CN104174433A - An n-butylene isomerization catalyst and a preparing method thereof - Google Patents
An n-butylene isomerization catalyst and a preparing method thereof Download PDFInfo
- Publication number
- CN104174433A CN104174433A CN201310195713.3A CN201310195713A CN104174433A CN 104174433 A CN104174433 A CN 104174433A CN 201310195713 A CN201310195713 A CN 201310195713A CN 104174433 A CN104174433 A CN 104174433A
- Authority
- CN
- China
- Prior art keywords
- sapo
- catalyst
- composite molecular
- molecular screen
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
An n-butylene isomerization catalyst is provided. An SAPO-11/SAPO-46 composite molecular sieve with multistage pore channels is adopted as a carrier. A VIB-group metal is adopted as an active component. A preparing method of the catalyst is also provided. The method includes: controlling a raw material ratio in a synthetic process, preparing the SAPO-11/SAPO-46 composite molecular sieve by adoption of a proper crystallization manner and a proper crystallization temperature, and loading the VIB-group metal (such as chromium or molybdenum) to make the catalyst a bifunctional catalyst with the metal and an acid center. The preparing method is simple, low in cost and suitable for industrial production. The catalyst is high in catalytic activity and isobutylene selectivity when the catalyst is used for isobutylene preparation by n-butylene skeletal isomerization.
Description
Technical field
The present invention relates to olefin isomerization catalyst field, be specifically related to a kind of n-butene isomerization catalyst and preparation method thereof.
Background technology
Isobutene is a kind of important Organic Chemicals, is mainly used to produce the multiple Organic chemical products such as methyl tertiary butyl ether(MTBE) (MTBE), the tert-butyl alcohol, butyl rubber, polyisobutene, methyl methacrylate, tert-butyl mercaptan.In recent years, because the demand of isobutene sharply increases, particularly be used for the demand rapid growth in the world of the friendly type gasoline additive of production environment MTBE, 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.
In twentieth century the seventies and eighties, the n-butene isomerization catalyst of development is mainly and adds the acidic oxidation Al catalysts that halide and Si oxide obtain in the world.Since nineteen nineties, external each major oil companies develop zeolite-type molecular sieves or non-zeolitic molecular sieves one after another as n-butene skeletal isomerization catalyst.Catalysis material used has SAPO (SAPO) molecular sieve analog, ZSM-5, ZSM-22, ZSM-23, ZSM-35 molecular sieve, modenite, beta-zeolite etc.These molecular sieve catalyst reaction temperatures low (300-400 DEG C), catalyst coking, inactivation are slow, and stability is better, isobutene selectively also high; If want industrialization also not need to use moving bed, fluidized-bed reactor, it is also few than the situation of the catalyst that is carrier with aluminium oxide that required fixed bed switches number of reactors, greatly reduces like this investment to process units and the separating difficulty of product.Especially SAPO molecular sieve analog, distributes and special pore structure and other features because it has suitable acid site, and its performance is more outstanding, becomes the focus of external each major company research.
SAPO molecular sieve analog is the novel non-zeolitic molecular sieves of a class that U.S. combinating carbide company releases for 1984.SAPO-n replaces AlPO by Si atom
4after P in-n skeleton or Al atom, form by AlO
4, PO
4and SiO
4the non-neutral framework of molecular sieve that tetrahedron forms, therefore 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; Pore volume (the H of SAPO-n type molecular sieve
2o) be 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 sieve family, belongs to mesoporous molecular sieve, has the oval duct of 10 rings of three-dimensional non-intersection, and aperture is 0.39 × 0.64nm.It is reported, SAPO-11 molecular sieve is at present studied widely or is applied in the multiple refining and chemical industry industry such as catalytic cracking, hydrocracking, isomerization, alkylation, isomerization dewaxing and light olefin polymerization with side chain aromatic hydrocarbons.
Patent CN1283668A discloses the preparation method of the molecular sieve carried catalyst of a kind of SAPO-11, adopting phosphoric acid or aluminum phosphate is 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, synthesize SAPO-11 molecular sieve by hydrothermal synthesis method, then the compound of load P d or Pt or both mixtures obtain molecular sieve carried catalyst, and this catalyst is used for to hydroisomerization reaction of alkane, experimental result shows its isomerization selectively and isomerization product yield obviously improves.
Summary of the invention
The invention provides a kind of taking novel SAPO-11/SAPO-46 composite molecular screen as carrier, the Catalysts and its preparation method taking the group vib such as chromium and molybdenum metal as active component.The carrier S APO-11/SAPO-46 composite molecular screen that catalyst provided by the invention uses contains multistage pore canal, has good catalytic performance; The such as molybdenum of group vib metal of load etc. make catalyst there is metal and acid site difunctional, therefore this catalyst has higher catalytic activity in n-butene isomerization reaction, isomerization target product has higher selective.
According to the present invention, provide a kind of n-butene isomerization catalyst, taking SAPO-11/SAPO-46 composite molecular screen as carrier, taking group vib metal as active component.Described group vib metal is chromium, molybdenum and tungsten, and it can exist with metal simple-substance form or compound form in catalyst.
In the present invention, term " SAPO-11/SAPO-46 composite molecular screen " refers to the complex type molecular sieve of the structure simultaneously with SAPO-11 molecular sieve and SAPO-46 molecular sieve.
In catalyst provided by the invention, the gross weight meter based on described catalyst, the content of carrier is 90-99 % by weight, is preferably 90-97 % by weight, the content of active component is counted 1-10 % by weight with group vib metallic atom, is preferably 3-10 % by weight.
Above-mentioned group vib metal is preferably chromium and/or molybdenum, more preferably molybdenum.
Preferably, in SAPO-11/SAPO-46 composite molecular screen in molal quantity Al
2o
3: P
2o
5: SiO
2=1:0.5-2.5:0.2-2.0, preferably Al
2o
3: P
2o
5: SiO
2=1:0.8-1.0:0.2-1.0.
In the X-ray powder diffraction spectrogram of described SAPO-11/SAPO-46 composite molecular screen, be 8.1 °-8.3 °, 9.3 °-9.5 °, 13.1 °-13.3 ° at 2 θ, and 6.5 °-6.7 °, 7.6 °-7.8 ° and 19.8 °-20.0 ° etc. locate all to occur characteristic peak.
The preparation method who the invention provides n-butene isomerization catalyst as above, comprising: step I: the aqueous solution of the solubility group vib slaine that configuration concentration is 0.03-0.3mol/L; Step II: the SAPO-11/SAPO-46 composite molecular screen after moulding is placed in to the solution that step I obtains, mixes 1-24 hour at 50-90 DEG C; Step III: the reactant mixture of step II is filtered, washing, then dry.
Solubility group vib slaine in step I is solubility chromic salts and/or soluble molybdenum salt, is preferably five water nitric acid molybdenums and/or nine water chromic nitrates.In step II, the shaking bath that preferably container that reactant mixture is housed is placed in to 50-100 DEG C is placed 1-24 hour.The baking temperature of step III is preferably 80-120 DEG C.
In one embodiment, said method also comprises the preparation process of SAPO-11/SAPO-46 composite molecular screen, comprise: step I): aluminium source, phosphorus source, organic formwork agent, silicon source and water are mixed to get to colloid admixture, wherein in described colloidal mixture in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:0.2-5.0:0.6-2.0:0.1-1.5:15-80, preferably Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:2.0-3.0:0.8-1.0:0.8-1.0:30-50, wherein R is organic formwork agent; Step I is i): by step I) the colloidal mixture crystallization that obtains, then by crystallization product washing, dry, roasting, extrusion modling.
The aluminium source, silicon source, phosphorus source and the organic formwork agent that in the inventive method, use are conventional.Aluminium source is preferably for example, in aluminium hydroxide, hydrated alumina (boehmite), aluminium isopropoxide, aluminum nitrate, aluminum sulfate and aluminum phosphate one or more.Phosphorus source is preferably one or both in phosphoric acid and phosphorous acid.Organic formwork agent is preferably one or more in di-n-propyl amine, diisopropylamine and diethylamide.Silicon source is preferably one or more in White Carbon black, ethyl orthosilicate, solid silicone and Ludox.
In a preferred embodiment of the inventive method, phosphorus source used is phosphoric acid, and aluminium source is boehmite, and silicon source is Ludox, and organic formwork agent is di-n-propyl amine.
After obtaining colloidal mixture, preferably this mixture is carried out aging.Therefore, method of the present invention can also be included in step I i) before by step I) colloidal mixture that obtains carries out aging step, and wherein aging temperature is 80-130 DEG C, is preferably 80-110 DEG C, and the aging time is 1-6 hour, is preferably 2-6 hour.Particularly preferably be the aging 2-6 hour that carries out at the temperature of 80-110 DEG C.
Step I crystallization i) is advantageously undertaken by hydrothermal crystallizing, conventionally in closed container, carries out.The crystallization temperature of hydrothermal crystallizing and time are conventional.Typically, crystallization temperature is 100-200 DEG C, is preferably 150-200 DEG C, more preferably 180-200 DEG C, and pressure is self-generated pressure (pressure producing while reaction in closed reactor), crystallization time is 1-24 hour, is preferably 2-24 hour.Particularly preferably be, hydrothermal crystallizing carries out 2-24 hour under the temperature of 180-200 DEG C and self-generated pressure.
Step I i) in, dry and roasting is conventional.Dry temperature is preferably 80-130 DEG C, more preferably 110-130 DEG C.Be generally 2-48 hour drying time, be preferably 2-24 hour.The temperature of roasting is preferably 500-600 DEG C, more preferably 550-600 DEG C.Roasting time is generally 2-12 hour, is preferably 3-10 hour.This roasting can be carried out in Muffle furnace.Experiment discovery, number and the position of the SAPO-11/SAPO-46 composite molecular screen of preparing according to method of the present invention characteristic diffraction peak in the X-ray powder diffraction spectrogram before and after roasting almost do not change.
Before for the preparation of catalyst, conventionally by the SAPO-11/SAPO-46 composite molecular screen carrier extrusion modling obtaining by above-mentioned steps, for example it is mixed with adhesive, extruded moulding, dry, pulverize and sieve, obtain the catalyst carrier of a certain size (being generally in the present invention 20-40 order).Adhesive is the conventional adhesive of Kaolinite Preparation of Catalyst, for example hydrated alumina.
Related washing step in the methods of the invention, it is conventional, conventionally can use the washing methods such as filtration washing, centrifuge washing, preferably uses centrifuge washing.
The present invention also provides a kind of catalyst of preparing by said method to prepare the application in isobutene reaction in n-butene isomerization.The isomerized reaction temperature of preferred described n-butene is 300-450 DEG C, and reaction pressure is normal pressure, and the mass space velocity of raw material n-butene is 1.0-2.0h
-1.
In the method for preparing SAPO-11/SAPO-46 composite molecular screen supported catalyst of the present invention, by control the proportioning of raw material in building-up process, and adopt suitable crystal pattern and crystallization temperature to prepare SAPO-11/SAPO-46 composite molecular screen, shorten crystallization time, the product degree of crystallinity of preparing is high, for example, by supported V IB family metal (chromium or molybdenum), make this catalyst become the bifunctional catalyst with metal and acid site simultaneously.
The experiment proved that, prepared according to the methods of the invention have higher catalytic activity taking the SAPO-11/SAPO-46 composite molecular screen with multi-stage artery structure as the loaded catalyst of carrier in the time preparing isobutene for n-butene skeletal isomerization, and the target product obtaining has higher selective.Meanwhile, preparation method provided by the invention is easy, and cost is low, is applicable to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of the SAPO-11/SAPO-46 composite molecular screen for preparing of embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but scope of invention is not limited to these embodiment.
In following examples, identify the structure of the SAPO-11/SAPO-46 composite molecular screen of preparing by the inventive method by X-ray diffraction spectrum figure.The instrument adopting is the ARL X ' TRA of power & light company of U.S. type diffractometer, is specifically 35kV at x-ray tube voltage, and electric current is 30mA, and sweep limits is 3-40 °, and sweep speed is, under the condition of 2 °/min, sample is carried out to qualitative analysis.
The microreactor using in each 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 packs in reactor flat-temperature zone with fixed bed form, two ends filling quartz sand.
Embodiment 1
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Take 9.52g(0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stir 0.5h.Under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 4.78ml(0.035mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 10.08g(0.042mol) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, in this colloid admixture in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:0.5:1:0.6:50, wherein R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation, at 80 DEG C of aging 4h, is then warming up to 180 DEG C, hydrothermal crystallizing 22h under self-generated pressure.By cooling crystallization products therefrom, centrifuge washing, then in 120 DEG C of dry 12h.Obtain SAPO-11/SAPO-46 composite molecular screen, its X-ray powder diffraction figure as shown in Figure 1.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in to Muffle furnace in 550 DEG C of roasting 4h, then mixes with boehmite (as adhesive), extruded moulding, in 120 DEG C of dry 8h, pulverizes and sieves, and obtains 20-40 object catalyst carrier.
2) preparation of catalyst
The five water nitric acid molybdenum aqueous solution of preparation 0.03mol/L, take appropriate above-mentioned carrier and be placed in prepared solution, in the shaking bath of 100 DEG C, place 12 hours, filter, the solid obtaining is washed by deionized water, dry at 120 DEG C, obtain loaded catalyst, wherein, based on total catalyst weight meter, the content of molybdenum is 1 % by weight.
3) application of catalyst in n-butene isomerization reaction
Get the above-mentioned catalyst preparing of 2.0g and put into microreactor, with mixing carbon four unstrpped gases after ether, (" after ether, mixing carbon four unstrpped gases " used in the present invention refers to the residue of taking out after methyl tertiary butyl ether(MTBE) in the reactant mixture that isobutene and methyl alcohol reaction synthesize methyl tert-butyl ether obtains and mixes 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 320 DEG C, mixes the mass space velocity of carbon four unstrpped gases and count 1.0h with n-butene after ether
-1.The n-butene conversion ratio obtaining is 45%, and selective isobutene is 93%.
Embodiment 2
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Take 9.52g(0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stir 0.5h.Under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 7.64ml(0.056mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 10.08g(0.042mol) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, in this colloid admixture in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:0.8:1:0.6:40, wherein R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation, at 100 DEG C of aging 3h, is then warming up to 180 DEG C, hydrothermal crystallizing 12h under self-generated pressure.By cooling crystallization products therefrom, centrifuge washing, then, in 110 DEG C of dry 12h, obtains SAPO-11/SAPO-46 composite molecular screen.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in to Muffle furnace in 550 DEG C of roasting 4h, then mixes with boehmite (as adhesive), extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, and obtains 20-40 object catalyst carrier.
2) preparation of catalyst
The five water nitric acid molybdenum aqueous solution of preparation 0.15mol/L, take a certain amount of above-mentioned carrier and be placed in prepared solution, in the shaking bath of 100 DEG C, place 12 hours, filter, the solid obtaining is washed by deionized water, dry at 120 DEG C, obtain loaded catalyst, wherein, based on total catalyst weight meter, the content of molybdenum is 5 % by weight.
3) application of catalyst in n-butene isomerization reaction
Get the above-mentioned catalyst preparing of 2.0g and put into microreactor, evaluate with mixing carbon four unstrpped gases after ether.Reaction temperature is 340 DEG C, mixes the mass space velocity of carbon four unstrpped gases and count 1.0h with n-butene after ether
-1.The n-butene conversion ratio obtaining is 47%, and selective isobutene is 97%.
Embodiment 3
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Take 9.52g(0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stir 0.5h.Under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h; Measuring 14.3ml(0.105mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 13.44g(0.056mol) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, in this colloid admixture in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:1.5:1:0.8:50, wherein R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation, at 110 DEG C of aging 4h, is then warming up to 180 DEG C, hydrothermal crystallizing 8h under self-generated pressure.By cooling crystallization products therefrom, centrifuge washing, then, in 120 DEG C of dry 6h, obtains SAPO-11/SAPO-46 composite molecular screen.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in to Muffle furnace in 600 DEG C of roasting 4h, then mixes with boehmite (as adhesive), extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, and obtains 20-40 object catalyst carrier.
2) preparation of catalyst
The five water nitric acid molybdenum aqueous solution of preparation 0.3mol/L, take a certain amount of above-mentioned carrier and be placed in prepared solution, in the shaking bath of 100 DEG C, place 12 hours, filter, the solid obtaining is washed by deionized water, dry at 120 DEG C, obtain loaded catalyst, wherein, based on total catalyst weight meter, the content of molybdenum is 10 % by weight.
3) application of catalyst in n-butene isomerization reaction
Get the above-mentioned catalyst preparing of 2.0g and put into microreactor, evaluate with mixing carbon four unstrpped gases after ether.Reaction temperature is 380 DEG C, mixes the mass space velocity of carbon four unstrpped gases and count 1.0h with n-butene after ether
-1.The n-butene conversion ratio obtaining is 48%, and selective isobutene is 95%.
Embodiment 4
1) preparation of SAPO-11/SAPO-46 composite molecular screen
The step 1) of specific experiment operating process and embodiment 2 is roughly the same, and difference is, the quantitative change of the di-n-propyl amine using becomes 1.91ml (0.014mol), in the colloidal mixture obtaining in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:0.2:1:0.6:50.
2) preparation of catalyst
The step 2 of specific experiment operating process and embodiment 2) roughly the same, difference is five water nitric acid molybdenums to replace to nine water chromic nitrates, and the loaded catalyst preparing is based on total catalyst weight meter, and the content of chromium is 3 % by weight.
3) application of catalyst in n-butene isomerization reaction
Get the above-mentioned catalyst preparing of 2.0g and put into microreactor, evaluate with mixing carbon four unstrpped gases after ether.Reaction temperature is 400 DEG C, mixes the mass space velocity of carbon four unstrpped gases and count 1.5h with n-butene after ether
-1.The n-butene conversion ratio obtaining is 46%, and selective isobutene is 96%.
Embodiment 5
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Take 9.52g(0.07mol) boehmite, be dissolved in 10g deionized water and be made into the boehmite aqueous solution, stir 0.5h.Under vigorous stirring, splash into wherein 16.14g(0.14mol) H
3pO
4(the 85 % by weight aqueous solution), then stir 1h.Measuring 19.1ml(0.14mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then taking again 15.12g(0.063mol) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, in this colloid admixture in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:2.0:1:0.9:50, wherein R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 190 DEG C under air-tight state, hydrothermal crystallizing 21h under self-generated pressure.By cooling crystallization products therefrom, centrifuge washing, then in 130 DEG C of dry 12h, obtains SAPO-11/SAPO-46 composite molecular screen product.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in to Muffle furnace in 600 DEG C of roasting 4h, then mixes with boehmite (as adhesive), extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, and obtains 20-40 object catalyst carrier.
2) preparation of catalyst
The step 2 of specific experiment operating process and embodiment 2) identical.
3) application of catalyst in n-butene isomerization reaction
Get the above-mentioned catalyst preparing of 2.0g and put into microreactor, evaluate with mixing carbon four unstrpped gases after ether.Reaction temperature is 340 DEG C, mixes the mass space velocity of carbon four unstrpped gases and count 1.0h with n-butene after ether
-1.The n-butene conversion ratio obtaining is 47%, and selective isobutene is 97%.
As shown in Figure 1,2 θ are the characteristic peak that 8.2 °, 9.4 ° and 13.2 ° etc. locate all to have occurred SAPO-11,2 θ are the characteristic peak that 6.6 °, 7.7 ° and 19.9 ° etc. locate all to have occurred SAPO-46, have shown that composite molecular screen that embodiment 1 obtains has the architectural feature of SAPO-11 molecular sieve and SAPO-46 molecular sieve simultaneously.In addition, in experimentation, find, the composite molecular screen that the composite molecular screen of embodiment 2-5 obtains with embodiment 1 has identical structure.
From above embodiment, adopting SAPO-11/SAPO-46 composite molecular screen according to the present invention is carrier, and the catalyst taking group vib metal as active component obtains the selective of higher target product isobutene in n-butene isomerization reaction.
Claims (12)
1. a n-butene isomerization catalyst, is characterized in that, taking SAPO-11/SAPO-46 composite molecular screen as carrier, taking group vib metal as active component.
2. catalyst according to claim 1, is characterized in that, the gross weight meter based on described catalyst, and the content of carrier is 90-99 % by weight, the content of active component is counted 1-10 % by weight with group vib metallic atom.
3. catalyst according to claim 1 and 2, is characterized in that, described group vib metal is chromium and/or molybdenum.
4. catalyst according to claim 1 and 2, is characterized in that, in SAPO-11/SAPO-46 composite molecular screen in molal quantity Al
2o
3: P
2o
5: SiO
2=1:0.5-2.5:0.2-2.0, preferably Al
2o
3: P
2o
5: SiO
2=1:0.8-1.0:0.2-1.0.
5. catalyst according to claim 1, it is characterized in that, in the X-ray powder diffraction spectrogram of described SAPO-11/SAPO-46 composite molecular screen, be 8.1 °-8.3 °, 9.3 °-9.5 °, 13.1 °-13.3 ° at 2 θ, and 6.5 °-6.7 °, 7.6 °-7.8 ° and 19.8 °-20.0 ° are located all to occur characteristic peak.
6. a method of preparing the catalyst as described in any one in claim 1-5, comprising:
Step I: the aqueous solution of the solubility group vib slaine that configuration concentration is 0.03-0.3mol/L;
Step II: the SAPO-11/SAPO-46 composite molecular screen after moulding is placed in to the solution that step I obtains, mixes 1-24 hour at 50-100 DEG C;
Step III: the reactant mixture of step II is filtered, washing, then dry.
7. method according to claim 6, is characterized in that, described solubility group vib slaine is solubility chromic salts and/or soluble molybdenum salt, is preferably five water nitric acid molybdenums and/or nine water chromic nitrates.
8. according to the method described in claim 6 or 7, it is characterized in that, described method also comprises the preparation process of SAPO-11/SAPO-46 composite molecular screen, comprising:
Step I): aluminium source, phosphorus source, organic formwork agent, silicon source and water are mixed to get to colloid admixture, wherein in described colloidal mixture in molal quantity Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:0.2-5.0:0.6-2.0:0.1-1.5:15-80, preferably Al
2o
3: R:P
2o
5: SiO
2: H
2o=1:2.0-3.0:0.8-1.0:0.8-1.0:30-50, wherein R is organic formwork agent;
Step I is i): by step I) the colloidal mixture crystallization that obtains, then by crystallization product washing, dry, roasting, extrusion modling.
9. method according to claim 8, is characterized in that, aluminium source is one or more in aluminium hydroxide, hydrated alumina, aluminium isopropoxide, aluminum nitrate, aluminum sulfate and aluminum phosphate; Phosphorus source is one or both in phosphoric acid and phosphorous acid; Organic formwork agent is one or more in di-n-propyl amine, diisopropylamine and diethylamide; Silicon source is one or more in White Carbon black, ethyl orthosilicate, solid silicone and Ludox.
10. method according to claim 8, it is characterized in that, described method is also included in step I i) before by step I) colloidal mixture that obtains carries out aging step, and wherein aging temperature is 80-130 DEG C, be preferably 80-110 DEG C, the aging time is 1-6 hour.
11. method according to claim 8, is characterized in that, step I crystallization i) is undertaken by hydrothermal crystallizing, and crystallization temperature is 100-200 DEG C, is preferably 180-200 DEG C, and pressure is self-generated pressure, and crystallization time is 1-24 hour; Step I i) in dry temperature be 80-130 DEG C, the temperature of roasting is 300-900 DEG C, is preferably 500-600 DEG C.
12. the application of the catalyst preparing according to the method described in any one in claim 6-11 in n-butene isomerization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310195713.3A CN104174433B (en) | 2013-05-23 | 2013-05-23 | A kind of n-butene isomerization catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310195713.3A CN104174433B (en) | 2013-05-23 | 2013-05-23 | A kind of n-butene isomerization catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104174433A true CN104174433A (en) | 2014-12-03 |
| CN104174433B CN104174433B (en) | 2016-08-17 |
Family
ID=51955943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310195713.3A Active CN104174433B (en) | 2013-05-23 | 2013-05-23 | A kind of n-butene isomerization catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104174433B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108014845A (en) * | 2016-11-03 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of catalyst for being catalyzed butane production isobutene and its application |
| CN115282992A (en) * | 2022-05-09 | 2022-11-04 | 中国石油大学(华东) | Preparation method of in-situ synthesis multi-stage pore ZSM-5 molecular sieve loaded amorphous nickel phosphide catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316485A (en) * | 2000-04-05 | 2001-10-10 | 中国科学院大连化学物理研究所 | Process for modifying gasoline by isomerizing hydrogenation |
| 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 |
| CN1552624A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Modified molecular sieve and preparing method thereof |
| CN101081370A (en) * | 2006-05-31 | 2007-12-05 | 中国石油大学(北京) | ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the methoer for preparing the same |
-
2013
- 2013-05-23 CN CN201310195713.3A patent/CN104174433B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316485A (en) * | 2000-04-05 | 2001-10-10 | 中国科学院大连化学物理研究所 | Process for modifying gasoline by isomerizing hydrogenation |
| 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 |
| CN1552624A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Modified molecular sieve and preparing method thereof |
| CN101081370A (en) * | 2006-05-31 | 2007-12-05 | 中国石油大学(北京) | ZSM-5/SAPO-11 composite zeolite and catalytically cracked gasoline hydrogenation quality-improved catalyzer and the methoer for preparing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108014845A (en) * | 2016-11-03 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of catalyst for being catalyzed butane production isobutene and its application |
| CN108014845B (en) * | 2016-11-03 | 2020-11-10 | 中国石油化工股份有限公司 | Catalyst for producing isobutene by catalyzing butane and application thereof |
| CN115282992A (en) * | 2022-05-09 | 2022-11-04 | 中国石油大学(华东) | Preparation method of in-situ synthesis multi-stage pore ZSM-5 molecular sieve loaded amorphous nickel phosphide catalyst |
| CN115282992B (en) * | 2022-05-09 | 2023-09-05 | 中国石油大学(华东) | Preparation method of amorphous nickel phosphide catalyst loaded by in-situ synthesized multistage hole ZSM-5 molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104174433B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555022A (en) | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve | |
| CN102530988B (en) | Method for preparing SAPO-11 molecular sieve and application of SAPO-11 molecular sieve | |
| CN104828842B (en) | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO | |
| CN103011195B (en) | One-step preparation method for hydrogen type multistage pore molecular sieve with SAPO-5 and SAPO-34 symbiosis | |
| CN103878015B (en) | For the molecular sieve catalyst and preparation method thereof of preparing propylene from methanol | |
| CN105312082A (en) | SAPO-34/ZSM-5 composite molecular sieve, and preparation method application thereof | |
| CN104108726A (en) | Silicoaluminophosphate molecular sieve with high silica-alumina ratio and CHA structure, and synthetic method thereof | |
| CN101503201B (en) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst | |
| CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
| CN103833047B (en) | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same | |
| CN103878016A (en) | Composite molecular sieve catalyst for MTP (methanol to propylene) as well as application thereof | |
| CN103706394B (en) | Submicron SAPO-5/SAPO-18 composite molecular sieve and preparation method thereof | |
| CN104174433B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN103263947A (en) | Composite molecular sieve for preparing catalyst for producing light olefins from organic oxygen-containing compound, and preparation method thereof | |
| CN104174435B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN103285915A (en) | Preparation method of palladium catalyst loaded on silicoaluminophosphate (SAPO)-11 molecular sieve carrier | |
| CN104174434A (en) | An n-butylene isomerization catalyst and a preparing method thereof | |
| CN106179481A (en) | A kind of metal-modified composite molecular screen, preparation method and the application in preparing propylene by methanol transformation, butene reaction thereof | |
| CN105271302A (en) | SAPO-18 molecular sieve, method for synthesizing SAPO-18 molecular sieve and method for preparing olefin from methanol | |
| CN105665007B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN104174432A (en) | An n-butylene isomerization catalyst and a preparing method thereof | |
| CN104174432B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN105665008B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN105665006B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN105665009B (en) | A kind of n-butene isomerization catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |