CN106890669B - A kind of catalyst producing methyl acetate, preparation method and application - Google Patents
A kind of catalyst producing methyl acetate, preparation method and application Download PDFInfo
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- CN106890669B CN106890669B CN201510964581.5A CN201510964581A CN106890669B CN 106890669 B CN106890669 B CN 106890669B CN 201510964581 A CN201510964581 A CN 201510964581A CN 106890669 B CN106890669 B CN 106890669B
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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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7019—EMT-type, e.g. EMC-2, ECR-30, CSZ-1, ZSM-3 or ZSM-20
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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Abstract
This application discloses a kind of catalyst of Dimethyl ether carbonylation production methyl acetate, which is characterized in that contains the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation in the catalyst.By using using the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation as active component, the selectivity of methyl acetate and the stability of catalyst can be greatly improved.
Description
Technical field
This application involves catalyst, preparation method and the applications of a kind of Dimethyl ether carbonylation production methyl acetate, belong to
Chemical field.
Background technique
With the rapid development of modern industry, energy supply and demand contradiction is increasingly prominent.China is as energy-consuming big country, simultaneously
It is energy shortage big country again, there is an urgent need to find fungible energy source.Ethyl alcohol has and dissolves each other well as a kind of clean energy resource
Property, can be used as blending component is spiked into gasoline, part replacing gasoline, and improves the octane number and oxygen content of gasoline, effectively
Promote the full combustion of gasoline, reduces the discharge amount of carbon monoxide, hydro carbons in vehicle exhaust.Part of the ethyl alcohol as vehicle fuel
Substitute can make the vehicle fuel in China that the structure feature of diversification be presented.China is mainly at present with grain especially corn
Raw material Fuel Alcohol Development, it has also become be only second to Brazil, the third-largest fuel ethanol production in the U.S. and country of consumption, but according to China
National conditions carry out ethyl alcohol production there are many unfavorable factors by raw material of grain, and following China's alcohol fuel development is more
Non- grain route.
It is an important side of China's New Coal Chemical Industry development through synthesis gas production ethyl alcohol from coal resources
To having a vast market foreground.This alleviates petroleum resources contradiction in short supply, improves China's energy to coal resources clean utilization
Source safety, has important strategic importance and profound influence.Currently, the process route of coal ethyl alcohol is broadly divided into 2 kinds: first is that closing
At gas ethyl alcohol directly processed, but Noble Metal Rhodium catalyst is needed, the higher cost of catalyst and the limits throughput of rhodium；Second is that synthesis gas
Through acetic acid preparation of ethanol by hydrogenating, synthesis gas is first through methanol liquid-phase carbonylation acetic acid, and then hydrogenation synthesis ethyl alcohol.This route technique at
It is ripe, but equipment needs erosion-resisting special alloy, higher cost.
Using dimethyl ether as raw material, by the way that direct synthesis of acetic acid methyl esters is carbonylated, the route of repeated hydrogenation ethyl alcohol is still to be in
Conceptual phase, but very promising completely new route.Nineteen eighty-three Fujimoto (Appl Catal 1983,7 (3),
Dimethyl ether carbonylation gas-solid phase reaction 361-368) is carried out by catalyst of Ni/AC, in 2.4~4 range of CO/DME molar ratio,
It was found that dimethyl ether can be reacted with CO generates methyl acetate, for selectivity between 80~92%, highest yield is 20%.Then, phase
After the research for having carried out heteropolyacid salt and MOR, FER, OFF molecular sieve catalytic dimethyl ether carbonylation reaction, and by research hotspot collection
In on MOR molecular sieve catalyst, various study on the modification have been carried out to it.CN101613274A is changed using pyridines organic amine
Sex pilus optical molecule sieve element sieve catalyst, it is found that the modification of molecular sieve can increase substantially the stability of catalyst.Dimethyl ether
Conversion ratio 10-60%, methyl acetate is selectively greater than 99%, and keeps stablizing in 48 hours rear catalyst activity of reaction.
Aforementioned patents disclose a large amount of Dimethyl ether carbonylation results of study, catalyst stabilization is run less than 100h, and pole
Easy in inactivation.
Summary of the invention
According to the one aspect of the application, a kind of catalyst of Dimethyl ether carbonylation production methyl acetate is provided.By adopting
To be active component by the Hydrogen EMT zeolite molecular sieve of silicon tetrachloride steam dealuminzation, the choosing of methyl acetate can be greatly improved
The stability of selecting property and catalyst.
The catalyst of the Dimethyl ether carbonylation production methyl acetate, which is characterized in that contain process in the catalyst
The Hydrogen EMT zeolite molecular sieve of silicon tetrachloride steam dealuminzation.The Hydrogen EMT zeolite molecular sieve is by EMT zeolite molecular sieve through ammonium
Roasting obtains after exchange.
Preferably, the sial atomic ratio Si/Al in the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
It is 5~40.It is further preferred that the sial atom in the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
It is 6~30 than Si/Al.
It preferably, is 100 containing specific surface area in the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
~900m2·g-1, pore volume is 0.15~0.30cm3·g-1It is mesoporous.
Preferably, by the weight percent of the Hydrogen EMT zeolite molecular sieve of silicon tetrachloride steam dealuminzation in the catalyst
Content is not less than 50%.
As an implementation, the catalyst is by the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
Composition.
As an implementation, the catalyst also includes binder, by the Hydrogen EMT of silicon tetrachloride steam dealuminzation
The weight percentage of zeolite molecular sieve in the catalyst is 50~90wt%.Those skilled in the art can select according to actual needs
Select suitable binder, it is preferable that the binder is selected from least one of aluminium oxide, silica or titanium oxide.
Preferably, the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation is by Hydrogen EMT zeolite molecular sieve
It contacts to obtain at 500~700 DEG C with silicon tetrachloride steam.It is further preferred that Hydrogen EMT zeolite molecular sieve and silicon tetrachloride
The time of contact of steam is 2~24 hours.
Preferably, the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation is by Hydrogen EMT zeolite molecular sieve
After being contacted at 500~700 DEG C with silicon tetrachloride steam, 65~150 DEG C at a temperature of be added expanding agent, processing 5~24 is small
Shi Hou is obtained through drying, roasting.It is further preferred that the expanding agent is selected from cetrimonium bromide, hydroxide
At least one of sodium, sodium carbonate, tetrapropylammonium hydroxide.
As a kind of specific embodiment, the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
Preparation process includes at least following steps:
A) Hydrogen EMT zeolite molecular sieve is contacted at 500~700 DEG C with silicon tetrachloride steam, is obtained described through tetrachloro
The Hydrogen EMT zeolite molecular sieve of SiClx steam dealuminzation；
B) by obtained by step a) through the Hydrogen EMT zeolite molecular sieve of silicon tetrachloride steam dealuminzation after drying and roasting, i.e.,
Obtain the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation.
As a kind of specific embodiment, the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
Preparation process includes at least following steps:
A) Hydrogen EMT zeolite molecular sieve is contacted at 500~700 DEG C with silicon tetrachloride steam, is obtained described through tetrachloro
The Hydrogen EMT zeolite molecular sieve of SiClx steam dealuminzation；
B) by the Hydrogen EMT zeolite molecular sieve through silicon tetrachloride steam dealuminzation obtained by step a), expanding agent is added, manufacture is situated between
Hole；
C) the mesoporous Hydrogen Hydrogen EMT zeolite molecular sieve of step b) gained is arrived into the warp after drying and roasting
Cross the Hydrogen EMT zeolite molecular sieve of silicon tetrachloride steam dealuminzation.
As a preferred embodiment, the Hydrogen EMT zeolite molecular sieve by silicon tetrachloride steam dealuminzation
Preparation process includes at least following steps:
(1) the silicon tetrachloride steam that nitrogen carries is passed through to Hydrogen EMT zeolite molecular sieve；Handle the time be 2~for 24 hours, place
Managing temperature is 500~700 DEG C, N2Flow is 3~10mL/gmin.
(2) step (1) obtained solid sample wash, be separated by filtration through deionized water, 100 DEG C~120 DEG C dryings 1~5 it is small
When；300 DEG C~600 DEG C roast 2~8 hours.
(3) by step (2) resulting solid and cetrimonium bromide, sodium hydroxide, sodium carbonate and/or 4 third
The effect manufacture of base ammonium hydroxide is mesoporous；Treatment temperature is 65~180 DEG C, and the processing time is 4~15h；Through deionized water washing, mistake
Filter separation, 100 DEG C~120 DEG C after drying 1~5 hour to get the Hydrogen EMT zeolite molecules of process silicon tetrachloride steam dealuminzation
Sieve.
As a preferred embodiment, the preparation process of the catalyst, includes at least following steps:
(1) by it is above-mentioned it is any mixed by the Hydrogen EMT zeolite molecular sieve of silicon tetrachloride steam dealuminzation with binder, obtain
Catalyst pulp；
(2) it after being formed using spray drying or extrusion method to catalyst pulp, is fired and obtains the dimethyl ether
The catalyst of carbonylation production methyl acetate.
According to the another aspect of the application, a kind of method of Dimethyl ether carbonylation production methyl acetate is provided, using described
Catalyst.Those skilled in the art can according to actual needs, select unstripped gas in dimethyl ether, carbon monoxide and hydrogen ratio,
The operating conditions such as reaction temperature, reaction pressure and air speed.
As an implementation, the method for the Dimethyl ether carbonylation production methyl acetate, which is characterized in that will contain
The unstripped gas of dimethyl ether, carbon monoxide and hydrogen is passed through reactor, contacts with the catalyst containing EMT molecular sieve, anti-
Answering 150~240 DEG C of temperature, 1.0~10.0MPa of reaction pressure, dimethyl ether mass space velocity is 0.01~1.5h-1Under conditions of it is anti-
It answers, produces methoxy menthyl acetate；
In the unstripped gas, the molar ratio of dimethyl ether, carbon monoxide and hydrogen is dimethyl ether: carbon monoxide: hydrogen=
1:1~10:0.5~5.
It is further preferred that the reaction temperature is 180~240 DEG C, reaction pressure is 4~6MPa, and dimethyl ether quality is empty
Speed is 0.05~1h-1。
Those skilled in the art can select suitable reactor according to needs of production.Preferably, the reactor by
At least one fixed bed reactors composition.
The beneficial effect of the application includes but is not limited to:
(1) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided herein has purpose product selectivity
Height, the long advantage of catalyst life.
(2) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided herein reduces urging for unit product
Agent dosage reduces investment.
(3) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided herein reduces catalyst loading and unloading frequency,
Reduce maintenance cost.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
In embodiment, mesopore surface area uses U.S. Micromeritics company's T ristar3000 type physical adsorption appearance
Measurement.Before carrying out nitrogen physisorption characterization, need to pre-process obtained sample.Steps are as follows: at normal temperature
Sieve sample is vacuumized；After reaching vacuum condition, in 130 DEG C of processing 2h；Later in 350 DEG C of processing 2h.Specific surface by
BET method acquires, and pore volume is calculated by the corresponding adsorbance of relative pressure 0.99 in nitrogen adsorption isotherm.
In embodiment, product analysis carries out on 7890 type gas chromatograph of Agilent Agilent, PONA column, FID inspection
Survey device.
In embodiment, the carbon molal quantity that the conversion ratio of dimethyl ether and the selectivity of methyl acetate are all based on dimethyl ether is counted
It calculates:
Dimethyl ether conversion rate=[(dimethyl ether carbon molal quantity in unstripped gas)-(dimethyl ether carbon molal quantity in product)] ÷ is (former
Expect dimethyl ether carbon molal quantity in gas) × (100%)
Methyl acetate selectivity=(2/3 × (methyl acetate carbon molal quantity in product) [(dimethyl ether carbon rubs ÷ in unstripped gas
That number)-(dimethyl ether carbon molal quantity in product)] × (100%)
The preparation of 1 Hydrogen EMT zeolite molecular sieve of embodiment
According to document Synthesis of silica-rich faujasite using crown-ethers as
Method in templates:F.Delprato et, ZEOLITES, 1990, VOl 10:546, it is 4.2 that silica alumina ratio, which is prepared,
EMT molecular sieve.
EMT molecular sieve 0.5mol/L ammonium nitrate is exchanged three times (2 hour/time), is washed with deionized, it is dry,
550 DEG C roast 4 hours, obtain Hydrogen EMT zeolite molecular sieve, are denoted as sample 1#。
The preparation of 2 silicon tetrachloride steam dealuminzation Hydrogen EMT zeolite molecular sieve of embodiment
The Hydrogen EMT zeolite molecular sieve of 1g is weighed, both ends are fixed in quartz ampoule with silica wool, are passed through nitrogen carrying
273K is saturated silicon tetrachloride steam.Obtained solid sample arrives after deionized water is washed, is separated by filtration, dries and is roasted
Catalyst for Dimethyl ether carbonylation production methyl acetate.The temperature and time of silicon tetrachloride vapor processing, solid sample are dry
The relationship of dry and roasting temperature and time and sample number into spectrum is as shown in table 1.
Table 1
The preparation (using expanding agent) of 3 silicon tetrachloride steam dealuminzation Hydrogen EMT zeolite molecular sieve of embodiment
By 1.00g sample 6#Expanding agent is added, is then filtered, washed, dried, roasted, 2 catalyst samples are made.Institute
Using expanding agent, treatment temperature and time, the relationship of the mesopore surface area of gained sample and volume and sample number into spectrum, such as table 2
It is shown.
Table 2
The catalyst preparation of the addition binder of embodiment 4
Take sample 11#It is dry through kneading, extruded moulding after being uniformly mixed with binder with 10% dust technology, it is roasted at 550 DEG C
It burns 4 hours, catalyst is made, gained catalyst number and the relationship of raw material type and ratio are shown in Table 3.After being mixed with binder,
Catalyst is made respectively and is shown in Table 3 for extruded moulding.
Table 3
The evaluation of 5 catalyst reaction performance of embodiment
By gained sample 1#~20#Through tabletting, pulverize, to sieve 40~60 obtained mesh samples raw for Dimethyl ether carbonylation
Produce the reactivity worth measurement of methyl acetate.1.0g catalyst is packed into reactor, by the mixing of dimethyl ether, hydrogen, carbon monoxide
Gas passes through reactor under conditions of 200 DEG C of temperature, pressure 5MPa, air speed=1500mL/g/h.Wherein gas flow 25ml/
Min, CO/DME/H2=30/5/60 (volume ratio).100 hours results of catalyst reaction are listed in table 4.
Table 4
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (11)
1. a kind of catalyst of Dimethyl ether carbonylation production methyl acetate, which is characterized in that containing by four in the catalyst
The Hydrogen EMT zeolite molecular sieve of chlorination silicon vapor dealuminzation.
2. catalyst according to claim 1, which is characterized in that the Hydrogen EMT by silicon tetrachloride steam dealuminzation
Sial atomic ratio Si/Al in zeolite molecular sieve is 5~40.
3. catalyst according to claim 1, which is characterized in that the Hydrogen EMT by silicon tetrachloride steam dealuminzation
Sial atomic ratio Si/Al in zeolite molecular sieve is 6~30.
4. catalyst according to claim 1, which is characterized in that the Hydrogen EMT by silicon tetrachloride steam dealuminzation
Containing specific surface area in zeolite molecular sieve is 100~900m2·g-1, pore volume is 0.15~0.30cm3·g-1It is mesoporous.
5. catalyst according to claim 1, which is characterized in that by silicon tetrachloride steam dealuminzation in the catalyst
The weight percentage of Hydrogen EMT zeolite molecular sieve is not less than 50%.
6. catalyst according to claim 1, which is characterized in that the Hydrogen EMT by silicon tetrachloride steam dealuminzation
Zeolite molecular sieve at 500~700 DEG C is contacted to obtain by Hydrogen EMT zeolite molecular sieve with silicon tetrachloride steam.
7. catalyst according to claim 4, which is characterized in that the Hydrogen EMT by silicon tetrachloride steam dealuminzation
After zeolite molecular sieve is contacted at 500~700 DEG C by Hydrogen EMT zeolite molecular sieve with silicon tetrachloride steam, at 65~150 DEG C
At a temperature of be added expanding agent, after processing 5~24 hours, obtained through drying, roasting.
8. catalyst according to claim 7, which is characterized in that the expanding agent is selected from cetyltrimethylammonium base
At least one of ammonium, sodium hydroxide, sodium carbonate, tetrapropylammonium hydroxide.
9. catalyst according to claim 1, which is characterized in that the catalyst also includes binder, by four chlorinations
The weight percentage of the Hydrogen EMT zeolite molecular sieve of silicon vapor dealuminzation in the catalyst is 50~90wt%.
10. a kind of method of Dimethyl ether carbonylation production methyl acetate, which is characterized in that will containing dimethyl ether, carbon monoxide and
The unstripped gas of hydrogen is passed through reactor, contacts with the described in any item catalyst of claim 1 to 9, reaction temperature 150~
240 DEG C, 1.0~10.0MPa of reaction pressure, dimethyl ether mass space velocity be 0.01~1.5h-1Under conditions of react, produce acetic acid first
Ester；
In the unstripped gas, the molar ratio of dimethyl ether, carbon monoxide and hydrogen is dimethyl ether: carbon monoxide: hydrogen=1:1~
10:0.5~5.
11. according to the method described in claim 10, it is characterized in that, the reactor is by least one fixed bed reactors group
At.
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| EP3689848A4 (en) * | 2017-09-29 | 2021-05-12 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Method for directly producing methyl acetate and/or acetic acid from syngas |
| CN108586247B (en) * | 2018-07-02 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Method for preparing methyl acetate by carbonylation of dimethyl ether |
| EA202192150A1 (en) * | 2019-02-02 | 2021-11-03 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс | METHOD FOR PRODUCING METHYL ACETATE BY CARBONYLATION OF DIMETHYL ETHER |
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| CN1455701A (en) * | 2000-07-17 | 2003-11-12 | 埃克森美孚化学专利公司 | Synthesis of molecular sieve catalysts |
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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 |
| CN101903325A (en) * | 2007-12-20 | 2010-12-01 | 英国石油化学品有限公司 | Carbonylation process for the production of acetic acid and/or methyl acetate |
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| CN1455701A (en) * | 2000-07-17 | 2003-11-12 | 埃克森美孚化学专利公司 | Synthesis of molecular sieve catalysts |
| CN1856362A (en) * | 2003-09-22 | 2006-11-01 | 埃克森美孚化学专利公司 | Molecular sieve catalyst composition, its making and use in conversion processes |
| CN101903100A (en) * | 2007-12-19 | 2010-12-01 | 英国石油化学品有限公司 | Carbonylation process |
| CN101903325A (en) * | 2007-12-20 | 2010-12-01 | 英国石油化学品有限公司 | Carbonylation process for the production of acetic acid and/or methyl acetate |
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