CN106000269B - It is a kind of for the Reaction Separation double-function catalyzing film reaction device of catalysis methanol dehydration dimethyl ether-preparing and its application - Google Patents
It is a kind of for the Reaction Separation double-function catalyzing film reaction device of catalysis methanol dehydration dimethyl ether-preparing and its application Download PDFInfo
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- CN106000269B CN106000269B CN201610343926.XA CN201610343926A CN106000269B CN 106000269 B CN106000269 B CN 106000269B CN 201610343926 A CN201610343926 A CN 201610343926A CN 106000269 B CN106000269 B CN 106000269B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2475—Membrane reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
Abstract
The present invention relates to a kind of for the Reaction Separation double-function catalyzing film reaction device of catalysis methanol dehydration dimethyl ether-preparing and its application.Specifically, the reaction unit includes inner chamber and exocoel, and the inner chamber includes successively from inside to outside：Porous matrix, the first molecular screen membrane for being incorporated into the porous matrix surface and the second molecular screen membrane for being incorporated into the first molecular screen membrane surface, and it is used for filling material gas methanol between the inner chamber and the exocoel.When preparing dimethyl ether using described device, second molecular screen membrane not only can catalytic reaction progress, while also effectively can avoid or reduce the generation of accessory substance；First molecular screen membrane can high selectivity separation reaction product water vapour, so as to break the limitation of the balance of reaction, improve the yield of dimethyl ether.Therefore, the reaction unit provides a kind of new selection for the preparation of dimethyl ether.
Description
Technical field
The present invention relates to dimethyl ether preparing technical field, is used for catalysis methanol dehydration dimethyl ether-preparing more particularly to one kind
Reaction Separation double-function catalyzing film reaction device and its application.
Background technology
With China's sustained economic development, the contradiction of energy demand, it has a strong impact on and constrained China's warp
Help social comprehensive coordinate and sustainable development.Develop the new replacement energy such as coal-based methanol, coal base dimethyl ether, wood-based composites
Source has great strategic importance to alleviating domestic petroleum short supply contradiction and reducing dependence of the China to international petroleum.Its
In, the dimethyl ether for being referred to as " 21 century clean fuel " has very excellent combustibility, and as it has, Cetane number is high, fires
The advantages of burning efficiency high and good power performance；Few using dimethyl ether fuel pollution, tail gas can be with row without catalyzed conversion processing
Put；Dimethyl ether easily be easy to store and utilize by liquefaction.So as vehicle alternative fuel, dimethyl ether have natural gas, methanol,
The incomparable comprehensive advantage such as ethanol, propane, butane, diesel oil, thus there is boundless market application foreground.
The technology of production dimethyl ether mainly includes the synthesis of methanol Direct Dehydration at present and synthesis gas directly synthesizes two kinds of techniques.
Wherein, methanol Direct Dehydration synthetic method is that methanol Direct Dehydration is generated into dimethyl ether in a reactor；Synthesis gas directly closes
It is using natural gas or the synthesis gas of coal vaporization generation as raw material into method, methanol-fueled CLC and dehydration is completed simultaneously in a reactor
Two courses of reaction of dimethyl ether are prepared.
Methanol Direct Dehydration method is current most ripe, the most widely used technology for preparing dimethyl ether, and the method mainly uses
Solid acid catalyst include aluminum oxide and acidic molecular sieve, such as γ-Al2O3, HZSM-5, HY, HZSM-22, MFI etc..Wherein,
γ-Al2O3Because cost is relatively low, acid weaker and be widely used.But γ-Al2O3Low activity and hydrothermal stability make
Obtaining its catalytic performance and life-span can quickly reduce.In molecular sieve catalyst, HZSM-5 due to excellent catalytic performance and
Stability, thus as the most commonly used catalyst of research.However, HZSM-5 acidity is stronger, when using it as catalyst,
DME synthesis can be caused easily to cause the generation of accessory substance and catalyst carbon deposition in reaction in reacting, and then cause catalytic performance
It is greatly reduced.
Further, since methanol dehydration dimethyl ether-preparing is a reversible balanced reaction, as shown in reactional equation (1).Passing
In the fixed bed reactors of system, with the progress of reaction, the yield of dimethyl ether is extremely limited, and raw in course of reaction
Into water byproduct steam can greatly reduce the catalytic activity of catalyst.So how to break the balance limitation of reaction, so as to
The yield and selectivity for improving dimethyl ether are still a huge challenge.
2CH3OH=CH3OCH3(DME)+H2O Δs H=-23.4kJ/mol (1)
Membrane catalytic reaction is the novel catalytic reaction technology with wide application prospect that developed recently gets up, and it can be same
When complete catalytic reaction and product and separate two processes, so as to realize the purpose of catalysis-reaction-isolation integral.Film is urged
Changing reaction not only has the advantages that simple flow, reduces investment outlay, reduces energy consumption, and to those by thermodynamical equilibrium limited without
The chemical reaction of conversion ratio can be improved, its can by the way that selectively reaction product is constantly separated from reaction system,
To break the limitation of its original thermodynamical equilibrium, so as to greatly improve the conversion of the selectivity of catalytic reaction and reactant
Rate.The key of membrane catalytic reaction technology application is to develop not only to have high catalytic activity to reactant but also to reaction production with core
Thing has high separation selectivity and has high thermal stability and the Reaction Separation double-function catalyzing film of chemical stability concurrently simultaneously.
Molecular-sieve film catalytic due to good catalytic activity and molecule sieve performance and higher heat endurance and
Chemical stability, it is increasingly becoming the study hotspot of catalysis and material subject intersection.Molecular sieve be it is a kind of with silicon-oxy tetrahedron and/or
Aluminum-oxygen tetrahedron is basic structural unit, has the porous crystalline inorganic material in the neat duct of specification, and it has excellent acid
Catalytic activity, catalyst is particularly widely used as in petrochemical industry in the industry.Since the 1990s, molecule
The preparation and application study of sieve membrane receive significant attention, up to now it has been reported that 20 different kinds of molecules sieve membranes.Wherein, ZSM-5,
FAU, MOR and SAPO equimolecular sieve catalytic membrane in ethylbenzene catalytic dehydrogenation reaction, methyl hydride catalyzed preparing synthetic gas, methanol oxidation diformazan
Ether and ethene, dehydrogenation of isoamylene preparing isoprene react, dehydrogenation of isopropanol acetone reacts, butylene dehydrogenation butadiene reacts,
The courses of reaction such as preparing isobutene through dehydrogenation of iso-butane reaction, nitrobenzene dehydrogenation aniline are applied.But point reported at present
Sub- sieve membrane reactor generally only has single reaction or separation function, can not meet to react and separate difunctional coupling simultaneously
It is required that exploitation efficient catalytic transformation of synthetic gas prepares the bifunctional molecule sieve membrane reactor of dimethyl ether integrated reaction and separation still
It is a huge challenge.
The content of the invention
It is an object of the invention to provide a kind of double work(of Reaction Separation that dimethyl ether is prepared particularly suitable for methanol Direct Dehydration
Can molecular-sieve film catalytic reaction unit.
The first aspect of the present invention, there is provided a kind of Reaction Separation for catalysis methanol dehydration dimethyl ether-preparing is difunctional
Catalytic membrane reaction unit, the reaction unit include inner chamber and exocoel, and the inner chamber includes successively from inside to outside：Porous matrix,
The first molecular screen membrane for being incorporated into the porous matrix surface and the second molecular sieve for being incorporated into the first molecular screen membrane surface
Film, and it is used for filling material gas methanol between the inner chamber and the exocoel.
In another preference, first molecular screen membrane is hydrophilic molecule sieve membrane, is reacted for Selective Separation
The water vapour formed in journey.
In another preference, the thickness of first molecular screen membrane is 1-50 μm, preferably 2-30 μm, more preferably 3-10
μm。
In another preference, first molecular screen membrane is LTA molecular screen membranes.
In another preference, first molecular screen membrane is incorporated into the porous matrix table by Covalently attached interaction
Face.
In another preference, second molecular screen membrane is FAU molecular screen membranes, and diformazan is prepared for catalysis methanol dehydration
The reaction of ether.
In another preference, the thickness of second molecular screen membrane is 1-30 μm, preferably 2-20 μm, more preferably 3-10
μm。
In another preference, second molecular screen membrane is incorporated into first molecular screen membrane by Covalently attached interaction
Surface.
In another preference, second molecular screen membrane is in faintly acid.
In another preference, " being in faintly acid " refers to second molecular screen membrane in ammonia detachment assays,
The ammonia desorption peaks of strong acid site are not observed between 400 DEG C -600 DEG C.
In another preference, the porous matrix is selected from the group：Porous alumina ceramic, porous titanium dioxide ceramic,
Porous stainless steel, stainless (steel) wire.
In another preference, first molecular screen membrane and/or second molecular screen membrane are crystal.
In another preference, the sial of the silica alumina ratio of second molecular screen membrane and first molecular screen membrane rubs
Ratio >=1 of your ratio, preferably >=2, more preferably >=3, preferably 3.5-6.
In another preference, first molecular screen membrane (is preferably to selectivity >=99% of reaction product dimethyl ether
100%)；And/or
The reaction unit is in 310 DEG C of conversion ratio >=80% to methanol.
In another preference, the reaction unit is in 310 DEG C of conversion ratio >=85% to methanol, preferably >=87%.
In another preference, the exocoel is membrane module, and the molecular screen membrane being prepared can be fixed in membrane module.
In another preference, the inner chamber prepares as follows：
I) provide porous matrix, first modification solution, second modification solution, the first molecular screen membrane synthetic solvent, second point
Sub- sieve membrane synthetic solvent and ion exchange liquid；
II) porous matrix is placed in the first modification solution and modified, obtains the porous matrix through modification；
III) porous matrix through modification is placed in the first molecular screen membrane synthetic solvent, reaction is obtained through institute
State the porous matrix of the first molecular screen membrane cladding；
IV) porous matrix through first molecular screen membrane cladding is placed in the second modification solution and repaiied
Decorations, obtain the porous matrix of the first molecular screen membrane cladding through modification；
V) that the porous matrix that first molecular screen membrane through modification coats is placed in into the second molecular screen membrane synthesis is molten
In liquid, reaction obtains the porous matrix (i.e. inner chamber) coated through the molecular screen membrane of the second molecular screen membrane-the first；
VI the porous matrix through the molecular screen membrane of the second molecular screen membrane-the first cladding optionally) is placed in ion
Exchange in liquid, reaction obtains the porous matrix of second the-the first molecular screen membrane of molecular screen membrane cladding through ion-exchange treatment (in i.e.
Chamber).
In another preference, the first modification solution and the second modification solution may be the same or different, only respectively
On the spot comprising the one or more materials being selected from the group：APTES、DICB、CPTMS、CPTCS、CPDMS、CPCS、BPTMS、
BPPCS and IPTMS.
In another preference, the solvent of the first modification solution and the second modification solution may be the same or different,
The separately material to be selected from the group：Toluene, methanol, N,N-dimethylformamide or its combination.
In another preference, the composition of the first molecular screen membrane synthetic solvent is aNa2O:bAl2O3:5SiO2:cH2O,
Wherein a=(20-100), b=(0.1-5), c=(500-2000).
In another preference, the composition of the first molecular screen membrane synthetic solvent is aNa2O:bAl2O3:5SiO2:cH2O,
Wherein a=(30-80), b=(0.5-3), c=(800-1500).
In another preference, the composition of the second molecular screen membrane synthetic solvent is aNa2O:bAl2O3:20SiO2:
cH2O, wherein a=(30-100), b=(0.1-5), c=(1000-3000).
In another preference, the composition of the second molecular screen membrane synthetic solvent is aNa2O:bAl2O3:20SiO2:
cH2O, wherein a=(50-85), b=(0.5-3), c=(1500-2500).
In another preference, the ion exchange liquid includes the ion exchange material being selected from the group：Ammonium nitrate, acetic acid
Ammonium, acetone, ethanol or its combination.
In another preference, the concentration of ion exchange material described in the ion exchange liquid is 0.001-0.1mol/
L。
In another preference, step III) reaction and/or step V) reaction may be the same or different, and it is only respectively
On the spot it is selected from the group：Microwave attenuation materials reaction, Vacuum-assisted method reaction.
In another preference, step III) reaction and/or step V) reaction temperature of the reaction is 50-120
DEG C, preferably 50-100 DEG C.
In another preference, the reaction time of the Vacuum-assisted method reaction is 2-60h, preferably 10-30h.
In another preference, the reaction time of the microwave attenuation materials reaction is 10-120min, preferably 20-
60min。
In another preference, the step VI) described in the reaction temperature reacted be 10-80 DEG C；And/or
The step VI) described in reaction time for reacting be 1-90h.
In another preference, the step VI) described in the reaction temperature reacted be 20-60 DEG C, preferably 25-45
℃。
In another preference, the step VI) described in reaction time for reacting be 5-60h, preferably 10-50h.
The second aspect of the present invention, there is provided a kind of purposes of the reaction unit described in first aspect present invention, for urging
Change methanol dehydration dimethyl ether-preparing.
The third aspect of the present invention, there is provided a kind of reaction unit using described in first aspect present invention prepares dimethyl ether
Method, methods described comprises the following steps：
I) the filling material gas methanol between the inner chamber of the reaction unit and exocoel, and optionally filled out in the interior intracavitary
Fill purge gass high pure nitrogen；
Ii the reaction unit) is heated up to 150-400 DEG C by 0.1-5min/ DEG C of programming rate, and reaction obtains dimethyl ether.
In another preference, in step ii) also include step afterwards：Using the group of dimethyl ether obtained by gas chromatographic analysis
Into.
In another preference, the filling flow of unstripped gas described in step i) is 0.01-1g/h, preferably 0.05-
0.5g/h, more preferably 0.1-0.3g/h.
In another preference, the filling flow of purge gass described in step i) is 1-50ml/min, preferably 3-30ml/
min。
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, so as to form new or preferable technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description of the drawings
Fig. 1 is that Reaction Separation double-function catalyzing film reaction device of the present invention is used for efficient catalytic methanol dehydration preparation two
The schematic diagram of methyl ether.
Fig. 2 is the porous matrix of the gained cladding LTA molecular screen membranes of embodiment 1 and coats the porous of FAU-LTA molecular screen membranes
The surface of matrix and section SEM test results.
Fig. 3 is the XRD test knots of LTA molecular sieves, FAU molecular sieves and the gained FAU-LTA Zeolite composite films of embodiment 1
Fruit.
Fig. 4 is that the gained FAU-LTA molecular-sieve film catalytic reactors of embodiment 1 prepare dimethyl ether selection during dimethyl ether
The result that property and methanol conversion change with reaction temperature.
Embodiment
The present inventor's in-depth study by long-term, unexpectedly it is prepared a kind of especially suitable for methanol dehydration preparation
Having concurrently for dimethyl ether is catalyzed and separated difunctional molecular film reactor.Specifically, a species three is prepared in the present inventor
The molecular-sieve film catalytic reactor of Mingzhi's structure, the reactor are included as the FAU molecular sieve layers of Catalytic Layer and as separation
Layer LAT molecular sieve layers, during the course of the reaction, the FAU molecular sieve layers can efficient catalytic methanol decomposition, simultaneously because its have
There is the generation that faintly acid also effectively can avoid or reduce accessory substance；The LAT molecular sieve layers are due to can be in the original location with hydrophily
Reaction gained water byproduct steam is separated and removed, so as to break reaction balance, makes the direction that reaction is generated towards dimethyl ether not
It is disconnected to carry out, so as to obtain very high yield of dimethyl ether.The use of the reaction unit for dimethyl ether provide a kind of low energy consumption,
Inexpensive, efficient preparation method.On this basis, inventor completes the present invention.
Term
As used herein, term " is used for the Reaction Separation double-function catalyzing film reaction of catalysis methanol dehydration dimethyl ether-preparing
Device ", " reaction unit ", " molecular-sieve film catalytic reactor ", " membrane catalytic reactor " or " reactor " are used interchangeably.
Reaction unit
The invention provides a kind of Reaction Separation double-function catalyzing film reaction for catalysis methanol dehydration dimethyl ether-preparing
Device, the reaction unit include inner chamber and exocoel, and the inner chamber includes successively from inside to outside：Porous matrix, be incorporated into it is described
First molecular screen membrane on porous matrix surface and the second molecular screen membrane for being incorporated into the first molecular screen membrane surface, and it is described
It is used for filling material gas methanol between inner chamber and the exocoel.
In the present invention, first molecular screen membrane is hydrophilic molecule sieve membrane, in Selective Separation course of reaction
The water vapour of formation.
In another preference, the thickness of first molecular screen membrane is not particularly limited, preferably 1-50 μm, preferably
2-30 μm, more preferably 3-10 μm.
In another preference, first molecular screen membrane is LTA molecular screen membranes.
In another preference, first molecular screen membrane is incorporated into the porous matrix table by Covalently attached interaction
Face.
In the present invention, second molecular screen membrane is FAU molecular screen membranes, for catalysis methanol dehydration dimethyl ether-preparing
Reaction.
In another preference, the thickness of second molecular screen membrane is not particularly limited, preferably 1-30 μm, preferably
2-20 μm, more preferably 3-10 μm.
In another preference, second molecular screen membrane is incorporated into first molecular screen membrane by Covalently attached interaction
Surface.
In the present invention, second molecular screen membrane is in faintly acid.
In another preference, " being in faintly acid " refers to second molecular screen membrane in ammonia detachment assays,
The ammonia desorption peaks of strong acid site are not observed between 400 DEG C -600 DEG C.
In another preference, the porous matrix includes (but being not limited to)：Porous alumina ceramic, porous silica
Titanium ceramics, porous stainless steel, stainless (steel) wire.
In another preference, first molecular screen membrane and/or second molecular screen membrane are crystal.
In another preference, the sial of the silica alumina ratio of second molecular screen membrane and first molecular screen membrane rubs
Ratio >=1 of your ratio, preferably >=2, more preferably >=3, preferably 4-10.
In the present invention, first molecular screen membrane (is preferably to selectivity >=99% of reaction product dimethyl ether
100%)；And/or
The reaction unit is in 310 DEG C of conversion ratio >=80% to methanol.
In another preference, the reaction unit is in 310 DEG C of conversion ratio >=85% to methanol, preferably >=87%.
In another preference, the exocoel is membrane module, and the molecular screen membrane being prepared can be fixed in membrane module.
In the present invention, the inner chamber prepares as follows：
I) provide porous matrix, first modification solution, second modification solution, the first molecular screen membrane synthetic solvent, second point
Sub- sieve membrane synthetic solvent and ion exchange liquid；
II) porous matrix is placed in the first modification solution and modified, obtains the porous matrix through modification；
III) porous matrix through modification is placed in the first molecular screen membrane synthetic solvent, reaction is obtained through institute
State the porous matrix of the first molecular screen membrane cladding；
IV) porous matrix through first molecular screen membrane cladding is placed in the second modification solution and repaiied
Decorations, obtain the porous matrix of the first molecular screen membrane cladding through modification；
V) that the porous matrix that first molecular screen membrane through modification coats is placed in into the second molecular screen membrane synthesis is molten
In liquid, reaction obtains the porous matrix (i.e. inner chamber) coated through the molecular screen membrane of the second molecular screen membrane-the first；
VI the porous matrix through the molecular screen membrane of the second molecular screen membrane-the first cladding optionally) is placed in ion
Exchange in liquid, reaction obtains the porous matrix of second the-the first molecular screen membrane of molecular screen membrane cladding through ion-exchange treatment (in i.e.
Chamber).
In another preference, the first modification solution and the second modification solution may be the same or different, only respectively
On the spot selected from the one or more materials for including (but being not limited to) the following group：APTES、DICB、CPTMS、CPTCS、CPDMS、
CPCS, BPTMS, BPPCS and IPTMS.
In another preference, the solvent of the first modification solution and the second modification solution may be the same or different,
Separately selected from the material for including (but being not limited to) the following group：Toluene, methanol, N,N-dimethylformamide or its combination.
In another preference, the composition of the first molecular screen membrane synthetic solvent is aNa2O:bAl2O3:5SiO2:cH2O,
Wherein a=(20-100), b=(0.1-5), c=(500-2000).
In another preference, the composition of the first molecular screen membrane synthetic solvent is aNa2O:bAl2O3:5SiO2:cH2O,
Wherein a=(30-80), b=(0.5-3), c=(800-1500).
In another preference, the composition of the second molecular screen membrane synthetic solvent is aNa2O:bAl2O3:20SiO2:
cH2O, wherein a=(30-100), b=(0.1-5), c=(1000-3000).
In another preference, the composition of the second molecular screen membrane synthetic solvent is aNa2O:bAl2O3:20SiO2:
cH2O, wherein a=(50-85), b=(0.5-3), c=(1500-2500).
In another preference, the ion exchange liquid includes the ion exchange material being selected from the group：Ammonium nitrate, acetic acid
Ammonium, acetone, ethanol or its combination.
In another preference, the concentration of ion exchange material is not particularly limited described in the ion exchange liquid, excellent
Elect 0.001-0.1mol/L as.
In another preference, step III) reaction and/or step V) reaction may be the same or different, and it is only respectively
On the spot it is selected from the group：Microwave attenuation materials reaction, Vacuum-assisted method reaction.
In another preference, step III) reaction and/or step V) reaction temperature of the reaction is 50-120
DEG C, preferably 50-100 DEG C.
In another preference, the reaction time of the Vacuum-assisted method reaction is 2-60h, preferably 10-30h.
In another preference, the reaction time of the microwave attenuation materials reaction is 10-120min, preferably 20-
60min。
In the present invention, the step VI) described in the reaction temperature reacted be 10-80 DEG C；And/or
The step VI) described in reaction time for reacting be 1-90h.
In another preference, the step VI) described in the reaction temperature reacted be 20-60 DEG C, preferably 25-45
℃。
In another preference, the step VI) described in reaction time for reacting be 5-60h, preferably 10-50h.
It should be understood that in device of the present invention, the difference of the FAU molecular screen membranes and the LTA molecular screen membranes is
The two silica alumina ratio is different, wherein, the silica alumina ratios of FAU molecular screen membranes is 1-10 (preferably 1-5, more preferably 1-3), LTA molecules
Silica alumina ratio≤3 of sieve membrane are (preferably≤2.5, preferably 1.0).In molecular screen membrane, silica alumina ratio is smaller, and hydrophily is better, silicon
Aluminum ratio is higher, acid stronger.In addition, the aperture of FAU molecular screen membranes is 0.5-1nm (being preferably 0.74nm), and LTA molecular screen membranes
Aperture be 0.2-0.5nm (be preferably 0.4nm).
It should be understood that weakly acidic second molecular screen membrane obtained by ion exchange can effectively be kept away during the course of the reaction
Exempt from or reduce the generation of accessory substance.
In the present invention, second molecular screen membrane is as Catalytic Layer, not only can catalytic reaction progress, while can also have
Effect avoids or reduced the generation of accessory substance；First molecular screen membrane, can high selectivity separation reaction product as separating layer
Water vapour, so as to break the limitation of the balance of reaction；The catalytic reaction and the synchronous progress of the separation, are remarkably improved methanol
The yield of conversion ratio and dimethyl ether, and then reduce reaction cost.
Using
Present invention also offers a kind of purposes of described reaction unit, for catalysis methanol dehydration dimethyl ether-preparing.
Fig. 1 is that Reaction Separation double-function catalyzing film reaction device of the present invention is used for efficient catalytic methanol dehydration preparation two
The schematic diagram of methyl ether.
Present invention also offers the method that the reaction unit described in a kind of use prepares dimethyl ether, methods described includes as follows
Step：
I) the filling material gas methanol between the inner chamber of the reaction unit and exocoel, and optionally filled out in the interior intracavitary
Fill purge gass high pure nitrogen；
Ii the reaction unit) is heated up to 150-400 DEG C by 0.1-5min/ DEG C of programming rate, and reaction obtains dimethyl ether.
In another preference, in step ii) also include step afterwards：Using the group of dimethyl ether obtained by gas chromatographic analysis
Into.
In the present invention, the filling flow of unstripped gas described in step i) is 0.01-1g/h, preferably 0.05-0.5g/h,
More preferably 0.1-0.3g/h.
In another preference, the filling flow of purge gass described in step i) is 1-50ml/min, preferably 3-30ml/
min。
Compared with prior art, the present invention has following major advantage：
(1) reaction unit has catalytic reaction and the function of accessory substance separation concurrently, can effectively break methanol dehydration preparation
The balance limitation of dimethyl ether, so as to significantly improve the yield of dimethyl ether；
(2) reaction unit has high catalytic performance, excellent high-temperature stability and high yield of dimethyl ether；
(3) using the reaction unit prepare dimethyl ether have raw material availability is high, reaction cost is low, technological process is short,
The advantages that reaction efficiency is high, energy consumption is small.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to conventional strip
Part or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number are calculated by weight.
Unless otherwise defined, anticipated known to all specialties used in text and scientific words and one skilled in the art
Justice is identical.In addition, any method similar or impartial to described content and material all can be applied in the inventive method.Wen Zhong
Described preferable implementation only presents a demonstration with material to be used.
Embodiment 1FAU-LTA molecular-sieve film catalytics reactor 1
Preparation process
Step 1: functional modification porous matrix
By synthesizing molecular sieve films such as porous alumina ceramic, porous titanium dioxide ceramic, porous stainless steel and stainless (steel) wires
Matrix be respectively put into dissolved with 0.2mol/L APTES, DICB, CPTMS, CPTCS, CPDMS, CPCS, BPTMS, BPPCS and
In the toluene solution of the organosilans such as IPTMS, 0.5~3h is reacted at 110 DEG C, so as in matrix surface introducing-NH2,-
The organo-functional groups such as NCO ,-Cl ,-Br and-I, form the porous matrix of the functional modification for molecular screen membrane synthesis.
Step 2: prepare the synthetic solvent of molecular screen membrane
Weigh a certain amount of NaOH to be dissolved in distilled water, aluminium foil is added after clarification, stirring forms aluminum solutions；Measured amounts
Ludox be added in pre-heated distilled water, be sufficiently stirred；Pre-heated aluminum solutions are slowly added in Ludox, filled
Divide stirring, subsequent solution continues to stir 24h at room temperature, and finally the composition (mol ratio) of each component is in gained synthetic solvent
50Na2O:Al2O3:5SiO2:1000H2O。
Step 3: covalent bonding Hydrothermal Synthesiss LTA type molecular screen membranes
It is placed on after the porous matrix of functional modification is fixed in the reactor equipped with step 2 gained synthetic solvent,
Taken out at 60 DEG C after Vacuum-assisted method 24h, be cooled to room temperature, be washed with distilled water to neutrality, used after being dried at a temperature of 110 DEG C
Tested in characterizing with next step.
Step 4: functional modification LTA molecular screen membranes
By step 3 prepare LTA molecular screen membranes be put into APTES, DICB dissolved with 0.2mol/L, CPTMS, CPTCS,
In the toluene solution of the organosilans such as CPDMS, CPCS, BPTMS, BPPCS and IPTMS, 0.5~3h is reacted at 110 DEG C, so as to
In LTA molecular screen membranes surface introducing-NH2,-NCO ,-Cl, the organo-functional group such as-Br and-I be used to further synthesize.
Step 5: covalent bonding Hydrothermal Synthesiss FAU type molecular screen membranes
It is placed on after the LTA molecular screen membranes of step 4 functional modification are fixed equipped with FAU molecular screen membranes synthetic solvent (system
The same step 2 of Preparation Method, difference are that it is 70Na to form2O:Al2O3:20SiO2:2000H2O it is former at 75 DEG C in reactor)
Taken out after the Hydrothermal Synthesiss 24h of position, be cooled to room temperature, be washed with distilled water to neutrality, be used to characterize after drying at a temperature of 110 DEG C and
It is catalyzed test experiments.
Step 6: ion exchange improves the acidity on FAU-LTA molecular screen membranes surface
The FAU-LTA Zeolite composite films with sandwich structure that step 5 is prepared are put into 0.01mol/L's
In ammonium nitrate solution, ion exchange 24h under normal temperature.Then take out drying for standby.
Performance testing process
The catalytic performance test of FAU-LTA molecular film reactors
The FAU-LTA molecular film reactors prepared in step 6 are sealed in membrane module with high temperature gasket, had point
Sub- sieve membrane side is passed through methanol, and the opposite side of film is passed through high pure nitrogen as purge gass.Unstripped gas generates two after catalytic reaction
Methyl ether and water vapour, wherein water vapour penetrate into the opposite side of membrane reactor through the selection separation of LTA molecular screen membranes.Reaction product passes through
Six-way valve sampling respectively enters gas-chromatography and carries out component analysis, difunctional so as to evaluate the integrated reaction and separation being prepared
Molecular-sieve film catalytic reactor prepares the selectivity of dimethyl ether reaction and the yield of dimethyl ether in syngas catalytic conversion.
Specific experiment condition is as follows：Material flow：0.15g/h, purge throughput：10ml/min.Temperature setting：With 0.5
DEG C/min programming rate rises to temperature spot to be measured from room temperature.Each temperature point sampling 10h, measured temperature is respectively 200 DEG C,
220℃、240℃、260℃、280℃、300℃、310℃。
Fig. 2 is the porous matrix of the gained cladding LTA molecular screen membranes of embodiment 1 and coats the porous of FAU-LTA molecular screen membranes
The surface of matrix and section SEM test results.
Figure it is seen that LTA molecular screen membranes and FAU molecular screen membranes are respectively provided with very fine and close structure, and the LTA
Molecular screen membrane is combined closely in the porous matrix surface, and the FAU molecular screen membranes are combined closely in the LTA molecular sieves
Film surface.
Fig. 3 is the XRD test knots of LTA molecular sieves, FAU molecular sieves and the gained FAU-LTA Zeolite composite films of embodiment 1
Fruit.
From figure 3, it can be seen that there is no stray crystal generation in the gained FAU-LTA Zeolite composite films of embodiment 1.
Fig. 4 is that the gained FAU-LTA molecular-sieve film catalytic reactors of embodiment 1 prepare dimethyl ether selection during dimethyl ether
The result that property and methanol conversion change with reaction temperature.
Wherein, " dimethyl ether selectivity " refers to the production effect that dimethyl ether is generated in methanol dehydration dimethyl ether-preparing course of reaction
Rate, dimethyl ether selectivity is higher, and its production efficiency is higher；" methanol conversion " nail alcohol reacts the degree for being converted into product,
Conversion ratio is higher, and product is more.From fig. 4, it can be seen that with the rise of reaction temperature, methanol conversion increase, at 310 degree
When conversion ratio up to 90.9%；Dimethyl ether selectivity is 100%.As a result show, divided by the difunctional FAU-LTA of Reaction Separation
Sub- sieve membrane reactor, can greatly improve the conversion ratio of methanol and the selectivity of dimethyl ether.It is catalyzed compared to simple FAU, this
Invention described device is remarkably improved Catalytic Layer FAU catalytic stability.
Embodiment 2FAU-LTA molecular-sieve film catalytics reactor 2
With embodiment 1, difference is preparation process：The ion-exchange time of step 6 is 36h.
With embodiment 1, difference is performance testing process：Material flow is 0.20g/h.
Embodiment 3FAU-LTA molecular-sieve film catalytics reactor 3
With embodiment 1, difference is preparation process：The ion-exchange time of step 6 is 48h.
With embodiment 1, difference is performance testing process：Material flow is 0.25g/h, and catalyst is in 280 DEG C of guarantors
Temperature test long-time stability.
Embodiment 4FAU-LTA molecular-sieve film catalytics reactor 4
With embodiment 1, difference is preparation process：The Hydrothermal Synthesiss of step 3 are carried out at 70 DEG C, water described in step 5
Thermal synthesis is carried out at 75 DEG C.
Performance testing process is the same as embodiment 1.
Embodiment 5FAU-LTA molecular-sieve film catalytics reactor 5
With embodiment 1, difference is preparation process：The Hydrothermal Synthesiss of step 3 carry out 20h at 80 DEG C, described in step 5
Hydrothermal Synthesiss carry out 20h at 85 DEG C.
Performance testing process is the same as embodiment 1.
Embodiment 6FAU-LTA molecular-sieve film catalytics reactor 6
With embodiment 1, difference is preparation process：The Hydrothermal Synthesiss of step 3 are the microwave that 30min is carried out at 90 DEG C
Hydrothermal Synthesiss.
Performance testing process is the same as embodiment 1.
Comparative example 1FAU molecular sieve catalysts C1
FAU molecular sieve powders are soaked into 48h in 0.01mol/L ammonium nitrate solution, done overnight in 120 DEG C of baking ovens
It is dry, 5h is calcined at 500 DEG C in air atmosphere, is down to room temperature, obtains acidified FAU molecular sieve catalysts C1.
Take 0.5g catalyst C1 to be placed in U-shaped microreactor, simulate fixed bed reactors, carry out catalyst methanol and take off
Water prepares the activity rating of dimethyl ether, records the content of reactant and product under corresponding temperature.
Table 1 is that the reactor 1-6 that 1-6 of the embodiment of the present invention is prepared and the gained catalyst C1 of comparative example 1 take off to methanol
Water prepares the catalytic effect of dimethyl ether.
Table 1
| Maximum conversion | |
| Embodiment 1 | 90.9 |
| Embodiment 2 | 88.4 |
| Embodiment 3 | 87.2 |
| Embodiment 4 | 89.5 |
| Embodiment 5 | 89.9 |
| Embodiment 6 | 90.2 |
| Comparative example 1 | 9.5 |
As it can be seen from table 1 it is fine using the repeatability of inventive film catalytic reactor, compared with fixed bed reactors
(conversion ratio only has 9.5%), the performance of inventive film catalytic reactor greatly improve.
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (12)
1. a kind of Reaction Separation double-function catalyzing film reaction device for catalysis methanol dehydration dimethyl ether-preparing, its feature exists
In the reaction unit includes inner chamber and exocoel, and the inner chamber includes successively from inside to outside：Porous matrix, be incorporated into it is described more
First molecular screen membrane of hole matrix surface and the second molecular screen membrane for being incorporated into the first molecular screen membrane surface, and it is described interior
It is used for filling material gas methanol between chamber and the exocoel；
Wherein, first molecular screen membrane is LTA molecular screen membranes；Second molecular screen membrane is FAU molecular screen membranes, for being catalyzed
The reaction of methanol dehydration dimethyl ether-preparing；
The exocoel is membrane module, and the molecular screen membrane being prepared can be fixed in membrane module.
2. reaction unit as claimed in claim 1, it is characterised in that first molecular screen membrane is hydrophilic molecule sieve membrane,
For the water vapour formed in Selective Separation course of reaction.
3. reaction unit as claimed in claim 1, it is characterised in that second molecular screen membrane is in faintly acid.
4. reaction unit as claimed in claim 1, it is characterised in that first molecular screen membrane is to reaction product dimethyl ether
Selectivity >=99%；And/or
The reaction unit is in 310 DEG C of conversion ratio >=80% to methanol.
5. reaction unit as claimed in claim 1, it is characterised in that first molecular screen membrane is to reaction product dimethyl ether
Selectivity is 100%；And/or
The reaction unit is in 310 DEG C of conversion ratio >=80% to methanol.
6. reaction unit as claimed in claim 1, it is characterised in that the inner chamber prepares as follows：
I) porous matrix, the first modification solution, the second modification solution, the first molecular screen membrane synthetic solvent, the second molecular sieve are provided
Film synthetic solvent and ion exchange liquid；
II) porous matrix is placed in the first modification solution and modified, obtains the porous matrix through modification；
III) porous matrix through modification is placed in the first molecular screen membrane synthetic solvent, reaction is obtained through described the
The porous matrix of one molecular screen membrane cladding；
IV) porous matrix through first molecular screen membrane cladding is placed in the second modification solution and modified,
Obtain the porous matrix of the first molecular screen membrane cladding through modification；
V) porous matrix that first molecular screen membrane through modification coats is placed in the second molecular screen membrane synthetic solvent,
Reaction obtains the porous matrix coated through the molecular screen membrane of the second molecular screen membrane-the first；
VI the porous matrix through the molecular screen membrane of the second molecular screen membrane-the first cladding optionally) is placed in ion exchange
In liquid, reaction obtains the porous matrix of second the-the first molecular screen membrane of molecular screen membrane cladding through ion-exchange treatment.
7. reaction unit as claimed in claim 6, it is characterised in that the step VI) described in the reaction temperature reacted be
10-80℃；And/or
The step VI) described in reaction time for reacting be 1-90h.
8. the purposes of the reaction unit described in a kind of claim 1, it is characterised in that prepare diformazan for catalysis methanol dehydration
Ether.
9. the method that the reaction unit described in a kind of usage right requirement 1 prepares dimethyl ether, it is characterised in that methods described includes
Following steps：
I) the filling material gas methanol between the inner chamber of the reaction unit and exocoel, and optionally blown in the interior intracavitary filling
Scavenging high pure nitrogen；
Ii the reaction unit) is heated up to 150-400 DEG C by 0.1-5min/ DEG C of programming rate, and reaction obtains dimethyl ether.
10. method as claimed in claim 9, it is characterised in that the filling flow of unstripped gas described in step i) is 0.01-
1g/h。
11. method as claimed in claim 9, it is characterised in that the filling flow of unstripped gas described in step i) is 0.05-
0.5g/h。
12. method as claimed in claim 9, it is characterised in that the filling flow of unstripped gas described in step i) is 0.1-
0.3g/h。
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