CN102453501B - Hydrocarbon oil conversion method - Google Patents
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- CN102453501B CN102453501B CN201010519280.9A CN201010519280A CN102453501B CN 102453501 B CN102453501 B CN 102453501B CN 201010519280 A CN201010519280 A CN 201010519280A CN 102453501 B CN102453501 B CN 102453501B
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Abstract
The invention relates to a hydrocarbon oil conversion method, which comprises the following steps that: the hydrocarbon oil is subjected to thermal cracking in a lift pipe reaction vessel under the partial thermal cracking condition, and in addition, products generated by the partial thermal cracking and catalytic cracking catalyst particles take contact reaction under the catalytic pyrolysis condition. After the method is adopted, the yield of ethylene during low-carbon olefin preparation from the hydrocarbon oil, particularly from the heavy oil can be effectively improved, and simultaneously, the yield of propylene can be ensured not to be reduced but even higher.
Description
Technical field
The present invention relates to a kind of conversion method for hydrocarbon oil.
Background technology
Ethene and propylene are important industrial chemicals, the very vigorous and constantly growth to its demand.More than 95% ethene, the propylene of existing market provided by naphtha steam cracking and heavy-oil catalytic preparing low-carbon olefins technology.Heavy-oil catalytic preparing low-carbon olefins operator utilizes catalytic pyrolysis technology, and energy consumption is low, and ingredient requirement is low, and product profile adjustment is flexible, has larger development prospect meeting in the ever-increasing demand in future market.
Riser reactor has that unit volume treatment capacity is large, gas-solid contact efficiency advantages of higher and widespread use.In riser catalytic cracking reaction process, the hydrocarbon ils after preheating, after nozzle enters reactor, contacts, vaporizes and react with the high temperature catalyst from revivifier, and the reaction times is greatly about 3 seconds.But due to gas-solid, also the contrary gravity field of stream is mobile, in riser tube, have the ununiformity of larger axle radial flow, gas-solid back-mixing is large, residence time skewness etc., and because the sedimentation of coke generating in reaction process is on catalyst surface and active centre, the activity of catalyzer is sharply declined.Research shows, the catalyst activity at leg outlet place only has 1/3 left and right of initial activity at present, and reaction was carried out about 1 second, the activity of catalyzer 50% left and right that declines.Like this, in the second half section of riser reactor, the activity of catalyzer sharply declines, and katalysis greatly weakens, and heat cracking reaction increases, and produces more dry gas and increases content of olefin in gasoline.
Catalytic cracking reaction is a complicated reaction system, is a parallel consecutive reaction process on the whole.Main reaction has the reactions such as cracking, cyclisation, isomerization, aromizing, hydrogen transference, alkylation, condensation.These several reactions are all the important reactions in catalytic cracking process, but their reaction conditions is contradiction.For addressing this problem, software engineering researchers invent many relevant art solve, such as ending agent technology, two-stage riser technology (CN1118539C), series connection riser tube technology MIP (CN1237477A), double lifting leg technology (CN1069054A) technology etc.CN1237477A has proposed catalyst cracker to be divided into the concept of Liang Ge reaction zone, and has developed corresponding riser reactor.Its main thought be the first reaction zone riser tube take generate alkene cracking reaction as main, generate the second reaction zone that the intermediate product that is rich in alkene enters hole enlargement again and carry out secondary reaction.The reaction of second reaction zone mainly comprises the cracking of isomerization, hydrogen transference and appropriateness, reaches the object that reduces gasoline olefin increased low carbon olefine output.
In addition, raw material becomes the ability that Chong Bianlie， refinery requires to improve catalyzer pressure fuel gradually in recent years, improves the particularly productive rate of ethene of low-carbon alkene, therefore, also harsher to the requirement of its supporting catalyzer.
What the process of heavy oil catalytic pyrolysis preparing ethylene was pursued is some intermediates in a series of consecutives and parallel reactor, belong to irreversible complex reaction network, there is competition in thermal response and catalyzed reaction, finally can generate such as coke, methane, H in reaction times and level of response
2etc. non-target product, side reaction is many, and inactivation is fast.Compare with DCC with FCC, catalytic thermal cracking catalyst primary first-order equation is different from secondary reaction type, need the side reaction of inhibition also different, degree and selectivity how to control thermal response and catalyzed reaction are most important, and catalyzer should fully take into account the balance of this two classes reaction in preparation process.
For example, CN1031029A discloses a kind of cracking catalyst of clay molecular sieve with layer structure.Prepare this catalyzer sodium type laminated clay used and be with sodium chloride aqueous solution and natural calcium type soil exchanging, after filtration, drip washing makes; Or with the mix and blend exchange 8 hours in water of highly acid polystyrene sodium type Zeo-karb and natural calcium type soil, the particle diameter that hold over night ，Qu upper strata suspends is less than that the clay of 2 microns makes.Although preparing the micro-anti-initial activity of light oil of this catalyzer with calcium type laminated clay is 46%, the catalytic cracking light oil microactivity of processing after 4 hours through 800 ℃ of water vapor deactivations only has 28%, can not meet the requirement of industry to catalyst stability.
And for example, CN1031489A discloses the preparation method of a kind of complex carrier that contains clay molecular sieve with layer structure or catalyzer, by each component raw material of this complex carrier or catalyzer: the laminated clay of montomorillonite class or regularly interstratified mineral structure, zeolite molecular sieve, refractory oxide, clay are in required ratio mixing moulding, then carry out crosslinking reaction with linking agent, and make required carrier or catalyzer through steps such as aging, roastings.
For another example, CN1211470A points out, catalytic pyrolysis catalyst for making ethylene need to increase uncle's carbonium ion and generate and directly cracking, suppresses isomery.The method adopts the modified molecular screen increases such as alkaline earth metals calcium, magnesium to select shaped reaction performance.But catalyst activity is still on the low side, in production, must strengthen catalyzer usage quantity, strengthen agent consumption, the active requirement that could keep required catalyzer.
Summary of the invention
The object of the present invention is to provide that a kind of new heavy oil cracking ability is strong, the low-carbon olefines high-output conversion method for hydrocarbon oil of ethene particularly.
The invention provides a kind of conversion method for hydrocarbon oil, wherein, the method is included under the condition that makes hydrocarbon ils generation part thermo-cracking, in riser reactor, make hydrocarbon ils thermo-cracking, and under catalytic pyrolysis condition, will product and the catalyst cracking particles contact reacts of part thermo-cracking occur.
Adopt method of the present invention can effectively improve the particularly productive rate of the ethene of heavy oil producing light olefins of hydrocarbon ils, can guarantee that the productive rate of propylene does not reduce even higher simultaneously.For example, according to a kind of embodiment of the present invention, at riser reactor, be provided with catalyst feeds, hydrocarbon oil feed mouth, described riser reactor also comprises sleeve pipe, one end of described sleeve pipe is communicated with hydrocarbon oil feed mouth, the other end is positioned at riser reactor, and the position of the other end of sleeve pipe is higher than the position of catalyst feeds, catalyzer is entered in riser reactor under the castering action of pre-lift medium, in from hydrocarbon ils nozzle to sleeve pipe, carry hydrocarbon ils, owing to forming inertia area in sleeve pipe, and make hydrocarbon ils temporarily not reach catalyzer, and catalyzer passes through from sleeve pipe surrounding, then touch hydrocarbon ils, carry out again catalyzed reaction separated with conventional finish, catalyst regeneration process.Under thermo-cracking condition, there is thermo-cracking in described hydrocarbon ils, then the product that part thermo-cracking occurs is contacted and proceeds catalytic cracking reaction with catalyzer, thereby improved the productive rate of ethene in sleeve pipe.In addition, under preferable case, adopt the supporting catalyzer of conversion method for hydrocarbon oil provided by the invention, can further improve the productive rate of ethene and propylene.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of riser reactor used in method of the present invention.
Embodiment
According to conversion method for hydrocarbon oil provided by the invention, described method is included under the condition that makes hydrocarbon ils generation part thermo-cracking, in riser reactor, makes hydrocarbon ils thermo-cracking, and under catalytic pyrolysis condition, product and the catalyst cracking particles contact reacts of part thermo-cracking will be there is.
According to method of the present invention, as long as can realize, make under the condition of hydrocarbon ils generation part thermo-cracking, in riser reactor, make hydrocarbon ils thermo-cracking, and under catalytic pyrolysis condition, product and the catalytic variety of way of catalyst cracking particles that part thermo-cracking occurs are all applicable to the present invention.
According to method of the present invention, described riser reactor is provided with catalyst feeds and hydrocarbon oil feed mouth, described riser reactor also comprises sleeve pipe, one end of described sleeve pipe is communicated with hydrocarbon oil feed mouth, the other end is positioned at riser reactor, and the position of the other end of sleeve pipe is higher than the position of catalyst feeds, thereby catalyst cracking particles is not entered in sleeve pipe.According to of the present invention a kind of concrete preferred embodiment, described conversion method for hydrocarbon oil comprises sends into riser reactor by catalyst feeds and hydrocarbon oil feed mouth respectively by catalytic cracking catalyst and hydrocarbon ils; In described sleeve pipe, occurring, under the condition of part thermo-cracking, to make hydrocarbon ils thermo-cracking, and on the other end of sleeve pipe, under catalytic pyrolysis condition, will product and the catalyst cracking particles contact reacts of part thermo-cracking occur.Catalytic cracking catalyst and hydrocarbon ils are entered by catalyst feeds and hydrocarbon oil feed mouth respectively in riser reactor, can carry out also can proceed step by step simultaneously, as long as guarantee in the sleeve pipe of described riser reactor, occurring under the condition of part thermo-cracking, make hydrocarbon ils thermo-cracking, and on the other end of sleeve pipe, under catalytic pyrolysis condition, product and the catalyst cracking particles contact reacts of part thermo-cracking will be there is.
Under preferable case, in order to guarantee in sleeve pipe, occurring under the condition of part thermo-cracking, make hydrocarbon ils thermo-cracking, then under catalytic pyrolysis condition, to product and the catalyzer contact reacts of part thermo-cracking occur, the height of described sleeve pipe is the 1/7-1/2 of riser reactor total height, more preferably 1/6-1/3.
According to the present invention, described riser reactor can be selected from equal diameter riser tube, etc. linear speed riser tube and variously straighten any one in the riser tube of footpath.
The present invention is not particularly limited the shape of the sleeve pipe in the shape of described riser reactor main body and described riser reactor, and generally, described riser reactor main body and sleeve pipe can be all right cylinder.The selectable range of the pipe diameter of described riser reactor main body and sleeve pipe is also wider, in order to be beneficial to the hydrocarbon ils that makes of the present invention, there is reaction under part thermo-cracking condition and under catalytic pyrolysis condition, by there is the product of part thermo-cracking and the catalytic coordination of catalyzer, undertaken, for the consideration of optimizing reaction efficiency, the pipe diameter of described sleeve pipe can be the 1/3-1/2 of the pipe diameter of riser reactor main body.Described sleeve pipe can be positioned at any side near riser reactor main body tube wall, also central zone that can be between the two side of riser reactor main body, for the consideration of optimizing reaction efficiency, the central zone of described sleeve pipe between the two side of riser reactor main body, as, described sleeve pipe can coaxially arrange with riser tube.
Described hydrocarbon oil feed mouth is communicated with one end of sleeve pipe, and can make hydrocarbon ils enter in sleeve pipe, and described hydrocarbon oil feed mouth can be positioned on sleeve pipe sidewall or diapire.The quantity of its opening for feed also can suitably increase and decrease according to the needs of the inlet amount of hydrocarbon ils, for example, can be 1-3.In order to make hydrocarbon ils better carry out described part heat scission reaction in described sleeve pipe, preferably sleeve pipe height (preferably identical with the height from hydrocarbon oil feed mouth to discharge port) is the 1/7-1/2 of riser tube total height, more preferably 1/6-1/3.
According to the present invention, in order to be beneficial to, the hydrocarbon ils in sleeve pipe is heated, the position of the other end of described sleeve pipe is higher than the position of catalyst feeds, under preferable case, described hydrocarbon oil feed Kou position is higher than the position of catalyst feeds, for example, and for being highly the riser reactor of 25-35 rice, described hydrocarbon oil feed Kou position can be higher than the position 5-10 rice of catalyst feeds, more preferably 6-8 rice.Under preferable case, in order to make catalyzer be raised homogeneous media in riser reactor, promote, described catalyst feeds can be the 1/6-1/3 of riser reactor height to the distance of riser reactor bottom.
Under preferable case, in order to make catalytic cracking catalyst promote operation in riser reactor, described riser reactor can also be provided with pre-lift medium inlet, and described pre-lift medium inlet is generally positioned at the bottom of riser reactor.Described pre-lift medium can be dry gas, steam or their mixture.
Above-mentioned riser reactor can be by set up a sleeve pipe in existing riser reactor, and one end of sleeve pipe and the hydrocarbon oil feed mouth of riser reactor are communicated with, and the other end of sleeve pipe is positioned at the conversion zone of riser reactor.As long as can meeting, the size of described sleeve pipe makes occurring under the condition of part thermo-cracking, make hydrocarbon ils thermo-cracking in sleeve pipe, and preferably meet reaction times of the thermo-cracking in sleeve pipe, as long as the size of described riser reactor equally also meets on the other end of sleeve pipe, under catalytic pyrolysis condition, to there is product and the catalyst cracking particles contact reacts of part thermo-cracking, and preferably meet the reaction times of catalytic cracking.Generally, the height of described riser reactor can be generally 5-100 rice, is preferably 10-90 rice; Caliber can be 0.01-3 rice, is preferably 0.1-1.5 rice.
Wherein, make the condition of hydrocarbon ils generation part thermo-cracking can comprise the time of temperature and the thermo-cracking of thermo-cracking, the selectable range of the temperature of described thermo-cracking is wider, problem for fear of the issuable catalyst member inactivation of excess Temperature or structural breakdown, the lower problem of the too low issuable thermal response degree of temperature, the temperature of described thermo-cracking can be 500-700 ℃, is preferably 550-650 ℃; The selectable range of the time of described thermo-cracking is wider, problem for fear of the issuable product distribution of the overlong time variation of thermo-cracking, time of thermo-cracking is too short may produce stock oil thermal response problem not too fully, under preferable case, the time of described thermo-cracking can be 0.01-1.5 second, is preferably 0.05-1 second.
According to the present invention, the condition of described catalytic pyrolysis can comprise temperature of reaction and reaction times, and the selectable range of the temperature of described catalytic pyrolysis is wider, and described temperature of reaction can be 500-700 ℃, is preferably 550-700 ℃; The reaction times of catalytic pyrolysis can be 1-5 second, is preferably 2-4 second.
According to the present invention, the consumption of described catalytic cracking catalyst can for known in those skilled in the art can be under catalytic pyrolysis condition, product and the catalytic conventional amount used of catalyzer of part thermo-cracking will be there is, under preferable case, for cost with further improve the considering of productive rate of ethene and propylene, the weight ratio of described catalyst cracking particles and hydrocarbon ils can be 3-30: 1, and 6-20 more preferably: 1.
According to the present invention, described catalytic cracking catalyst can be the various various catalytic cracking catalysts that hydrocarbon oil conversion is low-carbon alkene technique that are applicable to, under preferable case, described catalyst cracking particles contains particle a and particle b, zeolite, y-type zeolite, clay and heat-resistant inorganic oxide matrix that described particle a contains MFI structure, described particle b contains rectorite and heat-resistant inorganic oxide matrix.
According to the present invention, the selectable range of the weight ratio of described particle a and particle b is wider, generally, can be according to the demand flexible particle a of catalytic cracking reaction and the weight ratio of particle b, in order to obtain better catalytic cracking effect, the weight ratio of described particle a and particle b can be 0.5-15: 1, be preferably 1-10: 1.
According to the present invention, in described catalyzer, can also contain rare earth compound, for example, in described particle a and/or particle b, can contain rare earth compound.The content of described rare earth compound can be the content of the rare earth compound of this area routine, and under preferable case, the gross weight of catalyzer of take is benchmark, with RE
2o
3meter, the consumption of described rare earth compound makes the content of Rare Earths in Catalyst oxide compound be no more than 8 % by weight.Described rare earth compound can be introduced by existing variety of way (for example method of dipping), as long as make catalyzer of the present invention contain rare earth oxide.
According to the present invention, the described particle a that contains molecular sieve active component can be the various particles that contain molecular sieve active component, under preferable case, described in contain molecular sieve active component the preparation method of particle a comprise the zeolite of MFI structure mixed and contacted with By Amine Solutions; The mixture obtaining is mixed and contacted with y-type zeolite, isolate the solid in mixture and be dried, by the dry solid obtaining and clay and silicon sol making beating, by the slurry dried obtaining roasting.
In the method for the particle that contains molecular sieve active component in preparation of the present invention, owing to having introduced organic amine in building-up process, thereby make the particle that contains molecular sieve active component of the present invention there is the advantages such as higher activity, heat and hydrothermal stability.Therefore, make heavy oil cracking ability by the catalyzer of the particle a that contains molecular sieve active component provided by the invention and the particle b that contains clay and heat-resistant inorganic oxide matrix strong, the high stock oil of blending ratio is had to good heavy oil conversion performance, particularly the productive rate of ethene is high to make low-carbon olefines high-output.And catalyzer of the present invention is due to the particle a that contains molecular sieve active component described in containing, and make type and the degree of primary first-order equation when the reaction of fcc raw material oil of the catalytic cracking catalyst that obtains and secondary reaction also controlled.
Although as long as can obtain according to method of the present invention the particle that contains molecular sieve active component, but the present inventor finds, when the mol ratio of the zeolite of described organic amine and MFI structure is 0.2-7: 1, be preferably 0.2-5: 1, the mol ratio of the zeolite of described y-type zeolite and MFI structure is 0.01-1: 1, be preferably 0.1-0.75: 1, it is outstanding that the particle that contains molecular sieve active component being synthesized has advantages of that catalytic activity is higher, performance is more stable etc.
The present invention is not particularly limited the concentration of described By Amine Solutions, as long as guarantee to make the organic amine in the solution of organic amine to contact with the zeolite with MFI structure.Under preferable case, for make organic amine with have MFI structure zeolite contact more effectively, the concentration of described By Amine Solutions is generally 0.05-15 % by weight, is preferably 0.1-10 % by weight.Under preferable case, described in there is the zeolite of MFI structure and the weight ratio of By Amine Solutions is 1-60: 100,5-30 more preferably: 100.In addition, preferably y-type zeolite and the gross weight with the zeolite of MFI structure are no more than 60 % by weight of the weight of By Amine Solutions.
According to the present invention, the kind of described organic amine can be various organic amines known in the field, for example, can be selected from polyvinylamine, polymine and N, one or more in N-dimethyl alkylamine.Wherein, the number-average molecular weight of described polyvinylamine can be 1000-10000, is preferably 1000-5000, more preferably 1000-3000; The number-average molecular weight of described polymine can be 1000-10000, is preferably 1000-5000, more preferably 1000-3000.To described N, the carbonatoms of the alkyl in N-dimethyl alkylamine is not particularly limited, it can be generally the carbonatoms straight or branched alkyl that is 1-15, for example, N, N-dimethyl methylamine, N, N-dimethyl amine, N, N-dimethyl n propylamine, N, N-dimethyl butylamine, N, N-dimethyl cyclopentamine, N, N-dimethylhexylamine, N, N-dimethyl octylame, N, N-dimethyl nonyl amine, N, N-dimethyl decyl amine, N, N-dimethyl undecyl amine, N, N-dimethyl lauryl amine, N, N-dimethyl tetradecylamine and N, at least one in N-dimethyl pentadecyl amine.The solvent that forms By Amine Solutions also can, for the solvent of various routines known in the field, be preferably water.
According to the present invention, the zeolite with MFI structure and By Amine Solutions are mixed to condition contact and generally comprise and mix the time that the temperature of contact contacts with mixing.The temperature of described mixing contact can be selected in wide temperature range, for example, it can be 20-80 ℃ that the zeolite of the described MFI of having structure mixes with By Amine Solutions the temperature contacting, be preferably 40-70 ℃, the prolongation that mixes duration of contact makes the further raising of the performance of the particle that contains molecular sieve active component that makes, but mixing is long to the increase rate of their performances not obvious duration of contact, therefore, generally, the time that described contact mixes can be 30-60 minute, is preferably 35-50 minute.
The present invention mixes to the mixture obtaining and y-type zeolite the mode contacting and is not particularly limited, as long as make the mixture obtaining mix and contact with y-type zeolite, but the present inventor finds, y-type zeolite is joined in described mixture in batches, the resulting particle that contains molecular sieve active component has better ethylene selectivity, there is better heavy oil conversion performance, therefore the present invention preferably joins y-type zeolite in described mixture in batches, under preferable case, the add-on of every batch of y-type zeolite is at most 80 % by weight of the total consumption of y-type zeolite, be preferably 30-70 % by weight, between the step of adjacent two batch mixing, also comprise the timed interval, the described timed interval can be 5-120 minute, be preferably 15-60 minute.
According to the present invention, the zeolite of the described MFI of having structure can be the various zeolites with MFI structure known in those skilled in the art, be preferably HZSM-5 zeolite and/or element modified ZSM zeolite, for example, one or more in the ZSM-5 zeolite of the ZSM-5 zeolite of phosphorus modification, phosphorus and rare earth modified ZSM-5, phosphorus and iron modification, in the ZRP zeolite of phosphorus modification and the ZSP zeolite of phosphorus modification, further under preferable case, described in there is the silica alumina ratio (SiO of the zeolite of MFI structure
2/ Al
2o
3) being preferably 15-300, silica alumina ratio is especially preferably 30-200.
According to the present invention, the various y-type zeolites that described y-type zeolite can be known to the skilled person, for example, can be selected from one or more in REY, REHY, USY, HY, REUSY, PREY, PREHY zeolite.
In the present invention; by the method for the solid obtaining and clay and silicon sol making beating, it can be the methods of beating of routine known in the field; therefore; weight ratio to the mixture of the described solid obtaining and clay and silicon sol does not have particular requirement; generally; the weight ratio of the mixture of the solid obtaining and clay and silicon sol can be 1: 0.2-10, is preferably 1: 0.5-6, and after conventionally mixing, the solid content of gained mixture is 3-40 % by weight.
The selectable range of the weight ratio of described clay and silicon sol is wider, but under preferable case, the weight ratio of described clay and silicon sol can be 0.01-10: 1, and 0.1-4 more preferably: 1.
Wherein, the weight of described clay is with its butt weighing scale, and the weight of described silicon sol is with SiO
2meter.
Described silicon sol can be the conventional silicon sol in this area, can commercially availablely also can prepare according to method known in those skilled in the art.
Under preferable case, the step of the solid obtaining and clay and silicon sol making beating can also be comprised and adds rare earth compound, the gross weight of the particle that contains molecular sieve active component that obtains of take is benchmark, with RE
2o
3meter, the content of the particle middle rare earth that contains molecular sieve active component described in the consumption of described rare earth compound makes is no more than 8 % by weight.Wherein, RE represents rare earth element.
Wherein, the various clays that described clay can this area routine, for example, can be selected from one or more in rectorite, kaolin, polynite, diatomite, halloysite, saponite, sepiolite, attapulgite, hydrotalcite and wilkinite.
Described rare earth compound can be the various rare earth compounds of this area routine, for example, can be one or more in muriate, bromide and the nitrate of rare earth, in addition, can be a kind of salt of rare earth element, can be also the mixed rare earth compound that comprises multiple rare earth element conventional in catalyst preparation process.Described rare earth element is preferably selected from one or more in lanthanon.Described rare earth compound can add with solid form or with the form of the aqueous solution of rare earth compound, and the concentration of the aqueous solution of described rare earth compound can be generally 20-60 % by weight.
According to the present invention, described dry method can adopt the drying means of various routines known in the field, its operational condition also can be carried out according to condition known in those skilled in the art, for example, and one or more during seasoning, vacuum-drying and spraying are dry; Be preferably spraying dry, it can be 100-200 ℃ that described dry condition generally comprises dry temperature, and the dry time can 1-10 hour.
The method of described roasting can adopt the method for various routines known in the field, and its operational condition also can be carried out according to condition known in those skilled in the art, as long as can make organic amine remove.For example, the temperature of roasting can be 400-650 ℃, and the time of roasting can be 0.5-6 hour.
According to a kind of embodiment having of the present invention, the preparation method of described combination of molecular sieve and the particle that contains molecular sieve active component comprises following concrete steps:
(1) zeolite of MFI structure is mixed with By Amine Solutions (mass percent concentration is 0.05-15 % by weight), stir 30-60 minute;
(2) y-type zeolite is divided the many batches of mixtures that obtain with step (1) mix, the add-on of every batch of y-type zeolite is at most 80 % by weight of the total consumption of y-type zeolite, is preferably 30-70 % by weight, and the timed interval is 5-120 minute, and stirs 60-120 minute;
(3) combination of molecular sieve step (2) being obtained filters, dries, obtains solid;
(4) prepare the silicon sol that pH value is 1-3, the preparation method of described silicon sol can be prepared according to ordinary method, for example, and can be by water glass solution (SiO
2concentration is preferably 15-40 % by weight), modulus of water glass is 3-3.5) join in sulfuric acid (preferred mass percentage concentration is 15-50%), first add soon, and stir, slowly add after adding half, and stop stirring, maintenance slurry pH value is 1-3;
(5) clay is mixed with the silicon sol that step (4) obtains, and the mixture that obtains containing clay and silicon sol (weight ratio of clay and silicon sol is 0.1-10: 1, and the weight of clay is with its butt weighing scale, and the weight of silicon sol is with SiO
2meter);
(6) clay that solid step (3) being obtained obtains with step (5) mixes with the mixture of silicon sol that (weight ratio of the solid that step (3) obtains and the mixture of clay and silicon sol is 1: 0.2-10; and after conventionally mixing, the solid content of gained mixture is 3-40 % by weight); stir, spray drying forming, roasting.
Under optimum condition, in described particle b, the weight ratio 0.5-15 of rectorite and heat-resistant inorganic oxide matrix: 1, be preferably 1-10: 1.
According to the present invention, the kind of described heat-resistant inorganic oxide matrix can adopt the conventional heat-resistant inorganic oxide matrix in this area.For example, described heat-resistant inorganic oxide matrix can be selected from one or more in silicon oxide, gama-alumina, magnesium oxide, silica-alumina and aluminum oxide-phosphorus oxide, is preferably silicon oxide.
Described rectorite is preferably basal spacing d
001value be 2.7-5.0nm, BET specific surface area is 100-300m
2the rectorite of/g.
According to the present invention, under preferable case, described heat-resistant inorganic oxide matrix contains silicon-dioxide, and the preparation method of described particle b comprises: sulfuric acid is mixed with water glass, obtain the slurries that pH value is 1-3, rectorite is mixed with the slurries that obtain, dry and roasting.
Described rectorite is wider with the adjustable extent of the weight ratio of the slurries that obtain, as long as guarantee, in described particle b, contain rectorite and heat-resistant inorganic oxide matrix, and preferably make the weight ratio 0.5-15 of rectorite and heat-resistant inorganic oxide matrix: 1, be preferably 1-10: 1.Therefore, generally, described rectorite can be 1 with the weight ratio of the slurries that obtain: 1.5-50.
Described method and condition dry, roasting describe in detail in the preceding article, do not repeat them here.
Under preferable case, in the process of preparing particle b, introduce rare earth compound (being that particle b contains rare earth compound), specifically, can, before being dried, rectorite be mixed with rare earth compound with the mixture of the slurries that obtain.The gross weight of catalyzer of take is benchmark, with RE
2o
3meter, the consumption of described rare earth compound makes the content of Rare Earths in Catalyst oxide compound be no more than 8 % by weight.
Except providing according to method of the present invention particle a and particle b, catalyzer of the present invention can be by after the particle a making respectively and particle b moulding, with 0.5-15: 1, be preferably 1-10: 1 weight ratio mixes and can make.
Isometrical riser reactor take below as example, by reference to the accompanying drawings a kind of embodiment of method provided by the present invention is further detailed, similarly, the present invention repeats no more the reactor that all the other are various can realize method of the present invention.
As shown in Figure 1, hydrocarbon ils for example, carries by thinner (atomized water steam) sleeve pipe 4 that is entered riser reactor by the hydrocarbon oil feed mouth that is positioned at sleeve pipe sidewall through pipeline 3, under the condition that part thermo-cracking occurs, makes hydrocarbon ils thermo-cracking; Through pipeline 1, the bottom feed mouth by riser reactor 2 enters pre-lift medium, from the catalytic cracking catalyst of pipeline 5 under the castering action of pre-lift medium, along riser tube, move upward, the product of the generation part thermo-cracking of discharging with sleeve pipe 4 is mixed in riser tube is incorporated in contact reacts under catalytic cracking condition.Wherein, the catalytic cracking catalyst being carried by pre-lift medium is passed in riser reactor by pipeline 5, and can the hydrocarbon ils being carried by thinner (as atomizing steam) be passed in sleeve pipe by pipeline 3 simultaneously, the catalytic cracking catalyst being carried by pre-lift medium and by thinner (as atomizing steam) as long as the passing into and guaranteeing in the sleeve pipe of riser reactor along moving upward of pipe of the hydrocarbon ils carrying, make hydrocarbon ils heat that part thermo-cracking occur, and on the other end of sleeve pipe, under catalytic pyrolysis condition, product and the catalyst cracking particles contact reacts of part thermo-cracking will be there is.
Preparation Example below and embodiment will be further described the present invention, but not thereby limiting the invention.
In each embodiment and comparative example, Na in zeolite
2o, Fe
2o
3, NiO, Al
2o
3, SiO
2content adopt the mensuration of x-ray fluorescence method mensuration, micro-activity and abrasion index (AI) referring to [nineteen ninety publishes for " Petrochemical Engineering Analysis method " (RIPP experimental technique), Yang Cuiding Deng Bian， Science Press].
800 ℃/4h active (MA) is defined as: the activity data of surveying after 4 hours with 100% steam aging at 800 ℃, MA method is measured referring to [" Petrochemical Engineering Analysis method " (RIPP experimental technique), Yang Cui Ding Dengbian， Science Press, nineteen ninety publishes].
In embodiment, hydrocarbon oil composition used is as shown in table 1.
Preparation Example 1
This Preparation Example is for illustrating the preparation of catalytic cracking catalyst.
A: prepare combination of molecular sieve and particle a
(1) at 30 ℃, by 14kg ZSP-3 molecular sieve (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, ZSP-3 silica alumina ratio=40), (number-average molecular weight of polyvinylamine is 1800 (purchased from westernization instrument (Beijing) Science and Technology Ltd.s) with the 100kg polyvinylamine aqueous solution, the mass percent concentration of the polyvinylamine aqueous solution is 3%) mix, stir 40 minutes, obtain slurries 114kg;
(2), at 40 ℃, the slurries that 4kg DASY2.0 molecular sieve (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica alumina ratio is 5.6) is obtained with step (1) mix, and stir and within 40 minutes, obtain slurries 118kg;
(3) at 40 ℃, then the slurries that 4kg DASY2.0 molecular sieve (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica alumina ratio is 5.6) is obtained with step (2) mix, and stir and obtain slurries 122kg in 20 minutes, obtain combination of molecular sieve;
(4) combination of molecular sieve step (3) being obtained filters, and dries 5 hours at 120 ℃, obtains solid 22.2kg;
(5) preparation of silicon sol: by 20kg decationized Y sieve water and 35kg water glass (SiO
2content 28.4 % by weight, modulus of water glass 3.1) mix, join the H of 30kg
2sO
4in solution (mass percent concentration is 30 % by weight), the speed adding is 60kg/ hour, and the silicon sol slurries 85kg that stirring obtains pH=1.6 is (with SiO
2meter, silicon sol is 9.9kg);
(6) by 19kg halloysite (Suzhou china clay company Industrial products, solid content 72.3 % by weight) slurries that obtain with step (5) mix, stir 30 minutes, obtain the mixture 104kg (solid content of mixture is 22.7 % by weight) of kaolin and silicon sol slurries;
(7) in the kaolin that solid step (4) being obtained and step (6) obtain and the mixture of silicon sol slurries, stir 20 minutes, (drying temperature is 120 ℃ to spray drying forming, be 3 hours time of drying), roasting (maturing temperature is 550 ℃, and roasting time is 2 hours) obtains the particle a that contains molecular sieve active component.
B: prepare particle b
(1) by 10kg decationized Y sieve water and 18kg water glass (SiO
2content 28.4 % by weight, modulus 3.1) mix, join the H of 10kg
2sO
4in solution (mass percent concentration is 50%), the speed adding is 60kg/ hour, stirs the slurries 38kg that obtains pH=1.6;
(2) by 15kg rectorite (From Zhongxiang Hubei rectorite, solid content 87 % by weight, basal spacing d
001value be 4nm, specific surface area is 200m
2/ g) mix with the slurries of step (1), stirring and obtaining pH value is 1.8 slurries, and spraying is dried (drying temperature is 120 ℃, and be 3 hours time of drying) and obtains particle b.
C: catalyzer preparation
Particle a and particle b were mixed by weight 10: 1, after roasting (maturing temperature is 550 ℃, and roasting time is 2 hours), with deionized water wash, remove free Na
+ion, dry (drying temperature is 150 ℃, and be 2 hours time of drying), obtains catalyzer 1.
Preparation Example 2
This Preparation Example is for illustrating the preparation of catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of Preparation Example 1, different is, in preparing the step of particle a: (number-average molecular weight of polymine is 3000 (purchased from the good companies of Beijing Cohan) to change 100kg polyvinylamine solution into 280kg polyethyleneimine: amine aqueous solution, the mass percent concentration of polyethyleneimine: amine aqueous solution is 5%), the ZSP-3 molecular sieve of 14kg is by 20kg ZRP (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica alumina ratio is 60) replace, the consumption of DASY2.0 molecular sieve is 3kg (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica alumina ratio is 4.9) (in step (2) and (3), adding 1kg and 2kg respectively), particle a and particle b were mixed by weight 5: 1 simultaneously, obtain catalyzer 2.
Preparation Example 3
This Preparation Example is for illustrating the preparation of catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of Preparation Example 1, different is, change 100kg polyvinylamine solution into 500kg N, N-dimethyl dodecyl amine aqueous solution (N, N-dimethyl lauryl amine is purchased from Wuhan Yuancheng Technology Development Co., Ltd.), N, the mass percent concentration of N-dimethyl dodecyl amine aqueous solution is 10%), the ZSP-3 molecular sieve of 14kg is by HZSM-5 (catalyzer asphalt in Shenli Refinery of the China Petrochemical Industry product of 10kg, silica alumina ratio is 45), DASY2.0 molecular sieve (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, silica alumina ratio is 3.6) consumption be 7.5kg (adding 5kg and 2.5kg respectively in step (2) and (3)), particle a and particle b were mixed by weight 15: 1 simultaneously, obtain catalyzer 3.
Preparation Example 4
This Preparation Example is for illustrating the preparation of catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of Preparation Example 1, different, particle a and particle b are mixed to get by weight at 1: 1.Obtain catalyzer 4.
Preparation Example 5
This Preparation Example is for illustrating the preparation of catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of Preparation Example 1, different, by the DASY2.0 molecular sieve of 8kg disposable adding in step (2).Obtain catalyzer 5.
Preparation Example 6
This Preparation Example is for illustrating the preparation of catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of Preparation Example 1, different, in preparing the step (2) of particle b by the chlorination mixed rare earth solution of 0.4kg (with RE
2o
3the concentration of meter is 23.5 % by weight, and Gansu rare earth new material company limited produces, La in rare earth oxide
2o
3account for 23 % by weight, CeO
2account for 46 % by weight, other rare earth oxide content is 31 % by weight (other rare earth oxide comprises Praseodymium trioxide and rubidium oxide)) and rectorite together with join in the slurries of the step (1) of preparing particle b.Obtain catalyzer 6.
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
Adopt the isometrical riser reactor shown in Fig. 1, wherein, the pipe diameter of riser reactor 2 is 1.5 meters, and total height is 30 meters, hydrocarbon oil feed mouth is positioned on the sidewall of 5 meters of riser reactor 2 bottoms, and catalyst feeds is positioned on the sidewall of 1 meter of riser reactor 2 bottom; The pipe diameter that is set in the sleeve pipe 4 in riser reactor 2 is 0.6 meter, be highly 5 meters, and coaxially arrange with riser reactor 2, and one end of sleeve pipe 4 is connected and is communicated with (0.2 meter of the positional distance sleeve bottom that sleeve pipe 4 is connected with hydrocarbon oil feed mouth) with hydrocarbon oil feed mouth, the other end of sleeve pipe 4 is that the position of exit end is higher than the hydrocarbon ils entrance location of sleeve pipe 4.
Hydrocarbon ils is preheating to 300 ℃ to be entered in sleeve pipe 4 by hydrocarbon oil feed mouth through pipeline 3, hydrocarbon ils is in the interior reaction of sleeve pipe 4, temperature of reaction is 600 ℃, reaction times is 1 second, the product of the part thermo-cracking obtaining is entered in riser reactor 2 by the other end port of sleeve pipe 4, up under the interior castering action that contacts and entered by pipeline 1 the pre-lift medium (280 ℃ of high-temperature vapors of preheating) in riser reactor 2 of riser reactor 2 with the catalyst cracking particles being made by Preparation Example 1 being entered by catalyst feeds through pipeline 5, in the interior reaction of riser reactor 2, temperature of reaction is 640 ℃, the weight ratio of catalyst cracking particles and hydrocarbon ils is 12: 1, total reaction time in riser reactor 2 is 3 seconds.Reaction product in riser reactor 2 is carried out to finish separation, and products therefrom forms as shown in table 2.
Comparative example 1
This comparative example is for illustrating the method for transformation of the hydrocarbon ils of prior art.
According to the method coverting hydrocarbon oils of embodiment 1, different, in described reactor without sleeve pipe, directly make hydrocarbon ils and catalyzer under the catalytic pyrolysis condition identical with embodiment 1 in riser reactor contact reacts.Result is as shown in table 2.
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
Adopt the isometrical riser reactor shown in Fig. 1, wherein, the pipe diameter of riser reactor 2 is 1.5 meters, and total height is 30 meters, hydrocarbon oil feed mouth is positioned on the sidewall of 7 meters of riser reactor 2 bottoms, and catalyst feeds is positioned on the sidewall of 1 meter of riser reactor 2 bottom; The pipe diameter that is set in the sleeve pipe 4 in riser reactor 2 is 0.6 meter, be highly 10 meters, and coaxially arrange with riser reactor 2, and one end of sleeve pipe 4 is connected and is communicated with (0.5 meter of the positional distance sleeve bottom being connected with hydrocarbon oil feed mouth of sleeve pipe 4) with hydrocarbon oil feed mouth, sleeve pipe 4 the other ends are that the position of exit end is higher than the hydrocarbon ils entrance location of sleeve pipe 4.
300 ℃ of hydrocarbon ils and preheating are entered in sleeve pipe 4 by hydrocarbon oil feed mouth through pipeline 3, hydrocarbon ils is in the interior reaction of sleeve pipe 4, temperature of reaction is 550 ℃, reaction times is 0.05 second, the product of the part thermo-cracking obtaining is entered in riser reactor 2 by the other end port of sleeve pipe 4, up under the interior castering action that contacts and entered by pipeline 1 the pre-lift medium (280 ℃ of high-temperature vapors of preheating) in riser reactor 2 of riser reactor 2 with the catalyst cracking particles being made by Preparation Example 1 being entered by catalyst feeds through pipeline 5, in the interior reaction of riser reactor 2, temperature of reaction is 600 ℃, the weight ratio of catalyst cracking particles and hydrocarbon ils is 20: 1, total reaction time in riser reactor 2 is 4 seconds.Reaction product in riser reactor 2 is carried out to finish separation, and products therefrom forms as shown in table 2.
Comparative example 2
This comparative example is for illustrating the method for transformation of the hydrocarbon ils of prior art.
According to the method coverting hydrocarbon oils of embodiment 2, different, in described reactor without sleeve pipe, directly make hydrocarbon ils and catalyzer under the catalytic pyrolysis condition identical with embodiment 2 in riser reactor contact reacts.Result is as shown in table 2.
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
Adopt the isometrical riser reactor shown in Fig. 1, wherein, the pipe diameter of riser reactor 2 is 1.5 meters, and total height is 30 meters, hydrocarbon oil feed mouth is positioned on the sidewall of 6 meters of riser reactor 2 bottoms, and catalyst feeds is positioned on the sidewall of 1 meter of riser reactor 2 bottom; The pipe diameter that is set in the sleeve pipe 4 in riser reactor 2 is 0.6 meter, be highly 6 meters, and coaxially arrange with riser tube 2, and one end of sleeve pipe 4 is connected and is communicated with (0.3 meter of the positional distance sleeve bottom being connected with hydrocarbon oil feed mouth of sleeve pipe 4) with hydrocarbon oil feed mouth, sleeve pipe 4 the other ends are that exit end position is higher than the hydrocarbon ils entrance location of sleeve pipe 4.
300 ℃ of hydrocarbon ils and preheating are entered in sleeve pipe 4 by hydrocarbon oil feed mouth through pipeline 3, hydrocarbon ils is in the interior reaction of sleeve pipe 4, temperature of reaction is 640 ℃, reaction times is 0.08 second, the product of the part thermo-cracking obtaining is entered in riser reactor 2 by the other end port of sleeve pipe 4, up under the interior castering action that contacts and entered by pipeline 1 the pre-lift medium (280 ℃ of high-temperature vapors of preheating) in riser reactor 2 of riser reactor 2 with the catalyst cracking particles being made by Preparation Example 1 being entered by catalyst feeds through pipeline 5, in the interior reaction of riser reactor 2, temperature of reaction is 700 ℃, the weight ratio of catalyst cracking particles and hydrocarbon ils is 6: 1, total reaction time in riser reactor 2 is 2 seconds.Reaction product in riser reactor 2 is carried out to finish separation, and products therefrom forms as shown in table 2.
Comparative example 3
This comparative example is for illustrating the method for transformation of the hydrocarbon ils of prior art.
According to the method coverting hydrocarbon oils of embodiment 3, different, in described reactor without sleeve pipe, directly make hydrocarbon ils and catalyzer under the catalytic pyrolysis condition identical with embodiment 3 in riser reactor contact reacts.Result is as shown in table 2.
Embodiment 4
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
According to the method coverting hydrocarbon oils of embodiment 1, different, the catalyzer 2 that adopts Preparation Example 2 to make.Result is as shown in table 3.
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
According to the method coverting hydrocarbon oils of embodiment 1, different, the catalyzer 3 that adopts Preparation Example 3 to make.Result is as shown in table 3.
Embodiment 6
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
According to the method coverting hydrocarbon oils of embodiment 1, different, the catalyzer 4 that adopts Preparation Example 4 to make.Result is as shown in table 3.
Embodiment 7
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
According to the method coverting hydrocarbon oils of embodiment 1, different, the catalyzer 5 that adopts Preparation Example 5 to make.Result is as shown in table 3.
Embodiment 8
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
According to the method coverting hydrocarbon oils of embodiment 1, different, the catalyzer 6 that adopts Preparation Example 6 to make.Result is as shown in table 3.
Embodiment 9
The present embodiment is used for illustrating conversion method for hydrocarbon oil provided by the invention.
According to the method coverting hydrocarbon oils of embodiment 1, different, adopt the method that in CN101210187A, embodiment 1 provides to prepare cracking catalyst D1.Result is as shown in table 3.
Comparative example 4
This comparative example is for illustrating the method for transformation of the hydrocarbon ils of prior art.
According to the method coverting hydrocarbon oils of comparative example 1, different, adopt the method that in CN101210187A, embodiment 1 provides to prepare cracking catalyst D1.Result is as shown in table 3.
Table 1
Table 2
Table 3
From the result of table 2 and table 3, can find out, by embodiment 1 and comparative example 1, comparative example 4, embodiment 2 and comparative example 2, embodiment 3 and comparative example 3, and relatively can the finding out of embodiment 10 and comparative example 4, method provided by the invention can effectively improve the particularly productive rate of the ethene of heavy oil producing light olefins of hydrocarbon ils, can guarantee that the productive rate of propylene does not reduce even higher simultaneously.In addition, by embodiment 1 can be found out with the contrast of embodiment 9, in the situation that other condition is all identical, adopt preferred catalytic cracking catalyst of the present invention can further improve low-carbon alkene, the productive rate of ethene particularly, and liquefied gas yield improves, coke yield reduces, and heavy oil yield reduces.
Claims (20)
1. a conversion method for hydrocarbon oil, is characterized in that, the method is included under the condition that makes hydrocarbon ils generation part thermo-cracking, in riser reactor, make hydrocarbon ils thermo-cracking, and under catalytic pyrolysis condition, will product and the catalyst cracking particles contact reacts of part thermo-cracking occur;
Wherein, described catalyst cracking particles contains particle a and particle b, zeolite, y-type zeolite, clay and heat-resistant inorganic oxide matrix that described particle a contains MFI structure, and described particle b contains rectorite and heat-resistant inorganic oxide matrix;
The preparation method of described particle a comprises the zeolite of MFI structure is mixed and contacted with By Amine Solutions; The mixture obtaining is mixed and contacted with y-type zeolite, isolate the solid in mixture and be dried, by the dry solid obtaining and clay and silicon sol making beating, by the slurry dried obtaining roasting.
2. method according to claim 1, wherein, described riser reactor is provided with catalyst feeds, hydrocarbon oil feed mouth, described riser reactor also comprises sleeve pipe, one end of described sleeve pipe is communicated with hydrocarbon oil feed mouth, the other end is positioned at riser reactor, and the position of the other end of sleeve pipe is higher than the position of catalyst feeds, and catalyst cracking particles and hydrocarbon ils are sent into riser reactor by catalyst feeds and hydrocarbon oil feed mouth respectively; In described sleeve pipe, occurring, under the condition of part thermo-cracking, to make hydrocarbon ils thermo-cracking, and on the other end of sleeve pipe, under catalytic pyrolysis condition, will product and the catalyst cracking particles contact reacts of part thermo-cracking occur.
3. method according to claim 2, wherein, the height of sleeve pipe is the 1/7-1/2 of riser reactor total height.
4. according to the method described in any one in claim 1-3, wherein, make the condition of hydrocarbon ils generation part thermo-cracking comprise that the temperature of thermo-cracking is 500-700 ℃, the time of thermo-cracking is 0.01-1.5 second.
5. method according to claim 4, wherein, makes the condition of hydrocarbon ils generation part thermo-cracking comprise that the temperature of thermo-cracking is 550-650 ℃, and the time of thermo-cracking is 0.05-1 second.
6. according to the method described in any one in claim 1-3, wherein, catalytic pyrolysis condition comprises that temperature of reaction is 500-700 ℃, and the catalytic time is 1-5 second, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 3-30:1.
7. method according to claim 6, wherein, catalytic pyrolysis condition comprises that temperature of reaction is 550-700 ℃, and the catalytic time is 1-4 second, and the weight ratio of catalyst cracking particles and hydrocarbon ils is 6-20:1.
8. method according to claim 1, wherein, by weight, the ratio of described particle a and particle b is 0.5-15:1.
9. method according to claim 8, wherein, by weight, the ratio of described particle a and particle b is 1-10:1.
10. method according to claim 1, wherein, described particle a and/or particle b also contain rare earth compound, and the gross weight of catalyzer of take is benchmark, with RE
2o
3meter, the consumption of described rare earth compound makes the content of Rare Earths in Catalyst oxide compound be no more than 8 % by weight.
11. methods according to claim 1, wherein, the weight ratio of the zeolite of described organic amine and MFI structure is 0.2-7:1, the weight ratio of the zeolite of described y-type zeolite and MFI structure is 0.01-1:1.
12. methods according to claim 11, wherein, the weight ratio of the zeolite of described organic amine and MFI structure is 0.2-5:1, the weight ratio of the zeolite of described y-type zeolite and MFI structure is 0.1-0.75:1.
13. methods according to claim 1, wherein, described clay is selected from one or more in kaolin, polynite, diatomite, halloysite, saponite, sepiolite, attapulgite, hydrotalcite and wilkinite.
14. methods according to claim 1, wherein, the concentration 0.5-15 % by weight of described By Amine Solutions.
15. according to the method described in any one in claim 1 and 11-14, and wherein, described organic amine is selected from polyvinylamine, polymine and N, one or more in N-dimethyl alkylamine.
16. methods according to claim 1, wherein, the zeolite of described MFI structure mixes with By Amine Solutions the temperature 20-80 ℃ contacting, and the time is 30-60 minute, the mixture obtaining is mixed to the temperature 40-80 ℃ contacting with y-type zeolite, and the time is 60-120 minute.
17. according to the method described in claim 1 or 16, wherein, the mixture obtaining and y-type zeolite is mixed to the method contacting and comprise y-type zeolite is joined in described mixture in batches.
18. methods according to claim 17, the add-on of every batch of y-type zeolite is at most 80 % by weight of the total consumption of y-type zeolite, also comprises that the timed interval, the described timed interval are 5-120 minute between the step of adjacent two batch mixing.
19. methods according to claim 1, wherein, described heat-resistant inorganic oxide matrix contains silicon-dioxide, the preparation method of described particle b comprises sulfuric acid is mixed with water glass, obtain the slurries that pH value is 1.5-3, rectorite is mixed and contacted with the slurries that obtain, dry and roasting.
20. in accordance with the method for claim 19, wherein, and the basal spacing d of described rectorite
001value be 2.7-5.0nm, BET specific surface area is 100-300m
2/ g.
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