CN101935047B - MAPSO (Modified Adaptive Particle Swarm Optimization) molecular sieve and synthetic method thereof - Google Patents
MAPSO (Modified Adaptive Particle Swarm Optimization) molecular sieve and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses a MAPSO (Modified Adaptive Particle Swarm Optimization) molecular sieve and a synthetic method thereof. The molecular sieve is characterized in that X-ray diffraction data obtained before roasting and removing a template at least comprises a diffraction peak in a table (1), and X-ray diffraction data obtained after roasting and removing the template at least comprises a diffraction peak in a table (2). The molecular sieve is prepared by mixing an aluminum source, a phosphorus source, a silicon source and an organic template into glue at 5-100 DEG C, aging the glue for 5-80 h at 5-90 DEG C for 5-80 h, and adding and hydrothermally crystallizing an IIA-group metal element compound and 0.1-15 percent by weight of seed crystal in dry basis, and hydrothermally crystallizing.
Description
Technical field
The invention relates to a kind of MAPSO molecular sieve and compound method thereof.
Background technology
Aluminium phosphate molecular sieve is the of new generation molecular sieve (USP4310440) of U.S. UCC company in the invention early 1980s; The characteristics of this molecular sieve analog are that its skeleton alternately is formed by connecting on phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron; Because framework of molecular sieve is electroneutral, therefore there are not cation exchange property and catalytic perfomance.Aluminium phosphate molecular sieve is a series of molecular sieves; Have unique XRD characteristic spectrogram and data respectively; Wherein existing and existing al silicate molecular sieve has the molecular sieve of same crystal structure, and the molecular sieve of the novel texture that does not have in the existing al silicate molecular sieve is also arranged.
In the aluminium phosphate molecular sieve skeleton, introduce silicon, then become silicoaluminophosphamolecular molecular sieves, be i.e. SAPO series molecular sieve (U.S. UCC company; USP4440871); Its framework of molecular sieve is made up of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron, because skeleton is electronegative, skeleton has balance cation to exist outward; Therefore has cation exchange property, when the skeleton outer cationic is H
+The time, molecular sieve has acid sites, therefore has the acidic catalyst reactivity worth.Silicoaluminophosphamolecular molecular sieves has been widely used in oil refining and the field of petrochemical industry as the activity of such catalysts constituent element, like the conversion of catalytic cracking, hydrogen cracking, isomerizing, alkylating aromatic hydrocarbon, oxygen-containing organic compound etc.
Aluminium phosphate molecular sieve and silicoaluminophosphamolecular molecular sieves since its widely purposes and potential Application Areas obtained developing fast, the molecular sieve and the compound method of novel texture constantly invent.
Chinese patent CN 1485272A announces a kind of silicoaluminophosphamolecular molecular sieves (SRM-2) with novel texture, and the XRD data before its roasting removed template method contain just like the diffraction peak shown in the Table A at least: the X-ray diffraction data behind the roasting removed template method contain the diffraction peak of showing B at least; Mole composition before this molecular sieve roasting removed template method uses the anhydrous chemical formulation of oxide form to be Al
2O
3: yP
2O
5: zSiO
2, wherein the value of y is 0.01～1.5, the value of z is 0.05～50; Mole before this molecular sieve roasting removed template method is xR: Al when forming the anhydrous chemical formulation of using oxide form
2O
3: yP
2O
5: zSiO
2,
Table A
*W0～20％，M20～60％，S60～80％，VS80～100％。
Table B
Summary of the invention
The purpose of this invention is to provide a kind of MAPSO molecular sieve and its compound method is provided, when this molecular sieve is applied in the catalytic conversion reaction process of oxygenatedchemicals especially, have outstanding catalytic performance.
The present invention provides a kind of MAPSO molecular sieve, it is characterized in that the X-ray diffraction data before the roasting removed template method contain the diffraction peak shown in the table 1 at least, and the X-ray diffraction data behind the roasting removed template method contain the diffraction peak of table 2 at least; Its mole composition uses the anhydrous chemical formulation of oxide form to be xR: Al
2O
3: yP
2O
5: zSiO
2: nMO; Wherein R is the template that is present in the molecular sieve crystal duct, and the value of x is 0.01～8.0, and is preferred 0.02～7.0, more preferably 0.05～6.0; The value of y is 0.01～1.5, and is preferred 0.10～1.4, more preferably 0.15～1.2; The value of z is 0.01～30, and is preferred 0.02～20, more preferably 0.05～10; The value of n is 0.001～1.0, and is preferred 0.002～0.8, more preferably 0.003～0.6.When this molecular sieve is used for the reaction for preparing light olefins from methanol process, compare, have higher selectivity of light olefin with the SRM-2 sieve catalyst; In the producing ethylene from dehydration of ethanol reaction, compare with the SAPO-34 sieve catalyst, have higher selectivity.
Table 1
Table 2
The compound method of synthetic above-mentioned molecular sieve provided by the present invention is to contain but a kind of or any several kinds of miscellanys that are not limited to following P contained compound such as phosphoric acid, Hypophosporous Acid, 50, phosphoric acid salt and Organophosphorous compounds are phosphorus source, wherein preferably phosphoric acid; With hydrated aluminum oxide (pseudo-boehmite thing phase), aluminum isopropylate or a kind of or any several kinds of miscellanys of phosphagel phosphaljel is the aluminium source, preferred hydrated aluminum oxide (pseudo-boehmite thing phase) and aluminum isopropylate; Organic a kind of or any several kinds of mixtures with IIA family metal oxide, IIA family metal-salt and IIA family metal are IIA family metallic element compound; Wherein preferred IIA family metal-salt and metal IIA family metal oxide, the more preferably sulphate cpd of the nitrate compound of the haloid compound of IIA family metal oxide, IIA family metal, IIA family metal and IIA family metal.A kind of or any several kinds of miscellanys with silicon sol, active silica, tetraethoxy or solid silicone are the silicon source, are template with the mixture of any one or two kinds in diethylamine, diethylamine and triethylamine, the di-n-propylamine.Above-mentioned raw materials is pressed feed ratio aR: Al
2O
3: bP
2O
5: cSiO
2: dMO: eH
2O is mixed into glue with aluminium source, phosphorus source, silicon source and organic formwork agent, and colloid added IIA family metallic element compound after 5-90 ℃ of aging 5-80 hour, adds the crystal seed in butt 0.1～15 weight %; With its hydrothermal crystallizing and reclaim product, wherein a is the mole number of template, and its value is 0.01～10.0; Preferred 0.2～8.0, more preferably 0.5～7.0, the value of b is 0.1～2.5; Preferred 0.5～2.0, more preferably 0.6～1.5; The value of c is 0.01～30, and is preferred 0.02～20, more preferably 0.05～10, and the value of d is 0.001～1.0, and is preferred 0.002～0.8, more preferably 0.003～0.6; The value of e is 5～150, and is preferred 10～120, more preferably 15～100.
In method provided by the invention; Although become the glue temperature and add under the condition of an amount of crystal seed with preferred at preferred feed ratio; To adding crystal seed and the requirement that becomes the glue order not necessarily, but under general above-mentioned condition, select the crystallization velocity of certain inferior ordered pair raising molecular sieve that feeds intake; Thereby the shortening crystallization time, the percent crystallinity that improves product all has significant advantage.Wherein the order that feeds intake of the raw material except that metal-salt preferably can have following several kinds:
Phosphorus source, aluminium source are mixed with the water random order, and water once adds or repeatedly adds, and after stirring, adds template, silicon source and crystal seed with random order.
Aluminium source and water are mixed, add the mixing solutions of phosphoric acid and water then, after stirring, add template, silicon source and crystal seed with random order again.
Phosphorus source and aluminium source are mixed with portion water, after stirring, add template, silicon source, crystal seed and remainder water with random order, remainder water is in time adding of any step 1 or repeatedly adding.
Silicon source, aluminium source and phosphorus source are mixed, after stirring, add template, crystal seed and water with random order, water is in time adding of any step 1 or repeatedly adding.
Portion water, silicon source, aluminium source, phosphorus source are mixed, after stirring, add template, crystal seed and remainder water with random order, water is in time adding of any step 1 or repeatedly adding.
In addition; Molecular sieve crystal seed of the present invention is selected from Chinese patent CN 1485272A synthetic molecular sieve (SRM-2) or molecular sieve of the present invention; As the above-mentioned molecular sieve of crystal seed, no matter whether the roasting removed template method, all is suitable for using as crystal seed in the compound method provided by the invention; The crystal seed add-on is 0.1～15m% of molecular sieve butt, preferred 0.5～14m%.
In compound method provided by the invention, said one-tenth glue temperature is 5～100 ℃, and preferred 10～90 ℃, preferred temperature is 15～80 ℃; Crystallization temperature is 100～250 ℃; Crystallization time is 4～500 hours, wherein preferred 10～100 hours.
In the compound method provided by the invention, said crystallization condition can be to be warmed up to 100-160 ℃ earlier, and constant temperature 0.5～20 hour is warmed up to 165～250 ℃ again and continued crystallization 3～200 hours, preferred 6～100 hours.
The condition that molecular sieve provided by the invention, said roasting are deviate from template is 300～800 ℃ of following roastings 1～30 hour.
Although under static and dynamic condition, can both synthesize the MAPSO molecular sieve of this novel texture, preferred crystallization is under autogenous pressure, dynamically to carry out, as under agitation condition, heating up and thermostatic crystallization.This agitation condition removes the homogeneity of increase system in the general sense, also comprises the efficient that increases heat transfer and mass transfer, and inhibition CHA phase, AFO are reached other stray crystal phase mutually all has tangible advantage.
Molecular sieve provided by the present invention can be used for the conversion reaction of hydro carbons; Acidic components like catalyzer such as catalytic cracking, hydrogen cracking, isomerizing, catalytic dewaxings; Also can be used for the conversion reaction of oxygen-containing organic compound, like the conversion reaction of methyl alcohol, ethanol, dme etc.
Embodiment
Following embodiment will be described further the present invention, but therefore not 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.
Comparative Examples 1
The explanation of this Comparative Examples is carried out the synthetic of SRM-2 structure molecular screen with the method for CN 1485272A.
With the 147.58 gram phosphoric acid (H that contain 85 weight %
3PO
4) and 593.43 gram deionized waters join the colloid generating kettle that places 50 ℃ of water-baths and mix and stir, stirs after 30 minutes to wherein adding 117.53 and restrains hydrated aluminum oxides and (be pseudo-boehmite, contain the Al of 69.4 weight %
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod), mixed 2 hours.Then, 118.21 gram diethylamine are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour after, add the 96.13 gram silicon sol (SiO that contain 30 weight %
2, Beijing flying dragon equine trade ltd), the back that stirs adds 11.79 gram SRM-2 molecular sieves, fully stirs 2 hours, processes reaction mixture.Reaction mixture dress is enclosed the stainless steel crystallizing kettle, 185 ℃ with autogenous 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 the X-ray powder diffraction and measure (sweep limit is 2 θ=5 °-35 °, down with), its presentation of results institute synthetic molecular sieve is the SRM-2 structure molecular screen.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.78P
2O
5: 0.56SiO
2
Comparative Examples 2
Carry out the synthetic of SAPO-34 molecular sieve with the method for patent ZL99126308.1.
With the 249.4 gram phosphoric acid (H that contain 88.5 weight %
3PO
4) with 1025 gram deionized waters in mixes and stirs at the colloid generating kettle that places 25 ℃ of water-baths, stir after 30 minutes to wherein adding 204 and restrain hydrated aluminum oxides and (be pseudo-boehmite, contain the Al of 72 weight %
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod) mixed 2 hours.Then, 105.0 gram diethylamine (chemically pure reagent) and 57.2 gram triethylamines are joined in the above-mentioned colloid generating kettle, continued to mix 1 hour.At last, add the 194.1 gram silicon sol (SiO that contain 26 weight %
2, Haiyang Chemical Plant, Qingdao's commerical prod) fully stirred 2 hours, process reaction mixture.Reaction mixture dress is enclosed the stainless steel crystallizing kettle, 180 ℃ with autogenous 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.Get this crystallization product of part and make X-ray powder diffraction mensuration, its presentation of results synthetic molecular sieve is the CHA structure molecular screen, i.e. the SAPO-34 molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.75P
2O
5: 0.52SiO
2
Embodiment 1
The mixed solution of 184.47 gram phosphoric acid and 605.07 gram deionized waters is joined the colloid generating kettle that places 50 ℃ of water-baths mix and stirred 30 minutes, add 117.53 gram hydrated aluminum oxides and (be pseudo-boehmite, contain the Al of 69.4 weight %
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod, down together), continue to stir after 2 hours, add the 64.09 gram silicon sol (SiO that contain 30 weight %
2, Beijing flying dragon equine trade ltd), fully stirred 2 hours, add 118.21 gram diethylamine again in above-mentioned colloid generating kettle, at room temperature static wearing out 16 hours after stirring adds the 8.30 gram magnesium chloride crystal (MgCl that contain 98 weight %
26H
2O, down together, Tianjin recovery fine chemistry industry institute); Stir after 30 minutes; The molecular screen primary powder that adds 14.32 gram SRM-2 continues to stir 30 minutes, and reaction mixture is encapsulated into the stainless steel crystallizing kettle; Temperature is raised to 150 ℃ stirs constant temperature after 16 hours, rise to 185 ℃ again and under autogenous pressure, stirred crystallization 84 hours.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 mensuration, result such as table 7, it meets table 1, explains that it is the SRM-6 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 8; X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.89P
2O
5: 0.43SiO
2: 0.076MgO.
Table 3
Table 4
Embodiment 2
1121.49 gram silicon sol, 117.53 gram hydrated aluminum oxides and 294.24 gram deionized waters are joined the colloid generating kettle that places 70 ℃ of water-baths to be mixed and stirred 30 minutes; After stirring 2 hours in the 221.36 gram phosphoric acid adding colloid generating kettles; 354.62 gram diethylamine are joined in the above-mentioned colloid generating kettle; Fully stirred 2 hours, process reaction mixture.Stir the back 35 ℃ of static down wearing out 24 hours, then, add the 6.55 gram magnesium oxide powder (MgO that contain 98.5 weight %; Down together, Chemical Reagent Co., Ltd., Sinopharm Group), stir after 30 minutes; Add the molecular screen primary powder of 48.49 gram SRM-2, stirred 30 minutes, reaction mixture is encapsulated into the stainless steel crystallizing kettle; Temperature is raised to 120 ℃ stirs constant temperature after 4 hours, rise to 210 ℃ again and under autogenous pressure, stirred crystallization 20 hours.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 mensuration, result such as table 5, it meets table 1, explains that it is the SRM-6 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 6; X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.32P
2O
5: 5.34SiO
2: 0.25MgO.
Table 5
Table 6
Embodiment 3
117.53 gram hydrated aluminum oxides 305.72 gram deionized waters are joined the colloid generating kettle that places 25 ℃ of water-baths mix and stir and stirred 30 minutes, with the 147.58 gram phosphoric acid (H that contain 85 weight %
3PO
4, down together) add in the colloid generating kettle, continue to stir 2 hours.After joining 88.65 gram diethylamine in the above-mentioned colloid generating kettle; Stir after 1 hour; Add 96.13 and restrain silicon sol, stirred under 50 ℃ aging 10 hours the back that stirs, and adding 16.37 gram magnesium oxide powders stirrings added the molecular sieve of the SRM-2 after the 14.15 gram roastings in 30 minutes; Fully stirred 2 hours, process reaction mixture.Reaction mixture is encapsulated into the stainless steel crystallizing kettle, 185 ℃ with the following stirring crystallization 48 hours of autogenous pressure.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 mensuration, result such as table 3, it meets table 1, explains that it is the SRM-6 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 4; X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.73P
2O
5: 0.54SiO
2: 0.39MgO.
Table 7
Table 8
Embodiment 4
117.53 gram hydrated aluminum oxides and 488.87 gram deionized waters are joined the colloid generating kettle that places 35 ℃ of water-baths mix and stirred 30 minutes, add 129.13 gram phosphoric acid, continue to stir 2 hours; 118.21 gram diethylamine are joined in the above-mentioned colloid generating kettle, and the back that stirs added 16.60 gram magnesium chloride crystal at 60 times static aging 15 hours; Stir after 30 minutes; The molecular screen primary powder that adds 14.07 gram SRM-2, restir added 32.04 gram silicon sol after 30 minutes; Fully stirred 2 hours, process reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 130 ℃ stirs constant temperature after 8 hours, rise to 200 ℃ again and under autogenous pressure, stirred crystallization 36 hours.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 mensuration, result such as table 9, it meets table 1, explains that it is the SRM-6 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 10; X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.83P
2O
5: 0.35SiO
2: 0.15MgO.
Table 9
Table 10
Embodiment 5
117.53 gram hydrated aluminum oxides and 376.67 gram deionized waters are joined the colloid generating kettle that places 60 ℃ of water-baths mix and stirred 30 minutes, 184.47 gram phosphoric acid are added in the colloid generating kettles mixed 2 hours.160.21 gram silicon sol are joined in the above-mentioned colloid generating kettle; After continuing to mix 1 hour, add 147.76 gram diethylamine, fully stir and processed reaction mixture in 2 hours; At room temperature static aging 24 hours, the calcium chloride hydrate (CaCl that contains 98 weight % of adding 30.00 grams
22H
2O; Strand, Tianjin City Tanggu chemical industry electric refrigerator factory); Stirring adds 33.49 gram SRM-2 molecular screen primary powders stirrings 30 minutes, and the partial reaction mixture is encapsulated into the stainless steel crystallizing kettle; Temperature is raised to 140 ℃ stirs constant temperature after 8 hours, rise to 175 ℃ again and under autogenous pressure, stirred crystallization 36 hours.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 mensuration, its result such as table 11, it meets the characteristic of table 1, explains that it is SRM-6.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 12; The mole that the skeleton mole of x-ray fluorescence spectrometry sample molecule sieve is formed with anhydrous oxide consists of: Al
2O
3: 0.64P
2O
5: 0.79SiO
2: 0.19CaO.
Table 11
Table 12
Embodiment 6
117.53 gram hydrated aluminum oxides and 351.01 gram deionized waters are joined the colloid generating kettle that places 50 ℃ of water-baths to be mixed and stirs and stirred 30 minutes; After mixing 30 minutes in the 147.58 gram phosphoric acid adding colloid generating kettles; Wore out 20 hours down at 25 ℃, add the strontium chloride crystal (SrCl that contains 100 weight % of 31.99 grams
26H
2O, chemical reagent factory of Beijing Xinhua).Evenly stir after 2 hours 7.36 gram SRM-2 molecular screen primary powders joined in the above-mentioned colloid generating kettle, continue to mix 30 minutes after, the deionized water and stirring that adds 351.01 grams is after 30 minutes; The diethylamine that adds 118.21 grams; Stir after 10 minutes, add 163.56 di-n-propylamines, stir adding 128.17 gram silicon sol after 1 hour; Fully stirred 2 hours, process reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 130 ℃ stirs constant temperature after 15 hours, rise to 200 ℃ again and under autogenous pressure, stirred crystallization 16 hours.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 mensuration, result such as table 13, it meets the characteristic of table 1, explains that it is SRM-6.Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then, get this crystallization product of part and make the X-ray powder diffraction and measure result such as table 14; The mole that the skeleton mole of x-ray fluorescence spectrometry sample molecule sieve is formed with anhydrous oxide consists of: Al
2O
3: 0.78P
2O
5: 0.63SiO
2: 0.081SrO.
Table 13
Table 14
Comparative Examples 3
117.53 gram hydrated aluminum oxide and 605 gram deionized waters join the colloid generating kettle mixing that places 40 ℃ of water-baths and stirred 30 minutes; After stirring 2 hours in the 147.6 gram phosphoric acid adding colloid generating kettles; 32.04 gram silicon sol, 103.4 gram diethylamine are joined in the above-mentioned colloid generating kettle; Fully stirred 30 minutes, process reaction mixture.Add the 6.55 gram magnesium oxide powder (MgO that contain 98.5 weight % then; Down together, Chemical Reagent Co., Ltd., Sinopharm Group), stir after 30 minutes; The molecular screen primary powder that adds 40 gram SRM-2; Stirred 30 minutes, reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 185 ℃ stirred constant temperature 48 hours.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 mensuration, the result shows that product is the mixture of SRM-6 and a large amount of MgALPO-34 and a small amount of SAPO-41.
Embodiment 7
Present embodiment explains that molecular sieve provided by the invention prepares the effect in the reaction of alkene at methyl alcohol.
Comparative Examples 1 and embodiment 1-6 synthetic molecular screen primary powder after 550 ℃ of roastings roasting in 4 hours, are cooled to room temperature, and the particle that with a part of compressing tablet, smashes, sieves out 20-40 order granularity is as catalyzer DB-1 and catalyst A-F.
Reaction evaluating carries out on the pulse micro-inverse device.Its test parameter is: temperature of reaction is 500 ℃, and pressure is normal pressure.The catalyzer loading amount is 100mg; Reactant is a methyl alcohol, and sample size is 0.5 μ l, and reaction product is analyzed by on-line gas chromatography.Chromatographic condition is: hydrogen and nitrogen flow are 30mL/min; Air flow quantity is 300mL/min, and 40 ℃ of chromatographic column initial temperatures are behind 40 ℃ of constant temperature 1min; With the heat-up rate temperature programming to 150 of 10 ℃/min ℃; At 150 ℃ of constant temperature 2min, injector temperature is 150 ℃ then, and the fid detector temperature is 180 ℃.Reaction product is with C
2-C
4Alkene is title product.Evaluation result is seen table 15.
Table 15
Compare with the SRM-2 sieve catalyst from table 15 is visible, molecular sieve provided by the invention is used for catalysis MTO reaction and has higher selectivity of light olefin.
Embodiment 8
Present embodiment is explained the effect of molecular sieve provided by the invention in the reaction of ethanol preparation ethene.
Preparation of Catalyst is with embodiment 7.
The catalyzer of Comparative Examples 2 preparations is DB-2.
Reaction evaluating carries out on the pulse micro-inverse device.Its test parameter is: temperature of reaction is 350 ℃, and pressure is normal pressure.The catalyzer loading amount is 100mg; Reactant is an ethanol, and sample size is 0.5 μ l, and reaction product is analyzed by on-line gas chromatography.Chromatographic condition is: hydrogen and nitrogen flow are 30mL/min, and air flow quantity is 300mL/min; 40 ℃ of chromatographic column initial temperatures, behind 40 ℃ of constant temperature 1min, with the heat-up rate temperature programming to 150 of 10 ℃/min ℃, then at 150 ℃ of constant temperature 2min, injector temperature is 150 ℃, the fid detector temperature is 180 ℃.
Reaction product is with C
2Alkene is title product.
Evaluation result is seen shown in the table 16.
Table 16
| Catalyzer | Ethanol conversion (%) | Ethylene selectivity (%) |
| DB-2 | 100 | 98.54 |
| A | 100 | 99.84 |
| B | 100 | 99.70 |
| C | 100 | 99.68 |
| D | 100 | 99.91 |
| E | 100 | 99.45 |
| F | 100 | 99.51 |
From shown in the table 16, with the SAPO-34 sieve catalyst relatively, molecular sieve of the present invention is used for that the catalysis ethanol dehydration is ethylene reaction produced to have a higher selectivity.
Claims (18)
1. MAPSO molecular sieve; It is characterized in that the X-ray diffraction data before the roasting removed template method contain the diffraction peak shown in the table 1 at least, the X-ray diffraction data behind the roasting removed template method contain the diffraction peak of table 2 at least and anhydrous chemical formulation that its mole composition uses oxide form is Al
2O
3: yP
2O
5: zSiO
2: nMO, M are IIA family metallic element, and wherein the value of y is 0.01～1.5, and the value of z is 0.01～30; The value of n is 0.001～1.0, and W, M, S, VS represent that W is 0～20% with respect to the relative intensity of the strongest diffraction peak in the table, and M is 20～60%; S is 60～80%, and VS is 80～100%
Table 1
Table 2
2. according to the molecular sieve of claim 1, wherein the value of y is 0.1～1.4; The value of z is 0.02～20; The value of n is 0.002～0.8.
3. according to the molecular sieve of claim 1, the mole before its roasting removed template method is xR: Al when forming the anhydrous chemical formulation of using oxide form
2O
3: yP
2O
5: zSiO
2: nMO; Wherein R is the template that is present in the molecular sieve crystal duct, and the value of x is 0.01～8.0, the value of y, z and n such as claim 1 definition.
4. according to the molecular sieve of claim 3, the value of x is 0.02～7.0.
5. the compound method of the said molecular sieve of claim 1 is characterized in that under 5～100 ℃ by feed ratio aR: Al
2O
3: bP
2O
5: cSiO
2: dMO: eH
2O; Aluminium source, phosphorus source, silicon source, water and organic formwork agent are mixed into glue, and colloid added IIA family metallic element compound after 5-90 ℃ of aging 5-80 hour, add the crystal seed in butt 0.1～15 weight % again; 100～250 ℃ of following hydrothermal crystallizings 4～500 hours; With crystallization product filter, washing and 100～110 ℃ of oven dry, obtain the molecular screen primary powder product, get the above-mentioned molecular screen primary powder of part; In stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, and in air, naturally cooled to room temperature then; Wherein R is an organic formwork agent, and the value of a is 0.1～10.0; The value of b is 0.1～2.5, and the value of c is 0.01～30.0, and the value of d is 0.001～1.0, and the value of e is 5～150, and crystal seed is selected from the SRM-2 silicoaluminophosphamolecular molecular sieves.
6. according to the method for claim 5; Wherein said aluminium source is selected from a kind of or any several kinds of mixtures of pseudo-boehmite thing phase hydrated aluminum oxide, aluminum isopropylate and phosphagel phosphaljel; Said silicon source is selected from a kind of or any several kinds of mixtures of silicon sol, tetraethoxy or solid silicone; Said phosphorus source is selected from a kind of or any several kinds of mixtures of phosphoric acid, Hypophosporous Acid, 50, phosphoric acid salt and Organophosphorous compounds; Said organic formwork agent is diethylamine or is the mixture of diethylamine and di-n-propylamine, and said IIA family metallic element compound is the MOX or the metal-salt of IIA family element.
7. according to the method for claim 6, wherein said aluminium source is hydrated aluminum oxide or aluminum isopropylate, and said phosphorus source is a phosphoric acid.
8. according to the method for claim 6, wherein, the metal-salt of IIA family element is magnesium chloride, calcium chloride or strontium chloride.
9. according to the method for claim 5, wherein said crystal seed, its add-on is 0.5～14 weight %.
10. according to the method for claim 5, wherein said one-tenth glue, its temperature is 10～90 ℃.
11. according to the method for claim 5, crystallization condition is to be warmed up to 100-160 ℃ earlier, constant temperature 0.5～20 hour is warmed up to 165～250 ℃ again and continued crystallization 3～200 hours.
12. according to the method for claim 5, the value of a is 0.2～8.0.
13. according to the method for claim 5, wherein the value of b is 0.5～2.0.
14. according to the method for claim 5, wherein the value of c is 0.02～20.0.
15. according to the method for claim 5, wherein the value of d is 0.002～0.8.
16. according to the method for claim 5, wherein the value of e is 10～120.
17. according to the method for claim 5, wherein said aging, its temperature is 10-70 ℃, digestion time is 10-50 hour.
18. according to the method for claim 5, wherein said hydrothermal crystallizing, its process is static or dynamically carry out under the autogenous pressure.
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| US4567029A (en) * | 1983-07-15 | 1986-01-28 | Union Carbide Corporation | Crystalline metal aluminophosphates |
| US4793984A (en) * | 1984-04-13 | 1988-12-27 | Union Carbide Corporation | Molecular sieve compositions |
| CN1485272A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
| CN101269820A (en) * | 2007-03-21 | 2008-09-24 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesizing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4567029A (en) * | 1983-07-15 | 1986-01-28 | Union Carbide Corporation | Crystalline metal aluminophosphates |
| US4793984A (en) * | 1984-04-13 | 1988-12-27 | Union Carbide Corporation | Molecular sieve compositions |
| CN1485272A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
| CN101269820A (en) * | 2007-03-21 | 2008-09-24 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesizing process |
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