CN103285915A - Preparation method of palladium catalyst loaded on silicoaluminophosphate (SAPO)-11 molecular sieve carrier - Google Patents
Preparation method of palladium catalyst loaded on silicoaluminophosphate (SAPO)-11 molecular sieve carrier Download PDFInfo
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Abstract
The invention provides a preparation method of a palladium catalyst loaded on a silicoaluminophosphate (SAPO)-11 molecular sieve carrier. The method comprises the following steps of: I, mixing an organic template agent R, an aluminum source, a phosphorus source, a silicon source and water to obtain a colloidal mixture with the molar ratio of R:Al2O3:P2O5:SiO2:H2O being (0.05-1.5):1:(0.2-12):(0.1-1.5):(15-80), wherein the phosphorus source is a mixed phosphorus source of phosphoric acid and phosphorous acid in a molar ratio of (1-5):1; II, performing crystallization and aftertreatment on the colloidal mixture obtained in the step I to obtain the SAPO-11 molecular sieve carrier; and III, dipping the SAPO-11 molecular sieve carrier obtained in the step II into a palladium salt solution to obtain the palladium catalyst. When the catalyst prepared by the method is used for catalyzing isomerization of an n-butene framework to prepare isobutene, the conversion ratio of the n-butene can be increased and the selectivity of the isobutene can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of palladium catalyst of the SAPO-11 of being carried on molecular sieve carrier; The invention still further relates to this catalyst and prepare purposes in the isobutene at the n-butene skeletal isomerization.
Background technology
Isobutene is a kind of important Organic Chemicals, and can take full advantage 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 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 be used for the demand rapid growth in the world of the friendly gasoline additive MTBE of production environment, and the isobutene output that traditional oil Deep Catalytic Cracking process obtains far can not satisfy industrial requirement, has therefore extensively carried 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 the linear alpha-olefin surplus preferably and need increase production problem with isobutene, by each big petro-chemical corporation of the world is paid close attention to, become the method that the volume increase isomeric olefine of development potentiality is arranged at present most, realize that the key of isomerization of butene then is the development of effective catalyst.
SAPO type (SAPO) molecular sieve is the novel non-zeolitic molecular sieves of a class of U.S. UCC company report.SAPO-n replaces AlPO by the Si atom
4Form behind P in the-n skeleton or the Al atom by AlO
4, PO
4And SiO
4Therefore the non-neutral framework of molecular sieve that tetrahedron constitutes has tradable cation, and has proton 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 subjected to extensive attention in catalytic field.The SAPO-11 molecular sieve belongs to mesoporous molecular sieve as a member in the SAPO-n type molecular sieve family, has 10 yuan of oval ducts of ring of three-dimensional non-intersection, and the aperture is 0.39 * 0.64nm.It is reported that the SAPO-11 molecular sieve is studied widely or used at present in multiple oil refining such as catalytic cracking, hydrocracking, isomerization, isomerization dewaxing and light olefin polymerization and chemical engineering industry.
CN1283668A discloses the molecular sieve carried Preparation of catalysts method of a kind of SAPO-11, adopting phosphoric acid or aluminum phosphate is the phosphorus source, Ludox or solid silicone are the silicon source, boehmite, aluminum phosphate, aluminium isopropoxide, hydrated alumina or aluminium hydroxide are the aluminium source, di-n-propylamine, diisopropylamine or their mixture are organic formwork agent, by the synthetic SAPO-11 molecular sieve of hydrothermal synthesis method, the compound of load P d or Pt or both mixtures obtain molecular sieve carried catalyst then, and this catalyst is used for hydroisomerization reaction of alkane, experimental result shows that the selective and isomerization product yield of its isomerization obviously improves.At document Applied Catalysis A; General 2004, among the 259:227-234, people such as Ville Nieminen are used for the n-butene skeletal isomerization with the SAPO-11 molecular sieve, and investigated different silica sources and the influence of different generated times to the SAPO-11 catalytic performance, result of study shows that SAPO-11 has good active and selective.At document Catalysis Today 2008, (133-135): among the 120-128, people such as Carmen M.L ó pez have carried out the catalytic performance investigation to SAPO-11 molecular sieve synthetic in the short time, and it is good selective that the result shows that the SAPO-11 molecular sieve shows olefin skeletal isomerization.
Summary of the invention
The invention provides a kind of preparation method of palladium catalyst of the SAPO-11 of being carried on molecular sieve carrier, may further comprise the steps, step I: organic formwork agent R, aluminium source, phosphorus source, silicon source and water are mixed, and 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 are that mol ratio is 1～5: 1 phosphoric acid and the mixing phosphorus source of phosphorous acid; Step II: colloidal mixture crystallization and post processing with step I obtains get the SAPO-11 molecular sieve carrier; With Step II I, the described SAPO-11 molecular sieve carrier of Step II be impregnated in the palladium salting liquid, obtain described palladium catalyst.
In the preparation method of the palladium catalyst that is carried on the SAPO-11 molecular sieve carrier of the present invention, mix the phosphorus source by in the carrier building-up process, using, the product cut size of preparing is even, and defective is few, is orientated crystal perfection, degree of crystallinity height, good product performance.Simultaneously, catalyst of the present invention makes this catalyst become the bifunctional catalyst with metal and acid site by supported precious metal palladium.
The aluminium source of using in the inventive method, silicon source and organic formwork agent are conventional.As the aluminium source, can use any aluminium source for the synthesis of the SAPO-11 molecular sieve.As the example in aluminium source, can mention aluminium hydroxide, hydrated alumina (as boehmite), aluminium isopropoxide, aluminum nitrate, aluminum sulfate, aluminum phosphate or their any combination.As the silicon source, can use any silicon source for the synthesis of the SAPO-11 molecular sieve.As the example in silicon source, can mention White Carbon black, ethyl orthosilicate, solid silicone, Ludox or their any combination.As organic formwork agent, can use any organic formwork agent for the synthesis of the SAPO-11 molecular sieve.As the example of organic formwork agent, can mention di-n-propyl amine, diisopropylamine, diethylamide or their any mixture, for example the mixture of di-n-propyl amine and diisopropylamine.In a preferred embodiment of the inventive method, used phosphorus source is the mixture of phosphoric acid and phosphorous acid, and the aluminium source is boehmite or aluminium isopropoxide, and the silicon source is Ludox or ethyl orthosilicate, and organic formwork agent is di-n-propyl amine or diethylamide.
Mol ratio is R: Al in the preferred colloidal mixture of the present invention
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, phosphorus source described in the preferred steps I is that mol ratio is 1～3: 1 phosphoric acid and phosphorous acid.
The hydrothermal crystallizing of crystallization in the preferred described Step II in closed container, carrying out, the hydrothermal crystallizing temperature is 100～200 ℃, crystallization time is 1～24 hour.More preferably described crystallization temperature is 180～200 ℃, 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 the Step II comprises crystallization product washing, drying, moulding and roasting; Wherein washing methods is centrifuge washing or filtration washing, preferably uses centrifuge washing; Each baking temperature is 80～130 ℃, preferred 110-130 ℃; Be 2～48 hours drying time, preferred 2-24 hour; Be shaped to extruded moulding; Each sintering temperature is 500～600 ℃, and preferred 550-600 ℃, roasting time is 2～12 hours, and preferred 3-10 hour, this roasting can be carried out in Muffle furnace.After the roasting, obtain the SAPO-11 molecular sieve carrier.
The salting liquid of palladium described in the preferred steps III is soluble palladium salt, and described palladium concentration of salt solution is 0.01～0.1mol/L.Described dipping places shaking bath to place 1～24 hour for the container that will contain palladium salt and described molecular sieve, filters, and washing, drying, roasting obtained described catalyst in 2～24 hours again.Preferred described soluble palladium salt is palladium bichloride and/or dichloro four ammonia palladiums; Described bath temperature is 50～100 ℃, and baking temperature is 80～120 ℃, and sintering temperature is 300～900 ℃, more preferably 500-600 ℃.The load capacity of Pd is 0.1-5wt% in the preferred described catalyst.
The present invention also provides more than one catalyst of stating method preparation to prepare application in the isobutene at positive isomerisation of olefin.The reaction temperature of preferred described positive isomerisation of olefin is 300～450 ℃, 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 is being used for having advantages of high catalytic activity and selective when the n-butene skeletal isomerization prepares isobutene.Simultaneously, preparation method provided by the invention is easy, and cost is low, suitability for industrialized production.
Description of drawings
Fig. 1 is the XRD spectra of SAPO-11 molecular sieve among the embodiment 1;
Fig. 2 is the SEM figure of SAPO-11 molecular sieve among the embodiment 1.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but scope of invention is not limited to these embodiment.
Below the microreactor that uses among each embodiment be tubular fixed-bed reactor, its internal diameter is 9mm, capacity is 25ml, the device pipeline all adopts stainless steel pipe, catalyst is packed into the fixed bed form in the reactor flat-temperature zone, two ends filling quartz sand.
Embodiment 1
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; And then take by weighing 5.74g (0.07mol) H
3PO
3Be dissolved in the 10g water and form phosphorous acid aqueous solution, this phosphorous acid solution is poured in the gained boehmite aqueous solution, then under vigorous stirring to wherein splashing into 8.07g (0.07mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; The mol ratio of phosphoric acid and phosphorous acid is 1: 1 in the described mixing phosphorus source; Measure 4.78ml (0.035mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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 for preparing in the steps A is being warming up to 180 ℃ of hydrothermal crystallizing 3h under self-generated pressure under the air-tight state;
C: step B products therefrom is leached, cooling, centrifuge washing is then in 120 ℃ of dry 12h;
D: place Muffle furnace in 550 ℃ of roasting 4h the product of the drying that obtains among the step C, obtain the SAPO-11 molecular sieve;
E: with step D gained SAPO-11 molecular sieve mix with adhesive, extruded moulding, in 120 ℃ of dry 8h, in 550 ℃ of roasting 5h and crushing screening, get 20-40 molecules of interest sieve carrier;
F: the palladium chloride aqueous solution of preparation 0.01mol/L, step e gained carrier is placed the solution of preparing (20ml), in 100 ℃ shaking bath, placed 12 hours, filter, the solid that obtains is spent deionised water, dry under 120 ℃, obtain loaded catalyst.
G: get the catalyst that the 2.0g step F obtains and put into microreactor, (should " mix carbon four unstrpped gases behind the ether " and referred in isobutene and the reactant mixture that methyl alcohol reaction synthesize methyl tert-butyl ether obtains the residue behind the taking-up methyl tertiary butyl ether(MTBE) and mix C-4-fraction with mixing carbon four unstrpped gases behind the ether, main component is n-butene and iso-butane, and its content is respectively 25 volume % and 35 volume %) estimate; Reaction temperature is 340 ℃, and the n-butene air speed is 1.0h
-1, the n-butene conversion ratio of acquisition is 45%, 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 the characteristic peak that 8.15 °, 9.40 °, 13.20 ° and 15.57 ° etc. locate all to have occurred SAPO-11 at 2 θ, illustrate that embodiment 1 step D products therefrom is the SAPO-11 molecular sieve.The sample particle diameter that makes simultaneously is even, the crystal perfection, and the degree of crystallinity height, its SEM figure sees Fig. 2.
Comparative Examples 1
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; Then under vigorous stirring to wherein splashing into 16.14g (0.14mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; Measure 4.78m (0.035mol) l di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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.
The n-butene conversion ratio is 42% as a result, and selective isobutene is 90%.
Embodiment 2
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; And then take by weighing 3.82g (0.046mol) H
3PO
3Be dissolved in the 10g water and form phosphorous acid aqueous solution, this phosphorous acid aqueous solution is poured in the gained boehmite aqueous solution, then under vigorous stirring to wherein splashing into 10.76g (0.093mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; The mol ratio of phosphoric acid and phosphorous acid is 2: 1 in the described mixing phosphorus source; Measure 2.86ml (0.021mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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 for preparing in the steps A is being warming up to 200 ℃ of hydrothermal crystallizing 2h under self-generated pressure under the air-tight state;
C: step B products therefrom is leached, cooling, centrifuge washing is then in 110 ℃ of dry 12h;
D: place Muffle furnace in 550 ℃ of roasting 8h the product of the drying that obtains among the step C, obtain the SAPO-11 molecular sieve, its X-ray powder diffraction figure and Fig. 1 are basic identical, SEM figure also with Fig. 2 basically identical;
E: with the step e of embodiment 1;
F: the palladium chloride aqueous solution of preparation 0.05mol/L, step e gained carrier is placed the solution of preparing (20ml), in 100 ℃ shaking bath, placed 12 hours, filter, the solid that obtains is spent deionised water, dry under 120 ℃, obtain loaded catalyst.
G: basic identical with the step G of embodiment 1, difference is: reaction temperature is 380 ℃, and the n-butene conversion ratio of acquisition is 47%, and selective isobutene is 98%.
Comparative Examples 2
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; Then under vigorous stirring to wherein splashing into 16.14g (0.14mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; Measure 2.86ml (0.021mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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.
The n-butene conversion ratio is 44% as a result, and selective isobutene is 92%.V embodiment 3
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; And then take by weighing 2.87g (0.035mol) H
3PO
3Be dissolved in the 10g water and form phosphorous acid aqueous solution, this phosphorous acid aqueous solution is poured in the gained boehmite aqueous solution, then under vigorous stirring to wherein splashing into 12.10g (0.105mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; The mol ratio of phosphoric acid and phosphorous acid is 3: 1 in the described mixing phosphorus source; Measure 1.91ml (0.014mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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 for preparing in the steps A is being warming up to 190 ℃ of hydrothermal crystallizing 6h under self-generated pressure under the air-tight state;
C: step B products therefrom is leached, cooling, centrifuge washing is then in 130 ℃ of dry 12h;
D: place Muffle furnace in 550 ℃ of roasting 10h the product of the drying that obtains among the step C, obtain the SAPO-11 molecular sieve, its X-ray powder diffraction figure and Fig. 1 are basic identical, SEM figure also with Fig. 2 basically identical;
E: with the step e of embodiment 1;
F: the palladium chloride aqueous solution of preparation 0.1mol/L, step e gained carrier is placed the solution of preparing (20ml), in 100 ℃ shaking bath, placed 12 hours, filter, the solid that obtains is spent deionised water, dry under 120 ℃, obtain loaded catalyst.
G: basic identical with the step G of embodiment 1, difference is: reaction temperature is 400 ℃, and the n-butene air speed is 1.5h
-1, the n-butene conversion ratio of acquisition is 50%, selective isobutene is 98%.
Comparative Examples 3
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; Then under vigorous stirring to wherein splashing into 16.14gH
3PO
4(0.14mol) (the 85 weight % aqueous solution) stirs 1h again; Measure 1.91ml (0.014mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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.
The n-butene conversion ratio is 45% as a result, and selective isobutene is 95%.
Embodiment 4
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; And then take by weighing 1.88g (0.023mol) H
3PO
3Be dissolved in the 10g water and form phosphorous acid aqueous solution, this phosphorous acid aqueous solution is poured in the gained boehmite aqueous solution, then under vigorous stirring to wherein splashing into 13.49g (0.117mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; The mol ratio of phosphoric acid and phosphorous acid is 5: 1 in the described mixing phosphorus source; Measure 2.86ml (0.021mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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 for preparing in the steps A is being warming up to 200 ℃ of hydrothermal crystallizing 2h under self-generated pressure under the air-tight state;
C: step B products therefrom is leached, cooling, centrifuge washing is then in 110 ℃ of dry 12h;
D: place Muffle furnace in 550 ℃ of roasting 8h the product of the drying that obtains among the step C, obtain the SAPO-11 molecular sieve, its X-ray powder diffraction figure and Fig. 1 are basic identical, SEM figure also with Fig. 2 basically identical;
E: with the step e of embodiment 1;
F: the palladium chloride aqueous solution of preparation 0.05mol/L, step e gained carrier is placed the solution of preparing (20ml), in 100 ℃ shaking bath, placed 12 hours, filter, the solid that obtains is spent deionised water, dry under 120 ℃, obtain loaded catalyst.
G: basic identical with the step G of embodiment 1, difference is: reaction temperature is 380 ℃, and the n-butene conversion ratio of acquisition is 46%, and selective isobutene is 96%.
Comparative Examples 4
A: take by weighing 9.52g (0.07mol) boehmite, be dissolved in and be made into the boehmite aqueous solution in the 10g deionized water, stir 0.5h; Then under vigorous stirring to wherein splashing into 16.14g (0.14mol) H
3PO
4(the 85 weight % aqueous solution) stirs 1h again; Measure 2.86ml (0.021mol) di-n-propyl amine and be added drop-wise in the above-mentioned solution, stir 1h; Then taking by weighing 10.08g (0.042mol) Ludox again joins in the 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.
The n-butene conversion ratio is 44% as a result, and selective isobutene is 92%.
From above-described embodiment result as seen, 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%; Conversion ratio and selective data are all apparently higher than corresponding Comparative Examples among each embodiment.
Claims (10)
1. preparation method who is carried on the palladium catalyst of SAPO-11 molecular sieve carrier may further comprise the steps:
Step I mixes organic formwork agent R, aluminium source, phosphorus source, silicon source and water, and 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 are that mol ratio is 1～5: 1 phosphoric acid and the mixing phosphorus source of phosphorous acid;
Step II, colloidal mixture crystallization and post processing with step I obtains get the SAPO-11 molecular sieve carrier;
Step II I impregnated in the described SAPO-11 molecular sieve carrier of Step II in the palladium salting liquid, obtains described palladium catalyst.
2. method according to claim 1, it is characterized in that: the aluminium source among the described step I is aluminium hydroxide, hydrated alumina, aluminium isopropoxide, aluminum nitrate, aluminum sulfate, aluminum phosphate or their any combination; The 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. method according to claim 1, it is characterized in that: mol ratio is R: Al in the described colloidal mixture
2O
3: P
2O
5: SiO
2: H
2O=0.2～0.6: 1: 0.8～1.0: 0.5～0.7: 40～50.
4. according to any described method in the claim 1 to 3, it is characterized in that: the source of phosphorus described in the step I is that mol ratio is 1～3: 1 phosphoric acid and phosphorous acid.
5. method according to claim 1 is characterized in that: the hydrothermal crystallizing of the crystallization in the described Step II in closed container, carrying out, and the hydrothermal crystallizing temperature is 100～200 ℃, crystallization time is 1～24 hour; Preferred crystallization temperature is 180～200 ℃, and pressure is self-generated pressure, and crystallization time is 2～24 hours.
6. method according to claim 1 is characterized in that: last handling process described in the Step II comprises crystallization product washing, dry, moulding and roasting; Wherein washing methods is centrifuge washing or filtration washing; Each baking temperature is 80～130 ℃, and be 2～48 hours drying time; Be shaped to extruded moulding; Each sintering temperature is 500～600 ℃, and roasting time is 2～12 hours.
7. method according to claim 1, it is characterized in that: the salting liquid of palladium described in the Step II I is soluble palladium salt, the palladium concentration of salt solution is 0.01～0.1mol/L.
8. method according to claim 7, it is characterized in that: described soluble palladium salt is palladium bichloride and/or dichloro four ammonia palladiums; Described dipping places shaking bath to place 1～24 hour for the container that will contain palladium salt and described molecular sieve, filters, and washing, drying, roasting obtained described catalyst in 2～24 hours again; Wherein bath temperature is 50～100 ℃, and baking temperature is 80～120 ℃, and sintering temperature is 300～900 ℃, preferred 500～600 ℃.
9. one kind prepares application in the isobutene according to the catalyst of any described method preparation in the claim 1～8 at positive isomerisation of olefin.
10. method according to claim 9, it is characterized in that: the reaction temperature that described positive isomerisation of olefin prepares isobutene is 300～450 ℃, 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107649175A (en) * | 2017-10-23 | 2018-02-02 | 上海歌通实业有限公司 | A kind of preparation method of Ga Ge doping MnOx SAPO molecular sieve catalyst |
| CN109395772A (en) * | 2017-08-18 | 2019-03-01 | 中国石油大学(华东) | A kind of isomerization catalyst and its preparation method and application |
| CN109879296A (en) * | 2019-04-02 | 2019-06-14 | 中国科学院上海高等研究院 | The preparation method and application of monocrystalline SAPO-11 molecular sieve, hydroisomerization catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395772A (en) * | 2017-08-18 | 2019-03-01 | 中国石油大学(华东) | A kind of isomerization catalyst and its preparation method and application |
| CN109395772B (en) * | 2017-08-18 | 2021-05-11 | 中国石油大学(华东) | Isomerization catalyst and preparation method and application thereof |
| CN107649175A (en) * | 2017-10-23 | 2018-02-02 | 上海歌通实业有限公司 | A kind of preparation method of Ga Ge doping MnOx SAPO molecular sieve catalyst |
| CN107649175B (en) * | 2017-10-23 | 2020-11-03 | 上海歌通实业有限公司 | Preparation method of Ga-Ge-doped MnOx-SAPO molecular sieve catalyst |
| CN109879296A (en) * | 2019-04-02 | 2019-06-14 | 中国科学院上海高等研究院 | The preparation method and application of monocrystalline SAPO-11 molecular sieve, hydroisomerization catalyst |
| CN109879296B (en) * | 2019-04-02 | 2022-07-08 | 中国科学院上海高等研究院 | Preparation method and application of single crystal SAPO-11 molecular sieve and hydroisomerization catalyst |
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| CN103285915B (en) | 2016-03-30 |
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