CN1566273A - Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof - Google Patents

Abstract

The molecular sieve containing cracking catalyst comprises a heat resistant inorganic oxide and a metal component, wherein the molecular sieve is a mixture of a first zeolite and a second zeolite, the first zeolite is a type Y zeolite, the second level pore volume of the type Y zeolite amounts to 20-80% of the total pore volume, the second zeolite comprises silicon oxide and aluminium oxide whose mol ratio is greater than 20 based on total catalyst amount, the content of the first zeolite is 1-50 wt%, the content of the second zeolite is 1-40 wt%, the content of the heat resistant inorganic oxide is 2-80 wt%, the content of the clay is 0-80 wt%, based on the metallic oxides of the maximum valence, the content of the metallic constituent is 0.1-30 wt%, the metal constituents exists substantially in a deacidized valence state.

Description

A kind of hydrocarbon cracking catalyzer that contains molecular sieve and preparation method thereof

Technical field

The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof, more particularly, is about a kind of hydrocarbon cracking catalyzer that contains molecular sieve and preparation method thereof.

Background technology

Market is in great demand to diesel oil and liquefied gas (LPG's), therefore, wish and can obtain more diesel oil and more liquefied gas simultaneously by catalytic cracking process, this just need develop can obtain more diesel oil, can obtain the hydrocarbon cracking catalyzer of more liquefied gas again.

CN 1307087A discloses a kind of petroleum catalytic cracking catalyzer, this catalyzer contains the carrier of 50-80 weight % by butt weight, the Y zeolite of 10-50 weight %, shape-selective molecular sieve with 3-15 weight %, the relative crystallinity of described Y zeolite is 70-90%, and its second hole volume accounts for the 20-80% of total pore volume.This catalyzer can improve plant catalytic cracked fuel oil and liquefied gas yield.

On the other hand, 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.Corresponding is, the heaviness tendency of catalytically cracked material is serious day by day, the proportion of middle-eastern crude in the shared crude oil in Chinese refinery with higher sulfur content is also increasing, therefore, need develop the cracking catalyst with higher cracking activity and desulfurization performance.

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, by cracking, and all particles that comprise granules of catalyst are constantly in cracking hydrocarbon district and a catalyst regeneration zones circulation a zone of cracking.Wherein, contain another particle 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 additive 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 additive 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), overstable gamma zeolite (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 has the silicate (as metal silicate metallosilicate, titanosilicate titanosilicate) of Different Silicon aluminum ratio, 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 silicoalumino-phosphates (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.

Though desulphurizing activated the improving of the disclosed catalyzer of above-mentioned prior art,, on the one hand, use above-mentioned catalyzer, diesel oil and yield of liquefied gas are lower, and on the other hand, its desulfurization performance is still waiting to improve.Because above-mentioned catalyzer all through super-dry, roasting and/or hydrothermal treatment consists, does not have reduction process in preparation process, metal component contained in the above-mentioned catalyzer all exists with its highest oxidation state.

CN1382199A discloses a kind of adsorbent composition, and said composition is made up of bimetal promotor and granular carrier, and described bimetal promotor is gone up substantially with the reduction valence state and existed, and the amount of its existence can remove sulphur from pressure gasoline under desulfurization condition.Described bimetal promotor be selected from cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony and vanadium any two or more.Described carrier is by forming with the zinc oxide of any suitable inorganic and organic carrier combination.Described inorganic carrier comprises silicon oxide, silica gel, aluminum oxide, clay, pure aluminium silicate, silica-alumina, titanium oxide, zirconium white, Zinc aluminate, zinc titanate, zinc silicate, calcium aluminate, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium aluminate, magnesium titanate, synthetic zeolite and natural zeolite.Said composition is as the sorbent material that removes sulphur from pressure gasoline and diesel oil fuel, rather than cracking catalyst.

The purpose of this invention is to provide a kind of new yield that can improve diesel oil and liquefied gas, and have the cracking catalyst that contains molecular sieve of higher desulfurization performance.

The present inventor finds, if in cracking catalyst, introduce the metal component of going back ortho states, not only can improve the desulfurization performance of cracking catalyst, and, unexpectedly, the cracking activity of cracking catalyst can be significantly improved, by using suitable zeolite component, the yield of diesel oil and liquefied gas can also be obviously improved again.

Catalyzer provided by the invention contains molecular sieve, heat-resistant inorganic oxide and a kind of metal component, contain or argillaceous not, wherein, described molecular sieve is the mixture of first kind of zeolite and second kind of zeolite, described first kind of zeolite is y-type zeolite, the second hole volume of this y-type zeolite accounts for the 20-80% of total pore volume, the mol ratio that second kind of zeolite is silicon oxide and aluminum oxide is the zeolite more than 20, with the catalyzer total amount is benchmark, the content of first kind of zeolite is 1-50 weight %, the content of second kind of zeolite is 1-40 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 0-80 weight %, metal oxide in described maxivalence attitude, the content of metal component is 0.1-30 weight %, described metal component exists with the reduction valence state basically, and it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more.

Preparation of catalysts method provided by the invention comprises and will contain the metal component compound, molecular sieve, the composition of heat-resistant inorganic oxide and clay contacts with the atmosphere that contains reducing gas, the temperature of described contact is enough to make the average valence of described metal component to be lower than its highest oxidation state with the time that contacts, described molecular sieve is the mixture of first kind of zeolite and second kind of zeolite, described first kind of zeolite is y-type zeolite, the second hole volume of this y-type zeolite accounts for the 20-80% of total pore volume, the mol ratio that second kind of zeolite is silicon oxide and aluminum oxide is the zeolite more than 20, described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, each components contents makes in the final catalyzer and contains in the composition, with the catalyzer total amount is benchmark, first kind of zeolite of 1-50 weight %, second kind of zeolite of 1-40 weight %, the heat-resistant inorganic oxide of 2-80 weight %, the clay of 0-80 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.1-30 weight %.

Compared with prior art, catalyzer provided by the invention can improve the yield of diesel oil and liquefied gas, has more high desulfurization activity, and unexpectedly, also has higher cracking activity.

For example, adopting y-type zeolite content provided by the invention is 24 weight %, and the ZRP-1 zeolite content is 6 weight %, the content of aluminum oxide is 31 weight %, and the content of rare earth oxide is 1.5 weight %, and the content of MgO is 1.5 weight %, kaolinic content is 35 weight %, with Co ₂O ₃Meter, cobalt contents is 1 weight %, the average valence of cobalt is+1.5 or the catalyzer of zeroth order (average valence of cobalt is 0.5 or 0 for the ratio with the maxivalence attitude of cobalt), (through 800 ℃/4 hours steam agings, restore after the deactivation), be 480 ℃ in temperature of reaction, weight hourly space velocity is 16 hours ^-1The agent weight of oil is than being under 4.0 the condition, to sulphur content is 2.0 weight %, boiling range is that 329-550 ℃ decompressed wax oil carries out catalytic cracking, transformation efficiency is up to 76.4-77.1 weight %, liquefied gas yield is up to 19.6-20.1 weight %, and diesel yield is up to 16.5-16.9 weight %, and the sulphur content in the gasoline product has only the 414.7-486.5 mg/litre.And adopt zeolite content identical, the cracking catalyst that does not contain cobalt is all identical with each component concentration, just the valence state of cobalt is the catalyzer of its maxivalence attitude (+divalent), under identical condition, identical stock oil is carried out catalytic cracking, and transformation efficiency has only 74.8-75.9 weight % respectively, and liquefied gas yield has only 16.7-17.6 weight % respectively, diesel yield has only 16.0-16.3 weight % respectively, and the sulphur content in the gasoline product is respectively up to the 673.4-762.9 mg/litre.

Embodiment

According to catalyzer provided by the invention, with the catalyzer total amount is benchmark, the content of first kind of zeolite is that the content of 1-50 weight %, second kind of zeolite is 1-40 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 0-80 weight %, in the metal oxide of described maxivalence attitude, the content of metal component is 0.1-30 weight %.Under the preferable case, with the catalyzer total amount is benchmark, the content of first kind of zeolite is that the content of 10-50 weight %, second kind of zeolite is 1-30 weight %, the content of heat-resistant inorganic oxide is 5-60 weight %, the content of clay is 5-60 weight %, in the metal oxide of described maxivalence attitude, the content of metal component is 0.5-20 weight %.More under the preferable case, with the catalyzer total amount is benchmark, the content of first kind of zeolite is that the content of 10-50 weight %, second kind of zeolite is 3-20 weight %, the content of heat-resistant inorganic oxide is 10-50 weight %, the content of clay is 15-60 weight %, in the metal oxide of described maxivalence attitude, the content of metal component is 0.5-20 weight %.

First kind of zeolite is y-type zeolite, and the second hole volume of this y-type zeolite accounts for the 20-80% of total pore volume, preferably accounts for the 25-70% of total pore volume.The definition and the measuring method of described second hole volume describe in detail in CN1307087A.

The y-type zeolite that described second hole volume accounts for total pore volume 20-80% can be the commercially available y-type zeolite that meets this condition, can adopt the method preparation of conventional hydrothermal calcine.Adopt disclosed method preparation among the CN1307087A under the preferable case.Though the y-type zeolite with higher crystallinity (70-90%) according to disclosed method preparation among the CN1307087A is preferred,, this does not also mean that the y-type zeolite that has than low-crystallinity is unavailable.In fact, if the degree of crystallinity of described y-type zeolite is lower, can equally also can reach purpose of the present invention by adding more described y-type zeolite.

The mol ratio that second kind of zeolite is silicon oxide and aluminum oxide is the zeolite more than 20.The mol ratio of preferred silicon oxide and aluminum oxide is 20-500, more preferably the zeolite of 25-100.Described second kind of zeolite can be selected from the zeolite with MFI structure, the zeolite with MFI structure of phosphorous, rare earth and/or alkaline-earth metal, Beta zeolite, the mordenite of Beta zeolite, phosphorous, rare earth and/or alkaline-earth metal, one or more in the mordenite of phosphorous, rare earth and/or alkaline-earth metal.Be preferably zeolite, the zeolite with MFI structure of phosphorous and/or rare earth, one or more in the Beta zeolite of Beta zeolite, phosphorous and/or rare earth metal with MFI structure.The zeolite example of the described MFI of having structure comprises ZSM-5 zeolite, ZSM-8.That the zeolite example with MFI structure of phosphorous, rare earth and/or alkaline-earth metal comprises is phosphorous, the ZSM-5 zeolite of rare earth and/or alkaline-earth metal, the zeolite (ZRP zeolite) that the disclosed phosphorated of ZSM-8 zeolite, CN1194181A of phosphorous, rare earth and/or alkaline-earth metal has the MFI structure.

Described reduction valence state refers to that the average valence of described metal is zeroth order or is higher than zeroth order and is lower than its highest oxidation state.Under the preferable case, the ratio of the average valence of described metal and its maxivalence attitude is 0-0.95, and more preferably under the situation, this ratio is 0.1-0.7.

The maxivalence attitude of metal described here is meant after abundant oxidation, the highest oxidation state of metal described in the metal oxide of energy stable existence.For example, the highest oxidation state of the non-aluminum metal of periodic table of elements IIIA family is generally+3 valencys (as gallium); The highest oxidation state of IVA family metal is generally+4 valencys; The highest oxidation state of VA family metal is generally+5 valencys; The highest oxidation state of IB family metal is generally+divalent (as copper) or+1 valency (as silver); The highest oxidation state of IIB family metal is generally+divalent; The highest oxidation state of VB family metal is generally+5 valencys; The highest oxidation state of group vib metal is generally+6 valencys; The highest oxidation state of VIIB family metal is generally+4 valencys (as manganese) or+7 valencys (as rhenium); The non-noble metal highest oxidation state of VIII family is generally+3 valencys (as iron or cobalt) or+divalent (as nickel).

The method of measuring described metal average valence is as follows:

Accurately take by weighing about 0.4 gram catalyzer, put into the sample pool of TPD/R/O analysis tester, feeding hydrogen content is the hydrogen of 5 volume % and the gas mixture of nitrogen, the flow of hydrogen is 20 ml/min, with the speed of sample pool with 10 ℃/minute, be warming up to 1000 ℃ from room temperature, the catalyzer in the sample pool is carried out temperature programmed reduction(TPR), measure before the reduction respectively and the reduction rear catalyst on the TPR characteristic peak of metal component, calculate the average valence of metal according to following formula:

β _M＝β _M′-2f(A ₁-A)/N

Wherein: β _MBe the average valence of metal component M in the catalyzer, β _M' be the maxivalence attitude of metal component M in the catalyzer; The TPR characteristic peak area of metal M in the A catalyzer that to be metal component M exist with the reduction valence state; A ₁The TPR characteristic peak area of metal M in the catalyzer that exists with highest oxidation state for metal component M; N is the content (unit is mole) of metal component M in the catalyzer; F is a correction factor, and its measuring method is as follows: accurately take by weighing the sample pool that about 6.5 milligrams of CuO put into above-mentioned TPD/R/O analysis tester, under these conditions, measure the TPR characteristic peak area K that CuO is reduced fully ₂, calculate hydrogen-consuming volume (mole) K by the stoichiometric number of reduction reaction ₁, f is the ratio of hydrogen-consuming volume and TPR characteristic peak area, i.e. f=K ₁/ K ₂, the unit of f is a mole/TPR characteristic peak area.

Because therefore the position difference of the TPR characteristic peak of each metal, even contain metal component more than 2 kinds in the catalyzer, also can determine the TPR characteristic peak of each metal.

Described metal component is selected from one or more in the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, group vib metal, VIIB family metal, the VIII family base metal.The non-aluminum metal of described IIIA family comprises gallium, indium, thallium.Described IVA family metal comprises germanium, tin, lead.Described VA family metal comprises antimony, bismuth.Described IB family metal comprises copper, silver.Described IIB family metal comprises zinc, cadmium.Described VB family metal comprises vanadium, niobium, tantalum.Described group vib metal comprises chromium, molybdenum, tungsten.Described VIIB family metal comprises manganese, technetium, rhenium.Described VIII family base metal comprises iron, cobalt, nickel.Described metal component is preferably one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel, more preferably one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.

Described metal component can be present in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and the clay simultaneously, also may reside in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay.

According to specific embodiment of the present invention, described metal component particularly when described metal component is vanadium, nickel and/or iron, is present in heat-resistant inorganic oxide and/or the clay.

According to another one specific embodiment of the present invention, described metal component particularly when described metal component is iron, is present in first kind of zeolite and/or the second kind of zeolite.

The kind of described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of cracking catalyst matrix and binder component one or more, as in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, the boron oxide one or more.In preferred aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, the titanium oxide one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.

Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Preferred clay is a kaolin.These clays are conventionally known to one of skill in the art.

Catalyzer provided by the present invention can also and preferably contain alkaline-earth metal, described alkaline-earth metal can be present in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and the clay simultaneously, also may reside in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay.With the catalyzer total amount is benchmark, and in oxide compound, the content of described alkaline-earth metal group is 0-5 weight %.Described alkaline-earth metal is with alkaline earth metal compounds, and as the oxide compound of alkaline-earth metal, the form of the salt of alkaline-earth metal exists.Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, preferably magnesium and/or calcium.

Catalyzer provided by the invention can also contain rare earth metal, and described rare earth metal exists with the form of metal and/or compound (as the oxide compound of rare earth metal, the salt of rare earth).Described rare earth metal can be present in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and the clay simultaneously, also may reside in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay.Described rare earth metal is selected from one or more in group of the lanthanides and the actinium series rare earth metal, be preferably in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more, more preferably lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.With the catalyzer total amount is benchmark, and in oxide compound, the content of described rare earth metal is 0-50 weight %, is preferably 0-15 weight %.

Catalyzer provided by the invention can also contain phosphorus, and described phosphorus is with the compound of phosphorus, as the oxide compound and/or the existence of phosphatic form of phosphorus.Described phosphorus can be present in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and the clay simultaneously, also may reside in first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and clay.With the catalyzer total amount is benchmark, and in element phosphor, the content of described phosphorus is 0-15 weight %, is preferably 0-8 weight %.

In an embodiment of the present invention, when if rare earth metal and/or phosphorus are the preparation catalyzer, used first kind of zeolite or second kind of zeolite itself contain, the content of described first kind of zeolite or second kind of zeolite is to contain the first kind of zeolite of rare earth metal and/or phosphorus or the content of second kind of zeolite, the content of phosphorus and rare earth metal does not calculate separately, does not provide separately yet.

According to Preparation of catalysts method provided by the invention, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.

The example of described pure reducing gas comprises hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more, preferably includes in hydrogen, carbon monoxide, methane, ethane, propane, butane and various isomer thereof, pentane and the various isomer thereof one or more.

Described rare gas element refers to not the gas with described composition or metallic compound generation chemical action, as periodic table of elements O family gas, one or more in nitrogen, the carbonic acid gas.

The described example that contains reducing gas and inert gas atmosphere comprises hydrogen, carbon monoxide, contain one or more the mixture in one or more and the rare gas element in the hydro carbons of 1-5 carbon atom, the dry gas in the refinery.

In the described atmosphere that contains reducing gas, the concentration of reducing gas is not particularly limited, as long as the amount of used reducing gas can be with described metallic reducing.Under the preferable case, in the described atmosphere that contains reducing gas, reducing gas content is at least 10 volume %, more preferably 50 volume %.

The temperature of described contact is enough to make the average valence of described metal component and the ratio of its maxivalence attitude to be reduced to 0-0.95 with the time that contacts, and is preferably 0.1-0.7.In general, the temperature of described contact can be 100-900 ℃, is preferably 400-700 ℃, and the time of contact is 0.1 second to 10 hours, is preferably 1 second-5 hours.Described contact can be a Static Contact, and promptly in an airtight container, the atmosphere that will contain reducing gas contacts with described composition.Described contact can be dynamic contact also, is about to the described bed that contains the atmosphere of reducing gas by described composition.The pressure of described contact both can carry out under normal pressure without limits, also can carry out being higher or lower than under the normal pressure.The consumption that contains the atmosphere of reducing gas is that every gram catalyzer per hour is not less than 5 milliliters of reducing gass, and preferred every gram catalyzer per hour is not less than 10 milliliters of reducing gass, and more preferably every gram catalyzer is 100-2000 milliliter reducing gas per hour.

Each components contents preferably makes in the final catalyzer and contains in the composition, in the catalyzer total amount, first kind of zeolite of 10-50 weight %, second kind of zeolite of 1-30 weight %, the heat-resistant inorganic oxide of 5-60 weight %, the clay of 5-60 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.Each components contents more preferably makes in the final catalyzer and contains in the composition, in the catalyzer total amount, first kind of zeolite of 10-50 weight %, second kind of zeolite of 3-20 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 15-60 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.

The described composition that contains metal component compound, molecular sieve, heat-resistant inorganic oxide and clay can adopt any one or a few method preparation described below.These methods are conventional method.

One of method

(1) a. is with the precursor and/or the clay of the first kind of zeolite of solution impregnation that contains described metal component compound and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide, and is dry or moist then; B. or the precursor and/or the clay of the solution that will contain described metal component compound and first kind of zeolite and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide mix, dry or moist then; C. or with the precursor and/or the clay of described metal component compound and first kind of zeolite and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide carry out physical mixed; D. or the precursor and/or the clay of the solution that will contain described metal component compound and first kind of zeolite and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide mix, the precipitation agent that adds described metal component compound, described metal component is deposited in the precursor and/or clay of first kind of zeolite and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide, dry or moist; E. or the precursor and/or the clay of the solution that will contain described metal component compound and first kind of zeolite and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide mix, the slurry preparation that obtains is become colloid; F. or with the precursor of water-fast described metal component compound and first kind of zeolite and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide and/or clay and deionized water mix, the slurry preparation that obtains is become colloid, dry or moist;

(2) will introduce the precursor and/or the clay of first kind of zeolite of described metal component compound and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide, or described mixture, or colloid and deionized water and the not precursor and/or the clay making beating of first kind of zeolite of metallic components compound and/or second kind of zeolite, heat-resistant inorganic oxide, heat-resistant inorganic oxide, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting.

Two of method

Precursor, clay and deionized water making beating with first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting, then, with the dried solid of the solution impregnation that contains described metal component compound, perhaps the solution with described metal component compound mixes with dried solid, then, drying, roasting or not roasting.

Three of method

Precursor, clay, deionized water and the making beating of described metal component compound with first kind of zeolite, second kind of zeolite, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, being prepared into solid content is 10-50 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting.

Can adopt top method separately or introduce alkaline-earth metal when introducing above-mentioned metal component if also contain alkaline-earth metal in the catalyzer, just replace the compound of above-mentioned metal component to get final product with alkaline earth metal compound.Described alkaline-earth metal can also be that commercially available first kind of zeolite and/or second kind of zeolite itself have.

If also contain rare earth metal and/or phosphorus in the catalyzer, can adopt top method separately or introduce rare earth metal and/or phosphorus when introducing above-mentioned metal component, just replace the compound of above-mentioned metal component to get final product with rare earth compound and/or phosphorus compound.Described rare earth metal and/or phosphorus can also be the y-type zeolite or the overstable gamma zeolite of rare earth and/or phosphorus (as contain) that commercially available first kind of zeolite and/or second kind of zeolite itself are had.

Wherein, the drying behind the described introducing metal component compound and the drying means of slurries and condition are conventionally known to one of skill in the art, for example, the exsiccant method can be dry, oven dry, forced air drying, spraying drying.The method of the drying means preferably spray drying of slurries.The exsiccant temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.Roasting condition behind roasting after the described slurry dried and the impregnating metal compound also is conventionally known to one of skill in the art, in general, maturing temperature behind roasting after the described slurry dried and the impregnating metal compound is 400-700 ℃, be preferably 450-650 ℃, roasting time was at least 0.5 hour, be preferably 0.5-100 hour, more preferably 0.5-10 hour.

The precursor of described heat-resistant inorganic oxide refers in described cracking catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminum oxide can be selected from hydrated aluminum oxide (as pseudo-boehmite) and/or aluminium colloidal sol.The precursor of silicon oxide can be selected from silicon sol, one or more in silicon gel and the water glass.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.The precursor of other heat-resistant inorganic oxide can be selected from its oxyhydroxide, as oxyhydroxide, the boric acid of zirconium, titanium.

Described metal component compound can be water-soluble compound of described metal, also can be to be insoluble in water and/or water-fast compound, as the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, the non-noble metal nitrate of VIII family, muriate, oxyhydroxide, in the oxide compound one or more, particularly gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the nitrate of cobalt, muriate, oxyhydroxide, in the oxide compound one or more.

Described alkaline earth metal compound can be water-soluble compound of alkaline-earth metal, also can be to be insoluble in water and/or water-fast compound, as in the muriate of alkaline-earth metal, nitrate, oxyhydroxide, the oxide compound one or more.

Described rare earth compound can be water-soluble compound of rare earth metal, also can be to be insoluble in water and/or water-fast compound, as in the muriate of rare earth metal, nitrate, oxyhydroxide, the oxide compound one or more.

Described phosphorus compound can be water-soluble compound of described phosphorus, also can be to be insoluble in water and/or water-fast compound, as phosphoric acid, phosphorous acid, and the oxide compound of the phosphoric acid salt of ammonium, alkali-metal phosphoric acid salt, phosphorus, in the aluminum phosphate one or more.

Catalyzer provided by the invention can be used as the FCC catalyzer and uses separately, is used for producing diesel oil and liquefied gas, and reduces the sulphur content in gasoline and the diesel oil, particularly gasoline simultaneously.Catalyzer provided by the invention also can be used as desulfurizing assistant agent and mixes use with various cracking catalyst, to reduce the sulphur content in gasoline and the diesel oil, particularly gasoline.When catalyzer provided by the invention uses as desulfurizing assistant agent, content and the desired sulphur content of gasoline products according to sulphur in the stock oil, determine the ratio of contained catalyzer provided by the invention in the catalyst mixture, generally, catalyzer provided by the invention accounts at least 0.1 weight % of catalyst mixture, be preferably at least 1 weight %, more preferably at least 5 weight %, preferably at least 10 weight %.In addition, as the cracking catalysis agent aid, catalyzer provided by the invention also can with other auxiliary agent, mix use with existing cracking catalyst together as ignition dope, sulfur transfer catalyst, octane enhancing additive etc.

No matter catalyzer provided by the invention is as Primary Catalysts or auxiliary agent, and the condition of its use is the reaction conditions of general cracking hydrocarbon process routine, is 400-700 ℃ as temperature of reaction, is preferably 450-600 ℃, and weight hourly space velocity is 10-120 hour ^-1, be preferably 10-80 hour ^-1, the agent weight of oil is preferably 3-15 than for 1-20.Also can be used for deep catalytic cracking technology or Deep Catalytic Cracking process.

Catalyzer provided by the invention can be used as Primary Catalysts the hydrocarbon ils of sulfur-bearing is not carried out catalytic cracking, to improve the transformation efficiency of hydrocarbon ils, produces diesel oil and liquefied gas.Catalyzer provided by the invention also can be used as Primary Catalysts or auxiliary agent, and hydrocarbon oil containing surphur is carried out catalytic cracking, to improve the transformation efficiency of hydrocarbon ils, produces diesel oil and liquefied gas, and reduces the sulphur content in the crackate simultaneously.Described hydrocarbon ils is selected from oil and various petroleum fractions, particularly oil and boiling range are greater than 330 ℃ various petroleum fractionss, as sulfur-bearing or not long residuum, vacuum residuum, the decompressed wax oil of sulfur-bearing, the normal pressure wax oil, straight-run gas oil, propane is light/heavily de-oiling and wax tailings and through long residuum, vacuum residuum, the decompressed wax oil of hydrotreatment, one or more in the normal pressure wax oil.

The following examples will the present invention will be further described.

Unless stated otherwise, used kaolin is that Suzhou kaolin company produces among the embodiment, and its solid content is 76 weight %; Used pseudo-boehmite is that Shandong Zibo 501 factories produce, and its solid content is 62 weight %; Used aluminium colloidal sol is produced its Al for the Shandong catalyst plant ₂O ₃Content is 21 weight %; Used silicon sol is produced its SiO for the Shandong catalyst plant ₂Content is 27 weight %; All cpds is chemical pure.

The cracking activity of fresh cracking catalyst mesolite is very high, in the industrial production of reality, catalyst recirculation is used, live catalyst is after reaction for some time, its activity reaches a level relatively stably, therefore, the true activity of judging catalyzer just should with the catalyzer deactivation extremely with industrial poiser corresponding horizontal, this can reach zeolite deactivation wherein by catalyzer is carried out hydrothermal aging.In the following examples of the present invention, the step of an aging catalyst was arranged all before reduction, adding this step is for the ease of the judge activity of such catalysts, rather than says that Preparation of catalysts method provided by the invention needs this aged step.In fact, in industrial production, this aging step is unnecessary.

Embodiment 1

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

(1) be the NaY type zeolite (Na of 2.473 nanometers with 1000 gram (dry basis) lattice constants ₂O content is 14 weight %, and Qilu Petrochemical company Zhou village catalyst plant is produced) and 20 liters of (NH that concentration is 5 weight % ₄) ₂SO ₄The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain NH with the deionized water wash filter cake ₄NaY type zeolite records its Na ₂O content is 4.9 weight %.

NH with 900 gram (dry basis) above-mentioned preparations ₄NaY type zeolite is at 1000 gram silicon sol (SiO ₂Content is 12 weight %, Changhong chemical plant, Beijing commerical prod) in soaked 30 minutes, 120 ℃ of dryings 2 hours, obtain containing 10 weight %SiO then ₂NH ₄The NaY zeolite.

The SiO that contains with 800 gram (dry basis) above-mentioned preparations ₂NH ₄The NaY zeolite is in 650 ℃, with roasting in the water vapour atmosphere 16 hours, and the product that obtains with the deionized water wash that is equivalent to 20 times of solid weights again, 120 ℃ of oven dry obtain y-type zeolite A1.The composition of A1, lattice constant, relative crystallinity and specific surface area and second hole volume account for the percentage ratio of total pore volume, and as follows (degree of crystallinity of definition raw material NaY type zeolite is 100%, the relative crystallinity of the zeolite that obtains is the degree of crystallinity with respect to raw material NaY type zeolite, the measuring method of relative crystallinity is referring to " petrochemical complex analytical procedure (RIPP test method) " PP414-415, Yang Cui waits volume, Science Press, 1990 surely; The content of sodium oxide, aluminum oxide and silicon oxide all adopts x-ray fluorescence spectrometry, and lattice constant adopts X-ray diffraction method to measure, and specific surface and pore volume adopt cryogenic nitrogen absorption BET method to measure):

Zeolite numbering A1 lattice constant, nanometer 2.450 relative crystallinities, % 82 specific surface areas, rice 2/ gram 648 total pore volumes, milliliter/gram 0.388 micro pore volume, milliliter/gram 0.273 second hole volume, milliliter/gram 0.115 second hole volume/total pore volume, % 30 chemical constitutions, weight % Na 2O?????????????????????4.1 ????Al 2O 3???????????????????22.8 ????SiO 2?????????????????????73.1

(2) take by weighing 34.0 kilograms pseudo-boehmite and 170 kilograms deionized water and mix, add 4.0 kilograms of rare earth chloride RECl _x(Baotou rare earth factory in the Inner Mongol produces, the rare earth oxide (RE that described rare earth chloride records after rich a hour through 800 ℃ of roastings ₂O ₃) content is 46 weight %, wherein the contents on dry basis of each component is La ₂O ₃24.5 weight %, CeO ₂6.0 weight %, Pr ₂O ₃6.0 weight %, Nd ₂O ₃9.5 weight %), the concentration that under agitation adds 4.0 kilograms is the concentrated hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) of 36 volume %, the gained mixture is warming up to 70 ℃ wore out 1.5 hours, the pseudo-boehmite after obtaining wearing out.Butt with the pseudo-boehmite after aging is a benchmark, and in rare earth oxide, the content of rare earth metal is 8.0 weight %.

(3) magnesium chloride brine that is 10 weight % with kaolin, above-mentioned pseudo-boehmite, aluminium colloidal sol, the concentration that contains rare earth metal, the cobalt nitrate aqueous solution that concentration is 30 weight %, above-mentioned y-type zeolite A1, (the industrial trade mark is ZRP-1 to have the zeolite of MFI structure, in element phosphor, phosphorus content is 2.0 weight %, and rare earth oxide content is 1.0 weight %, wherein, lanthanum trioxide content is 0.53 weight %, cerium oxide content is 0.13 weight %, and other rare earth oxide content is 0.34 weight %, Na ₂O content is less than 0.1 weight %, SiO ₂With Al ₂O ₃Mol ratio be 60, the Shandong catalyst plant is produced) and deionized water mix.It is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain.The consumption of kaolin, pseudo-boehmite, aluminium colloidal sol, y-type zeolite, ZRP-1 zeolite, cobalt nitrate aqueous solution and magnesium chloride brine after aging makes kaolin butt weight, Al ₂O ₃, y-type zeolite butt weight, ZRP-1 zeolite butt weight (comprising wherein contained phosphorus and rare earth), Co ₂O ₃, rare earth oxide (RE ₂O ₃, do not comprise contained rare earth in the ZRP-1 zeolite) and the ratio of the weight of MgO be 35.0: 31.0: 24.0: 6.0: 1.0: 1.5: 1.5.

With the slurries spraying drying under 150 ℃ temperature that obtains,,, wore out 4 hours with 100% water vapour then at 800 ℃ 550 ℃ of following roastings 1 hour.The catalyzer 200 that obtains is restrained in the fixed bed reduction reactor of packing into, under 400 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 0.5 hour with described solid, the temperature of reactor is reduced to room temperature, unload the solid after the reduction, obtain catalyzer C1 provided by the invention.The ratio of the composition of catalyzer C1 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.

Catalyzer is formed by calculating, and the content of metal component is in the oxide compound of described metal component highest oxidation state.Wherein, in table 1 and following each table, the content of ZRP-1 zeolite comprises wherein contained phosphorus and rare earth, and the content of described rare earth oxide does not comprise the content of contained rare earth in the ZRP-1 zeolite.

Embodiment 2

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

Method by embodiment 1 prepares catalyzer, and different is, the temperature that described solid contacts with hydrogen is 500 ℃, and be 3 hours duration of contact, obtains catalyzer C2 provided by the invention.The ratio of the composition of catalyzer C2 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.

Embodiment 3

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

With 3.64 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of cobalt nitrate hexahydrate aqueous solution dipping of 10 weight %, 120 ℃ of oven dry, and 600 ℃ of roastings 1 hour obtain containing Co ₂O ₃2.78 the kaolin of weight %.

Method by (3) among the embodiment 1 prepares catalyzer, and different is with containing Co ₂O ₃2.78 the kaolin of weight % replaces embodiment 1 described kaolin, does not add cobalt nitrate aqueous solution, obtains catalyzer C3 provided by the invention.The ratio of the composition of catalyzer C3 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.

Comparative Examples 1

This Comparative Examples illustrates reference catalyst of metallic components not and preparation method thereof.

Method by embodiment 1 prepares catalyzer, different is not add cobalt nitrate aqueous solution, the process that in fixed-bed reactor, solid is not contacted with hydrogen, and the consumption of kaolin, the pseudo-boehmite after wearing out, aluminium colloidal sol, y-type zeolite A1, ZRP-1 zeolite, magnesium chloride brine makes kaolin butt weight, Al ₂O ₃, y-type zeolite butt weight, ZRP-1 zeolite butt weight, RE ₂O ₃With the ratio of the weight of MgO be 35.0: 32.0: 24.0: 6.0: 1.5: 1.5.Obtain zeolite, kaolin, RE ₂O ₃Identical with MgO content, the reference catalyst CB1 of metallic components not.The composition of CB1 is listed in the table 1.

Comparative Examples 2

The explanation of this Comparative Examples contains reference catalyst of highest oxidation state metal component and preparation method thereof.。

Method by embodiment 1 prepares catalyzer, and different is that the process that in fixed-bed reactor solid is not contacted with hydrogen obtains reference catalyst CB2.The composition of CB2 is listed in the table 1.

Comparative Examples 3

The explanation of this Comparative Examples contains reference catalyst of highest oxidation state metal component and preparation method thereof.

Method by embodiment 3 prepares catalyzer, and different is that the process that in fixed-bed reactor solid is not contacted with hydrogen obtains reference catalyst CB3.The composition of CB3 is listed in the table 1.

Table 1

Example number	????1	????2	????3	Comparative Examples 1	Comparative Examples 2	Comparative Examples 3
							The catalyzer numbering	????C1	????C2	????C3	????CB1	????CB2	????CB3
The molecular sieve kind	????A1/ZRP-1	????A1/ZRP-1	????A1/ZRP-1	????A1/ZRP-1	????A1/ZRP-1	????A1/ZRP-1
							Molecular sieve content, weight %	????24.0/6.0	????24.0/6.0	????24.0/6.0	????24.0/6.0	????24.0/6.0	????24.0/6.0
The heat-resistant inorganic oxide kind	????Al 2O 3	????Al 2O 3	????Al 2O 3	????Al 2O 3	????Al 2O 3	????Al 2O 3
							Heat-resistant inorganic oxide content, weight %	????31.0	????31.0	????31.0	????32.0	????31.0	????31.0
RE 2O 3, weight %	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5
							MgO, weight %	????1.5	????1.5	????1.5	????1.5	????1.5	????1.5
Clay types	Kaolin	Kaolin	Kaolin	Kaolin	Kaolin	Kaolin
							Clay content, weight %	????35.0	????35.0	????35.0	????35.0	????35.0	????35.0
The metal component kind	????Co	????Co	????Co	????-	????Co	????Co
							Metal oxide content, weight %	????1.0	????1.0	????1.0	????-	????1.0	????1.0
The metal component average valence	????+1.5	????0	????+1.5	????-	????+3	????+3
							The ratio of metal component average valence and its maxivalence attitude	????0.5	????0	????0.5	????-	????1	????1
Metal component distributes	Be evenly distributed in the catalyzer	Be evenly distributed in the catalyzer	Be evenly distributed in the clay	????-	Be evenly distributed in the catalyzer	Be evenly distributed in the clay

Embodiment 4

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

(1) be the NaY type zeolite (Na of 2.473 nanometers with 1000 gram (dry basis) lattice constants ₂O content is 14 weight %, and Qilu Petrochemical company Zhou village catalyst plant is produced) and 20 liters of (NH that concentration is 10 weight % ₄) ₂SO ₄The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain NH with the deionized water wash filter cake ₄NaY type zeolite records its Na ₂O content is 3.7 weight %.

NH with 900 gram (dry basis) above-mentioned preparations ₄NaY type zeolite is at 1000 gram water glass (SiO ₂Content is 10 weight %, modulus 3.3, Zhou village catalyst plant product) in soaked 30 minutes, 120 ℃ of dryings 2 hours, obtain containing 8.5 weight %SiO then ₂The NH of silicon dipping ₄The NaY zeolite.

The SiO that contains with 800 gram (dry basis) above-mentioned preparations ₂NH ₄The roasting 8 hours in 700 ℃ of water vapour atmospheres of NaY zeolite, the product that obtains with the deionized water wash that is equivalent to 20 times of solids again, 120 ℃ of oven dry obtain y-type zeolite A2.It is as follows that the composition of A2, lattice constant, relative crystallinity and specific surface area and second hole volume account for the percentage ratio of total pore volume:

Zeolite numbering A2 lattice constant, nanometer 2.448 relative crystallinities, % 80 specific surface areas, rice 2/ gram 656 total pore volumes, milliliter/gram 0.384 micro pore volume, milliliter/gram 0.253 second hole volume, milliliter/gram 0.131 second hole volume/total pore volume, % 34 chemical constitutions, weight % Na 2O????????????????????3.3 ????Al 2O 3??????????????????21.2 ????SiO 2????????????????????75.5

(2) method by (2) in the example 1 prepares the aged pseudo-boehmite, the consumption of different is rare earth chloride is 6.5 kilograms, butt with the pseudo-boehmite after aging is a benchmark, and in rare earth oxide, the content of the pseudo-boehmite middle-weight rare earths metal after wearing out is 12.4 weight %.

(3) with 3.15 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of zinc nitrate aqueous solution dipping of 7.0 weight %, 120 ℃ of oven dry, 600 ℃ of roastings 1 hour obtain containing the kaolin of ZnO 3.1 weight %.

Method by (3) among the embodiment 1 prepares catalyzer, different is replaces embodiment 1 described kaolin with the kaolin of the above-mentioned ZnO of containing, do not add cobalt nitrate aqueous solution, replace the described pseudo-boehmite after aging of example 1 with the described pseudo-boehmite after aging of this example (2), replace y-type zeolite A1 with y-type zeolite A2; The consumption of the kaolin of the described ZnO of containing, pseudo-boehmite, aluminium colloidal sol, y-type zeolite A2, ZRP-1 zeolite and magnesium chloride brine after aging makes kaolin butt weight, Al ₂O ₃, y-type zeolite A2 butt weight, ZRP-1 zeolite butt weight, ZnO, RE ₂O ₃With the ratio of the weight of MgO be 25.0: 16.2: 45.0: 10.0: 0.8: 1.0: 2.0; Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the flow of gas mixture is 2000 ml/min, the temperature that described solid contacts with gas mixture is 800 ℃, and be 3 hours duration of contact, obtains catalyzer C4 provided by the invention.The ratio of the composition of catalyzer C4 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Embodiment 5

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

(1) method by (2) in the example 1 prepares the aged pseudo-boehmite, the consumption of different is rare earth chloride is 6.5 kilograms, butt with the pseudo-boehmite after aging is a benchmark, and in rare earth oxide, the content of the pseudo-boehmite middle-weight rare earths metal after wearing out is 12.4 weight %.

(2) with 2.90 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of iron nitrate aqueous solution dipping of 10 weight %, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing Fe ₂O ₃3.1 the kaolin of weight %.

Method by (3) among the embodiment 1 prepares catalyzer, and different is with the above-mentioned Fe of containing ₂O ₃Kaolin replace embodiment 1 described kaolin, do not add cobalt nitrate aqueous solution, replace the described pseudo-boehmite after aging of example 1 with the described pseudo-boehmite after aging of this example (1), replace y-type zeolite A1 with y-type zeolite A2, use ZSM-5 zeolite (SiO ₂With Al ₂O ₃Mol ratio be 62, Na ₂O content is 0.08 weight %, and the Shandong catalyst plant is produced) replacement ZRP-1 zeolite; The described Fe that contains ₂O ₃Kaolin, the consumption of pseudo-boehmite, aluminium colloidal sol, y-type zeolite A2, ZSM-5 zeolite and magnesium chloride brine after aging make kaolin butt weight, Al ₂O ₃, y-type zeolite A2 butt weight, ZSM-5 zeolite butt weight, Fe ₂O ₃, RE ₂O ₃With the ratio of the weight of MgO be 25.0: 16.2: 45.0: 10.0: 0.8: 1.0: 2.0; Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the flow of gas mixture is 1200 ml/min, the temperature that described solid contacts with gas mixture is 600 ℃, be 0.5 hour duration of contact, obtains catalyzer C5 provided by the invention.The ratio of the composition of catalyzer C5 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Embodiment 6

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

(1) be the NaY type zeolite (Na of 2.473 nanometers with 1000 gram (dry basis) lattice constants ₂O content is 14 weight %, and Qilu Petrochemical company Zhou village catalyst plant is produced) and 20 liters of (NH that concentration is 5 weight % ₄) ₂SO ₄The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain NH with the deionized water wash filter cake ₄NaY type zeolite records its Na ₂O content is 4.9 weight %.

NH with 900 gram (dry basis) above-mentioned preparations ₄NaY type zeolite soaked 30 minutes in the ammonium fluosilicate solution of 2000 milliliters of 0.5M, 120 ℃ of dryings 2 hours, obtained containing 5.6 weight %SiO then ₂NH ₄The NaY zeolite.

The SiO that contains with 800 gram (dry basis) above-mentioned preparations ₂NH ₄The roasting 4 hours in 750 ℃ of water vapour atmospheres of NaY zeolite, the product that obtains with the deionized water wash that is equivalent to 20 times of solid weights again, 120 ℃ of oven dry obtain y-type zeolite A3.It is as follows that the composition of A3, lattice constant, relative crystallinity and specific surface area and second hole volume account for the percentage ratio of total pore volume:

Zeolite numbering A3 lattice constant, nanometer 2.449 relative crystallinities, % 78 specific surface areas, rice 2/ gram 626 total pore volumes, milliliter/gram 0.372 micro pore volume, milliliter/gram 0.234 second hole volume, milliliter/gram 0.138 second hole volume/total pore volume, % 37 chemical constitutions, weight % Na 2O????????????????????3.8 ????Al 2O 3??????????????????22.7 ????SiO 2????????????????????73.5

(2) method by (2) in the example 1 prepares the aged pseudo-boehmite, the consumption of different is rare earth chloride is 9.0 kilograms, butt with the pseudo-boehmite after aging is a benchmark, and in rare earth oxide, the content of the pseudo-boehmite middle-weight rare earths metal after wearing out is 16.4 weight %.

(3) be 2.925 kilograms of (dry basis) kaolin of copper nitrate aqueous solution dipping of 20 weight % and the mixture of 0.075 kilogram of titanium dioxide with 3.36 kilograms of concentration, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing CuO 8.68 weight %, TiO ₂2.3 the kaolin of weight %.

Method by (3) among the embodiment 1 prepares catalyzer, and different is with above-mentioned CuO of containing and TiO ₂Kaolin replace embodiment 1 described kaolin, do not add Xiao Suangu and magnesium chloride brine, replace the described pseudo-boehmite after aging of example 1 with the described pseudo-boehmite after aging of this example (2), with y-type zeolite A3 replacement y-type zeolite A1; Described CuO and the TiO of containing ₂Kaolin, the pseudo-boehmite after aging, aluminium colloidal sol, y-type zeolite A3, the consumption of ZRP-1 zeolite make kaolin butt weight, TiO ₂, Al ₂O ₃, y-type zeolite A3 butt weight, ZRP-1 zeolite butt weight, CuO and RE ₂O ₃The ratio of weight be 39.0: 1.0: 24.0: 25: 5: 3.8: 2.2; Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the flow of gas mixture is 1000 ml/min, the temperature that described solid contacts with gas mixture is 400 ℃, be 0.5 hour duration of contact, obtains catalyzer C6 provided by the invention.The ratio of the composition of catalyzer C6 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Embodiment 7

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

With 1000 gram (dry basis) lattice constants is the ultrastable Y (Na of 2.443 nanometers ₂O content is 0.8 weight %, and Qilu Petrochemical company Zhou village catalyst plant is produced) and 20 liters of Na that concentration is 5 weight % ₂SO ₄The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain HNaY type zeolite, record its Na with the deionized water wash filter cake ₂O content is 4.5 weight %.

The HNaY type zeolite of 900 gram (dry basis) above-mentioned preparations is restrained SiO 100 ₂Content is to soak 30 minutes in the dimethyl-silicon aqueous solution of 5.0 weight %, 120 ℃ of dryings 2 hours, obtains containing 4.5 weight %SiO then ₂The HNaY zeolite.

The SiO that contains with 800 gram (dry basis) above-mentioned preparations ₂The roasting 10 hours in 600 ℃ of water vapour atmospheres of HNaY zeolite, the product that obtains with the deionized water wash that is equivalent to 20 times of solid weights again, 120 ℃ of oven dry obtain y-type zeolite A4.It is as follows that the composition of A4, lattice constant, relative crystallinity and specific surface area and second hole volume account for the percentage ratio of total pore volume:

Zeolite numbering A4 lattice constant, nanometer 2.438 relative crystallinities, % 75 specific surface areas, rice 2/ gram 588 total pore volumes, milliliter/gram 0.354 micro pore volume, milliliter/gram 0.168 second hole volume, milliliter/gram 0.186 second hole volume/total pore volume, % 53 chemical constitutions, weight % Na 2O????????????????????4.0 ????Al 2O 3??????????????????19.8 ????SiO 2????????????????????76.2

(2) method by (2) in the example 1 prepares the aged pseudo-boehmite, and different is not add rare earth chloride, the pseudo-boehmite after obtaining wearing out.

(3) with 3.2 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of manganese nitrate aqueous solution dipping of 5.0 weight %, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain containing MnO ₂2.63 the kaolin of weight %.

Method by (3) among the embodiment 1 prepares catalyzer, and different is with the above-mentioned MnO of containing ₂Kaolin replace embodiment 1 described kaolin, do not add cobalt nitrate aqueous solution, replace the described pseudo-boehmite after aging of example 1 with the described pseudo-boehmite after aging of this example (2), with y-type zeolite A4 replacement A1; The described MnO that contains ₂Kaolin, the consumption of pseudo-boehmite, aluminium colloidal sol, y-type zeolite A4, ZRP-1 zeolite and magnesium chloride brine after aging make kaolin butt weight, Al ₂O ₃, y-type zeolite A4 butt weight, ZRP-1 zeolite butt weight MnO ₂With the ratio of the weight of MgO be 37.0: 25.5: 28.0: 7.0: 1.0: 1.5; Reductive atmosphere is hydrogen content 80 volume % and the hydrogen of propane content 20 volume % and the gas mixture of propane, the flow of gas mixture is 1500 ml/min, the temperature that described solid contacts with gas mixture is 500 ℃, and be 1 hour duration of contact, obtains catalyzer C7 provided by the invention.The ratio of the composition of catalyzer C7 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.

Table 2

Example number	????4	????5	????6	????7
					The catalyzer numbering	????C4	????C5	????C6	????C7
The molecular sieve kind	????A2/ZRP-1	????A2/ZSM-5	????A3/ZRP-1	????A4/ZRP-1
					Molecular sieve content, weight %	????45.0/10.0	????45.0/10.0	????25.0/5.0	????28.0/7.0
The heat-resistant inorganic oxide kind	????Al 2O 3	????Al 2O 3	????Al 2O 3/TiO2	????Al 2O 3
					Heat-resistant inorganic oxide content, weight %	????16.2	????16.2	????24.0/1.0	????25.5
RE 2O 3, weight %	????1.0	????1.0	????2.2	????0
					MgO, weight %	????2.0	????2.0	????0	????1.5
Clay types	Kaolin	Kaolin	Kaolin	Kaolin
					Clay content, weight %	????25.0	????25.0	????39.0	????37.0
The metal component kind	????Zn	????Fe	????Cu	????Mn
					Metal oxide content, weight %	????0.8	????0.8	????3.8	????1.0
The metal component average valence	????1.4	????2.0	????0.6	????1.5
					The ratio of metal component average valence and its maxivalence attitude	????0.70	????0.67	????0.3	????0.38
Metal component distributes	Be evenly distributed in the clay	Be evenly distributed in the clay	Be distributed in clay and the heat-resistant inorganic oxide	Be evenly distributed in the clay

Embodiment 8

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

(1) method by (2) in the example 1 prepares the aged pseudo-boehmite, the consumption of different is rare earth chloride is 6.5 kilograms, butt with the pseudo-boehmite after aging is a benchmark, and in rare earth oxide, the content of the pseudo-boehmite middle-weight rare earths metal after wearing out is 12.4 weight %.

(2) with 3.22 kilograms of concentration be the ammonium molybdate ((NH of 5.0 weight % ₄) ₆Mo ₇O ₂₄.6H ₂O) (solid content is 85.0 weight % for the aqueous solution 3.0 kilograms of (dry basis) kaolin of dipping and 0.5 kilogram of (dry basis) diatomite, Shengzhou, Zhejiang Province city China power diatomite factory product) mixture, 120 ℃ of oven dry, and then with the silver nitrate aqueous solution of 2.25 kilogram of 2.0 weight % dipping, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing MoO ₃3.58 weight % and Ag ₂The kaolin of O 0.90 weight % and diatomaceous mixture.

Method by (3) among the embodiment 1 prepares catalyzer, and different is with the above-mentioned MoO of containing ₃And Ag ₂The kaolin of O replaces embodiment 1 described kaolin, does not add cobalt nitrate aqueous solution, and the pseudo-boehmite after wearing out with this example (1) is described replaces the pseudo-boehmite after example 1 described the wearing out; The described MoO that contains ₃And Ag ₂The consumption of the kaolin of O, pseudo-boehmite, aluminium colloidal sol, y-type zeolite A1, ZRP-1 zeolite and magnesium chloride brine after aging makes kaolin butt weight, Al ₂O ₃, y-type zeolite A1 butt weight, ZRP-1 zeolite butt weight, MoO ₃, Ag ₂O, RE ₂O ₃With the ratio of the weight of MgO be 32.0: 19.0: 35.0: 10.0: 1.2: 0.3: 1.0: 1.5; Reductive atmosphere is the nitrogen of hydrogen content 50 volume % and mixing of hydrogen, and the flow of gas mixture is 2500 ml/min, and the temperature that described solid contacts with gas mixture is 650 ℃, and be 1 hour duration of contact, obtains catalyzer C8 provided by the invention.The ratio of the composition of catalyzer C8 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Embodiment 9

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

(1) method by (2) in the example 1 prepares the aged pseudo-boehmite, the consumption of different is rare earth chloride is 5.4 kilograms, butt with the pseudo-boehmite after aging is a benchmark, and in rare earth oxide, the content of the pseudo-boehmite middle-weight rare earths metal after wearing out is 10.5 weight %.

(2) under agitation, with 2.96 kilograms of concentration be the ammonium meta-vanadate (NH of 2.0 weight % ₄VO ₃) 3.0 kilograms of (dry basis) kaolin of aqueous solution dipping and 0.08 kilogram of magnesian mixture, 120 ℃ of slurries that oven dry obtains, 550 ℃ of roastings 2 hours obtain containing MgO 2.6 weight %, V ₂O ₅1.5 the kaolin of weight %.

Method by (3) among the embodiment 1 prepares catalyzer, and different is with above-mentioned MgO of containing and V ₂O ₅Kaolin replace embodiment 1 described kaolin, do not add cobalt nitrate aqueous solution and magnesium chloride brine, replace the described pseudo-boehmite after aging of example 1 with the described pseudo-boehmite after aging of this example (2), with y-type zeolite A2 replacement A1; Described MgO and the V of containing ₂O ₅Kaolin, the pseudo-boehmite after aging, aluminium colloidal sol, y-type zeolite A2, the consumption of ZRP-1 zeolite make kaolin butt weight, magnesium oxide, Al ₂O ₃, y-type zeolite A2 butt weight, ZRP-1 zeolite butt weight V ₂O ₅And RE ₂O ₃The ratio of weight be 39.0: 1.0: 23.0: 28.0: 7.0: 0.6: 1.4; The temperature that described solid contacts with hydrogen is 550 ℃, and the flow of hydrogen is 1000 ml/min, and be 1 hour duration of contact, obtains catalyzer C9 provided by the invention.The ratio of the composition of catalyzer C9 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Embodiment 10

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

With 2.74 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of gallium chloride aqueous solution dipping of 40 weight % and the mixture of 0.86 kilogram of (dry basis) pseudo-boehmite, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain containing Ga ₂O ₃13.1 the kaolin of weight % and the mixture of aluminum oxide.

To contain Ga ₂O ₃Kaolin and mixture, silicon sol, calcium chloride water and the deionized water of aluminum oxide mix, add y-type zeolite A3 and ZSM-5 zeolite (specification is with embodiment 5) again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains Ga ₂O ₃Kaolin and the consumption of mixture, silicon sol, y-type zeolite A3, ZSM-5 zeolite and the calcium chloride water of aluminum oxide make kaolin butt weight, aluminum oxide, silicon oxide, y-type zeolite A3 butt weight, ZSM-5 zeolite butt weight, Ga ₂O ₃With the ratio of the weight of CaO be 35.0: 10: 11.7: 28: 7: 6.8: 1.5.

With the slurries spraying drying under 150 ℃ temperature that obtains,,, wore out 8 hours with 100% water vapour then at 800 ℃ 550 ℃ of following roastings 2 hours.The solid 200 that obtains is restrained in the fixed bed reduction reactor of packing into, and under 600 ℃ of temperature, feeding flow is the hydrogen of 3000 ml/min, make hydrogen contact 2 hours with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain catalyzer C10 provided by the invention.The ratio of the composition of catalyzer C10 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Embodiment 11

Present embodiment illustrates Catalysts and its preparation method provided by the invention.

With 3.1 kilograms of concentration is the tin protochloride SnCl of 6.0 weight % ₂The aqueous solution, 0.6 kilogram of (dry basis) silicon sol and 3.0 kilograms of (dry basis) kaolin mix, 120 ℃ of oven dry, and 550 ℃ of roastings 3 hours obtain containing SnO ₂4.0 the kaolin of weight % and the mixture of silicon oxide.

To contain SnO ₂Kaolin and the mixture of silicon oxide, aluminium colloidal sol, mix with deionized water, add y-type zeolite A4 and ZSM-5 zeolite (specification is with embodiment 5) again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains SnO ₂Kaolin and the consumption of the mixture of silicon oxide, aluminium colloidal sol, y-type zeolite A4, ZSM-5 zeolite make kaolin butt weight, aluminum oxide, silicon oxide, y-type zeolite A4 butt weight, ZSM-5 zeolite butt weight, SnO ₂The ratio of weight be 40.0: 20.0: 8.0: 25: 5: 2.0.With the slurries spraying drying under 150 ℃ temperature that obtains,,, wore out 8 hours with 100% water vapour then at 800 ℃ 550 ℃ of following roastings 2 hours.

The solid 200 that obtains is restrained in the fixed bed reduction reactor of packing into, and under 650 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 1 hour with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain catalyzer C11 provided by the invention.The ratio of the composition of catalyzer C11 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.

Table 3

Example number	????8	????9	????10	????11
					The catalyzer numbering	????C8	????C9	????C10	????C11
The molecular sieve kind	????A1/ZRP-1	????A2/ZRP-1	????A3/ZSM-5	????A4/ZSM-5
					Molecular sieve content, weight %	????35.0/10.0	????28.0/7.0	????28.0/7.0	????25.0/5.0
The heat-resistant inorganic oxide kind	????Al 2O 3	????Al 2O 3	????Al 2O 3/SiO 2	????Al 2O 3/SiO 2
					Heat-resistant inorganic oxide content, weight %	????19.0	????23.0	????10/11.7	????20/8.0
RE 2O 3, weight %	????1.0	????1.4	????0	????0
					MgO, weight %	????1.5	????1.0	????0	????0
CaO,, weight %	????0	????0	????1.5	????0
					Clay types	Kaolin+diatomite	Kaolin	Kaolin	Kaolin
Clay content, weight %	????32.0	????39.0	????35.0	????40.0
					The metal component kind	????Mo/Ag	????V	????Ga	????Sn
Metal oxide content, weight %	????1.2/0.3	????0.6	????6.8	????2.0
					The metal component average valence	????3.0/0	????2.3	????1.5	????2.2
The ratio of metal component average valence and its maxivalence attitude	????0.5/0	????0.46	????0.5	????0.55
					Metal component distributes	Be evenly distributed in the clay	Be evenly distributed in clay and the inorganic oxide	Be distributed in clay and the inorganic oxide	Be distributed in clay and the inorganic oxide

Embodiment 12-22

The following examples illustrate the catalytic performance of catalyzer provided by the invention.

On the small stationary bed reaction device, adopt catalyzer C1-C11 provided by the invention, his-and-hers watches 4 listed boiling ranges are that 329-550 ℃ sulfur-bearing decompressed wax oil carries out catalytic cracking, catalyzer loading amount 4.0g.Reaction conditions and reaction result are listed among the table 5-7.Sulphur content adopts gas-chromatography-atomic emission spectrometry in the crackate, measures on HP 6890GC-G2350A AED gas-chromatography-Atomic Emission SpectrometerAES.

Wherein, agent-oil ratio refers to the weight ratio of catalyzer and described stock oil.

Comparative Examples 4-6

The catalytic performance of following Comparative Examples explanation reference catalyst.

Method by embodiment 12 is carried out catalytic cracking to identical stock oil, and different is that catalyst system therefor is respectively reference catalyst CB1, CB2 and CB3, and reaction conditions and reaction result are listed in the table 5.

Table 4

The stock oil title	Long residuum	Decompressed wax oil
			Density (20 ℃), grams per cubic centimter	????0.8906	????0.9154
Viscosity, the milli m2/S
			????50℃	????-	????34.14
????100℃	????24.84	????6.96
			Bituminous matter, weight %	????0.8	????0.0
Conradson carbon residue, weight %	????4.3	????0.18
			S, weight %	????0.13	????2.0
Boiling range, ℃
			????IBP	????282	????329
????10％	????370	????378
			????50％	????553	????436
????90％	????-	????501
			????95％	????-	????518
????FBP	????-	????550

Table 5

Example number	????12	????13	????14	Comparative Examples 4	Comparative Examples 5	Comparative Examples 6
							The catalyzer numbering	????C1	????C2	????C3	????CB1	????CB2	????CB3
Temperature of reaction, ℃	????500	????500	????500	????500	????500	????500
							Weight hourly space velocity, hour -1	????16	????16	????16	????16	????16	????16
Agent-oil ratio	????6.0	????6.0	????6.0	????6.0	????6.0	????6.0
							Transformation efficiency, weight %	????77.1	????76.4	????76.8	????75.9	????75.4	????74.8
Product yield, weight %
							Dry gas	????1.8	????1.7	????1.9	????1.5	????1.4	????1.4
Liquefied gas	????18.7	????18.6	????19.1	????16.6	????15.7	????15.9
							Gasoline	????50.8	????50.4	????50.0	????52.3	????52.6	????51.8
Diesel oil	????16.8	????16.9	????16.5	????16.3	????16.0	????16.1
							Heavy oil	????6.1	????6.7	????6.7	????7.8	????8.6	????9.1
Coke	????5.8	????5.7	????5.8	????5.5	????5.7	????5.7
							Gasoline sulfure content, mg/litre	????424.3	????486.5	????414.7	????762.9	????691.7	????673.4

The presentation of results of table 5, identical with zeolite content, the catalyzer of metallic components and each component concentration are not identical, be that described metal component is compared with the catalyzer that oxidation state exists, catalyzer provided by the invention has higher cracking activity, higher diesel oil and yield of liquefied gas, simultaneously higher is desulphurizing activated.

Table 6

Example number	????15	????16	????17	????18
					The catalyzer numbering	????C4	????C5	????C6	????C7
Temperature of reaction, ℃	????480	????480	????500	????500
					Weight hourly space velocity, hour -1	????16	????16	????16	????16
Agent-oil ratio	????5	????5	????6	????6
					Transformation efficiency, weight %	????80.9	????80.4	????75.3	????78.3
Product yield, weight %
					Dry gas	????2.5	????2.4	????1.6	????2.6
Liquefied gas	????23.4	????22.8	????18.5	????20.3
					Gasoline	????48.5	????48.8	????49.8	????49.4
Diesel oil	????13.3	????13.6	????17.6	????15.1
					Heavy oil	????5.8	????6.0	????7.1	????6.6
Coke	????6.5	????6.4	????5.4	????6.0
					Gasoline sulfure content, mg/litre	????536.9	????558.4	????436.4	????451.5

Table 7

Example number	????19	????20	????21	????22
					The catalyzer numbering	????C8	????C9	????C10	????C11
Temperature of reaction, ℃	????500	????500	????520	????520
					Weight hourly space velocity, hour -1	????16	????16	????20	????20
Agent-oil ratio	????5.0	????5.0	????5.0	????5.0
					Transformation efficiency, weight %	????79.5	????78.9	????75.3	????71.5
Product yield, weight %
					Dry gas	????2.9	????2.7	????2.0	????1.6
Liquefied gas	????20.2	????19.8	????18.1	????17.2
					Gasoline	????50.0	????50.2	????49.6	????47.6
Diesel oil	????14.2	????14.6	????16.9	????19.3
					Heavy oil	????6.3	????6.5	????7.8	????9.2
Coke	????6.4	????6.2	????5.6	????5.1
					Gasoline sulfure content, mg/litre	????426.3	????418.2	????527.6	????494.0

Example 23-25

Following example illustrates the catalytic performance of catalyzer provided by the invention.

On small fixed flowing bed-tion reacting device, adopt catalyzer C1 provided by the invention, C4 and C11, long residuum content shown in the his-and-hers watches 4 is that 20 weight % and decompressed wax oil content are that the mixing oil of 80 weight % carries out catalytic cracking, catalyzer loading amount 90 grams.Reaction conditions and reaction result are listed in the table 8.

Table 8

Example number	????23	????24	????25
				The catalyzer numbering	????C1	????C4	????C11
Temperature of reaction, ℃	????520	????500	????500
				Weight hourly space velocity, hour -1	????16	????16	????16
Agent-oil ratio	????5.0	????5.0	????6.0
				Transformation efficiency, weight %	????75.3	????77.9	????70.9
Product yield, weight %
				Gas	????18.8	????21.6	????18.1
Gasoline	????50.5	????49.4	????47.3
				Diesel oil	????17.4	????15.4	????18.8
Heavy oil	????7.3	????6.7	????10.3
				Coke	????6.0	????6.9	????5.5
Gasoline sulfure content, mg/litre	????420.8	????524.1	????482.6

Claims (31)

1. hydrocarbon cracking catalyzer that contains molecular sieve, this catalyzer contains molecular sieve, heat-resistant inorganic oxide and a kind of metal component, contain or argillaceous not, it is characterized in that, described molecular sieve is the mixture of first kind of zeolite and second kind of zeolite, first kind of zeolite is y-type zeolite, the second hole volume of this y-type zeolite accounts for the 20-80% of total pore volume, the mol ratio that second kind of zeolite is silicon oxide and aluminum oxide is the zeolite more than 20, with the catalyzer total amount is benchmark, the content of first kind of zeolite is 1-50 weight %, the content of second kind of zeolite is 1-40 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 0-80 weight %, metal oxide in described maxivalence attitude, the content of metal component is 0.1-30 weight %, described metal component exists with the reduction valence state basically, and it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more.

2. catalyzer according to claim 1, it is characterized in that, with the catalyzer total amount is benchmark, the content of first kind of zeolite is that the content of 10-50 weight %, second kind of zeolite is 1-30 weight %, the content of heat-resistant inorganic oxide is 5-60 weight %, the content of clay is 5-60 weight %, and in the metal oxide of described maxivalence attitude, the content of metal component is 0.5-20 weight %.

3. catalyzer according to claim 2, it is characterized in that, with the catalyzer total amount is benchmark, the content of first kind of zeolite is that the content of 10-50 weight %, second kind of zeolite is 3-20 weight %, the content of heat-resistant inorganic oxide is 10-50 weight %, the content of clay is 15-60 weight %, and in the metal oxide of described maxivalence attitude, the content of metal component is 0.5-20 weight %.

4. catalyzer according to claim 1 is characterized in that, the second hole volume of described y-type zeolite accounts for total pore volume 25-70%.

5. according to claim 1 or 4 described catalyzer, it is characterized in that the relative crystallinity of described y-type zeolite is 70-90%.

6. catalyzer according to claim 1 is characterized in that, second kind of zeolite is the zeolite of the mol ratio 20-500 of silicon oxide and aluminum oxide.

7. according to claim 1 or 6 described catalyzer, it is characterized in that, described second kind of zeolite is selected from the zeolite with MFI structure, the zeolite with MFI structure of phosphorous, rare earth and/or alkaline-earth metal, Beta zeolite, the mordenite of Beta zeolite, phosphorous, rare earth and/or alkaline-earth metal, one or more in the mordenite of phosphorous, rare earth and/or alkaline-earth metal.

8. catalyzer according to claim 1 is characterized in that, the ratio of the average valence of described metal and its maxivalence attitude is 0-0.95.

9. catalyzer according to claim 8 is characterized in that, the ratio of the average valence of described metal and its maxivalence attitude is 0.1-0.7.

10. according to claim 1,8 or 9 described catalyzer, it is characterized in that described metal is selected from one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel.

11. catalyzer according to claim 10 is characterized in that, described metal is selected from one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.

12. catalyzer according to claim 1 is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, the boron oxide.

13. catalyzer according to claim 1 is characterized in that, described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.

14. catalyzer according to claim 1 is characterized in that, this catalyzer also contains alkaline-earth metal, is benchmark with the catalyzer total amount, and in oxide compound, the content of described alkaline-earth metal is 0-5 weight %.

15. catalyzer according to claim 14 is characterized in that, described alkaline-earth metal is magnesium and/or calcium.

16. catalyzer according to claim 1 is characterized in that, this catalyzer also contains rare earth metal, is benchmark with the catalyzer total amount, and in oxide compound, the content of described rare earth metal is 0-50 weight %.

17. catalyzer according to claim 16 is characterized in that, is benchmark with the catalyzer total amount, in oxide compound, and the content 0-15 weight % of described rare earth metal.

18., it is characterized in that described rare earth metal is selected from lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal according to claim 16 or 17 described catalyzer.

19. catalyzer according to claim 1 is characterized in that, this catalyzer also contains phosphorus, is benchmark with the catalyzer total amount, and in element phosphor, the content of described phosphorus is 0-15 weight %.

20. catalyzer according to claim 18 is characterized in that, is benchmark with the catalyzer total amount, in element phosphor, the content of described phosphorus is 0-8 weight %.

21 claim 1 Preparation of catalysts methods, it is characterized in that, this method comprises and will contain the metal component compound, molecular sieve, the composition of heat-resistant inorganic oxide and clay contacts with the atmosphere that contains reducing gas, the temperature of described contact is enough to make the average valence of described metal component to be lower than its highest oxidation state with the time that contacts, described molecular sieve is the mixture of first kind of zeolite and second kind of zeolite, described first kind of zeolite is y-type zeolite, the second hole volume of this y-type zeolite accounts for the 20-80% of total pore volume, the mol ratio that second kind of zeolite is silicon oxide and aluminum oxide is the zeolite more than 20, described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, each components contents makes in the final catalyzer and contains in the composition, with the catalyzer total amount is benchmark, first kind of zeolite of 1-50 weight %, second kind of zeolite of 1-40 weight %, the heat-resistant inorganic oxide of 2-80 weight %, the clay of 0-80 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.1-30 weight %.

22. method according to claim 21 is characterized in that, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.

23. method according to claim 22 is characterized in that, described pure reducing gas is selected from hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more.

24. method according to claim 22, it is characterized in that, describedly contain reducing gas and inert gas atmosphere is selected from hydrogen, carbon monoxide, contains one or more the mixture in one or more and the rare gas element in the hydro carbons of 1-5 carbon atom, the dry gas in the refinery.

25. method according to claim 21 is characterized in that, the temperature of described contact is enough to make the average valence of described metal component and the ratio of its maxivalence attitude to be reduced to 0-0.95 with the time that contacts.

26. method according to claim 25 is characterized in that, the temperature of described contact is enough to make the average valence of described metal component and the ratio of its maxivalence attitude to be reduced to 0.1-0.7 with the time that contacts.

27. method according to claim 21 is characterized in that, the temperature of described contact is 100-900 ℃, and the time of contact is 0.1 second to 10 hours.

28. method according to claim 21 is characterized in that, the consumption that contains the atmosphere of reducing gas is that every gram catalyzer per hour is not less than 5 milliliters of reducing gass.

29. method according to claim 21, it is characterized in that, each components contents makes in the final catalyzer and contains in the composition, in the catalyzer total amount, first kind of zeolite of 10-50 weight %, second kind of zeolite of 1-30 weight %, the heat-resistant inorganic oxide of 5-60 weight %, the clay of 5-60 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.

30. method according to claim 29, it is characterized in that, each components contents makes in the final catalyzer and contains in the composition, in the catalyzer total amount, first kind of zeolite of 10-50 weight %, second kind of zeolite of 3-20 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 15-60 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.

31. a hydrocarbon cracking catalyzer that contains molecular sieve, this catalyzer contain molecular sieve, heat-resistant inorganic oxide and a kind of metal component, contain or argillaceous not, it is characterized in that, this catalyzer adopts any described method preparation among claim 21-30.