CN105665006B - 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
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Abstract
The invention provides a kind of n-butene isomerization catalyst, including the composite molecular screens of SAPO 11/SAPO 46 with multistage pore canal as carrier, and be carried on the carrier and as the IB races metal of 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 the composite molecular screens of SAPO 11/SAPO 46 are prepared using appropriate crystal pattern and crystallization temperature, then IB races metal is loaded so that the catalyst turns into the bifunctional catalyst with metal and acid site.The preparation method is easy, non-environmental-pollution, is adapted to industrialized production.Catalyst provided by the present invention for n-butene skeletal isomerization when preparing isobutene with higher catalytic activity and higher selective isobutene.
Description
Technical field
The present invention relates to olefin isomerization catalyst field, and in particular to a kind of n-butene isomerization catalyst and its preparation
Method.
Background technology
Isobutene is a kind of important Organic Chemicals, be mainly used to produce methyl tertiary butyl ether(MTBE) (MTBE), the tert-butyl alcohol,
A variety of Organic chemical products such as butyl rubber, polyisobutene, methyl methacrylate, tert-butyl mercaptan.In recent years, due to isobutyl
The demand of alkene sharply increases, particularly for production environment friendly gasoline additive MTBE demand in the world
It is swift and violent to increase, and the isobutene yield that traditional oil Deep Catalytic Cracking process obtains is far from meeting industrial requirement, therefore it is domestic
The outer research and development for having carried out isobutene production new technology extensively.
In twentieth century the seventies and eighties, the n-butene isomerization catalyst developed in the world predominantly add halide and
The acidic oxidation Al catalysts that Si oxide obtains.Since nineteen nineties, external each major oil companies grind one after another
Zeolite-type molecular sieves or non-zeolitic molecular sieves processed are as n-butene skeletal isomerisation catalyst.Catalysis material used has phosphoric acid
Sial (SAPO) molecular sieve analog, ZSM-5, ZSM-22, ZSM-23, ZSM-35 molecular sieve, modenite, beta-zeolite etc..These points
Sub- sieve catalyst reaction temperature is low (300-400 DEG C), and catalyst coking, inactivation are slow, and stability is preferable, the selectivity of isobutene
Also it is high；Also compare also without using moving bed, fluidized-bed reactor, required fixed bed switching number of reactors to industrialization
Situation with the catalyst that aluminum oxide is carrier is few, so greatly reduces the investment to process units and the separation hardly possible of product
Degree.Especially SAPO molecular sieve analogs, because it has suitable acid site distribution and special pore structure and other features, its property
It can more protrude, turn into the focus of external each major company's research.
SAPO molecular sieve analogs are the U.S. combinating carbide company a kind of new non-zeolitic molecular sieves released in 1984.
SAPO-n is to substitute AlPO by Si atoms4Formed after P or Al atoms in-n skeletons by AlO4、PO4And SiO4Tetrahedron is formed
Non-neutral framework of molecular sieve, therefore there is tradable cation, and there is Bronsted acidity.While SAPO-n type molecular sieves
Aperture is 0.3-0.8nm, almost whole pore diameter ranges including zeolite molecular sieve；Pore volume (the H of SAPO-n type molecular sieves2O)
For 0.18-0.48cm3/g.As generation novel molecular sieve, SAPO-n type molecular sieves are in widespread attention in catalytic field.
SAPO-11 molecular sieves belong to mesoporous molecular sieve, have the non-crossing of three-dimensional as a member in SAPO-n type molecular sieves
10 yuan of rings ellipse ducts, aperture are 0.39 × 0.64nm.It is reported that SAPO-11 molecular sieves are at present in catalytic cracking, hydrogenation
A variety of oil refining such as cracking, isomerization, the alkylation with side chain aromatic hydrocarbons, isomerization dewaxing and light olefin polymerization in chemical engineering industry with obtaining
To extensive research or application.
It is different that patent application CN103145521A, which discloses a kind of molecular sieve catalyst with gold-supported by normal butylenes,
The method of butylene, after this method carries out sufficient negative pressure degasification purified treatment to molecular sieve, then using negative-pressure deposition precipitation method handle
Golden presoma and the second metal precursor are loaded on molecular sieve carrier, are obtained load type gold catalyst, are subsequently used for n-butene
Skeletal isomerization generates isobutene.Document disclosed above employs negative-pressure deposition precipitation method and HZSM-5 molecular sieve carriers are prepared for
Load gold catalyst, but be that complex for operation step, carrier duct is single the shortcomings that this method, cost is high, and catalytic effect is not good enough
Deng.
The content of the invention
The invention provides a kind of SAPO-11/SAPO-46 composite molecular screens using novelty as carrier, with copper, Yin Deng IB races
Metal is catalyst of active component and preparation method thereof.Carrier S APO-11/ used in catalyst provided by the invention
SAPO-46 composite molecular screens contain multistage pore canal, have preferable catalytic performance；The IB races metal of load to urge such as copper
Agent has that metal and acid site are difunctional, therefore the catalyst in n-butene isomerization reaction there is higher catalysis to live
Property, isomerization target product has higher selectivity.
According to the present invention, there is provided a kind of n-butene isomerization catalyst, including the SAPO-11/SAPO-46 as carrier
Composite molecular screen, and the IB races metal as active component being carried on the carrier.IB races metal is in catalyst
In can exist in the form of metal simple-substance, ion or compound.
In the present invention, term " SAPO-11/SAPO-46 composite molecular screens " refer to be different from SAPO-11 molecular sieves and
A kind of new molecular sieve of SAPO-46 molecular sieves, it has the structure of SAPO-11 molecular sieves and SAPO-46 molecular sieves simultaneously
Feature, and wherein multistage pore canal is uniformly distributed.
In a preferred embodiment of the invention, the SAPO-11/SAPO-46 used in catalyst provided by the present invention
Composite molecular screen be not simply by SAPO-11 molecular sieves and SAPO-46 molecular sieves are mutually mixed to obtain, it is but logical
Following steps are crossed to prepare：Step i)：Silicon source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, its
In in the 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, preferably Al2O3:R:P2O5:SiO2:H2O=1:2.0-3.0:0.8-1.0:0.8-1.0:30-50, wherein R are organic mould
Plate agent；Step ii)：The colloidal mixture crystallization that step i) is obtained, then washs crystallization product, dries, and roasting, is squeezed into
Type.Wherein, used silicon source, silicon source, phosphorus source and organic formwork agent are conventional.Silicon source is preferably aluminium hydroxide, hydration oxygen
Change the one or more in aluminium (such as boehmite), aluminium isopropoxide, aluminum nitrate, aluminum sulfate and aluminum phosphate.Phosphorus source is preferably
One or both of phosphoric acid and phosphorous acid.Organic formwork agent is preferably in di-n-propyl amine, diisopropylamine and diethylamide
One or more.Silicon source is preferably the one or more in White Carbon black, tetraethyl orthosilicate, solid silicone and Ludox.Pass through
The SAPO-11/SAPO-46 composite molecular screens that the above method is prepared are provided simultaneously with SAPO-11 molecular sieves and SAPO-46 molecules
The architectural feature of sieve, and the duct of SAPO-11 molecular sieves and SAPO-46 molecular sieve features is represented respectively in the compound molecule
It is evenly distributed in sieve, not by SAPO-11 molecular sieves and SAPO-46 molecular sieves, simply physical mixed can obtain this structure
Arrive.
In the X-ray powder diffraction spectrogram of SAPO-11/SAPO-46 composite molecular screens used in the present invention, it is in 2 θ
8.1 ° -8.3 °, 9.3 ° -9.5 °, 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 ° etc. go out
Existing characteristic peak.
Preferably, the Al in terms of molal quantity in SAPO-11/SAPO-46 composite molecular screens2O3: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 catalyst provided by the invention, based on the gross weight meter of the catalyst, the content of carrier is 94-99.5 weights
Measure %, preferably 95-99 weight %；The content of active component is calculated as 0.5-6 weight %, preferably 1-5 with IB races metallic atom
Weight %.
In catalyst provided by the invention, IB races metal can be at least one of copper, silver and gold, and be preferably
Copper.
The invention provides the preparation method of n-butene isomerization catalyst as described above, including：Step I：Prepare dense
Spend the aqueous solution of the soluble IB races metal salt for 0.04-0.4mol/L；Step II：By the SAPO-11/SAPO-46 after shaping
Composite molecular screen is placed in the solution that step I obtains, and 1-24 hours are mixed at 50-90 DEG C；Step III：By the reaction of step II
Mixture separation of solid and liquid, for example filter, wash simultaneously drying solid.
Soluble IB races metal salt in step I is preferably soluble copper salt and/or soluble silver salt, is more preferably
At least one of copper nitrate (such as nitrate trihydrate copper), copper chloride and silver nitrate.In step II, it is mixed preferably reaction will to be housed
The container of compound is placed in placement 1-24 hours in 50-100 DEG C of shaking bath.The drying temperature of step III is preferably 80-120
℃。
In one embodiment, the above method also includes the preparation process of SAPO-11/SAPO-46 composite molecular screens, bag
Include：Step i)：Silicon source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, wherein being mixed in the colloidal state
The Al in terms of molal quantity in compound2O3: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 are organic formwork agent；Step
ii)：The colloidal mixture crystallization that step i) is obtained, then washs crystallization product, dries, roasting, extrusion forming.
Silicon source, silicon source, phosphorus source and the organic formwork agent used in the inventive method is conventional.Silicon source is preferably hydroxide
One or more in aluminium, hydrated alumina (such as boehmite), aluminium isopropoxide, aluminum nitrate, aluminum sulfate and aluminum phosphate.Phosphorus
Source is preferably one or both of phosphoric acid and phosphorous acid.Organic formwork agent is preferably di-n-propyl amine, diisopropylamine and two
One or more in ethylamine.Silicon source is preferably one kind or more in White Carbon black, tetraethyl orthosilicate, solid silicone and Ludox
Kind.
In a preferred embodiment of the inventive method, phosphorus source used is phosphoric acid, and silicon source is boehmite, silicon
Source is Ludox, and organic formwork agent is di-n-propyl amine.
After colloidal mixture is obtained, the mixture is preferably subjected to aging.Therefore, method of the invention can also wrap
Include in step ii) before the colloidal mixture that obtains step i) the step of carrying out aging, wherein the temperature of aging is 80-130
DEG C, preferably 80-110 DEG C, the time of aging is 1-6 hours, preferably 2-6 hours.It is particularly preferred that aging is in 80-110
2-6 hours are carried out at a temperature of DEG C.
Step ii) crystallization carried out advantageous by hydrothermal crystallizing, carried out preferably in closed container.The temperature of hydrothermal crystallizing
Degree is preferably 100-200 DEG C, also preferably 150-200 DEG C, more preferably 180-200 DEG C；Pressure is self-generated pressure (i.e. closed
Caused pressure when being reacted in reactor)；Crystallization time is 1-24 hours, preferably 2-24 hours.It is particularly preferred that water
Thermal crystallisation carries out 2-24 hours at 180-200 DEG C of temperature and self-generated pressure.
In step ii) in, dry and roasting is conventional.Dry temperature is preferably 80-130 DEG C, more preferably 110-
130℃.Drying time is usually 2-48 hours, preferably 2-24 hours.The temperature of roasting is preferably 500-600 DEG C, more preferably
For 550-600 DEG C.Roasting time is usually 2-12 hours, preferably 3-10 hours.The roasting can be carried out in Muffle furnace.It is real
Issue after examination and approval now, spread out according to SAPO-11/SAPO-46 composite molecular screens prepared by the method for the present invention in the front and rear x-ray powder of roasting
The number of characteristic diffraction peak and position in spectrogram is penetrated almost not change.
In the SAPO-11/SAPO-46 compound molecules for before preparing catalyst, will generally be obtained by above-mentioned steps
Carrier extrusion forming is sieved, such as it is mixed with adhesive, extruded moulding, dry, pulverize sieving, obtains a certain size (at this
In invention be usually 20-40 mesh) catalyst carrier.Adhesive is the traditional binders for preparing catalyst, such as aqua oxidation
Aluminium.
Washing step involved in the methods of the invention, it is conventional, generally filtration washing, centrifugation can be used to wash
The washing methods such as wash, preferably use centrifuge washing.
It is anti-that in n-butene isomerization isobutene is prepared present invention also offers a kind of catalyst prepared by the above method
Application in answering.It is preferred that the reaction temperature of the n-butene isomerization is 300-450 DEG C, reaction pressure is normal pressure, the positive fourth of raw material
The mass space velocity of alkene is 1.0-2.0h-1。
In the method for the catalyst for preparing SAPO-11/SAPO-46 composite molecular screens load IB races metal of the present invention,
SAPO-11/ is prepared by controlling the proportioning of raw material in building-up process, and using appropriate crystal pattern and crystallization temperature
SAPO-46 composite molecular screens, shorten crystallization time, and the product crystallinity prepared is high, while by loading IB races metal (example
Such as copper) so that the catalyst turns into the bifunctional catalyst with metal and acid site.
It the experiment proved that, it is provided by the invention with the SAPO-11/SAPO-46 composite molecular screens with multi-stage artery structure
There is unique acidity and multi-stage artery structure for the support type IB races metallic catalyst of carrier, it is different for n-butene skeleton
With higher catalytic activity when structure prepares isobutene, obtained target product has higher selectivity.Meanwhile the present invention
The method for preparing catalyst of offer is easy, non-environmental-pollution, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram for the SAPO-11/SAPO-46 composite molecular screens that embodiment 1 is prepared.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described, but the scope invented is not limited to these
Embodiment.
In the examples below, the SAPO-11/SAPO- being prepared by the method for the present invention surely by X-ray diffraction spectrum illustrated handbook
The structure of 46 composite molecular screens.Used instrument is power ＆ light company of U.S. ARLX ' TRA type diffractometers, specifically in X-ray tube
Voltage is 35kV, and electric current 30mA, scanning range is 3-40 °, and sweep speed carries out qualitative to sample under conditions of being 2 °/min
Analysis.
The microreactor used in each embodiment is tubular fixed-bed reactor, and device pipeline uses stainless steel tube
Material, catalyst are loaded in reactor flat-temperature zone with fixed bed form, both ends filling quartz sand.
Embodiment 1
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 16.14g (0.14mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h.
Measure 4.78ml (0.035mol) di-n-propyl amine to be added drop-wise in above-mentioned solution, stir 1h.Then 10.08g is weighed again
(0.042mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:0.5:1:0.6:50, wherein R are di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation in 80 DEG C of aging 4h, 180 DEG C are then heated to, hydro-thermal is brilliant at autogenous pressures
Change 22h.Crystallization products therefrom is cooled down, centrifuge washing, then in 120 DEG C of dry 12h.It is compound to obtain SAPO-11/SAPO-46
Molecular sieve, its X-ray powder diffraction figure are as shown in Figure 1.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 550 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, pulverizes and sieves, and the catalyst for obtaining 20-40 mesh carries
Body.
2) preparation of catalyst
0.04mol/L nitrate trihydrate copper liquor is prepared, appropriate above-mentioned carrier is weighed and is placed in prepared solution,
Placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, dried at 120 DEG C,
Loaded catalyst is obtained, wherein based on overall catalyst weight gauge, the content of copper is 0.5 weight %.
3) application of the catalyst in n-butene isomerization reaction
The above-mentioned catalyst being prepared of 2.0g is taken to be put into microreactor, with mixing carbon four unstrpped gas (this after ether
" unstrpped gas of carbon four is mixed after ether " used in invention and refer to that isobutene obtains with methanol reaction synthesizing methyl tertbutyl ether
Reactant mixture in take out the remaining mixing C-4-fraction after methyl tertiary butyl ether(MTBE), main component is n-butene and iso-butane,
Its content is respectively 25 volume % or so and 35 volume % or so) evaluated.Reaction temperature is 320 DEG C, and carbon four is mixed after ether
The mass space velocity of unstrpped gas is calculated as 1.0h with n-butene-1.The n-butene conversion of acquisition is 46%, and selective isobutene is
93%.
Embodiment 2
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 16.14g (0.14mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h.
Measure 7.64ml (0.056mol) diisopropylamine to be added drop-wise in above-mentioned solution, stir 1h.Then 10.08g is weighed again
(0.042mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:0.8:1:0.6:40, wherein R are diisopropylamine.
By the colloidal mixture of above-mentioned preparation in 100 DEG C of aging 3h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 12h.Crystallization products therefrom is cooled down, centrifuge washing, then in 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 and answer
Close molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 550 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
0.24mol/L nitrate trihydrate copper liquor is prepared, a certain amount of above-mentioned carrier is weighed and is placed in prepared solution
In, placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, done at 120 DEG C
It is dry, loaded catalyst is obtained, wherein based on overall catalyst weight gauge, the content of copper is 3 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 340 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 48%, selective isobutene 98%.
Embodiment 3
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 16.14g (0.14mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h；
Measure 14.3ml (0.105mol) di-n-propyl amine to be added drop-wise in above-mentioned solution, stir 1h.Then 13.44g is weighed again
(0.056mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:1.5:1:0.8:50, wherein R are di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation in 110 DEG C of aging 4h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 8h.Crystallization products therefrom is cooled down, centrifuge washing, then in 120 DEG C of dry 6h, it is compound to obtain SAPO-11/SAPO-46
Molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 600 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
0.4mol/L nitrate trihydrate copper liquor is prepared, a certain amount of above-mentioned carrier is weighed and is placed in prepared solution
In, placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, done at 120 DEG C
It is dry, loaded catalyst is obtained, wherein based on overall catalyst weight gauge, the content of copper is 6 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 380 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 49%, selective isobutene 96%.
Embodiment 4
1) preparation of SAPO-11/SAPO-46 composite molecular screens
46.65g (0.07mol) Patent alum is weighed, is dissolved in 10g deionized waters and is made into boehmite water
Solution, stir 0.5h.Instill 16.14g (0.14mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), then stir
Mix 1h；Measure 14.3ml (0.105mol) di-n-propyl amine to be added drop-wise in above-mentioned solution, stir 1h.Then 13.44g is weighed again
(0.056mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:1.5:1:0.8:50, wherein R are di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation in 110 DEG C of aging 4h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 8h.Crystallization products therefrom is cooled down, centrifuge washing, then in 120 DEG C of dry 6h, it is compound to obtain SAPO-11/SAPO-46
Molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 600 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
0.3mol/L nitrate trihydrate copper liquor is prepared, a certain amount of above-mentioned carrier is weighed and is placed in prepared solution
In, placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, done at 120 DEG C
It is dry, loaded catalyst is obtained, wherein based on overall catalyst weight gauge, the content of copper is 0.5 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 380 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 50%, selective isobutene 97%.
Embodiment 5
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 14.53g (0.126mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h.
Measure 22.92ml (0.168mol) diisopropylamine to be added drop-wise in above-mentioned solution, stir 1h.Then 15.12g is weighed again
(0.063mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:2.4:0.9:0.9:40, wherein R are diisopropylamine.
By the colloidal mixture of above-mentioned preparation in 100 DEG C of aging 3h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 12h.Crystallization products therefrom is cooled down, centrifuge washing, then in 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 and answer
Close molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 550 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
0.15mol/L nitrate trihydrate copper liquor is prepared, a certain amount of above-mentioned carrier is weighed and is placed in prepared solution
In, placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, done at 120 DEG C
It is dry, loaded catalyst is obtained, wherein based on overall catalyst weight gauge, the content of copper is 1.5 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 340 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 52%, selective isobutene 97%.
Embodiment 6
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 12.91g (0.112mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h.
Measure 28.65ml (0.21mol) diisopropylamine to be added drop-wise in above-mentioned solution, stir 1h.Then 15.12g is weighed again
(0.063mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:3:0.8:0.9:40, wherein R are diisopropylamine.
By the colloidal mixture of above-mentioned preparation in 100 DEG C of aging 3h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 12h.Crystallization products therefrom is cooled down, centrifuge washing, then in 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 and answer
Close molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 550 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
0.15mol/L nitrate trihydrate copper liquor is prepared, a certain amount of above-mentioned carrier is weighed and is placed in prepared solution
In, placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, done at 120 DEG C
It is dry, loaded catalyst is obtained, wherein based on overall catalyst weight gauge, the content of copper is 3 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 340 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 51%, selective isobutene 98%.
Embodiment 7
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 14.53g (0.126mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h.
Measure 22.92ml (0.168mol) diisopropylamine to be added drop-wise in above-mentioned solution, stir 1h.Then 15.12g is weighed again
(0.063mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:2.4:0.9:0.9:40, wherein R are diisopropylamine.
By the colloidal mixture of above-mentioned preparation in 100 DEG C of aging 3h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 12h.Crystallization products therefrom is cooled down, centrifuge washing, then in 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 and answer
Close molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 550 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
Prepare 0.15mol/L the Copper dichloride dihydrate aqueous solution, weigh a certain amount of above-mentioned carrier be placed in prepared it is molten
In liquid, placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, at 120 DEG C
Dry, obtain loaded catalyst, wherein based on overall catalyst weight gauge, the content of copper is 1.5 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 340 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 48%, selective isobutene 97%.
Embodiment 8
1) preparation of SAPO-11/SAPO-46 composite molecular screens
9.52g (0.07mol) boehmite is weighed, is dissolved in 10g deionized waters and is made into the boehmite aqueous solution,
Stir 0.5h.Instill 14.53g (0.126mol) H thereto with vigorous stirring3PO4(the 85 weight % aqueous solution), is stirred for 1h.
Measure 22.92ml (0.168mol) diisopropylamine to be added drop-wise in above-mentioned solution, stir 1h.Then 15.12g is weighed again
(0.063mol) Ludox is added in above-mentioned solution.Water is added, 1h is stirred, colloidal mixture is obtained, in the colloidal mixture
In the Al in terms of molal quantity2O3:R:P2O5:SiO2:H2O=1:2.4:0.9:0.9:40, wherein R are diisopropylamine.
By the colloidal mixture of above-mentioned preparation in 100 DEG C of aging 3h, 180 DEG C are then heated to, at autogenous pressures hydro-thermal
Crystallization 12h.Crystallization products therefrom is cooled down, centrifuge washing, then in 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 and answer
Close molecular sieve, its X-ray powder diffraction figure (not shown) and Fig. 1 are essentially identical, 2 θ be 8.1 ° -8.3 °, 9.3 ° -9.5 °,
There is characteristic peak at 13.1 ° -13.3 °, and 6.5 ° -6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
The SAPO-11/SAPO-46 composite molecular screens of gained are placed in Muffle furnace and are calcined 4h in 550 DEG C, it is then thin with plan
Diaspore (as adhesive) mixes, and extruded moulding, in 120 DEG C of dry 8h, then pulverizes and sieves, obtains the catalysis of 20-40 mesh
Agent carrier.
2) preparation of catalyst
0.15mol/L silver nitrate aqueous solution is prepared, a certain amount of above-mentioned carrier is weighed and is placed in prepared solution, in
Placed 12 hours in 100 DEG C of shaking bath, filter, obtained solid is washed with deionized, dried, obtain at 120 DEG C
To loaded catalyst, wherein based on overall catalyst weight gauge, silver-colored content is 1.5 weight %.
3) application of the catalyst in n-butene isomerization reaction
Take the above-mentioned catalyst being prepared of 2.0g to be put into microreactor, carried out with the unstrpped gas of carbon four is mixed after ether
Evaluation.Reaction temperature is 340 DEG C, and the mass space velocity that the unstrpped gas of carbon four is mixed after ether is calculated as 1.0h with n-butene-1.Obtain just
Butene conversion is 48%, selective isobutene 97%.
Comparative example 1
1) preparation of SAPO-11 molecular sieves and SAPO-46 molecular sieves
SAPO-11 molecular sieves and SAPO-46 molecules are prepared respectively with reference to patent document US4440871 and CN101229921A
Sieve, respectively takes 10g uniformly to be mixed, is then mixed with boehmite (as adhesive), extruded moulding, in 120 DEG C of dryings
8h, then pulverize and sieve, obtain the catalyst carrier of 20-40 mesh.
2) preparation of catalyst
Catalyst is prepared with reference to the step 2) of embodiment 1, difference is, the carrier used is 1) this comparative example step is prepared
Catalyst carrier.
3) application of the catalyst in n-butene isomerization reaction
N-butene isomerization reaction is carried out with reference to the step 3) of embodiment 1, difference is that the catalyst used is this contrast
Catalyst prepared by example step 2).As a result the n-butene conversion obtained is 40%, selective isobutene 92%.
Comparative example 2
1) preparation of SAPO-11 molecular sieves and SAPO-46 molecular sieves
SAPO-11 molecular sieves and SAPO-46 molecules are prepared respectively with reference to patent document US4440871 and CN101229921A
Sieve, respectively takes 10g uniformly to be mixed, is then mixed with boehmite (as adhesive), extruded moulding, in 120 DEG C of dryings
8h, then pulverize and sieve, obtain the catalyst carrier of 20-40 mesh.
2) preparation of catalyst
Catalyst is prepared with reference to the step 2) of embodiment 2, difference is, the carrier used is 1) this comparative example step is prepared
Catalyst carrier.
3) application of the catalyst in n-butene isomerization reaction
N-butene isomerization reaction is carried out with reference to the step 3) of embodiment 2, difference is that the catalyst used is this contrast
Catalyst prepared by example step 2).As a result the n-butene conversion obtained is 43%, selective isobutene 93%.
As shown in figure 1,2 θ, which are 8.2 °, 9.4 ° and 13.2 ° etc., there is SAPO-11 characteristic peak, 2 θ are 6.6 °,
7.7 ° and 19.9 ° etc. there is SAPO-46 characteristic peak, indicate the composite molecular screen that embodiment 1 obtains while have
The architectural feature of SAPO-11 molecular sieves and SAPO-46 molecular sieves.In addition, being found in experimentation, embodiment 2-8's is compound
The composite molecular screen that molecular sieve obtains with embodiment 1 has identical structure.
From above example, SAPO-11/SAPO-46 composite molecular screens are used as carrier according to the present invention, with IB races
Metal obtains the selectivity of very high target product isobutene, example for the catalyst of active component in n-butene isomerization reaction
Such as reach 98%, the conversion ratio of n-butene also reaches 52%.By contrast, prepared respectively in comparative example SAPO-11 molecular sieves and
SAPO-46 molecular sieves, the catalyst then prepared using its simple mixtures as carrier, obtained in n-butene isomerization reaction
More obvious than the embodiment of the present invention low selective isobutene and n-butene conversion.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that each side of the invention recorded, different embodiments
Each several part and the various features enumerated can be combined or all or part of exchange.In above-mentioned each embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, and this is by by this area skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that description above is only the mode of example, not purport
In the limitation present invention.
Claims (18)
1. a kind of n-butene isomerization catalyst, it is characterised in that the catalyst includes the SAPO-11/SAPO- as carrier
46 composite molecular screens, and be carried on the carrier and as the IB races metal of active component；
Wherein, the preparation process of the SAPO-11/SAPO-46 composite molecular screens includes：
Step i)：Silicon source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, wherein being mixed in the colloidal state
The Al in terms of molal quantity in compound2O3:R:P2O5:SiO2:H2O=1:0.2-5.0:0.6-2.0:0.1-1.5:15-80, wherein R are
Organic formwork agent；
Step ii)：The colloidal mixture crystallization that step i) is obtained, then washs crystallization product, dries, and roasting, is squeezed into
Type.
2. catalyst according to claim 1, it is characterised in that the gross weight meter based on the catalyst, carrier contain
Measure and 0.5-6 weight % is calculated as with IB races metallic atom for 94-99.5 weight %, the content of active component.
3. catalyst according to claim 1, it is characterised in that IB races metal is at least one of copper and silver.
4. catalyst according to claim 1, it is characterised in that IB races metal is copper.
5. catalyst according to claim 1, it is characterised in that to rub in SAPO-11/SAPO-46 composite molecular screens
You are number meter Al2O3:P2O5:SiO2=1:0.5-2.5:0.2-2.0.
6. catalyst according to claim 1, it is characterised in that to rub in SAPO-11/SAPO-46 composite molecular screens
You are number meter Al2O3:P2O5:SiO2=1:0.8-1.0:0.2-1.0.
7. according to the catalyst any one of claim 1-6, it is characterised in that answered in the SAPO-11/SAPO-46
It is 8.1 ° -8.3 °, 9.3 ° -9.5 °, 13.1 ° -13.3 ° in 2 θ in the X-ray powder diffraction spectrogram for closing molecular sieve, and 6.5 ° -
There is characteristic peak at 6.7 °, 7.6 ° -7.8 ° and 19.8 ° -20.0 °.
8. a kind of method for preparing the catalyst as any one of claim 1-7, including：
Step I：Configuration concentration is the aqueous solution of 0.04-0.4mol/L soluble IB races metal salt；
Step II：SAPO-11/SAPO-46 composite molecular screens after shaping are placed in the solution that step I obtains, in 50-100
1-24 hours are mixed at DEG C；
Step III：By the reactant mixture separation of solid and liquid of step II, simultaneously drying solid is washed.
9. according to the method for claim 8, it is characterised in that the soluble IB races metal salt be soluble copper salt and/
Or soluble silver salt.
10. according to the method for claim 9, it is characterised in that the soluble IB races metal salt is copper nitrate, copper chloride
At least one of with silver nitrate.
11. according to the method described in any one in claim 8-10, it is characterised in that methods described also includes SAPO-11/
The preparation process of SAPO-46 composite molecular screens, including：
Step i)：Silicon source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, wherein being mixed in the colloidal state
The Al in terms of molal quantity in compound2O3:R:P2O5:SiO2:H2O=1:0.2-5.0:0.6-2.0:0.1-1.5:15-80, wherein R are
Organic formwork agent；
Step ii)：The colloidal mixture crystallization that step i) is obtained, then washs crystallization product, dries, and roasting, is squeezed into
Type.
12. according to the method for claim 11, it is characterised in that the Al in terms of molal quantity in the colloidal mixture2O3:
R:P2O5:SiO2:H2O=1:2.0-3.0:0.8-1.0:0.8-1.0:30-50.
13. according to the method for claim 11, it is characterised in that source of aluminium is aluminium hydroxide, hydrated alumina, isopropyl
One or more in aluminium alcoholates, aluminum nitrate, aluminum sulfate and aluminum phosphate；Phosphorus source is one kind or two in phosphoric acid and phosphorous acid
Kind；The organic formwork agent is the one or more in di-n-propyl amine, diisopropylamine and diethylamide；The silicon source is white
One or more in carbon black, tetraethyl orthosilicate, solid silicone and Ludox.
By step before 14. according to the method for claim 11, it is characterised in that methods described is additionally included in step ii)
I) colloidal mixture obtained is carried out the step of aging, and wherein the temperature of aging is 80-130 DEG C, and the time of aging is small for 1-6
When.
15. according to the method for claim 14, it is characterised in that the temperature of the aging is 80-110 DEG C.
16. crystallization according to the method for claim 11, it is characterised in that step ii) is carried out by hydrothermal crystallizing, crystallization
Temperature is 100-200 DEG C, and pressure is self-generated pressure, and crystallization time is 1-24 hours；Step ii) in dry temperature be 80-130
DEG C, the temperature of roasting is 300-900 DEG C.
17. crystallization temperature according to the method for claim 16, it is characterised in that step ii) is 180-200 DEG C, roasting
Temperature be 500-600 DEG C.
18. the catalyst that the method according to any one of claim 8-17 is prepared is in n-butene isomerization reaction
Application.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888921A (en) * | 1995-10-25 | 1999-03-30 | Abb Lummus Global Inc. | Binary molecular sieves having a core and shell of different structures and compositions |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888921A (en) * | 1995-10-25 | 1999-03-30 | Abb Lummus Global Inc. | Binary molecular sieves having a core and shell of different structures and compositions |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
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