CN1269570C - MOlecular sieve catalyst composition its making method and use in conversion processes - Google Patents

Abstract

The invention relates to a molecular sieve catalyst composition, to a method of making or forming the molecular sieve catalyst composition, and to a conversion process using the catalyst composition. In particular, the invention is directed to making a formulated molecular sieve catalyst composition from a slurry of formulation composition of a synthesized molecular sieve that has not been fully dried, a binder and an optional matrix material. In a more preferred embodiment, the weight ratio of the binder to the molecular sieve and/or the solid content of the slurry is controlled to provide an improved attrition resistant catalyst composition, particularly useful in a conversion process for producing olefin(s), preferably ethylene and/or propylene, from a feedstock, preferably an oxygenated containing feedstock.

Description

Molecular sieve catalyst composition, its manufacture method and the purposes in conversion process

The field of the invention

The present invention relates to molecular sieve catalyst composition, relate to the manufacture method that forms molecular sieve catalyst composition and relate to the conversion process of using this carbon monoxide-olefin polymeric.

Background of the present invention

Alkene is to produce from petroleum by catalysis or steam cracking process traditionally.These cracking process, especially steam cracking is produced light olefin from various hydrocarbon raw materials, as ethene and/or propylene.Ethene and propylene are the important goods petroleum chemicals that can be used for making many methods of plastics and other compound.

Known oxygen compound (oxygenate) in the petro chemical industry, especially alcohol changes into the light olefin class some times.There are a lot of technology to can be used for the production oxygenate, comprising the synthesis gas of deriving from natural gas, petroleum liquid, carbonaceous material (comprising coal), the plastics of reuse, the fermentation of municipal waste or any other organic material or reaction.Generally, the production of synthesis gas comprises that the combustion reaction of natural gas (main methane) and oxygen source forms hydrogen, carbon monoxide and/or carbon dioxide.The synthesis gas manufacture process is well known, and comprises common steam reformation, self-heating recapitalization, or two kinds associating.

Methyl alcohol is used for the preferred alcohol of light-olefin production, be typically from hydrogen, and carbon monoxide and/or the carbon dioxide catalytic reaction in the presence of heterogeneous catalysis in methanol reactor is synthetic.For example, in a kind of building-up process, methyl alcohol is by using copper/zinc oxide catalyst to produce in the tubular type methanol reactor of water-cooled.Preferred methanol conversion process generally is meant " methyl alcohol-to-olefin hydrocarbon ", and wherein methyl alcohol mainly changes into ethene and/or propylene in the presence of molecular sieve.

Molecular sieve is the porous solid with hole of different size, as zeolite or zeolite-type molecular sieves, and carbon and oxide.The most useful industrial molecular sieve that is used for oil and petrochemical industry is known as zeolite, for example aluminosilicate molecular sieves.Zeolite has one dimension usually, two-dimentional or three-dimensional crystal pores gap structure, and the latter has the hole of the uniform-dimension of molecular size, and this hole optionally absorbs the molecule that can enter hole and gets rid of those too big molecules.

Have that many dissimilar molecular sieves are known can especially to contain the raw material of oxygenate with raw material (feedstock), change into one or more alkene.For example, US patent No 5,367,100 has described well-known zeolite, and ZSM-5 becomes methanol conversion the purposes of alkene; US patent No 4,062,905 has discussed for example zeolite T of use crystal type aluminosilicate zeolite, ZK-5, and erionite and chabasie become methyl alcohol the process of ethene and propylene with other oxygenate conversion; US patent No.4,079,095 has described the method for using ZSM-34 methanol conversion to be become hydrocarbon products such as ethene and propylene; With US patent No.4,310,440 describe use crystal aluminate or phosphate (usually by ALPO ₄Expression) produces the method for light olefin from alcohol.

Being used for methanol conversion is become a kind of of the most useful molecular sieve of alkene is silicoaluminophosphamolecular molecular sieve.Silicoaluminophosphate (SAPO) molecular sieve contains [SiO ₂], [AlO ₂] and [PO ₂] angle shares the three-dimensional micropore crystal frame structure of tetrahedron element.The synthetic US patent No.4 that is described in of SAPO, in 440,871, it is for reference that it all is introduced into this paper.SAPO generally by silicon-, aluminium-and the hydrothermal crystallization methods of the reactant mixture of phosphorus-source and at least a template agent synthesize.SAPO molecular sieve synthetic, it is mixed with SAPO catalyst and it hydrocarbon raw material is changed into the purposes of alkene, and especially wherein this raw material is a methyl alcohol, in US patent 4,499,327,4,677,242,4,677,243,4,873,390,5,095,163,5,714, in 662 and 6,166,282 description is arranged, it is for reference that they all are introduced into this paper.

Typically, molecular sieve is formed molecular sieve catalyst composition to improve in industrial conversion process their durability.At catalyst combination composition granule itself, reactor wall, and the conflict in commercial process between other reactor system can cause breakage of particles become to be known as particulate (fine) than granule.The physics of molecular sieve catalyst composition particle breaks to be known as and grinds.Particulate usually leaves this reactor in effluent stream, cause the problems in recovery system.Have the fewer purpose particulate of catalyst combination deposits yields than high abrasion fragility energy, transforming needs less carbon monoxide-olefin polymeric and causes lower running cost the service life of length.

Molecular sieve catalyst composition is in the presence of binding agent molecular sieve and matrix material blending to be formed usually.The purpose of binding agent is that this matrix material (usually being clay) is fixed on the molecular sieve.The use in the formation of molecular sieve catalyst composition of binding agent and matrix material is called optical imaging for many commercial processes.Also be known that wherein and make or the method for this molecular sieve catalyst composition of prescription design will influence carbon monoxide-olefin polymeric and grind.

The example of making the method for carbon monoxide-olefin polymeric comprises: US patent No.5,126,298 discussed by in independent slurry with two kinds of different clay particles and zeolite slurry and the blending of phosphorus source, then pH is lower than the mixture spray-drying of 3 slurry, makes the method for Cracking catalyst with high-wearing feature; US patent No.4,987,110 and 5,298,153 relate to the catalytic cracking process that uses spray-dired wearability catalyst, and this catalyst contains above being scattered in of 25wt% has synthetic silica-molecular sieve in the clay matrix of alumina component; US patent No 5,194,412 and 5,286,369 discloses the formation molecular sieve and has had the 20m of being lower than ²The method of the surface area of/g and the catalytic cracking catalyst of the crystal phosphoric acid al binder of the total pore space volume that is lower than 0.1cc/g; US patent No.4,542,118 relate to the method for the particulate inorganic oxide compound that forms zeolite and aluminium hydroxychloride (aluminum chlorhydrol) (it and ammonia react form the cohesion binding agent); US patent No.6,153,552 have required as right by dry SAPO molecular sieve, and the slurry in inorganic oxide sol and outside phosphorus source is made the method for catalyst; US patent No.5,110,776 have illustrated by with containing this zeolite of phosphatic solution modification contains the catalyst of catalytic action with formation the method for zeolite; US patent No.5,348,643 relate to the zeolite slurry that will have clay and a phosphorus source is being lower than spray-dired method under 3 the pH; US patent application No.4,973,792 relate to the conversion process of the molecular sieve catalyst composition that uses preparation, yet, do not mention the solids content of spray-dired slurry, do not have any discussion yet about the amount of the liquid medium among the SAPO-34 in being added to slurry; The US patent application No.09/891 of June 25 calendar year 2001 application, 674 have discussed molecular sieve have been carried out steam treatment to remove the method for halogen; US patent No.5,248,647 illustrated will with the spray-dired method of SAPO-34 molecular sieve of kaolin and silicon dioxide gel blending; US patent No.5,346,875 disclose the method that the pH that is matched with inorganic oxide sol by the isoelectric point with each component of frame structure makes catalytic cracking catalyst; People such as Maurer, Aggregation and Peptization Behavior of Zeolite Crystals inSols and Suspensions, Ind.Eng.Chem.Vol.40, the 2573-2579 page or leaf, 2001 have discussed in isoelectric point or coalescent near the zeolite of isoelectric point; PCT publication WO99/21651 has described the method for making catalyst by the mixture of dry alumina colloidal sol and SAPO molecular sieve; PCT publication WO 02/05950 has described the method for making the carbon monoxide-olefin polymeric of molecular sieve, and this molecular sieve contains the particle that grinds with fresh molecular sieve; The matrix material of crystalline metal-aluminophosphate molecular sieve and inorganic oxide binder and filler is disclosed with WO02/05952, wherein molecular sieve be with the amount that is lower than 40wt% (with respect to catalyst weight) exist and the preferred weight ratio of this binding agent and molecular sieve near 1.

Though above-described these molecular sieve catalyst compositions can be used in the hydrocarbon conversion process, still wishing has a kind of improved molecular sieve catalyst composition, and it has better wear resistence and industrial desirable operability and cost advantage.

The present invention's general introduction

The method that the invention provides manufacturing or prescription design molecular sieve catalyst composition is used for conversion process so that feedstock conversion is become one or more alkene with relating to it.

In one embodiment, the present invention relates to prepare the method for molecular sieve catalyst composition, this method may further comprise the steps: (a) providing does not have fully dry synthesis of molecular sieve, or partly dry in addition synthesis of molecular sieve; (b) make synthesis of molecular sieve, the slurry of binding agent and optional matrix material; (c) form this slurry to produce the molecular sieve catalyst composition of preparation.In preferred embodiments, synthesis of molecular sieve is from the silicon source, and at least two kinds bond in phosphorus source and the aluminium source is chosen wantonly in the presence of the template agent, synthetic.In the most preferred embodiment, the slurry in step (c) forms by spray-drying.In a further preferred embodiment, the weight ratio of binding agent and molecular sieve is greater than 0.12 to about 0.45 in the slurry of step (c).In another embodiment again, this slurry contains 20% to about 80% the solids content of having an appointment, based on the gross weight by the slurry of calcination basis amount (on a calcined basis).Solid comprises this molecular sieve, this binding agent and optional matrix material.In still another embodiment in above-mentioned any process, in step (b) afterwards and in step (c) before, this slurry mixes, and contains diameter up to the slurry of 90 volume % and is lower than 20 μ m, preferably is lower than the particle of 10 μ m.

In one embodiment, the present invention relates to prepare the method for molecular sieve catalyst composition, this method may further comprise the steps: (a) provide synthesis of molecular sieve in the presence of liquid medium; (b) introduce binding agent and randomly add identical or different liquid medium and/or matrix material; (c) mix and form this slurry to produce the molecular sieve catalyst composition of preparation, wherein synthesis of molecular sieve is not dry fully or partly dry before in step (a).In preferred embodiments, this liquid medium be water and before drying the amount of liquid medium be to the scope of 70wt%, based on the gross weight of molecular sieve and liquid medium at 20wt%.Preferred this synthesis of molecular sieve is a silicoaluminophosphate, aluminate or phosphate and/or chabasie (CHA) framework type molecular sieve.In another embodiment again, the weight ratio of binding agent and molecular sieve is greater than 0.12 to being lower than 0.45, is silicoaluminophosphate and binding agent is alumina and molecular sieve.In another embodiment again, this slurry contains has an appointment 30% to about 50%, and preferred about 35% to about 50% and more preferably from about 40% to about 50% solids content is based on by the basic gross weight of measuring the slurry of (on a calcined basis) of calcination.In still another embodiment in above-mentioned any process, this slurry mixes, and has up at least 90 volume % of solid particle in slurry to be lower than 20 μ m, preferably is lower than the diameter of 10 μ m.

In another preferred embodiment, the present invention relates to make the method for preparation molecular sieve catalyst composition, this method may further comprise the steps: (a) utilize liquid medium, at least two kinds bond from silicon source, phosphorus source and aluminium source, choose wantonly in the presence of the template agent, synthesis of molecular sieve forms slurry; (b) from slurry, tell this molecular sieve; (c) dry this molecule is sieved to the level in the scope of 20wt%-80wt% liquid medium, based on the gross weight of this liquid medium and this molecular sieve; (d) with this molecular sieve and binding agent and randomly add identical or different liquid medium and/or with the matrix material blending, form the formulation composition; (e) dry and/or formation formulation composition, thus the molecular sieve catalyst composition of preparing formed.In preferred embodiments, this slurry is dried to the level in the scope of 30wt%-70wt% liquid medium (preferred water) in step (c), based on the gross weight of liquid medium (preferred water) and molecular sieve.In another embodiment, this formulation composition is to form the molecular sieve catalyst composition of preparing by this formulation composition of spray-drying to form in step (e).In another embodiment, in step (c) and/or (e) before, this slurry and/or this formulation composition wash in liquid, preferably this liquid identical with liquid medium and most preferably this liquid be water.In a further preferred embodiment, this method further comprises step (f), and wherein the molecular sieve catalyst composition that should prepare is by calcination.In another embodiment, the weight ratio of binding agent and molecular sieve is greater than 0.1 to the scope that is lower than 0.5, preferably greater than 0.12 to 0.45 scope with most preferably in 0.13 to about 0.40 scope.In another embodiment again of above any process, this slurry contains 35% to about 50% the solids content of having an appointment, based on the gross weight by the slurry of calcination basis amount (on acalcined basis).In still another embodiment in above-mentioned any process, the blending of this slurry comprises the step that the slurry that will comprise liquid and solid particle mixes, have up to the solid particle of at least 90 volume % and to be lower than 20 μ m, preferably be lower than till the diameter of 10 μ m.

In another embodiment again, the present invention relates in the presence of any above-mentioned preparation molecular sieve catalyst composition, produce the technology of alkene.Especially, there is a kind of raw material of conversion down in the molecular sieve catalyst composition that this technology is included in one or more preparation discussed above, preferably contains the raw material of oxygenate, more preferably contains the raw material of alcohol, the raw material that most preferably contains methyl alcohol, technology in produce alkene.

Detailed description of the present invention

Introduce

The present invention relates to molecular sieve catalyst composition, its manufacture method and it are used for hydrocarbon raw material is changed into the purposes of one or more alkene.This molecular sieve catalyst composition is from molecular sieve, binding agent and optional, most preferably, the bond manufacturing of matrix material or formation.Typically at the molecular sieve of drying or calcination in the art with binding agent and/or matrix material blending.Yet, found surprisingly by use with binding agent and/or matrix material blending also not have a fully molecular sieve of drying, made the molecular sieve catalyst composition of improved preparation.Yet,, cause producing the molecular sieve catalyst composition of preparation with improved wear-resisting fragility energy by the dry molecular sieve of part is used with binding agent and/or matrix material.This causes having obtained more anti-division and the improved catalyst composition that therefore has the catalyst life of prolongation in conversion process.In addition, this molecular sieve of not calcination also can reduce with synthetic cost related and also improve its sensitiveness to deactivation after synthetic, especially in storage and transportation.

Show that in the art change wt% of molecular sieve in total catalyst composition is important.Yet, find surprisingly that also the weight ratio of binding agent and molecular sieve is important for making or forming the wear resistence carbon monoxide-olefin polymeric, especially when this molecular sieve as discussed above during like that by drying partly.Be not subjected to the constraint of any particular theory, can believe when weight ratio when binding agent and molecular sieve is too high, then the surface area of carbon monoxide-olefin polymeric can descend and cause lower conversion rate, with when the weight ratio of binding agent and molecular sieve is too low, then carbon monoxide-olefin polymeric more easily splits into fine grained.

Also have been found that, except the dry of molecular sieve and in the formulation of molecular sieve catalyst composition binding agent and the molecular sieve ratio, the amount of the solid that exists in being used for the slurry of being made of (randomly comprising matrix material) molecular sieve and binding agent of spray-drying process for example also is important.When the solids content of slurry was too low or too high, the abrasion resistance of molecular sieve catalyst composition can reduce.The amount of solid combines with other discovery discussed above and has also determined concrete molecular sieve catalyst composition to have the wear resistence of what level.

Molecular sieve and its catalyst

Molecular sieve has various chemistry and physical property, framework, characteristic.Molecular sieve has been carried out perfect classification by theStructure Commission of the International Zeolite Association according to the rule of the relevant zeolite nomenclature of IUPAC Commission.Framework type has been described and has been constituted the connectivity that particular characteristic this framework and that make these materials becomes the tetrahedral coordination atom of abstract, topological structure.Frame-type zeolite and the zeolite-type molecular sieves of having determined structure have been given three alphanumeric codes and have been described in the Atlas of ZeoliteFramework Types, the 5th edition, Elsevier, London, England (2001), it is all introduced for reference here.

The non-limitative example of these molecular sieves is small pore molecular sieves, 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, THO and its replacement form; Mesoporous molecular sieve, AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, the form of TON and their replacement; And large pore molecular sieve, EMT, the form of FAU and their replacement.Other molecular sieve comprises ANA, BEA, CFI, CLO, DON, GIS, LTL, MER, MOR, MWW and SOD.Preferred molecular sieve, the feedstock conversion that is particularly useful for containing oxygenate becomes alkene, non-limitative example comprise AEL, AFY, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON.In a preferred embodiment, molecular sieve of the present invention has AEI frame-type or cha framework type, or their bond, most preferably cha framework type.

Molecular screen material all has the angle and shares TO ₄Tetrahedral 3-dimension frame structure, wherein T is the cation of any tetrahedral coordination.These molecular sieves are typically described according to the size of the ring that limits hole, and wherein this size is based on the number of T atom in the ring.Other frame-type characteristic comprises the arrangement of the ring that constitutes cage and when existing, the size of passage, and the spacing between cage.Referring to people such as van Bekkum, Introduction to Zeolite Science andPractice, Second Completely Revised and Expanded Edition, 137 volumes, 1-67 page or leaf, Elsevier Science, B.V., Amsterdam, Netherlands (2001).

Little, in and large pore molecular sieve have 4-and encircle 12-ring or bigger frame-type.In preferred embodiments, this zeolite molecular sieve has 8-, 10-or 12-ring structure or more macrostructure and the average pore size between about 3 dust to 15 dusts.In the most preferred embodiment, molecular sieve of the present invention, preferred silicoaluminophosphamolecular molecular sieve have the 8-ring and are lower than about 5 dusts, preferably at 3 dusts between about 5 dusts, more preferably 3 dusts to about 4.5 dusts and most preferably 3.5 dusts to the average pore size of about 4.2 dusts.

Molecular sieve, zeolite and zeolite-type molecular sieves preferably have one especially, and preferably [TO is shared at two or more angles ₄] tetrahedron element, more preferably, two or more [SiO ₄], [AlO ₄] and/or [PO ₄] tetrahedron element and [SiO most preferably ₄], [AlO ₄] and [PO ₄] the branch subframe of tetrahedron element.These silicon, aluminium and phosphorus type molecular sieve and metallic silicon, aluminium and phosphorus type molecular sieve have been described in detail in a lot of publications, comprising for example, US patent No.4,567,029 (MeAPO, wherein Me is Mg, Mn, Zn or Co), US patent No.4,440,871 (SAPO), European patent application EP-A-0 159 624 (ELAPSO, wherein EL is As, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), US patent No.4,554,143 (FeAPO), US patent No.4,822,478,4,683,217,4,744,885 (FeAPSO), EP-A-0 158 975 and US patent No.4,935,216 (ZnAPSO), EP-A-0 161 489 (CoAPSO), EP-A-0 158976 (ELAPO, wherein EL is Co, Fe, Mg, Mn, Ti or Zn), US patent No.4,310,440 (AlPO ₄), EP-A-0 158 350 (SENAPSO), US patent No.4,973,460 (LiAPSO), US patent No.4,789,535 (LiAPO), US patent No.4,992,250 (GeAPSO), US patent No.4,888,167 (GeAPO), US patent No.5,057,295 (BAPSO), US patent No.4,738,837 (CrAPSO), US patent Nos.4,759,919 and 4,851,106 (CrAPO), US patent Nos.4,758,419,4,882,038,5,434,326 and 5,478,787 (MgAPSO), US patent No.4,554,143 (FeAPO), US patent No.4,894,213 (AsAPSO), US patent No.4,913,888 (AsAPO), US patent Nos.4,686,092,4,846,956 and 4,793,833 (MnAPSO), US patent 5,345,011 and 6,156,931 (MnAPO), US patent No.4,737,353 (BeAPSO), US patent No.4,940,570 (BeAPO), US patent Nos.4,801,309,4,684,617 and 4,880,520 (TiAPSO), US patent Nos.4,500,651,4,551,236 and 4,605,492 (TiAPO), US patent No.4,824,554,4,744,970 (CoAPSO), US patent No.4,735,806 (GaAPSO), (QAPSO, wherein Q is framework oxide unit [QO to EP-A-0 293 937 ₂]), and US patent No.4,567,029,4,686,093,4,781,814,4,793,984,4,801,364,4,853,197,4,917,876,4,952,384,4,956,164,4,956,165,4,973,785,5,241,093,5,493,066 and 5,675,050, they all are hereby incorporated by reference.Other molecular sieve is described in R.Szostak, Handbook of MolecularSieves, and Van Nostrand Reinhold, New York, New York (1992), they all introduce for reference here.

Preferred siliceous, the molecular sieve of aluminium and/or phosphorus and contain aluminium, phosphorus and optional silicon, molecular sieve comprise aluminate or phosphate (ALPO) molecular sieve and silicoaluminophosphate (SAPO) molecular sieve and replacement, preferable alloy replaces, ALPO and SAPO molecular sieve.Most preferred molecular sieve is the SAPO molecular sieve that SAPO molecular sieve and metal replace.In one embodiment, this metal is the alkali metal of the IA family of the periodic table of elements, the alkaline-earth metal of the IIA family of the periodic table of elements, and the rare earth metal of IIIB family is comprising lanthanide series: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; With the scandium or the yttrium of the periodic table of elements, the IVB of the periodic table of elements, VB, VIB, VIIB, the transition metal of VIIIB and IB family, or the mixture of any of these metallics.In a preferred embodiment, this metal is to be selected from Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr and their mixture.In another preferred embodiment, these metallic atoms discussed above by tetrahedron element as [MeO ₂] be inserted in the framework of molecular sieve, and carry the net charge that depends on the substituent valence state of metal.For example, in one embodiment, when the metal substituting group have+2 ,+3 ,+4 ,+5, or+during 6 valence state, the net charge of tetrahedron element be-2 and+2 between.

In one embodiment, this molecular sieve as described in many above-mentioned US patents, is by following empirical formula, represents by anhydrous basis:

mR：(M _xAl _yP _z)O ₂

Wherein R represents at least a template agent, preferred organic formwork agent; M is the (M of mol number/every mol of R _xAl _yP _z) O ₂Have 0 to 1 with m, preferred 0 to 0.5 and 0 to 0.3 value most preferably; X, y and z represent the M as tetrahedral oxide, the molar fraction of Al and P, wherein M is the IA that is selected from the periodic table of elements, IIA, IB, IIIB, IVB, VB, VIB, VIIB, the metal in VIIIB and the lanthanide series, preferred M is selected from Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, the metal among Zn and the Zr.In one embodiment, m is more than or equal to 0.2, and x, and y and z are more than or equal to 0.01.In another embodiment, m is greater than 0.1 to about 1, and x is greater than 0 to about 0.25, y be 0.4 to 0.5 and z be 0.25 to 0.5, more preferably m is 0.15 to 0.7, x is 0.01 to 0.2, y be 0.4 to 0.5 and z be 0.3 to 0.5.

The non-limitative example of SAPO of the present invention and ALPO molecular sieve comprises SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (US patent No.6,162,415), SAPO-47, SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, a kind of or bond among the ALPO-46, and their metallic molecular sieve.Preferred zeolite-type molecular sieves comprises SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, a kind of or bond among ALPO-18 and the ALPO-34, even more preferably SAPO-18, SAPO-34, a kind of or bond among ALPO-34 and the ALPO-18, with their metallic molecular sieve and a kind of or bond and their the metallic molecular sieve among SAPO-34 and the ALPO-18 most preferably.

In one embodiment, this molecular sieve is the symbiosis intergrowth material that has two or more clear phases of crystal structure in a kind of combination of molecular sieve.Especially, symbiosis intergrowth molecular sieve is described in the US patent application serial number No.09/924 of application on August 7 calendar year 2001, and among the PCT WO 98/15496 that on April 16th, 016 and 1998 published, both all are hereby incorporated by reference for they.For example, SAPO-18, ALPO-18 and RUW-18 have the AEI framework type and SAPO-34 has the CHA framework type.In another embodiment, at least a symbiosis intergrowth that this molecular sieve comprises AEI and cha framework type mutually, preferably this molecular sieve has more substantial cha framework type, compare with the AEI frame-type and more preferably the ratio of CHA and AEI be greater than 1: 1.

Molecular sieve is synthetic

Molecular sieve synthetic is described in many lists of references of above-mentioned discussion.Generally, molecular sieve is by the aluminium source, the phosphorus source, and the silicon source, the hydrothermal crystallization of one or more in template agent and the metallic compound synthesizes.Typically, silicon, the bond in aluminium and phosphorus source, choose wantonly with one or more template agent and/or one or more metallic compounds and be placed in the sealed pressure vessel, the latter is optional to be lined with inert plastic such as polytetrafluoroethylene (PTFE), and heats under crystallization pressure and temperature, till forming crystal molecule sieve material, by filtering, centrifugal and/or decantation reclaims then.

For the purpose of present patent application and claims, this term " deficiently dry " is defined as being included in the molecular sieve that obtains after synthetic does not have dry status to arrive molecular sieve drying but the state of calcining not.

For present patent application and claims, this term " partly () drying " be defined as comprising with molecular sieve drying to a kind of level, wherein, after drying, this molecular sieve contains at about 50wt%, preferred about 60wt%, more preferably from about 70wt% and most preferably from about 80wt% to the template agent of that interior content of the scope that is used to form crystal molecule sieve material or the template agent of synthesis of molecular sieve at first of the primary quantity of 100wt%.

In a further preferred embodiment, molecular sieve is moistening, preferably uses water-wet.Most preferably, this molecular sieve is in " wet cake " state, and it refers to this molecular sieve in crystallization of molecular sieves and drying, and is preferably partly dry, is recovered afterwards.At the wet cake state, the template agent is not removed or only partly removes from molecular sieve.

In a special embodiment, crystal molecule sieve material or synthesis of molecular sieve are randomly dry, preferably in air, to a kind of level, make synthesis of molecular sieve have the liquid to about 80wt% scope at about 0wt%, preferably this liquid is water, gross weight based on synthesis of molecular sieve and liquid, preferred this scope be greater than 5wt% to about 70wt%, more preferably from about 10wt% to about 70wt% and most preferably from about 20wt% arrive about 60wt%.

Purpose for patent specification and claims, the mensuration of the percentage of the percentage of liquid or liquid medium and template agent is undertaken by using following thermogravimetric analysis (TGA) technology: with a certain amount of SAPO-34 molecular screen material, sample, be loaded in from CahnInstrument, Inc., Cerritos is on the sample weighting disk of the Cahn TG-121 microbalance that California obtains.In the TGA technology, use the flow velocity of 114cc/min (STP) air.Sample is heated to 180 ℃ with the speed of 30 ℃/min from 25 ℃ then, 180 ℃ kept 3 hours down or up to the weight of this sample become constant till.The percentage that then is considered to liquid or liquid medium as the loss in weight with respect to the percentage test of initial SAPO-34 molecular screen material.

Subsequently, sample is heated to 650 ℃ and kept 2 hours down at 650 ℃ with 30 ℃/min from 180 ℃.The loss in weight that is considered to the template agent as this loss in weight of the percentage of original example weight in this processing.This total weight loss as the percentage that calculates according to initial first example weight in this whole TGA handles is defined as loss on ignition (LOI).

In preferred embodiments, after synthetic, do not have dry just from the molecular sieve synthetic mixture, reclaim after this crystal molecule sieve or synthesis of molecular sieve directly uses, form the slurry of this crystal molecule sieve or synthesis of molecular sieve, binding agent and optional matrix material then, then this slurry is mixed with molecular sieve catalyst composition of the present invention.

In preferred embodiments, molecular sieve is by formation aluminium source, the phosphorus source, and the silicon source, the product of organic formwork agent (preferred nitrogenous organic formwork agent) is synthesized.This particularly preferred embodiment has caused the synthetic of silicoaluminophosphate crystalline material, then by filter, centrifugal and/or decantation separates.

The non-limitative example in silicon source comprises silicate, fumed silica, for example, can be from Degussa Inc., New York, the Aerosil-200 that New York is purchased, and CAB-O-SILM-5, silicon compound such as orthosilicic acid tetraalkyl ester, for example, original quanmethyl silicate (TMOS) and tetraethyl orthosilicate (TEOS), colloidal silica or their water slurry, for example can be from E.I.duPont de Nemours, the Ludox-HS-40 colloidal sol that Wilmington, Delaware are purchased, silicic acid, alkali silicate, or their any bond.Preferred silicon source is a silicon dioxide gel.

The non-limitative example in aluminium source comprises composition such as the aluminium-alcohol salt that contains aluminium, aluminum isopropoxide for example, aluminum phosphate, aluminium hydroxide, sodium aluminate, pseudobochmite, gibbsite and alchlor, or their any bond.Preferred aluminium source is a pseudobochmite, especially when producing silicoaluminophosphamolecular molecular sieve.

The non-limitative example in phosphorus source, it also comprises the phosphorus composition that contains aluminium, comprises phosphorous inorganic or organic composite, as phosphoric acid, organophosphorus ester such as triethyl phosphate, crystal or unbodied aluminate or phosphate such as ALPO ₄, phosphorous salts, or their bond.Preferred phosphorus source is a phosphoric acid, especially when producing silicoaluminophosphate.

The template agent generally is the element that contains the VA family of the periodic table of elements, special nitrogen, phosphorus, arsenic and antimony, more preferably nitrogen or phosphorus, and nitrogen, compound.The typical template agent of the VA family of the periodic table of elements also contains at least one alkyl or aryl group, preferably has the alkyl or aryl group of 1 to 10 carbon atom and preferred 1 to 8 carbon atom.Preferred template agent is nitrogen-containing compound such as amine and quaternary ammonium compound.

In one embodiment, this quaternary ammonium compound is by general formula R ₄N ⁺Expression, wherein each R is the alkyl of hydrogen or alkyl or replacement, preferably has the alkyl or aryl of 1-10 carbon atom.In one embodiment, this template agent comprise one or more quaternary ammonium compounds with single-, two-or triamine in one or more bond.

The non-limitative example of template agent comprises: tetraalkyl ammonium compound (salt that comprises it), and as tetramethyl-ammonium compound (salt that comprises it), tetraethyl ammonium compound (salt that comprises it), tetrapropyl ammonium (salt that comprises it), and TBuA (salt that comprises it), cyclohexylamine, morpholine, di-n-propyl amine (DPA), tripropylamine, triethylamine (TEA), triethanolamine, piperidines, cyclohexylamine, 2-picoline, N, N-dimethyl benzyl amine, N, N-diethanol amine, dicyclohexylamine, N, N-dimethylethanolamine, choline, N, N '-lupetazin, 1,4-diazabicyclo (2,2,2) octane, N ', N ', N, N-tetramethyl (1,6) hexamethylene diamine, N methyldiethanol amine, N-methyl-monoethanolamine, N-methyl piperidine, 3-methyl-piperidines, N-methylcyclohexyl amine, 3-picoline, 4-methyl-pyridine, quinuclidine, N, N '-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; Di-n-butylamine, neopentyl amine, two n-pentyl amine, isopropylamine, tert-butylamine, ethylenediamine, pyrrolidines, polymine and 2-imidazolidinone.

Preferred template agent or template are the tetraethyl ammonium compounds, and as tetraethyl ammonium hydroxide (TEAOH), the phosphoric acid tetraethyl ammonium is fluoridized tetraethyl ammonium, tetraethylammonium bromide, tetraethyl ammonium chloride(TEAC and acetate tetraethyl ammonium.Most preferred template agent is tetraethyl ammonium hydroxide and its salt, especially when producing silicoaluminophosphamolecular molecular sieve.In one embodiment, the bond of two or more in any above-mentioned template agent can with silicon-, aluminium-, and in phosphorus-source one or more are united use.

Synthetic mixture contain a spot of silicon-, aluminium-and/or phosphorus-composition and template agent be sealed in the container and heating, preferably under self-generated pressure, to about 80 ℃ to about 250 ℃ and more preferably about 150 ℃ of temperature to about 180 ℃ scope.For form the needed time of crystalline product typically from once to several weeks, the length of this time depends on temperature usually; Temperature is high more, and the time is short more.Typically, form crystal molecule sieve product, present slurry state usually, and by well-known any standard technique in the prior art, decantation for example, centrifugal or filter, reclaim.

In preferred embodiments, the crystalline product of this segregation or separation, synthesis of molecular sieve is washed, and typically uses liquid such as water, once arrives many times, or reach variable time span in semi-continuous or continuous mode.The crystalline product of washing is randomly dry, preferably in air, to a kind of level, make crystalline product or synthesis of molecular sieve have the liquid to about 80wt% scope at about 0wt%, preferably this liquid is water, based on the gross weight of crystalline product or synthesis of molecular sieve and liquid medium, preferred this scope is to about 80wt% greater than 1wt%, more preferably from about 10wt% is to about 70wt%, in addition more preferably from about 20wt% to about 60wt% and most preferably from about 40wt% arrive about 60wt%.This contains the crystalline product of liquid, and synthesis of molecular sieve or wet cake are used in the preparation of molecular sieve catalyst composition of the present invention then below.

In one embodiment, wherein this synthesis of molecular sieve is partly dry, and for example by heating, this temperature and time length is enough to the template agent of main ratio is retained in the molecular sieve, and wherein the template agent more than 50% is retained.Be used in addition to heat the preferred temperature of synthesis of molecular sieve about typically 180 ℃ or 180 below, preferably be lower than 150 ℃, even, reach about below 3 hours or 3 hours more preferably less than 120 ℃.

Molecular sieve has high silicon (Si) and aluminium (Al) ratio or low silicon and aluminum ratio, yet low Si/Al ratio is synthetic for SAPO to be preferred.In one embodiment, this molecular sieve has and is lower than 0.65, preferably is lower than 0.40, more preferably less than 0.32 with most preferably be lower than 0.20 Si/Al ratio.In another embodiment, molecular sieve has about 0.65 to about 0.10, preferably approximately 0.40 to about 0.10, more preferably about 0.32 to about 0.10 and more preferably about 0.32 to about 0.15 Si/Al ratio.

Make the method for molecular sieve catalyst composition

In case synthetic as described above this molecular sieve then depends on the requirement of concrete method for transformation, this molecular sieve is formulated into molecular sieve catalyst composition then, is used in particular for commercial Application.More than He Cheng molecular sieve is molecular sieve and the binding agent and optional by synthesizing, but preferred, the matrix material blending forms the formulation composition and makes or be mixed with molecular sieve catalyst composition.This formulation composition is by well-known technology such as spray-drying, and granulation such as extrudes at the particle that is formed useful shape and size, and wherein spray-drying is most preferred.Also preferably, after spray-drying for example, the calcination then of formulation composition.

In one embodiment, the weight ratio of binding agent and molecular sieve is in about scope of 0.1 to 0.5, preferably 0.1 to the scope that is lower than 0.5, more preferably in 0.11 to 0.48 scope, even more preferably 0.12 to about 0.45 scope, again even more preferably 0.13 to being lower than 0.45 and most preferably in 0.15 to about 0.4 scope.In another embodiment, the weight ratio of binding agent and molecular sieve is the scope 0.11 to 0.45, preferably about 0.12 to the scope that is lower than 0.40, more preferably in 0.15 to about 0.35 scope with most preferably in 0.2 to about 0.3 scope.Whole values in these scopes are included in this patent specification.

In another embodiment, the molecular sieve catalyst composition of this molecular sieve catalyst composition or preparation has with m ²The measured micropore surface of/g-molecular sieve long-pending (MSA), it is MSA about 70% of molecular sieve itself, preferably approximately 75%, more preferably 80%, even more preferably 85% and most preferably about 90%.This term " based on the MSA on the contained molecular sieve basis of molecular sieve itself " or term " Xm ²The MSA of/g-molecular sieve " be meant that the calculating MSA of molecular sieve catalyst compound is the comprise mark of the MSA of measurement divided by this molecular sieve.For example, has 200m ²The measured MSA of/g is had 200m with the molecular sieve catalyst compound that contains 40% molecular sieve by calculating ²/ g/0.4=500m ²/ g-comprises molecular sieve " based on the MSA on the contained molecular sieve basis of molecular sieve itself ".

In one embodiment, this carbon monoxide-olefin polymeric has at 400m ²/ g-molecular sieve is to about 600m ²" based on the MSA on the contained molecular sieve basis of molecular sieve itself " of/g-molecular sieve scope, preferred MSA is at 425m ²/ g-molecular sieve is to about 575m ²The scope of/g-molecular sieve is more preferably at 425m ²/ g-molecular sieve is to about 550M ²The scope of/g-molecular sieve and most preferably at about 450m ²/ g-molecular sieve is to about 550m ²The scope of/g-molecular sieve.

Existing many different binding agents can be used for forming this molecular sieve catalyst composition.The non-limitative example that uses separately or unite the binding agent of use comprises various types of hydrated aluminas, silica, and/or other inorganic oxide sol.A kind of colloidal sol that preferably contains alumina is aluminium hydroxychloride (aluminum chlorhydrate).This inorganic oxide sol resembles glue using, and it after heat treatment, is bondd with synthetic molecular sieve and other material such as matrix material together especially.By heating, this inorganic oxide sol preferably has low viscosity, changes into the inorganic oxide matrix component.For example, alumina colloidal sol will change into alumina substrate after heat treatment.

The aluminium hydroxychloride contains the hydroxylating aluminium type colloidal sol of chlorine counter ion counterionsl gegenions, has chemical formula Al _mO _n(OH) _oCl _pX (H ₂O), wherein m is 1-20, and n is 1-8, and o is 5-40, and p is that 2-15 and x are 0-30.In one embodiment, this binding agent is Al ₁₃O ₄(OH) ₂₄Cl ₇12 (H ₂O), as at G.M.Wolterman etc., Stud.Surf.Sci.and Catal., 76, described in the 105-144 page or leaf (1993), the document is introduced into for reference here.In another embodiment, other the non-limitative example of alumina material of one or more binding agents and one or more is united use, and the latter for example has, aluminum oxyhydroxide, γ-alumina, boehmite, the alumina of diaspore and transition such as alph-alumine, β-alumina, γ-alumina, δ-alumina, ε-alumina, κ-alumina, and ρ-alumina, the aluminium trihydroxide, as gibbsite, bayerite, the promise gibbsite, doyelite and their mixture.

In another embodiment, this binding agent is an alumina colloidal sol, mainly comprises aluminium oxide, optional some silicon that comprise.In another embodiment again, this binding agent is by with acid, and hydrated alumina such as pseudobochmite are handled in preferably not halogen-containing acid, with preparation colloidal sol or aluminium ion solution, the alumina of prepared peptizationization.The non-limitative example of commercially available colloidal alumina colloidal sol comprises can be from Nalco Chemical Co., Naperville, the Nalco 8676 that Illinois obtains and can be from Nyacol Nano Technologies, Inc., Ashland, the Nyacol AL20DW that Massachusetts obtains.

In preferred embodiments, above-mentioned synthesis of molecular sieve and binding agent and one or more matrix material blending.Matrix material is typically reducing total body catalyst cost, as hot cave (thermal sinks) participate in protection for example in regenerative process from the heat of carbon monoxide-olefin polymeric, make this carbon monoxide-olefin polymeric densified, the various aspects that improve catalyst strength such as crushing strength and wear resistence and be controlled at the conversion rate in the detailed process are effective.

The non-limitative example of matrix material comprises following one or more: rare earth metal, and inactive metal oxide is comprising titanium dioxide, zirconium dioxide, magnesia, thorium anhydride, beryllium oxide, quartz, silica or colloidal sol and their mixture, silica-magnesia for example, silica-zirconium dioxide, silica-titanium dioxide, silica-alumina and silica-alumina-thorium anhydride.In one embodiment, matrix material is a natural clay, if you would take off in soil and the kaolin families those.These natural claies comprise sabbentonite and are known as for example Dixie, McNamee, those kaolin of Georgia and Florida carclazyte (Florida clay).The non-limitative example of other matrix material comprises: haloysite, kaolinite, dickite, nacrite, or anauxite.In one embodiment, this matrix material, preferably any in this clay accepted well-known modification and handled, as calcining and/or acid treatment and/or chemical treatment.

In a preferred embodiment, this matrix material is clay or clay type composition, preferably have the clay of low iron or content of titanium dioxide or clay-type composition and most preferably this matrix material be kaolin.Kaolin has been found that and can form pumpable, highly filled slurry that it has low unsalted surface and amasss and can easily be deposited in together because of its laminated structure.Matrix material, kaolin most preferably, preferred average particle size be that about 0.1 μ m is to about 0.6 μ m, wherein d ₉₀Size distribution is lower than about 1 μ m.

In one embodiment, this binding agent, this synthesis of molecular sieve, with this matrix material be in the presence of liquid such as water by blending to form molecular sieve catalyst composition, wherein the amount of binding agent is that about 2wt% arrives about 30wt%, and preferably approximately 5wt% arrives about 15wt% to about 20wt% and more preferably about 7wt%, based on the gross weight of binding agent, molecular sieve and matrix material, do not comprise this liquid.

By this synthesis of molecular sieve of blending in liquid and matrix material, optional with binding agent, to form slurry, to mix, preferred violent the mixing is that to produce the homogeneous mixture basically that contains synthesis of molecular sieve needed.The non-limitative example of suitable liquid comprises water, alcohol, ketone, aldehyde, and/or a kind of in the ester or their bond.Most preferred liquid is water.In one embodiment, this slurry is accepted the colloid mill grinding and is reached a period of time, and it is enough to produce required slurry texture, inferior granularity, and/or inferior size distribution.

Contain synthesis of molecular sieve and matrix material and optional binding agent, liquid be identical or different liquid, and according to any order, together, simultaneously, in order, or these combination is carried out blending.In preferred embodiments, use identical liquid, preferred water.

In preferred embodiments, molecular sieve catalyst composition is to contain molecular sieve by preparation, binding agent, and optional and slurry preferred matrix material makes.The solids content of preferred slurry comprises the molecular sieve of about 20% to about 50% (by weight), preferably approximately 30% to the molecular sieve of about 48% (by weight), the molecular sieve of more preferably about 40% to about 48% (by weight), about 5% to about 20%, preferably approximately 8% to the binding agent of about 15% (by weight), with about 30% to about 80%, the matrix material of 40% to about 60% (by weight) preferably approximately.

In another the most preferred embodiment, solids content in slurry comprises molecular sieve, binding agent and optional matrix material, with liquid medium is to arrive about 80wt% scope at about 20wt%, more preferably in the scope of 30wt% to about 70wt%, even more preferably in the scope of 35wt% to 60wt%, still even more preferably in the scope of about 36wt% to about 50wt%, again even more preferably at 37wt% to the scope of about 45wt% with most preferably arrive the scope of about 45wt% at 38wt%.

When slurry mixed, the solid preference aggregation in slurry contained the degree of solid molecular sieves catalyst combination composition granule to this slurry.Preferably, these particles are little and have uniform grain sizes and distribute, and make the d of these particles ₉₀Diameter is to be lower than 20 μ m, more preferably less than 15 μ m with most preferably be lower than 10 μ m.For the purpose of present patent application and claims, d ₉₀The particle that is meant 90 volume % in slurry has the d of being lower than ₉₀The particle diameter of value.For the purpose of this definition, be used to define this d ₉₀Size distribution be to measure by the well-known laser scattering technology that use to adopt Honeywell (MicrotracModel 3000 particle size analyzers, from Microtrac, Inc., Clearwater, Florida obtains).In one embodiment, slurry of the present invention contains the molecular sieve catalyst composition particle that comprises molecular sieve, binding agent and optional matrix material of at least 90 volume %, this particle has and is lower than 20 μ m, preferably is lower than 15 μ m and most preferably is lower than the diameter of 10 μ m.

Particularly, in a preferred embodiment, the method for manufacturing molecular sieve catalyst composition of the present invention may further comprise the steps: the slurry that a) molecular sieve, binding agent and optional matrix material blending is formed solid particle in liquid medium; B) this slurry of high shear mixing is till the particle of at least 90% volume has the diameter that is lower than 10 μ m; (c) slurry is guided in the building mortion to form catalyst granules.

In another preferred embodiment, this slurry comprises liquid part and solid portion, and wherein solid portion comprises solid particle, and this solid particle comprises molecular sieve, binding agent and/or matrix material; Wherein this slurry contains the 30wt% that has an appointment to the solid particle of about 50wt%, and preferably about 35wt% is to 45wt%, and this solid particle of at least 90% has and be lower than 20 μ m, preferably is lower than the diameter of 10 μ m.

This molecular sieve catalyst composition particle contains some water, template agent or other liquid component, and therefore, the percetage by weight of describing solids content in the slurry is preferably measured, does not preferably calculate water, template agent and/or be included in the amount of intragranular other liquid.Be according to calcination basis amount (calcined basis) in the condition of most preferred measurement solids content.Therefore, the weight of solids content equals or is very similar to the weight of calcination molecular sieve catalyst composition in slurry.By calcination basis amount, the solids content in slurry, more particularly, the molecular sieve catalyst composition particle in slurry, be about 20wt% to the 45wt% molecular sieve, 5wt% to 20wt% binding agent and about 30wt% to the 80wt% matrix material.

In one embodiment, the slurry of synthesis of molecular sieve, binding agent and matrix material mixes or grinds full and uniform slurry with the submicron particle that obtains molecular sieve catalyst composition, and it is added in the building mortion that can produce molecular sieve catalyst composition or preparation molecular sieve catalyst composition then.In preferred embodiments, this building mortion is a spray dryer.Typically, this building mortion is maintained at is enough to remove from slurry and from formed molecular sieve catalyst composition under a kind of temperature of most liquid.Formed carbon monoxide-olefin polymeric when being shaped by this way, is preferably taked the form of microsphere.

When spray dryer is used as this building mortion, typically, any in the above-mentioned slurry or their bond, more particularly the slurry of this synthesis of molecular sieve, matrix material and binding agent is added in the spray dryer with dry gas jointly, wherein average inlet temperature is that 200 ℃ to 550 ℃ and the outlet temperature of mixing are 100 ℃ to about 225 ℃.In one embodiment, the average diameter of the carbon monoxide-olefin polymeric that spray-drying is shaped is that about 40 μ m are to about 300 μ m, preferably approximately 50 μ m are to about 250 μ m, and more preferably about 50 μ m arrive about 90 μ m to about 200 μ m and most preferably about 65 μ m.

In spray-drying process, this slurry passes nozzle slurry is distributed into little drop, is similar to aerosol spray and is mapped in the hothouse.Atomizing is by forcing slurry to pass single-nozzle or a plurality of nozzle is realized with 100psig to the pressure drop of 1000psig (690kPaa is to 6895kPaa) scope.In another embodiment, this slurry passes single-nozzle or a plurality of nozzle with atomizing fluids such as the common feeding of air, steam, flue gas or any other suitable gas.

In another embodiment, the periphery that above-mentioned slurry is directed to swiveling wheel is distributed into little drop with slurry, its granularity is to be controlled by many factors, these factors comprise slurry viscosity, surface tension, flow velocity, pressure, with the temperature of slurry, its shape of nozzle and size, or the speed of rotation of wheel.These drops are dried in also stream that flows through spray dryer or counter-current flow then, form dry or dry basically molecular sieve catalyst composition, more particularly, and the molecular sieve catalyst composition of powder or microspheres form.

Generally, the size of microsphere is controlled to a certain degree by the solids content of slurry.Yet the control of the size of carbon monoxide-olefin polymeric and its spherical characteristic also can be controlled by the condition that changes slurry feeding material character and atomizing.

Other method that forms molecular sieve catalyst composition is described in the US patent application serial number 09/617,714 of application on July 17th, 2000 (using the spray-drying of the molecular sieve catalyst composition of recirculation), and the document is introduced into for reference here.

In another embodiment, the molecular sieve catalyst composition of preparation contains about 1% to about 99%, preferably approximately 10% to about 90%, more preferably about 10% to about 80%, even more preferably about 20% to about 70%, this molecular sieve of most preferably about 25% to about 60% (by weight) is based on the gross weight of molecular sieve catalyst composition.

In case this molecular sieve catalyst composition is to form with dry or dry basically form,, preferably heat-treat at elevated temperatures as calcining so that further harden and/or activate formed carbon monoxide-olefin polymeric.Common calcination environment is the air that typically comprises a small amount of water vapor.Typical calcining heat is to arrive about 1 at about 400 ℃, 000 ℃, preferably approximately 500 ℃ to about 800 ℃, most preferably about 550 ℃ are arrived about 700 ℃ of scopes, preferably such as air, nitrogen, helium, the flue gas combustion product of oxygen (lack), or in the calcination environment of their bond and so on.In one embodiment, the calcining of the molecular sieve catalyst composition of being prepared is to carry out in many well-known equipment, comprising the rotary calcining stove, and fluidized bed calcination stove, batch furnace etc.Calcination time typically depends on the hardenability and the temperature of molecular sieve catalyst composition, and is at about 15 minutes to about 20 hours.In preferred embodiments, this molecular sieve catalyst composition heats under about 700 ℃ temperature in about 600 ℃ in nitrogen atmosphere.This heating has been carried out typically 15 minutes to 15 hours, and preferred 30 minutes to about 10 hours, more preferably from about 30 minutes arrived about 5 hours a period of time.

In one embodiment, the wear resistence of molecular sieve catalyst composition is to grind speed index (ARI) by use to measure, and grinds carbon monoxide-olefin polymeric/per hour measurement with wt%.ARI adds granularity and measures at about 53 microns 6.0g carbon monoxide-olefin polymerics to about 125 microns scope by grinding to hardened steel in the groove.About 23, the nitrogen of 700cc/min is passed moisture bubbler with this nitrogen of damping by bubbling.Wet nitrogen passes and grinds groove, and leaves this grinding mechanism via the porous fibre sleeve pipe.This flowing nitrogen is removed thinner particle, and bigger particle is retained in the groove.This porous fibre sleeve pipe is isolated thin catalyst granules from the nitrogen that leaves via this sleeve pipe.The fine grained that is retained in the sleeve pipe has been represented the carbon monoxide-olefin polymeric that divides by grinding.Flowing through this nitrogen stream that grinds groove kept 1 hour.The particulate that is collected in the sleeve pipe is discharged from this device.New sleeve pipe is installed then.The catalyst of staying in the grinding mechanism was ground other 3 hours under same air-flow and moisture.The particulate that is collected in the sleeve pipe is recovered.Gleanings to the thin catalyst granules that separated by sleeve pipe after first hour carries out weighing.Fine grain amount (gram) per hour to be that express on the basis, is ARI divided by putting into the initial amount that grinds the catalyst in the groove, wt%/per hour (wt%/hr).ARI is represented by formula: ARI=C/ (B+C)/D multiply by 100%, wherein B is a weight of staying the carbon monoxide-olefin polymeric in the groove after grinding test, C be the weight of thin catalyst granules collected after first hour grind handled and D be ground in first hour and to handle the processing time afterwards (hour).

In one embodiment, the ARI that molecular sieve catalyst composition had of this molecular sieve catalyst composition or preparation is lower than 15wt%/per hour, preferably be lower than 10wt%/per hour, more preferably less than 5wt%/per hour, with in addition more preferably less than 2wt%/per hour and most preferably be lower than 1wt%/per hour.In one embodiment, the ARI that molecular sieve catalyst composition had of this molecular sieve catalyst composition or preparation is to being lower than 5wt%/per hour at 0wt%/per hour, more preferably approximately 0.05wt%/per hour to being lower than 3wt%/per hour and most preferably about 0.01wt%/per hour to being lower than 2wt%/per hour.

In an embodiment preferred of the present invention, this molecular sieve catalyst composition or preparation molecular sieve catalyst composition comprise the synthesis of molecular sieve of 20wt% to 60wt%, 5wt% is to the binding agent of 50wt%, matrix material with 0-78wt%, gross weight and this carbon monoxide-olefin polymeric based on carbon monoxide-olefin polymeric after the calcining have from 0.1 to the binding agent and the molecular sieve weight ratio that are lower than 0.5.In addition, the carbon monoxide-olefin polymeric of this embodiment has 450m ²/ g-molecule is sieved to 550m ²The MSA based on the contained molecular sieve basis of molecular sieve itself of/g-molecular sieve, and/or be lower than 2wt%/ARI hourly.

Use the technical process of molecular sieve catalyst composition

Above-described molecular sieve catalyst composition or preparation molecular sieve catalyst composition can be used in many technical process, comprising: cracking, for example feed naphtha is cracked into light olefin (US patent No.6,300,537) or HMW (Mw) cracking hydrocarbon becomes low MW hydro carbons; Hydrocrack, for example hydrocrack of heavy oil and/or ring-type raw material; Isomerization, for example isomerization of aromatic hydrocarbon such as dimethylbenzene, polymerization, for example polymer product is produced in one or more olefinic polymerizations; Reform; Hydrogenation; Dehydrogenation; Dewaxing, for example the dewaxing of hydro carbons is to remove linear paraffin; Absorb, for example the absorption of alkyl aromatic hydrocarbon compound is to isolate its isomers; Alkylation, for example aromatic hydrocarbon is as benzene and alkylbenzene, the alkylation (to produce cumene) of optional and propylene or with the alkylation of long-chain olefin; Transalkylation, for example transalkylation of the bond of aromatic hydrocarbon and many alkylaromatic hydrocarbons; Dealkylation; Hydrogenated ring-opened; Disproportionation, for example the disproportionation of toluene is with preparation benzene and paraxylene; Oligomeric, for example straight chain and branched-chain alkene is oligomeric; And dehydrocyclization.

Preferred process is a conversion process, and they comprise: naphtha changes into the height aromatic mixtures; Light olefin changes into gasoline, distillate and lubricant; Oxygenate conversion becomes alkene; Light paraffins changes into alkene and/or aromatic hydrocarbon; Change into aldehydes with unsaturated hydro carbons (ethene and/or acetylene), further change into alcohol, acid and ester.Most preferred process of the present invention relates to comprise that the feedstock conversion of one or more oxygenate becomes the process of one or more alkene.

Above-described molecular sieve catalyst composition is particularly useful for the conversion process of different material.Typically, this raw material contains the compound of one or more fatty family bases, and these comprise alcohol, and amine, carbonyls is aldehydes, ketone and carboxylic acids for example, ether, halide, mercaptan, sulfide etc. and their mixture.The aliphatic structure part that contains the compound of fatty group typically contains about 50 carbon atoms of 1-, preferred 1-20 carbon atom, more preferably 1-10 carbon atom and most preferably 1-4 carbon atom.

The non-limitative example that contains the compound of fatty group comprises: alcohols such as methyl alcohol and ethanol, alkyl hydrosulfide such as methyl mercaptan and ethyl mercaptan, alkyl sulfur compounds such as dimethyl disulfide, alkylamine such as methylamine, alkyl ether such as dimethyl ether, diethyl ether and methyl ethyl ether, alkyl halide such as methyl chloride and ethyl chloride, alkyl ketone such as dimethyl ketone, formaldehydes and various acid such as acetate.

In the preferred embodiment of process of the present invention, this raw material contains one or more oxygenate, more particularly, contains one or more organic compounds of at least one oxygen atom.In the most preferred embodiment of process of the present invention, the oxygenate in the raw material is one or more alcohol, preferred aliphatic series alcohol, and wherein Chun aliphatic structure partly has 1 to 20 carbon atom, preferred 1 to 10 carbon atom and 1 to 4 carbon atom most preferably.The alcohol that is used as raw material in process of the present invention comprises lower straight and branched aliphatic alcohol and their unsaturated homologue.

The non-limitative example of oxygenate comprises methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, methyl ethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetate and their mixture.In the most preferred embodiment, this raw material is to be selected from methyl alcohol, ethanol, dimethyl ether, one or more in diethyl ether or their bond, more preferably methyl alcohol and dimethyl ether and most preferably methyl alcohol.

Various raw material discussed above especially contains oxygenate especially, specifically contains the raw material of alcohol, mainly changes into one or more alkene.Typically have 2-30 carbon atom from this alkene or the olefinic monomer of raw material production, preferred 2-8 carbon atom, more preferably 2-6 carbon atom, more preferably 2-4 carbon atom and most preferably ethene/or propylene again.The non-limitative example of olefinic monomer comprises ethene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1 and decylene-1, optimal ethylene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1 and their isomers.Other olefinic monomer comprises unsaturated monomer, has the alkadienes of 4 to 18 carbon atoms, conjugation or non-conjugated diene, polyene, vinyl monomer and cyclic olefin.

In the most preferred embodiment, this raw material, the preferred raw material of one or more oxygenate changes in the presence of molecular sieve catalyst composition of the present invention and has 2 to 6 carbon atoms, the alkene of preferred 2 to 4 carbon atoms.Most preferably, this alkene separately or associating, is from containing oxygenate, preferred alcohols, methyl alcohol most preferably, feedstock conversion become preferred alkene (class) ethene and/or propylene.

In another the most preferred embodiment, this raw material comprises methyl alcohol, and alkene, and alkene comprises that ethene and propylene and molecular sieve are silicoaluminophosphates.

Existing many methods are used for feedstock conversion is become alkene, and they comprise various cracking process, as steam cracking, and the cracking of heat regeneration, fluid bed cracking, fluid catalytic cracking, DCC, and visbreaking.Most preferred process is generally known as gas-to-alkene (GTO) process or in addition, methyl alcohol-to-alkene (MTO) process.In the GTO process, typically conversion of natural gas becomes synthesis gas, and the latter changes into the raw material of oxygenate, preferably contains methyl alcohol, and wherein the raw material of oxygenate changes into one or more alkene, optimal ethylene and/or propylene in the presence of molecular sieve catalyst composition.In the MTO process, the raw material of oxygenate typically most preferably contains the raw material of methyl alcohol, is converted to one or more alkene in the presence of its molecular sieve catalyst composition, and preferably and mainly, ethene and/or propylene usually are called light olefin.

At raw material, preferably contain the raw material of one or more oxygenate, an embodiment of conversion process in, amount based on the alkene of being produced of the hydro carbons gross weight of being produced is greater than 50wt%, be preferably greater than 60wt%, more preferably greater than 70wt% with most preferably greater than 75wt%.Become in another embodiment of process of one or more alkene in one or more oxygenate conversion, based on the ethene of being produced of the hydrocarbon products gross weight of being produced and/or the amount of propylene is greater than 65wt%, be preferably greater than 70wt%, more preferably greater than 75wt% with most preferably greater than 78wt%.

Become in another embodiment of process of one or more alkene in one or more oxygenate conversion, amount (wt%) based on the ethene of being produced of the hydrocarbon products gross weight of being produced is greater than 30wt%, more preferably greater than 35wt% with most preferably greater than 40wt%.Become in another embodiment again of process of one or more alkene in one or more oxygenate conversion, amount based on the propylene of being produced of the hydrocarbon products gross weight of being produced is greater than 20wt%, be preferably greater than 25wt%, more preferably greater than 30wt% with most preferably greater than 35wt%.

This raw material in one embodiment, contains one or more diluents, typically is used to reduce concentration and general and this raw material or the molecular sieve catalyst composition Fails To Respond of this raw material.The non-limitative example of diluent comprises helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, water, (alkane especially is as methane for the alkane of nonreactive activity basically, ethane, and propane), the aromatic compounds of nonreactive activity and their mixture basically.Most preferred diluent is water and nitrogen, and wherein water is particularly preferred.

This diluent, water is with liquid or vapor form, or two kinds bond form is used.This diluent directly adds in the raw material that enters reactor or directly adds in the reactor, or adds with molecular sieve catalyst composition.In one embodiment, the amount of diluent is to arrive about 99mol% scope about 1 in raw material, based on the total mole number of raw material and diluent, preferably approximately 1 arrives 80mol%, more preferably about 5 to about 50 and most preferably about 5 to about 25.

In one embodiment, other hydro carbons adds in the raw material directly or indirectly, and comprises alkene, alkane, aromatic hydrocarbon is (referring to for example US patent No.4,677,242, the interpolation of aromatic hydrocarbon) or their mixture, preferred propylene, butylene, amylene, with other hydro carbons with 4 or 4 above carbon atoms, or their mixture.

In the presence of molecular sieve catalyst composition of the present invention, be used to transform raw material, especially the raw material that contains one or more oxygenate, process be to carry out in the course of reaction in reactor, wherein this process is a fixed bed process, fluid-bed process (comprising the turbulent bed process), preferably continuous flowing bed process and most preferably continuous high speed degree fluid-bed process.

This course of reaction can be carried out in many catalytic reactors, as has the even dense bed that is connected together or the mixing reactor of fixed bed reaction district and/or fast fluidized bed reaction zone, circulating fluid bed reactor, and riser reactor, or the like.Suitable common response device type is described in for example US patent No.4,076,796, US patent No.6,287,522 (double lifting legs) and Fluidization Engineering, D.Kunii and O.Levenspiel, Robert E.Krieger Publishing Company, New York, among the New York 1977, they all are hereby incorporated by reference.This preferred type of reactor is a riser reactor, general description is at Riser Reactor, Fluidization and Fluid-Particle Systems, 48 to 59 pages, F.A.Zenz and D.F.Othmo, Reinhold PublishingCorporation, New York, 1960 and US patent No.6,166,282 (fast fluidized bed reactors), with the US patent application serial number No.09/564 of application on May 4th, 2000, in 613 (the multiple riser reactors), they are all introduced for reference here.

In preferred embodiments, fluid-bed process or high-speed fluidisation bed process comprise reactor assembly, regenerative system and recovery system.

Preferably a kind of fluidized bed reactor system of this reactor assembly, it has first reaction zone and second reaction zone at least one breaks away from container (preferably including one or more cyclone separators) in one or more riser reactors.In one embodiment, one or more riser reactors and disengaging (disengaging) container is installed within the single reaction vessel.Fresh raw material, preferably contain one or more oxygenate, choose wantonly with one or more diluents, be added in one or more riser reactors, molecular sieve catalyst composition or its coking modification (coked version) are introduced in the reactor.In one embodiment, before in being introduced in riser reactor, this molecular sieve catalyst composition or its coking modification and liquid or gas or their bond contact, and preferably this liquid is that water or methyl alcohol and gas are inert gas such as nitrogen.

In one embodiment, individually or with the amount that steam feed is added into the fresh feed in the reactor assembly is to about 85wt% at 0.1wt%, preferably approximately 1wt% is to about 75wt%, more preferably approximately 5wt% to the scope of about 65wt%, based on the gross weight of the raw material that is included in wherein contained any diluent.This liquid preferably has similar or identical composition with steam feed, or contains the identical or different raw material of different proportion and identical or different diluent.

The raw material that enters in the reactor assembly preferably partially or even wholly changes into gaseous effluent in first reactor zone, the latter imports in this disengaging container with the molecular sieve catalyst composition of coking.In preferred embodiments, the cyclone separator in breaking away from container is designed molecular sieve catalyst composition, and the molecular sieve catalyst composition of preferred coking separates with the gaseous effluent that contains one or more alkene in the abscission zone.Cyclone separator is preferred, yet the gravitational effect in breaking away from container also can be separated carbon monoxide-olefin polymeric with gaseous effluent.A kind of method that carbon monoxide-olefin polymeric is separated with gaseous effluent comprises plate, cover, the use of ell etc.

In an embodiment of detachment system, this detachment system comprises the disengaging container, and typically this disengaging container is the extracting district than lower part.The molecular sieve catalyst composition of coking and gas in the extracting district, a kind of in the middle of preferred steam, methane, carbon dioxide, carbon monoxide, hydrogen or inert gas such as the argon gas or their bond, preferred steam, contact, so that reclaim the hydro carbons that is adsorbed from coked molecular sieve catalyst composition, this carbon monoxide-olefin polymeric is introduced in the regenerative system then.In another embodiment, this extracting district be with break away from the container that container separates and gas is with 1hr ^-1To about 20,000hr ^-1Gas apparent velocity (GHSV) (based on the volume of gas and the ratio of the volume of coked molecular sieve catalyst composition) per hour, preferably at 250 ℃ to about 750 ℃, preferably approximately under 350 ℃ to 650 ℃ the rising temperature, on the molecular sieve catalyst composition of coking, pass through.

In this conversion process, specifically in reactor assembly, employed conversion temperature is at about 200 ℃ to about 1000 ℃, preferably approximately 250 ℃ to about 800 ℃, more preferably about 250 ℃ to about 750 ℃, more preferably about again 300 ℃ to about 650 ℃, again in addition more preferably about 350 ℃ to about 600 ℃ and most preferably about 350 ℃ to about 550 ℃ scope.

In this conversion process, specifically in this reactor assembly, transfer pressure will in wide region, change, comprise self-generated pressure.This transfer pressure be with raw material not very the dividing potential drop during wherein any diluent be basic calculation.The transfer pressure that typically is used for this process is to arrive about 5MPaa at about 0.1kPaa, and preferably approximately 5kPaa arrives the scope of about 500kPaa to about 1MPaa and most preferably about 20kPaa.

Weight (hourly) space velocity (WHSV) (WHSV), in reaction zone, in the presence of molecular sieve catalyst composition, will contain especially in the process that the raw material of one or more oxygenate transformed, be defined as getting rid of the molecular sieve in the molecular sieve catalyst composition in reaction zone of the gross weight of this raw material that joins any diluent in the reaction zone/per hour/per unit weight.This WHSV be maintained at be enough to keep this carbon monoxide-olefin polymeric in reactor on the level of fluidisation attitude.

Typically, this WHSV is about 1hr ^-1To about 5000hr ^-1, 2hr preferably approximately ^-1To about 3000hr ^-1, more preferably about 5hr ^-1To about 1500hr ^-1And most preferably about 10hr ^-1To about 1000hr ^-1In a preferred embodiment, this WHSV is greater than 20hr ^-1, preferably the WHSV for the conversion of the raw material that contains methyl alcohol and dimethyl ether is at about 20hr ^-1To about 300hr ^-1Scope.

The superficial gas velocity (SGV) that comprises the raw material of diluent and product in reactor assembly preferably is enough to make the molecular sieve catalyst composition fluidization in the reaction zone of reactor.In this process, specifically in reactor assembly, more particularly within riser reactor, SGV be at least 0.1 meter/per second (m/sec), be preferably greater than 0.5m/sec, more preferably greater than 1m/sec, more preferably greater than 2m/sec, again more preferably greater than 3m/sec with most preferably greater than 4m/sec.Referring to, the US patent application serial number No.09/708 of on November 8th, 2000 application for example, 753, the document is introduced into for reference here.

Using the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric oxygenate conversion to be become in the preferred embodiment of process of alkene, this process is at 20hr at least ^-1WHSV and be lower than 0.016, preferably be less than or equal to 0.01 temperature correction nominal methane selectively (Temperature Corrected Normalized Methane Selectivity, i.e. TCNMS).Referring to for example US patent No.5,952,538, it is all introduced for reference here.Using molecular sieve catalyst composition oxygenate such as methanol conversion to be become in another embodiment of process of one or more alkene, under about 350 ℃ to 550 ℃ temperature and at 300 to 2500 silica and Me ₂O ₃Under (Me is the IIIA or the VIII family element of the periodic table of elements) molar ratio, WHSV is 0.01hr ^-1To about 100hr ^-1Referring to for example EP-0 642 485B1, it all is hereby incorporated by reference.Use molecular sieve catalyst composition to become other process of one or more alkene to be described in the PCT WO01/23500 (propane is reduced by at least 1.0 under the contact of average catalyst raw material) of publication on April 5 calendar year 2001 oxygenate such as methanol conversion, the document is introduced into for reference here.

This coked molecular sieve catalyst composition is discharged from this disengaging container, preferably utilizes one or more cyclone separators, and introduces in the regenerative system.Regenerative system comprises regenerator, and wherein this coking catalyst composition and regenerating medium preferably contain the gas of aerobic, under the regeneration condition of general temperature, pressure and the time of staying, contact.The non-limitative example of regenerating medium comprises oxygen, O ₃, SO ₃, N ₂O, NO, NO ₂, N ₂O ₅, air, with nitrogen or carbon dioxide, oxygen and water-reducible air (US patent No.6,245,703), carbon monoxide and/or hydrogen.This regeneration condition is the coke burning that can cause from the coking catalyst composition, and preferred burn is to those conditions of the level that is lower than 0.5wt%, based on the gross weight of the coked molecular sieve catalyst composition that enters regenerative system.The coked molecular sieve catalyst composition of discharging from regenerator has formed the molecular sieve catalyst composition of regeneration.

Regeneration temperature is at about 200 ℃ to about 1500 ℃, and preferably approximately 300 ℃ to about 1000 ℃, more preferably about 450 ℃ are arrived about 750 ℃ and most preferably about 550 ℃ to 700 ℃ scope.Regeneration pressure is to about 500psia (3448kPaa) at about 15psia (103kPaa), preferably approximately 20psia (138kPaa) is to about 250psia (1724kPaa), more preferably about 25psia (172kPaa) arrives the scope of about 60psia (414kPaa) to about 150psia (1034kPaa) and most preferably about 30psia (207kPaa).The preferred time of staying of molecular sieve catalyst composition in regenerator is to several hrs at about 1 minute, most preferably about 1 minute to 100 minutes and the preferred oxygen capacity in gas are based on about 0.01mol% of volume of gas to about 5mol%.

In one embodiment, regeneration accelerator typically contains the compound of metal such as platinum, palladium etc., is joined directly or indirectly in the regenerator, for example with the coking catalyst composition.Equally, in another embodiment, fresh molecular sieve catalyst composition is added in the regenerator of the regenerating medium that contains aerobic and water, and as at US patent No.6, described in 245,703, it is all introduced for reference here.In another embodiment again, part from the coked molecular sieve catalyst composition in the regenerator directly turns back in one or more riser reactors, or indirectly, by contacting with raw material, or contact, or contact with the molecular sieve catalyst composition of regeneration as described below or the molecular sieve catalyst composition of chilled regeneration with fresh molecular sieve catalyst composition.

The burning of coke is exothermic reaction, in one embodiment, temperature in regenerative system is to control by the various technology in this area, comprising chilled gas being joined with intermittence, continuously, or semicontinuous mode, or in the regeneration container of the combining form of these modes operation.Preferred technology comprises that the molecular sieve catalyst composition of discharging the molecular sieve catalyst composition of regeneration and allowing regeneration from regenerative system by catalyst cooler, has formed the molecular sieve catalyst composition of chilled regeneration.This catalyst cooler in one embodiment, is a heat exchanger, and it is positioned at the inside or the outside of regenerative system.In one embodiment, the molecular sieve catalyst composition of cooler regeneration turns back in the regenerator in the circulation continuously, additionally, (referring to the US patent application serial number No.09/587 of application on June 6th, 2000,766) molecular sieve catalyst composition of Yi Bufen chilled regeneration turns back in the regeneration container in the continuous circulation, turn back in the riser reactor directly or indirectly with the molecular sieve catalyst composition of this chilled regenerating molecular sieve of another part, or the molecular sieve catalyst composition of the molecular sieve catalyst composition of regeneration of a part or chilled regeneration contacts (PCTWO00/49106 of publication on August 24th, 2000) with accessory substance in the gaseous effluent, and these documents are all introduced for reference here.In another embodiment, with alcohol, preferred alcohol, the 1-propyl alcohol, the regenerated molecular sieve catalyst composition of 1-butanols or the contact of their mixture is introduced in the reactor assembly, as the US patent application serial number No.09/785 in February 16 calendar year 2001 application, in 122, it is all introduced for reference here.Other method of operation regenerative system has been disclosed in US patent No.6,290,916 (control moisture), and it is all introduced for reference here.

From regenerative system, the molecular sieve catalyst composition of the regenerated molecular sieve catalyst composition of preferably from catalyst cooler, discharging and fresh molecular sieve catalyst composition and/or recirculation and/or raw material and/or fresh gas or liquid blending, and turn back in the riser reactor.In another embodiment, the regenerated molecular sieve catalyst composition of discharging from regenerative system directly turns back in the riser reactor, chooses wantonly after passing catalyst cooler.In one embodiment, carrier gas, as inert gas, raw material vapor, steam or analog semi-continuously or continuously, promote the molecular sieve catalyst composition of regeneration to be incorporated in the reactor assembly, preferably are incorporated in one or more riser reactors.

In one embodiment, the optimised quantity of coke is that the molecular sieve catalyst composition of the regeneration of molecular sieve catalyst composition by control regeneration or cooling flow to reactor assembly from regenerative system and keeps i.e. holomorphosis on molecular sieve catalyst composition in reaction zone.Existing many technology can be used for controlling flowing of molecular sieve catalyst composition, as at MichaelLouge, Experimental Techniques, Circulating Fluidized Beds, Grace, Avidan and Knowlton, editor, Blackie, described in 1997 (336-337), the document is introduced into for reference here.In another embodiment, the optimised quantity of coke is to keep by the flow velocity that the control oxygen-containing gas flows in the regenerator on molecular sieve catalyst composition in reaction zone, i.e. partial regeneration.Coke level on molecular sieve catalyst composition is to measure by a certain moment in this process discharges molecular sieve catalyst composition and measures it from conversion process carbon content.After regeneration, the levels typical of coke is to about 15wt% at 0.01wt% on molecular sieve catalyst composition, preferably approximately 0.1wt% is to about 10wt%, more preferably approximately 0.2wt% arrives about 5wt%, most preferably about 0.3wt% is to the scope of about 2wt%, based on the gross weight of molecular sieve rather than the gross weight of molecular sieve catalyst composition.

In a preferred embodiment, the mixture of the molecular sieve catalyst composition of the fresh molecular sieve catalyst composition in reaction zone and/or the molecular sieve catalyst composition of regeneration and/or chilled regeneration contains from about 1 to 50wt%, preferably approximately 2 arrive 30wt%, more preferably about 2 to about 20wt%, most preferably about 2 to coke or the carbonaceous sediment of about 10wt%, based on the gross weight of the mixture of molecular sieve catalyst composition.Referring to for example US patent No.6,023,005, it is all introduced for reference here.Have realized that the molecular sieve catalyst composition in reaction zone is made up of the carbon with different amounts and the mixture with fresh molecular sieve catalyst composition regeneration of carbon shape deposit (coke).The measured level of these deposits (specifically coke) has been represented the mean value of the level on each molecular sieve catalyst composition particle.

Gaseous effluent discharges and passes recovery system from detachment system.Existing many well-known recovery systems, technology can be used for separating alkene and purification alkene with sequence from gaseous effluent.Recovery system generally comprises tower, post, current divider or the group system of various separation, fractionation and/or distillation, reaction system such as ethylbenzene manufacturing (US patent No.5,476,978) and other derivative process such as aldehydes, ketone and ester manufacturing (US patent No.5,675,041) and for example various condensers of Other related equipment, heat exchanger, refrigeration system or cooling group system, compressor, knock-out drum or jar (pot), pump, or the like in the combination of one or more or they.These separately or unite the tower of use, post, the non-limitative example of current divider or group system comprises domethanizing column, preferred high temperature domethanizing column, dethanizer, depropanizing tower, preferably wet depropanizing tower, scrubbing tower (usually being called caustic wash tower) and/or flash cold column, absorber, absorber, film, ethene (C ₂) current divider, propylene (C ₃) current divider, butylene (C ₄) current divider, or the like in one or more.

Can be used for reclaiming alkene in the highest flight, preferred rudimentary or light olefin such as ethene, the various recovery systems of propylene and/or butylene have been described in US patent No.5,960,643 (the secondary ethylene streams that are rich in), US patent No 5,019,143,5,452,581 and 5,082,481 (film separation), US patent 5,672,197 (pressure dependence adsorbents), US patent No.6,069,288 (hydrogen removes), US patent No.5,904,880 (methyl alcohol that reclaims in a step becomes hydrogen and carbon dioxide), US patent No.5,927,063 (methyl alcohol of recovery forwards the gas-turbine power plant to) and US patent No.6,121,504 (directly product quenchings), US patent No.6,121,503 (high purity olefin of not having super separation) and US patent No.6,293,998 (pressure-swing (swing) absorption), they all introduce for reference here.

What generally follow most recovery system is addition product with preferred major product, and the production of byproduct and/or pollutant produces or gathers.Preferred major product, light olefin such as ethene and propylene are typically purified to be used for derivative manufacture process such as polymerization process.Therefore, in the most preferred embodiment of recovery system, this recovery system also comprises purification system.For example, the light olefin of producing in the MTO process passes purification system especially, removes the byproduct or the pollutant of low-level amount.The non-limitative example of pollutant and byproduct generally comprises polar compound such as water, alcohols, carboxylic acids, ethers, oxycarbide, sulfur-containing compound such as hydrogen sulfide, carbonyl sulphide and mercaptan, ammonia and other nitrogen compound, arsine, phosphine and chloride.Other pollutant or byproduct comprise hydrogen and hydro carbons such as acetylene, allylene, allene, butadiene and butine.

Comprise other recovery system of purification system, for example be used for the purification of alkene, have been described in Kirk-Othmer Encyclopedia of Chemical Technology, the 4th edition, 9 volumes, John Wiley﹠amp; Sons, 1996,249-271 page or leaf and 894-899 page or leaf, the document is introduced into for reference here.Purification system for example also is described in, US patent No.6,271,428 (purifications of alkadienes hydrocarbon stream), US patent No.6,293,999 (from the propane separation of propylene), with the US patent application No.09/689 of application on October 20th, 2000,363 (using the hydration catalyst purge stream), the document is introduced into for reference here.

Typically, the alkene one or more oxygenate conversion being become to have 2 or 3 carbon atoms forms or has produced a certain amount of hydro carbons, and alkene especially especially has alkene and other byproduct of 4 or 4 above carbon atoms.Be included in the recovery system of the present invention is to be used for transforming at the contained product of the discharge gas of discharging from reactor or to be used to transform the reaction system of those products of producing because of employed recovery system.

In one embodiment, the discharge gas of discharging from reactor passes recovery system, produces the product stream that contains one or more hydro carbons, especially contains three or three above carbon atom (C ₃ ⁺) the product stream of hydro carbons.In this embodiment, contain C ₃ ⁺The product stream of hydro carbons passes the first fractionation section and produces the thick C that contains ₃Hydrocarbon and C ₄ ⁺The product stream of hydrocarbon contains C ₄ ⁺The product stream of hydrocarbon passes the after-fractionating section and produces the thick C that contains ₄Hydrocarbon and C ₅ ⁺The product stream of hydrocarbon.The hydro carbons of these four or four above carbon comprises butylene such as butene-1 and butene-2, butadiene, saturated butanes, and iso-butane.

From conversion process, especially the discharge gas of discharging in the MTO process typically has a spot of hydro carbons with 4 or 4 above carbon atoms.Amount with hydro carbons of 4 or 4 above carbon atoms is lower than 20wt% typically, preferably is lower than 10wt%, more preferably less than 5wt% with most preferably be lower than 2wt%, based on the gross weight of the discharge gas of discharging from the MTO process, but does not include water.Particularly utilize molecular sieve catalyst composition to become the process of alkene, the discharge gas that is obtained typically to comprise the ethene of main amount and/or product and other byproduct of propylene and a spot of four carbon or higher carbon number oxygenate conversion, do not comprise water.

Suitable well-known reaction system as the part of recovery system mainly utilizes the product of lesser value and they is changed into high-value product.For example, C ₄Hydro carbons, butene-1 and butene-2 are used to make alcohols and other the professional chemicals with 8 to 13 carbon atoms, isobutene is used to make gasoline additive, methyl tertiary butyl ether(MTBE), the butadiene in selecting hydrogenation plant is converted to butene-1 and butene-2 and butane and can be used as fuel.The non-limitative example of reaction system comprises US patent No.5,955,640 (product of 4 carbon is converted into butene-1), US patent No.4,774,375 (iso-butane and butene-2 are oligomeric to be gasoline alkylate), US patent No.6,049,017 (dimerization of n-butene), US patent Nos.4,287,369 and 5,763,678 (carbonylation or the hydroformylation of higher alkene and carbon dioxide and hydrogen prepare carbonyls), US patent No.4,542,252 (multistage adiabatic technologies), US patent No.5,634,354 (olefin-hydrogen recovery) and Cosyns J. etc. are used for upgrading C ₃, C ₄And C ₅The method of olefin stream, Pet.﹠amp; Coal, 37 volumes, No.4 (1995) (dimerization of propylene, butylene and amylene or oligomeric), they are all introduced for reference here.

By any process in the said process, preferred conversion process, the preferred light olefin of being produced is to contain greater than 80wt%, be preferably greater than 90wt%, more preferably greater than 95wt%, most preferably be not less than the high-purity low-class alkene of single carbon number alkene of about 99wt%, based on the gross weight of this alkene.In one embodiment, high-purity low-class alkene is in the present invention with greater than 5 kilograms/every day, is preferably greater than 10 kilograms/every day, more preferably greater than 20 kilograms/every day with most preferably greater than the speed production of 50 kilograms/every day.In another embodiment, high-purity ethylene and/or high-purity propylene be by process of the present invention with greater than 4,500 kilograms/every day, be preferably greater than 100,000 kilogram/every day, more preferably greater than 500,000 kilograms/every day, even more preferably greater than 1,000,000 kilogram/every day, again even more preferably greater than 1,500,000 kilogram/every day, still again more preferably greater than 2,000,000 kilogram/every day, most preferably greater than 2,500, the speed of 000 kilogram/every day is produced.

Other conversion process, especially, in the presence of molecular sieve catalyst composition from oxygenate to one or more conversion of olefines processes, especially when molecular sieve be from silicon-, phosphorus-and alumina-source synthetic the time, comprise those processes that are described in for example following document: US patent No.6,121,503 (being less than or equal to 0.05 alkane and the olefin product of alkene weight ratio prepares plastics) with having, US patent No.6,187,983 (being applied to the electromagnetic energy of reaction system), the PCT WO99/18055 (heavy hydrocarbon in joining the discharge gas of another reactor) that on April 15th, 1999 published, the US patent application serial number No.09/627 of PCT WO01/60770 that publish August 23 calendar year 2001 and application on July 28th, 2000,634 (high pressure), the US patent application serial number No.09/507 of application on February 22nd, 2000,838 (injections of classification raw material), US patent application serial number No.09/785 with application on February 16 calendar year 2001,409 (acetone is reinforced altogether), they all are hereby incorporated by reference.

In one embodiment, comprehensive technical process is from hydrocarbon raw material, preferred hydrocarbon gas raw material, and more preferably methane and/or ethane are produced light olefin.First step in this process is to allow gaseous feed, preferably combines with current, is passed in the synthesis gas production area to produce synthesis gas (syngas) product stream.Synthesis gas production is that called optical imaging and typical synthesis gas temperature are to be to arrive the scope of about 100MPa at about 2MPa at about 700 ℃ to about 1200 ℃ scope and synthesis gas pressure.Synthetic air is from natural gas, petroleum liquid and carbonaceous material such as coal, and reground plastics, municipal waste or any other organic material are produced, and preferred synthetic air is to produce via the steam reformation of natural gas.Generally, heterogeneous catalysis, copper type catalyst typically, with synthetic air, typically carbon dioxide and carbon monoxide and hydrogen contact to produce alcohol, and particular methanol usually has water concurrently.In one embodiment, pass the oxycarbide zone of transformation and produce the product stream that contains oxygenate to the synthetic air under the synthesis pressure of about 10MPa scope to the synthesis temperature of about 450 ℃ of scopes and at about 150 ℃ at about 5MPa.

This contains product stream of oxygenate, or thick methyl alcohol, typically contains pure product and various other component such as ether, dimethyl ether especially, ketone, aldehydes, dissolved gases such as hydrogen, methane, oxycarbide and nitrogen, and fusel oil.In preferred embodiments, contain the product stream of oxygenate, thick methyl alcohol passes well-known purification process, and distillation separates and fractionation, has caused forming the product stream that contains oxygenate of purifying, for example, and technical grade A and AA methyl alcohol.The product stream that contains oxygenate that contains the product stream of oxygenate or purify, optional with one or more diluents, with contact in one or more above-mentioned molecular sieve catalyst compositions any in said process, produce many after-products, light olefin, ethene and/or propylene especially.The non-limitative example of this composite technology process is described among the EP-B-0 933 345, and it is all introduced for reference here.In another more complete comprehensive technical process, optional with above-mentioned composite technology process, the alkene of being produced relates to, and in one embodiment, is used to produce various polyolefinic one or more polymerization processes.(referring to for example US patent application serial number No.09/615 of application on July 13rd, 2000,376, it is all introduced for reference here)

Polymerization process comprises solution, gas phase, slurry phase and high-pressure process, or their combination.Particularly preferably be the gas phase or the slurry phase polymerisation of one or more alkene, at least a in this alkene is ethene or propylene.These polymerization processes are utilized polymerization catalyst, the latter comprises the bond of any or these catalyst in the molecular sieve catalyst of above-mentioned discussion, yet, preferred polymerization catalyst is those Ziegler-Natta, the Phillips-type, metallocene, metallocene-type and senior polymerization catalyst and their mixture.The polymer of being produced by above-mentioned polymerization process comprises LLDPE, elastomer, plastic body, high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene and polypropylene copolymer.The propylene based polymer of being produced by this polymerization process comprises atactic polypropylene, isotatic polypropylene, and syndiotactic polypropylene and propylene are random, block or impact copolymer.

In preferred embodiments, this composite technology process is included in the polymer reactor that one or more alkene carry out polymerization to produce the process of one or more polymer products in the presence of polymerisation catalyst system, wherein one or more alkene transform alcohol by using molecular sieve catalyst composition, methyl alcohol especially, and make.Preferred polymerization process be gas-phase polymerization processes and this alkene at least a be ethene or propylene and preferably this polymerisation catalyst system be the metallocene catalyst system of load.In this embodiment, the metallocene catalyst system of load comprises carrier, metallocene or metallocene-type compound and activator, preferably this activator is the anion or the aikyiaiurnirsoxan beta of non-coordination, or their bond and most preferably this activator be aikyiaiurnirsoxan beta.

Except that polyolefin, much other alkene derived product is any from via the said process, conversion process especially, and more particularly the alkene that reclaimed of GTO process or MTO process forms.These include, but not limited to aldehydes, alcohols, acetate, linear alpha-alkene, vinyl acetate, dichloroethylene and vinyl chloride, ethylbenzene, oxirane, cumene, isopropyl alcohol, methacrylaldehyde, allyl chloride, expoxy propane, acrylic acid, EP rubbers, and acrylonitrile, and the trimer of ethene, propylene or butylene and dimer.

Embodiment

For to the present invention, comprise that its representational advantage has better understanding, provides the following example.

Each composition that is used to prepare this mixture of catalysts generally contains volatile component, and the latter includes but not limited to, water and, for the situation of molecular sieve, organic formwork agent.Common way is to describe the amount or the ratio of these compositions, based on " calcination basis amount (calcined basis) ".Calcining is included in air and exists down and to be enough to dry and to remove heating material (650 ℃, 1 or more a plurality of hours) under the rising temperature of content of any contained volatility, combustibility or pyrolysis.For purpose of the present invention, be defined as by " calcination basis amount ", for after then the expectation loss in weight that can take place is carried out mathematical conversion as fruit component calcination, the amount of remaining each component or mark.Therefore, the component that contains 25% template agent of 10 grams will be described as " by the 7.5g of calcination basis amount ".SAPO-34 molecular sieve synthetic is called optical imaging and has about 450m in the following embodiments ²/ g is to 550m ²The MSA of/g molecular sieve.

The mensuration of the percentage of the percentage of liquid or liquid medium and template agent is undertaken by using following thermogravimetric analysis (TGA) technology: with a certain amount of SAPO-34 molecular screen material, sample, be loaded in Instrument from Cahn, Inc., Cerritos is on the sample weighting disk of the CahnTG-121 microbalance that California obtains.In the TGA technology, use the flow velocity of 114cc/min (STP) air.Sample is heated to 180 ℃ with the speed of 30 ℃/min from 25 ℃ then, 180 ℃ kept 3 hours down or up to the weight of this sample become constant till.The percentage that then is considered to liquid or liquid medium as the loss in weight with respect to the percentage test of initial SAPO-34 molecular screen material.Subsequently, sample is heated to 650 ℃ and kept 2 hours down at 650 ℃ with 30 ℃/min from 180 ℃.The loss in weight that is considered to the template agent as this loss in weight of the percentage of original example weight in this processing.This total weight loss as the percentage that calculates according to initial first example weight in this whole TGA handles is defined as loss on ignition (LOI).

Micropore surface long-pending (MSA) is the measuring of amount of the micropore that exists in porous material.MSA be the BET surface area of total surface area-measure from the relative pressure that obtains linearity curve (linear plot) with from the difference between the external surface area of the slope calculating of the range of linearity of t-curve, (the same basis) carries out little correction to this t-curve according to the basis same with the BET surface area.This approximate calculation method has been used to be determined at the amount [M.F.L.Johnson, J.Catal., 52,425-431 (1978)] of Cracking catalyst mesolite by Johnson.The t-curve is the conversion of adsorption isotherm, and wherein relative pressure is by t, under corresponding relative pressure on imporous material the statistical thickness of adsorption layer, replace; Referring to being used to measure the various characteristics of pore system such as Lippens and the de Boer[B.C.Lippens and the J.H.de Boer of pore shape, J.Catal., 4,319 (1965)].Sing[K.S.W.Sing, Chem.Ind., 829 (1967)] by the agency of, linear t-curve extrapolation will obtain the volume of micropore to t=0.

MSA is by using from Micromeritics Instrument Corporation Norcross, MICROMERITICS Gemini 2375 mensuration that GA obtains.During 0.15g pack into sample cell to the sample of the consumption of 0.6g, 300 ℃ of degassings at least 2 hours down.In analytic process, emptying time (Evacuation Time) is 1.0 minutes, does not use the sample rate of free space and use 1.0g/cc.Ten three (13) individual adsorption number strong points are to be collected with following absorption target:

Data point	Absorption target (p/p o)	Data point	Absorption target (p/p o)
				1	0.00500	8	0.25000
2	0.07500	9	0.30000
				3	0.01000	10	0.40000
4	0.05000	11	0.60000
				5	0.10000	12	0.75000
6	0.15000	13	0.95000
				7	0.20000

Correction factor in the t-curve map is 0.975.Do not collect the desorb point.Other analytical parameters comprises, analysis mode: Equilibrate; Equilibration time: 5 seconds; Sweep speed: 10 seconds.From 0.00000 to 0.90000 t-curve map makes up (H-J Model): t (p)=(13.99/ (0.034-log (p/p by using Harkins and the equational ASTM checking of Jura form _o))) ^0.5By Cape and Kibby[J.A.Cape and C.L.Kibby, J.Colloids and Interface Science, 138,516-520 (1990)] disclose, the common BET surface area of microporosity material can resolve into outer area quantitatively and become outer area and micropore volume with micropore, and this can be expressed by the following equation that provides: S _Micro=S _Tot-S _Ext=ν _m/ d _j, ν wherein _mBe micropore volume, S _MicroBe from S _TotAnd S _ExtThe micropore area that calculates.S _TotBe to provide by common BET method, and S _ExtIt is the outer area of getting from the t-curve map.d _jBe non-physical length, its value depends on the pressure that uses in experiment.Proportionality factor, d _j, measure quantitatively by the pressure that in BET match (BET fit), uses.

For the purpose of present patent application and claims, " solids content " is that slurry sample is weighed, this slurry sample of calcination, preferably 550 ℃ under 750 ℃, this calcination sample of weighing is again measured; Solids content equals the calcination example weight and multiply by 100 divided by the weight of slurry sample.

Embodiment 1

In the following example, use do not have bone dry and also undried SAPO-34 molecular sieve from hydro-thermal well known in the art is synthesized, reclaim and obtain.Comprise 45wt% solid (by calcination basis amount) (40% is the SAPO-34 molecular sieve that does not have bone dry or calcining in solid, the 10.6%th, Al ₂O ₃(alumina colloidal sol, binding agent), with 49.4% be clay (matrix material)) slurry prepare according to following program: (a) with the SAPO-34 molecular sieve wet cake of 2988.93g (by calcination basis amount, 1621.29g) (liquid medium content 34.68wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 1703.84g, with by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 1500RPM, mixed 15 minutes and handle and reach 10 minutes by using Silverson high speed shear blender L4RT-A under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.3 the pH value of measuring down at 26 ℃.(B) ACH solution: 869.03g (is measured by the calcination basis, 429.64g) Reheis MicroDry aluminium hydroxychloride (Reheis Inc., Berkeley Heights, New Jersey) joins the deionized water neutralization of 859.12g by using Yamato 4000D blender (YamatoScientific America Inc., Orangeburg, New York) mixed 15 minutes at 1500RPM, use Silverson high speed shear blender to carry out the high speed shear processing subsequently and reach 10 minutes at 6000RPM.This solution has 3.3 the pH value of measuring down at 31 ℃.(C) above SAPO-34 molecular sieve slurry (A) and aluminium hydroxychloride solution (B) are by using Yamato4000D blender (Yamato Scientific America Inc., Orangeburg, NewYork) blending and mixing reach 15 minutes under 1500RPM, then by using Silverson high speed shear blender to mix 10 minutes under 6000RPM.This slurry has 4.2 the pH value of measuring down at 30 ℃.(D) under the constant mixing of 250-400RPM, 2302.3g (is measured by the calcination basis, 2002.30g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific America Inc. then, Orangeburg, New York) under 1500RPM, mixed 15 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 10 minutes.(E) solids content of slurry contains 45% solid after regulating, the deionized water of 283.97g consumption joined contain the SAPO-34 molecular sieve, in the above slurry of ACH (binding agent) and kaolinton (matrix material), use the Yamato blender to carry out the 1500RPM processing subsequently and reach 15 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear mixing then and reach 10 minutes.This final slurry has 3.8 the pH value of measuring down at 36 ℃.This has caused obtaining containing the 8000g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 10.6%th, alumina binding agent and 49.4% is the matrix of clay material.The weight ratio of binding agent and molecular sieve be about 0.265 and MSA be 489m ²/ g-molecular sieve.

Embodiment 2

(Yamato Scientific America, Orangeburg NewYork) carries out the spray-drying of the slurry of embodiment 1 by using Yamato DL-41 spray dryer.The slurry of 750g consumption is by spray-drying.This spray dryer is to operate in the mode of downward spraying by the atomizer that uses 1mm.The spray-drying condition is: feed rate: 40g/min; Inlet temperature: 350 ℃; Atomizing pressure: 14psig (96.5kPag); Full setting value 60% under carrier gas (nitrogen) stream.The spray-drying product, the preparation molecular sieve catalyst composition is collected in the cyclone separator.This carbon monoxide-olefin polymeric was calcined 2 hours down and in air at 650 ℃ in Muffle furnace then.The carbon monoxide-olefin polymeric of this calcination is used for wear test and grain size analysis.The wear resistence of spray-dried catalyst composition is measured by using nozzle-groove grinding mechanism.Because what so obtain grinds, particulate generation hourly is defined as ARI.ARI is high more, grind speed high more or the preparation molecular sieve catalyst composition weak more or soft more.Molecular sieve catalyst composition according to 2 spray-dired embodiment 1 of embodiment has 0.95wt%/ARI hourly.

Embodiment 3

Comprise 45wt% solid (by calcination basis amount) (40% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 5.3%th, Al ₂O ₃(binding agent), with 54.7% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve of 332.1g, wet cake is (by calcination basis amount, 180.01g) (liquid medium content 34.72wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 201.82g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.9 the pH value of measuring down at 30 ℃.(B) ACH solution: 48.28g (is measured by the calcination basis, 23.85g) Reheis MicroDry aluminium hydroxychloride (Reheis Inc., Berkeley Heights, New Jersey) joins the deionized water neutralization of 100.91g by using Yamato 4000D blender (YamatoScientific America Inc., Orangeburg, New York) under 700RPM, mixed 7 minutes, use Silverson high speed shear blender to carry out the high speed shear processing subsequently and reach 3 minutes at 6000RPM.This solution has 4.0 the pH value of measuring down at 25 ℃.(C) above SAPO-34 slurry (A) and aluminium hydroxychloride solution (B) are by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) blending and mixing reach 10 minutes under 700RPM, then by using Silverson high speed shear blender to mix 3 minutes under 6000RPM.This slurry has 4.2 the pH value of measuring down at 30 ℃.(D) under the constant mixing of 250-400RPM, 283.28g (is measured by the calcination basis, 246.16g) the ultra-fine kaolinton of ASP (matrix material) (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific America Inc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.(E) solids content of slurry contains 45% solid after regulating, the deionized water of 33.64g consumption joined contain the SAPO-34 molecular sieve, in the above slurry of ACH solution and kaolinton, use the Yamato blender to carry out the 700RPM processing subsequently and reach 15 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear mixing then and reach 3 minutes.This final slurry has 4.2 the pH value of measuring down at 27 ℃.This has caused obtaining containing the 1000g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 5.3%th, alumina binding agent and 54.7% is the matrix of clay material.The slurry of embodiment 3 uses then with program identical described in the embodiment 2 and carries out spray-drying, and wherein the slurry of embodiment 1 replaces with the slurry of embodiment 3.Molecular sieve catalyst composition according to 2 spray-dired embodiment 3 of embodiment has 5.77wt%/ARI hourly.The weight ratio of binding agent and molecular sieve be about 0.13 and MSA be 511m ²/ g-molecular sieve.

Embodiment 4

Comprise 45wt% solid (by calcination basis amount) (40% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 15.9%th, Al ₂O ₃(binding agent), with 44.1% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve of 332.1g, wet cake is (by calcination basis amount, 180.00g) (liquid medium content 34.72wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 176.82g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.8 the pH value of measuring down at 31 ℃.(B) ACH solution: 144.84g (is measured by the calcination basis, 71.55g) Reheis MicroDry aluminium hydroxychloride (binding agent) (Reheis Inc., Berkeley Heights, New Jersey) joins the deionized water neutralization of 88.41g by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 700RPM, mixed 7 minutes, use Silverson high speed shear blender to carry out the high speed shear processing subsequently and reach 3 minutes at 6000RPM.This solution has 3.1 the pH value of measuring down at 32 ℃.(C) above SAPO-34 molecular sieve slurry (A) and aluminium hydroxychloride solution (B) are by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) blending and mixing reach 10 minutes under 700RPM, then by using Silverson high speed shear blender to mix 3 minutes under 6000RPM.This slurry has 3.7 the pH value of measuring down at 37 ℃.(D) under the constant mixing of 250-400RPM, 228.37g (is measured by the calcination basis, 198.45g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific America Inc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.(E) solids content of slurry contains 45% solid after regulating, the deionized water of 29.47g consumption joined contain the SAPO-34 molecular sieve, in the above slurry of ACH solution and kaolinton, use the Yamato blender to carry out the 700RPM processing subsequently and reach 15 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear mixing then and reach 3 minutes.This final slurry has 3.8 the pH value of measuring down at 33 ℃.This has caused obtaining containing the 1000g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 15.9%th, alumina binding agent and 44.1% is the matrix of clay material.The slurry of embodiment 4 uses then with program identical described in the embodiment 2 and carries out spray-drying, and wherein the slurry of embodiment 1 replaces with the slurry of embodiment 4.Molecular sieve catalyst composition according to 2 spray-dired embodiment 4 of embodiment has 0.38wt%/ARI hourly.The weight ratio of binding agent and molecular sieve be about 0.40 and MSA be 470m ²/ g-molecular sieve.

Embodiment 5

Comprise 45wt% solid (by calcination basis amount) (60% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 7.1%th, Al ₂O ₃(binding agent), with 32.9% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve of 498.15g, wet cake is (by calcination basis amount, 270.00g) (liquid medium content 34.72wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 160.08g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.6 the pH value of measuring down at 30 ℃.(B) ACH solution: 64.68g (is measured by the calcination basis, 31.95g) Reheis MicroDry aluminium hydroxychloride (binding agent) (Reheis Inc., Berkeley Heights, New Jersey) joins the deionized water neutralization of 80.04g by using Yamato 4000D blender (YamatoScientific America Inc., Orangeburg, New York) under 700RPM, mixed 7 minutes, use Silverson high speed shear blender to carry out the high speed shear processing subsequently and reach 3 minutes at 6000RPM.This solution has 3.6 the pH value of measuring down at 26 ℃.(C) above SAPO-34 molecular sieve slurry (A) and aluminium hydroxychloride solution (B) are by using Yamato4000D blender (Yamato Scientific America Inc., Orangeburg, NewYork) blending and mixing reach 10 minutes under 700RPM, then by using Silverson high speed shear blender to mix 3 minutes under 6000RPM.This slurry has 4.1 the pH value of measuring down at 32 ℃.(D) under the constant mixing of 250-400RPM, 170.37g (is measured by the calcination basis, 148.05g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride (binding agent), use Yamato4000D blender (Yamato Scientific America Inc. then, Orangeburg, NewYork) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.(E) solids content of slurry contains 45% solid after regulating, the deionized water of 26.68g consumption joined contain the SAPO-34 molecular sieve, in the above slurry of ACH solution and kaolinton, use the Yamato blender to carry out the 700RPM processing subsequently and reach 15 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear mixing then and reach 3 minutes.This final slurry has 3.9 the pH value of measuring down at 32 ℃.This has caused obtaining containing the 1000g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 7.1%th, alumina binding agent and 32.9% is the matrix of clay material.The slurry of embodiment 5 uses then with program identical described in the embodiment 2 and carries out spray-drying, and wherein the slurry of embodiment 1 replaces with the slurry of embodiment 5.Molecular sieve catalyst composition according to 2 spray-dired embodiment 5 of embodiment has 12.54wt%/ARI hourly.The weight ratio of binding agent and molecular sieve be about 0.12 and MSA be 508m ²/ g-molecular sieve.

Embodiment 6

Comprise 45wt% solid (by calcination basis amount) (20% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 14.1%th, Al ₂O ₃(binding agent), with 65.9% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve of 166.05g, wet cake is (by calcination basis amount, 90.00g) (liquid medium content 34.72wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 218.55g, with by using Yamato 4000D blender (Yamato Scientific AmericaInc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.8 the pH value of measuring down at 25 ℃.(B) ACH solution: 128.44g (is measured by the calcination basis, 63.45g) Reheis MicroDry aluminium hydroxychloride (binding agent) (Reheis Inc., Berkeley Heights, New Jersey) joins the deionized water neutralization of 109.28g by using Yamato 4000D blender (YamatoScientific America Inc., Orangeburg, New York) under 700RPM, mixed 7 minutes, use Silverson high speed shear blender to carry out the high speed shear processing subsequently and reach 3 minutes at 6000RPM.This solution has 3.5 the pH value of measuring down at 28 ℃.(C) above SAPO-34 molecular sieve slurry (A) and aluminium hydroxychloride solution (B) are by using Yamato4000D blender (Yamato Scientific America Inc., Orangeburg, NewYork) blending and mixing reach 10 minutes under 700RPM, then by using Silverson high speed shear blender to mix 3 minutes under 6000RPM.This slurry has 4.0 the pH value of measuring down at 28 ℃.(D) under the constant mixing of 250-400RPM, 341.25g (is measured by the calcination basis, 296.55g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific AmericaInc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.(E) solids content of slurry contains 45% solid after regulating, the deionized water of 36.43g consumption joined contain the SAPO-34 molecular sieve, in the above slurry of ACH solution and kaolinton, use the Yamato blender to carry out the 700RPM processing subsequently and reach 15 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear mixing then and reach 3 minutes.This final slurry has 3.7 the pH value of measuring down at 31 ℃.This has caused obtaining containing the 1000g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 14.1%th, alumina binding agent and 65.9% is the matrix of clay material.The slurry of embodiment 6 uses then with program identical described in the embodiment 2 and carries out spray-drying, and wherein the slurry of embodiment 1 replaces with the slurry of embodiment 6.Molecular sieve catalyst composition according to 2 spray-dired embodiment 6 of embodiment has 0.33wt%/ARI hourly.The weight ratio of binding agent and molecular sieve be about 0.71 and MSA be 482m ²/ g-molecular sieve.

Embodiment 7

Conversion process

The catalytic performance of molecular sieve catalyst composition that is used for the conversion of methyl alcohol is tested by using microreactor apparatus.Employed reaction condition is: the feed rate of 100g-methyl alcohol/every gram molecule sieve; 475 ℃ of temperature; Pressure is 25psig (273kpag).The carbon monoxide-olefin polymeric with 2-200 micron-scale of 35mg and 100mg carborundum (100 microns, can be from Carborundum Abrasives G.B.Limited, Trafford Park, Manchester, UK obtains) mix, form mixture.This mixture be loaded into then by 316 stainless steels structures and have in the tubular reactor of 4mm internal diameter.This carbon monoxide-olefin polymeric bed is the interlude that is fixed on reactor by means of two silica wool stoppers in the top of carbon monoxide-olefin polymeric bed and bottom.This carbon monoxide-olefin polymeric is then at 50cm ³Heat-treat from 40 ℃ to 475 ℃ with the gradual speed (ramp rate) of 100 ℃/min in the helium flow of/min (STP) and descend to keep 30 minutes, just introduce methyl alcohol afterwards at 475 ℃.Methyl alcohol (FisherScientific, Fair Lawn, New Jersey, 99.9% purity) utilizes Cole-Palmer74900 series syringe pump to be imported in the evaporimeter that remains under 225 ℃ with the feed rate of 29.59ml/ per minute.Methyl alcohol is downward through the reaction tube of this heating.Gas-phase product and unreacted methanol and 50cm ³/ min (STP) helium combines in the exit, and catches periodic sample in online sample storage (16-loop (loop), 150ml/ loop) valve.All pipeline and sample valve are heated and trace back to 225 ℃ to prevent any condensation of unreacted methanol or product.Collected sample is equipped with fid detector and PLOT fused silica post (CP-PoraPLOT Q by use then, 10m * 0.53mm ID * 20 micron coating thickness, can be from Varian, Inc, Mitchell Dr., Walnut Creek, California obtains) online GC (Hewlett Packard 6890 GC, Palo Alto California) analyzes.This reactor effluent is analyzed: methane, methyl alcohol, dimethyl ether, ethane, ethene, propane, propylene, iso-butane, butene-1, cis-butene-2, and trans-2-butene-2, C ₅More senior, C ₆More senior, C ₇More senior and C ₈More senior product.

Conversion of methanol is defined as

[(X _{CH3OH in the raw material}-X _{CH3OH in the product})/X _{CH3OH in the raw material}] * 100%;

Each product components selection is defined as

(X _Product/ X _{CH3OH in the raw material}) * 100,

Wherein X is the anhydrous weight fraction from each component of FID calculated signals.Coke selectivity is to estimate from the hydrogen balance of raw material and product.The selectivity of product result who is reported is the conversion weighted average of selectivity of product in whole experiment, the methanol conversion of the final conversion ratio of the initial conversion ratio of this experiment measuring from about 100% to about 10%.

The catalytic performance of carbon monoxide-olefin polymeric of embodiment 2 that is used for the conversion of methyl alcohol is by using that above-mentioned process is estimated and having shown accumulative total quantity of methyl alcohol that every gram molecule sieve of 12.6g-methyl alcohol/g-molecular sieve is transformed and 75.2% weighted average ethene and propylene selectivity.

The catalytic performance of carbon monoxide-olefin polymeric of embodiment 4 that is used for the conversion of methyl alcohol is by using that above-mentioned process is estimated and having shown accumulative total quantity of methyl alcohol that every gram molecule sieve of 11.4g-methyl alcohol/g-molecular sieve is transformed and 74.3% weighted average ethene and propylene selectivity.

The catalytic performance of carbon monoxide-olefin polymeric of embodiment 6 that is used for the conversion of methyl alcohol is by using that above-mentioned process is estimated and having shown accumulative total quantity of methyl alcohol that every gram molecule sieve of 12.4g-methyl alcohol/g-molecular sieve is transformed and 74.6% weighted average ethene and propylene selectivity.

Embodiment 8

(50% molecular sieve, binding agent/molecular sieve ratio is 0.265)

Comprise 45wt% solid (by calcination basis amount) (50% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 13.25%th, Al ₂O ₃(alumina colloidal sol, binding agent), with 36.75% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve wet cake of 334.9g (by calcination basis amount, 180.0g) (liquid medium content 35.28wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 212.9g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 7.1 the pH value of measuring down at 30 ℃.(B) 96.9g (is measured by the calcination basis, 47.7g) Reheis MicroDry aluminium hydroxychloride (Reheis Inc., Berkeley Heights, New Jersey) joins in the above SAPO-34 molecular sieve slurry (A), use Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes, use Silverson high speed shear blender under 6000RPM, to mix 3 minutes subsequently.This slurry (C) has 4.0 the pH value of measuring down at 30 ℃.(D) under the constant mixing of 250-400RPM, 155.6g (is measured by the calcination basis, 132.3g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific America Inc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.This final slurry has 3.9 the pH value of measuring down at 38 ℃.This has caused obtaining containing the 800.0g slurry of 45% solid (by calcination basis amount), wherein, the 50%th, the SAPO-34 molecular sieve, the 13.25%th, alumina binding agent and 36.75% is the matrix of clay material.The weight ratio of binding agent and molecular sieve be about 0.265 and MSA be 498m ²/ g-molecular sieve.

Embodiment 9

The spray-drying of the slurry of embodiment 8 is undertaken by using Yamato DL-41 spray dryer (Yamato Scientific America, Orangeburg, New York).The slurry of 800g consumption is by spray-drying.This spray dryer is to operate in the mode of downward spraying by the atomizer that uses 1mm.The spray-drying condition is: feed rate: 40g/min; Inlet temperature: 350 ℃; Atomizing pressure: 14psig (96.5kPag); Full setting value 60% under carrier gas (nitrogen) stream.The spray-drying product, the molecular sieve catalyst composition of preparation is collected in the cyclone separator.This carbon monoxide-olefin polymeric was calcined 2 hours down and in air at 650 ℃ in Muffle furnace then.The carbon monoxide-olefin polymeric of this calcination is used for wear test and grain size analysis.The wear resistence of spray-dried catalyst composition is measured by using nozzle-groove grinding mechanism.Because what so obtain grinds, particulate generation hourly is defined as ARI.ARI is high more, grind speed high more or the preparation molecular sieve catalyst composition weak more or soft more.Molecular sieve catalyst composition according to 9 spray-dired embodiment 8 of embodiment has 0.24wt%/ARI hourly.

Embodiment 10

(60% molecular sieve, binding agent/molecular sieve ratio is 0.265)

Comprise 45wt% solid (by calcination basis amount) (60% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 15.9%th, Al ₂O ₃(alumina colloidal sol, binding agent), with 24.1% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve wet cake of 854g (by calcination basis amount, 459g) (liquid medium content 35.28wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 383g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.5 the pH value of measuring down at 29 ℃.(B) 246.2g (is measured by the calcination basis, 121.64g) Reheis MicroDry aluminium hydroxychloride (Reheis Inc., Berkeley Heights, New Jersey) joins in the above SAPO-34 molecular sieve slurry (A), use Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes, use Silverson high speed shear blender under 6000RPM, to mix 3 minutes subsequently.This slurry (C) has 3.54 the pH value of measuring down at 30 ℃.(D) under the constant mixing of 250-400RPM, 216.8g (is measured by the calcination basis, 184.37g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) joins in the above slurry that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific America Inc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.This final slurry has 3.5 the pH value of measuring down at 33 ℃.This has caused obtaining containing the 1700.0g slurry of 45% solid (by calcination basis amount), wherein, the 60%th, the SAPO-34 molecular sieve, the 15.9%th, alumina binding agent and 24.1% is the matrix of clay material.The weight ratio of binding agent and molecular sieve be about 0.265 and MSA be 499m ²/ g-molecular sieve.

Embodiment 11

The spray-drying of the slurry of embodiment 10 is undertaken by using Yamato DL-41 spray dryer (Yamato Scientific America, Orangeburg, New York).The slurry of 850g consumption is by spray-drying.This spray dryer is to operate in the mode of downward spraying by the atomizer that uses 1mm.The spray-drying condition is: feed rate: 40g/min; Inlet temperature: 350 ℃; Atomizing pressure: 14psig (96.5kPag); Full setting value 60% under carrier gas (nitrogen) stream.The spray-drying product, the molecular sieve catalyst composition of preparation is collected in the cyclone separator.This carbon monoxide-olefin polymeric was calcined 2 hours down and in air at 650 ℃ in Muffle furnace then.The carbon monoxide-olefin polymeric of this calcination is used for wear test and grain size analysis.The wear resistence of spray-dried catalyst composition is measured by using nozzle-groove grinding mechanism.Because what so obtain grinds, particulate generation hourly is defined as ARI.ARI is high more, grind speed high more or the preparation molecular sieve catalyst composition weak more or soft more.Molecular sieve catalyst composition according to 11 spray-dired embodiment 10 of embodiment has 0.23wt%/ARI hourly.

Embodiment 12

Prepare according to following program and to contain SAPO-34, the slurry of alumina binding agent and clay (as matrix material): (A) with the SAPO-34 molecular sieve filter cake of 332.1g (Gan Zao molecular sieve partly, the molecular sieve that does not have calcination fully) (liquid medium content 34.72wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 189.32g and use Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 1000RPM, mixed 2 minutes.This SAPO-34 slurry has 6.4 the pH value of measuring down at 22 ℃.(B) by ReheisMicroDry aluminium hydroxychloride (Reheis Inc. with 96.56g, Berkeley Heights, New Jersey) joins the deionized water neutralization of 94.66g by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 1000RPM, mixes and prepared aluminium hydroxychloride solution in 2 minutes.This solution has 3.8 the pH value of measuring down at 26 ℃.(C) the aluminium hydroxychloride solution of SAPO-34 slurry in step (A) and preparation in step (B) is by using Yamato 4000D blender (YamatoScientific America Inc., Orangeburg, New York) under 1000RPM, mixed 2 minutes.This second slurry has 4.3 the pH value of measuring down at 23 ℃.(D) under 250-300RPM under the situation of constant mixing with the ultra-fine kaolinton of ASP (the Engelhard Corporation of the Engelhard company of 255.81g, Iselin, New Jersey) joins in second slurry that in step (C), obtains, then by using Yamato 4000D blender (Yamato Scientific AmericaInc., Orangeburg, New York) under 1000RPM, mixed 2 minutes.The 3rd slurry has 4.2 the pH value of measuring down at 23 ℃.(E) deionized water with 31.55g joins in the 3rd slurry that obtains in step (D), then by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 1000RPM, mixed 2 minutes.The slurry of the present invention of the 1000g that is obtained contains 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 10.6%th, alumina binding agent and 49.4% is the matrix of clay material.

The results of grain size analysis that obtains on Microtrac S3000 instrument has shown that peak center is respectively in the bimodal size distribution at 0.9 micron and 5 microns place.The size distribution of slurry is shown in Table 1.

Table 1

Percentile (percentile)	Granularity (micron)
		10％	0.754
20％	0.801
		30％	0.833
40％	0.859
		50％	0.883
60％	0.908
		70％	0.936
80％	0.971
		90％	4.990
95％	6.143

Embodiment 13

The slurry that in embodiment 12, obtains reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to handle (Silverson Machines, Inc., EastLongmeadow, Massachusetts).The results of grain size analysis that obtains on Microtrac S3000 instrument has shown that also peak center is respectively in the bimodal size distribution at 0.9 micron and 5 microns place.The size distribution of this slurry is shown in Table 2.

Table 2

Percentile	Granularity (micron)
		10％	0.561
20％	0.662
		30％	0.724
40％	0.775
		50％	0.823
60％	0.869
		70％	0.919
80％	0.981
		90％	1.102
95％	4.243

In this embodiment 13, be about 6% greater than the amount of 4 microns particles, this has represented to have an appointment greater than 3 microns particle and 50% has reduced, when with table 1 in provide the data contrast time.And this result shows that the significant size for whole particle size range reduces, and has illustrated that high speed shear is blended in the benefit on the control granularity.

Embodiment 14

According to embodiment 12 preparation slurry, further under 200RPM, mixed 10 minutes and be introduced in the spray dryer and and carry out spray-drying according to follow procedure according to the slurry that embodiment 13 prepares with Yamato 4000D blender.The spray-drying of slurry is undertaken by using Yamato DL-41 spray dryer (Yamato Scientific America, Orangeburg, New York).Each slurry of 750g consumption is by spray-drying.This spray dryer is to operate in the mode of downward spraying by the atomizer that uses 1mm.The spray-drying condition is: feed rate: 40g/min; Inlet temperature: 350 ℃; Atomizing pressure: 1 crust (metric unit); Full setting value 60% under carrier gas (nitrogen) stream.The spray-drying product is collected in the cyclone separator.

They were calcined 2 hours down and in air at 650 ℃ in Muffle furnace then.The spray-dired molecular sieve catalyst composition of embodiment 12 and 13 calcination or tested the grinding property of molecular sieve catalyst composition and the size distribution of preparation.

Yet, in embodiment 12 in the spray-drying process of slurry of preparation with plug nozzle, because in slurry, there is cake mass.Spray-drying has to interrupt three times to take off nozzle and this obstruction of cleaning.The wear resistence of embodiment 12 and 13 spray-dired molecular sieve catalyst composition has 2.51%/per hour and 0.95%/ARI hourly respectively.Measure ARI by this nozzle-groove wear test of using the front in patent specification, to describe.

Embodiment 15

Comprise 45wt% solid (by calcination basis amount) (40% is the SAPO-34 molecular sieve that does not have bone dry or not have to calcine in this solid, the 10.6%th, Al ₂O ₃(alumina colloidal sol, binding agent), with 49.4% be clay (matrix material)) slurry prepare according to following program: (A) with the SAPO-34 molecular sieve wet cake of 527.3g (by calcination basis amount, 306.0g) (liquid medium content 30.12wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 337.4g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 5 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 7.0 the pH value of measuring down at 32 ℃.(B) 164.1g (is measured by the calcination basis, 81.1g) Reheis MicroDry aluminium hydroxychloride (Reheis Inc., Berkeley Heights, New Jersey) joins in the deionized water of 1168.76g, use Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes, use Silverson high speed shear blender under 6000RPM, to mix 3 minutes subsequently.This slurry (B) has 3.5 the pH value of measuring down at 37 ℃.(C) slurry (A) is added in the slurry (B), by using Yamato 4000D blender (Yamato Scientific AmericaInc., Orangeburg, New York) under 700RPM, mixed 10 minutes, then by using Silverson high speed shear blender under 6000RPM, to mix 5 minutes.This slurry (C) has 4.0 the pH value of measuring down at 34 ℃.(D) under the constant mixing of 200-400RPM with the ultra-fine kaolinton (EngelhardCorporation of ASP of the Engelhard company of 446.2g, Iselin, New Jersey, by calcination basis amount, 377.8g)) and the 56.2g deionized water join in the above slurry (C) that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific AmericaInc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.This final slurry has 4.1 the pH value of measuring down at 35 ℃.This has caused obtaining containing the 1699.9g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 10.6%th, alumina binding agent and 49.4% is the matrix of clay material.

Embodiment 16

The spray-drying of the slurry of embodiment 15 is undertaken by using Yamato DL-41 spray dryer (Yamato Scientific America, Orangeburg, New York).The slurry of 800g consumption is by spray-drying.This spray dryer is to operate in the mode of downward spraying by the atomizer that uses 1mm.The spray-drying condition is: feed rate: 40g/min; Inlet temperature: 350 ℃; Atomizing pressure: 14psig (96.5kPag); Full setting value 60% under carrier gas (nitrogen) stream.The spray-drying product, the molecular sieve catalyst composition of preparation is collected in the cyclone separator.This carbon monoxide-olefin polymeric was calcined 2 hours down and in air at 650 ℃ in Muffle furnace then.The carbon monoxide-olefin polymeric of this calcination is used for wear test and grain size analysis.The wear resistence of spray-dried catalyst composition is measured by using nozzle-groove grinding mechanism.Because what so obtain grinds, particulate generation hourly is defined as ARI.ARI is high more, grind speed high more or the preparation molecular sieve catalyst composition weak more or soft more.

Molecular sieve catalyst composition according to 16 spray-dired embodiment 15 of embodiment has 1.03wt%/ARI hourly.

Embodiment 17

Comprise 45wt% solid (by calcination basis amount) (40% is the SAPO-34 molecular sieve of part drying in this solid, the 10.6%th, Al ₂O ₃(alumina colloidal sol, binding agent), with 49.4% be clay (matrix material)) slurry prepare according to following program: (A) with 483.7g 60 ℃ down dry 3 hours SAPO-34 molecular sieve (by calcination basis amount, 324.0g) (liquid medium content 19.34wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 403.1g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 6.4 the pH value of measuring down at 27 ℃.(B) 173.8g (is measured by the calcination basis, 85.9g) Reheis MicroDry aluminium hydroxychloride (ReheisInc., Berkeley Heights, New Jersey) joins in the deionized water of 201.6g, use Yamato 4000D blender (Yamato Scientific AmericaInc., Orangeburg, New York) under 700RPM, mixed 10 minutes, use Silverson high speed shear blender under 6000RPM, to mix 3 minutes subsequently.This slurry (B) has 3.0 the pH value of measuring down at 30 ℃.(C) slurry (B) is added in the slurry (A), by using Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes, then by using Silverson high speed shear blender under 6000RPM, to mix 3 minutes.This slurry (C) has 3.8 the pH value of measuring down at 29 ℃.(D) under the constant mixing of 250-400RPM, 470.6g (is measured by the calcination basis, 401.8g) the ultra-fine kaolinton of ASP (the Engelhard Corporation of Engelhard company, Iselin, New Jersey) and the deionized water of 67.2g join in the above slurry (C) that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato Scientific AmericaInc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.This final slurry has 3.8 the pH value of measuring down at 31 ℃.This has caused obtaining containing the 1800.0g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 10.6%th, alumina binding agent and 49.4% is the matrix of clay material.

Molecular sieve catalyst composition according to 16 spray-dired embodiment 17 of embodiment has 0.75wt%/ARI hourly.

Embodiment 18

Comprise 45wt% solid (by calcination basis amount) (40% is the SAPO-34 molecular sieve of part drying in this solid, the 10.6%th, Al ₂O ₃(alumina colloidal sol, binding agent), with 49.4% be clay (matrix material)) slurry prepare according to following program: (A) with 212.5g at the SAPO-34 molecular sieve at 25 ℃ of following dry nights (by calcination basis amount, 144.0g) (liquid medium content 18.40wt%, gross weight based on molecular sieve and liquid medium) joins in the deionized water of 301.1g, with by using Yamato 4000D blender (Yamato ScientificAmerica Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes and handle and reach 3 minutes by using Silverson high speed shear blender under 6000RPM, to carry out high speed shear subsequently.This slurry has 5.9 the pH value of measuring down at 29 ℃.(B) 77.2g (is measured by the calcination basis, 38.2g) Reheis MicroDry aluminium hydroxychloride (Reheis Inc., Berkeley Heights, New Jersey) joins in the slurry (A), use Yamato 4000D blender (Yamato Scientific America Inc., Orangeburg, New York) under 700RPM, mixed 10 minutes, use Silverson high speed shear blender under 6000RPM, to mix 3 minutes subsequently.This slurry (B) has 3.3 the pH value of measuring down at 33 ℃.(C) under the constant mixing of 250-400RPM, 209.2g (is measured by the calcination basis, 177.8g) join in the above slurry (B) that contains SAPO-34 molecular sieve and aluminium hydroxychloride, use Yamato 4000D blender (Yamato ScientificAmerica Inc. then, Orangeburg, New York) under 700RPM, mixed 10 minutes, use the Silverson blender under 6000RPM, to carry out the high speed shear blend step subsequently and reach 3 minutes.This final slurry has 3.4 the pH value of measuring down at 33 ℃.This has caused obtaining containing the 800.0g slurry of 45% solid (by calcination basis amount), wherein, the 40%th, the SAPO-34 molecular sieve, the 10.6%th, alumina binding agent and 49.4% is the matrix of clay material.

Molecular sieve catalyst composition according to 16 spray-dired embodiment 18 of embodiment has 1.03wt%/ARI hourly.

Although the present invention is described and illustrates that those of skill in the art will recognize that the present invention is applicable to not necessarily the version of explanation therein with reference to specific embodiment.For example, can think that this molecular sieve catalyst composition can be used for the mutual conversion of alkene, oxygenate is to the gasoline conversion reaction, and maleic anhydride, phthalic anhydride and acrylonitrile are prepared, the synthetic and various Fischer-Tropsch reactions of vapor phase methyl alcohol.It is also conceivable that, piston flow, fixed bed or fluid-bed process can be united use, are particularly useful in list or the intrasystem differential responses of multiple reactor district.It is also conceivable that molecular sieve catalyst composition described here can be used as absorbent, adsorbent, gas release agent, washing agent, water scavengine agent and other various uses such as agricultural and gardening.Can consider that in addition this molecular sieve catalyst composition comprises one or more other molecular sieves that combine.For that reason, for the purpose of determining true scope of the present invention, should be uniquely with reference to claims.

Claims (25)

1. prepare the preparation method of molecular sieve catalyst composition, this method may further comprise the steps: (a) from the silicon source, at least two kinds bond in phosphorus source and the aluminium source is chosen wantonly in the presence of the template agent, forms slurry and synthesis of molecular sieve in liquid medium; (b) from slurry, remove molecular sieve; (c) molecular sieve drying is arrived greater than 1wt% level, based on the gross weight of liquid medium and molecular sieve to the 80wt% liquid medium; (d) with molecular sieve and binding agent blending, and add identical or different liquid medium and optional matrix material, to form composition prepared; (e) drying and/or shaping composition prepared are to form the molecular sieve catalyst composition of preparation.

2. the process of claim 1 wherein that slurry is dried to the level of 20wt%-80wt% liquid medium in step (c), based on the gross weight of liquid medium and molecular sieve.

3. the process of claim 1 wherein that slurry is dried to the level of 30wt%-70wt% liquid medium in step (c), based on the gross weight of liquid medium and molecular sieve.

4. the method for any one in the claim 1 to 3 wherein in step (e), forms compositions formulated by the spray-drying compositions formulated with the molecular sieve catalyst composition that forms preparation.

5. the process of claim 1 wherein in step (c) and/or (e) before, wash slurry and/or compositions formulated with water.

6. the method for claim 1 further comprises the step (f) of calcining the molecular sieve catalyst composition of preparing.

7. the process of claim 1 wherein binding agent and molecular sieve weight ratio greater than 0.1 in less than 0.5 scope.

8. the process of claim 1 wherein that compositions formulated has the solid content of 35wt%-50wt% in step (d), based on the gross weight of the slurry of calcined basis amount.

9. the process of claim 1 wherein that compositions formulated in the blend step (d) is till the solid particle of at least 90% volume has the diameter that is lower than 20 μ m.

10. the process of claim 1 wherein that compositions formulated in the blend step (d) is till the solid particle of at least 90% volume has the diameter that is lower than 10 μ m.

11. the process of claim 1 wherein after the drying in step (c) that molecular sieve contains in steps the amount of template agent of the 50wt%-100wt% of the original template agent content that uses in (a).

12. the process of claim 1 wherein that molecular sieve is a wet-cake form after the drying in step (c).

13. the drying of the step of the process of claim 1 wherein (c) is to heat being lower than under 180 ℃ the temperature.

14. the process of claim 1 wherein that liquid medium is a water.

15. the process of claim 1 wherein that molecular sieve is a silicoaluminophosphate, aluminate or phosphate and/or cha framework type molecular sieve.

16. the process of claim 1 wherein that binding agent is an alumina colloidal sol.

17. the process of claim 1 wherein that binding agent is the aluminium hydroxychloride.

18. molecular sieve catalyst composition by the preparation of the method preparation of any one in the claim 1 to 17.

19. in the presence of the molecular sieve catalyst composition of the preparation of claim 18, feedstock conversion is become the method for one or more alkene.

20. the method for claim 19, wherein raw material comprises at least a oxygenate.

21. the method for claim 19 or 20, wherein from former expect one or more conversions of olefines be reactor assembly, carry out and this method further comprise from reactor assembly discharge effluent stream and allow this eluting gas by recovery system to reclaim the step of one or more alkene at least.

22. the method for claim 19 or 20, wherein this method further comprises molecular sieve catalyst composition is incorporated in the regenerative system with the molecular sieve catalyst composition that forms regeneration with the molecular sieve catalyst composition of regeneration and is incorporated into step in the reaction system.

23. the method for claim 19 or 20, wherein raw material comprises methyl alcohol, and alkene, and alkene comprises that ethene and propylene and molecular sieve are silicoaluminophosphates.

24. the method for claim 19, wherein raw material is to produce synthetic air by at least a hydrocarbon by the synthesis gas production area to make; And the synthetic air that obtains contacts the raw material that comprises at least a oxygenate with formation with catalyst.

25. the method for claim 19 or 20, wherein this method further is included in polymerization catalyst and exists one or more olefinic polymerizations are become polyolefinic step.