CN1566276A - Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof - Google Patents
Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a cracking catalyst for hydrocarbon containing molecular sieve, wherein the catalyst comprises alkaline-earth metal molecular sieve, heat resistant inorganic oxide and a metal component, it may contain clay or not, the content of the alkaline earth metal containing molecular sieve is 1-90 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. Compared with the prior art, the catalyst has higher desulfurizing activity, the yield rate of the light oil can be increased substantially, the catalyst also has higher cracking activity.
Description
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 increases day by day to the demand of lightweight oil, and the heaviness of catalytically cracked stock tendency is serious day by day, have higher cracking activity for adapting to the requirement of market, need developing to the lightweight oil demand growth, and the hydrocarbon cracking catalyzer of light oil with high yield.
EP256 discloses a kind of catalyzer that is used for cracking of oil in 771, and the usefulness that this catalyzer contains 40-90 weight % is the SiO that makes of glue method altogether
2-MgO matrix, the zeolite of 5-40 weight %, the Al of 0-40 weight %
2O
3Binding agent with 0-50 weight %.This catalyzer has higher gasoline and diesel yield and high-wearing feature energy.
USP4,784,750 disclose a kind of method of cracking hydrocarbons raw material, this method is included in cracking conditions and there is the described hydrocarbon raw material of processing down in a kind of catalyzer, this catalyzer contains the matrix of 50-95 weight % and the zeolite that 5-50 weight % has specific physico-chemical parameter, and described matrix is selected from one group that is made up of aluminum oxide, clay, silicon oxide, silica-alumina, silicon oxide-boron oxide, magnesium oxide, silicon oxide-magnesium oxide, zirconium white and titanium oxide.This catalyzer has the selectivity of cracking activity and intermediate oil preferably.
CN 1297018A discloses catalytic cracking catalyst of a kind of light oil with high yield and preparation method thereof, and this catalyzer is made up of the molecular sieve of the alkaline including earth metal of carrier that accounts for catalyst weight 50-95 weight % and 5-50 weight %.This catalyzer has high yield of light oil, high diesel and gasoline ratio and lower gas and coking 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 that 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 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 silicoaluminophosphates (SAPO), gallium germanate (gallogermanates) and their combination.
CN1261618A discloses a kind of sulfur method of catalytic cracking gasoline cut, this method is included under the existence of high temperature, cracking catalyst and product desulfurization catalyst, to contain the petroleum cut catalytic cracking of organosulfur compound, produce the liquid crackate of low sulfur content.Described product desulfurization catalyst contains a kind of porous molecular screen, this molecular sieve contains first metal component and second metal component, first metal component is positioned at Molecular Sieve Pore inside and oxidation state greater than zero, and second metal component comprises at least a rare earth element that is positioned at Molecular Sieve Pore inside.Described first kind of metal component is selected from periodic table of elements period 4 and IIB, VB, IIIA, the metal, particularly vanadium of VIII family, zinc, iron, gallium.
Though desulphurizing activated the improving of the disclosed catalyzer of above-mentioned prior art,, on the one hand, use above-mentioned catalyzer, yield of light oil is 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 and a kind ofly new can improve yield of light oil in the crackate, particularly diesel yield, and have the more cracking catalyst that contains molecular sieve of high desulfurization activity.
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 lightweight oil 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 molecular sieve of alkaline including earth metal, molecular sieve with described alkaline including earth metal is a benchmark, in oxide compound, the content of alkaline-earth metal is 0.1-40 weight %, with the catalyzer total amount is benchmark, the content of the molecular sieve of alkaline including earth metal is 1-90 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 and heat-resistant inorganic oxide, contain or composition not argillaceous contacts with the atmosphere that contains reducing gas, wherein, 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 molecular sieve that contains alkaline-earth metal, molecular sieve with described alkaline including earth metal is a benchmark, in oxide compound, the content of alkaline-earth metal is 0.1-25 weight %, 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, the molecular sieve of the alkaline including earth metal of 1-90 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 has more high desulfurization activity, adopts catalyzer cracking hydrocarbon ils provided by the invention, can significantly improve lightweight oil, the yield of diesel oil particularly, and unexpectedly, catalyzer provided by the invention also has higher cracking activity.
For example, adopting the overstable gamma zeolite content of the MgO of containing provided by the invention is 30 weight %, and the content of aluminum oxide is 34 weight %, and 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 72.1-73.2 weight %, yield of light oil is up to 78.1-78.6 weight %, and wherein diesel yield is up to 20.2-20.3 weight %, and the sulphur content in the gasoline product has only the 408.6-436.7 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 70.7-71.5 weight %, and yield of light oil has only 75.0-76.1 weight %, diesel yield has only 19.7-19.9 weight % respectively, and the sulphur content in the gasoline product is up to the 660.5-785.6 mg/litre.
Embodiment
According to catalyzer provided by the invention, the content of the molecular sieve of described alkaline including earth metal is 1-90 weight %, and the content of heat-resistant inorganic oxide is 2-80 weight %, and the content of clay is 0-80 weight %, in the oxide compound of maxivalence attitude metal, the content of described metal component is 0.1-30 weight %.Under the preferable case, the content of the molecular sieve of described alkaline including earth metal is 10-60 weight %, and the content of heat-resistant inorganic oxide is 10-50 weight %, and the content of clay is 20-60 weight %, in the oxide compound of maxivalence attitude metal, the content of described metal component is 0.5-20 weight %.
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 molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, 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 the molecular sieve.
According to catalyzer provided by the invention, be benchmark with the molecular sieve of described alkaline including earth metal, in oxide compound, the content of described alkaline-earth metal is 0.1-40 weight %, is preferably 0.2-25 weight %.Described alkaline-earth metal is with alkaline earth metal compound, exists as the form of the salt of the oxide compound of alkaline-earth metal and/or alkaline-earth metal.Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, is preferably magnesium and/or calcium.
Described molecular screening is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.These zeolites and molecular sieve are conventionally known to one of skill in the art.
Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.
Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as zeolite (as the ZSM-5 zeolite) with MFI structure, in the zeolite with MFI structure (as phosphorous and/or rare earth ZSM-5 zeolite, the zeolite that the disclosed phosphorated of CN1194181A has the MFI structure) of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more.
Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by the molecular sieve of one or more replacements in other element such as phosphorus, titanium, gallium, the germanium.These examples of molecular sieve comprise that the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate, titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.One or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve particularly.
Under the preferable case, described molecular screening is from the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.
Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of existing cracking catalyst matrix and binder component one or more, as in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide one or more.In preferred aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, magnesium oxide, the calcium 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 invention can also contain rare earth metal, and described rare earth metal exists with the form of metal and/or compound.Described rare earth metal can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, 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 molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, 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 example of the present invention, if when rare earth metal and/or phosphorus were the preparation catalyzer, used molecular sieve contained itself, the content of described molecular sieve is the content that contains the molecular sieve of rare earth metal and/or phosphorus, 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, with the catalyzer total amount is benchmark, the molecular sieve of the alkaline including earth metal of 10-60 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 20-60 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.
According to the invention provides the Preparation of catalysts method, the molecular sieve of described alkaline including earth metal can adopt existing prepared in various methods, as adopting following method preparation:
(1) adopt the ion exchange method preparation, promptly the aqueous solution and the molecular sieve with the alkaline including earth metal compound carries out ion-exchange, dry and roasting;
(2) adopt immersion process for preparing, promptly use the aqueous solution impregnated zeolite of alkaline including earth metal compound, dry and roasting;
(3) will dissolve or the alkaline earth metal compound after abundant wet-milling is dispersed in the molecular sieve pulp, and add or do not add ammoniacal liquor, mix after drying, roasting;
(4) will be dispersed in through the molecular sieve after the abundant wet-milling in the solution of alkaline including earth metal compound, and add ammoniacal liquor and mix after-filtration, washing, drying, roasting.
Wherein, described drying temperature can be below room temperature to 500 ℃, and roasting condition is 500-650 ℃, and roasting time is more than 0.5 hour, preferred 1-5 hour.
Wherein, (1) and the alkaline earth metal compound described in (2) be water-soluble alkaline earth metal compound, (3) and the compound described in (4) can be water-soluble alkaline earth metal compound, also can be to be insoluble in or water-fast alkaline earth metal compound.The example of water-soluble alkaline earth metal compound comprises the muriate of alkaline-earth metal, the nitrate of alkaline-earth metal etc.Be insoluble in or the example of water-fast alkaline earth metal compound comprises the oxide compound of alkaline-earth metal, the oxyhydroxide of alkaline-earth metal, the phosphoric acid salt of alkaline-earth metal etc.
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 solution impregnation molecular sieve, the heat-resistant inorganic oxide that contain described metal component compound, heat-resistant inorganic oxide, and is dry or moist then; B. or the solution that will contain described metal component compound mix with the precursor and/or the clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, dry or moist then; C. or with the precursor and/or the clay of described metal component compound and molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide carry out physical mixed; D. or the solution that will contain described metal component compound mix with the precursor and/or the clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, the precipitation agent that adds described metal component compound, described metal component is deposited in the precursor and/or clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, dry or moist; E. or the solution that will contain described metal component compound mix with the precursor and/or the clay of molecular sieve, heat-resistant inorganic oxide, heat-resistant inorganic oxide, the slurry preparation that obtains is become colloid; F. or with the precursor of water-fast described metal component compound and molecular sieve, 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 molecular sieve, the heat-resistant inorganic oxide of described metal component compound, the precursor and/or the clay of heat-resistant inorganic oxide, or described mixture, or colloid and deionized water and not molecular sieve, heat-resistant inorganic oxide, the precursor and/or the clay making beating of heat-resistant inorganic oxide of metallic components compound, 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.
Wherein, the process of preparation alkaline including earth metal molecular sieve can in molecular sieve, introduce described metallic compound before, while or carry out afterwards.
Two of method
Precursor, clay and deionized water making beating with molecular sieve, heat-resistant inorganic oxide and/or the heat-resistant inorganic oxide of alkaline including earth metal, 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 molecular sieve, heat-resistant inorganic oxide and/or the heat-resistant inorganic oxide of alkaline including earth metal, 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.
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 molecular sieve itself is 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, alkaline-earth metal.
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 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, to produce light-end products.Also can be used as desulfurizing assistant agent and mix use, to reduce the sulphur content in gasoline and the diesel oil, particularly gasoline with existing various cracking catalyst.When catalyzer provided by the invention, when using 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, is 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 light-end products.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 light-end products, and reduces the sulphur content in the crackate simultaneously.These hydrocarbon ils are selected from oil and various cut thereof, particularly oil and boiling point be greater than 330 ℃ cut, as sulfur-bearing or not long residuum, vacuum residuum, the decompressed wax oil of sulfur-bearing, normal pressure wax oil, straight-run gas oil, propane is light/heavy one or more in de-oiling and the wax tailings.
The following examples will the present invention will be further described.
Unless stated otherwise, used kaolin is that Suzhou kaolin company produces in the example, 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 %; Compound used therefor 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 example below 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) gets 33 kilograms of MgCl
26H
2O (Beijing dicyclo chemical reagent factory, content is not less than 97.0 weight %) adds 30 kilograms of deionized waters, obtains MgCl
2Solution.
(note is REUSY, and Qilu Petrochemical company catalyst plant is produced, and lattice constant is 24.47 dusts, Na to get the overstable gamma zeolite that 100 kilograms (dry basises) contain rare earth
2O content 1.4 weight %, rare earth oxide content 0.67 weight %, wherein, lanthanum trioxide content is 0.35 weight %, and cerium oxide content is 0.09 weight %, and other rare earth oxide content is 0.23 weight %), add 180 kilograms of wet-millings of deionized water, must contain the slurries of zeolite.
With above-mentioned MgCl
2Solution is dispersed in the slurries that contain zeolite, dries slurries under 120 ℃ temperature, again in 500 ℃ of roastings 5 hours, obtains containing the overstable gamma zeolite that MgO is 6.1 weight %.
(2) cobalt nitrate aqueous solution with kaolin, pseudo-boehmite, concentration 30 weight % mixes, and adds deionized water, mixes, slowly adding concentration under stirring fast is the hydrochloric acid of 36.5 volume %, regulate the pH value to 2.0 of slurries, add the described overstable gamma zeolite that contains MgO, 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, the overstable gamma zeolite that contains MgO and cobalt nitrate aqueous solution makes kaolin butt weight, Al
2O
3, contain overstable gamma zeolite butt weight and the Co of MgO
2O
3The ratio of weight be 35.0: 34.0: 30.0: 1.0.
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 in the table 1, and the content of metal component is in the oxide compound of described metal component highest oxidation state.
Embodiment 2
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Method by (2) in the example 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 (2) in the example 1 prepares catalyzer, and different is with containing Co
2O
32.78 the kaolin of weight % replaces example 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 (2) in the example 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 kaolin, pseudo-boehmite, the consumption that contains the overstable gamma zeolite of MgO make kaolin butt weight, pseudo-boehmite butt weight, the ratio that contains the overstable gamma zeolite butt weight of MgO is 35.0: 35.0: 30.0.It is identical with kaolin content to obtain zeolite, not the reference catalyst CB1 of metallic components.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 (2) in the example 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 example 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 | ??REUSY | ??REUSY | ??REUSY | ???REUSY | ??REUSY | ??REUSY |
| The molecular sieve content of alkaline including earth metal, weight % | ??30.0 | ??30.0 | ??30.0 | ???30.0 | ??30.0 | ??30.0 |
| 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 % | ??34.0 | ??34.0 | ??34.0 | ???35.0 | ??34.0 | ??34.0 |
| 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.
Get 64 kilograms of MgSO
47H
2O (Red Star chemical plant, Beijing, content are not less than 98.0 weight %) adds 400 kilograms of deionized waters, obtains MgSO
4Solution.
With 100 kilograms of (dry basis) rare earth hydrogen Y zeolite (REHY, Qilu Petrochemical company catalyst plant is produced, lattice constant is 24.69 dusts, rare earth oxide content is 12.3 weight %, wherein, lanthanum trioxide content is 6.5 weight %, and cerium oxide content is 1.6 weight %, other rare earth oxide content is 4.2 weight %, Na
2O content 4.4 weight %) add the water wet-milling, under fully stirring, it is added above-mentioned MgSO then
4In the solution, and add ammoniacal liquor (Beijing Yili Fine Chemicals Co., Ltd., NH
3Content is 25-28 weight %) 87 liters.The gained mixed serum is filtered, and with 1500 liters of deionized water wash.The gained wet cake in 120 ℃ of oven dry, again in 500 ℃ of roastings 5 hours, is promptly got and contains the rare earth hydrogen y-type zeolite that MgO is 7.9 weight %.
With 1.6 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of zinc nitrate aqueous solution dipping of 7.0 weight %, 120 ℃ of oven dry, and 600 ℃ of roastings 1 hour obtain containing the kaolin of ZnO 1.6 weight %.
Method by (2) in the example 1 prepares catalyzer, and different is replaces example 1 described kaolin with the kaolin of the above-mentioned ZnO of containing, does not add Xiao Suangu, contains the overstable gamma zeolite of MgO with the rare earth hydrogen Y zeolite replacement of the above-mentioned MgO of containing; The kaolin of the described ZnO of containing, pseudo-boehmite, the consumption that contains the rare earth hydrogen Y zeolite of MgO make kaolin butt weight, Al
2O
3, the ratio that contains the weight of the rare earth hydrogen Y zeolite butt weight of MgO and ZnO is 50.0: 24.2: 25.0: 0.8; 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.
Get 45 kilograms of Ca (NO
3)
24H
2O (Red Star chemical plant, Beijing, content is not less than 99.0%) adds 600 kilograms of deionized waters, obtains Ca (NO
3)
2Solution.
100 kilograms (dry basises) are contained extremely steady y-type zeolite of rare earth (specification is with embodiment 1) wet-milling, under fully stirring, it is added above-mentioned Ca (NO then
3)
2In the solution, and add ammoniacal liquor (specification is with embodiment 4) 54 liters.The gained mixed serum is filtered, and with 1500 liters of deionized water wash.The gained wet cake in 120 ℃ of oven dry, again in 500 ℃ of roastings 5 hours, is promptly got and contains the overstable gamma zeolite that CaO is 6.7 weight %.
With 1.60 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of iron nitrate aqueous solution dipping of 10 weight %, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain containing Fe
2O
31.7 the kaolin of weight %.
Method by (2) in the example 1 prepares catalyzer, and different is with the above-mentioned Fe of containing
2O
3Kaolin replace example 1 described kaolin, do not add Xiao Suangu, with the overstable gamma zeolite replacement example 1 described overstable gamma zeolite that contains MgO of the above-mentioned CaO of containing; The described Fe that contains
2O
3Kaolin, pseudo-boehmite, the consumption that contains the overstable gamma zeolite of CaO make kaolin butt weight, Al
2O
3, contain overstable gamma zeolite butt weight and the Fe of CaO
2O
3The ratio of weight be 45.0: 24.2: 30.0: 0.8; 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.
Get 33 kilograms of (dry basis) magnesium oxide (Dunhuang Chenical Plant, Shanghai, minimum content is not less than 98.0%), add 50 kilograms of wet-millings of deionized water and become slurries.
(the industrial trade mark is DASY, and lattice constant is 24.45 dusts, Na to get 93.33 kilograms of (dry basis) overstable gamma zeolites
2O content is 1.5 weight %, the Shandong catalyst plant is produced), (the industrial trade mark is ZRP-1, and in element phosphor, phosphorus content is 2.0 weight % to have the zeolite of MFI structure with 6.67 kilograms (dry basises), rare earth oxide content is 1.0 weight %, wherein, lanthanum trioxide content is 0.53 weight %, and cerium oxide content is 0.13 weight %, 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), add 180 kilograms of wet-millings of deionized water, must contain the slurries of zeolite.
Above-mentioned magnesium oxide slurries are dispersed in the slurries that contain zeolite, the gained mixed serum in 120 ℃ of oven dry, again in 650 ℃ of roastings 2 hours, is promptly got the zeolite that MgO content is 24.8 weight %.
With 3.36 kilograms of concentration is 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, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain containing the kaolin of CuO 8.68 weight %.
Method by (2) in the example 1 prepares catalyzer, and different is replaces example 1 described kaolin with the kaolin of the above-mentioned CuO of containing, does not add Xiao Suangu, with the zeolite replacement example 1 described overstable gamma zeolite that contains MgO of the above-mentioned MgO of containing; Contain kaolin, the pseudo-boehmite of CuO, the consumption that contains the zeolite of MgO makes kaolin butt weight, TiO
2, Al
2O
3, the ratio that contains the weight of the DASY zeolite butt weight of MgO, the ZRP-1 zeolite butt weight that contains MgO and CuO is 39.0: 1.0: 26.2: 28.0: 2.0: 3.8; 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.
Get 2.6 kilograms of MgCl
26H
2O (specification is with embodiment 1) adds the deionized water 120 kg, obtains MgCl
2Solution.
(the industrial trade mark is MOY, and lattice constant is 24.59 dusts, Na to get the HY zeolite of 100 kilograms (dry basis) phosphorous and rare earth
2O content is 1.5 weight %, in element phosphor, phosphorus content is 1.2 weight %, and rare earth oxide content is 8.5 weight %, wherein, lanthanum trioxide content is 4.5 weight %, cerium oxide content is 1.1 weight %, and other rare earth oxide content is 2.9 weight %, and the Shandong catalyst plant is produced), add 180 kilograms of wet-millings of deionized water, must contain the slurries of zeolite.
With above-mentioned MgCl
2Solution is dispersed in the zeolite slurry, and adds 1 liter of ammoniacal liquor (specification is with embodiment 4).The gained mixed serum in 120 ℃ of oven dry, again in 500 ℃ of roastings 5 hours, is promptly got and contains the MOY zeolite that MgO is 0.5 weight %.
With 3.2 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of manganese nitrate aqueous solution dipping of 5.0 weight %, 120 ℃ of oven dry, and 550 ℃ of roastings 2 hours obtain containing MnO
22.63 the kaolin of weight %.
Method by (2) in the example 1 prepares catalyzer, and different is with the above-mentioned MnO of containing
2Kaolin replace example 1 described kaolin, do not add Xiao Suangu; MOY zeolite with the above-mentioned MgO of containing replaces the example 1 described overstable gamma zeolite that contains MgO; Contain MnO
2Kaolin, pseudo-boehmite, the consumption that contains the MOY zeolite of MgO make kaolin butt weight, Al
2O
3, contain MOY zeolite butt weight and the MnO of MgO
2The ratio of weight be 37.0: 27.0: 35.0: 1.0.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 |
| Zeolite type | ??REHY | ??REUSY | ????DASY/ZRP-1 | ??MOY |
| The molecular sieve content of alkaline including earth metal, weight % | ??25.0 | ??30.0 | ????30.0 | ??35.0 |
| The heat-resistant inorganic oxide kind | ??Al 2O 3 | ??Al 2O 3 | ????Al 2O 3/TiO 2 | ??Al 2O 3 |
| Heat-resistant inorganic oxide content, weight % | ??24.2 | ??24.2 | ????27.2 | ??27.0 |
| Clay types | Kaolin | Kaolin | Kaolin | Kaolin |
| Clay content, weight % | ??50.0 | ??45.0 | ????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.
With 3.22 kilograms of concentration is 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 (2) in the example 1 prepares catalyzer, and different is with the above-mentioned MoO of containing
3And Ag
2The kaolin of O and diatomite replace example 1 described kaolin, do not add Xiao Suangu, contain MoO
3And Ag
2The kaolin of O and diatomite, pseudo-boehmite, the consumption that contains the overstable gamma zeolite of MgO make kaolin and diatomite butt weight, Al
2O
3, contain overstable gamma zeolite butt weight, the MoO of MgO
3And Ag
2The ratio of the weight of O is 32.0: 21.5: 45.0: 1.2: 0.3.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.
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 (2) in the example 1 prepares catalyzer, and different is with above-mentioned MgO of containing and V
2O
5Kaolin replace example 1 described kaolin, do not add Xiao Suangu, with the rare earth hydrogen Y zeolite replacement example 1 described overstable gamma zeolite that contains MgO of the embodiment 4 described MgO of containing; Contain MgO and V
2O
5Kaolin, pseudo-boehmite, the consumption that contains the rare earth hydrogen Y zeolite of MgO make contained magnesium oxide, Al in kaolinic butt weight, the kaolin
2O
3, contain rare earth hydrogen Y zeolite butt weight and the V of MgO
2O
5The ratio of weight be 39.0: 1.0: 24.4: 35.0: 0.6; 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 and the deionized water of aluminum oxide mix, add the overstable gamma zeolite of the embodiment 5 described CaO of containing 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 mixture, the silicon sol of aluminum oxide, the consumption that contains the overstable gamma zeolite of CaO make kaolin butt weight, aluminum oxide, silicon oxide, contain overstable gamma zeolite butt weight and the Ga of CaO
2O
3The ratio of weight be 35.0: 10.0: 13.2: 35.0: 6.8.
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 mixture, aluminium colloidal sol and the deionized water of silicon oxide mix, add the zeolite of the embodiment 6 described MgO of containing 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 mixture, the aluminium colloidal sol of silicon oxide, the consumption that contains the zeolite of MgO make kaolin butt weight, aluminum oxide, silicon oxide, contain MgO DASY zeolite butt weight, contain ZRP-1 zeolite butt weight and the SnO of MgO
2The ratio of weight be 40.0: 20.0: 8.0: 28.0: 2.0: 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 |
| Zeolite type | ???REUSY | ??REHY | ????REUSY | ????DASY/ZRP-1 |
| The molecular sieve content of alkaline including earth metal, weight % | ???45.0 | ??35.0 | ????35.0 | ????30.0 |
| The heat-resistant inorganic oxide kind | ???Al 2O 3 | ??Al 2O 3/MgO | ????Al 2O 3/SiO 2 | ????Al 2O 3/SiO 2 |
| Heat-resistant inorganic oxide content, weight % | ???21.5 | ??25.4 | ????23.2 | ????28.0 |
| 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 magnesium oxide | Be distributed in clay and the aluminum oxide | Be distributed in clay and the silicon oxide |
Example 12-18
Following example illustrates the catalytic performance of catalyzer provided by the invention.
On the small stationary bed reaction device, adopt catalyzer C1-C7 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 5-6.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 example 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, ℃ | ????480 | ????480 | ????480 | ????480 | ????480 | ????480 |
| Weight hourly space velocity, hour -1 | ????16 | ????16 | ????16 | ????16 | ????16 | ????16 |
| Agent-oil ratio | ????6 | ????6 | ????6 | ????6 | ????6 | ????6 |
| Transformation efficiency, weight % | ????73.2 | ????72.1 | ????73.0 | ????71.5 | ????70.9 | ????70.7 |
| Product yield, weight % | ||||||
| Gas | ????11.1 | ????10.5 | ????11.0 | ????11.5 | ????11.6 | ????11.5 |
| Gasoline | ????56.3 | ????55.8 | ????56.3 | ????54.2 | ????53.3 | ????53.2 |
| Diesel oil | ????20.2 | ????20.3 | ????20.3 | ????19.9 | ????19.7 | ????19.8 |
| Heavy oil | ????6.6 | ????7.6 | ????6.7 | ????8.6 | ????9.4 | ????9.5 |
| Coke | ????5.8 | ????5.8 | ????5.7 | ????5.8 | ????6.0 | ????6.0 |
| Gasoline+diesel oil, weight % | ????76.5 | ????76.1 | ????76.6 | ????74.1 | ????73.0 | ????73.0 |
| Gasoline sulfure content, mg/litre | ????427.6 | ????436.7 | ????408.6 | ????785.6 | ????660.5 | ????675.4 |
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 yield of light oil, particularly higher diesel yield, simultaneously higher is desulphurizing activated.
Table 6
| Example number | ????15 | ????16 | ????17 | ????18 |
| The catalyzer numbering | ????C4 | ????C5 | ????C6 | ????C7 |
| Temperature of reaction, ℃ | ????500 | ????500 | ????500 | ????500 |
| Weight hourly space velocity, hour -1 | ????16 | ????16 | ????16 | ????16 |
| Agent-oil ratio | ????5 | ????5 | ????5 | ????5 |
| Transformation efficiency, weight % | ????61.4 | ????69.2 | ????59.7 | ????74.4 |
| Product yield, weight % | ||||
| Gas | ????9.4 | ????10.8 | ????9.2 | ????13.6 |
| Gasoline | ????46.6 | ????52.8 | ????45.5 | ????54.8 |
| Diesel oil | ????22.8 | ????20.2 | ????23.4 | ????17.4 |
| Heavy oil | ????15.8 | ????10.6 | ????16.9 | ????8.2 |
| Coke | ????5.4 | ????5.6 | ????5.0 | ????6.0 |
| Gasoline+diesel oil, weight % | ????69.4 | ????73.0 | ????68.9 | ????72.2 |
| Gasoline sulfure content, mg/litre | ????538.3 | ????456.6 | ????512.9 | ????443.2 |
Example 19-22
Following example illustrates the catalytic performance of catalyzer provided by the invention.
On small fixed flowing bed-tion reacting device, adopt catalyzer C8-C11 provided by the invention, 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 7.
Table 7
| Example number | ????19 | ????20 | ????21 | ????22 |
| The catalyzer numbering | ????C8 | ????C9 | ????C10 | ????C11 |
| Temperature of reaction, ℃ | ????520 | ????520 | ????520 | ????520 |
| Weight hourly space velocity, hour -1 | ????24 | ????24 | ????24 | ????24 |
| Agent-oil ratio | ????4 | ????4.5 | ????5 | ????5 |
| Transformation efficiency, weight % | ????76.4 | ????70.7 | ????72.0 | ????59.8 |
| Product yield, weight % | ||||
| Gas | ????13.7 | ????11.2 | ????11.8 | ????9.3 |
| Gasoline | ????56.5 | ????53.6 | ????54.2 | ????45.7 |
| Diesel oil | ????16.0 | ????20.7 | ????19.8 | ????23.3 |
| Heavy oil | ????7.6 | ????8.6 | ????8.2 | ????16.9 |
| Coke | ????6.2 | ????5.9 | ????6.0 | ????4.8 |
| Gasoline+diesel oil, weight % | ????72.5 | ????74.3 | ????74.0 | ????69.0 |
| Gasoline sulfure content, mg/litre | ????426.9 | ????436.1 | ????512.6 | ????496.5 |
Claims (27)
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 molecular sieve of alkaline including earth metal, molecular sieve with described alkaline including earth metal is a benchmark, in oxide compound, the content of alkaline-earth metal is 0.1-40 weight %, with the catalyzer total amount is benchmark, the content of the molecular sieve of alkaline including earth metal is 1-90 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 %, and 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 the molecular sieve of described alkaline including earth metal is 10-60 weight %, the content of heat-resistant inorganic oxide is 10-50 weight %, the content of clay is 20-60 weight %, and in the oxide compound of maxivalence attitude metal, the content of described metal component is 0.5-20 weight %.
3. 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.
4. catalyzer according to claim 3 is characterized in that, the ratio of the average valence of described metal and its maxivalence attitude is 0.1-0.7.
5. catalyzer according to claim 1 and 2 is characterized in that described metal component 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.
6. catalyzer according to claim 5 is characterized in that described metal component is selected from one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.
7. catalyzer according to claim 1 is characterized in that, is benchmark with the molecular sieve of described alkaline including earth metal, and in oxide compound, the content of described alkaline-earth metal is 0.2-25 weight %.
8. catalyzer according to claim 1 is characterized in that, described alkaline-earth metal is magnesium and/or calcium.
9. catalyzer according to claim 1 is characterized in that, described molecular screening one or more in macropore zeolite and mesopore zeolite.
10. catalyzer according to claim 9, it is characterized in that, described molecular screening is from the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.
11. 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, boron oxide, the alkaline earth metal oxide.
12. 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.
13. 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 %.
14. catalyzer according to claim 13 is characterized in that, is benchmark with the catalyzer total amount, in oxide compound, the content of described rare earth metal is 0-15 weight %.
15., 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 13 or 14 described catalyzer.
16. 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 %.
17. catalyzer according to claim 16 is characterized in that, is benchmark with the catalyzer total amount, in element phosphor, the content of described phosphorus is 0-8 weight %.
18. claim 1 Preparation of catalysts method, it is characterized in that, this method comprises and will contain the metal component compound, molecular sieve and heat-resistant inorganic oxide, contain or composition not argillaceous contacts with the atmosphere that contains reducing gas, wherein, 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 molecular sieve that contains alkaline-earth metal, molecular sieve with described alkaline including earth metal is a benchmark, in oxide compound, the content of alkaline-earth metal is 0.1-25 weight %, 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, the molecular sieve of the alkaline including earth metal of 1-90 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 %.
19. method according to claim 18 is characterized in that, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.
20. method according to claim 19 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.
21. method according to claim 19, 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.
22. method according to claim 18 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.
23. method according to claim 22 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.
24. method according to claim 18 is characterized in that, the temperature of described contact is 100-900 ℃, and the time of contact is 0.1 second to 10 hours.
25. method according to claim 18 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.
26. method according to claim 18, it is characterized in that, each components contents makes in the final catalyzer and contains in the composition, with the catalyzer total amount is the molecular sieve of the alkaline including earth metal of benchmark 10-60 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 20-60 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.
27. 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 18-26.
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