CN101935048B - Titanium-contained silicon-aluminum phosphate molecular sieve and synthesis thereof - Google Patents
Titanium-contained silicon-aluminum phosphate molecular sieve and synthesis thereof Download PDFInfo
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Abstract
The invention discloses a titanium-contained silicon-aluminum phosphate molecular sieve and a synthetic method thereof, wherein the molecular sieve is characterized in that X-ray diffraction data before roasting for removing a template agent at least contains a diffraction peak shown in a table 1, and the X-ray diffraction data after roasting for removing the template agent at least contains the diffraction peak of a table 2; and the molecular sieve is obtained according to the following steps of: mixing and gelatinizing the compound of an aluminum source, a phosphorus source, a silicon source and metallic titanium as well as an organic template agent at the temperature of 5-100 DEG C, aging the obtained colloid for 5-80 hours at the temperature of 5-90 DEG C, adding 0.1-15wt% of crystal seed on a dry basis, and then carrying out hydrothermal crystallization for 4-500 hours at the temperature of 100-250 DEG C. A catalyst using the molecular sieve provided by the invention as an active component can be used for the conversion reaction of oxygen-contained organic compounds.
Description
Technical field
The invention relates to a kind of titaniferous silicoaluminophosphamolecular molecular sieves and synthetic.
Background technology
Aluminium phosphate molecular sieve is that U.S. UCC company is at the molecular sieve of new generation (USP4310440) of the invention early 1980s, the characteristics of this molecular sieve analog are that its skeleton alternately is formed by connecting by phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, because framework of molecular sieve is electric neutrality, therefore there are not cation exchange property and catalytic perfomance.Aluminium phosphate molecular sieve is a series of molecular sieves, have respectively unique XRD feature spectrogram and data, 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, it is SAPO Series Molecules sieve (U.S. UCC company, USP4440871), its framework of molecular sieve is made 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 extraframework cation 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 active component of catalyzer, such as the conversion of catalytic cracking, hydrocracking, isomerization, 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 fast development, molecular sieve and the synthetic method of novel texture constantly invent.
Chinese patent CN1485272A announces a kind of silicoaluminophosphamolecular molecular sieves (SRM-2) with novel texture, and the XRD data before its roasting removed template method contain diffraction peak as shown in table 1 at least: the XRD data behind its roasting removed template method contain diffraction peak as shown in table 2 at least: the anhydrous chemical formulation that the mole before this molecular sieve roasting removed template method forms with oxide form is Al
2O
3: yP
2O
5: zSiO
2, wherein the value of y is that the value of 0.01～1.5, z is 0.05～50; Mole before this molecular sieve roasting removed template method is xR:Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2,
Table A
*W?0～20％，M?20～60％，S?60～80％，VS?80～100％。
Table B
Summary of the invention
The purpose of this invention is to provide a kind of titaniferous silicon aluminium phosphate TiAPSO molecular sieve (SRM-7) and its synthetic method is provided, when this molecular sieve is applied in the catalytic conversion reaction process of oxygenatedchemicals especially, have outstanding catalytic performance.
Titaniferous silicoaluminophosphamolecular molecular sieves provided by the invention, it is characterized in that the XRD data before the roasting removed template method contain diffraction peak as shown in table 1 at least, XRD data behind the roasting removed template method contain diffraction peak as shown in table 2 at least, and its mole composition is xR:Al with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2: nMO
mWherein 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.
Table 1
Table 2
When molecular sieve provided by the invention is used for the catalytic conversion reaction process of preparing light olefins from methanol, compare with the SRM-2 molecular sieve catalyst, have higher selectivity of light olefin; When this molecular sieve is used for the catalytic conversion process of producing ethylene with ethyl alcohol, compare with the SAPO-34 molecular sieve catalyst, have higher ethylene selectivity.
Molecular sieve provided by the invention can be used for the conversion reaction of hydro carbons, acidic components such as catalyzer such as catalytic cracking, hydrocracking, isomerization, catalytic dewaxings, also can be used for the conversion reaction of oxygen-containing organic compound, such as the conversion reaction of methyl alcohol, ethanol, dme etc.
The present invention also provides the method for synthetic above-mentioned molecular sieve, to contain but a kind of or any several miscellany that is not limited to following P contained compound such as phosphoric acid, Hypophosporous Acid, 50, phosphoric acid salt and Organophosphorous compounds is phosphorus source, wherein preferably phosphoric acid; Take a kind of or any several miscellany of hydrated aluminum oxide (pseudo-boehmite phase), aluminum isopropylate or aluminum phosphate as the aluminium source, preferred hydrated aluminum oxide (pseudo-boehmite phase) and aluminum isopropylate; Titanium metal oxide compound, inorganic salt compound and organic a kind of or any several mixture are titanium metal compound; In preferential oxidation titanium, oxychlorination titanium, titanium tetrachloride, titanium sulfate, titanyl sulfate, butyl (tetra) titanate, metatitanic acid methyl esters, isopropyl titanate, the titanate etc. one or more; More preferably one or more in titanium oxide, chlorination oxygen titanium, titanium tetrachloride, titanium sulfate, titanyl sulfate, the butyl (tetra) titanate etc.; Wherein organo titanium compounds can with organic solvent dissolution after add again reaction mixture or carry out independent hydrolysate, the preferred alcohol organic solvent of this organic solvent.Take a kind of or any several miscellany of silicon sol, active silica, tetraethoxy or solid silicone as the silicon source.The mixture of one or both in diethylamine, diethylamine and triethylamine or the di-n-propylamine is as template.
Above-mentioned raw materials is pressed feed ratio aR: Al
2O
3: bP
2O
5: cSiO
2: dMOm: eH
2O is mixed into glue, colloid 5-90 ℃ lower aging 5-80 hour, hydrothermal crystallizing and reclaim product then, wherein a is the mole number of template, its value is 0.01～10.0, and is preferred 0.2～8.0, more preferably 0.5～7.0, the value of b is 0.1～2.5, and is 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.The contriver finds that in synthetic this titaniferous silicoaluminophosphamolecular molecular sieves, the step that wherein colloid is aging has promoted titanium to enter framework of molecular sieve, forms the molecular sieve crystal formation of SRM-7.
In addition, molecular sieve crystal seed of the present invention is selected from synthetic molecular sieve (SRM-2) or molecular sieve of the present invention with Chinese patent CN 1485272A, above-mentioned molecular sieve as crystal seed, no matter whether the roasting removed template method, all be suitable for using as crystal seed in the synthetic method provided by the invention, the crystal seed add-on is 0.1～15m% of molecular sieve butt, preferred 0.5～14m%.
In synthetic 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 synthetic method provided by the invention, said crystallization condition can be to be warmed up to first 100-160 ℃, 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 lower roastings 1～30 hour.
Although can both synthesize the silicoaluminophosphamolecular molecular sieves of this novel texture under the Static and dynamic condition, preferred crystallization is dynamically to carry out under autogenous pressure, heats up and thermostatic crystallization under at agitation condition.This agitation condition removes the homogeneity of increase system in the general sense, comprises the efficient that increases heat transfer and mass transfer, and inhibition CHA phase, AFO are reached other stray crystal phase mutually obvious advantage.
Synthetic method provided by the invention, preferred raw material release sequence has following several:
At first phosphorus source and aluminium source are mixed with water, water once adds or repeatedly adds, and after stirring, adds template, titanium metal compound, silicon source and crystal seed with random order.
Aluminium source and water are mixed, after stirring, then add the solution of phosphoric acid and water, add titanium metal compound, template, silicon source and crystal seed with random order again.
Phosphorus source and aluminium source are mixed with part water, after stirring, add template, silicon source, titanium metal compound, crystal seed and remaining water with random order, remaining water can or repeatedly add in time adding of any step 1.
Silicon source, aluminium source and phosphorus source are mixed, after stirring, add template, titanium metal compound, crystal seed and water with random order, water can or repeatedly add in time adding of any step 1.
Aluminium source and phosphorus source part water are mixed, and titanium metal compound, organic solvent, deionized water hybrid reaction after stirring, add template, silicon source, crystal seed and water with random order, and water can or repeatedly add in time adding of any step 1.
Embodiment
The following examples will the invention will be further described, but content not thereby limiting the invention.
The X-ray powder diffraction of molecular sieve mensuration instrument is that Germany produces Bruker D5005 in each embodiment and the Comparative Examples, adopts the CuK alpha-ray; Molecular sieve forms uses x-ray fluorescence spectrometry.
Comparative Examples 1
The building-up process of SRM-2 structure molecular screen is carried out in the explanation of this Comparative Examples with the method for CN 1485272A.
With the 147.58 gram phosphoric acid (H that contain 85 % by 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 and backwardly wherein added 117.53 and restrain hydrated aluminum oxides and (be pseudo-boehmite, contain the Al of 69.4 % by weight in 30 minutes
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod), mix 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 % by weight
2, Beijing flying dragon equine trade company limited), the rear adding 11.79 gram SRM-2 molecular sieves that stir fully stirred 2 hours, made reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 185 ℃ and autogenous pressure, stirred crystallization 40 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the 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 °, lower with), the molecular sieve that its presentation of results synthesized 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, then in air, naturally cool to room temperature.X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.81P
2O
5: 0.56SiO
2
Comparative Examples 2
The building-up process of SAPO-34 molecular sieve is carried out in the explanation of this Comparative Examples with the method for ZL99126308.1.
With the 249.4 gram phosphoric acid (H that contain 88.5 % by weight
3PO
4) with 1025 gram deionized waters in mixes and stirs at the colloid generating kettle that places 25 ℃ of water-baths, stir and backwardly wherein added 204 and restrain hydrated aluminum oxides and (be pseudo-boehmite, contain the Al of 72 % by weight in 30 minutes
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod) and mix 2 hours.Then, 105.0 gram diethylamine (chemically pure reagent) and 57.2 gram triethylamines are joined in the above-mentioned colloid generating kettle, continue to mix 1 hour.At last, add the 194.1 gram silicon sol (SiO that contain 26 % by weight
2, Haiyang Chemical Plant, Qingdao's commerical prod) fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 180 ℃ and autogenous pressure, stirred crystallization 48 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the molecular screen primary powder product.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, 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, then in air, naturally cool to room temperature.X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.75P
2O
5: 0.52SiO
2
Embodiment 1
117.53 gram hydrated aluminum oxides and 368.21 gram deionized waters are joined the colloid generating kettle that places 60 ℃ of water-baths to be mixed and stirs and it was mixed in 30 minutes, after mixing 30 minutes in the 147.58 gram phosphoric acid adding colloid generating kettles, add the titanium tetrachloride solution (TiCl that contain 99.7 % by weight of 30.66 grams
4, Beijing Yili Fine Chemicals Co., Ltd.).Uniform stirring adds 96.13 gram silicon sol after 2 hours, stir after 1 hour, add 368.21 gram deionized water and stirring after 1 hour, the diethylamine that adds 118.21 grams, after continuing to mix 1 hour, colloid at room temperature static aging 20 hours joins 6.27 gram SRM-2 molecular screen primary powders in the above-mentioned colloid generating kettle, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 130 ℃ stirs constant temperature and rise to again 200 ℃ after 8 hours and under autogenous pressure, stirred crystallization 36 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the molecular screen primary powder product.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 3, the feature that it meets table 1 illustrates that it is SRM-7.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, then in air, naturally cool to room temperature.Get this crystallization product of part and make X-ray powder diffraction mensuration, result such as table 4.The mole that the skeleton mole of x-ray fluorescence spectrometry sample molecule sieve forms with anhydrous oxide consists of: Al
2O
3: 0.71P
2O
5: 0.56SiO
2: 0.19TiO
2
Table 3
Table 4
Embodiment 2
With 1121.49 gram silicon sol, 117.53 gram hydrated aluminum oxide and 293.56 gram deionized waters join the colloid generating kettle mixing that places 70 ℃ of water-baths and stirred 30 minutes, after stirring 2 hours in the 221.36 gram phosphoric acid adding colloid generating kettles, the titanium oxide (98% that adds 8.14 grams, Guanghua Science ﹠ Technology Co., Ltd., Shanghai) continues to stir 1 hour, 177.31 gram diethylamine are joined in the above-mentioned colloid generating kettle, stir after 10 minutes, the di-n-propylamine that adds 245.33 grams, continue to stir after 1 hour, colloid is lower static aging 15 hours at 40 ℃, add the molecular screen primary powder of 48.49 gram SRM-2, fully stirred 2 hours, make reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 185 ℃ under autogenous pressure, stirred crystallization 48 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the 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, illustrates that it is the SRM-7 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, then in air, naturally cool to room temperature.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: 0.38P
2O
5: 5.38SiO
2: 0.14TiO
2
Table 5
Table 6
Embodiment 3
First with 100 the gram deionized waters as in the beaker in 50 ℃ of water-baths, at the uniform velocity stir 30 minutes after, with 13.89 the gram tetra-n-butyl titanates and 11.09 the gram dehydrated alcohols mixed solutions slowly be added drop-wise to make in the water its hydrolysis, with the hydrolysis after product stand-by.Then the mixed solutions of 184.47 gram phosphoric acid and 298.74 gram deionized waters being joined the colloid generating kettle that places 50 ℃ of water-baths mixes and stirred 30 minutes, add 117.53 gram hydrated aluminum oxides, continue to stir after 2 hours, the hydrolysate of tetra-n-butyl titanate and alcohol mixeding liquid is added in the colloid generating kettle, continue to stir 1 hour, add 147.75 gram diethylamine, stir after 1 hour, add 160.22 gram silicon sol, fully stirred 2 hours, make reaction mixture, colloid descended static aging 5-80 hour at 5-90 ℃, added the molecular screen primary powder of 37.24 gram SRM-2.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 150 ℃ stirs constant temperature after 16 hours, rise to again 190 ℃ and under autogenous pressure, stirred crystallization 84 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the 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, illustrates that it is the SRM-7 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, then in air, naturally cool to room temperature.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: 0.70P
2O
5: 0.75SiO
2: 0.083TiO
2
Table 7
Table 8
Embodiment 4
117.53 gram hydrated aluminum oxides (are pseudo-boehmite, contain the Al of 69.4 % by weight
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod, lower with) and 353.35 gram deionized waters join the colloid generating kettle that places 25 ℃ of water-baths and mix and stir and stirred 30 minutes, restrain the phosphoric acid (H that contain 85 % by weight with 129.13
3PO
4, lower same) add in the colloid generating kettle, continue to stir 2 hours.Tetra-n-butyl titanate (the tetra-n-butyl titanate that contains 98.00 % by weight that adds 138.92 grams, Chemical Reagent Co., Ltd., Sinopharm Group, lower with) and 110.9 mixed solutions that restrain dehydrated alcohols, continue to stir 1 hour, after joining 88.65 gram diethylamine in the above-mentioned colloid generating kettle, stir after 1 hour, add the 32.04 gram silicon sol (SiO that contain 30 % by weight
2, Beijing flying dragon equine trade company limited), after stirring, colloid is 60 ℃ of lower wearing out 32 hours, and the molecular sieve of the SRM-2 after the adding 6.03 gram roastings fully stirred 2 hours, made reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 120 ℃ stirs constant temperature after 4 hours, rise to again 210 ℃ and under autogenous pressure, stirred crystallization 20 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the 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, illustrates that it is the SRM-7 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, then in air, naturally cool to room temperature.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: 0.0.87P
2O
5: 0.32SiO
2: 0.43TiO
2
Table 9
Table 10
Comparative Examples 3
117.53 gram hydrated aluminum oxides (are pseudo-boehmite, contain the Al of 69.4 % by weight
2O
3, Chang Ling petro-chemical corporation catalyst plant commerical prod, lower with) and 353.35 gram deionized waters join the colloid generating kettle that places 25 ℃ of water-baths and mix and stir and stirred 30 minutes, restrain the phosphoric acid (H that contain 85 % by weight with 129.13
3PO
4, lower same) add in the colloid generating kettle, continue to stir 2 hours.Tetra-n-butyl titanate (the tetra-n-butyl titanate that contains 98.00 % by weight that adds 138.92 grams, Chemical Reagent Co., Ltd., Sinopharm Group, lower with) and 110.9 mixed solutions that restrain dehydrated alcohols, continue to stir 1 hour, after joining 88.65 gram diethylamine in the above-mentioned colloid generating kettle, stir after 1 hour, add the 32.04 gram silicon sol (SiO that contain 30 % by weight
2, Beijing flying dragon equine trade company limited), after stirring, the molecular sieve of the SRM-2 after the adding 6.03 gram roastings fully stirred 2 hours, made reaction mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 185 ℃ stirred constant temperature 48 hours.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, namely get the 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 TAPSO-34 and a small amount of SRM-7.
Embodiment 5
Present embodiment illustrates the effect of molecular sieve provided by the invention in the standby reaction of alkene of Methanol.
The molecular screen primary powder that Comparative Examples 1 and embodiment 1-4 is synthetic is cooled to room temperature after 550 ℃ of roastings roasting in 4 hours, with a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyzer DB-1 and catalyst A-D.
Reaction evaluating carries out at 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 methyl alcohol, and sample size is 0.5 μ l.Reaction product is analyzed by on-line gas chromatography, and chromatographic condition is: hydrogen and nitrogen flow are 30mL/min, and air flow quantity is 300mL/min; 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 ℃, then at 150 ℃ of constant temperature 2min; Injector temperature is 150 ℃; The fid detector temperature is 180 ℃.
Reaction product is with C
2-C
4Alkene is target product.
Its reaction evaluating the results are shown in Table shown in 11.
Table 11
As seen from Table 11, compare with the SRM-2 molecular sieve catalyst, sample provided by the invention has higher ethene for catalysis MTO reaction and adds Propylene Selectivity.
Embodiment 6
Present embodiment illustrates the effect of molecular sieve provided by the invention in the reaction of preparation of bio-ethylene.
The molecular screen primary powder that Comparative Examples 2 is synthetic is cooled to room temperature after 550 ℃ of roastings roasting in 4 hours, with a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyzer DB-2.
Reaction evaluating carries out at 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 ethanol, and sample size is 0.5 μ l.Reaction product is analyzed by on-line gas chromatography, and chromatographic condition is: hydrogen and nitrogen flow are 30mL/min, and air flow quantity is 300mL/min; 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 ℃, then at 150 ℃ of constant temperature 2min; Injector temperature is 150 ℃; The fid detector temperature is 180 ℃.
Reaction product is with C
2Alkene is target product.
The result is as shown in table 12 for its reaction evaluating.
Table 12
It can be seen from the table, compare with the SAPO-34 molecular sieve catalyst, sample provided by the invention is used for catalysis ethanol Dehydration ethylene reaction and has higher selectivity.
Claims (30)
1. the titaniferous silicoaluminophosphamolecular molecular sieves 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; X-ray diffraction data behind the roasting removed template method contain the diffraction peak of table 2 at least; The anhydrous chemical formulation that mole forms with oxide form is Al
2O
3: yP
2O
5: zSiO
2: nMO
2, M is the metal titanium element, wherein the value of y is that the value of 0.01～1.5, 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 strong diffraction peak in the table, and M is 20～60%, S is that 60～80%, VS is 80～100%
Table 1
Table 2
, this titaniferous silicoaluminophosphamolecular molecular sieves is by feed ratio aR: Al under 5～100 ℃
2O
3: bP
2O
5: cSiO
2: dMO
2: eH
2O is mixed into glue with compound and the organic formwork agent of aluminium source, phosphorus source, silicon source, metal titanium, colloid 5-90 ℃ lower aging 5-80 hour, add the crystal seed in butt 0.1～15 % by weight, obtained in 4～500 hours at 100～250 ℃ of lower hydrothermal crystallizings; Wherein R is organic formwork agent, and the value of a is 0.1～10.0; The value of b is that the value of 0.1～2.5, c is that the value of 0.01～30.0, d is that the value of 0.001～1.0, e is 5～150, and crystal seed is selected from the molecular sieve itself of SRM-2 silicoaluminophosphamolecular molecular sieves or claim 1.
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 2, wherein the value of y is 0.15～1.2; The value of z is 0.05～10; The value of n is 0.003～0.6.
4. according to the molecular sieve of claim 1, the mole before its roasting removed template method is xR: Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2: nMO
2Wherein R is the template that is present in the molecular sieve crystal duct, the value of x be 0.01～8.0, y, z and n value such as claim 1 definition.
5. according to the molecular sieve of claim 4, the value of x is 0.02～7.0.
6. according to the molecular sieve of claim 5, the value of x is 0.05～6.0.
7. according to the molecular sieve of claim 1, wherein the condition of said roasting removed template method is 300～700 ℃ of lower roastings 1～30 hour.
8. according to the molecular sieve of claim 1, wherein said aluminium source is selected from pseudo-boehmite phase hydrated aluminum oxide, one or more mixture of aluminum isopropylate and aluminum phosphate, said silicon source is selected from silicon sol, active silica, the mixture of one or more in tetraethoxy and the solid silicone, said phosphorus source is selected from phosphoric acid, Hypophosporous Acid, 50, the mixture of one or more of phosphoric acid salt or Organophosphorous compounds, said organic formwork agent is diethylamine, the mixture of one or both in diethylamine and triethylamine or the di-n-propylamine, the compound of said metal titanium are the metal titanyl compound, inorganic salt compound and organic compound or any two or more mixtures in them.
9. according to the molecular sieve of claim 8, wherein said aluminium source is hydrated aluminum oxide or aluminum isopropylate, and said phosphorus source is phosphoric acid.
10. according to the molecular sieve of claim 8, the inorganic salt compound of titanium and its organic compound are one or more in titanium oxide, oxychlorination titanium, titanium tetrachloride, titanium sulfate, titanyl sulfate, butyl (tetra) titanate, metatitanic acid methyl esters, isopropyl titanate, the titanate.
11. according to the molecular sieve of claim 10, the compound of metal titanium is one or more in titanium oxide, chlorination oxygen titanium, titanium tetrachloride, titanium sulfate, titanyl sulfate, the butyl (tetra) titanate.
12. according to the molecular sieve of claim 8, the organic compound of said titanium independently be hydrolyzed or partial hydrolysis after join in the reaction mixture again, or directly add and be hydrolyzed in the reaction mixture or partial hydrolysis.
13. according to the molecular sieve of claim 12, the organic compound of titanium is first with carrying out the independence hydrolysis behind the organic solvent dissolution again or adding reaction mixture.
14. according to the molecular sieve of claim 13, organic solvent is alcohols.
15. according to the molecular sieve of claim 1, aging temperature is 10-70 ℃, digestion time is 10-50 hour.
16. the molecular sieve of claim 1, wherein said crystal seed add-on is 0.5～14 heavy %.
17. the molecular sieve of claim 1, wherein the temperature during said one-tenth glue is 10～90 ℃.
18. according to the molecular sieve of claim 1, wherein said crystallization temperature is 100～250 ℃, said crystallization time is 10～100 hours.
19. according to the molecular sieve of claim 18, crystallization condition is to be warmed up to first 100-160 ℃, constant temperature 0.5～20 hour is warmed up to 165～250 ℃ again and continued crystallization 3～200 hours.
20. according to the molecular sieve of claim 1, the value of a is 0.2～8.0.
21. according to the molecular sieve of claim 1, wherein the value of b is 0.5～2.0.
22. according to the molecular sieve of claim 1, wherein the value of c is 0.02～20.0.
23. according to the molecular sieve of claim 1, wherein the value of d is 0.002～0.8.
24. according to the molecular sieve of claim 1, wherein the value of e is 10～120.
25. according to the molecular sieve of claim 1, wherein, the mix-order of raw material replaces with at first phosphorus source and aluminium source are mixed with water, water once adds or repeatedly adds, and after stirring, adds template, titanium metal compound, silicon source and crystal seed with random order.
26. according to the molecular sieve of claim 1, wherein, the mix-order of raw material replaces with aluminium source and water is mixed, and after stirring, then adds the solution of phosphoric acid and water, adds titanium metal compound, template, silicon source and crystal seed with random order again.
27. the molecular sieve according to claim 1, wherein, the mix-order of raw material replaces with at first phosphorus source and aluminium source is mixed with part water, after stirring, add template, silicon source, titanium metal compound, crystal seed and remaining water with random order, remaining water is in time adding of any step 1 or repeatedly adding.
28. the molecular sieve according to claim 1, wherein, the mix-order of raw material replaces with at first silicon source, aluminium source and phosphorus source is mixed, after stirring, add template, titanium metal compound, crystal seed and water with random order, water is in time adding of any step 1 or repeatedly adding.
29. the molecular sieve according to claim 1, wherein, the mix-order of raw material replaces with at first aluminium source and phosphorus source part water is mixed, titanium metal compound, organic solvent, deionized water hybrid reaction, after stirring, add template, silicon source, crystal seed and water with random order, water is in time adding of any step 1 or repeatedly adding.
30. according to the molecular sieve of claim 1, said hydrothermal crystallizing wherein, its process is static under the autogenous pressure or dynamically carries out.
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| CN1195679C (en) * | 2002-09-28 | 2005-04-06 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
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| CN1195679C (en) * | 2002-09-28 | 2005-04-06 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
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