CN107537547A - A kind of catalyst of Dimethyl ether carbonylation and preparation method thereof, application - Google Patents
A kind of catalyst of Dimethyl ether carbonylation and preparation method thereof, application Download PDFInfo
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- CN107537547A CN107537547A CN201710735185.4A CN201710735185A CN107537547A CN 107537547 A CN107537547 A CN 107537547A CN 201710735185 A CN201710735185 A CN 201710735185A CN 107537547 A CN107537547 A CN 107537547A
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Abstract
The present invention relates to a kind of catalyst of Dimethyl ether carbonylation and preparation method thereof, application, belong to chemical catalysis technical field.The preparation method of the catalyst of Dimethyl ether carbonylation of the present invention, comprises the following steps：1) hydrogen type molecular sieve after activation and small organic molecule are subjected to catalytic reaction in 300~600 DEG C, stop reaction when small organic molecule conversion ratio is less than 5%, obtain precursor A；A diameter of 0.4~the 0.7nm of molecular dynamics of the small organic molecule；2) precursor A and dispersant, ball milling are obtained into mixed slurry, afterwards separation of solid and liquid, washing, are drying to obtain, the dispersant is any one or a few in water, methanol, ethanol.The catalyst of the Dimethyl ether carbonylation obtained by the inventive method has high selectivity during methyl acetate is prepared and service life is grown.
Description
Technical field
The present invention relates to a kind of catalyst of Dimethyl ether carbonylation and preparation method thereof, application, belong to chemical catalysis technology
Field.
Background technology
Methyl acetate (methyl acetate) is widely used in the industries such as weaving, spices and medicine, is a kind of important to have
Machine raw material midbody, downstream product mainly have acetic acid, aceticanhydride, methyl acrylate and vinyl acetate, acetamide etc..At home,
The production of methyl acetate is mainly traditional esterifications method.The method exist product separated with catalyst complicated and Noble Metal Rhodium it is expensive with tightly
The problem of lacking, and iodide are serious to equipment corrosion.Solid acid catalysis Dimethyl ether carbonylation methyl acetate is a novelty
Path, during the catalyst that uses be solid catalyst, it is corrosion-free easily separated, and can solve the problems, such as DME production capacity surpluses.
At present, it is mainly mordenite molecular sieve to study more, good catalytic activity catalyst.The skeleton of modenite
Along [001] direction there is 12 yuan of rings and 8 yuan of rings straight hole roads in structure, 8 membered ring channels are between 12 membered ring channels, edge
[010] there is also 8 yuan of rings straight hole roads in direction.12 yuan of rings apertures are oval, and size is 0.65nm × 0.70nm, [001] direction 8
Yuan of rings port size is 0.26nm × 0.57nm, and the yuan of rings port size of [010] direction side-seam pkt. 8 is 0.34nm × 0.48nm.Grind
Study carefully the dimethyl ether carbonylation reaction shown for molecular sieve catalytic, the activity of the acidic site in 8 membered ring channels is higher, and position
It is closely related in the acidic site in 12 membered ring channels and the inactivation of molecular sieve catalyst.Therefore, in order to improve the stabilization of catalyst
Property and methyl acetate selectivity, it is necessary to optionally weaken or eliminate work of the acidic site in reaction system in 12 yuan of rings
With.
Therefore, people take a variety of methods to realize this target.Conventional mainly has two kinds of pyridine adsorption and dealuminzation
Method.There is the slow desorption of pyridine adsorption agent in the method for pre- Adsorption of Pyridine, unavoidable to influence product product in use
Matter.In terms of acid treatment or steam treatment dealuminzation, the poor selectivity of dealuminzation be present, and the problems such as molecular sieve structure easily caves in.
The pre- carbon distribution technology of molecular sieve is a kind of method of effectively modified catalyst acidic site.
Publication No. CN 101475432A Chinese invention patent discloses a kind of butylenes double-bond isomerization reaction selectivity
Method, the aluminosilicate catalyst of pre- carbon distribution is prepared using the method for pre- carbon distribution to improve the selection of butylenes double-bond isomerization
Property, but the starting point of the patent is the strong acid site in pre- carbon distribution covering duct, and the weak acid position worked to isomerization is not
Covered, and the aperture of molecular sieve is easily blocked in the preparation method of pre- carbon deposition catalyst, to follow-up Isomerization of butene
Reactivity it is unfavorable.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the catalyst of Dimethyl ether carbonylation.
Second object of the present invention is to provide a kind of catalyst of Dimethyl ether carbonylation, and the Dimethyl ether carbonylation is urged
Agent selectivity in dimethyl ether carbonylation reaction is high, long lifespan.
3rd purpose of the invention is to provide a kind of catalyst of above-mentioned Dimethyl ether carbonylation anti-in Dimethyl ether carbonylation
Application in answering.
To achieve the above object, the technical scheme is that：
A kind of preparation method of the catalyst of Dimethyl ether carbonylation, comprises the following steps：
1) hydrogen type molecular sieve after activation and small organic molecule are subjected to catalytic reaction in 300~600 DEG C, treat small molecule
Conversion rate of organic matter stops reaction when being less than 5%, obtains precursor A；The molecular dynamics a diameter of 0.4 of the small organic molecule
~0.7nm；
2) precursor A and dispersant, ball milling are obtained into mixed slurry, afterwards separation of solid and liquid, washing, are drying to obtain, institute
It is any one or a few in water, methanol, ethanol to state dispersant.
Hydrogen type molecular sieve in step 1) is h-mordenite or Hydrogen ZSM-35 molecular sieve.The modenite has
MOR structures.The ZSM-35 molecular sieve has FER structures.
The activation method of the hydrogen type molecular sieve is：Hydrogen type molecular sieve is activated in activation phenomenon in 300 DEG C~600 DEG C
0.5~4h.
The activation phenomenon is any one in nitrogen, air, oxygen, helium.
The hydrogen type molecular sieve is that molecular sieve is transformed into hydrogen type molecular sieve using ammonia exchange process.
The molecular dynamics diameter of step 1) small molecular organic matter is preferably 0.5~0.7nm.
The small organic molecule is any one or a few in propylene, butylene, amylene, toluene, dimethylbenzene.It is described small
The molecular diameter of molecular organic, can selectivity between the twelve-ring/between ten-ring and octatomic ring of molecular sieve
The acidic site in twelve-ring/ten-ring duct is selected using the method for pre- carbon distribution into twelve-ring/ten-ring duct
Selecting property is covered, and the acidic site of octatomic ring is substantially unaffected.
Above-mentioned butylene is that four molecular formula are C4H8Isomer in any one or a few.
Above-mentioned amylene is that six molecular formula are C5H10Isomer in any one or a few.
Above-mentioned dimethylbenzene is any one or a few in ortho-xylene, paraxylene, meta-xylene.
Cooled after stopping reaction in step 1) using inert gas, the inert gas is nitrogen or helium.
Reaction in step 1) is carried out in the reactor.The reactor is in fixed bed, fluid bed, moving-burden bed reactor
Any one.
Dispersant and the mass ratio of precursor A are 1~50 in step 2):1.
Water in step 2) is deionized water.
Ball milling is with 200~600rpm 1~12h of rotating speed ball milling in step 2).
The ball milling uses planetary ball mill.The cumulative volume of the precursor A and dispersant is less than ball milling tank volume
3/4.Add dispersant and carry out wet ball grinding, sieve sample is crushed using the method for wet ball grinding, makes molecular sieve sample
Size in product is more uniformly distributed, and fully discharges octatomic ring duct and extraneous connectedness, and then improve the work of Dimethyl ether carbonylation
Property and stability.
A kind of catalyst of Dimethyl ether carbonylation, is made using the preparation method of the catalyst of above-mentioned Dimethyl ether carbonylation.
The catalyst of Dimethyl ether carbonylation of the present invention can be used for preparing methyl acetate using dimethyl ether carbonylation reaction.
Application of the catalyst of above-mentioned Dimethyl ether carbonylation in dimethyl ether carbonylation reaction.
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present invention, using the method for pre- carbon distribution by 12 yuan of molecular sieve
Acidic site in the membered ring channel of ring/10 carries out selective covering, using the method for ball milling fully discharge 8 membered ring channels with it is extraneous
Connectedness, and then improve the Activity and stabill of Dimethyl ether carbonylation.The duct containing octatomic ring obtained by the inventive method
Molecular sieve catalyst has high selectivity in the reaction for prepare methyl acetate and service life is grown.
Brief description of the drawings
Fig. 1 is the process flow diagram of the preparation method of the catalyst of Dimethyl ether carbonylation in embodiment 1.
Embodiment
Embodiments of the present invention are described further below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, as shown in figure 1, comprising the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in fixed bed reactors
H-mordenite, and 400 DEG C of activation 1h are heated in a nitrogen atmosphere；
2) after activating, 350 DEG C is cooled to and is passed through propylene progress catalytic reaction to beds, treats that the conversion ratio of propylene is low
When 5%, stop substrate charging, using nitrogen purging beds cooling, obtain precursor A；
3) precursor A obtained by step 2) is mixed with dispersant deionized water, be placed in planetary ball mill with 200rpm
Rotating speed ball milling 12h, filter, wash, be drying to obtain afterwards, the mass ratio of deionized water and precursor A is 30:1.
Embodiment 2
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in a fluidized bed reactor
H-mordenite, and 500 DEG C of activation 1h are heated in a nitrogen atmosphere；
2) after activating, kept for 500 DEG C be passed through 1- butylene to beds and paraxylene carries out catalytic reaction, 1- butylene
Mol ratio with paraxylene is 1:1, when the conversion ratio of 1- butylene and paraxylene is below 5%, stops substrate charging, adopt
Cooled with helium purge beds, obtain precursor A；
3) precursor A obtained by step 2) is mixed with dispersant deionized water, be placed in planetary ball mill with 350rpm
Rotating speed ball milling 8h, filter, wash, be drying to obtain afterwards, the mass ratio of deionized water and precursor A is 25:1.
Embodiment 3
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in a fluidized bed reactor
H-mordenite, and 450 DEG C of activation 2h are heated in a nitrogen atmosphere；
2) after activating, kept for 450 DEG C be passed through iso-amylene to beds and carry out catalytic reaction, treat the conversion ratio of iso-amylene
During less than 5%, stop substrate charging, cooled using helium purge beds, obtain precursor A；
3) precursor A obtained by step 2) is mixed with dispersant methanol, is placed in planetary ball mill and is turned with 300rpm
Fast ball milling 8h, filters, washs, is drying to obtain afterwards, and the mass ratio of methanol and precursor A is 1:1.
Embodiment 4
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in moving-burden bed reactor
H-mordenite, and 400 DEG C of activation 4h are heated in a nitrogen atmosphere；
2) after activating, kept for 400 DEG C be passed through isobutene to beds and carry out catalytic reaction, treat the conversion ratio of isobutene
During less than 5%, stop substrate charging, using nitrogen purging beds cooling, obtain precursor A；
3) precursor A obtained by step 2) is mixed with dispersant methanol, is placed in planetary ball mill and is turned with 400rpm
Fast ball milling 5h, filters, washs, is drying to obtain afterwards, and the mass ratio of methanol and precursor A is 10:1.
Embodiment 5
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in moving-burden bed reactor
H-mordenite, and 400 DEG C of activation 3h are heated in a nitrogen atmosphere；
2) after activating, kept for 400 DEG C be passed through isobutene to beds and toluene carries out catalytic reaction, isobutene and first
The mol ratio of benzene is 1:1, when the conversion ratio of isobutene and toluene is below 5%, stop substrate charging, urged using nitrogen purging
Agent bed cools, and obtains precursor A；
3) precursor A obtained by step 2) is mixed with dispersant ethanol, is placed in planetary ball mill and is turned with 400rpm
Fast ball milling 5h, filters, washs, is drying to obtain afterwards, and the mass ratio of ethanol and precursor A is 15:1.
Embodiment 6
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in moving-burden bed reactor
H-mordenite, and 600 DEG C of activation 0.5h are heated under helium atmosphere；
2) after activating, kept for 600 DEG C be passed through paraxylene to beds and 2- amylenes carry out catalytic reaction, treated to two
When the conversion ratio of toluene and 2- amylenes is below 5%, stop substrate charging, cooled using nitrogen purging beds, before obtaining
Drive body A；
3) precursor A obtained by step 2) is mixed with dispersant ethanol, deionized water, be placed in planetary ball mill with
600rpm rotating speed ball milling 1h, filters, washs, is drying to obtain afterwards, wherein, the mass ratio of ethanol and water is 1:1, ethanol, go
The gross mass of ionized water and the mass ratio of precursor A are 30:1.
Embodiment 7
The preparation method of the catalyst of the Dimethyl ether carbonylation of the present embodiment, comprises the following steps：
1) mordenite molecular sieve is changed into by h-mordenite using ammonia exchange process, loaded in moving-burden bed reactor
H-mordenite, and 300 DEG C of activation 4h are heated in a nitrogen atmosphere；
2) after activating, kept for 300 DEG C be passed through butadiene to beds and paraxylene carries out catalytic reaction, wherein,
The mol ratio of butadiene and paraxylene is 1:1；When the conversion ratio of butadiene and paraxylene is below 5%, stop substrate
Charging, using nitrogen purging beds cooling, obtain precursor A；
3) precursor A obtained by step 2) is mixed with dispersant deionized water, be placed in planetary ball mill with 500rpm
Rotating speed ball milling 3h, filter, wash, be drying to obtain afterwards, the quality of deionized water and the mass ratio of precursor A are 50:1.
Experimental example catalyst reaction is evaluated
The activity rating of catalyst is carried out on the pressurization stainless steel fixed bed reactors (internal diameter 8mm) continuously flowed
, catalyst fines obtained by embodiment 1-7 is obtained into 40~60 mesh particles through tabletting, screening and is used for Dimethyl ether carbonylation production second
The reactivity worth evaluation of sour methyl esters.Control sample is the h-mordenite molecular sieve without any processing.By each catalyst of 1.0g
It is respectively charged into reactor, 200 DEG C, after temperature stabilization is cooled to after inert atmosphere activation, by dimethyl ether, hydrogen, carbon monoxide
Gaseous mixture in pressure be 2.0MPa, gas volume flow velocity feeds reaction under conditions of being 1500ml/g/h.Wherein hydrogen and two
The total flow of methyl ether is 16.4ml/min, dimethyl ether：Carbon monoxide：Hydrogen is 5:35:60 (volume ratios), catalyst reaction result
It is shown in Table 1.
The catalytic reaction result of catalyst and control sample catalyst obtained by the embodiment 1-7 of table 1
Note：a：Maximum conversion in course of reaction；b：In course of reaction during maximum conversion methyl acetate selectivity；c：
Conversion ratio is reduced to the time used in maximum conversion half.
Claims (10)
1. a kind of preparation method of the catalyst of Dimethyl ether carbonylation, it is characterised in that comprise the following steps：
1) hydrogen type molecular sieve after activation and small organic molecule are subjected to catalytic reaction in 300~600 DEG C, treat that small molecule is organic
Thing conversion ratio stops reaction when being less than 5%, obtains precursor A；The molecular dynamics a diameter of 0.4 of the small organic molecule~
0.7nm；
2) precursor A and dispersant, ball milling are obtained into mixed slurry, afterwards separation of solid and liquid, washing, are drying to obtain, described point
Powder is any one or a few in water, methanol, ethanol.
2. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 1, it is characterised in that in step 1)
Hydrogen type molecular sieve is h-mordenite or Hydrogen ZSM-35 molecular sieve.
3. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 1, it is characterised in that the Hydrogen point
Son sieve activation method be：Hydrogen type molecular sieve is activated into 0.5~4h in activation phenomenon in 300 DEG C~600 DEG C.
4. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 3, it is characterised in that the activation gas
Atmosphere is any one in nitrogen, air, oxygen, helium.
5. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 1, it is characterised in that the small molecule
Organic matter is any one or a few in propylene, butylene, amylene, toluene, dimethylbenzene.
6. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 1, it is characterised in that stop in step 1)
Cooled after only reacting using inert gas, the inert gas is nitrogen or helium.
7. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 1, it is characterised in that divide in step 2)
Powder and the mass ratio of precursor A are 1~50:1.
8. the preparation method of the catalyst of Dimethyl ether carbonylation according to claim 1, it is characterised in that ball in step 2)
Grind as with 200~600rpm 1~12h of rotating speed ball milling.
9. a kind of catalyst of Dimethyl ether carbonylation, it is characterised in that using Dimethyl ether carbonylation as claimed in claim 1
The preparation method of catalyst is made.
10. application of the catalyst of Dimethyl ether carbonylation as claimed in claim 9 in dimethyl ether carbonylation reaction.
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| CN101475432A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for improving butene double bond isomerization reaction |
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
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| CN102421740A (en) * | 2009-05-14 | 2012-04-18 | 英国石油化学品有限公司 | Carbonylation process |
| CN103170360A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院大连化学物理研究所 | Dimethyl ether carbonylation catalyst, and preparation method and application thereof |
| CN104689845A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院大连化学物理研究所 | Catalyst used for preparing methyl acetate through dimethyl ether carbonylation, preparation method and application thereof |
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2017
- 2017-08-24 CN CN201710735185.4A patent/CN107537547B/en active Active
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| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| US20110306785A1 (en) * | 2008-10-13 | 2011-12-15 | Gareth Gerald Armitage | Selective dealumination of mor type zeolites |
| CN101475432A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for improving butene double bond isomerization reaction |
| CN102421740A (en) * | 2009-05-14 | 2012-04-18 | 英国石油化学品有限公司 | Carbonylation process |
| CN103170360A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院大连化学物理研究所 | Dimethyl ether carbonylation catalyst, and preparation method and application thereof |
| CN104689845A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院大连化学物理研究所 | Catalyst used for preparing methyl acetate through dimethyl ether carbonylation, preparation method and application thereof |
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