CN103285915B - A kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier - Google Patents
A kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier Download PDFInfo
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Abstract
The invention provides a kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier, comprise the following steps: step I, by organic formwork agent R, aluminium source, phosphorus source, silicon source and water mixing, obtaining mol ratio is R: Al
2o
3: P
2o
5: SiO
2: H
2o=0.05 ~ 1.5: the colloidal mixture of 1: 0.2 ~ 12: 0.1 ~ 1.5: 15 ~ 80, to be mol ratio be in wherein said phosphorus source 1 ~ 5: 1 phosphoric acid and phosphorous acid as mixing phosphorus source; Step II, the colloidal mixture crystallization obtain step I and post processing, obtain SAPO-11 molecular sieve carrier; With Step II I, the SAPO-11 molecular sieve carrier described in Step II be impregnated in palladium salting liquid, obtain described palladium catalyst.The catalyst prepared by the inventive method, when preparing isobutene for catalysis n-butene skeletal isomerization, can improve the conversion ratio of n-butene and the selective of isobutene.
Description
Technical field
The present invention relates to a kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier; The invention still further relates to this catalyst and prepare purposes in isobutene at n-butene skeletal isomerization.
Background technology
Isobutene is a kind of important Organic Chemicals, and can make full use of isobutene be C
4the key point of hydro carbons comprehensive utilization, it has become the focus of current petrochemical industry development.Isobutene is mainly used to produce the multiple Organic Chemicals such as methyl tertiary butyl ether(MTBE) (MTBE), the tert-butyl alcohol (TBA), butyl rubber, polyisobutene, methyl methacrylate.In recent years, because the demand of isobutene sharply increases, particularly being used for the demand of the friendly gasoline additive MTBE of production environment rapidly increases in the world, and the isobutene output that traditional oil Deep Catalytic Cracking process obtains far can not meet industrial requirement, therefore extensively carry out the research and development of isobutene production new technology both at home and abroad.Isomerization technique, especially n-butene skeletal isomerization preparing isobutene technology, solve linear alpha-olefin surplus preferably and need stimulation problems with isobutene, by Ge great petro-chemical corporation of the world is paid close attention to, become the method having the volume increase isomeric olefine of development potentiality at present most, the key realizing isomerization of butene is then the development of effective catalyst.
Silicon phosphate aluminium profiles (SAPO) molecular sieve is the novel non-zeolitic molecular sieves of a class of UCC company of U.S. report.SAPO-n replaces AlPO by Si atom
4formed after P or Al atom in-n skeleton by AlO
4, PO
4and SiO
4the non-neutral framework of molecular sieve that tetrahedron is formed, therefore has tradable cation, and has Bronsted acidity; The aperture of SAPO-n type molecular sieve is 0.3-0.8nm simultaneously, almost comprises whole pore diameter ranges of zeolite molecular sieve; The pore volume of SAPO-n type molecular sieve is 0.18-0.48cm
3/ g.As generation novel molecular sieve, SAPO-n type molecular sieve is in widespread attention in catalytic field.SAPO-11 molecular sieve, as a member in SAPO-n type molecular sieves, belongs to mesoporous molecular sieve, and have the oval duct of 10 rings of three-dimensional non-crossing, aperture is 0.39 × 0.64nm.It is reported, SAPO-11 molecular sieve is studied widely or is applied at present in the multiple refining and chemical industry industry such as catalytic cracking, hydrocracking, isomerization, isomerization dewaxing and light olefin polymerization.
CN1283668A discloses the preparation method of the molecular sieve carried catalyst of a kind of SAPO-11, phosphoric acid or aluminum phosphate is adopted to be phosphorus source, Ludox or solid silicone are silicon source, boehmite, aluminum phosphate, aluminium isopropoxide, hydrated alumina or aluminium hydroxide are aluminium source, di-n-propylamine, diisopropylamine or their mixture are organic formwork agent, by hydrothermal synthesis method synthesis SAPO-11 molecular sieve, then the compound of load P d or Pt or both mixtures obtain molecular sieve carried catalyst, and this catalyst is used for hydroisomerization reaction of alkane, experimental result shows that its isomerisation selectivity and isomerization product yield significantly improve.At document AppliedCatalysisA; General2004, in 259:227-234, SAPO-11 molecular sieve is used for n-butene skeletal isomerization by the people such as VilleNieminen, and investigated different silica sources and different generated time to the impact of SAPO-11 catalytic performance, result of study shows that SAPO-11 has good activity and selectivity.At document CatalysisToday2008, (133-135): in 120-128, the people such as CarmenM.L ó pez have carried out catalytic performance investigation to the SAPO-11 molecular sieve synthesized in the short time, and it is good selective that result shows that SAPO-11 molecular sieve shows olefin skeletal isomerization.
Summary of the invention
The invention provides a kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier, comprise the following steps, step I: by organic formwork agent R, aluminium source, phosphorus source, silicon source and water mixing, obtaining mol ratio is R: Al
2o
3: P
2o
5: SiO
2: H
2o=0.05 ~ 1.5: the colloidal mixture of 1: 0.2 ~ 1.2: 0.1 ~ 1.5: 15 ~ 80, wherein said phosphorus source is mol ratio is the phosphoric acid of 1 ~ 5: 1 and the mixing phosphorus source of phosphorous acid; Step II: the colloidal mixture crystallization obtain step I and post processing, obtain SAPO-11 molecular sieve carrier; With Step II I, the SAPO-11 molecular sieve carrier described in Step II be impregnated in palladium salting liquid, obtain described palladium catalyst.
Be carried in the preparation method of the palladium catalyst of SAPO-11 molecular sieve carrier of the present invention, by using mixing phosphorus source in carrier building-up process, the product cut size prepared is even, and defect is few, and orientation is good, and crystal is perfect, and degree of crystallinity is high, good product performance.Meanwhile, catalyst of the present invention, by supported precious metal palladium, makes this catalyst become the bifunctional catalyst with metal and acid site.
The aluminium source used in the inventive method, silicon source and organic formwork agent are conventional.As aluminium source, any aluminium source for the synthesis of SAPO-11 molecular sieve can be used.As the example in aluminium source, aluminium hydroxide, hydrated alumina (as boehmite), aluminium isopropoxide, aluminum nitrate, aluminum sulfate, aluminum phosphate or their any combination can be mentioned.As silicon source, any silicon source for the synthesis of SAPO-11 molecular sieve can be used.As the example in silicon source, White Carbon black, ethyl orthosilicate, solid silicone, Ludox or their any combination can be mentioned.As organic formwork agent, any organic formwork agent for the synthesis of SAPO-11 molecular sieve can be used.As the example of organic formwork agent, di-n-propyl amine, diisopropylamine, diethylamide or their any mixture can be mentioned, the mixture of such as di-n-propyl amine and diisopropylamine.In a preferred embodiment of the inventive method, phosphorus source used is the mixture of phosphoric acid and phosphorous acid, and aluminium source is boehmite or aluminium isopropoxide, and silicon source is Ludox or ethyl orthosilicate, and organic formwork agent is di-n-propyl amine or diethylamide.
In preferred colloidal mixture of the present invention, mol ratio is R: Al
2o
3: P
2o
5: SiO
2: H
2o=0.2 ~ 0.6: 1: 0.8 ~ 1.0: 0.5 ~ 0.7: 40 ~ 50.In addition, to be mol ratio be in phosphorus described in preferred steps I source 1 ~ 3: 1 phosphoric acid and phosphorous acid.
Crystallization in preferred described Step II is the hydrothermal crystallizing carried out in closed container, and hydrothermal crystallizing temperature is 100 ~ 200 DEG C, and crystallization time is 1 ~ 24 hour.More preferably described crystallization temperature is 180 ~ 200 DEG C, and pressure is self-generated pressure, and crystallization time is 2 ~ 24 hours.
In a specific embodiment of the present invention, post processing described in Step II comprises crystallization product washing, dry, shaping and roasting; Wherein washing methods is centrifuge washing or filtration washing, preferably uses centrifuge washing; Each baking temperature is 80 ~ 130 DEG C, preferred 110-130 DEG C; Drying time is 2 ~ 48 hours, preferred 2-24 hour; Be shaped to extruded moulding; Each sintering temperature is 500 ~ 600 DEG C, preferred 550-600 DEG C, and roasting time is 2 ~ 12 hours, preferred 3-10 hour, and this roasting can be carried out in Muffle furnace.After roasting, obtain SAPO-11 molecular sieve carrier.
The salting liquid of palladium described in preferred steps III is soluble palladium salt, and described palladium concentration of salt solution is 0.01 ~ 0.1mol/L.Described dipping is the container containing palladium salt and described molecular sieve is placed in shaking bath to place 1 ~ 24 hour, filters, washing, dry, then roasting obtains described catalyst in 2 ~ 24 hours.Preferably described soluble palladium salt is palladium bichloride and/or dichloro four ammonia palladium; Described bath temperature is 50 ~ 100 DEG C, and baking temperature is 80 ~ 120 DEG C, and sintering temperature is 300 ~ 900 DEG C, more preferably 500-600 DEG C.In preferred described catalyst, the load capacity of Pd is 0.1-5wt%.
The application in isobutene prepared by the present invention's also provide more than one to state catalyst prepared by method at positive isomerisation of olefin.The reaction temperature of preferred described positive isomerisation of olefin is 300 ~ 450 DEG C, and reaction pressure is normal pressure, and the air speed of raw material n-butene is 1.0 ~ 2.0h
-1.
Palladium catalyst prepared according to the methods of the invention has higher catalytic activity and selective when preparing isobutene for n-butene skeletal isomerization.Meanwhile, preparation method provided by the invention is easy, and cost is low, and suitability for industrialized is produced.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of SAPO-11 molecular sieve in embodiment 1;
Fig. 2 is the SEM figure of SAPO-11 molecular sieve in embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but scope of invention is not limited to these embodiments.
The microreactor used in following embodiment is tubular fixed-bed reactor, and its internal diameter is 9mm, and capacity is 25ml, and device pipeline all adopts stainless steel pipe, and catalyst loads in reactor flat-temperature zone with fixed bed form, two ends filling quartz sand.
Embodiment 1
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; And then take 5.74g (0.07mol) H
3pO
3be dissolved in 10g water and form phosphorous acid aqueous solution, this phosphorous acid solution is poured in the gained boehmite aqueous solution, then instills 8.07g (0.07mol) H with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; In described mixing phosphorus source, the mol ratio of phosphoric acid and phosphorous acid is 1: 1; Measuring 4.78ml (0.035mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.5R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B: the colloidal mixture prepared in steps A is warming up under air-tight state 180 DEG C of hydrothermal crystallizing 3h at autogenous pressures;
C: step B products therefrom is leached, cooling, centrifuge washing, then in 120 DEG C of dry 12h;
D: the product of the drying obtained in step C is placed in Muffle furnace in 550 DEG C of roasting 4h, obtains SAPO-11 molecular sieve;
E: step D gained SAPO-11 molecular sieve is mixed with adhesive, extruded moulding, in 120 DEG C of dry 8h, in 550 DEG C of roasting 5h with pulverize and sieve, obtains 20-40 molecules of interest sieve carrier;
F: the palladium chloride aqueous solution of preparation 0.01mol/L, is placed in prepared solution (20ml) by step e gained carrier, places 12 hours in the shaking bath of 100 DEG C, filter, the solid obtained is spent deionized water, dry at 120 DEG C, obtain loaded catalyst.
G: get the catalyst that 2.0g step F obtains and put into microreactor, (should refer to " after ether, mixing carbon four unstrpped gas " with mixing carbon four unstrpped gas after ether and take out the residue after methyl tertiary butyl ether(MTBE) in the reactant mixture that isobutene and methyl alcohol Reactive Synthesis methyl tertiary butyl ether(MTBE) obtain and mix C-4-fraction, main component is n-butene and iso-butane, and its content is respectively 25 volume % and 35 volume %) evaluate; Reaction temperature is 340 DEG C, and n-butene air speed is 1.0h
-1, the n-butene conversion of acquisition is 45%, and selective isobutene is 96%.
The X-ray powder diffraction figure of step D products therefrom as shown in Figure 1.As can be seen from this figure, be that the characteristic peak of SAPO-11 has all appearred in the places such as 8.15 °, 9.40 °, 13.20 ° and 15.57 ° at 2 θ, illustrate that embodiment 1 step D products therefrom is SAPO-11 molecular sieve.Simultaneously obtained sample particle diameter is even, and crystal is perfect, and degree of crystallinity is high, and its SEM figure is shown in Fig. 2.
Comparative example 1
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; Then 16.14g (0.14mol) H is instilled with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; Measuring 4.78m (0.035mol) l di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.5R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B ~ G: step B, C, D, E, F and G are with embodiment 1.
Result n-butene conversion is 42%, and selective isobutene is 90%.
Embodiment 2
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; And then take 3.82g (0.046mol) H
3pO
3be dissolved in 10g water and form phosphorous acid aqueous solution, this phosphorous acid aqueous solution is poured in the gained boehmite aqueous solution, then instills 10.76g (0.093mol) H with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; In described mixing phosphorus source, the mol ratio of phosphoric acid and phosphorous acid is 2: 1; Measuring 2.86ml (0.021mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.3R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B: the colloidal mixture prepared in steps A is warming up under air-tight state 200 DEG C of hydrothermal crystallizing 2h at autogenous pressures;
C: step B products therefrom is leached, cooling, centrifuge washing, then in 110 DEG C of dry 12h;
D: the product of the drying obtained in step C is placed in Muffle furnace in 550 DEG C of roasting 8h, obtains SAPO-11 molecular sieve, its X-ray powder diffraction figure and Fig. 1 is substantially identical, SEM figure is also basically identical with Fig. 2;
E: with the step e of embodiment 1;
F: the palladium chloride aqueous solution of preparation 0.05mol/L, is placed in prepared solution (20ml) by step e gained carrier, places 12 hours in the shaking bath of 100 DEG C, filter, the solid obtained is spent deionized water, dry at 120 DEG C, obtain loaded catalyst.
G: substantially identical with the step G of embodiment 1, difference is: reaction temperature is 380 DEG C, and the n-butene conversion of acquisition is 47%, and selective isobutene is 98%.
Comparative example 2
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; Then 16.14g (0.14mol) H is instilled with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; Measuring 2.86ml (0.021mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.3R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B ~ G: step B, C, D, E, F and G are with embodiment 2.
Result n-butene conversion is 44%, and selective isobutene is 92%.V embodiment 3
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; And then take 2.87g (0.035mol) H
3pO
3be dissolved in 10g water and form phosphorous acid aqueous solution, this phosphorous acid aqueous solution is poured in the gained boehmite aqueous solution, then instills 12.10g (0.105mol) H with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; In described mixing phosphorus source, the mol ratio of phosphoric acid and phosphorous acid is 3: 1; Measuring 1.91ml (0.014mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.2R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B: the colloidal mixture prepared in steps A is warming up under air-tight state 190 DEG C of hydrothermal crystallizing 6h at autogenous pressures;
C: step B products therefrom is leached, cooling, centrifuge washing, then in 130 DEG C of dry 12h;
D: the product of the drying obtained in step C is placed in Muffle furnace in 550 DEG C of roasting 10h, obtains SAPO-11 molecular sieve, its X-ray powder diffraction figure and Fig. 1 is substantially identical, SEM figure is also basically identical with Fig. 2;
E: with the step e of embodiment 1;
F: the palladium chloride aqueous solution of preparation 0.1mol/L, is placed in prepared solution (20ml) by step e gained carrier, places 12 hours in the shaking bath of 100 DEG C, filter, the solid obtained is spent deionized water, dry at 120 DEG C, obtain loaded catalyst.
G: substantially identical with the step G of embodiment 1, difference is: reaction temperature is 400 DEG C, and n-butene air speed is 1.5h
-1, the n-butene conversion of acquisition is 50%, and selective isobutene is 98%.
Comparative example 3
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; Then 16.14gH is instilled wherein with vigorous stirring
3pO
4(0.14mol) (85 % by weight aqueous solution), then stir 1h; Measuring 1.91ml (0.014mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.2R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B ~ G: step B, C, D, E, F and G are with embodiment 3.
Result n-butene conversion is 45%, and selective isobutene is 95%.
Embodiment 4
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; And then take 1.88g (0.023mol) H
3pO
3be dissolved in 10g water and form phosphorous acid aqueous solution, this phosphorous acid aqueous solution is poured in the gained boehmite aqueous solution, then instills 13.49g (0.117mol) H with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; In described mixing phosphorus source, the mol ratio of phosphoric acid and phosphorous acid is 5: 1; Measuring 2.86ml (0.021mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.3R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B: the colloidal mixture prepared in steps A is warming up under air-tight state 200 DEG C of hydrothermal crystallizing 2h at autogenous pressures;
C: step B products therefrom is leached, cooling, centrifuge washing, then in 110 DEG C of dry 12h;
D: the product of the drying obtained in step C is placed in Muffle furnace in 550 DEG C of roasting 8h, obtains SAPO-11 molecular sieve, its X-ray powder diffraction figure and Fig. 1 is substantially identical, SEM figure is also basically identical with Fig. 2;
E: with the step e of embodiment 1;
F: the palladium chloride aqueous solution of preparation 0.05mol/L, is placed in prepared solution (20ml) by step e gained carrier, places 12 hours in the shaking bath of 100 DEG C, filter, the solid obtained is spent deionized water, dry at 120 DEG C, obtain loaded catalyst.
G: substantially identical with the step G of embodiment 1, difference is: reaction temperature is 380 DEG C, and the n-butene conversion of acquisition is 46%, and selective isobutene is 96%.
Comparative example 4
A: take 9.52g (0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stirs 0.5h; Then 16.14g (0.14mol) H is instilled with vigorous stirring wherein
3pO
4(85 % by weight aqueous solution), then stir 1h; Measuring 2.86ml (0.021mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h; Then taking 10.08g (0.042mol) Ludox again joins in above-mentioned solution; Add water, stir 1h, obtain colloidal mixture, its mole consists of 0.3R: Al
2o
3: P
2o
5: 0.6SiO
2: 50H
2o, wherein R is di-n-propyl amine;
B ~ G: step B, C, D, E, F and G are with embodiment 4.
Result n-butene conversion is 44%, and selective isobutene is 92%.
From above-described embodiment result, the molecular sieve carried palladium catalyst of SAPO-11 prepared in accordance with the present invention carries out the evaluation of n-butene isomerization reaction by fixed-bed micro-devices, and reaction-ure conversion-age is 45-50%, and selectivity of product is at 96-98%; In each embodiment, conversion ratio and selective data are all apparently higher than corresponding comparative example.
Claims (9)
1. the application in isobutene prepared by palladium catalyst in n-butene isomerization, and described palladium catalyst is the palladium catalyst being carried on SAPO-11 molecular sieve carrier, and its preparation method comprises the following steps:
Step I, by organic formwork agent R, aluminium source, phosphorus source, silicon source and water mixing, obtaining mol ratio is R:Al
2o
3: P
2o
5: SiO
2: H
2the colloidal mixture of O=0.05 ~ 1.5:1:0.2 ~ 1.2:0.1 ~ 1.5:15 ~ 80, wherein said phosphorus source is mol ratio is the phosphoric acid of 1 ~ 5:1 and the mixing phosphorus source of phosphorous acid;
Step II, the colloidal mixture crystallization that step I is obtained and post processing, obtain SAPO-11 molecular sieve carrier, wherein said crystallization is the hydrothermal crystallizing carried out in closed container, and hydrothermal crystallizing temperature is 100 ~ 200 DEG C, and crystallization time is 1 ~ 24 hour;
Step III, SAPO-11 molecular sieve carrier described in step II be impregnated in palladium salting liquid, obtain described palladium catalyst, wherein palladium concentration of salt solution is 0.01 ~ 0.1mol/L, described dipping is the container containing palladium salt and described molecular sieve is placed in shaking bath to place 1 ~ 24 hour, filters, washing, drying, then roasting obtains described catalyst in 2 ~ 24 hours; Wherein bath temperature is 50 ~ 100 DEG C, and baking temperature is 80 ~ 120 DEG C, and sintering temperature is 300 ~ 900 DEG C.
2. application according to claim 1, is characterized in that: the aluminium source in described step I is hydrated alumina, aluminium isopropoxide, aluminum nitrate, aluminum sulfate, aluminum phosphate or their any combination; Silicon source is White Carbon black, ethyl orthosilicate, solid silicone, Ludox or their any combination; Organic formwork agent is di-n-propyl amine, diisopropylamine, diethylamide or their any mixture.
3. application according to claim 2, is characterized in that: the aluminium source in described step I is aluminium hydroxide.
4. application according to claim 1, is characterized in that: in described colloidal mixture, mol ratio is R:Al
2o
3: P
2o
5: SiO
2: H
2o=0.2 ~ 0.6:1:0.8 ~ 1.0:0.5 ~ 0.7:40 ~ 50.
5. application as claimed in any of claims 1 to 4, is characterized in that: phosphoric acid and the phosphorous acid of to be mol ratio be in phosphorus described in step I source 1 ~ 3:1.
6. application according to claim 1, is characterized in that: last handling process described in step II comprises crystallization product washing, dry, shaping and roasting; Wherein washing methods is centrifuge washing or filtration washing; Each baking temperature is 80 ~ 130 DEG C, and drying time is 2 ~ 48 hours; Be shaped to extruded moulding; Each sintering temperature is 500 ~ 600 DEG C, and roasting time is 2 ~ 12 hours.
7. application according to claim 6, is characterized in that: described palladium salt is soluble palladium salt.
8. application according to claim 7, is characterized in that: described soluble palladium salt is palladium bichloride and/or dichloro four ammonia palladium.
9. application according to claim 1, is characterized in that: the reaction temperature that isobutene is prepared in described n-butene isomerization is 300 ~ 450 DEG C, and reaction pressure is normal pressure, and the air speed of raw material n-butene is 1.0 ~ 2.0h
-1.
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| CN1380251A (en) * | 2002-05-30 | 2002-11-20 | 复旦大学 | SAPO-11 molecular sieve catalyst and its preparation method |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
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| CN1283668A (en) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | Catalyst for hydroisomerizing paraffin |
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1380251A (en) * | 2002-05-30 | 2002-11-20 | 复旦大学 | SAPO-11 molecular sieve catalyst and its preparation method |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
Non-Patent Citations (1)
| Title |
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| "A one-step route to SAPO-46 using H3PO3-containing gel and its application as the catalyst for methanol dehydration";Wenbo Kong et al.;《Journal of Molecular Catalysis A: Chemical》;20090405;第308卷(第1-2期);第128页第2.2.2节、表1 * |
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