CN104174433B - A kind of n-butene isomerization catalyst and preparation method thereof - Google Patents
A kind of n-butene isomerization catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104174433B CN104174433B CN201310195713.3A CN201310195713A CN104174433B CN 104174433 B CN104174433 B CN 104174433B CN 201310195713 A CN201310195713 A CN 201310195713A CN 104174433 B CN104174433 B CN 104174433B
- Authority
- CN
- China
- Prior art keywords
- sapo
- catalyst
- crystallization
- molecular screen
- composite molecular
- 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.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a kind of n-butene isomerization catalyst, with there is multistage pore canal SAPO-11/SAPO-46 composite molecular screen as carrier, with group vib metal as active component.Present invention also offers the preparation method of above-mentioned catalyst, including the proportioning by controlling raw material in building-up process, and use suitable crystal pattern and crystallization temperature to prepare SAPO-11/SAPO-46 composite molecular screen, then supported V IB race metal (such as chromium or molybdenum) so that this catalyst becomes the bifunctional catalyst with metal and acid site.This preparation method is easy, low cost, is suitable for industrialized production.Catalyst provided by the present invention has the selective isobutene that higher catalysis is active and higher when preparing isobutene. for n-butene 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 methyl tertiary butyl ether(MTBE)
(MTBE), the tert-butyl alcohol, butyl rubber, polyisobutylene, methyl methacrylate, tert-butyl group sulfur
The multiple Organic chemical products such as alcohol.In recent years, owing to the demand of isobutene. sharply increases, special
It is not used to the demand of production environment friendly gasoline additive MTBE in the world
Swift and violent growth, and the isobutene. yield that traditional oil Deep Catalytic Cracking process obtains is far from meeting
Industrial requirement, has therefore extensively carried out the research and development work of isobutene. production new technology both at home and abroad
Make.
In twentieth century the seventies and eighties, the n-butene isomerization catalyst developed in the world is main
The acidic oxidation Al catalysts obtained for interpolation halogenide and Si oxide.From twentieth century 90
Since age, external each major oil companies develop zeolite-type molecular sieves or Non-zeolitic molecular one after another
Sieve is as n-butene skeletal isomerisation 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),
Slowly, stability is preferable, and the selectivity of isobutene. is the highest for catalyst coking, inactivation；To work
Industry is also without using moving bed, fluidized-bed reactor, and required fixed bed switches reactor
Number is also few than by the situation of the catalyst that aluminium oxide is carrier, so greatly reduces production
The investment of device and the separating difficulty of product.Especially SAPO molecular sieve analog, owing to it has
Suitable acid site distribution and special pore structure and other features, its performance is the most prominent, becomes
Focus for the research of external each major company.
SAPO molecular sieve analog is that the class that U.S. combinating carbide company releases for 1984 is novel
Non-zeolitic molecular sieves.SAPO-n is to be replaced AlPO by Si atom4P or Al in-n skeleton
After atom formed by AlO4、PO4And SiO4The non-neutral framework of molecular sieve that tetrahedron is constituted,
Therefore there is tradable cation, and there is Bronsted acidity.SAPO-n type molecular sieve simultaneously
Aperture be 0.3-0.8nm, almost include whole pore diameter ranges of zeolite molecular sieve；SAPO-n
Pore volume (the H of type molecular sieve2O) it is 0.18-0.48cm3/g.As generation novel molecular sieve,
SAPO-n type molecular sieve is in widespread attention in catalytic field.SAPO-11 molecular sieve conduct
A member in SAPO-n type molecular sieves, belongs to mesoporous molecular sieve, has the non-friendship of three-dimensional
10 ring ellipse ducts of fork, aperture is 0.39 × 0.64nm.It is reported, SAPO-11 divides
Before sub-sieve mesh catalytic cracking, be hydrocracked, isomerization, the alkylation of band side chain aromatic hydrocarbons,
The multiple oil refining such as isomerization dewaxing and light olefin polymerization are studied in chemical engineering industry widely
Or application.
Patent CN1283668A discloses the system of the molecular sieve carried catalyst of a kind of SAPO-11
Preparation Method, use phosphoric acid or aluminum phosphate be phosphorus source, Ludox or solid silicone be silicon source,
Boehmite, aluminum phosphate, aluminum isopropylate., hydrated alumina or aluminium hydroxide are aluminum source,
Di-n-propylamine, diisopropylamine or their mixture are organic formwork agent, pass through Hydrothermal Synthesis
Method synthesis SAPO-11 molecular sieve, then load P d or the compound of Pt or both mixture
Obtain molecular sieve carried catalyst, and this catalyst is used for hydroisomerization reaction of alkane, real
Test result and show that its isomerisation selectivity and isomerization product yield significantly improve.
Summary of the invention
The invention provides a kind of with novel SAPO-11/SAPO-46 composite molecular screen for carrying
Body, catalyst with the group vib metal such as chromium and molybdenum as active component and preparation method thereof.This
The carrier S APO-11/SAPO-46 composite molecular screen that the catalyst of bright offer is used contains many
Level duct, has preferable catalytic performance；The group vib metal such as molybdenum etc. of load makes catalysis
Agent has metal and acid site is difunctional, and therefore this catalyst has in n-butene isomerization reaction
Having higher catalysis activity, isomerization target product has higher selectivity.
According to the present invention, it is provided that a kind of n-butene isomerization catalyst, with
SAPO-11/SAPO-46 composite molecular screen is carrier, with group vib metal as active component.
Described group vib metal is chromium, molybdenum and tungsten, and it in the catalyst can be with metal simple-substance form
Or compound form exists.
In the present invention, term " SAPO-11/SAPO-46 composite molecular screen " refers to have simultaneously
There is the complex type molecular sieve of the structure of SAPO-11 molecular sieve and SAPO-46 molecular sieve.
In the catalyst that the present invention provides, gross weight meter based on described catalyst, carrier
Content is 90-99 weight %, and preferably 90-97 weight %, the content of active component is with VIB
Race's metallic atom is calculated as 1-10 weight %, preferably 3-10 weight %.
Above-mentioned group vib metal is preferably chromium and/or molybdenum, more preferably molybdenum.
Preferably, Al in terms of molal quantity in SAPO-11/SAPO-46 composite molecular screen2O3:
P2O5:SiO2=1:0.5-2.5:0.2-2.0, preferably Al2O3:P2O5:SiO2=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. all there is characteristic peak.
The invention provides the preparation method of n-butene isomerization catalyst as above, bag
Include: step I: configuration concentration is the water of the solubility group vib slaine of 0.03-0.3mol/L
Solution；Step II: the SAPO-11/SAPO-46 composite molecular screen after molding is placed in step
In I solution obtained, mix 1-24 hour at 50-90 DEG C；Step III: by step II
Reactant mixture filters, washing, is then dried.
Solubility group vib slaine in step I is solubility chromic salts and/or soluble molybdenum
Salt, preferably five liquid glauber salt acid molybdenums and/or nine water chromic nitrates.In step II, preferably will be equipped with
The container of reactant mixture is placed in the shaking bath of 50-100 DEG C placement 1-24 hour.Step III
Baking temperature be preferably 80-120 DEG C.
In one embodiment, said method also includes compound point of SAPO-11/SAPO-46
The preparation process of son sieve, including: step i): by aluminum source, phosphorus source, organic formwork agent, silicon
Source and water are mixed to get colloid admixture, wherein in described colloidal mixture in terms of molal quantity
Al2O3:R:P2O5:SiO2:H2O=1:0.2-5.0:0.6-2.0:0.1-1.5:15-80, preferably Al2O3:
R:P2O5:SiO2:H2O=1:2.0-3.0:0.8-1.0:0.8-1.0:30-50, wherein R is organic mould
Plate agent；Step is ii): the colloidal mixture crystallization obtained by step i), then by crystallization product
Washing, is dried, roasting, extruded.
The aluminum source, silicon source, phosphorus source and the organic formwork agent that use in the inventive method are conventional.
Aluminum source be preferably aluminium hydroxide, hydrated alumina (such as boehmite), aluminum isopropylate.,
One or more in aluminum nitrate, aluminum sulfate and aluminum phosphate.Phosphorus source is preferably phosphoric acid and phosphorous acid
In one or both.Organic formwork agent is preferably di-n-propyl amine, diisopropylamine and diethyl
One or more in base amine.Silicon source be preferably White Carbon black, tetraethyl orthosilicate, solid silicone and
One or more in Ludox.
In a preferred embodiment of the inventive method, phosphorus source used is phosphoric acid, aluminum source
For boehmite, 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, this
Bright method be additionally may included in step ii) before colloidal mixture that step i) is obtained carry out
Aging step, the most aging temperature is 80-130 DEG C, preferably 80-110 DEG C, aging
Time is 1-6 hour, preferably 2-6 hour.It is particularly preferred that it is aging at 80-110 DEG C
At a temperature of carry out 2-6 hour.
Step crystallization ii) is carried out advantageous by hydrothermal crystallizing, generally enters in hermetic container
OK.The crystallization temperature of hydrothermal crystallizing and time are conventional.Typically, crystallization temperature is
100-200 DEG C, preferably 150-200 DEG C, more preferably 180-200 DEG C, pressure is spontaneous pressure
Power (produced pressure when i.e. reacting in closed reactor), crystallization time is 1-24 hour,
It is preferably 2-24 hour.It is particularly preferred that hydrothermal crystallizing 180-200 DEG C temperature and from
Carry out 2-24 hour under raw pressure.
Step ii) in, be dried and roasting be conventional.The temperature being dried is preferably 80-130
DEG C, more preferably 110-130 DEG C.Being usually drying time 2-48 hour, preferably 2-24 is little
Time.The temperature of roasting is preferably 500-600 DEG C, more preferably 550-600 DEG C.Roasting time is led to
It is often 2-12 hour, preferably 3-10 hour.This roasting can be carried out in Muffle furnace.Real
Issuing after examination and approval existing, the SAPO-11/SAPO-46 composite molecular screen prepared according to the method for the present invention exists
In X-ray powder diffraction spectrogram before and after roasting, number and the position of characteristic diffraction peak almost do not have
Change.
Before be used for preparing catalyst, generally will be obtained by above-mentioned steps
SAPO-11/SAPO-46 composite molecular screen carrier is extruded, such as, it mixed with binding agent
Close, extruded moulding, dry, pulverize and sieve, obtain a certain size and (be usually in the present invention
20-40 mesh) catalyst carrier.Binding agent is the traditional binders preparing catalyst, such as
Hydrated alumina.
Washing step involved in the methods of the invention, it is conventional, generally can use
The washing methods such as filtration washing, centrifuge washing, preferably uses centrifuge washing.
Present invention also offers a kind of catalyst prepared by said method at n-butene isomery
The application in isobutene reaction is prepared in change.The reaction temperature of the most described n-butene isomerization is
300-450 DEG C, reaction pressure is normal pressure, and the mass space velocity of raw material n-butene is 1.0-2.0h-1。
The side preparing SAPO-11/SAPO-46 composite molecular screen supported catalyst in the present invention
In method, by controlling the proportioning of raw material in building-up process, and use suitable crystal pattern
Prepare SAPO-11/SAPO-46 composite molecular screen with crystallization temperature, shorten crystallization time,
The product degree of crystallinity prepared is high, simultaneously by supported V IB race's metal (such as chromium or molybdenum),
This catalyst is made to become the bifunctional catalyst with metal and acid site.
The experiment proved that, prepared according to the methods of the invention to have multi-stage artery structure
SAPO-11/SAPO-46 composite molecular screen is that the loaded catalyst of carrier is for n-butene
Skeletal isomerization has higher catalysis activity when preparing isobutene., the target product obtained has
Higher selectivity.Meanwhile, the preparation method that the present invention provides is easy, low cost, is suitable for work
Industry metaplasia is produced.
Accompanying drawing explanation
Fig. 1 is the X of the SAPO-11/SAPO-46 composite molecular screen that embodiment 1 prepares
X ray diffraction spectrogram.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but the scope of invention
It is not limited to these embodiments.
In the examples below, it is prepared by the method for the present invention by the qualification of X-ray diffraction spectrum figure
The structure of SAPO-11/SAPO-46 composite molecular screen.The instrument used is U.S.'s thermoelectricity
Company's ARL X ' TRA type diffractometer, is specifically 35kV at x-ray tube voltage, electric current
For 30mA, sweep limits is 3-40 °, and scanning speed is to carry out sample under conditions of 2 °/min
Qualitative analysis.
The microreactor used in each embodiment is tubular fixed-bed reactor, and its internal diameter is
9mm, capacity is 25ml, and device pipeline all uses stainless steel pipe, and catalyst is with fixed bed shape
Formula loads in reactor flat-temperature zone, two ends filling quartz sand.
Embodiment 1
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into
Boehmite aqueous solution, stirs 0.5h.Instill 16.14g the most wherein
(0.14mol) H3PO4(85 weight % aqueous solution), is stirred for 1h.Measure 4.78ml
(0.035mol), during di-n-propyl amine is added drop-wise to above-mentioned solution, 1h is stirred.Weigh the most again
10.08g(0.042mol) Ludox joins in above-mentioned solution.Add water, stir 1h,
To colloidal mixture, Al in terms of molal quantity in this colloid admixture2O3:R:P2O5:SiO2:
H2O=1:0.5:1:0.6:50, wherein R is di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation at 80 DEG C of aging 4h, then heat to 180 DEG C,
Hydrothermal crystallizing 22h under self-generated pressure.By crystallization products therefrom cool down, centrifuge washing, then in
120 DEG C of dry 12h.Obtain SAPO-11/SAPO-46 composite molecular screen, its x-ray powder
Diffraction pattern is as shown in Figure 1.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 550 DEG C
Roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C
It is dried 8h, pulverizes and sieves, obtain the catalyst carrier of 20-40 mesh.
2) preparation of catalyst
The five liquid glauber salt acid molybdenum aqueous solutions of preparation 0.03mol/L, weigh appropriate above-mentioned carrier and are placed in
In the solution prepared, place 12 hours in the shaking bath of 100 DEG C, filter, will obtain
Solid be washed with deionized, at 120 DEG C be dried, obtain loaded catalyst, wherein
Based on overall catalyst weight gauge, the content of molybdenum is 1 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, with mixing carbon after ether
(" mixing carbon four unstrpped gas after ether " used in the present invention refers to isobutene. to four unstrpped gases
Taking-up methyl tertbutyl is synthesized in the reactant mixture that methyl tertiary butyl ether(MTBE) obtains with methanol
Residue mixing C-4-fraction after ether, is mainly composed of n-butene and iso-butane, and its content is respectively
It is 25 volume % and 35 volume %) it is evaluated.Reaction temperature is 320 DEG C, mixes carbon after ether
The mass space velocity of four unstrpped gases is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is
45%, selective isobutene is 93%.
Embodiment 2
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into
Boehmite aqueous solution, stirs 0.5h.Instill 16.14g the most wherein
(0.14mol) H3PO4(85 weight % aqueous solution), is stirred for 1h.Measure 7.64ml
(0.056mol), during di-n-propyl amine is added drop-wise to above-mentioned solution, 1h is stirred.Weigh the most again
10.08g(0.042mol) Ludox joins in above-mentioned solution.Add water, stir 1h,
To colloidal mixture, Al in terms of molal quantity in this colloid admixture2O3:R:P2O5:SiO2:
H2O=1:0.8:1:0.6:40, wherein R is di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation at 100 DEG C of aging 3h, then heat to 180 DEG C,
Hydrothermal crystallizing 12h at autogenous pressures.Crystallization products therefrom is cooled down, centrifuge washing, then
In 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 composite molecular screen.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 550 DEG C
Roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C
It is dried 8h, then pulverizes and sieves, obtain the catalyst carrier of 20-40 mesh.
2) preparation of catalyst
The five liquid glauber salt acid molybdenum aqueous solutions of preparation 0.15mol/L, weigh a certain amount of above-mentioned carrier and put
In the solution prepared, place 12 hours in the shaking bath of 100 DEG C, filter, will
To solid be washed with deionized, at 120 DEG C be dried, obtain loaded catalyst, its
In based on overall catalyst weight gauge, the content of molybdenum is 5 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, with mixing carbon after ether
Four unstrpped gases are evaluated.Reaction temperature is 340 DEG C, mixes carbon four unstrpped gas after ether
Mass space velocity is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 47%, isobutene.
Selectivity is 97%.
Embodiment 3
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into
Boehmite aqueous solution, stirs 0.5h.Instill 16.14g the most wherein
(0.14mol) H3PO4(85 weight % aqueous solution), is stirred for 1h；Measure 14.3ml
(0.105mol), during di-n-propyl amine is added drop-wise to above-mentioned solution, 1h is stirred.Weigh the most again
13.44g(0.056mol) Ludox joins in above-mentioned solution.Add water, stir 1h,
To colloidal mixture, Al in terms of molal quantity in this colloid admixture2O3:R:P2O5:SiO2:
H2O=1:1.5:1:0.8:50, wherein R is di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation at 110 DEG C of aging 4h, then heat to 180 DEG C,
Hydrothermal crystallizing 8h at autogenous pressures.By crystallization products therefrom cool down, centrifuge washing, then in
120 DEG C of dry 6h, obtain SAPO-11/SAPO-46 composite molecular screen.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 600 DEG C
Roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C
It is dried 8h, then pulverizes and sieves, obtain the catalyst carrier of 20-40 mesh.
2) preparation of catalyst
The five liquid glauber salt acid molybdenum aqueous solutions of preparation 0.3mol/L, weigh a certain amount of above-mentioned carrier and are placed in
In the solution prepared, place 12 hours in the shaking bath of 100 DEG C, filter, will obtain
Solid be washed with deionized, at 120 DEG C be dried, obtain loaded catalyst, wherein
Based on overall catalyst weight gauge, the content of molybdenum is 10 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, with mixing carbon after ether
Four unstrpped gases are evaluated.Reaction temperature is 380 DEG C, mixes carbon four unstrpped gas after ether
Mass space velocity is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 48%, isobutene.
Selectivity is 95%.
Embodiment 4
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Specific experiment operating process is roughly the same with the step 1) of embodiment 2, and difference exists
In, the quantitative change of the di-n-propyl amine used becomes 1.91ml (0.014mol), in the colloidal state obtained
Al in terms of molal quantity in mixture2O3:R:P2O5:SiO2:H2O=1:0.2:1:0.6:50。
2) preparation of catalyst
Specific experiment operating process and the step 2 of embodiment 2) roughly the same, difference exists
In five liquid glauber salt acid molybdenums are replaced to nine water chromic nitrates, the loaded catalyst prepared is based on urging
Agent gross weight meter, the content of chromium is 3 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, with mixing carbon after ether
Four unstrpped gases are evaluated.Reaction temperature is 400 DEG C, mixes carbon four unstrpped gas after ether
Mass space velocity is calculated as 1.5h with n-butene-1.The n-butene conversion obtained is 46%, isobutene.
Selectivity is 96%.
Embodiment 5
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into
Boehmite aqueous solution, stirs 0.5h.Instill 16.14g the most wherein
(0.14mol) H3PO4(85 weight % aqueous solution), is stirred for 1h.Measure 19.1ml
(0.14mol), during di-n-propyl amine is added drop-wise to above-mentioned solution, 1h is stirred.Weigh 15.12g the most again
(0.063mol) during Ludox joins above-mentioned solution.Add water, stir 1h, obtain colloidal state
Mixture, Al in terms of molal quantity in this colloid admixture2O3:R:P2O5:SiO2:H2O=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, in spontaneous pressure
Hydrothermal crystallizing 21h under power.Being cooled down by crystallization products therefrom, centrifuge washing, then in 130 DEG C
It is dried 12h, obtains SAPO-11/SAPO-46 composite molecular screen product.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 600 DEG C
Roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120
DEG C dry 8h, then pulverizes and sieves, obtains the catalyst carrier of 20-40 mesh.
2) preparation of catalyst
Specific experiment operating process and the step 2 of embodiment 2) identical.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, with mixing carbon after ether
Four unstrpped gases are evaluated.Reaction temperature is 340 DEG C, mixes carbon four unstrpped gas after ether
Mass space velocity is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 47%, isobutene.
Selectivity is 97%.
As it is shown in figure 1,2 θ are 8.2 °, 9.4 ° and 13.2 ° etc. all occurs in that SAPO-11's
Characteristic peak, 2 θ are the characteristic peak that 6.6 °, 7.7 ° and 19.9 ° etc. all occur in that SAPO-46,
Indicate the composite molecular screen that embodiment 1 obtains have simultaneously SAPO-11 molecular sieve and
The architectural feature of SAPO-46 molecular sieve.Additionally, find in experimentation, embodiment 2-5
The composite molecular screen that obtains of composite molecular screen and embodiment 1 there is identical structure.
From above example, use compound point of SAPO-11/SAPO-46 according to the present invention
Son sieve is carrier, and the catalyst with group vib metal as active component is in n-butene isomerization reaction
The selectivity of the target product isobutene. that middle acquisition is higher.
Claims (16)
1. a n-butene isomerization catalyst, it is characterised in that with SAPO-11/SAPO-46 compound molecule
Sieve is carrier, with group vib metal as active component；
Wherein, the content of described active component is calculated as 1-10 weight % with group vib metallic atom；
Further, the preparation process of described SAPO-11/SAPO-46 composite molecular screen includes:
Step i): aluminum source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, its
In in described colloidal mixture Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:(0.2-5.0):
(0.6-2.0): (0.1-1.5): (15-80), R is organic formwork agent；
Step ii): the colloidal mixture crystallization that step i) is obtained, then crystallization product is washed, be dried,
Roasting, extruded；Wherein said crystallization is carried out by hydrothermal crystallizing, and crystallization temperature is 100-200 DEG C.
Catalyst the most according to claim 1, it is characterised in that gross weight meter based on described catalyst,
The content of carrier is 90-99 weight %.
Catalyst the most according to claim 1 and 2, it is characterised in that described group vib metal is chromium
And/or molybdenum.
Catalyst the most according to claim 1 and 2, it is characterised in that at SAPO-11/SAPO-46
Al in terms of molal quantity in composite molecular screen2O3:P2O5:SiO2=1:(0.5-2.5): (0.2-2.0).
Catalyst the most according to claim 1 and 2, it is characterised in that at SAPO-11/SAPO-46
Al in terms of molal quantity in composite molecular screen2O3:P2O5:SiO2=1:(0.8-1.0): (0.2-1.0).
Catalyst the most according to claim 1, it is characterised in that at described SAPO-11/SAPO-46
In the X-ray powder diffraction spectrogram of composite molecular screen, it is 8.1 °-8.3 °, 9.3 °-9.5 °, 13.1 °-13.3 ° at 2 θ,
And at 6.5 °-6.7 °, 7.6 °-7.8 ° and 19.8 °-20.0 °, characteristic peak all occurs.
7. the method preparing catalyst as according to any one of claim 1-6, including:
Step I: configuration concentration is the aqueous solution of the solubility group vib slaine of 0.03-0.3mol/L；
Step II: the SAPO-11/SAPO-46 composite molecular screen after molding is placed in the solution that step I obtains
In, mix 1-24 hour at 50-100 DEG C；
Step III: the reactant mixture of step II is filtered, washing, then it is dried；
Wherein, described method also includes the preparation process of described SAPO-11/SAPO-46 composite molecular screen, bag
Include:
Step i): aluminum source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, its
In in described colloidal mixture Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:(0.2-5.0):
(0.6-2.0): (0.1-1.5): (15-80), R is organic formwork agent；
Step ii): the colloidal mixture crystallization that step i) is obtained, then crystallization product is washed, be dried,
Roasting, extruded；Wherein said crystallization is carried out by hydrothermal crystallizing, and crystallization temperature is 100-200 DEG C.
Method the most according to claim 7, it is characterised in that described solubility group vib slaine is
Solubility chromic salts and/or soluble molybdenum salt.
Method the most according to claim 8, it is characterised in that described solubility group vib slaine is
Five liquid glauber salt acid molybdenums and/or nine water chromic nitrates.
Method the most according to claim 7, it is characterised in that in step i), described colloidal state mixes
Al in terms of molal quantity in thing2O3:R:P2O5:SiO2:H2O=1:(2.0-3.0): (0.8-1.0): (0.8-1.0):
(30-50), wherein R is organic formwork agent.
11. methods according to claim 7, it is characterised in that aluminum source be aluminium hydroxide, aluminum isopropylate.,
One or more in 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 white carbon
One or more in black, tetraethyl orthosilicate, solid silicone and Ludox.
12. methods according to claim 7, it is characterised in that described method is additionally included in step ii)
The colloidal mixture that step i) obtains being carried out aging step, the most aging temperature is 80-130 DEG C before,
The aging time is 1-6 hour.
13. methods according to claim 12, it is characterised in that aging temperature is 80-110 DEG C.
14. method according to claim 7, it is characterised in that step ii) crystallization temperature be
180-200 DEG C, pressure is self-generated pressure, and crystallization time is 1-24 hour；Step ii) in be dried temperature be
80-130 DEG C, the temperature of roasting is 300-900 DEG C.
15. methods according to claim 14, it is characterised in that the temperature of roasting is 500-600 DEG C.
16. catalyst prepared according to the method according to any one of claim 7-15 are at n-butene isomery
Change the application in 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 CN104174433A (en) | 2014-12-03 |
| CN104174433B true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104174433A (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437605B (en) | W-ZSM-5 molecular-sieve-based catalyst as well as preparation method and application of W-ZSM-5 molecular-sieve-based catalyst | |
| CN102319584A (en) | Comprise molecular sieve or the novel microporous crystalline material of zeolite with 8 yuan of ring open-celled structures | |
| 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 | |
| CN101450806A (en) | AEI/CHA eutectic molecular sieve containing triethylamine and synthetic method thereof | |
| CN104108726B (en) | High silica alumina ratio CHA structure silicoaluminophosphamolecular molecular sieves and its synthetic method | |
| CN101259431B (en) | Cobalt modification silicoaluminophosphate molecular sieve and its preparation and catalytic application in MTO | |
| CN101503201B (en) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst | |
| CN104174433B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN104718161A (en) | Metallophosphate molecular sieves, method of preparation and use | |
| CN104108727B (en) | ZSM-11/SAPO-11 binary structure zeolite and synthetic method thereof | |
| CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
| CN103706394B (en) | Submicron SAPO-5/SAPO-18 composite molecular sieve and preparation method thereof | |
| CN103285915B (en) | A kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier | |
| CN104174435B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN106179483A (en) | A kind of method preparing methanol-to-olefins catalyst based on mesopore molecular sieve | |
| CN104174434B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN104174432B (en) | A kind of n-butene isomerization catalyst and preparation method thereof | |
| CN105665007B (en) | A kind of n-butene isomerization catalyst and preparation 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 | |
| CN103030155B (en) | Synthesis method of silicoaluminophosphate (SAPO)-44 molecular sieve | |
| CN106824261B (en) | Ni-SSZ-13 catalyst, preparation method and its usage | |
| CN105271302A (en) | SAPO-18 molecular sieve, method for synthesizing SAPO-18 molecular sieve and method for preparing olefin from methanol | |
| CN105665008B (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 |