CN101676028B - Catalyst for preparing light olefin by carbinol - Google Patents

Abstract

The invention discloses a catalyst for preparing light olefin by carbinol, which is characterized in that the catalyst comprises silicoaluminophosphate (SAPO) molecular sieves, silicon-aluminium molecular sieves, inorganic oxide binding agent and clay; the framework molar composition of the silicoaluminophosphate (SAPO) molecular sieves is expressed by an anhydrous chemical formula in the form ofoxide as Al2O3: yP2O5:zSiO2; the molar composition of the silicoaluminophosphate (SAPO) molecular sieves before templates are removed by baking is expressed by an anhydrous chemical formula in the form of oxide as (x1R1+x2R2):Al2O3:yP2O5:zSiO2, wherein R1 and R2 are templates existing in the crystal pore canal of the molecular sieves, R1 is diethylamine, R2 is dipropylamine, the sum of x1 and x2 is 0.01-5.0, x1/x2=0.1-20, y value is 0.01-1.5, and z value is 0.01-30. The X-ray diffraction data of the molecular sieves before the templates are removed by baking at least comprises the diffractionpeak expressed in table A, and the X-ray diffraction data of the molecular sieves after the templates are removed by baking at least comprises the diffraction peak expressed in table B.

Description

A kind of catalyst that is used for preparing light olefin by carbinol

Technical field

The invention relates to a kind of being used for methanol conversion is the catalyst of light olefin, further say so about a kind of being used for methanol conversion be the catalyst that contains silicoaluminophosphamolecular molecular sieves of light olefin.

Background technology

Low-carbon alkene is (like C ₂-C ₄Alkene) be important petrochemical materials, the preparation method that generally adopts is to be the steam cracking of raw material with the natural gas; With naphtha or light diesel fuel is the pyrolysis in tubular furnace of raw material; The heat carrier cracking of heavy hydrocarbon and with the method for low-carbon alcohols catalyzed conversion.With the increase of restriction of oil supply amount and cost, the method for low-carbon alcohols catalyzed conversion more and more causes people's attention.Wherein therefore methyl alcohol can be methanol conversion that light olefin (refers to C from coal or a large amount of productions of natural gas via synthesis gas processing ₂-C ₄Alkene) be very attractive process.

After after U.S. Mobil company report in 1984 is with the preparing gasoline by methanol process modification, being used for preparing light olefins from methanol (MTO) (Chang, CD etc., J.Catal., SB, 289 (1984)), many alumino-silicates or zeolite are used as the MTO catalyst for reaction.Large pore zeolites such as Y zeolite, modenite for example, but catalysis methanol is converted into hydrocarbon, but C ₅ ⁺Hydrocarbon selective is high, and selectivity of light olefin is low; And erionite, pore zeolites such as T zeolite, chabasie, though can improve olefine selective, coking and deactivation is very fast.Thereby research is focusing more on the mesopore zeolite (US4238631B1, US4328384B1 and US4423274B1) like ZSM-5 zeolite etc.These patent documentations also disclose in order to increase the selectivity and reduction C to light olefin ₅ ⁺Byproduct generate and on zeolite deposit coke.CN1352627A discloses the ZSM-5 zeolite catalyst that uses the phosphorus modification with methyl alcohol or the dimethyl ether conversion method as light olefin.

In the prior art, being used for methanol conversion is that the another kind of important catalyst of alkene is SAPO (SAPO) family molecular sieves.U.S. UCC company introduces silicon in the aluminum phosphate family molecular sieves skeleton of the invention early 1980s, become silicoaluminophosphamolecular molecular sieves (USP4440871).Its framework of molecular sieve is made up of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron; Skeleton is electronegative; Therefore when balance cation outside the skeleton was H+, molecular sieve had acidity, can be used as solid acid catalyst and was applied in the reactions such as hydrocarbon cracking, isomerization, alkylation and dehydration of alcohols.

USP4499327B1 discloses many SAPO family molecular sieves can be converted into alkene by catalysis methanol, wherein the preferred molecular sieve aperture between adsorbs xenon (dynamically diameter be 4.0 dusts) with repel between the iso-butane (dynamically diameter is 5.0 dusts) especially preferred SAPO-34 molecular sieve.

CN1341584A discloses the abrasion-resisting catalyst that is used for light-olefin production, comprises the host material of crystal metal aluminophosphate molecular sieve (like SAPO-34), inorganic oxide adhesive and filler, wherein filler preferably clay (like kaolin)., the content of molecular sieve can significantly improve the abrasion performance of catalyst when being lower than 40 weight %.

Introduce other metallic elements in the aluminium phosphate molecular sieve skeleton and also can be used as solid acid catalyst.USP4752651B1 discloses and has used the reaction as alkene of ELAPO and MeAPO molecular sieve catalytic methanol conversion; CN1128676C disclose have the flat crystal structure, empirical formula is (EL _xAl _yP _z) O ₂The metal aluminophosphate molecular sieve, wherein EL is a metal, like silicon or magnesium, x, y and z are respectively the molfractions of EL, Al and P, as being the catalyst of light olefin with methanol conversion, products obtained therefrom contains the ethene (with respect to propylene) of more amount.

CN1704390A employing Zn-SAPO-34 molecular sieve and binding agent are as the catalyst of methanol conversion system alkene; In reaction temperature is 300-500 ℃; Reaction pressure is a normal pressure; The weight space velocity of methyl alcohol is 1.0-10h-1, and water/methyl alcohol weight ratio is to react under the 0-5 condition, and it is low to have improved ethene, propylene selectivity and yield.

CN1190395C discloses and has adopted the catalyst that contains ZSM series or SAPO series molecular sieve, the axial one or more location segment of fluidized-bed reaction section to inject for example methyl alcohol or dimethyl ether method that the product selectivity of ethylene is improved of oxygenatedchemicals.

" Industrial Catalysis .2001,9 (4): 3-8, Bai Erzheng " think with the SAPO-34 molecular sieve to be the catalyst of active constituent, and its methanol conversion generates selectivity of ethylene and obviously is superior to the ZSM-5 zeolite.

CN1525940A discloses the intergrowth silicoaluminophosphamolecular molecular sieves mutually that comprises at least a AEI of having and CHA framework types molecular sieve; Its powder x-ray diffraction figure; The ratio of AEI/CHA through the said intergrowth phase of DIFFaX assay determination is about 5/95 to 40/60, and this molecular sieve can be applicable to the catalyzed conversion of methyl alcohol to alkene.

Be that template has been synthesized a kind of silicoaluminophosphamolecular molecular sieves (SRM-2) with new structure with the diethylamine among the CN1485272A, before its roasting removed template method and the diffraction maximum behind the roasting removed template method have special XRD data.This molecular sieve can be used as the catalyst of oxygenate.

Summary of the invention

The purpose of this invention is to provide and a kind ofly contain novel silicoaluminophosphamolecular molecular sieves (SRM-4 molecular sieve), be used for from the preparing light olefin by carbinol catalyst for reaction.

The methanol conversion that is used for provided by the invention is the light olefin catalyst for reaction; It is characterized in that this catalyst contains silicoaluminophosphamolecular molecular sieves, Si-Al molecular sieve, inorganic oxide binder and clay, the skeleton mole composition of said silicoaluminophosphamolecular molecular sieves (SRM-4) uses the anhydrous chemical formulation of oxide form to be Al ₂O ₃: yP ₂O ₅: zSiO ₂, the anhydrous chemical formulation that the mole before the roasting removed template method is formed the use oxide form is (x1R1+x2R2): Al ₂O ₃: yP ₂O ₅: zSiO ₂, wherein R1 and R2 are the template that is present in the molecular sieve crystal duct, R1 is a diethylamine; R2 is a di-n-propylamine, and the value of x1+x2 is 0.01～5.0, x1/x2=0.1～20; The value of y is 0.01～1.5; The value of z is 0.01～30, and the X-ray diffraction data of this molecular sieve before the roasting removed template method contains the diffraction maximum shown in the table 1 at least, and the X-ray diffraction data behind the roasting removed template method contains the diffraction maximum shown in the table 2 at least; In table 1 and the table 2, W, M, S, VS represent diffraction peak intensity I and the strongest diffraction maximum I respectively ₀Relative ratio, W is 0～20%, M is 20～60%, S is 60～80%, VS is 80～100%.

Table 1

2θ(°)	I/I 0	2θ(°)	I/I 0
				8.08-8.29	VS	23.29-23.47	W
11.50-11.70	W	24.73-24.96	M-S
				14.13-14.31	S-VS	26.10-26.32	S-VS
16.35-16.53	M	28.65-28.86	W-M
				18.32-18.51	M	29.87-30.09	M
20.08-20.28	W	32.15-32.37	M
				21.76-21.96	M	33.21-33.44	W

Table 2

2θ(°)	I/I 0	2θ(°)	I/I 0
				8.20-8.42	VS	23.53-23.84	W-M
11.65-11.89	M	25.00-25.30	M-S
				14.32-14.56	VS	26.40-26.69	S-VS
16.55-16.81	W-M	28.99-29.29	W-M
				18.54-18.80	W-M	30.19-30.51	M
20.36-20.61	W	32.50-32.81	M
				21.97-22.27	W-M	33.58-33.95	W

Catalyst provided by the invention is silicoaluminophosphamolecular molecular sieves (SRM-4), the Si-Al molecular sieve of 0-50%, the inorganic oxide binder of 4-50% and the clay of 0-70% that benchmark has following composition: 1-90% with the catalyst weight; Preferred group becomes the silicoaluminophosphamolecular molecular sieves (SRM-4) of 10-50%, the Si-Al molecular sieve of 0-30%, the inorganic oxide binder of 10-30% and the clay of 10-50%.

Said SRM-4 molecular sieve in the catalyst provided by the invention, x ₁+ x ₂Value be preferably 0.02～3.0, x ₁/ x ₂Value be preferably 0.15～15, more preferably 0.25～10, most preferably 0.5～5; The value of y is preferably 0.1～1.4, and more preferably 0.15～1.2; The value of z is 0.02～20, is preferably 0.05～10.

Before the SRM-4 molecular sieve roasting removed template method ¹³The nuclear magnetic resonance peak that has 49.22 ± 2ppm, 42.85 ± 2ppm, 19.55 ± 2ppm and 11.61 ± 2ppm in the C MAS-NMR spectrogram; Wherein, Chemical shift 42.85 ± 2ppm and 11.61 ± 2ppm are the nuclear magnetic resonance peak of diethylamine; Chemical shift 49.22 ± 2ppm, 19.55 ± 2ppm and 11.61 ± 2ppm are the nuclear magnetic resonance peak of di-n-propylamine, explain that diethylamine and di-n-propylamine have all got into the duct of molecular sieve.Molecular sieve provided by the invention, the condition of said roasting removed template method are 300～800 ℃ of following roastings 1～10 hour, can adopt the method for temperature programming to carry out baking operation.

The building-up process of SRM-4 silicoaluminophosphamolecular molecular sieves also is summarized as follows at this: the SRM-4 molecular sieve is by (a under 5～100 ℃ ₁R ₁+ a ₂R ₂): Al ₂O ₃: bP ₂O ₅: cSiO ₂: dH ₂The rate of charge of O is mixed into glue with aluminium source, phosphorus source, silicon source, diethylamine, di-n-propylamine and water, add the crystal seed in gel butt 0.1～10 weight %, obtained in 4～500 hours at 120～250 ℃ of following hydrothermal crystallizings, wherein, said R ₁Be diethylamine, R ₂Be di-n-propylamine, a ₁+ a ₂Value be 0.1～10.0, a ₁/ a ₂Value be 0.05-50, the value of b is 0.1～1.5, the value of c is 0.01～30.0, the value of d is 5～150, said crystal seed is selected from SRM-2 molecular sieve and/or SRM-4 itself.

Said aluminium source is selected from but is not limited to one or more the mixture in hydrated alumina, aluminium isopropoxide and the aluminum phosphate of boehmite thing phase; Said silicon source is selected from but is not limited to a kind of or any several kinds of mixtures of Ludox, active silica, ethyl orthosilicate or solid silicone; Said phosphorus source is selected from but is not limited to a kind of or any several kinds of mixtures of phosphoric acid, hypophosphorous acid, phosphate and organic phosphorus compound.

In the method for synthetic SRM-4, the said raw material more preferably hydrated alumina or the aluminium isopropoxide of boehmite thing phase is the aluminium source, is the phosphorus source with phosphoric acid.

As SRM-2 molecular sieve and/or the SRM-4 of crystal seed, no matter whether the roasting removed template method, all is suitable for using as crystal seed.The addition of crystal seed is mixed into 0.1～10 weight %, preferred 0.5～8 weight % of the gel butt that glue obtains with aluminium source, phosphorus source, silicon source, diethylamine, di-n-propylamine and water.Wherein, can be as the SRM-2 molecular sieve of crystal seed with reference to disclosed content among the CN1485272A.

SRM-4 is that the mixture with diethylamine and di-n-propylamine is a template, and raw material is pressed rate of charge (a ₁R ₁+ a ₂R ₂): Al ₂O ₃: bP ₂O ₅: cSiO ₂: dH ₂O is mixed into glue, is mixed into the glue temperature and is preferably 10～90 ℃, more preferably 15～80 ℃.In said ingredient proportion, R ₁Be diethylamine, R ₂Be di-n-propylamine, be set at 1, a in the aluminium source molal quantity of aluminium oxide ₁Be the molal quantity of diethylamine, a ₂Be the molal quantity of di-n-propylamine, a ₁+ a ₂Value preferred 0.2～8.0, more preferably 0.5～5.0, a ₁/ a ₂Value be 0.1～10, more preferably 0.2～6.0, most preferably 0.5～5.0; The value of b is the molal quantity that feeds intake in the phosphorus source of phosphorus pentoxide, the value of b preferred 0.5～1.2, more preferably 0.6～1.1; The value of c is the molal quantity that feeds intake in the silicon source of silica; This method all can synthesize the SRM-4 of pure phase in very wide c value scope; For the SRM-4 of the synthetic low silicon content of difficulty, also can obtain the very high product of degree of crystallinity with this method, the value of c is preferably 0.02～15, more preferably 0.05～10; The value of d is the molal quantity of water, and it is worth preferred 10～120, more preferably 15～100.

In the synthetic method of SRM-4; Although become the glue temperature and add under the condition of an amount of crystal seed with preferred at preferred rate of charge; To adding crystal seed and the requirement that becomes the glue order not necessarily, but under these conditions, select the crystallization velocity of certain inferior ordered pair raising molecular sieve that feeds intake; Thereby the shortening crystallization time, the degree of crystallinity that improves product all has significant advantage.For example but the not exhaustive order that preferably feeds intake can have the three kinds of modes in following (1)～(4): at first mix phosphorus source and aluminium source (1) with water, after stirring, and random order adding template, silicon source and crystal seed; (2) the aluminium source is mixed with water, add the solution of phosphoric acid and water then, after stirring, add diethylamine, di-n-propylamine, silicon source and crystal seed with random order again; (3) at first phosphorus source and aluminium source are mixed with part water, after stirring, add diethylamine, di-n-propylamine, silicon source, crystal seed and remaining water with random order, said remaining water is in time adding of any step 1 or repeatedly adding; (4) at first silicon source, phosphorus source and aluminium source are mixed, after stirring, add template, crystal seed and water with random order, water can or repeatedly add in time adding of any step 1.Wherein said water is generally deionized water or distilled water.

Said hydrothermal crystallizing condition is 120～250 ℃ of crystallization 4～500 hours, preferred 150～240 ℃ of crystallization 6～100 hours.Although under static and dynamic condition, can both synthesize the silicoaluminophosphamolecular molecular sieves of this new structure, preferred crystallization is under self-generated pressure, dynamically to carry out, as under stirring condition, heating up and thermostatic crystallization.The benefit of this stirring condition is removed the uniformity of increase system in the general sense, and comprising increases outside the efficient of conducting heat with mass transfer, to suppress AEL, AFI, AFO and CHA thing mutually and other stray crystal thing phase tangible advantage is all arranged.

In the catalyst provided by the invention, can also contain Si-Al molecular sieve.Said Si-Al molecular sieve is selected from the mixture of one or more molecular sieves of crystal structures such as skeleton consists of sial oxygen, has FAU, MOR, MAZ, MFI, CHA.Wherein, preferred Si-Al molecular sieve is one or more the mixture in Y zeolite with FAU structure and the ZSM-5 molecular sieve with MFI structure.

The kind of said Y zeolite is known by those skilled in the art, comprises hydro-thermal method, method of chemical treatment (mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiCl ₄Vapor phase method) or combine with the chemical treatment super-stable Y molecular sieves of method preparation of hydro-thermal, contain REUSY, REHY, the REY of rare earth element, and phosphorous PUSY, PREHY, PREY etc.

Said ZSM-5 molecular sieve is also known by those skilled in the art; Include or the warp exchange later that organic-free template is synthetic, the Hydrogen ZSM-5 of calcination process preparation; PZSM-5 through the phosphorus modification; And phosphorous and alkali-earth metal modified ZSM-5, or through phosphorus and transition metal modified ZSM-5, PFeZSM-5 of phosphorus and magnesium-modified PMgZSM-5, phosphorus and iron modification or the like for example.

In the catalyst provided by the invention, can also contain inorganic oxide binder.The instance of said inorganic oxide binder includes but not limited to following kind: the mixture of one or more in aluminium oxide, silica, aluminum phosphate, amorphous aluminum silicide, zirconia and the titanium oxide.Its precursor of said aluminium oxide comprises the acidifying colloid of aluminium colloidal sol, polymeric aluminum chloride, boehmite and boehmite etc.; Said silica precursor comprises waterglass, Ludox etc.

In the catalyst provided by the invention, can also contain inorganic oxide binder.Said clay comprises the material of artificial synthetic or natural generation, like one or more the mixture in kaolin, kaolinite, montmorillonite, talcum and the bentonite, also can be by the product of above-mentioned clay after peracid or the processing of alkali treatment process.Preferred clay is a kaolin and through the product of acid or alkali treatment.

Catalyst provided by the invention, preferred composition are to contain SRM-4 silicoaluminophosphamolecular molecular sieves, USY and/or ZSM-5 Si-Al molecular sieve, silica or aluminium oxide (its precursor is Ludox or aluminium colloidal sol) and kaolin.

Catalyst provided by the invention, its preparation process is following but be not limited to this.

One of method for preparing catalyst of the present invention be with the crystallization product filter cake of SRM-4 molecular sieve or dried powder (be roasting removed template method before SRM-4) with or not with after Si-Al molecular sieve filter cake or dry powder mix; Add the water making beating; Pulling an oar with inorganic oxide binder slurries and clay slurry afterwards mixes, and spray-dried then granulating is through the microballoon of big or small 10-300 micron.Thus obtained microsphere is through 400-800 ℃, 0.1-8h roasting, so that remove the template in the SRM-4 molecular sieve crystal.Microballoon uses and is decided by residual alkali ions content situation after the roasting, can directly use when alkali metal ion content measured is very low; Can select when alkali metal ion content measured is high through containing H ⁺Or NH ₄ ⁺Aqueous solution exchange remove alkali metal ion unnecessary in the catalyst, use dry then back, the those skilled in the art that are operating as that this exchange removes alkali metal ion unnecessary in the catalyst are familiar with.

The another kind preparation process of catalyst of the present invention is with the crystallization product filter cake of SRM-4 molecular sieve or process 400-800 ℃, the 0.1-8h roasting earlier of dried powder; So that remove the template in the SRM-4 molecular sieve crystal; Then with SRM-4 molecular sieve powder, Si-Al molecular sieve filter cake or dry powder; Add the water making beating, pulling an oar with inorganic oxide binder slurries and clay slurry afterwards mixes the microballoon of spray-dried then one-tenth size 10-300 micron.Thus obtained microsphere still can be selected whether roasting.The use of microballoon still need be looked residual alkali ions content situation and decide, and can directly use when alkali metal ion content measured is very low; Can select when alkali metal ion content measured is high through containing H ⁺Or NH ₄ ⁺Aqueous solution exchange remove alkali metal ion unnecessary in the catalyst, use dry then back.

The fine powder that can not satisfy instructions for use in the microballoon that spray-drying obtains in the above method for preparing catalyst can circulate and together pull an oar with the molecular sieve powder and reclaim use, can improve the yield of catalyst prod.

Catalyst provided by the invention is used for methanol conversion and prepares the light olefin course of reaction; For example; Adopt fluidized-bed reactor, material benzenemethanol can also can add water vapour or inert gas and regulate the methanol feeding dividing potential drop for refining and moisture not refining methyl alcohol in the course of reaction.Used reaction temperature is 150 ℃-800 ℃, is preferably 250 ℃-600 ℃; Used reaction pressure is 0.1-100 atmospheric pressure, preferred 0.5-10 atmospheric pressure.Used weight space velocity (WHSV) is 0.01-100h ^-1, be preferably 0.1-40h ^-1

Catalyst provided by the invention catalysis methanol effectively transforms the preparation light olefin, and can obtain the ratio of different ethene and propylene neatly.

The specific embodiment

Through embodiment the present invention is described further below, but does not therefore limit content of the present invention.

The X-ray powder diffraction of molecular sieve is measured used instrument and is produced Bruker D5005 for Germany in each embodiment and the Comparative Examples, adopts the CuK alpha ray; The molecular sieve composition is used x-ray fluorescence spectrometry; Record molecular sieve with VarianINOVA300M type nuclear magnetic resonance spectrometer ¹³The nmr spectrum of C.

Measure the nitrogen content in the molecular sieve with standard method SH-T0656, standard method RIPP-106-90 measures the carbon content in the molecular sieve, calculates in the molecular sieve before the roasting mol ratio of organic amine amount in the molecular sieve and diethylamine and di-n-propylamine with this.

The preparation process of instance 1-7 explanation SRM-4 silicoaluminophosphamolecular molecular sieves.

Embodiment 1

With 1417 gram phosphoric acid (85% phosphoric acid, chemically pure reagent, down with) join the colloid generating kettle that places 45 ℃ of water-baths with 5530 gram deionized waters and mix and stir, stir after 30 minutes to wherein adding 1165 and restrain hydrated aluminas and (contain 72%Al ₂O ₃, Sinopec catalyst Chang Ling branch company produces, down together), mixed 2 hours.Then, 730 gram diethylamine (chemically pure reagent, down with) and 810 gram di-n-propylamines (chemically pure reagent, down with) are joined respectively in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 1538 and restrain Ludox and (contain 26%SiO ₂, Changhong chemical plant, Beijing produces, down together), the back that stirs adds 80 gram AFO structure aluminium phosphate molecular sieves (the said methods of patent such as CN03122858, CN02116279 of pressing are synthetic), fully stirs 2 hours, processes reactant mixture.Reactant mixture dress is enclosed the stainless steel crystallizing kettle, 190 ℃ with self-generated pressure stirring crystallization 40 hours down.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number A.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 3, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.42P ₂O ₅: 0.76SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has 49.218ppm, 42.853ppm, 19.547ppm, four formants of 11.609ppm.

According to nitrogen content and carbon content, calculate in the molecular sieve diethylamine and di-n-propylamine with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 0.469, the mol ratio of diethylamine/di-n-propylamine is 0.92.

The mole composition of sample is expressed as with anhydrous oxide before the roasting: (0.225DEA+0.244DPA): Al ₂O ₃: 0.42P ₂O ₅: 0.76SiO ₂

Get the above-mentioned molecular screen primary powder of part, under roaster air atmosphere, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then with the heating rate of 2 ℃ of per minutes.Sample after the roasting is measured its result data such as table 4 through X-ray powder diffraction.

Table 3

2θ，°	I/I 0，％	2θ，°	I/I0，％
				8.247	100.00	23.449	5.94
11.684	4.69	24.900	28.74
				14.304	44.70	26.269	36.88
16.524	13.77	28.822	9.68
				18.493	14.67	30.023	17.51
20.265	2.80	32.309	13.12
				21.913	20.95	33.432	0.64

Table 4

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.313	100.00	23.665	23.02
11.751	34.49	25.134	57.50
				14.421	93.72	26.519	78.41
16.673	34.87	29.105	19.52
				18.659	27.87	30.323	48.06
20.440	1.39	32.626	29.97
				22.112	25.46	33.744	4.55

Embodiment 2

1165 gram hydrated aluminas and 3500g deionized waters are joined after the colloid generating kettle that places 65 ℃ of water-baths mixes 30 minutes, add by 1417 gram phosphoric acid and 2180 and restrain the solution that deionized waters are configured to and mixed 2 hours.Then; Add 385 gram Ludox, stirred 0.5 hour, with 900 restrain diethylamine and 812 di-n-propylamines mixture join in the above-mentioned colloid generating kettle; After continuing to mix 1 hour; The back adding 60 that stirs restrains molecular screen primary powder synthetic in the foregoing descriptions 1, fully stirs 2 hours, processes reactant mixture.Reactant mixture is encapsulated into the stainless steel crystallizing kettle, 190 ℃ with the following stirring crystallization 48 hours of self-generated pressure.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number B.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 5, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.78P ₂O ₅: 0.24SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has 49.7122ppm, 43.012ppm, 19.139ppm and four formants of 11.811ppm.

According to nitrogen content and carbon content, calculate in the molecular sieve diethylamine and di-n-propylamine with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 0.522, the mol ratio of diethylamine/di-n-propylamine is 0.71.

Mole composition before this sieve sample roasting is expressed as with anhydrous oxide: (0.217DEA+0.305DPA): Al ₂O ₃: 0.78P ₂O ₅: 0.24SiO ₂

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through X-ray powder diffraction, and its result data is as shown in table 6.

Table 5

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.246	100.00	23.431	15.06
11.650	6.60	24.883	64.91
				14.287	75.23	26.252	81.53
16.506	26.97	28.805	21.97
				18.475	28.83	30.023	40.78
20.261	6.90	32.309	29.78
				21.913	46.09	33.413	1.90

Table 6

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.346	100.00	23.706	19.71
11.801	40.15	25.150	48.44
				14.454	86.34	26.535	61.73
16.691	29.19	29.122	14.02
				18.676	24.61	30.341	38.63
20.469	1.51	32.643	24.98
				22.239	10.63	33.744	4.54

Embodiment 3

1165 gram hydrated aluminas and 3912 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir and stirred 30 minutes, 1417 gram phosphoric acid are added in the colloid generating kettles mixed 2 hours.1020 gram diethylamine and 325 gram di-n-propylamines are joined respectively in the above-mentioned colloid generating kettle; After continuing to mix 1 hour, add 2164 gram Ludox, the back that stirs adds synthetic molecular screen primary powder among the 40 gram embodiment 1; Fully stirred 2 hours, process reactant mixture.Reactant mixture is encapsulated into the stainless steel crystallizing kettle, 185 ℃ with the following stirring crystallization 52 hours of self-generated pressure.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number C.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 7, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.71P ₂O ₅: 1.33SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has near four formants of 49.707ppm, 43.270ppm, 19.311ppm and 11.617ppm.

According to nitrogen content and carbon content, calculate in the molecular sieve diethylamine and di-n-propylamine with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 0.627, the mol ratio of diethylamine/di-n-propylamine is 4.4.

Mole composition before this sieve sample roasting is expressed as with anhydrous oxide: (0.511DEA+0.116DPA): Al ₂O ₃: 0.71P ₂O ₅: 1.33SiO ₂

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through X-ray powder diffraction, and its data are as shown in table 8.

Table 7

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.197	100.00	23.382	18.54
11.601	8.27	24.834	79.38
				14.237	84.53	26.202	100.00
16.457	31.60	28.755	28.52
				18.426	34.01	29.973	54.97
20.195	7.90	32.259	40.21
				21.847	53.60	33.310	2.41

Table 8

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.330	100.00	23.715	15.31
11.784	22.30	25.167	30.40
				14.454	90.68	26.552	37.07
16.707	21.42	29.138	13.87
				18.692	17.35	30.357	24.30
20.465	5.05	32.659	16.47
				22.162	15.63	33.767	6.05

Embodiment 4

1165 gram hydrated aluminas and 4550 gram deionized waters are joined the colloid generating kettle that places 60 ℃ of water-baths mix and stir and stirred 30 minutes, 1329 gram phosphoric acid are added in the colloid generating kettles mix, stirred 2 hours after adding 2000 gram deionized waters again.The mixture of 650 gram diethylamine and 1020 gram di-n-propylamines is joined in the above-mentioned colloid generating kettle; After continuing to mix 1 hour, add 192 gram Ludox, add synthetic molecular screen primary powder in 80 gram the foregoing descriptions 1; Fully stirred 2 hours, process reactant mixture.Reactant mixture is encapsulated into the stainless steel crystallizing kettle, 190 ℃ with the following stirring crystallization 28 hours of self-generated pressure.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number D.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 9, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.88P ₂O ₅: 0.17SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has near four formants of 49.155ppm, 42.371ppm, 18.613ppm and 11.056ppm.

According to nitrogen content and carbon content, calculate in the molecular sieve diethylamine and di-n-propylamine with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 0.601, the mol ratio of diethylamine/di-n-propylamine is 1.3.

Mole composition before this sieve sample roasting is expressed as with anhydrous oxide: (0.340DEA+0.261DPA): Al ₂O ₃: 0. ₈₈P205:0.17SiO ₂

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through X-ray powder diffraction, and its data are as shown in table 10.

Table 9

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.080	100.00	23.298	7.52
11.501	5.77	24.734	34.98
				14.137	52.33	26.102	43.65
16.356	17.35	28.655	11.58
				18.326	49.88	29.873	21.09
20.088	6.75	32.159	15.91
				21.763	25.74	33.219	1.15

Table 10

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.263	100.00	23.632	25.13
11.717	28.97	25.084	61.06
				14.387	92.42	26.468	81.00
16.640	25.74	29.055	20.74
				18.626	27.55	30.290	47.49
20.417	0.61	32.593	28.32
				22.080	26.16	33.698	2.00

Embodiment 5

1165 gram hydrated aluminas and 3102 gram deionized waters are joined the colloid generating kettle that places 40 ℃ of water-baths mix and stir and stirred 30 minutes, 1240 gram phosphoric acid are added in the colloid generating kettles mixed 2 hours.960 gram diethylamine are joined in the above-mentioned colloid generating kettle and stir; Add 4807 gram Ludox; After adding 650 grams again di-n-propylamines continuing to mix 1 hour, add 4807 gram Ludox, add synthetic molecular screen primary powder in 50 gram the foregoing descriptions 1; Fully stirred 2 hours, process reactant mixture.Reactant mixture is encapsulated into the stainless steel crystallizing kettle, 190 ℃ with the following stirring crystallization 60 hours of self-generated pressure.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number E.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 11, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.45P ₂O ₅: 2.28SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has near four formants of 49.464ppm, 42.784ppm, 18.604ppm and 11.166ppm.。

According to nitrogen content and carbon content, calculate in the molecular sieve, diethylamine and di-n-propylamine are with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 0.716, the mol ratio of diethylamine/di-n-propylamine is 2.3.

Mole composition before this sieve sample roasting is expressed as with anhydrous oxide: (0.499DEA+0.217DPA): Al ₂O ₃: 0.45P ₂O ₅: 2.28SiO ₂

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through X-ray powder diffraction, and its data are as shown in table 12.

Table 11

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.246	100.00	23.431	6.00
11.667	5.09	24.884	27.62
				14.287	42.04	26.252	35.14
16.523	13.81	28.821	9.01
				18.492	12.90	30.023	17.11
20.125	2.98	32.292	0.21
				21.913	20.42	33.386	1.78

Table 12

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.246	100.00	23.615	26.77
11.701	39.40	25.083	64.98
				14.371	99.62	26.468	87.42
16.623	37.78	29.055	21.30
				18.609	29.16	30.273	51.98
20.412	1.57	32.576	33.49
				22.082	27.97	33.726	5.14

Embodiment 6

8653 gram Ludox are joined the colloid generating kettle that places 60 ℃ of water-baths, add 1165 gram hydrated aluminas and mix and stir and stirred 30 minutes, 1240 gram phosphoric acid are added in the colloid generating kettles mixed 2 hours.600 gram diethylamine and 1230 gram di-n-propylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add synthetic molecular screen primary powder in 200 gram the foregoing descriptions 1, fully stir and add 2000 gram deionized waters after 2 hours, process reactant mixture.Reactant mixture is encapsulated into the stainless steel crystallizing kettle, 190 ℃ with the following stirring crystallization 65 hours of self-generated pressure.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number F.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 13, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.38P ₂O ₅: 4.20SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has near four formants of 49.686ppm, 42.896ppm, 19.277ppm and 11.814ppm.

According to nitrogen content and carbon content, calculate in the molecular sieve diethylamine and di-n-propylamine with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 0.908, the mol ratio of diethylamine/di-n-propylamine is 1.4.

Mole composition before this sieve sample roasting is expressed as with anhydrous oxide: (0.530DEA+0.379DPA): Al ₂O ₃: 0.38P ₂O ₅: 4.20SiO ₂

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through X-ray powder diffraction, and its data are as shown in table 14.

Table 13

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.247	100.00	23.430	5.81
11.667	4.59	24.883	26.93
				14.304	39.77	26.250	33.96
16.523	13.47	28.805	9.51
				18.492	13.17	30.007	16.54
20.133	3.37	32.293	12.25
				21.913	20.20	33.342	1.22

Table 14

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.414	100.00	23.832	11.73
11.885	26.20	25.300	26.49
				14.554	54.23	26.686	32.84
16.807	18.70	29.289	9.04
				18.793	14.18	30.507	18.99
20.606	0.91	32.809	11.44
				22.263	11.73	33.947	0.62

Embodiment 7

14422 gram Ludox are joined the colloid generating kettle that places 50 ℃ of water-baths, add 1165 gram hydrated aluminas and mix and stir and stirred 30 minutes, 1240 gram phosphoric acid are added in the colloid generating kettles mixed 2 hours.1200 gram diethylamine and 812 di-n-propylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add synthetic molecular screen primary powder in 70 gram the foregoing descriptions 1, fully stirred 2 hours, process reactant mixture.Reactant mixture is encapsulated into the stainless steel crystallizing kettle, 190 ℃ with the following stirring crystallization 70 hours of self-generated pressure.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product, number G.Get this crystallization product of part and make X-ray powder diffraction mensuration, its result data is seen table 15, is pure phase SRM-4.

The mole composition of x-ray fluorescence spectrometry sample molecule sieve skeleton frame is expressed as with anhydrous oxide: Al ₂O ₃: 0.32P ₂O ₅: 7.3SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has near four formants of 49.308ppm, 42.926ppm, 18.597ppm and 10.383ppm.

According to nitrogen content and carbon content, calculate in the molecular sieve diethylamine and di-n-propylamine with respect to Al ₂O ₃Molar ratio, promptly x1+x2 is 1.401, the mol ratio of diethylamine/di-n-propylamine is 0.4.

Mole composition before this sieve sample roasting is expressed as with anhydrous oxide: (0.400DEA+1.001DPA): Al ₂O ₃: 0.32P ₂O ₅: 7.3SiO ₂

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 570 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through X-ray powder diffraction, and its data are shown in table 16.

Table 15

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.213	100.00	23.398	5.79
11.634	4.58	24.850	26.20
				14.254	39.63	26.218	34.43
16.490	13.73	28.771	9.45
				18.442	13.10	29.973	16.75
20.241	3.03	32.259	12.47
				21.863	20.11	33.351	0.89

Table 16

2θ，°	I/I 0，％	2θ，°	I/I 0，％
				8.296	100.00	23.698	12.96
11.751	26.52	25.167	32.09
				14.421	61.41	26.569	41.05
16.674	21.89	29.156	11.73
				18.676	16.03	30.374	23.46
20.494	0.83	32.693	14.19
				22.163	14.19	33.807	1.53

Comparative Examples 1

With 2882 gram phosphoric acid (88.5% phosphoric acid, industrial phosphoric acid, down with) join the colloid generating kettle that places 45 ℃ of water-baths with 9052 gram deionized waters and mix and stir, stir after 30 minutes to wherein adding 1781 and restrain hydrated aluminas and (contain 72%Al ₂O ₃, the Chang Ling catalyst plant is produced, down together), mixed 2 hours.Then; 2250 gram diethylamine and 122 gram di-n-propylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 1731 gram Ludox; Stirring, back adding 158 gram SRM-2 (synthesize, and its mole consists of 0.62 diethylamine: Al by the said method of CN1485272A ₂O ₃: 0.53P ₂O ₅: 0.72SiO ₂) molecular sieve, fully stirred 2 hours, process reactant mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, 185 ℃ with self-generated pressure stirring crystallization 80 hours down.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction and measure (sweep limits be 2 θ=5 °-35 °), its result meets SRM-2 spectral data among the CN1485272A, numbering X1.

The mole of x-ray fluorescence spectrometry method working sample framework of molecular sieve consists of: Al ₂O ₃: 0.53P ₂O ₅: 0.72SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C, ¹³C MAS-NMR spectrogram has 10.393ppm and two formants of 43.105ppm.

Analyze nitrogen, carbon content, according to nitrogen content and carbon content, the mol ratio that calculates diethylamine/di-n-propylamine in the molecular sieve is 28.

The mole composition is expressed as with anhydrous oxide before this comparative sample roasting: (0.602DEA+0.021DPA): Al ₂O ₃: 0.53P ₂O ₅: 0.72SiO ₂

Get the above-mentioned molecular screen primary powder of part, under roaster air atmosphere, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then with the heating rate of 2 ℃ of per minutes.Sample after the roasting is measured through X-ray powder diffraction, and its result meets SRM-2 spectral data among the CN1485272A.

Comparative Examples 2

2882 gram phosphoric acid and 9052 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths mix and stir, stirs after 30 minutes and restrain hydrated aluminas, mixed 2 hours to wherein adding 178.1.Then, 3036 gram di-n-propylamines and 88 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add 2302 gram Ludox, the back that stirs adds 200 gram SRM-2 molecular sieves, fully stirs 2 hours, processes reactant mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, 185 ℃ with self-generated pressure stirring crystallization 40 hours down.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction and measure (sweep limits is 2 θ=5 °-35 °, down with), its result meets SRM-2 spectral data among the CN1485272A, numbering X2.

The skeleton mole composition of x-ray fluorescence spectrometry method working sample molecular sieve is expressed as with anhydrous oxide: Al ₂O ₃: 0.40P ₂O ₅: 0.88SiO ₂

Get this crystallization product of part and on the magic-angle-spinning nuclear magnetic resonance spectrometer, record molecular sieve ¹³The nmr spectrum of C. ¹³C MAS-NMR spectrogram has 50.351ppm, 20.432 and three formants of 11.609ppm.

According to nitrogen content and carbon content, the mol ratio that calculates diethylamine/di-n-propylamine in the molecular sieve is 0.042.

The mole composition is expressed as with anhydrous oxide before this contrast sieve sample roasting: (0.029DEA+0.683DPA): Al ₂O ₃: 0.40P ₂O ₅: 0.88SiO ₂

Get the above-mentioned molecular screen primary powder of part, under roaster air atmosphere, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then with the heating rate of 2 ℃ of per minutes.Sample after the roasting is measured through X-ray powder diffraction, and its result meets SRM-2 data among the CN1485272A.

Embodiment 8-14 explains Preparation of catalysts process provided by the invention.

Embodiment 8

With 1.78Kg decationized Y sieve water with 1.43Kg kaolin (China Kaolin Co., Ltd's industrial products, the heavy % of solid content 84, down with) and 2.79Kg aluminium colloidal sol (Sinopec catalyst Shandong branch company product, Al ₂O ₃Content is 21.5%, down together) pull an oar evenly, the former powder A of SRM-4 molecular sieve crystallization (butt is 1.2Kg) that adds embodiment 1 preparation pulls an oar into slurries 4.0Kg with decationized Y sieve water; Homogeneous stirs; Spray drying forming, thus obtained microsphere are warming up to 570 ℃ in Muffle furnace, and constant temperature 10h; Be cooled to room temperature and promptly get catalyst sample C-1, form and see table 17.

Embodiment 9

Pull an oar into slurries 4.5Kg with decationized Y sieve water after SRM-4 sieve sample B (butt the is 1.35Kg) roasting with the foregoing description 2; It is even with 1.46Kg decationized Y sieve water 1.25Kg kaolin and 2.79Kg Ludox to be pulled an oar in addition, stirs spray drying forming after adding above-mentioned molecular sieve pulp; Thus obtained microsphere is warming up to 550 ℃ in Muffle furnace; And constant temperature 1h, promptly get catalyst sample C-2, form and see table 17.

Embodiment 10

With 0.17Kg decationized Y sieve water 0.54Kg kaolin is evenly become the kaolin mixed serum with the making beating of 2.79Kg aluminium colloidal sol; In addition (butt is 0.6Kg with the former powder C of SRM-4 molecular sieve crystallization (butt is 1.35Kg) of embodiment 3 preparations and ZRP5 molecular sieve; Sinopec catalyst Shandong branch company product; Hydrogen phosphorous modified ZSM-5 molecular sieve, Al ₂O ₃Content is 3.5%; Down together) adding decationized Y sieve water is pulled an oar into molecular sieve mix slurry 6.5Kg, adds to stir spray drying forming in the above-mentioned kaolin mixed serum; Thus obtained microsphere is warming up to 570 ℃ in Muffle furnace; And constant temperature 3h, be cooled to room temperature and promptly get catalyst sample C-3, form and see table 17.

Embodiment 11

With 0.5Kg decationized Y sieve water 0.71Kg kaolin is evenly become the kaolin mixed serum with the making beating of 2.79Kg aluminium colloidal sol; (butt is 0.75Kg with the ZSP molecular sieve after SRM-4 molecular sieve (butt the is 1.05Kg) roasting with the foregoing description 4 preparations in addition; Sinopec catalyst Shandong branch company product; The ZSM-5 molecular sieve of phosphorus and iron modification, Al ₂O ₃Content is 3.8%, down with) add decationized Y sieve water and pull an oar into molecular sieve mix slurry 6.0Kg, add and stir in the above-mentioned kaolin mixed serum, spray drying forming promptly get catalyst sample C-4, composition is seen table 17.

Embodiment 12

With 1.78Kg decationized Y sieve water 0.54Kg kaolin is evenly become the kaolin mixed serum with the making beating of 4.19Kg aluminium colloidal sol, (butt is 0.15Kg, the Sinopec catalyst Shandong USY of branch company zeolite product for the former powder E of SRM-4 molecular sieve crystallization (butt is 0.75Kg), ZRP5 molecular sieve (butt is 0.75Kg) and the DASY molecular sieve that in addition the foregoing description 5 are prepared; Lattice constant is 2.445nm; Down together) adding decationized Y sieve water is pulled an oar into molecular sieve mix slurry 5.5Kg, adds to stir spray drying forming in the above-mentioned kaolin mixed serum; Thus obtained microsphere is warming up to 570 ℃ in Muffle furnace; And constant temperature 3h, be cooled to after the room temperature with ammonium chloride solution (ammonium chloride content is 1 heavy %) washing the flush away Na+ that dissociates; The thousand dry catalyst sample C-5 that promptly get form and see table 17.

Embodiment 13

With 0.62Kg decationized Y sieve water 0.89Kg kaolin is evenly become the kaolin mixed serum with the making beating of 3.49Kg Ludox; Pull an oar into molecular sieve mix slurry 5.0Kg with adding decationized Y sieve water with ZRP5 molecular sieve (butt is 0.45Kg) and DASY molecular sieve (butt is 0.3Kg) after SRM-4 molecular sieve F (butt the is 0.75Kg) roasting of the foregoing description 6 preparations in addition; Add in the above-mentioned kaolin mixed serum and stir; Spray drying forming; With ammonium chloride solution (ammonium chloride content be 1 heavy %) washing, the flush away Na that dissociates ⁺, the thousand dry catalyst sample C-6 that promptly get form and see table 17.

Embodiment 14

With 0.74Kg decationized Y sieve water 1.07Kg kaolin is evenly become the kaolin mixed serum with the making beating of 4.19Kg Ludox; (butt is 0.9Kg with the PMZ molecular sieve after SRM-4 molecular sieve G (butt the is 0.3Kg) roasting with the foregoing description 7 preparations in addition; Sinopec catalyst Shandong branch company product; Phosphorus and magnesium-modified ZSM-5 molecular sieve, Al ₂O ₃Content is 5.4%) add decationized Y sieve water and pull an oar into molecular sieve mix slurry 4.0Kg; Add in the above-mentioned kaolin mixed serum and stir; Spray drying forming, with ammonium chloride solution (ammonium chloride content be 1 heavy %) washing, the flush away Na+ that dissociates; The thousand dry catalyst sample C-7 that promptly get form and see table 17.

Comparative Examples 3

Prepare wear-resistant catalyst by CN1341584A.

2494 gram phosphoric acid and 10250 are restrained in the deionized waters at the colloid generating kettle that places 25 ℃ of water-baths mix and stir; Stirring after 30 minutes to wherein adding 2040 gram hydrated aluminas (is boehmite; The A1203 that contains 72 weight %, Sinopec catalyst Chang Ling branch company product) mixed 2 hours.Then, 840 gram diethylamine (chemically pure reagent) and 1145 gram triethylamines are joined in the above-mentioned colloid generating kettle, continued to mix 1 hour.At last, add 1941 gram Ludox (SiO2 that contains 26 weight %, Haiyang Chemical Plant, Qingdao's commercial product) and fully stirred 2 hours, process reactant mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, 180 ℃ with self-generated pressure stirring crystallization 48 hours down.Then with crystallization product filter, washing and 100～110 ℃ of oven dry, promptly get molecular screen primary powder product DB-A.Get this crystallization product of part and make X-ray powder diffraction mensuration, the synthetic molecular sieve of its presentation of results is the CHA structure molecular screen.

Get the above-mentioned molecular screen primary powder of part, in roaster, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.The mole of sample consists of after the roasting: Al ₂O ₃: 0.45P ₂O ₅: 0.59SiO ₂

With 1.0Kg decationized Y sieve water that 1.9Kg kaolin and the making beating of 3.72Kg aluminium colloidal sol is even; Add the slurries 4.88Kg of good CHA structure molecular screen of above-mentioned roasting (butt is 1.6Kg) and decationized Y sieve water making beating, stir spray drying forming; Promptly get catalyst sample DB1, form and see table 17.

Comparative Examples 4

With embodiment 1, difference is that the contrast molecular sieve X1 that obtains with Comparative Examples 1 replaces SRM-4 molecular sieve F.Obtain catalyst sample DB2, form and see table 17.

Comparative Examples 5

With embodiment 1, difference is that the contrast molecular sieve X2 that obtains with Comparative Examples 2 replaces SRM-4 molecular sieve F.Obtain catalyst sample DB3, form and see table 17.

Comparative Examples 6

The ZSM-5 zeolite catalyst for preparing phosphorous modification by CN1352627A.

With 0.38Kg decationized Y sieve water that 0.71Kg kaolin and the making beating of 3.72Kg aluminium colloidal sol is even; Add the slurries 7.92Kg of ZRP5 molecular sieve (butt is 2.6Kg) and decationized Y sieve water making beating, stir spray drying forming; Promptly get catalyst sample DB4, form and see table 17.

Table 17

Embodiment	8	9	10	11	12	13	14	Comparative Examples 3	Comparative Examples 4	Comparative Examples 5	Comparative Examples 6
												Catalyst	C-1	C-2	C-3	C-4	C-5	C-6	C-7	DB1	DB2	DB3	DB4
Form heavy %
												Kaolin	40	35	15	20	15	25	30	40	40	40	15
Aluminium colloidal sol	20		20	20	30			20	20	20	20
												Ludox		20				25	30
SRM-4 molecular sieve (sample number into spectrum)	40?(A)	45?(B)	45?(C)	35?(D)	25?(E)	25?(F)	10?(G)		40?( X1)	40?( X2)
												The SAPO-34 molecular sieve								40
The ZSM-5 molecular sieve			20	25	25	15	30				65
												Y molecular sieve					5	10

Embodiment 15

Present embodiment explanation catalyst of the present invention and comparative catalyst are used for the effect of MTO reaction.

In the small fixed flowing bed reactor, the catalyst sample of the foregoing description and Comparative Examples is carried out the catalysis methanol conversion test.600 ℃ on warp, aging 2 hours of 100% steam before the evaluating catalyst, loading amount 150 grams.Reaction condition is a normal pressure, 470 ℃ of reaction temperatures, 650 ℃ of regeneration temperatures.Material benzenemethanol is pure for analyzing, the charging of water vapour stripping, and water is 0.15 with the methanol quality ratio, charging methyl alcohol weight (hourly) space velocity (WHSV) (WHSV) is 2.15 hours ^-1The metering cracked gas is long-pending and with its composition of gc analysis in the reaction evaluating; Water sample after the gas-liquid separation adopts gas chromatograph for determination methyl alcohol and water-soluble product content, is decided charcoal appearance mensuration COx concentration and is calculated the green coke amount by infrared after catalyst carbon deposit regeneration adopts oxygen to burn.Product light olefin selective meter is shown detailed hydrocarbon and accounts for the mass percent in total hydrocarbon products.Evaluation result is seen table 18,19.

Table 18

The catalyst numbering	C-1	C-2	DB1	DB2	DB3
						Selectivity of product, %
C2 ＝	34.2	35.7	45.4	34.0	34.3
						C3 ＝	43.3	42.7	31.5	42.7	41.4
C4 ＝	13.4	14.6	11.8	12.6	12.1
						Methanol conversion, heavy %	100.0	100.0	100.0	100.0	100.0
Calculating parameter
						C2 ＝+C3 ＝, heavy %	77.5	78.4	76.9	76.7	75.7
C3 ＝/C2 ＝	1.27	1.20	0.69	1.26	1.21

Table 19

The catalyst numbering	C-3	C-4	DB4	C-5	C-6	C-7
							Selectivity of product, %
C2 ＝	37.7	34.3	17.2	25.3	22.1	19.2
							C3 ＝	42.1	47.5	25.5	35.4	33.2	27.5
C4 ＝	9.5	7.71	13.1	12.9	14.9	13.0
							Methanol conversion, heavy %	100.0	100.0	100.0	100.0	100.0	100.0
Calculating parameter
							C2 ＝+C3 ＝, heavy %	79.8	81.8	42.7	60.7	55.3	46.7
C3 ＝/C2 ＝	1.12	1.38	1.48	1.40	1.50	1.43

Obviously can find out from table 18 and 19; Compare with the catalyst of prior art; Adopt catalyst of the present invention effectively catalysis methanol be converted into low-carbon alkene; And have higher ethene and propylene selectivity, and the ratio of propylene/ethylene can be in regulated in wider range simultaneously, and this provides flexibility to suitability for industrialized production.

Claims (18)

1. catalyst that is used for preparing light olefin by carbinol; It is characterized in that with the catalyst weight being benchmark; This catalyst has the silicoaluminophosphamolecular molecular sieves of following composition: 1-90%, the Si-Al molecular sieve of 0-50%, the inorganic oxide binder of 4-50% and the clay of 0-70%, and wherein the skeleton mole of said silicoaluminophosphamolecular molecular sieves composition uses the anhydrous chemical formulation of oxide form to be Al ₂O ₃: yP ₂O ₅: zSiO ₂, the anhydrous chemical formulation that the mole before the roasting removed template method is formed the use oxide form is (x1R1+x2R2): Al ₂O ₃: yP ₂O ₅: zSiO ₂, wherein R1 and R2 are the template that is present in the molecular sieve crystal duct, R1 is a diethylamine; R2 is a di-n-propylamine, and the value of x1+x2 is 0.01～5, x1/x2=0.1～20; The value of y is 0.01～1.5; The value of z is 0.01～30, and the X-ray diffraction data of this molecular sieve before the roasting removed template method contains the diffraction maximum shown in the Table A at least, and the X-ray diffraction data behind the roasting removed template method contains the diffraction maximum shown in the table B at least; Among Table A and the table B, W, M, S, VS represent diffraction peak intensity I and the strongest diffraction maximum I respectively ₀Relative ratio, W is 0～20%, M is 20～60%, S is 60～80%, VS is 80～100%,

Table A

20(°) I/I ₀ 2θ(°) I/I ₀ 8.08-8.29 VS 23.29-23.47 W 11.50-11.70 W 24.73-24.96 M-S 14.13-14.31 S-VS 26.10-26.32 S-VS 16.35-16.53 M 28.65-28.86 W-M 18.32-18.51 M 29.87-30.09 M 20.08-20.28 W 32.15-32.37 M 21.76-21.96 M 33.21-33.44 W

Table B

20(°) I/I ₀ 20(°) I/I ₀ 8.20-8.42 VS 23.53-23.84 W-M 11.65-11.89 M 25.00-25.30 M-S 14.32-14.56 VS 26.40-26.69 S-VS 16.55-16.81 W-M 28.99-29.29 W-M 18.54-18.80 W-M 30.19-30.51 M 20.36-20.61 W 32.50-32.81 M 21.97-22.27 W-M 33.58-33.95 W

。

2. according to the catalyst of claim 1, wherein the value of x1+x2 is 0.02～3.

3. according to the catalyst of claim 1, x1/x2=0.15～15 wherein.

4. according to the catalyst of claim 1, wherein the value of y is 0.1～1.4, and the value of z is 0.02～20.

5. according to the catalyst of claim 1, it is characterized in that having in the preceding 13C MAS-NMR spectrogram of silicoaluminophosphamolecular molecular sieves roasting removed template method the nuclear magnetic resonance peak of 49.22 ± 2ppm, 42.85 ± 2ppm, 19.55 ± 2ppm and 11.61 ± 2ppm.

6. according to the catalyst of claim 1, the condition of wherein said molecular sieve roasting removed template method is 300～800 ℃ of following roastings 1～10 hour.

7. according to the catalyst of claim 1, wherein said Si-Al molecular sieve is selected from one or more the mixture in the Si-Al molecular sieve that crystal structure is FAU, MOR, MAZ, MFI, CHA.

8. according to the catalyst of claim 1, the Si-Al molecular sieve of wherein said FAU structure is a Y zeolite.

9. according to the catalyst of claim 8, wherein said Y zeolite is a ultra-steady Y molecular sieve.

10. according to the catalyst of claim 8, wherein said Y zeolite is selected from the Y zeolite of rare earth and/or phosphorus modification.

11. according to the catalyst of claim 10, the Y zeolite of wherein said rare earth and/or phosphorus modification is REUSY, REHY, REY, PUSY, PREHY, PREY.

12. according to the catalyst of claim 7, the Si-Al molecular sieve of wherein said MFI structure is the ZSM-5 molecular sieve.

13. according to the catalyst of claim 12, wherein said ZSM-5 molecular sieve is the PZSM-5 through the phosphorus modification, or through phosphorus and alkali-earth metal modified, or through phosphorus and transition metal modified.

14. according to the catalyst of claim 13, wherein said alkaline-earth metal is Mg, said transition metal is Fe.

15. according to the catalyst of claim 1, wherein said inorganic oxide binder is selected from one or more the mixture in aluminium oxide, silica, amorphous aluminum silicide, zirconia and the titanium oxide.

16. according to the catalyst of claim 1, wherein said clay is selected from one or more mixtures in kaolin, kaolinite, montmorillonite, talcum and the bentonite, perhaps is the product of above-mentioned clay after peracid or the processing of alkali treatment process.

17. according to the catalyst of claim 1, said clay is its kaolin through acid or alkali treatment.

18. according to the catalyst of claim 1, it is characterized in that said Si-Al molecular sieve is that USY and/or ZSM-5, clay are kaolin, inorganic oxide binder is aluminium oxide or silica.