase spectrogram measures.According to 2 θ in the spectrogram ₁Locate the peak for=28.63 ° and (belong to CeO ₂Characteristic diffraction peak) peak width at half height B ₁(baseline with spectrogram is a benchmark, the peak width that diffraction peak 1/2 is highly located), and 2 θ ₂The peak width at half height B at peak ,=42.722 place (belonging to the characteristic diffraction peak of ZnO) ₂, calculate by the Scherrer equation:

CeO ₂Average particulate diameter $D_1=\frac{0.89\mathrm{\λ}}{{\mathrm{\β}}_1\mathrm{COS}{\mathrm{\θ}}_1}$ , β wherein ₁=β ₁-b ₀

The average particulate diameter of ZnO $D_2=\frac{0.89\mathrm{\λ}}{{\mathrm{\β}}_2\mathrm{COS}{\mathrm{\θ}}_2}$ , β wherein ₂=β ₂-b ₀

B under this experiment condition ₀=0.09.λ is a wavelength, is 1.54 15 dusts under this experiment condition.θ ₁And θ ₂Be respectively CeO ₂XRD feature diffraction angle with ZnO.

With the sulfur transfer catalyst is benchmark, the content of the spinel composition of alkaline including earth metal, aluminium is 50-90 weight %, and the content of cerium oxide and zinc oxide is 10-50 weight %, under the preferable case, the content of cerium oxide is 5-25 weight %, and the content of zinc oxide is 5-25 weight %.

According to embodiment preferred of the present invention, with the sulfur transfer catalyst is benchmark, the content of the spinel composition of alkaline including earth metal, aluminium is 60-85 weight %, the content of cerium oxide and zinc oxide is 15-40 weight %, under the preferable case, the content of cerium oxide is 7.5-20 weight %, and the content of zinc oxide is 7.5-20 weight %.

The spinel composition of described alkaline including earth metal, aluminium contains alkaline-earth metal, aluminium, contains or does not contain rare earth metal except that cerium, contains or do not contain vanadium.Wherein, all or part of formation spinel structure of described alkaline-earth metal and aluminium, rare earth metal except that cerium and vanadium can be with compounds independently, exist as the form of oxide compound or salt, also can combine with magnesium and aluminium wherein, exist with the form of complex compound.The content range of alkaline-earth metal, aluminium, the rare earth metal except that cerium and vanadium is the content of alkaline-earth metal in the spinel composition of prior art alkaline including earth metal, aluminium, aluminium, the rare earth metal except that cerium and vanadium routine, in general, spinel composition with alkaline including earth metal, aluminium is a benchmark, in oxide compound, the content of alkaline-earth metal is 20-70 weight %, the content of aluminium is 30-80 weight %, and the content of the rare earth metal except that cerium is 0-15 weight %, and the content of vanadium is 0-15 weight %; Under the preferable case, the content of alkaline-earth metal is 30-60 weight %, and the content of aluminium is 35-65 weight %, and the content of the rare earth metal except that cerium is 2-10 weight %, and the content of vanadium is 1-10 weight %.

Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, is preferably magnesium and/or calcium.

Described rare earth metal except that cerium is preferably group of the lanthanides and in the actinium series rare earth metal one or more except that cerium, more preferably lanthanum or rich lanthanum and be substantially free of the mixture of the lanthanide rare metal of cerium.

In the method provided by the invention, described sulfur transfer catalyst has conventional specific surface and pore volume, and in general, after 650 ℃ of roastings, the specific surface of measuring with cryogenic nitrogen absorption BET method is not less than 30 meters ²/ gram preferably is not less than 50 meters ²/ gram, more preferably 70-120 rice ²/ gram, pore volume are not less than 0.15 milliliter/gram, preferred 0.2-0.5 milliliter/gram.

The preparation method of the described sulfur transfer catalyst of method provided by the invention comprises the spinel composition that floods a kind of alkaline including earth metal, aluminium with the solution one or many that contains the additional metal component composition, dry also roasting, wherein, the spinel composition of described alkaline including earth metal, aluminium contains alkaline-earth metal, aluminium, contains or does not contain rare earth metal except that cerium, contains or do not contain vanadium; Each dipping is described to contain the volumetric usage of solution of additional metal component composition greater than the water droplet method pore volume of the spinel composition of alkaline including earth metal and aluminium, the time of dipping is enough to make described additional metal component composition to be dispersed in the spinel composition of alkaline including earth metal, aluminium, and described additional metal component composition is the compound of cerium and the compound of zinc.

In the preparation method of described sulfur transfer catalyst, the concentration of the solution of additional metal component composition is not particularly limited, as long as through the one or many dipping, the additional metal component that can introduce q.s in catalyzer gets final product.When the concentration of the solution of additional metal component composition is higher, can carry out single-steeping and just can introduce the additional metal component of q.s, and the concentration of the solution of additional metal component composition can repeatedly be flooded when low, can carry out liquid-solid separation or not carry out liquid-solid separation behind each dipping, can be dry or moist, roasting or not roasting.Described liquid-solid isolating method adopts any liquid-solid isolating method, as method of filtering method, cyclonic separation etc.

Under the preferable case, at least 1.5 times of the water droplet method pore volume of the spinel composition that to flood the described volumetric usage that contains the solution of additional metal component composition be alkaline including earth metal, aluminium at every turn, more preferably 2-20 is doubly.The time of dipping generally is no less than 5 minutes, is preferably to be no less than 10 minutes.In general, dipping time surpassed after 120 minutes, and the additional metal component is adsorbed in alkaline including earth metal, aluminate composition can reach balance, and dipping time prolongs the influence of catalyzer very little again, therefore, and dipping time more preferably 10-120 minute.The consumption of each component makes in the catalyzer and contains, and is benchmark with the catalyzer, 50-90 weight %, the alkaline including earth metal of preferred 60-85 weight %, the spinel composition of aluminium, 10-50 weight %, cerium oxide and the zinc oxide of preferred 15-40 weight %.

The described solution that contains the additional metal component composition can be the aqueous solution or organic solution, is preferably the aqueous solution.

The compound of described cerium is preferably one or more in water-soluble compound of cerium, as in the muriate of cerium, nitrate, vitriol, phosphoric acid salt, the organic acid salt one or more, is preferably the muriate and/or the nitrate of cerium.The compound of described zinc is preferably one or more in water-soluble compound of zinc, as in the muriate of zinc, nitrate, vitriol, phosphoric acid salt, the organic acid salt one or more, is preferably the muriate and/or the nitrate of zinc.

Flood drying after the spinel composition of described alkaline including earth metal, aluminium and the condition of roasting is conventionally known to one of skill in the art with the solution one or many that contains the additional metal component composition.In general, the exsiccant temperature is a room temperature to 400 ℃, is preferably 100-300 ℃.Maturing temperature is generally 500-800 ℃, is preferably 550-750 ℃; Roasting time is 0.5-8 hour, preferred 1-5 hour.

The spinel composition of described alkaline including earth metal, aluminium can be according to any existing method, for example, and CN13343 16A, US4,472,532, US4,476,245, US4,492,677, US4,522,937, US4,497,902, US4, the preparation of 728,635 disclosed methods.

Under the preferable case, the preparation method of the spinel composition of described alkaline including earth metal, aluminium comprises pseudo-boehmite and water making beating even, adding acid makes the pH value of slurries be 1.0-3.5, be preferably 1.5-2.5, the solution and the making beating that add or do not add vanadium compound are even, add the oxide compound of alkaline including earth metal and/or the slurries of oxyhydroxide then, making beating evenly, it is 5-20 weight % that the consumption of each component makes the solid content of the slurries that obtain, be preferably 8-15 weight %, the slurries that dry then also roasting obtains.Arbitrary steps before drying adds the rare earth compound except that cerium.Under the preferable case, the consumption of each component contains the spinel composition of alkaline including earth metal, aluminium, is benchmark with the said composition, in oxide compound, the alkaline-earth metal of 20-70 weight %, the aluminium of 30-80 weight %, the rare earth metal of 0-15 weight % except that cerium, the vanadium of 0-15 weight %; More under the preferable case, the consumption of each component contains the spinel composition of alkaline including earth metal, aluminium, is benchmark with the said composition, in oxide compound, the alkaline-earth metal of 30-60 weight %, the aluminium of 35-65 weight %, the rare earth metal of 2-10 weight % except that cerium, the vanadium of 1-10 weight %.

Wherein, described vanadium compound is selected from any vanadium compound, as in the water-soluble and water-fast vanadium compound one or more, is preferably the muriate of vanadium, one or more in nitrate, oxide compound, oxyhydroxide, the complex compound.These vanadium compound are conventionally known to one of skill in the art.

Described rare earth compound except that cerium is selected from any rare earth compound except that cerium, as in the water-soluble and water-fast rare earth compound except that cerium one or more, be preferably the muriate of the rare earth metal except that cerium, one or more in nitrate, oxide compound, the oxyhydroxide.These rare earth compounds except that cerium are conventionally known to one of skill in the art.

In the preparation process of the spinel composition of described alkaline including earth metal, aluminium, the drying means of described slurries and condition are conventional drying means and condition.Can adopt as the exsiccant method dry, oven dry, forced air drying, spray-dired method.The method of preferably spray drying.The exsiccant temperature can be room temperature to 550 ℃, is preferably 100-300 ℃.The condition of roasting also is conventional roasting condition.Be generally 550-800 ℃ as maturing temperature, be preferably 600-750 ℃; Roasting time 0.5-8 hour, preferred 1-5 hour.

According to method provided by the invention, described hydrocarbon oil containing surphur hydrocarbon ils can be sulphur-bearing crude and various fraction thereof, particularly sulphur-bearing crude or boiling range are greater than 330 ℃ petroleum cuts, as sulfur containing atmospheric, vacuum residuum, vacuum gas oil, atmospheric gas oil, straight run gas oil, propane is light/in heavy deasphalted oil and the coker gas oil one or more.

The following examples will the invention will be further described, and the alkaline-earth metal in the described sulfur transfer catalyst is example with magnesium, substitutes magnesium with other alkaline-earth metal and also have similar effect.

Among the embodiment, used pseudo-boehmite (solid content 32.0 weight %) is a technical grade, and Shandong Aluminum Plant produces; In chlorination mishmetal (technical grade, the Shanghai allosaurus rare earth company limited produces) solution, in rare earth oxide, content of rare earth is 244.1 grams per liters, and wherein, the weight ratio of each rare earth component is La ₂O ₃: Sm ₂O ₃: Yb ₂O ₃: Lu ₂O ₃=79.0: 4.5: 1.9: 0.44; Light magnesium oxide is a technical grade, and producing in magnesium salts chemical plant, Yongchang, Xingtai, contains magnesium oxide 97 weight %, 35 meters of specific surfaces ²/ gram; V ₂O ₅Be analytical pure, chemical reagent work of Hunan coal science institute produces; Oxalic acid (H ₂C ₂O ₄.2H ₂O) be analytical pure, Beijing company of China Drug Co. produces; Cerous chlorate is a technical grade, and Yaolong Non-ferrous Metal Co. Ltd., Shanghai produces; Zinc chloride is an analytical pure, and Beijing dicyclo chemical reagent factory produces; Lanthanum trichloride is an analytical pure, and Beijing dicyclo chemical reagent factory produces.

The zinc oxide of catalyzer and cerium oxide content are by x-ray fluorescence spectrometry among the embodiment, and the content of the spinel composition of alkaline including earth metal and aluminium is by calculating.The specific surface of catalyzer, pore volume are measured with cryogenic nitrogen absorption BET method and water droplet method (referring to " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, PP71-72, Science Press, 1990) respectively.

Embodiment 1

Spinel composition of this example explanation alkaline including earth metal, aluminium and preparation method thereof.

In a stirring tank, add 17.1 kilograms in decationized Y sieve water, under agitation add 5.625 kilograms of pseudo-boehmites, add the aqueous hydrochloric acid that concentration is 18 weight % again, stir, it is 2.0 that the consumption of aqueous hydrochloric acid makes the pH value of slurries.Continue to add 5 liters of V ₂O ₅-oxalic acid complex solution stirs.Continue to add 2 kilograms of light magnesium oxides and 4.5 kilograms of decationized Y sieve water, making beating stirs, and obtains the slurries that solid content is 11.5 weight %.The slurries that obtain 500 ℃ of temperature ins, are carried out spraying drying under the condition that exhaust temperature is 180 ℃, then in 650 ℃ of following roastings 2 hours, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT ₁ZT ₁Composition, specific surface and pore volume list in the table 1.

Wherein, V ₂O ₅The preparation method of-oxalic acid complex solution is as follows: take by weighing 400 gram V ₂O ₅With 950 gram oxalic acid and 10 liters of decationized Y sieve water and mix, be warming up to 60 ℃ and reacted 1 hour under stirring, promptly generate mazarine V ₂O ₅-oxalic acid complex solution.

Embodiment 2

Spinel composition of this example explanation alkaline including earth metal, aluminium and preparation method thereof.

In a stirring tank, add 20.2 kilograms in decationized Y sieve water, under agitation add 7.63 kilograms of pseudo-boehmites and 0.655 liter of chlorination mixed rare earth solution, add the aqueous hydrochloric acid that concentration is 18 weight % again, stir, it is 1.65 that the consumption of aqueous hydrochloric acid makes the pH value of slurries.Continue to add 1 liter of example 1 described V ₂O ₅-oxalic acid complex solution stirs, and continues to add 1.4 kilograms of light magnesium oxides and 3.18 kilograms of slurries that the making beating of decationized Y sieve water forms, and stirs, and obtains the slurries that solid content is 11.5 weight %.The slurries that obtain 500 ℃ of temperature ins, are carried out spraying drying under the condition that exhaust temperature is 180 ℃, then in 650 ℃ of following roastings 2 hours, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT ₂ZT ₂Composition, specific surface and pore volume list in the table 1.

Embodiment 3

Spinel composition of this example explanation alkaline including earth metal, aluminium and preparation method thereof.

Method preparation by example 2 contains the magnesium-aluminium spinel composition, and different just pseudo-boehmite consumptions are 6.9 kilograms, and 1.676 liters of chlorination mixed rare earth solutions, light magnesium oxide consumption are 1.79 kilograms, V ₂O ₅The consumption of-oxalic acid complex solution is 4 liters, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT ₃ZT ₃Composition, specific surface and pore volume list in the table 1.

Embodiment 4

Spinel composition of this example explanation alkaline including earth metal, aluminium and preparation method thereof.

Method preparation by example 2 contains the magnesium-aluminium spinel composition, and different just pseudo-boehmite consumptions are 5.625 kilograms, and the light magnesium oxide consumption is 1.68 kilograms, V ₂O ₅The consumption of-oxalic acid complex solution is 8 liters, with 0.8 liter lanthanum chloride solution (La ₂O ₃Content 250 grams per liters) replace the chlorination mixed rare earth solution, obtain average particulate diameter and be 60 microns contain magnesium-aluminium spinel composition microballoon ZT ₄ZT ₄Composition, specific surface and pore volume list in the table 1.

Table 1

Example number	Composition no	MgO, weight %	Al 2O 3, weight %	RE 2O 3, weight %	V 2O 5, weight %	Specific surface, m 2/ gram	Pore volume, milliliter/gram
									The BET method	The water droplet method
							1	ZT 1			50.00	45.00	0.00	5.00	143	0.31	0.46
2	ZT 2	34.64	60.40	3.96①	1.00	125			0.29	0.44
							3	ZT 3			39.23	48.32	8.95①	3.50	114	0.27	0.41
4	ZT 4	42.00	45.00	5.00②	8.00	120			0.30	0.45

1. wherein, La ₂O ₃: Sm ₂O ₃: Yb ₂O ₃: Lu ₂O ₃=79.0: 4.5: 1.9: 0.44; 2. La ₂O ₃Content.

Embodiment 5

This example explanation sulfur transfer catalyst and preparation method thereof.

Take by weighing 3 kilograms of (butt) carrier ZT respectively ₁-ZT ₄, and, flood after drying and roasting respectively with the cerous chlorate aqueous solution and/or solder(ing)acid dipping at every turn, obtain sulfur transfer catalyst ZJ ₁-ZJ ₇Table 2-3 has provided the used solution composition of each dipping and consumption, dipping time, drying temperature, maturing temperature and roasting time.Table 4 has provided sulfur transfer catalyst ZJ ₁-ZJ ₇Composition.Table 5 has provided sulfur transfer catalyst ZJ ₁-ZJ ₇Specific surface and the pore volume measured with cryogenic nitrogen absorption BET method, and CeO in the sulfur transfer catalyst that records by XRD method ₂Average particulate diameter with ZnO.

Comparative Examples 1-2

Following Comparative Examples explanation reference sulfur transfer catalyst and preparation method thereof.

Method by example 6 and example 7 prepares sulfur transfer catalyst respectively, different when just flooding, adopt existing equi-volume impregnating, the volumetric usage that is dipping solution is identical with the pore volume of the spinel composition of alkaline including earth metal and aluminium, and employing is quantitatively flooded, make the content of cerium oxide and zinc oxide identical with example 6 respectively, obtain reference sulfur transfer catalyst DB with example 7 ₁And DB ₂Table 2-3 has provided the used solution composition of each dipping and consumption, dipping time, drying temperature, maturing temperature and roasting time.Table 4 has provided reference sulfur transfer catalyst DB ₁And DB ₂Composition.Table 5 has provided reference sulfur transfer catalyst DB ₁And DB ₂Specific surface and the pore volume measured with cryogenic nitrogen absorption BET method, and CeO in the reference sulfur transfer catalyst that records by XRD method ₂Grain size with the ZnO component.

Table 2

Example number	Composition therefor	The 1st dipping		The 2nd dipping
						Steeping fluid is formed	Preparation condition	Steeping fluid is formed	Preparation condition
		5	ZT 1	CeCl 3: 540 gram water: 8 liters	Dipping time: 20 minutes drying temperatures: 110 ℃ of maturing temperatures: 600 ℃ of roasting time: 90 minutes					ZnCl 2: 635 gram water: 8 liters	Dipping time: 20 minutes drying temperatures: 110 ℃ of maturing temperatures: 600 ℃ of roasting time: 90 minutes
6	ZT 2					CeCl 3: 430 gram ZnCl 2: 760 gram water: 12 liters	Dipping time: 45 minutes drying temperatures: 110 ℃ of maturing temperatures: 550 ℃ of roasting time: 180 minutes	Do not have	Do not have
		Comparative Examples 1	ZT 2	CeCl 3: 430 gram water: 1.3 liters	Dipping time: 15 minutes drying temperatures: 110 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes					ZnCl 2: 760 gram water: 1.3 liters	Dipping time: 20 minutes drying temperatures: 110 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes
7	ZT 2					CeCl 3: 840 gram water: 20 liters	Dipping time: 25 minutes drying temperatures: 100 ℃ of maturing temperatures: 550 ℃ of roasting time: 90 minutes	ZnCl 2: 530 gram water: 10 liters	Dipping time: 45 minutes drying temperatures: 100 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes
		Comparative Examples 2	ZT 2	CeCl 3: 840 gram water: 1.3 liters	Dipping time: 45 minutes drying temperatures: 110 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes					ZnCl 2: 530 gram water: 1.3 liters	Dipping time: 45 minutes drying temperatures: 110 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes

Table 3

Example number	Composition therefor	The 1st dipping		The 2nd dipping
						Steeping fluid is formed	Preparation condition	Steeping fluid is formed	Preparation condition
		8	ZT 2	CeCl 3: 1340 gram water: 25 liters	Dipping time: 60 minutes drying temperatures: 100 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes					ZnCl 2: 1170 grams; Water: 20 liters	Dipping time: 60 minutes drying temperatures: 100 ℃ of maturing temperatures: 650 ℃ of roasting time: 120 minutes
9	ZT 2					CeCl 3: 690 gram ZnCl 2: 800 gram water: 30 liters	Dipping time: 90 minutes drying temperatures: 60 ℃ of maturing temperatures: 600 ℃ of roasting time: 150 minutes	Do not have	Do not have
		10	ZT 3	CeCl 3: 690 gram ZnCl 2: 800 gram water: 20 liters	Dipping time: 120 minutes drying temperatures: 100 ℃ of maturing temperatures: 700 ℃ of roasting time: 90 minutes					Do not have	Do not have
11	ZT 4					ZnCl 2: 690 grams; Water: 15 liters	Dipping time: 45 minutes drying temperatures: 100 ℃ of maturing temperatures: 650 ℃ of roasting time: 60 minutes	CeCl 3: 800 gram water: 15 liters	Dipping time: 45 minutes drying temperatures: 100 ℃ of maturing temperatures: 650 ℃ of roasting time: 60 minutes

Table 4

Example number	Sulfur transfer catalyst	The composition kind	Composition levels, weight %	CeO 2Content, weight %	ZnO content, weight %
						5	ZJ 1	ZT 1	80.23	9.89	9.88
6	ZJ 2	ZT 2	79.88	8.07	12.05
						Comparative Examples 1	DB 1	ZT 2	79.88	8.06	12.06
7	ZJ 3	ZT 2	76.80	14.88	8.32
						Comparative Examples 2	DB 2	ZT 2	76.79	14.90	8.31
8	ZJ 4	ZT 2	65.40	19.78	14.82
						9	ZJ 5	ZT 2	75.99	11.89	12.12
10	ZJ 6	ZT 3	75.94	11.91	12.15
						11	ZJ 7	ZT 4	76.05	11.69	12.26

Table 5

Example number	Sulfur transfer catalyst	CeO 2Average particulate diameter, dust	The ZnO average particulate diameter, dust	Specific surface, rice 2/ gram	Pore volume, milliliter/gram
						5	ZJ 1	65.25	154.22	97	0.26
6	ZJ 2	47.85	162.43	95	0.27
						Comparative Examples 1	DB 1	135.14	589.62	62	0.19
7	ZJ 3	70.43	145.08	90	0.25
						Comparative Examples 2	DB 2	180.80	505.38	55	0.15
8	ZJ 4	80.27	191.84	85	0.24
						9	ZJ 5	68.13	158.76	93	0.26
10	ZJ 6	68.56	163.31	93	0.26
						11	ZJ 7	67.44	160.69	93	0.26

From the result of table 5 as can be seen, in the described sulfur transfer catalyst of method provided by the invention, the CeO that records by XRD method ₂Average particulate diameter all less than 130 dusts, the average particulate diameter of ZnO is all less than 300 dusts, and the CeO that adopts the reference sulfur transfer catalyst of prior art for preparing to be recorded by XRD method ₂Big a lot of with the average particulate diameter of ZnO, CeO ₂Average particulate diameter all greater than 130 dusts, the average particulate diameter of ZnO is all greater than 500 dusts.In addition, the pore volume of reference sulfur transfer catalyst obviously reduces, and may be that cause in the metal oxide particle obstruction duct of load.

Embodiment 12-18

Following example illustrates the SO of sulfur transfer catalyst of the present invention ₂Oxidation absorption and reducing/regenerating performance.

In the fixed fluidized-bed reactor of 3 centimetres of internal diameters, 28 centimetres of length, be respectively charged into the sulfur transfer catalyst ZJ of example 1-5 preparation ₁-ZJ ₇Each 3 gram and 27 restrains the mixture of commercial FCC catalyzer (the industrial trade mark is Orbit-3000, and Qilu Petrochemical company Zhou village catalyst plant is produced), and feeding flow is the nitrogen of 1150 ml/min, makes mixture be in fluidized, is warming up to 600 ℃ simultaneously.After treating catalyst mixture bed constant temperature, switching flow is the SO that contains 1900vppm of 1150 ml/min ₂, the oxygen of 5.0 volume %, all the other are the gas mixture of nitrogen, absorption reaction switches to nitrogen after 45 minutes again, purges 10 minutes.When adsorption process was carried out, tail gas was by the hydrogen peroxide solution of 1.2 weight %, to absorb the SO that is not adsorbed ₂, after absorption and purge is finished, be that the NaOH aqueous solution titration of 0.2 weight % is absorbed with SO with concentration ₂Hydrogen peroxide solution, be calculated as follows SO in 45 minutes inner catalyst mixtures ₂Absorption percentage ratio (SO ₂%):

SO ₂%=(the SO that the 1-absorption liquid absorbs ₂Total SO of mmole number/by the catalyst mixture bed ₂The mmole number) * 100=(1-V _Absorption/ V _Blank) * 100

Wherein, V _BlankBe 25 milliliters of NaOH titrating solution volumes that absorption liquid consumed behind logical 45 minutes gas mixtures of empty reactor, V _AbsorptionBehind logical 45 minutes gas mixtures of the reactor of loading catalyst mixture, 25 milliliters of NaOH titrating solution volumes that absorption liquid consumed.Indicator is methyl red and methylene blue mixture indicator during titration.

Catalyst mixture was through 45 minutes SO ₂Behind absorption and the 10 minutes nitrogen purgings, be the high-purity hydrogen of 1150 ml/min, switch the nitrogen that flow is 1150 ml/min after 60 minutes again, purge after 10 minutes, switch successively by above identical method again and contain SO in same temperature incision change of current amount ₂With gas mixture, the nitrogen of oxygen, and by the above-mentioned identical method calculating SO first time ₂SO in the desorption rear catalyst mixture ₂Absorption percentage ratio SO ₂(1) %.Carry out hydrogen reducing, SO equally once more ₂Behind absorption and the nitrogen purging, measure SO for the second time ₂SO in the desorption rear catalyst mixture ₂Absorption percentage ratio SO ₂(2) %.Test result is listed in the table 6.

Comparative Examples 3-4

The SO of following Comparative Examples explanation reference sulfur transfer catalyst ₂Oxidation absorption and reducing/regenerating performance.

Press the method for example 12-18 and measure SO ₂%, SO ₂(1) % and SO ₂(2) %, that different is the reference sulfur transfer catalyst DB that used sulfur transfer catalyst is respectively Comparative Examples 1 and Comparative Examples 2 preparations ₁And DB ₂, the results are shown in Table 6.

Table 6

Example number	Catalyzer	SO 2％	SO 2(1)％	SO 2(2)％
					12	ZJ 1	86.23	37.58	24.39
13	ZJ 2	85.40	38.30	24.25
					Comparative Examples 3	DB 1	80.93	30.55	20.25
14	ZJ 3	88.56	41.27	29.44
					Comparative Examples 4	DB 2	83.15	27.85	15.04
15	ZJ 4	91.24	50.43	31.00
					16	ZJ 5	87.80	39.00	27.45
17	ZJ 6	87.45	37.98	25.21
					18	ZJ 7	87.34	37.45	24.89

As can be seen from Table 6, identical with composition reference catalyst is compared sulfur transfer catalyst SO of the present invention ₂Oxidation absorption and reducing/regenerating performance increase substantially.This result shows that sulfur transfer catalyst of the present invention has the reduction FCC regenerated flue gas SO higher than prior art _xThe ability of discharging.Use the cracking method for hydrocarbon oil of this catalyzer must have higher reduction FCC regenerated flue gas SO _xThe ability of discharging.

Embodiment 19-25

Below example with reactor be fixed fluidized bed be example, illustrate that method provided by the invention can significantly reduce the sulphur content in the FCC gasoline product.

Respectively with 30 gram ZJ ₁-ZJ ₇Under 800 ℃, 100% steam atmosphere condition, carry out 4 hours burin-in process.Get the ZJ through burin-in process of different amounts ₁-ZJ ₇(the industrial trade mark is GOR-II with the industrial FCC equilibrium catalyst of different amounts.The FCC equilibrium catalyst, main character sees Table 7) mix.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, (vacuum residuum content is 30 weight % to the mixing oil of long residuum and decompressed wax oil shown in the his-and-hers watches 8, decompressed wax oil content is 70 weight %) carry out catalytic cracking, table 9-10 has provided the catalyst system therefor mixture and has formed reaction conditions and reaction result.Wherein, the sulphur content in the pressure gasoline adopts micro-coulometric determination.

Comparative Examples 5-7

Below Comparative Examples with reactor be fixed fluidized bed be example, the circulate situation of shifting catalyst of reference of using be described.

By the method among the example 19-25 same stock oil is carried out catalytic cracking, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst, uses DB1 and the mixture of industrial FCC equilibrium catalyst and the mixture of DB2 and industrial FCC equilibrium catalyst.Table 9 has provided the catalyst system therefor mixture and has formed reaction conditions and reaction result.

Table 7

Project	Industry equilibrium catalyst GOR-II
		Metal content, ppm Ni/V Fe/Sb Ca	6100/6500 8600/2800 4900
Little index alive	65

Table 8

The stock oil title	Long residuum	Decompressed wax oil
			Density (20 ℃), gram per centimeter 3Viscosity (100 ℃), millimeter 2/ second zero pour, ℃ carbon residue, weight %	0.8906 24.84 43 4.3	0.9154 6.962 35 0.18
Elementary composition, weight % C/H S/N	86.54/13.03 0.13/0.3	85.38/12.03 2.0/0.16
			Four components, weight % stable hydrocarbon aromatic hydrocarbons gum asphalt	51.2 29.7 18.3 0.8	64.0 32.0 4.0 0.0
Boiling range, ℃ IBP/5% 10%/30% 50%/70% 90%/95%	282/351 370/482 553/- -	329/363 378/410 436/462 501/518

Table 9

Example number catalyzer raw material oil sulphur content, weight % temperature of reaction, ℃ weight hourly space velocity, hour -1Agent weight of oil ratio	Comparative Examples 5 100% poisers 1.6 520 20 5	19 10％ZJ 2+ 90% poiser 1.6 520 20 5	Comparative Examples 6 10%DB 1+ 90% poiser 1.6 520 20 5	20 10％ZJ 3+ 90% poiser 1.6 520 20 5	Comparative Examples 7 10%DB 2+ 90% poiser 1.6 520 20 5
						Material balance, weight % gas C 5 +Gasoline, diesel heavy oil coke transformation efficiency, weight % content of sulfur in gasoline, mg/litre gasoline sulfur decrement, % 3.	12.6 42.0 20.1 19.1 6.2 60.8 705 -	12.0 41.7 21.1 19.2 6.0 59.7 582 17.4％	12.4 40.1 21.1 20.3 6.1 58.6 684 3.0％	12.0 41.8 20.8 20.2 6.2 60.0 494 29.8％	12.1 40.5 21.2 20.1 6.1 58.7 652 7.5％

3. the gasoline sulfur decrement is a criterion calculation with Comparative Examples 5.

As can be seen from Table 9, compare when only using poiser, use contains the catalyst mixture of reference sulfur transfer catalyst, basically do not reduce pressure gasoline The product sulfur content, and adopt method provided by the invention, use contains the catalyst mixture of sulfur transfer catalyst of the present invention, and the sulphur content of pressure gasoline product significantly reduces.

Table 10

The example number catalyzer	21 12％ZJ 1+ 88% poiser	22 10％ZJ 4+ 90% poiser	23 8％ZJ 5+ 92% poiser	24 10％ZJ 6+ 90% poiser	25 5％ZJ 7+ 95% poiser
						The stock oil sulphur content, weight % temperature of reaction, ℃ weight hourly space velocity, hour -1Agent-oil ratio	1.6 450 20 15	1.6 500 30 12	1.6 520 16 3	1.6 500 20 6	1.6 550 60 4.5
Material balance, weight % gas C 5 +Gasoline, diesel heavy oil coke transformation efficiency, weight %	11.8 41.4 20.9 19.6 6.3 59.5	12.6 43.4 20.0 17.2 6.8 62.8	12.2 42.1 19.8 19.5 6.4 60.7	12.3 41.2 20.7 19.4 6.4 59.9	12.5 41.3 20.0 19.7 6.5 60.3
						Content of sulfur in gasoline, mg/litre gasoline sulfur decrement, % is 3.	578 18.0 *	455 35.5	559 20.7	550 22.0	540 23.4

3. the gasoline decrement is a criterion calculation with Comparative Examples 5.

Example 26-32

Following example is that riser reactor is an example with the reactor, and method provided by the invention is described.

Respectively with ZJ ₁-ZJ ₇Under 800 ℃, 100% steam atmosphere condition, carry out 4 hours burin-in process.Get the ZJ through burin-in process of different amounts respectively ₁-ZJ ₇Mix with GOR-II industry equilibrium catalyst.Catalyst mixture is fed small-sized catalytic cracking riser reactor continuously, feed decompressed wax oil and water vapour shown in decompressed wax oil shown in the table 8 or the table 8 simultaneously continuously, described decompressed wax oil is contacted with catalyst mixture, catalyzer is separated with reaction product, isolated catalyzer enters revivifier regeneration, and the catalyst recirculation after the regeneration is returned riser reactor.Table 11 and table 12 have provided the catalyst system therefor mixture and have formed (being percent by weight), reaction conditions and reaction result.

Comparative Examples 8-10

Following Comparative Examples is that riser reactor is an example with the reactor, and the method for using the reference sulfur transfer catalyst is described.

By the method in the example 26 same stock oil is carried out catalytic cracking, different is that the catalyst system therefor mixture replaces with the mixture of 100% industrial FCC equilibrium catalyst, DB1 and industrial FCC equilibrium catalyst and the mixture of DB2 and industrial FCC equilibrium catalyst respectively.Table 11 has provided the catalyst system therefor mixture and has formed reaction conditions and reaction result.

Table 11

Example number	Comparative Examples 8	26	Comparative Examples 9	27	Comparative Examples 10
						Catalyzer	100% poiser	3％ZJ 2+ 97% poiser	3％DB 1+ 97% poiser	3％ZJ 3+ 97% poiser	3％DB 2+ 97% poiser
The stock oil sulphur content, weight %	2
						Reaction times, second	2.8
Regeneration temperature, ℃	670
						Temperature of reaction, ℃	500
Agent-oil ratio	4.0
						The water vapour add-on	The 10 weight % that are equivalent to described decompressed wax oil
Material balance, weight %
						Dry gas	1.43	1.48	1.49	1.45	1.46
Liquefied gas	10.07	9.81	9.93	9.94	9.93
						C 5 +Gasoline	46.21	46.03	46.05	45.94	46.10
Diesel oil	17.89	17.91	17.83	17.90	17.88
						Heavy oil	21.34	21.68	21.53	21.65	21.51
Coke	3.07	3.09	3.17	3.12	3.12
						Transformation efficiency, weight %	60.77	60.41	60.64	60.45	60.61
Gasoline is formed, weight %
						Alkane	26.13	25.12	25.06	26.4	25.41
Alkene	37.86	39.09	39.15	38.48	39.67
						Naphthenic hydrocarbon	9.40	9.57	9.72	9.56	9.14
Aromatic hydrocarbons	26.56	26.22	26.07	25.56	25.78
						Sulfur in gasoline, mg/litre	1985.00	1589.86	1941.50	1604.20	1894.59
The flue gas sulphur content, milligram/rice 3	540	70	90	37	105
						Flue gas desulphuization rate, weight %	0.0	87.0	83.3	93.1	80.6

Table 12

Example number	28	29	30	31	32
						Catalyzer	6％ZJ 1+ 94% poiser	3％ZJ 4+ 97% poiser	8％ZJ 5+ 92% poiser	10％ZJ 6+ 90% poiser	5％ZJ 7+ 95% poiser
The stock oil sulphur content, weight %	2	2	2	2	2
						Reaction times, second	2.0	2.5	1.5	3.5	3.0
Regeneration temperature, ℃	670	695	670	695	670
						Temperature of reaction, ℃	520	490	500	510	510
Agent-oil ratio	4.5	6	5	6.5	3.5
						Water vapour add-on (percent by weight that is equivalent to described decompressed wax oil)	0	10	5	15	0
Material balance, weight %
						Dry gas	1.42	1.51	1.46	1.61	1.41
Liquefied gas	10.77	1 1.81	11.27	12.78	10.02
						C 5 +Gasoline	48.29	52.03	49.38	52.60	46.95
Diesel oil	16.81	15.61	16.01	14.56	17.03
						Heavy oil	19.35	15.15	18.31	14.38	21.39
Coke	3.36	3.89	3.57	4.07	3.20
						Transformation efficiency, weight %	63.84	69.24	65.68	71.06	61.58
Gasoline is formed, weight %
						Alkane	29.69	32.20	30.12	31.40	24.41
Alkene	33.93	27.01	31.09	25.48	39.17
						Naphthenic hydrocarbon	9.23	10.48	9.57	9.56	9.64
Aromatic hydrocarbons	27.15	30.31	29.22	33.56	26.78
						Sulfur in gasoline, mg/litre	1465.20	1521.25	1421.50	1385.50	1504.59
The flue gas sulphur content, milligram/rice 3	35	65	15	5	52
						Flue gas desulphuization rate, weight %	93.5	88.0	97.2	99.1	90.4

Claims (14)

1. the cracking method of a hydrocarbon oil containing surphur, this method is included under the cracking hydrocarbon oil condition, hydrocarbon oil containing surphur is contacted with a kind of catalyst mixture that contains cracking catalyst and sulfur transfer catalyst, reclaim crackate, it is characterized in that, described sulfur transfer catalyst contains the spinel composition of alkaline including earth metal, aluminium and the oxide compound of additional metal component, and the spinel composition of described alkaline including earth metal, aluminium contains alkaline-earth metal, aluminium, contains or do not contain rare earth metal except that cerium, contains or do not contain vanadium; Described additional metal component oxide is cerium oxide and zinc oxide, with the sulfur transfer catalyst is benchmark, the content of the spinel composition of alkaline including earth metal and aluminium is 50-90 weight %, the content of cerium oxide and zinc oxide is 10-50 weight %, the content of cerium oxide wherein is 5-25 weight %, and the content of zinc oxide is 5-25 weight %; The average particulate diameter of the cerium oxide that records with XRD method is less than 130 dusts, and the average particulate diameter of zinc oxide is less than 300 dusts.

2. method according to claim 1 is characterized in that, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-650 ℃, and agent-oil ratio is 1-25.

3. method according to claim 2 is characterized in that, described cracking hydrocarbon oil condition comprises that temperature of reaction is 420-600 ℃, and agent-oil ratio is 3-20.

4. method according to claim 1 is characterized in that described contact is carried out in riser reactor, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-650 ℃, and agent-oil ratio is 1-25, and the reaction times is 0.5-15 second.

5. method according to claim 1 is characterized in that, is benchmark with the catalyst mixture, and the content of cracking catalyst is 75-99.5 weight %, and the content of sulfur transfer catalyst is 0.5-25 weight %.

6. method according to claim 5 is characterized in that, is benchmark with the catalyst mixture, and the content of cracking catalyst is 80-98 weight %, and the content of sulfur transfer catalyst is 2-20 weight %.

7. method according to claim 1 is characterized in that the average particulate diameter of cerium oxide is not more than 100 dusts, and the average particulate diameter of zinc oxide is not more than 200 dusts.

8. method according to claim 7 is characterized in that, the average particulate diameter of cerium oxide is the 20-100 dust, and the average particulate diameter of zinc oxide is the 120-200 dust.

9. method according to claim 1 is characterized in that, is benchmark with the sulfur transfer catalyst, and the content of the spinel composition of alkaline including earth metal, aluminium is 60-85 weight %, and the content of cerium oxide and zinc oxide is 15-40 weight %.

10. method according to claim 1, it is characterized in that, spinel composition with alkaline including earth metal, aluminium is a benchmark, in oxide compound, the content of alkaline-earth metal is 20-70 weight %, the content of aluminium is 30-80 weight %, and the content of the rare earth metal except that cerium is 0-15 weight %, and the content of vanadium is 0-15 weight %.

11. method according to claim 10, it is characterized in that, spinel composition with alkaline including earth metal, aluminium is a benchmark, in oxide compound, the content of alkaline-earth metal is 30-60 weight %, the content of aluminium is 35-65 weight %, and the content of the rare earth metal except that cerium is 2-10 weight %, and the content of vanadium is 1-10 weight %.

12., it is characterized in that described alkaline-earth metal is magnesium and/or calcium according to any described method in the claim 1,9,10,11.

13., it is characterized in that described rare earth metal except that cerium is lanthanum or rich lanthanum and do not contain the mixture of the lanthanide rare metal of cerium according to any described method in the claim 1,10,11.

14. method according to claim 1 is characterized in that, described hydrocarbon oil containing surphur is sulphur-bearing crude or boiling range greater than 330 ℃ sulfur-bearing oil fraction.