CN1223601A - Hydrocarbon conversion catalyst and its use - Google Patents

Abstract

The present invention provides catalysts and conversion processes for converting hydrocarbons using the catalysts. The catalysts comprise a first alumino-phospho-molecular sieves and a binder comprising a second alumino-phospho-molecular sieves. Exemplary conversion processes include the conversion of oxygenates to olefins, dewaxing, reforming, dealkylation, dehydrogenation, transalkylation, alkylation, and isomerization.

Description

Hydrocarbon conversion catalyst and application thereof

Invention field

The present invention relates to crystalline aluminium-phosphorus-molecular sieve and their application in hydrocarbon conversion process by crystalline aluminium-phosphorus-molecular sieve connection.

Background of invention

No matter the crystalline microporous molecular sieve is natural and synthetic, all shows to have catalytic performance for various types of hydrocarbon conversion process.In addition, the crystalline microporous molecular sieve has been used as the sorbent material and the support of the catalyst of various types of hydrocarbon conversion process and has done other application.These molecular sieves are the ordered porous crystalline materials with crystalline structure of determining that x-ray diffraction measures, and a large amount of less holes is arranged therein, and these holes can by many littler passages or the hole is inner connect.The size of the passage of these apertures is such, promptly allows the molecule of absorption certain size, does not adsorb the molecule of large-size together.The clearance space or the passage that are formed by crystalline network make molecular sieve can be used as the catalyzer and the support of the catalyst of the molecular sieve of sepn process, various hydrocarbon conversion process.

One class crystalline microporous molecular sieve is to contain the silicon-dioxide (SiO2) and the molecular sieve of the skeleton tetrahedron element of aluminum oxide (AlO2) arbitrarily.Another kind of crystalline microporous molecular sieve contains the skeleton tetrahedron element of aluminum oxide (AlO2) and phosphorus (PO2).At " Introduction To ZeoliteScience and Practice ", in (H.van Bekkum, E.M.Flanigen, J.C.Jansen ed.1991) these molecular sieves have been discussed, the document is classified reference as at this.The example of the molecular sieve of such ALPO base (" ABMS ") comprises SAPO, ALPO, MeAPO, MeAPOS, ELAPO and ELAPOS.The composition of these molecular sieves is disclosed in the table 1 below:

Table 1.ALPO ₄The tube that sill is formed claims to be called for short skeleton T-atom (Me that enumerates or ElT-atom) AlPO Al, PSAPO Si, Al, PMeAPO Me, Al, P (Co, Fe, Mg, Mn, Zn) MeAPSO Me, Al, P, Si (Co, Fe, Mg, Mn, Zn) ELAPO El, Al, P (As, B, Be, Ga, Ge, Li, Ti) ELAPSO El, AL, P, Si (As, B, Be, Ga, Ge, Li, Ti)

In the hole of crystalline molecular sieve, the hydrocarbon conversion reaction for example transalkylation of alkane isomerization, olefin skeletal or double-bond isomerization, disproportionation, alkylation and aromatic hydrocarbons is to be controlled by the constraint that channel sized applied of this molecular sieve.When to such an extent as to the cut of raw material is too heavy when reacting in advancing less than the hole, the selectivity of the thing that just reacts, and can not leave these passages or selectivity of product has just taken place during not with afterreaction when some product.Because the transition state selectivity, products distribution also may change, and wherein some reaction may not can take place, to such an extent as to because reaction transition state is difficult to too greatly form in the hole.The constraint of diffusion also may cause selectivity when bulk of molecule and pore system were suitable.In the lip-deep non-selective reaction of molecular sieve, for example in general not the meeting the requirements of the supercentral reaction of the surface acidity of molecular sieve, because the type of selecting that reaction produced that such reaction does not stand to take place in the passage of molecular sieve constraint.

The catalyzer that has used ABMS to transform in the past as hydrocarbon.U.S.P4 for example, 741,820 are included in the molecular sieve ASPO for example that uses medium hole size in the reforming process, and it is bonding by unformed material.

The normally crystallization by super-saturated synthetic mixture preparation of ABMS.Dry and the roasting of the crystallized product that obtains then obtains molecular sieve powder.Though this powder has good adsorption property, its application is seriously limited, because be difficult to fixed-bed operations with powder.Therefore, when in commercial run, using powder in the past, common bonding crystal.

General pass through that this molecular sieve is formed coacervate for example ball, bead or extrusion are come bonding this powder.Usually pass through in the presence of amorphous binding agent, the ABMS extrusion to be formed the extrusion thing, then the extrusion thing of drying and roasting formation.Used binding agent heatproof degree and other condition, mechanical wear for example, it takes place in various hydrocarbon conversion process.The example of binder material comprises amorphous material, for example aluminum oxide, silicon oxide, titanium oxide and various types of clay.General A BMS should be anti-mechanical wear, does not for example promptly form the particulate fine powder less than 20 microns.

Bonding although it is so aggregate has physical strength preferably than powder, but when such adhesives is used for catalytic conversion process, may because the performance of this binding agent and catalyzer for example activity, selectivity, active maintenance and their combination may reduce.For example, because the general amount of this binding agent is up to about 50% heavy crystallization, this binding agent dilutes the absorption property of this material.In addition, because prepare this bonding molecular sieve by extrusion, or form this molecular sieve with binding agent and its after drying and this extrusion thing of roasting in addition, this amorphous binding agent may penetrate the hole of molecular sieve or the hole that obstruction enters molecular sieve, or the speed of substance transfer in the hole of molecular sieve that slows down, when be used in hydrocarbon conversion process and other use in the time this molecular sieve effect may reduce.In addition, when this bonding molecular sieve is used for catalytic conversion process, this binding agent may influence the chemical reaction that produces in molecular sieve, the reaction that also may himself catalysis meet the requirements, and this reaction that does not meet the requirements may cause forming the product that does not meet the requirements.

Summary of the invention

The present invention relates to the bonding ABMS catalyzer of ABMS, this catalyzer comprises first crystal and a kind of second crystalline binding agent and the application of this catalyzer in hydrocarbon conversion process that contains the 2nd ABMS of an ABMS.The structure type of the one ABMS can be identical or different with the 2nd ABMS.Preferably will carefully control the acidity of the 2nd ABMS, for example the acidity of the 2nd ABMS can be identical with an ABMS crystal, or this ABMS crystalline acidity can be higher or lower than an ABMS crystalline acidity, to such an extent as to further strengthen the performance of catalyzer.

Catalyzer of the present invention has special purposes in hydrocarbon conversion process, be very important with the acidity of the catalyzer of ABMS textural association for the selectivity of reaction wherein.The example of such catalytic conversion process comprises catalytic cracking, alkylation, dealkylation, dehydrogenation, disproportionation and transalkylation reaction.Catalyzer of the present invention also can be used in other the hydrocarbon conversion process, and carbonaceous compound becomes the compound that contains different carbon atoms in these processes.The example of such process comprises hydrocracking, isomerization, dewaxing, oxidation conversion, oligomeric and reforming process.

The detailed description of invention

Catalyzer of the present invention comprises first crystal and a kind of second crystalline binding agent that contains the 2nd ABMS of an ABMS.The general A BMS catalyzer that is used for hydrocarbon conversion process uses silicon oxide, aluminum oxide or other normally used amorphous binding agent bonding usually, to strengthen the physical strength of this ABMS.

Not as the general crystalline molecular sieve that is used for hydrocarbon conversion process, these molecular sieves are bonding with silicon oxide or aluminum oxide or other normally used amorphous binding agent usually, to strengthen its physical strength, catalyzer of the present invention does not generally contain the amorphous binding agent of significant quantity.Preferably, based on the weight of an ABMS and the 2nd ABMS, this catalyzer contains and is less than 10% heavy noncrystalline binderless zeolite, more preferably contains and is less than 5% weight, and most preferably this catalyzer is substantially free of noncrystalline binderless zeolite.Preferably, the 2nd ABMS crystal forms a kind of matrix or bridge architecture thus by bonding to an ABMS crystalline surface bonding ABMS crystal that comes up, and this structure also keeps together first crystal grain.More preferably, the 2nd ABMS particle is by the bonding ABMS crystal of interior life, to such an extent as on a bigger ABMS crystal, form a coating or partial coating, most preferably, the 2nd ABMS crystal is by the bonding ABMS crystal of interior life, to form the anti-wear agent that transition increases on an ABMS crystal.

Though the present invention does not want to be subjected to the restriction of any theory of operation, but think, can obtain an advantage of the bonding ABMS catalyzer of ABMS of the present invention to the accessibility of the acid sites on the ABMS crystalline outside surface by the 2nd ABMS crystal control reactant.Because the acid sites that is present on the outside surface of ABMS catalyzer is not selected type,, these acid sitess have a negative impact so may leaving in the hole of ABMS the hole neutralized reaction product that reactant enters ABMS.According to this viewpoint, because the acidity of the 2nd ABMS and structure type can be careful selection, the 2nd ABMS can not leave in the ABMS hole reactant and produce disadvantageous effect significantly, and such situation may take place, and may leave product favorable influence in the ABMS hole to reactant with conventional bonding ABMS catalyzer.In addition, because the 2nd ABMS is not amorphous but molecular sieve, in the process that hydrocarbon transforms, may increase in the hole that hydrocarbon enters an ABMS.

The those skilled in the art of this area know term " acidity ", " the lower acidity " and " higher acidity " that is used for crystalline molecular sieve.The acidity of crystalline molecular sieve is known.But, for the present invention, must difference strength of acid and acid site density.The crystalline molecular sieve for example acidity center of ABMS can be bronsted acid and/or Lewis acid.The density of acid sites and the quantity of acid sites are very important when determining the acidity of ABMS.The factor that directly influences strength of acid is the chemical constitution of (ⅰ) ABMS skeleton, the i.e. relative concentration of tetrahedron atom and type; (ⅱ) concentration of the outer material of the skeleton of skeleton outer cationic and formation; (ⅲ) local structure of ABMS, promptly in crystallization or/near the aperture and the position on the surface of ABMS; (ⅳ) the co-adsorption molecule of pretreatment condition and existence.Refer to the concentration of acid sites of the intensity of the acid sites not considering as used herein term " acidity ", " lower acidity " and " higher acidity ", it is by the ammonia determination of adsorption method.

Used herein term " median size " meaning is the arithmetical av of the crystalline diameter Distribution of by volume.

First and second ABMS that are suitable for catalyzer of the present invention comprise wide aperture ABMS, middle aperture ABMS and small-bore ABMS.At " Atlas of Zeolite StructureType ", eds.W.H.Meier and D.H.Olson, Buttersworth-Heineman, Third Edition has introduced these crystalline molecular sieves in 1992, and the document is classified reference as at this.Wide aperture ABMS is general has aperture greater than 7 , comprises for example VFI, AET, AFI, AFO, ATS, FAU structure-type ABMS.The example of macropore ABMS comprises ALPO-8, ALPO-41, SAPO-37, ALPO-37, ALPO-5, SAPO-5, ALPO-54 and MAPO-36.What middle aperture ABMS was general has about 7 to the aperture that about 5 arrive about 6.8 , comprises for example AEL, AFR, AFS, AFY, ATO, AFY and APD structure-type ABMS.The example of mesopore ABMS comprises ELAPSO-11, ELAPSO-31, ELAPSO-40, ELAPSO-41, CoAPSO-11, CoAPSO-31, FeAPSO-11, FeAPSO-31, MgAPSO-11, MgAPSO-31, MnAPSO-11, MnAPSO-31, TiAPSO-11, ZnAPSO-11, ZnAPSO-31, CoMgAPSO-11, CoMnMgAPSO-11, MeAPO-11, TiAPO-11, TiAPO-31, ELAPO-11, ELAPO-31, ELAPO-40, ELAPO-41, SAPO-11, SAPO-31, SAPO-40, SAPO-41, ALPO-31 and ALPO-11.Aperture has the aperture of about 3 to about 5 through ABMS, comprises for example AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG and THO.Aperture comprises ALPO-17 through the example of ABMS, ALPO-18, ALPO-52, ALPO-22 and ALPO-25.

The one ABMS preferably will have acid activity, preferably will be that the other AIPO that joins is arranged therefore ₄The ABMS of the metal in the lattice is ASPO for example, MeASPO or ELASPO.The example of a preferred ABMS comprises SAPO-34, SAPO-11, GaSAPO-11, ZnSAPO-11, SAPO-17, NiSAPO-34, SAPO-5.

The structure type of the one ABMS will depend on the particular hydrocarbon course of processing of using this catalyzer.For example, when this catalyzer be used for the dewaxing, an ABMS is SAPO-11 or SAPO-40 preferably.

The preferably about 0.1-15 micron of the first crystalline median size.In a lot of application, the preferably about 1-6 micron of this median size.

The structure type of the 2nd ABMS can be identical or different with the structure type of an ABMS.Preferably, the 2nd ABMS will have low acidity, more preferably will not have acidity basically.This does not preferably have tart ABMS is aluminophosphates, ALPO-17 for example, ALPO-18, ALPO-11, ALPO-15, ALPO-41, GaALPO-11, ZnALPO-11.The aperture of the 2nd ABMS preferably will be that unconspicuous restriction hydrocarbon feed enters the aperture in the hole of an ABMS.For example, when the hydrocarbon feed that will transform has when being of a size of about 5 to 6.8 , the 2nd ABMS preferably will be wide aperture ABMS, or middle aperture ABMS.

Based on the weight of an ABMS, the preferably about 10%-60% of the amount of the 2nd ABMS is heavy in catalyzer, but the amount of the 2nd ABMS will depend on the hydrocarbon processing process of using catalyzer usually.More preferably the amount of the 2nd ABMS is about 20%-50% heavily.

Compare with an ABMS crystal, the 2nd ABMS crystal preferably has less size.The preferred mean pore size of the 2nd ABMS crystalline is less than 1 micron, and preferably about 0.1-is less than 0.5 micron.The 2nd ABMS crystal is except a bonding ABMS particle and making the performance maximum of catalyzer, preferably with alternate, and produces transition and increases, and its coating or part are coated on the ABMS.Preferably this coating will be anti abrasive.

Preferably prepare catalyzer of the present invention by three steps.The first step comprises a synthetic ABMS.The method for preparing an ABMS is well known in the art.

In next step,, but, prepare the bonding ABMS of aluminum oxide up to the uniform composition of the thickener form that forms extrusion preferably by the mixture that contains ABMS crystal, aluminum oxide, water and optional extrusion auxiliary agent is mixed.Used alumina binder alumina sol preferably in the bonding ABMS coacervate of this aluminum oxide of preparation.When the extrusion thing is exsiccant, the amount of the ABMS in the extrusion thing will be that about 30%-90% is heavy, and more preferably from about 40%-90% is heavy, and equal amount mainly is an aluminum oxide, the aluminum oxide that for example about 10%-60% is heavy.

Then, the paste molding that is generated, extrusion for example, and be cut into little slice, and the extrusion thing of for example about 2mm diameter, it was at 100-150 ℃ of dry 4-12 hour.Preferably then this exsiccant extrusion thing in air about 400-550 ℃ roasting temperature 1-10 hour.If the extrusion auxiliary agent exists, this calcination steps also destroys this extrusion auxiliary agent.

At random, the bonding aggregate of this aluminum oxide can make very little crystal, and it can be used in the fluid process of for example catalytic cracking.This comprises preferably ABMS is mixed with the matrix solution that contains aluminum oxide that so that form the aqueous solution of ABMS and alumina binder, but it can spraying drying form the bonding aggregate crystal of little fluidizing aluminum oxide.The those skilled in the art that prepare such aggregate crystalline method and be this area are known.In Scherzer (Octane-Enhancing Zeolite FCC Catalysts, Julius Scherzer, MarcelDekker, Inc.New York, 1990), introduced an a kind of like this example of method.But be somebody's turn to do the bonding aggregate crystallization of fluidizing aluminum oxide, resemble the bonding extrusion thing of above-mentioned aluminum oxide, it experiences last step described below then, and alumina binder is transformed into the 2nd ABMS.

Final step in this three steps catalyst preparation process is that the aluminum oxide that is present in the bonding catalyzer of aluminum oxide is converted into the 2nd ABMS, and the 2nd ABMS is used for resistates and ABMS crystal are bonded together.In order to prepare this catalyzer, the bonding aggregate of this aluminum oxide preferably at first wears out in the suitable aqueous solution under the temperature that improves.Secondly, should select the content and the temperature of the solution of aging this aggregate, be the 2nd ABMS to transform the amorphous alumina binding agent.Produce the ABMS of this new formation with the crystalline form.This crystallization can be grown and/or be bonded in the initial ABMS crystallization, also can produce this crystallization with the crystalline form of new growth inside, and the crystallization compared with the beginning that this crystallization is general is littler, for example sub-micron.The crystallization of these new formation can be grown together and is connected with inner, therefore causes bigger crystallization to bond together.

Can be used as the function of the composition of resulting solution for the second time and synthetic aging condition and change in the synthetic character that changes into the ABMS that forms among the ABMS of the aluminum oxide second time.This, resulting solution was the aquo ion solution that contains source of phosphoric acid and template second time, and it is enough to transform aluminum oxide is needed ABMS.

Catalyzer of the present invention can also carry out ion-exchange by method well known in the art, or replace at least a portion to be present in primary basic metal among the ABMS with different positively charged ion, said different positively charged ion for example the I B family of the periodic table of elements to the metal of VIII family for example nickel, copper, zinc, palladium, platinum, calcium or rare earth metal, perhaps with intermediate ammonium exchange basic metal, then roasting removes deammoniation and acidic hydrogen form, and the more catalyzer of polyacid form is provided.By use suitable acid reagent for example ammonium nitrate carry out the catalyzer that ion-exchange can prepare this acid form easily.Then this catalyzer of roasting temperature of 400-550 ℃ 10-45 hour to remove ammonium cation.Preferably after forming, catalyzer carries out ion-exchange.Particularly preferred positively charged ion provides the material of catalytic activity, and those positively charged ions of catalytic active substance particularly are provided for some hydrocarbon conversion reaction.They comprise hydrogen, the II A of the rare earth metal and the periodic table of elements, III A, IV A, V A, I B, II B, III B, IV B, V B, VI B, the metal of VII B and VIII family.The example of suitable metal comprises platinum, palladium, rhodium, iridium, iron, molybdenum, cobalt, tungsten, nickel, manganese, titanium, zirconium, vanadium, hafnium, zinc, tin, lead, chromium etc.By the weight of an ABMS, it is heavy that the preferred amount of catalytically-active metals is about 0.05%-3.0%.

In the processing hydrocarbon feed, can use catalyzer of the present invention.Hydrocarbon feed contains carbon compound, and a lot of different sources can be arranged, for example virgin petroleum fractions, circulation petroleum fractions, tar sand oil, and general can be any carbonaceous to the responsive fluid of zeolite catalysis reaction.According to the type of the hydrocarbon feed that will process, this raw material can contain metal or containing metal not.In addition, this raw material also can contain a large amount of or a spot of nitrogen or sulphur impurity.

Can be according to the type of needed process, in the mode of any routine, for example fluidized-bed, moving-bed or fixed-bed reactor carry out the hydrocarbon feed conversion.

For various organic compound hydrocarbon compound conversion process for example, can use catalyzer of the present invention separately or mix use with one or more catalytic active substances.The example of such hydrocarbon conversion process comprises, and is as the example of indefiniteness, as follows:

(A) catalytic cracking of the feed naphtha of production light olefin.General reaction conditions comprises about 500 ℃-750 ℃, and pressure is for being lower than normal atmosphere or normal pressure, and is general up to about 10 normal atmosphere (gauge pressure), the residence time (volume of catalyzer, raw material flow rate) about 10 milliseconds-10 seconds.

(B) the high-molecular weight hydrocarbon catalytic cracking is the hydrocarbon of lower molecular weight.The reaction conditions of general catalytic cracking comprises about 400 ℃-700 ℃ temperature, and pressure is about 0.1 barometric point (crust)-30 normal atmosphere, and weight hourly space velocity is about 0.1-100hr ^-1

(C) transalkylation of aromatic hydrocarbons in the presence of many alkylaromatic hydrocarbons.General reaction conditions comprises about 200 ℃-500 ℃ temperature, and pressure is about normal pressure-200 normal atmosphere, and weight hourly space velocity is about 1-1000hr ^-1, the mol ratio of aromatic hydrocarbons/many alkylaromatic hydrocarbons is about 1/1-16/1.

(D) isomerization of aromatic hydrocarbons (for example dimethylbenzene) feed composition.General reaction conditions comprises about 230 ℃～510 ℃ temperature, and pressure is about 0.5 normal atmosphere-50 normal atmosphere, and weight hourly space velocity is about 0.1-200hr ^-1, the mol ratio of hydrogen/hydrocarbon is about 0-100.

(E) dewaxing of the hydrocarbon by optionally removing straight-chain paraffin.Reaction conditions depends primarily on used raw material and desired pour point.General reaction conditions comprises about 200 ℃-450 ℃ temperature, and pressure is up to 300psig, and liquid hourly space velocity is 0.1-20hr ^-1

(F) alkylating agent for example alkene, formaldehyde, alkyl halide and have about 20 carbon atoms of 1-alcohol in the presence of, aromatic hydrocarbons is the alkylation of benzene and alkylbenzene for example.General reaction conditions comprises about 100 ℃-500 ℃ temperature, and pressure is about normal atmosphere-200 normal atmosphere, and weight hourly space velocity is about 1-100hr ^-1, the mol ratio of aromatic hydrocarbons/alkylating agent is about 1/1-20/1.

(G) aromatic hydrocarbons benzene and long-chain olefin C for example for example ₁₄The alkylation of alkene.General reaction conditions comprises about 50 ℃-200 ℃ temperature, and pressure is about normal atmosphere-200 normal atmosphere, and weight hourly space velocity is about 2-2000hr ^-1, the mol ratio of aromatic/olefin is about 1/1-20/1.Reacting resulting product is chain alkyl aromatic hydrocarbons, when sulfonation thereafter just has special purposes for example as synthetic detergent.

(H) alkylation of aromatic hydrocarbons and light olefin obtains the short-chain alkyl aromatic hydroxy compound, and for example the alkylation of benzene and propylene obtains cumene.General reaction conditions comprises about 10 ℃-200 ℃ temperature, and pressure is about the 1-30 normal atmosphere, and the weight hourly space velocity of aromatic hydrocarbons (WHS) is about 1-50hr ^-1

(I) hydrocracking of non-refinable crude raw material, cyclic hydrocarbon raw material and other hydrocarbon feed.Catalyzer will contain significant quantity at least a in hydrocracking catalyst the hydrogenation component of used type.

(J) alkylation of reformate that contains the benzene and the toluene of obvious amount and contain the fuel gas of short chain olefin (for example ethene and propylene) comes manufacture order or dialkyl group thing.General reaction conditions comprises about 100 ℃-250 ℃ temperature, and pressure is about 100-800psig, and the WHSV of alkene is about 0.4-0.8hr ^-1, the WHSV of reformate is about 1-2hr ^-1, arbitrarily, gas circulation is about 1.5-2.5 body/fluid fuel gas charging.

(K) aromatic hydrocarbons benzene,toluene,xylene and naphthalene and long-chain olefin C for example for example ₁₄Alkylating aromatic hydrocarbons lubrication base oil plant is produced in the alkylation of alkene.General reaction conditions comprises about 100 ℃-400 ℃ temperature, and pressure is about 50-450psig.

(L) long chain alkylphenol is produced in the alkylation of phenol and alkene or suitable alcohol.General reaction conditions comprises about 100 ℃-250 ℃ temperature, and pressure is about 1-300psig, and total WHSV is about 2-10hr ^-1

(M) for example at U.S.P5, disclosed in 283,563, light alkane is converted into alkene and/or aromatic hydrocarbons, and the document is classified reference as at this.General reaction conditions comprises about 425 ℃-760 ℃ temperature, and pressure is about 10-2000psig.

(N) light olefin is converted into the hydrocarbon of gasoline, distillate and lube range.General reaction conditions comprises about 175 ℃-375 ℃ temperature, and pressure is about 100-2000psig.

(O) initial boiling point is higher than the two-stage hydrocracking of 200 ℃ hydrocarbon stream upgrading, obtain the product of senior distillate and gasoline boiling spread, or as the raw material of other fuel, or as raw material first section chemical procedure of processing, the catalyzer that is used in first section contains one or more catalytic active substances, VIII family metal for example, first section effluent is using second section of second kind of catalyzer will react, this second kind of catalyzer contains one or more catalytic active substances, and for example VIII family metal is as catalyzer.General reaction conditions comprises about 315 ℃-455 ℃ temperature, and pressure is about 400-2500psig, the about 1000-10000SCF/bbl of recycle hydrogen, and liquid hourly space velocity (LHSV) is about 0.1-10hr ^-1

(P) hydrocracking in the presence of the catalyzer that contains hydrogenation component/dewaxing combined process.General reaction conditions comprises about 350 ℃-400 ℃ temperature, and pressure is about 1400-1500psig, and LHSV is about 0.4-0.6hr ^-1, the about 3000-5000SCF/bbl of recycle hydrogen.

(Q) pure and mild olefine reaction obtains mixed ether, and for example the reaction of methyl alcohol and iso-butylene and/or isopentene obtains methyl tertiary butyl ether (MTBE) and/or tert pentyl methyl ether (TAME).General conversion condition comprises about 20 ℃-200 ℃ temperature, and pressure is about 2-200atm, the about 0.1-200hr of WHSV (gram alkene/per hour restrain catalyzer) ^-1, alcohol is about 0.1/1-5/1 with the alkene molar feed ratio.

(R) toluene disproportionation is produced benzene and p-Xylol.General reaction conditions comprises about 200 ℃-760 ℃ temperature, and pressure is about normal pressure-60 normal atmosphere (crust), and WHSV is about 0.1-30hr ^-1

(S) petroleum naphtha (for example C6-C10) and similar mixture are converted into the higher aromatics mixture.So, can transform the positive structure or the hydrocarbon of side chain a little, preferred boiling spread is about more than 40 ℃ and be lower than about 200 ℃ hydrocarbon, production has the product of the aromaticity content of tangible higher octane, be about 400 ℃-600 ℃ temperature at reaction conditions, preferred 480-550 ℃, pressure is about normal pressure-40 crust, and liquid hourly space velocity (LHSV) is about 0.1-15hr ^-1Down, the hydrocarbon charging contacts with catalyzer.

(T) absorption of alkyl aromatic compound is so that separate the various isomer of this compound.

(U) oxygenatedchemicals is for example pure, as methyl alcohol, or ether such as dme, or the conversion of their mixture, obtaining comprising the hydrocarbon of alkene and aromatic hydrocarbons, reaction conditions comprises about 275 ℃-600 ℃ temperature, pressure is about 0.5 pressure-50 pressure, and liquid hourly space velocity is about 0.1-100hr ^-1

(V) has the oligomerisation of the straight or branched alkene of about 2-5 carbon atom.Oligopolymer as the product of this process is the solvent of heavy alkene, and it can be used as fuel for example gasoline or gasoline blending stock, and chemical.This oligomerisation process is general is that the alkene charging contacts with catalyzer and reacts in gas phase, about 250 ℃-800 ℃ of temperature of reaction, and LHSV is about 0.2-50hr ^-1, the about 0.1-50 normal atmosphere of hydrocarbon partial pressure.When raw material is liquid phase, contact with catalyzer, this raw material of oligomerisation can use and be lower than about 250 ℃ temperature.So,, can use about 10 ℃-250 ℃ temperature when when the liquid phase olefin charging contacts with catalyzer.

(W) C ₂Unsaturated hydrocarbons (ethene and/or acetylene) is converted into aliphatic C _6-12Aldehyde, and said aldehyde is converted into corresponding C _6-12Alcohol, acid or ester.

(X) ethylbenzene isomerization becomes dimethylbenzene.General reaction conditions comprises about 600-800 temperature, and pressure is about 50-500psig, and LHSV is about 1-10hr ^-1

Therefore, use the general catalyticing conversioning condition of catalyzer to comprise about 100 ℃-760 ℃ temperature, about 0.1 normal atmosphere of pressure (crust)-200 normal atmosphere (crust), weight hourly space velocity is about 0.08-2000hr ^-1

Though a lot of hydrocarbon conversion process preferably the 2nd ABMS crystal has lower acidity, so that reduce the reaction that does not meet the requirements of an ABMS crystal outside, but, some process preferably the 2nd ABMS crystal has higher acidity, this acidity Be Controlled for example is so that the desirable reaction of catalysis.These processes have two types, in first type, stipulate the 2nd ABMS crystalline acidity and structure type, so that be complementary with ABMS crystalline acidity and crystallization type.When doing like this, the catalytic active substance of the catalyzer of formed unit weight will increase, and therefore making has increased apparent catalyst activity.Such catalyzer also can be favourable, because adsorptive power is bigger, for example accessibility is bigger, and reduces nonselective surface acidity.

The process of this second type that may be favourable by the acidity of stipulating the 2nd ABMS phase is such process, and two or more reactions promptly take place in the ABMS catalyzer.In such process, can control the acidity and/or the structure type of the 2nd ABMS phase, so that it is different from the acidity and/or the structure type of an ABMS phase, but need there be acid sites basically.Such catalyzer will comprise two kinds of different ABMS, and these two kinds of different ABMS can be by independent control, to promote or to suppress different reactions.Using the process of such catalyzer is favourable from higher outward appearance catalyst activity, bigger ABMS accessibility aspect not only, and can reduce possible nonselective surface acidity with this catalyzer, and it also can be favourable aspect certain products.

It can be favourable using the xylol isomerization/ethylbenzene dealkylation process of such catalyzer.Can special isomerization/ethylbenzene dealkylation catalyzer, so as in an ABMS crystal main ethylbenzene dealkylation reaction, the main xylene isomerization reaction that takes place in the 2nd ABMS crystal of taking place.By with the special catalyzer of such method, can reach two kinds of balances between the reaction, and be inaccessible with the catalyzer that only contains a kind of ABMS.

In the described below method of catalyzer of the present invention is useful especially.

Contained long linear hydrocarbon is by contacting the process that is isomerizated into to branched-chain hydrocarbon with the bonding SAPO catalyzer of ALPO in high pour point and full-bodied hydrocarbon stream, obtains having the hydrocarbon stream of the viscosity of the pour point of reduction and reduction.This SAPO component is the molecular sieve in middle aperture, contains to carry out hydrogenation/dehydrogenation reactive activity metal, and it is a tart.This ALPO component can be identical structure type or different structure types, have seldom or do not have metal component, it is non-acid.At 150-650 ℃, in the presence of hydrogen is, be 0.1-20hr at pressure and the WHSV of 15-3000psig ^-1Condition under, this hydrocarbon contacts with catalyzer.

At 400-700 ℃, be 0.1-200hr at atmospheric pressure of 1-100 and WHSV ^-1Condition under, the bonding SAPO catalyzer of alkane and ALPO contacts C ₂-C ₅Alkane and conversion of olefines are the unit molecule aromatic hydroxy compound.This SAPO component is a mesoporous molecular sieve, and it can contain or not contain metal oxide component for example ZnO or Ga ₂O ₃This ALPO material can the identical structure type of yes or no, can contain metal oxide component for example ZnO or Ga ₂O ₃

Transforming methyl alcohol is the process of light olefin, wherein at 400-600 ℃, under the atmospheric pressure of 1-100, sometimes thinner for example steam in the presence of and WHSV be 0.1-100hr ^-1Condition under, the bonding SAPO catalyzer of methyl alcohol and ALPO contacts.At least a kind of of ALPO or SAPO component should have 8-ring perforate, for example SAPO-34, SAPO-17 or ALPO-17.It maybe may be 10-ring or the perforate of 12-ring that other component also may have the perforate of 8-ring.The mixture of possible indefiniteness is bonding SAPO-11 of ALPO-17 or the bonding SAPO-34 of ALPO-17.

Find that catalyzer of the present invention is specially adapted to comprise the reaction of aromizing and/or dehydrogenation.They are useful especially in the dehydrocyclization of acyclic hydrocarbous and/or isomerized process, wherein at 370 ℃-600 ℃, under preferred 430 ℃-550 ℃ temperature, this hydro carbons contacts with catalyzer, but the positively charged ion that this catalyzer preferably has at least 90% ion-exchange is alkalimetal ion for example, and adding at least a VIII family metal with dehydrogenation activity, is aromatic hydrocarbons so that be converted into the small part acyclic hydrocarbous.

Aliphatic hydrocrbon can be a for example hexane of straight or branched acyclic hydrocarbous, particularly alkane, though the mixture of hydrocarbon also can use, for example contains the alkane of certain limit and the aliphatic fraction of a spot of other hydrocarbon.Also can use for example methylcyclopentane of cycloaliphatic hydrocarbon.One preferred aspect in, the raw material of process of preparation aromatic hydrocarbons and particularly benzene contains hexane.The temperature of catalyzed reaction can be 370 ℃-600 ℃, and preferably 430 ℃-550 ℃, the preferred pressure that uses is to surpass normal atmosphere, for example up to 2000KPa, and more preferably 500-1000Kpa.In forming the process of aromatic hydrocarbons used usually hydrogen preferably the ratio of hydrogen and raw material for being less than 10.

The following examples explanation the present invention.

Embodiment 1

I. the bonding SAPO-34 of catalyst A-ALPO-5

By as follows, SAPO-34 bonding 30% heavy aluminum oxide forms the catalyzer of the bonding SAPO-34 of AIPO-5:

By listed order, the H of 4.18 grams 85% ₃PO ₄The aqueous solution, 10.78 gram water and 2.65 gram tripropyl amines (TPA) join in the autoclave of teflon lined of a 300ml.Stir this mixture, obtain uniform solution.Then, the exsiccant extrusion thing of 10 gram aluminum oxide bonding SAPO-34 (1/16 " diameter) is joined in the mixture of this autoclave.This extrusion thing is covered by liquid fully.The mole of this synthetic mixture is formed:

TPA/Al ₂O ₃/P ₂O ₅/H ₂O=0.63/1.0/0.62/23.4

In this mixture, the total amount of aluminum oxide only is the amount of the alumina binder of extrusion thing, P ₂O ₅Total amount only be 85% H ₃PO ₄The aqueous solution.Autoclave is sealed, in 2 hours,, and do not have to keep 24 hours under the condition of stirring at 200 ℃ mixture heating up to 200 ℃.Autoclave cool to room temperature and decant mother liquor.The extrusion thing with deionized water wash up to the electric conductivity of filtrate less than 100 micro-ohms.XRD analysis shows the spectrogram of typical SAPO-34 and ALPO-5.II. the bonding SAPO-34 of catalyst B-ALPO-11

By as follows, SAPO-34 bonding 25% heavy aluminum oxide forms the catalyzer of the bonding SAPO-34 of AIPO-11:

By listed order, the H of 6.36 grams 85% ₃PO ₄The aqueous solution, 18.02 gram water and 2.82 gram dipropyl amines (DPA) join in the autoclave of teflon lined of a 100ml.Stir this mixture, obtain uniform solution.Then, the exsiccant extrusion thing of 15.00 gram aluminum oxide bonding SAPO-34 (1/16 " diameter) is joined in the mixture of this autoclave.This extrusion thing is covered by liquid fully.The mole of this synthetic mixture is formed: DPA/Al ₂O ₃/ P ₂O ₅/ H ₂O=0.76/0.75/1.0/30.9

In this mixture, Al ₂O ₃Total amount only be the amount of the alumina binder of extrusion thing, P ₂O ₅Total amount only be 85% H ₃PO ₄The aqueous solution.Autoclave is sealed, in 2 hours,, and do not have to keep 22 hours under the condition of stirring at 200 ℃ mixture heating up to 200 ℃.Autoclave cool to room temperature and decant mother liquor.The extrusion thing with deionized water wash up to the electric conductivity of filtrate less than 100 micro-ohms.XRD analysis shows typical SAPO-34 and ALPO-11 spectrogram.III. the bonding SAPO-34 of catalyzer C-ALPO-17

By as follows, SAPO-34 bonding 25% heavy aluminum oxide forms the catalyzer of the bonding SAPO-34 of AIPO-5:

By listed order, the H of 6.35 grams 25% ₃PO ₄The aqueous solution, 17.60 gram water and 2.77 gram hexahydroaniline join in the autoclave of teflon lined of a 300ml.Stir this mixture, obtain uniform solution.Then, the exsiccant extrusion thing of 15.02 gram aluminum oxide bonding SAPO-34 (1/16 " diameter) is joined in the mixture of this autoclave.This extrusion thing is covered by liquid fully.The mole of this synthetic mixture is formed:

1.00R ₂O ₅/1.01R/1.00Al ₂O ₃/39H ₂O

In this mixture, the total amount of aluminum oxide only is the amount of the alumina binder of extrusion thing, P ₂O ₅Total amount only be 25% H ₃PO ₄The aqueous solution.Autoclave is sealed, in 2 hours,, and do not have to keep 48 hours under the condition of stirring at 200 ℃ mixture heating up to 200 ℃.The autoclave cool to room temperature, take out a spot of extrusion matter sample, then in 2 hours mixture heating up to 200 ℃, and kept again 48 hours at 200 ℃.The cooling of extrusion thing, with 800ml water washing 4 times.The electric conductivity of last washing water is less than 26 μ S/cm.Then, at this extrusion thing of 120 ℃ of dryings.The amount of the extrusion thing that obtains is 17.3 grams.XRD analysis shows the spectrogram of typical SAPO-34 and ALPO-5.

Embodiment 2

Catalyst A, catalyst B and catalyzer C are used for the test that oxygenate is an alkene.Make and carry out these tests in the following method: each catalyzer 5.0cc (about 2.7 gram) is mixed with 15cc quartz bead, be contained in 3/4 " in the 316 stainless steel tube reactors of external diameter, heat this reactor with three sections electric furnaces.First section as preheating section feed vaporization.The temperature regulation to 450 of stove central segment ℃, pressure remains on a normal atmosphere.At first use nitrogen with 50cc/ minute flow velocity purge 30 minutes.The water of charging and the mol ratio of methyl alcohol are 4: 1, with calibrated speed feedstock pump are delivered in the reactor, make the about 0.7hr of flow velocity ^-1WHSV.Use the online gas chromatographic analysis effluent that thermoelectric conductance detector and flame ionization detector are housed at predetermined interval.These tests the results are shown in following table 4:

Table 4

Olefins yield	Catalyst A	Catalyst B	Catalyzer C
				Transform (heavy %)
Methane	????5.7	????1.6	????1.5
				Ethene	????24	????45	????47
Propylene	????41	????38	????37
				????C 4	????27	????15	????14

These data show that these catalyzer have good ethene and propylene selectivity, use this special catalyzer can change product and distribute.

Claims (27)

1. bonding ABMS catalyzer of ABMS that does not contain the amorphous binding agent of significant quantity, it comprises:

(a) first crystal of an ABMS and

(b) a kind of second crystalline binding agent that contains the 2nd ABMS.

2. according to the catalyzer of claim 1, wherein second crystal is a growth inside, and forms at least a portion coating on first crystal.

3. according to the catalyzer of claim 1 or 2, based on the blended weight of an ABMS and the 2nd ABMS, it contains and is less than 5% heavy non-binderless zeolite.

4. according to the catalyzer of one of aforesaid right requirement, wherein, based on the first crystalline weight, the second crystalline amount is that 10-60% is heavy.

5. according to the catalyzer of one of aforesaid right requirement, wherein the first crystalline median size is greater than 0.1 micron.

6. according to the catalyzer of claim 5, wherein the first crystalline median size is the 1-6 micron.

7. according to the catalyzer of one of aforesaid right requirement, wherein the second crystalline median size is less than the first crystalline median size.

8. according to the catalyzer of one of aforesaid right requirement, wherein the second crystalline median size is the 0.1-0.5 micron.

9. according to the catalyzer of one of aforesaid right requirement, wherein the 2nd ABMS has the acidity less than an ABMS.

10. according to the catalyzer of one of claim 1-8, wherein the 2nd ABMS has the acidity greater than an ABMS.

11. according to the catalyzer of one of aforesaid right requirement, wherein an ABMS and the 2nd ABMS independently are selected from following structure type: VFI, AET, AFI, AFO, ATS, FAU respectively, AEL, AFR, AFS, AFY, ATO, APD, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG and THO.

12. according to the catalyzer of one of aforesaid right requirement, wherein an ABMS has different structure types with the 2nd ABMS.

13. according to the catalyzer of one of claim 1-11, wherein an ABMS has identical structure type with the 2nd ABMS.

14. according to the catalyzer of one of aforesaid right requirement, wherein the 2nd ABMS is ALPO.

15. according to the catalyzer of claim 14, wherein the 2nd ABMS is ALPO-17, ALPO-18, ALPO-11, ALPO-5, ALPO-41, GaALPO-11 or ZnALPO-11.

16. according to the catalyzer of one of aforesaid right requirement, wherein an ABMS is SAPO.

17. according to the catalyzer of one of aforesaid right requirement, wherein an ABMS is SAPO-34, SAPO-37, SAPO-40, SAPO-5, MAPO-36, SAPO-11, GaSAPO-11, ZnSAPO-11, SAPO-17 or NiSAPO-34.

18. according to the catalyzer of one of claim 1-15, wherein an ABMS is SAPO, MeAPO, MeAPO, ELAPO or ELAPSO.

19. according to the catalyzer of one of claim 1-15, wherein an ABMS and the 2nd ABMS are independently selected from ALPO-8, ALPO-41, SAPO-37, ALPO-37, SAPO-31, SAPO-40, SAPO-41, ALPO-5, SAPO-5, ALPO-54, MAPO-36, SAPO-11, ALPO-31, ALPO-11, ALPO-17, ALPO-18, ALPO-52, ALPO-22 and ALPO-25.

20. according to the catalyzer of one of claim 1-13, wherein an ABMS is that SAPO-34 and the 2nd ABMS are ALPO-5, ALPO-17 or ALPO-11.

21. the method for convert hydrocarbons or oxygenatedchemicals, it is included under the conversion condition of hydrocarbon or oxygenatedchemicals, and the charging of hydrocarbonaceous or oxygenatedchemicals contacts with the catalyzer of above-mentioned arbitrary claim.

22. according to the method for claim 21, wherein the aperture of an ABMS is greater than the aperture of the 2nd ABMS.

23. according to the method for claim 21, wherein the aperture of an ABMS is less than the aperture of the 2nd ABMS.

24. according to the method for claim 21,22 or 23, wherein an ABMS and the 2nd ABMS are intermediate pore size or small-bore ABMS independently.

25. method according to one of claim 21-24, wherein this conversion is selected from the cracking of hydrocarbon, the dealkylation of aromatic hydrocarbons, the isomerization of alkylaromatic hydrocarbon, the disproportionation of toluene, the dehydrogenation of hydrocarbon, the transalkylation of aromatic hydrocarbons, the alkylation of aromatic hydrocarbons, hydrocarbon becomes the reformation of aromatic hydrocarbons, alkane and/or alkene become the conversion of aromatic hydrocarbons, and oxygenatedchemicals becomes the conversion of hydrocarbon product, and petroleum naphtha becomes the cracking of light olefin and the dewaxing of hydrocarbon.

26. according to the method for claim 25, wherein this conversion is that oxygenatedchemicals becomes conversion of olefines.

27. according to the method for claim 25, wherein this conversion is the reformation that petroleum naphtha becomes aromatic hydrocarbons.