CN108212197A - A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application - Google Patents
A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application Download PDFInfo
- Publication number
- CN108212197A CN108212197A CN201810062962.8A CN201810062962A CN108212197A CN 108212197 A CN108212197 A CN 108212197A CN 201810062962 A CN201810062962 A CN 201810062962A CN 108212197 A CN108212197 A CN 108212197A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dimethyl ether
- zeolite
- composite oxides
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of dimethyl ether for the catalyst of polymethoxy dimethyl ether, belongs to polymethoxy dimethyl ether synthetic catalyst technical field.The catalyst is using zeolite as carrier, and in composite oxides/zeolite catalyst of supported on carriers composite oxides；Wherein zeolite accounts for the 95~99% of catalyst gross mass, and composite oxides account for the 1~5% of catalyst gross mass.The present invention also provides the preparation methods of catalyst, zeolite is impregnated with sulfuric acid, it is dried after washing to neutrality, it then will be on the mixing salt solution incipient impregnation to the zeolite after sulfuric acid modified of composite oxides, oscillation stirring fully after stand, drying, be ground up, sieved, roast after obtain composite oxides/zeolite catalyst.Composite oxides/zeolite catalyst of the present invention is using in being reacted with dimethyl ether for polymethoxy dimethyl ether, high conversion rate, catalytic activity are high, stability is good, DME conversion ratios 30%~50%, DMMx selectivity 80%~95%.
Description
Technical field
The invention belongs to polymethoxy dimethyl ether synthetic catalyst technical field, specially a kind of dimethyl ether is for poly- methoxy
The catalyst of base dimethyl ether and its preparation and application.
Background technology
Vehicle exhaust be the main reason for causing China's large area haze it, however caused by diesel vehicle pollution it is much high
In gasoline car.In addition to further diesel quality and engine technology is promoted, by developing novel diesel fuel additives, waste is reduced
Discharge be also to solve the problems, such as one of method.China Environmental Science Research Institute research shows that, polymethoxy dimethyl ether (DMMx, x
=1~8) mixture can be carried out with diesel oil well, and the discharge of motor vehicle particulate matter can be greatly reduced, is a kind of ideal
Diesel fuel additives.
DMMx is that one kind is birdsed of the same feather flock together by the low relative molecular mass acetal of parent, methylene oxygroup for main chain of dimethoxymethane
Object is closed, there is higher oxygen content and Cetane number, the combustibility of diesel oil can be significantly improved, effectively improve the thermal efficiency, is reduced
The formation of flue dust during burning.DMMx can be by acid catalysis by methanol, dimethyl ether (DME) or methoxyl group dimethyl ether at present
(DMM) it is made with formaldehyde (FA), metaformaldehyde (TOM) or paraformaldehyde (PF) condensation.Acid used in the synthesis of DMMx
Catalyst mainly has liquid acid, ion exchange resin, ionic liquid and molecular sieve etc..Such as patent CN102320941A with methanol and
FA is raw material, and solid acid synthesizes DMMx for catalyst；Patent US6166266 is using FA and methanol or DME as raw material, macropore sulfonic group
Cation exchange resin is catalyst preparation DMMx；Patent CN1020306A and CN101940940A divides using methanol as raw material
Son sieve is carrier, and iron and molybdenum oxides synthesize DMMx for active component direct oxidation；Patent CN102249868A using FA solution and
Methanol is raw material, and ionic liquid is catalyst synthesis DMMx.It is however traditional using methanol as raw material aldol condensation synthesis DMMx's
Technique is all there are the problem of long flow path, high energy consumption, big investment, and Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences develops one thus
Kind obtains the technique of DMMx by DME direct oxidations, and flow is short, investment is small and CO2It discharges low.Such as patent CN106378161A and
CN10378162A using DME as raw material, uses porous carbon materials (activated carbon, carbon nanotube and graphene etc.) as carrier, sulfuric acid
Salt is active component, and step oxidation DME obtains DMMx.But current this one-step oxidation process target product selectivity is not high, yield
Low, production, which is also not achieved, in catalyst is expected, and carbon based material cost is higher.
Invention content
The purpose of the present invention is to provide the diformazans that a kind of cost of material is low, high conversion rate, catalytic activity are high, stability is good
Ether prepares catalyst of polymethoxy dimethyl ether and its preparation method and application.The object of the invention is come real by the following technical programs
It is existing：
A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether, and the catalyst is using zeolite as carrier, and in carrier
Composite oxides/zeolite catalyst of upper load composite oxides；Wherein zeolite accounts for the 95~99% of catalyst gross mass, compound
Oxide accounts for the 1~5% of catalyst gross mass.
Zeolite is a kind of aqueous aluminosilicate mineral of porosity in rack-like structure of alkali metal containing, the silica four having
Face body structure makes its adsorption capacity strong, large amount of adsorption, inside there are uniform in size, fixed cavity and channels.In addition, zeolite
Alkali metal cation in crystalline framework contacts insecure with sial skeleton structure, it is made to have reversible ion within certain limits
It exchanges, easily does modification.Carbon nanometer can be used for polyoxy methyl dimethoxy ether catalyst carrier in presently disclosed dimethyl ether
Pipe, activated carbon, carbon fiber, carbon molecular sieve and graphene, because of the porosity characteristic of carbon-based material, load capacity is high, catalytic activity compared with
It is good, but the material costs such as one side carbon nanotube, carbon fiber, graphene are far above the price of general molecular sieve carrier；The opposing party
It faces one step oxidation of dimethyl ether and prepares the reaction of polyoxy methyl dimethoxy ether, carbon-supported catalysts easy carbon distribution during the reaction is made
It is blocked into catalyst inner duct, the reduced performance of catalyst, there is also larger problems for the at the same time regeneration of catalyst.The present invention
Carrier is done using zeolite, one side China zeolite rich reserves, cheap, raw material sources are very extensive；On the other hand this hair
Composite oxides/zeolite catalyst prepared by bright patent is made of Zeolite support and metal oxide, can pass through high-temperature activation
Regeneration, catalyst stability are preferable.
As a kind of dimethyl ether of the present invention for a specific embodiment of the catalyst of polymethoxy dimethyl ether, institute
Composite oxides are stated as TiO2- ZnO, TiO2-V2O5, SiO2-Al2O3, Al2O3-MoO3, Al2O3-Cr2O3In one kind, composite oxygen
Compound molar ratio 1:1.
Research shows that Lewis (L) acidic site amounts have the synthesis of DMMx larger impact, L acidity bit quantities are more, DMMx
Selectivity it is higher.Composite oxides TiO of the present invention2- ZnO, TiO2-V2O5, SiO2-Al2O3, Al2O3-MoO3,
Al2O3-Cr2O3Belong to solid acid, enough L acid centres can be provided for reaction, be conducive to improve the selection of DMMx.In addition,
The oxidation-reduction quality of catalyst also has significant impact to the selectivity of DMMx.TiO2The composite oxides such as-ZnO have redox
Ability while acid centre is provided to reaction, provides redox site, is conducive to CH2The growth and choosing of O- group chains
Selecting property combines so that DMMx is easier to generate, so as to improve the selectivity of the activity of reaction and DMMx and yield.If using single
One TiO2、ZnO、V2O3、CrO3It waits metal oxides that can not provide the L acidic sites needed for reaction, and can not have simultaneously
Redox ability, DMMx can be synthesized has certain inhibiting effect instead.
For a kind of dimethyl ether for the preparation method of the catalyst of polymethoxy dimethyl ether, the preparation method is with sulfuric acid pair
Zeolite is impregnated, and is dried after washing to neutrality, then by the mixing salt solution incipient impregnation of composite oxides to through sulfuric acid
On modified zeolite, oscillation stirring fully after stand, drying, be ground up, sieved, roast after obtain composite oxides/zeolite catalysis
Agent.
Zeolite is modified with sulfuric acid, dissolves the Fe inside zeolite2O3、SiO2With part organic impurities, make inside zeolite
Duct and channel are more smooth, while the Lewis acid sites exposure inside zeolite.Experimental study shows Lewis acidity bit quantities
Increase can enhance the adsorptivity of zeolite, so as to promote the high selectivity of DMMx.
Further, the volume fraction of the sulfuric acid is 2%~15%；The solid-to-liquid ratio of the sulfuric acid and zeolite is 1:35~
45；The drying temperature is 100~130 DEG C；The temperature that is slowly stirred is 55~65 DEG C, and the time is 2~3 hours；It is described quiet
It is 6~10 hours to put the time；The calcination temperature is 400~600 DEG C, and the time is 5~8h.
As a kind of dimethyl ether of the present invention for a tool of the preparation method of the catalyst of polymethoxy dimethyl ether
Body embodiment, when composite oxides are TiO2During-ZnO, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are washed till after neutrality at 120 DEG C
Drying；By the Zn (NO of 0.454g3)2·6H2O and 0.287g TiCl4It is added in suitable distilled water, incipient impregnation arrives
On the modified zeolite of 4.681g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then at a temperature of 120 DEG C
Drying, is ground up, sieved, and in 600 DEG C of roasting temperature 5h, obtains the TiO that composite oxides content is 5%2- ZnO/ zeolite catalysises
Agent.
As a kind of dimethyl ether of the present invention for a tool of the preparation method of the catalyst of polymethoxy dimethyl ether
Body embodiment, when composite oxides are TiO2-V2O5When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 15% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality
It is dry；By the five hydrated sulfuric acid vanadyl and 0.143g TiCl of 0.190g4It is added in suitable distilled water, incipient impregnation arrives
On the modified zeolite of 8.360g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then at a temperature of 120 DEG C
Drying, is ground up, sieved, and in 500 DEG C of roasting temperature 6h, obtains the TiO that composite oxides content is 2.3%2-V2O5/ zeolite is urged
Agent.
As a kind of dimethyl ether of the present invention for a tool of the preparation method of the catalyst of polymethoxy dimethyl ether
Body embodiment, when composite oxides are SiO2-Al2O3When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 8% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality
It is dry；By the Al of 1.067g2(SO4)3·18H2The H of O and 0.125g2SiO3It is added in suitable distilled water, incipient impregnation arrives
On the modified zeolite of 6.068g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then at a temperature of 120 DEG C
Drying, is ground up, sieved, and in 800 DEG C of roasting temperature 6h, obtains the SiO that composite oxides content is 4.1%2-Al2O3/ zeolite is urged
Agent.
As a kind of dimethyl ether of the present invention for a tool of the preparation method of the catalyst of polymethoxy dimethyl ether
Body embodiment, when composite oxides are Al2O3-MoO3When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 2% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality
It is dry；By the Al of 0.981g2(SO4)3·18H2The tetrahydrate ammonium molybdate of O and 1.818g is added in suitable distilled water, waits bodies
Product is impregnated on the modified zeolite of 10.945g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then 120
It dries, is ground up, sieved at a temperature of DEG C, in 800 DEG C of roasting temperature 8h, obtain the Al that composite oxides content is 3.2%2O3-
MoO3/ zeolite catalyst.
As a kind of dimethyl ether of the present invention for a tool of the preparation method of the catalyst of polymethoxy dimethyl ether
Body embodiment, when composite oxides are Al2O3-Cr2O3When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are washed till after neutrality at 120 DEG C
Drying.By the Al of 0.333g2(SO4)3·18H2The Cr of O and 0.196g2(SO4)3·6H2O is added in suitable distilled water, etc.
On volume impregnation to the modified zeolite of 12.558g acid.8h, Ran Hou are stood after shaking stirring 2.5 hours at a temperature of 60 DEG C
It dries, is ground up, sieved at a temperature of 120 DEG C, in 800 DEG C of roasting temperature 6h, obtain the Al that composite oxides content is 1%2O3-
Cr2O3/ zeolite catalyst.
A kind of dimethyl ether is for the application of the catalyst of polymethoxy dimethyl ether, and the catalyst is in dimethyl ether for poly- first
Application in oxygroup dimethyl ether.
As a kind of dimethyl ether of the present invention for a specific reality of the application of the catalyst of polymethoxy dimethyl ether
Example is applied, the catalyst is for the application conditions in polymethoxy dimethyl ether in dimethyl ether：Reactor is done using fixed bed, it is former
The molar ratio for expecting dimethyl ether and gaseous mixture is 8.5:1~1:1, it is reacted, is reacted in the fixed bed reactors continuously flowed
2500~4500h of air speed-1, 200~320 DEG C of reaction temperature, reaction pressure is normal pressure, and the reaction time is 10~40h, wherein gaseous mixture
It is 1 for molar ratio:1 nitrogen and oxygen.
The structural formula of dimethyl ether is CH3-O-CH3, C-O keys, the CH of generation are disconnected by catalyst3- O-, CH3Group is certainly
CH is synthesized by combining3O-CH2O-CH3(DMM).DMM is as feedstock, it is easier to generate-CH2O- groups, promote carbochain
Increase, obtain CH3O-(CH2O)x-CH3Polymer, therefore DMM and dimethyl ether etc. as raw material feed and to a certain extent can together
Enough effective yields for promoting DMMx.
Further, catalyst of the present invention is during specifically synthesis DMMx, using fixed bed as reactor, using two-stage reaction
Mode：The first step first by dimethyl ether and gaseous mixture charging synthesis DMM and isolates pure DMM, and second step is by dimethyl ether, mixing
Gas and the DMM chargings further generated, synthesize DMMx.
Compared with prior art, the invention has the advantages that：
1st, the present invention is derived from a wealth of sources using zeolite as catalyst carrier, cheap.
2nd, composite oxides of the present invention/zeolite catalyst high conversion rate, catalytic activity are high, stability is good, 200~320
DEG C reaction temperature under, DME conversion ratios 30%~50%, DMMx selectivity 80%~95%.
3rd, reaction process of the present invention is not limited to two-step reaction, has huge reference to the synthesis technology of DMMx
Value.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
The present embodiment uses TiO2- ZnO is used as composite oxides, and the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are washed till after neutrality at 120 DEG C
Drying；By the Zn (NO of 0.454g3)2·6H2O and 0.287g TiCl4It is added in suitable distilled water, incipient impregnation arrives
On the modified zeolite of 4.681g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then at a temperature of 120 DEG C
Drying, is ground up, sieved, and in 600 DEG C of roasting temperature 5h, obtains the TiO that composite oxides content is 5%2- ZnO/ zeolite catalysises
Agent.
The present embodiment catalyst is used for process of the dimethyl ether for polymethoxy dimethyl ether：
Raw material dimethyl ether and gaseous mixture (nitrogen and oxygen, molar ratio 1:1) molar ratio is 4.5:1, in continuous flow
It is reacted in dynamic fixed bed reactors, the reaction velocity of one, two section of fixed bed reactors, reaction temperature, reaction pressure are equal
Unanimously, reaction velocity 3200h-1, 220 DEG C of reaction temperature, reaction pressure is normal pressure, two-stage reaction total reaction time 18h.Dimethyl ether
Conversion ratio be 41.3%, DMMx overall selectivity 94.8%.
Embodiment 2
The present embodiment uses TiO2-V2O5As composite oxides, the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 15% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality
It is dry；By the five hydrated sulfuric acid vanadyl and 0.143g TiCl of 0.190g4It is added in suitable distilled water, incipient impregnation arrives
On the modified zeolite of 8.360g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then at a temperature of 120 DEG C
Drying, is ground up, sieved, and in 500 DEG C of roasting temperature 6h, obtains the TiO that composite oxides content is 2.3%2-V2O5/ zeolite is urged
Agent.
The present embodiment catalyst is used for process of the dimethyl ether for polymethoxy dimethyl ether：
Raw material dimethyl ether and gaseous mixture (nitrogen and oxygen, molar ratio 1:1) molar ratio is 8.5:1, in continuous flow
It is reacted in dynamic fixed bed reactors, the reaction velocity of one, two section of fixed bed reactors, reaction temperature, reaction pressure are equal
Unanimously, reaction velocity 4000h-1, 250 DEG C of reaction temperature, reaction pressure is normal pressure, two-stage reaction total reaction time 32h.Dimethyl ether
Conversion ratio be 30.9%, DMMx overall selectivity 82.5%.
Embodiment 3
The present embodiment uses SiO2-Al2O3As composite oxides, the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 8% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality
It is dry；By the Al of 1.067g2(SO4)3·18H2The H of O and 0.125g2SiO3It is added in suitable distilled water, incipient impregnation arrives
On the modified zeolite of 6.068g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then at a temperature of 120 DEG C
Drying, is ground up, sieved, and in 800 DEG C of roasting temperature 6h, obtains the SiO that composite oxides content is 4.1%2-Al2O3/ zeolite is urged
Agent.
The present embodiment catalyst is used for process of the dimethyl ether for polymethoxy dimethyl ether：
Raw material dimethyl ether and gaseous mixture (nitrogen and oxygen, molar ratio 1:1) molar ratio is 6:1, continuously flowing
Fixed bed reactors in reacted, the reaction velocity of one, two section of fixed bed reactors, reaction temperature, reaction pressure are uniform
It causes, reaction velocity 2500h-1,200 DEG C of reaction temperature, reaction pressure is normal pressure, two-stage reaction total reaction time 10h.Dimethyl ether
Conversion ratio be 38.8%, DMMx overall selectivity 81.2%.
Embodiment 4
The present embodiment uses Al2O3-MoO3As composite oxides, the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 2% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality
It is dry；By the Al of 0.981g2(SO4)3·18H2The tetrahydrate ammonium molybdate of O and 1.818g is added in suitable distilled water, waits bodies
Product is impregnated on the modified zeolite of 10.945g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then 120
It dries, is ground up, sieved at a temperature of DEG C, in 800 DEG C of roasting temperature 8h, obtain the Al that composite oxides content is 3.2%2O3-
MoO3/ zeolite catalyst.
The present embodiment catalyst is used for process of the dimethyl ether for polymethoxy dimethyl ether：
Raw material dimethyl ether and gaseous mixture (nitrogen and oxygen, molar ratio 1:1) molar ratio is 1:1, continuously flowing
Fixed bed reactors in reacted, the reaction velocity of one, two section of fixed bed reactors, reaction temperature, reaction pressure are uniform
It causes, reaction velocity 4500h-1, 320 DEG C of reaction temperature, reaction pressure is normal pressure, two-stage reaction total reaction time 40h.Dimethyl ether
The overall selectivity 88.3% that conversion ratio is 41.5%, DMMx.
Embodiment 5
The present embodiment uses Al2O3-Cr2O3As composite oxides, the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are washed till after neutrality at 120 DEG C
Drying.By the Al of 0.333g2(SO4)3·18H2The Cr of O and 0.196g2(SO4)3·6H2O is added in suitable distilled water, etc.
On volume impregnation to the modified zeolite of 12.558g acid.8h, Ran Hou are stood after shaking stirring 2.5 hours at a temperature of 60 DEG C
It dries, is ground up, sieved at a temperature of 120 DEG C, in 800 DEG C of roasting temperature 6h, obtain the Al that composite oxides content is 1%2O3-
Cr2O3/ zeolite catalyst.
The present embodiment catalyst is used for process of the dimethyl ether for polymethoxy dimethyl ether：
Raw material dimethyl ether and gaseous mixture (nitrogen and oxygen, molar ratio 1:1) molar ratio is 2.1:1, in continuous flow
It is reacted in dynamic fixed bed reactors, the reaction velocity of one, two section of fixed bed reactors, reaction temperature, reaction pressure are equal
Unanimously, reaction velocity 3800h-1, 240 DEG C of reaction temperature, reaction pressure is normal pressure, two-stage reaction total reaction time 28h.Dimethyl ether
Conversion ratio be 49.2%, DMMx overall selectivity 90.9%.
Comparative example 1
This comparative example is the comparison of embodiment 1, and composite oxides are changed to ZnO or TiO2In one kind,：
Using ZnO as active constituent, the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are washed till after neutrality at 120 DEG C
Drying.By the Zn (NO of 0.935g3)2·6H2O is added in suitable distilled water, and incipient impregnation is modified to 4.681g acid
On zeolite, concussion stirring is abundant.8h is stood after being slowly stirred at a temperature of 60 DEG C 2.5 hours, is then dried at a temperature of 120 DEG C
It is dry, it is ground up, sieved, in 600 DEG C of roasting temperature 5h, obtains the TiO that composite oxides content is 5%2- ZnO/ zeolite catalysts.
, the conversion of dimethyl ether same as Example 1 for the process of polymethoxy dimethyl ether for dimethyl ether of this comparative example catalyst
The overall selectivity 33.5% that rate is 13.2%, DMMx.
Active constituent is changed to TiO2, under identical catalyst preparation conditions and reaction condition, the conversion ratio of dimethyl ether
Overall selectivity 55.2% for 14.8%, DMMx.
Comparative example 2
This comparative example is the comparison of embodiment 5, and composite oxides are changed to only Al2O3Or Cr2O3In one kind：
Using Cr2O3As active constituent, the specific preparation process of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are washed till after neutrality at 120 DEG C
Drying.By the Cr of 0.327g2(SO4)3·6H2O is added in suitable distilled water, and incipient impregnation is modified to 12.558g acid
Zeolite on.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then dries, is ground up, sieved at a temperature of 120 DEG C,
In 800 DEG C of roasting temperature 6h, the Cr that composite oxides content is 1% is obtained2O3/ zeolite catalyst.This comparative example catalyst
Same as Example 5 for the process of polymethoxy dimethyl ether for dimethyl ether, the conversion ratio of dimethyl ether is 11.2%, DMMx's
Overall selectivity 20.5%.
Active constituent is changed to Al2O3, under identical catalyst preparation conditions and reaction condition, the conversion ratio of dimethyl ether
Overall selectivity 56.1% for 15.5%, DMMx.
Comparative example 3
This comparative example is the comparative example of embodiment 1, using TiO2- ZnO is used as composite oxides, and catalyst was specifically prepared
It is not acidified in journey：
By the Zn (NO of 0.454g3)2·6H2O and 0.287g TiCl4It is added in suitable distilled water, incipient impregnation
Onto the zeolite of 4.681g, concussion stirring is abundant.8h is stood after being slowly stirred at a temperature of 60 DEG C 2.5 hours, then at 120 DEG C
At a temperature of dry, be ground up, sieved, in 600 DEG C of roasting temperature 5h, obtain the TiO that composite oxides content is 5%2- ZnO/ boils
Stone catalyst., the diformazan same as Example 1 for the process of polymethoxy dimethyl ether for dimethyl ether of this comparative example catalyst
The conversion ratio of ether is the overall selectivity 69.8% of 18.5%, DMMx.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether, which is characterized in that the catalyst using zeolite as carrier,
And in composite oxides/zeolite catalyst of supported on carriers composite oxides；Wherein zeolite account for catalyst gross mass 95~
99%, composite oxides account for the 1~5% of catalyst gross mass.
2. a kind of dimethyl ether as described in claim 1 is for the catalyst of polymethoxy dimethyl ether, which is characterized in that described compound
Oxide is TiO2- ZnO, TiO2-V2O5, SiO2-Al2O3, Al2O3-MoO3, Al2O3-Cr2O3In one kind.
3. a kind of dimethyl ether as claimed in claim 1 or 2 is for the preparation method of the catalyst of polymethoxy dimethyl ether, feature
It is, the preparation method is dried, then by the mixed of composite oxides to be impregnated with sulfuric acid to zeolite after washing to neutrality
Close salting liquid incipient impregnation to the zeolite after sulfuric acid modified on, oscillation stirring fully after stand, drying, be ground up, sieved,
Composite oxides/zeolite catalyst is obtained after roasting.
4. a kind of dimethyl ether as claimed in claim 3 exists for the preparation method of the catalyst of polymethoxy dimethyl ether, feature
In when composite oxides are TiO2During-ZnO, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality；
By the Zn (NO of 0.454g3)2·6H2O and 0.287g TiCl4It is added in suitable distilled water, incipient impregnation to 4.681g
On the modified zeolite of acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then dries, grinds at a temperature of 120 DEG C
Honed sieve in 600 DEG C of roasting temperature 5h, obtains the TiO that composite oxides content is 5%2- ZnO/ zeolite catalysts.
5. a kind of dimethyl ether as claimed in claim 3 exists for the preparation method of the catalyst of polymethoxy dimethyl ether, feature
In when composite oxides are TiO2-V2O5When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 15% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality；It will
The five hydrated sulfuric acid vanadyl and 0.143g TiCl of 0.190g4It is added in suitable distilled water, incipient impregnation to 8.360g acid
On modified zeolite.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, is then dried at a temperature of 120 DEG C, is ground
Sieving in 500 DEG C of roasting temperature 6h, obtains the TiO that composite oxides content is 2.3%2-V2O5/ zeolite catalyst.
6. a kind of dimethyl ether as claimed in claim 3 exists for the preparation method of the catalyst of polymethoxy dimethyl ether, feature
In when composite oxides are SiO2-Al2O3When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 8% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality；It will
1.067g Al2(SO4)3·18H2The H of O and 0.125g2SiO3It is added in suitable distilled water, incipient impregnation to 6.068g
On the modified zeolite of acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then dries, grinds at a temperature of 120 DEG C
Honed sieve in 800 DEG C of roasting temperature 6h, obtains the SiO that composite oxides content is 4.1%2-Al2O3/ zeolite catalyst.
7. a kind of dimethyl ether as claimed in claim 3 exists for the preparation method of the catalyst of polymethoxy dimethyl ether, feature
In when composite oxides are Al2O3-MoO3When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 2% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality；It will
The Al of 0.981g2(SO4)3·18H2The tetrahydrate ammonium molybdate of O and 1.818g is added in suitable distilled water, isometric to soak
In stain to the modified zeolite of 10.945g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then in 120 DEG C of temperature
Degree is lower to dry, and is ground up, sieved, and in 800 DEG C of roasting temperature 8h, obtains the Al that composite oxides content is 3.2%2O3-MoO3/ boiling
Stone catalyst.
8. a kind of dimethyl ether as claimed in claim 3 exists for the preparation method of the catalyst of polymethoxy dimethyl ether, feature
In when composite oxides are Al2O3-Cr2O3When, the preparation method of catalyst is as follows：
The sulfuric acid of volume fraction 12.5% is taken, with solid-to-liquid ratio 1:40 pairs of zeolites impregnate for 24 hours, are dried at 120 DEG C after being washed till neutrality.
By the Al of 0.333g2(SO4)3·18H2The Cr of O and 0.196g2(SO4)3·6H2O is added in suitable distilled water, isometric to soak
In stain to the modified zeolite of 12.558g acid.8h is stood after shaking stirring 2.5 hours at a temperature of 60 DEG C, then in 120 DEG C of temperature
Degree is lower to dry, and is ground up, sieved, and in 800 DEG C of roasting temperature 6h, obtains the Al that composite oxides content is 1%2O3-Cr2O3/ boiling
Stone catalyst.
9. a kind of dimethyl ether as described in claim 1 is for the application of the catalyst of polymethoxy dimethyl ether, which is characterized in that institute
Catalyst is stated in dimethyl ether for the application in polymethoxy dimethyl ether.
10. a kind of dimethyl ether as claimed in claim 9 is for the application of the catalyst of polymethoxy dimethyl ether, which is characterized in that
The catalyst is for the application conditions in polymethoxy dimethyl ether in dimethyl ether：Reactor, raw material two are done using fixed bed
The molar ratio of methyl ether and gaseous mixture is 8.5:1~1:1, it is reacted in the fixed bed reactors continuously flowed, reaction velocity
2500~4500h-1, 200~320 DEG C of reaction temperature, reaction pressure is normal pressure, and the residence time is 10~40h, and wherein gaseous mixture is rubs
You are than being 1:1 nitrogen and oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810062962.8A CN108212197B (en) | 2018-01-23 | 2018-01-23 | Catalyst for preparing polymethoxy dimethyl ether from dimethyl ether and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810062962.8A CN108212197B (en) | 2018-01-23 | 2018-01-23 | Catalyst for preparing polymethoxy dimethyl ether from dimethyl ether and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108212197A true CN108212197A (en) | 2018-06-29 |
| CN108212197B CN108212197B (en) | 2019-12-10 |
Family
ID=62668632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810062962.8A Active CN108212197B (en) | 2018-01-23 | 2018-01-23 | Catalyst for preparing polymethoxy dimethyl ether from dimethyl ether and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108212197B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023914A (en) * | 2020-07-23 | 2020-12-04 | 广州维港环保科技有限公司 | Dioxin removal catalyst for incineration fly ash desorption treatment and preparation method thereof |
| CN112759508A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether by selective oxidation of dimethyl ether |
| CN114029072A (en) * | 2021-12-01 | 2022-02-11 | 万华化学集团股份有限公司 | Solid super acidic catalyst and method for preparing isooctyl p-methoxycinnamate by using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940940A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Catalyst for oxidizing and converting methanol |
| CN104549443A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether catalyst and application thereof |
| CN106513032A (en) * | 2016-11-02 | 2017-03-22 | 东方红升江苏新能源有限公司 | Molecular sieve catalyst for preparation of polyoxymethylene dimethyl ethers |
-
2018
- 2018-01-23 CN CN201810062962.8A patent/CN108212197B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940940A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Catalyst for oxidizing and converting methanol |
| CN104549443A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether catalyst and application thereof |
| CN106513032A (en) * | 2016-11-02 | 2017-03-22 | 东方红升江苏新能源有限公司 | Molecular sieve catalyst for preparation of polyoxymethylene dimethyl ethers |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759508A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether by selective oxidation of dimethyl ether |
| CN112759508B (en) * | 2019-10-21 | 2023-04-07 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether by selective oxidation of dimethyl ether |
| CN112023914A (en) * | 2020-07-23 | 2020-12-04 | 广州维港环保科技有限公司 | Dioxin removal catalyst for incineration fly ash desorption treatment and preparation method thereof |
| CN114029072A (en) * | 2021-12-01 | 2022-02-11 | 万华化学集团股份有限公司 | Solid super acidic catalyst and method for preparing isooctyl p-methoxycinnamate by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108212197B (en) | 2019-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108212197A (en) | A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application | |
| CN107694603B (en) | Immobilized ionic liquid catalyst and preparation method and application thereof | |
| Wang et al. | Two-step synthesis of dimethyl carbonate from urea, ethylene glycol and methanol using acid–base bifunctional zinc-yttrium oxides | |
| CN109225337B (en) | MOFs (metal-organic frameworks) -encapsulated ionic liquid catalyst and preparation and application thereof | |
| CN102295734B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN103381372B (en) | A kind of molecular sieve carried ionic-liquid catalyst and catalyze and synthesize the method for polyoxymethylene dimethyl ether | |
| CN103288607A (en) | Synthetic method of polymethoxy dimethylether | |
| CN103381373A (en) | Magnetic nano imidazolium-based ionic liquid catalyst and method for catalyzed synthesis of polyoxymethylene dimethyl ether through same | |
| CN105597772A (en) | Cobalt-based catalyst having core-shell structure, and preparation method thereof | |
| CN105964307B (en) | Dimethyl ether aoxidizes the catalyst for producing dimethoxy dimethyl ether and preparation method and application | |
| CN102040457B (en) | Method for preparing ethylbenzene and styrene by side chain alkylation reaction of phenylmethane and methanol | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN102824906A (en) | Loaded type molybdenum oxide catalyst for selectively oxidizing methanol to synthesize dimethoxymethane (DMM) and application | |
| CN103420816A (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN112275304B (en) | Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof | |
| CN102372549B (en) | Method for preparing ethylbenzene and styrene by side-chain alkylation reaction of toluene with methanol | |
| CN105642289A (en) | Preparation method of catalyst for complete methanation of syngas | |
| CN106890670A (en) | A kind of catalyst of Dimethyl ether carbonylation production methyl acetate and its application | |
| CN103769227A (en) | Modified silica gel carrier, and preparation method and applications thereof | |
| CN103420818B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN107915594B (en) | Synthetic method for polyformaldehyde dimethyl ether | |
| CN107915593B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN107915597B (en) | Catalyst for preparing polyformaldehyde dimethyl ether | |
| KR101652467B1 (en) | A Noble Catalyst Of Aqueous Phase Reforming Reaction, Using Mesoporous Alumina Carrier And Platinum, And Manufacturing Method Of The Same | |
| CN103537282A (en) | Rhodium-based catalyst for synthesis of ethanol and co-product methane from synthetic gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |