CN102029181B - Metal silicon aluminum phosphate molecular sieve-containing catalyst and application thereof - Google Patents
Metal silicon aluminum phosphate molecular sieve-containing catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a metal silicon aluminum phosphate molecular sieve-containing catalyst, which comprises 5 to 100 percent of metal silicon aluminum phosphate molecular sieve and 0 to 95 percent of binder, and is characterized in that: in the metal silicon aluminum phosphate molecular sieve, X-ray diffraction data before a template agent is roasted to be removed at least comprises a diffraction peak shown in a table 1; the X-ray diffraction data after the template agent is roasted to be removed at least comprises a diffraction peak shown in a table 2; the molar compositions are represented by an anhydrous chemical formula in an oxide form, namely Al2O3:yP2O5:zSiO2:nMOm, wherein M is a metal titanium element. The catalyst can be used for an oxygen-containing organic compound conversion reaction.
Description
Technical field
The invention relates to a kind of catalyst that contains silicoaluminophosphamolecular molecular sieves and this catalyst thereof oxygenatedchemicals transform application.
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 electroneutral, 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 new structure 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 centre, 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 catalyst, 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 obtained fast development, molecular sieve and the synthetic method of new structure constantly invent.
Chinese patent CN1485272A announces a kind of silicoaluminophosphamolecular molecular sieves (SRM-2) with new structure, and the XRD data before its roasting removed template method contain diffraction maximum as shown in table 1 at least: the X-ray diffraction data behind the roasting removed template method contain the diffraction maximum shown in the table 2 at least.It is characterized in that: the X-ray diffraction data before the roasting removed template method contain the diffraction maximum shown in the table 1 at least, and the X-ray diffraction data behind the roasting removed template method contain the diffraction maximum of table 2 at least; Its mole composition is Al with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2: nTiO
2, wherein the value of y is that the value of 0.01～1.5, z is that the value of 0.01～30, n is 0.001～1.0;
Table 1
*W 0～20％，M 20～60％，S 60～80％，VS 80～100％。
Table 2
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of catalyst that contains special metal silicon aluminum phosphate molecular sieve is provided, and provide this catalyst to be used for the catalytic conversion reaction process of oxygenatedchemicals.
Therefore, the catalyst that contains metal silicon aluminum phosphate molecular sieve provided by the invention, contain the metal silicon aluminum phosphate molecular sieve of 5-100% and the binding agent of 0-95%, it is characterized in that wherein said metal silicon aluminum phosphate molecular sieve, the X-ray diffraction data before the roasting removed template method contain the diffraction maximum shown in the table 3 at least; X-ray diffraction data behind the roasting removed template method contain the diffraction maximum of table 4 at least; The anhydrous chemical formulation that mole forms with oxide form is Al
2O
3: yP
2O
5: zSiO
2: nMOm, M are the Titanium element, and 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 maximum in the table, M is that 20～60%, S is that 60～80%, VS is 80～100%.
Table 3
Table 4
In the catalyst provided by the invention, said metal silicon aluminum phosphate molecular sieve (brief note is SRM-7), before the roasting removed template method, 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.
The SRM-7 molecular sieve is by rate of charge aR: Al under 5～100 ℃
2O
3: bP
2O
5: cSiO
2: dMOm: eH
2O is mixed into glue with compound and the organic formwork agent of aluminium source, phosphorus source, silicon source, 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 SRM-2 silicoaluminophosphamolecular molecular sieves or this molecular sieve itself.Inventor's discovery, 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 the synthetic method of above-mentioned molecular sieve, to contain but a kind of or any several mixture that is not limited to following phosphorus-containing compound such as phosphoric acid, hypophosphorous acid, phosphate and organic phosphorus compound is phosphorus source, wherein preferably phosphoric acid; Take a kind of or any several mixture of hydrated alumina (boehmite phase), aluminium isopropoxide or aluminum phosphate as the aluminium source, preferred hydrated alumina (boehmite phase) and aluminium isopropoxide; Titanium oxide, 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 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 titanate etc.; Wherein organo titanium compounds can with organic solvent dissolution after add again reactant mixture or carry out independent hydrolysis water hydrolysis products, the preferred alcohol organic solvent of this organic solvent.Take a kind of or any several mixture of Ludox, active silica, ethyl orthosilicate or solid silicone as the silicon source, the mixture of one or both in diethylamine, diethylamine and triethylamine and the di-n-propylamine is as template.Above-mentioned raw materials is pressed rate of charge aR: Al
2O
3: bP
2O
5: cSiO
2: dMOm: eH
2O is mixed into glue, and hydrothermal crystallizing also reclaims product, and wherein a is the molal quantity of template, and its value is 0.01～10.0, and is preferred 0.2～8.0, and 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.
In the synthetic method of described SRM-7 molecular sieve, also can add before the roasting removed template method or the SRM-2 molecular sieve behind the removed template method as crystal seed.The crystal seed addition is 0.1～15m% of molecular sieve butt, preferred 0.5～14m%.
Wherein, can be with reference to disclosed content among the CN1485272A as the SRM-2 molecular sieve of crystal seed.No matter whether the roasting removed template method, all is suitable for using as crystal seed in the synthetic method provided by the invention, and the crystal seed addition 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 new structure under the Static and dynamic condition, preferred crystallization is dynamically to carry out under self-generated pressure, heats up and thermostatic crystallization under at stirring condition.This stirring condition removes the uniformity 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.
Catalyst provided by the invention, wherein said binder content is 0-95 % by weight, preferred 20-80 % by weight.Said inorganic oxide can include but not limited to following kind: aluminium oxide, silica, aluminium oxide-silicon oxide, alumina silicate, magnesia, cupric oxide, iron oxide, titanium oxide, zirconia, nickel oxide, zinc oxide, cobalt oxide, rare earth oxide etc. or several mixture in them, preferential oxidation aluminium and silica.
The preparation process of catalyst provided by the invention is to carry out according to conventional method: then precursor and the kneading and compactings such as acid, deionized water and extrusion aid with SRM-7 silicoaluminophosphamolecular molecular sieves and inorganic oxide or inorganic oxide obtain the said catalyst of the present invention through super-dry, roasting.Preparation process also can add extrusion aid, is selected from sesbania powder, starch carboxymethyl cellulose etc.
In the catalyst provided by the invention, said SRM-7 silicoaluminophosphamolecular molecular sieves, can be before catalyst extruded forming the roasting removed template method, also can be at roasting removed template method after the extruded moulding, but no matter before extruded moulding or after roasting, molecular sieve can both keep stable crystal structure; The condition of said roasting removed template method is the condition that generally adopts in the prior art, and this condition is preferably 300～800 ℃ of lower constant temperature 1～20 hour, preferably 500～650 ℃ of lower roastings 2～10 hours.
Catalyst provided by the present invention can be used as the conversion process that catalyst is used for oxygenatedchemicals, for example, alcohol, ether, ketone, aldehyde etc. transform the reaction of alkene processed, the methanol conversion reaction of preparing dimethyl ether, in the conversion process of the light alkene of cracking hydrocarbon system, reaction raw materials can contain one or more in the hydro carbons.Used reaction condition is as follows: reaction temperature is 150 ℃-800 ℃, and preferable reaction temperature is 200 ℃-600 ℃.Used reaction pressure is the 0.1-1000 atmospheric pressure.Preferred 0.1-100 atmospheric pressure.Used air speed (WHSV) is 0.01-100h
-1, preferred air speed (WHSV) is 0.1-40h
-1
The conversion process of said oxygenatedchemicals can be carried out under the condition that steam or inert gas exist, and can be gas-phase reaction, also liquid phase reactor.
When this catalyst is used for the reaction for preparing light olefins from methanol process, compare with the SRM-2 molecular sieve catalyst, have higher selectivity of light olefin; In the producing ethylene from dehydration of ethanol course of reaction, with the SAPO-34 molecular sieve catalyst relatively, in the producing ethylene from dehydration of ethanol technology, show higher selective.
The specific embodiment
The following examples illustrate the present invention further, 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
Carry out the synthetic of SRM-2 structure molecular screen with the method for Chinese patent 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 aluminas and (be boehmite, contain the Al of 69.4 % by weight in 30 minutes
2O
3, Chang Ling petro-chemical corporation catalyst plant commercial product), 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 Ludox (SiO that contain 30 % by weight
2, Beijing flying dragon equine trade Co., Ltd), the rear adding 11.79 gram SRM-2 molecular sieves that stir fully stirred 2 hours, made reactant mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 185 ℃ and self-generated 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 limits 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 roaster, 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: 0.78P
2O
5: 0.56SiO
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, then in air, naturally cool to room temperature.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 2 data.
With said molecular screen primary powder obtained above and hydrated alumina (the same) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of aluminium oxide=70: 30 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as D-1.
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 % 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 aluminas and (be boehmite, contain the Al of 72 % by weight in 30 minutes
2O
3, Chang Ling petro-chemical corporation catalyst plant commercial product) 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 Ludox (SiO that contain 26 % by weight
2, Haiyang Chemical Plant, Qingdao's commercial product) fully stirred 2 hours, make reactant mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, under 180 ℃ and self-generated 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.X-ray fluorescence spectrometry framework of molecular sieve mole consists of: Al
2O
3: 0.75P
2O
5: 0.52SiO
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 with the heating rate of 2 ℃ of per minutes, then in air, naturally cool to room temperature.Sample after the roasting is measured through the X-ray powder diffraction, and the molecular sieve that its presentation of results synthesized is the SAPO-34 molecular sieve.
With said molecular screen primary powder obtained above and hydrated alumina (the same) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of aluminium oxide=70: 30 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as D-2.
Comparative Examples 3
117.53 gram hydrated aluminas (are boehmite, contain the Al of 69.4 % by weight
2O
3, Chang Ling petro-chemical corporation catalyst plant commercial product, 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 liquors that restrain absolute ethyl 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 Ludox (SiO that contain 30 % by weight
2, Beijing flying dragon equine trade Co., Ltd), after stirring, the molecular sieve of the SRM-2 after the adding 6.03 gram roastings fully stirred 2 hours, made reactant 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.
With said molecular screen primary powder obtained above and hydrated alumina (the same) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of aluminium oxide=70: 30 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as D-3.
Embodiment 1
117.53 gram hydrated aluminas and 381.5 gram deionized waters are joined the colloid generating kettle that places 60 ℃ of water-baths mixes 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 Ludox after 2 hours, stir after 1 hour, add the deionized water and stirring of 357.5 grams after 1 hour, the diethylamine that adds 118.21 grams, after continuing to mix 1 hour, 12.27 gram SRM-2 molecular screen primary powders are joined in the above-mentioned colloid generating kettle, fully stirred 2 hours, make reactant 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 self-generated 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 the above-mentioned molecular screen primary powder of part, in roaster, 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 5, the feature that it meets table 3 illustrates that it is SRM-7.
Get the above-mentioned molecular screen primary powder of part, in roaster, 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.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 5
Table 6
With said molecular screen primary powder obtained above and hydrated alumina (the same) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of aluminium oxide=70: 30 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as S1.
Embodiment 2
117.53 gram hydrated aluminas and 293.56 gram deionized waters are joined the colloid generating kettle that places 70 ℃ of water-baths mixes and stirred 30 minutes, after stirring 2 hours in the 231.36 gram phosphoric acid adding colloid generating kettles, add 1121.49 gram Ludox, continue to stir 1 hour, 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 continued to stir after 1 hour, added the molecular screen primary powder of 48.49 gram SRM-2, fully stirred 2 hours, make reactant mixture.The partial reaction mixture is encapsulated into the stainless steel crystallizing kettle, temperature is raised to 185 ℃ under self-generated 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 7, it meets table 3, illustrates that it is the SRM-7 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in roaster, 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: 0.38P
2O
5: 5.38SiO
2: 0.14TiO
2
Table 7
Table 8
With the molecular sieve after the roasting obtained above and hydrated alumina (the same) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of aluminium oxide=50: 50 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as S2.
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 absolute ethyl alcohols mixed liquors slowly be added drop-wise to make in the water its hydrolysis, with the hydrolysis after product stand-by.Then the mixed liquors of 184.47 gram phosphoric acid and 305.86 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 aluminas, continue to stir after 2 hours, the molecular screen primary powder that adds 43.48 gram SRM-2, continue to stir 1 hour, 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 Ludox, fully stirred 2 hours, make reactant mixture.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 self-generated 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 9, it meets table 3, illustrates that it is the SRM-7 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in roaster, 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: 0.70P
2O
5: 0.75SiO
2: 0.083TiO
2
Table 9
Table 10
With molecular screen primary powder obtained above and Ludox (25%) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of silica=40: 60 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as S3.
Embodiment 4
117.53 gram hydrated aluminas (are boehmite, contain the Al of 69.4 % by weight
2O
3, Chang Ling petro-chemical corporation catalyst plant commercial product, 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 129.49
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 liquors that restrain absolute ethyl 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 32.01 gram Ludox (SiO that contain 30 % by weight
2, Beijing flying dragon equine trade Co., Ltd), stirred 1 hour, add the molecular screen primary powder of 6.03 gram SRM-2, fully stirred 2 hours, make reactant 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 self-generated 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 11, it meets table 3, illustrates that it is the SRM-7 of indication of the present invention.
Get the above-mentioned molecular screen primary powder of part, in roaster, 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 12; 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 11
Table 12
With molecular screen primary powder obtained above and Ludox (25%) according to molecular sieve: extruded moulding was the Cylinder of 1.50mm after the butt weight ratio of silica=60: 40 was mixed.Through 120 ℃ of oven dry 6 hours, in roaster, be warming up to again 550 ℃ and constant temperature calcining 6 hours.With a part of compressing tablet, smash, sieve out the particle of 20-40 order granularity as catalyst, be designated as S4.
Embodiment 5
The present embodiment illustrates the effect of catalyst provided by the invention in the standby reaction of alkene of Methanol.
Reaction evaluating carries out at the pulse micro-inverse device.Its test parameters is: reaction temperature is 500 ℃, and pressure is normal pressure.The catalyst loading amount is 100mg; Reactant is methyl alcohol, and sample size is 0.5 μ l, and product is analyzed by on-line gas chromatography.Chromatographic condition is: hydrogen and nitrogen flow are 30mL/min, air mass flow is 300mL/min, 40 ℃ of chromatographic column initial temperatures, behind 40 ℃ of constant temperature 1min, with the programming rate temperature programming to 150 of 10 ℃/min ℃, then at 150 ℃ of constant temperature 2min, injector temperature is 150 ℃, and the fid detector temperature is 180 ℃.
Product is with C
2-C
4Alkene is target product.
The result is as shown in table 13 for its reaction evaluating.
Table 13
Compare with the catalyst that contains the SRM-2 molecular sieve (D-1), catalyst provided by the invention is used for catalysis MTO reaction and has higher selectivity of light olefin.
Embodiment 6
The present embodiment illustrates the effect of catalyst provided by the invention in the reaction of preparation of bio-ethylene.
Reaction evaluating carries out at the pulse micro-inverse device.Its test parameters is: reaction temperature is 350 ℃, and pressure is normal pressure.The catalyst loading amount is 100mg; Reactant is ethanol, and sample size is 0.5 μ l, and product is analyzed by on-line gas chromatography.Chromatographic condition is: hydrogen and nitrogen flow are 30mL/min, and air mass flow is 300mL/min; 40 ℃ of chromatographic column initial temperatures, behind 40 ℃ of constant temperature 1min, with the programming 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 ℃.
Product is with C
2Alkene is target product.
The result is as shown in table 14 for its reaction evaluating.
Table 14
| Catalyst | Ethanol conversion (%) | Ethylene selectivity (%) |
| D-2 | 100 | 98.65 |
| S1 | 100 | 99.82 |
| S2 | 100 | 99.91 |
| S3 | 100 | 99.88 |
| S4 | 100 | 99.89 |
With the catalyst that contains the SAPO-34 molecular sieve (D-2) relatively, catalyst provided by the invention is used for catalysis ethanol Dehydration ethylene reaction and has higher selective.
Claims (7)
1. catalyst that contains metal silicon aluminum phosphate molecular sieve, contain the metal silicon aluminum phosphate molecular sieve of 5-100% and the binding agent of 0-95%, it is characterized in that wherein said metal silicon aluminum phosphate molecular sieve, the X-ray diffraction data before the roasting removed template method contain the diffraction maximum shown in the Table A at least; X-ray diffraction data behind the roasting removed template method contain the diffraction maximum of showing B 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 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 maximum in the table, and M is 20～60%, S is that 60～80%, VS is 80～100%
Table A
Table B
2. according to the catalyst of claim 1, wherein the content of said metal silicon aluminum phosphate molecular sieve is 20-80%.
3. according to the catalyst of claim 1, wherein said binding agent is selected from one of aluminium oxide, silica, alumina silica, alumina silicate, magnesia, cupric oxide, iron oxide, titanium oxide, zirconia, nickel oxide, zinc oxide, cobalt oxide, rare earth oxide or several mixture in them.
4. according to the catalyst of claim 1, wherein said binding agent is selected from aluminium oxide, silica.
5. the method for transformation of an oxygen-containing organic compound is characterized in that adopting in the method the catalyst of one of claim 1-4.
6. according to the method for claim 5, wherein the conversion process of said oxygenatedchemicals is carried out under the condition of steam or inert gas existence.
7. according to the method for claim 5, the conversion process of said oxygenatedchemicals is gas-phase reaction or liquid phase reactor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103117A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1301597A (en) * | 1999-12-29 | 2001-07-04 | 中国科学院大连化学物理研究所 | MeAPSO-44 molecular sieve and its synthesizing method |
| 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 |
| CN1704390A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Method for preparing olefin by conversion of methanol |
-
2009
- 2009-09-29 CN CN 200910177436 patent/CN102029181B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103117A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1301597A (en) * | 1999-12-29 | 2001-07-04 | 中国科学院大连化学物理研究所 | MeAPSO-44 molecular sieve and its synthesizing method |
| 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 |
| CN1704390A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Method for preparing olefin by conversion of methanol |
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