CN106890669A - A kind of catalyst for producing methyl acetate, its preparation method and application - Google Patents
A kind of catalyst for producing methyl acetate, its preparation method and application Download PDFInfo
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- CN106890669A CN106890669A CN201510964581.5A CN201510964581A CN106890669A CN 106890669 A CN106890669 A CN 106890669A CN 201510964581 A CN201510964581 A CN 201510964581A CN 106890669 A CN106890669 A CN 106890669A
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- hydrogen
- catalyst
- molecular sieves
- silicon tetrachloride
- zeolite molecular
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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
-
- 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
-
- 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
Abstract
This application discloses the catalyst that a kind of Dimethyl ether carbonylation produces methyl acetate, it is characterised in that contain the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation in the catalyst.It is active component by using with the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation, the selectivity of methyl acetate and the stability of catalyst can be greatly improved.
Description
Technical field
The application be related to a kind of catalyst of Dimethyl ether carbonylation production methyl acetate, its preparation method and
Using belonging to chemical field.
Background technology
With developing rapidly for modern industry, energy supply and demand contradiction is protruded increasingly.China disappears as the energy
Take big country, while be again energy shortage big country, in the urgent need to finding fungible energy source.Ethanol is used as one
Clean energy resource is planted, with good intersolubility, can be spiked into gasoline as blending component, part
Replacing gasoline, and the octane number and oxygen content of gasoline are improved, the abundant burning of gasoline is effectively facilitated, subtract
Carbon monoxide, the discharge capacity of hydro carbons in few vehicle exhaust.Ethanol as vehicle fuel part substitute,
The architectural feature of the vehicle fuel presentation diversification of China can be made.Current China it is main with grain especially
Corn is raw material Fuel Alcohol Development, it has also become be only second to the third-largest alcohol fuel life in Brazil, the U.S.
Produce and country of consumption, but according to China's national situation, with grain as raw material carry out alcohol production exist it is many not
Sharp factor, following China's alcohol fuel development is more non-grain route.
It is the one of China's New Coal Chemical Industry development through synthesis gas production ethanol from coal resources
Individual important directions, with wide market prospects.This alleviates oil money to coal resources clean utilization
Source contradiction in short supply, improves Chinese energy safety, with important strategic importance and profound influence.Mesh
Before, the process route of coal ethanol is broadly divided into 2 kinds：One is synthesis gas directly ethanol processed, but is needed expensive
Metal rhodium catalyst, relatively costly and rhodium the limits throughput of catalyst；Two is synthesis gas through acetic acid
Preparation of ethanol by hydrogenating, synthesis gas is first through methyl alcohol liquid-phase carbonylation acetic acid, and then hydrogenation synthesis ethanol.This
Route technical maturity, but equipment needs erosion-resisting special alloy, it is relatively costly.
With dimethyl ether as raw material, methyl acetate, the road of repeated hydrogenation ethanol are directly synthesized by carbonylation
Line is still in conceptual phase, but very promising brand-new route.Nineteen eighty-three Fujimoto
(Appl Catal 1983,7 (3), 361-368) carries out Dimethyl ether carbonylation gas by catalyst of Ni/AC
Solid phase reaction, in the range of CO/DME mol ratios 2.4~4, it is found that dimethyl ether can react with CO and gives birth to
Into methyl acetate, between 80~92%, highest yield is 20% to selectivity.Then, carry out in succession
The research of heteropolyacid salt and MOR, FER, OFF molecular sieve catalytic dimethyl ether carbonylation reaction,
And concentrated on MOR molecular sieve catalysts study hotspot, various study on the modification have been carried out to it.
CN101613274A has found to divide using the modified mercerising molecular sieve molecular sieve catalyst of pyridines organic amine
The modified stability that can increase substantially catalyst of son sieve.The conversion ratio 10-60% of dimethyl ether,
Methyl acetate is selectively more than 99%, and keeps stabilization in 48 hours rear catalyst activity of reaction.
A large amount of Dimethyl ether carbonylation results of study are aforementioned patents disclosed, catalyst stabilization operation is not enough
100h, and easily inactivate.
The content of the invention
According to the one side of the application, there is provided a kind of Dimethyl ether carbonylation produces the catalysis of methyl acetate
Agent.It is activearm by using with the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation
Point, the selectivity of methyl acetate and the stability of catalyst can be greatly improved.
The Dimethyl ether carbonylation produces the catalyst of methyl acetate, it is characterised in that the catalyst
In containing by silicon tetrachloride steam dealuminzation Hydrogen EMT zeolite molecular sieves.The Hydrogen EMT boilings
Stone molecular sieve is calcined after being exchanged through ammonium by EMT zeolite molecular sieves and obtains.
Preferably, the silicon in the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation
Al atomic ratio Si/Al is 5~40.It is further preferred that described by silicon tetrachloride steam dealuminzation
Sial atomic ratio Si/Al in Hydrogen EMT zeolite molecular sieves is 6~30.
Preferably, contain in the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation
Specific surface area is 100~900m2·g-1, pore volume is 0.15~0.30cm3·g-1It is mesoporous.
Preferably, by the Hydrogen EMT zeolite molecules of silicon tetrachloride steam dealuminzation in the catalyst
The weight percentage of sieve is not less than 50%.
Used as a kind of implementation method, the catalyst is by the Hydrogen EMT by silicon tetrachloride steam dealuminzation
Zeolite molecular sieve is constituted.
Used as a kind of implementation method, the catalyst also includes binding agent, de- by silicon tetrachloride steam
The Hydrogen EMT zeolite molecular sieves of aluminium weight percentage in the catalyst is 50~90wt%.Ability
Field technique personnel can according to actual needs select suitable binding agent, it is preferable that the binding agent is selected from
At least one in aluminum oxide, silica or titanium oxide.
Preferably, the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation are by Hydrogen
EMT zeolite molecular sieves are contacted at 500~700 DEG C with silicon tetrachloride steam and obtained.Further preferably
Ground, Hydrogen EMT zeolite molecular sieves are 2~24 hours with the time of contact of silicon tetrachloride steam.
Preferably, the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation are by Hydrogen
After EMT zeolite molecular sieves are contacted with silicon tetrachloride steam at 500~700 DEG C, at 65~150 DEG C
At a temperature of add expanding agent, after treatment 5~24 hours, obtained through drying, roasting.Further preferably
Ground, the expanding agent is selected from cetrimonium bromide, NaOH, sodium carbonate, tetrapropyl
At least one in ammonium hydroxide.
As a kind of specific embodiment, the Hydrogen EMT by silicon tetrachloride steam dealuminzation
The preparation process of zeolite molecular sieve, including at least following steps：
A) Hydrogen EMT zeolite molecular sieves are contacted with silicon tetrachloride steam at 500~700 DEG C, is obtained
To the Hydrogen EMT zeolite molecular sieves through silicon tetrachloride steam dealuminzation；
B) by step a) gained through the Hydrogen EMT zeolite molecular sieves of silicon tetrachloride steam dealuminzation through drying
After roasting, obtain final product by the Hydrogen EMT zeolite molecular sieves of silicon tetrachloride steam dealuminzation.
As a kind of specific embodiment, the Hydrogen EMT by silicon tetrachloride steam dealuminzation
The preparation process of zeolite molecular sieve, including at least following steps：
A) Hydrogen EMT zeolite molecular sieves are contacted with silicon tetrachloride steam at 500~700 DEG C, is obtained
To the Hydrogen EMT zeolite molecular sieves through silicon tetrachloride steam dealuminzation；
B) step a) gained is added through the Hydrogen EMT zeolite molecular sieves of silicon tetrachloride steam dealuminzation
Expanding agent, manufactures mesoporous；
C) by step b) the mesoporous Hydrogen Hydrogen EMT zeolite molecular sieves of gained through drying and roasting after,
Obtain the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation.
As one kind preferred embodiment, the Hydrogen EMT by silicon tetrachloride steam dealuminzation
The preparation process of zeolite molecular sieve, including at least following steps：
(1) the silicon tetrachloride steam of nitrogen carrying is passed through to Hydrogen EMT zeolite molecular sieves；Process time
It is 2~24h, treatment temperature is 500~700 DEG C, N2Flow is 3~10mL/gmin.
(2) step (1) gained solid sample washed through deionized water, be separated by filtration, 100 DEG C~120 DEG C
Dry 1~5 hour；300 DEG C~600 DEG C are calcined 2~8 hours.
(3) by the solid obtained by step (2) and cetrimonium bromide, NaOH, carbonic acid
Sodium and/or TPAOH effect manufacture are mesoporous；Treatment temperature is 65~180 DEG C, process time
It is 4~15h；Washed through deionized water, be separated by filtration, after 100 DEG C~120 DEG C dryings 1~5 hour,
Obtain final product by the Hydrogen EMT zeolite molecular sieves of silicon tetrachloride steam dealuminzation.
As one kind preferred embodiment, the preparation process of the catalyst, including at least following step
Suddenly：
(1) by above-mentioned any Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation with it is viscous
Knot agent mixing, obtains catalyst pulp；
(2) it is fired to obtain final product after being molded to catalyst pulp using spray drying or extrusion method
The catalyst of methyl acetate is produced to the Dimethyl ether carbonylation.
According to the another aspect of the application, there is provided a kind of Dimethyl ether carbonylation produces the side of methyl acetate
Method, using the catalyst.Those skilled in the art can be selected two in unstripped gas according to actual needs
The operating conditions such as the ratio of methyl ether, carbon monoxide and hydrogen, reaction temperature, reaction pressure and air speed.
Used as a kind of implementation method, the Dimethyl ether carbonylation produces the method for methyl acetate, its feature
It is that the unstripped gas containing dimethyl ether, carbon monoxide and hydrogen is passed through reactor, contains with described
The catalyst contact of EMT molecular sieves, in 150~240 DEG C of reaction temperature, reaction pressure 1.0~10.0
MPa, dimethyl ether mass space velocity are 0.01~1.5h-1Under conditions of react, produce methoxy menthyl acetate；
In the unstripped gas, the molar ratio of dimethyl ether, carbon monoxide and hydrogen is dimethyl ether：One oxygen
Change carbon：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,
Dimethyl ether mass space velocity is 0.05~1h-1。
Those skilled in the art can select suitable reactor according to needs of production.Preferably,
The reactor is made up of at least one fixed bed reactors.
The beneficial effect of the application is included but is not limited to：
(1) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided herein, with mesh
Selectivity of product it is high, catalyst life advantage long.
(2) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided herein, reduces
The catalyst amount of unit product, reduces investment.
(3) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided herein, reduction is urged
Agent loads and unloads frequency, reduces maintenance cost.
Specific embodiment
With reference to embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
In embodiment, mesopore surface area uses U.S. Micromeritics company's T ristar3000 type things
Reason adsorption instrument is determined., it is necessary to be carried out to resulting sample pre- before carrying out nitrogen physisorption sign
Treatment.Step is as follows：Sieve sample is vacuumized at normal temperatures；After vacuum condition is reached,
130 DEG C for the treatment of 2h；Afterwards 2h is processed at 350 DEG C.Specific surface is tried to achieve by BET methods, pore volume
It is calculated by the corresponding adsorbance of relative pressure in nitrogen adsorption isotherm 0.99.
In embodiment, product analysis are carried out on the type gas chromatographs of Agilent Agilent 7890,
PONA posts, fid detector.
In embodiment, the carbon that the conversion ratio of dimethyl ether and the selectivity of methyl acetate are all based on dimethyl ether rubs
You are calculated number:
Dimethyl ether conversion rate=[(dimethyl ether carbon molal quantity in unstripped gas)-(dimethyl ether carbon mole in product
Number)] ÷ (dimethyl ether carbon molal quantity in unstripped gas) × (100%)
Methyl acetate selectivity=(2/3 × (methyl acetate carbon molal quantity in product) ÷ [(diformazans in unstripped gas
Ether carbon molal quantity)-(dimethyl ether carbon molal quantity in product)] × (100%)
The preparation of the Hydrogen EMT zeolite molecular sieves of embodiment 1
According to document Synthesis of silica-rich faujasite using crown-ethers as
templates:F.Delprato et,ZEOLITES,1990,VOl 10：Method in 546, prepares
Silica alumina ratio is 4.2 EMT molecular sieves.
EMT molecular sieves are exchanged into three times (2 hour/time) with 0.5mol/L ammonium nitrate, deionized water is used
Washing, dries, and is calcined 4 hours at 550 DEG C, obtains Hydrogen EMT zeolite molecular sieves, is designated as sample
Product 1#。
The preparation of the silicon tetrachloride steam dealuminzation Hydrogen EMT zeolite molecular sieves of embodiment 2
The Hydrogen EMT zeolite molecular sieves of 1g are weighed, two ends are fixed in quartz ampoule with silica wool, led to
Enter the 273K saturation silicon tetrachloride steams of nitrogen carrying.Gained solid sample through deionized water wash,
After being separated by filtration, dry and being calcined, that is, obtain being produced for Dimethyl ether carbonylation the catalysis of methyl acetate
Agent.The temperature and time of silicon tetrachloride vapor treatment, the temperature and time that solid sample is dried and is calcined
Relation with sample number into spectrum is as shown in table 1.
Table 1
The preparation of the silicon tetrachloride steam dealuminzation Hydrogen EMT zeolite molecular sieves of embodiment 3 (uses reaming
Agent)
By 1.00g samples 6#Expanding agent is added, then through filtering, washing, dry, roasting, is made
2 catalyst samples.Used expanding agent, treatment temperature and time, the mesoporous specific surface of gained sample
The relation of product and volume and sample number into spectrum, as shown in table 2.
Table 2
Embodiment 4 adds the catalyst preparation of binding agent
Take sample 11#Through kneading, extruded moulding after being well mixed with 10% dust technology with binding agent, do
It is dry, it is calcined 4 hours at 550 DEG C, catalyst, gained catalyst numbering and raw material type and ratio is obtained
The relation of example is shown in Table 3.After mixing with binding agent, extruded moulding is obtained catalyst and is shown in Table 3 respectively.
Table 3
The catalyst reaction performance evaluation of embodiment 5
By gained sample 1#~20#Through compressing tablet, pulverize, sieve 40~60 mesh samples that obtain and be used for diformazan
The reactivity worth of ether carbonylation production methyl acetate is determined.1.0g catalyst is loaded into reactor, by two
Methyl ether, hydrogen, the gaseous mixture of carbon monoxide are in 200 DEG C of temperature, pressure 5MPa, air speed
Pass through reactor under conditions of=1500mL/g/h.Wherein gas flow 25ml/min,
CO/DME/H2=30/5/60 (volume ratio).The catalyst reaction result of 100 hours is listed in table 4.
Table 4
The above, is only several embodiments of the application, and any type of limit is not done to the application
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, it is any
Those skilled in the art, are not departing from the range of technical scheme, are taken off using above-mentioned
The technology contents for showing make a little variation or modification is equal to equivalence enforcement case, belong to technology
In aspects.
Claims (10)
1. a kind of Dimethyl ether carbonylation produces the catalyst of methyl acetate, it is characterised in that described to urge
Contain the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation in agent.
2. catalyst according to claim 1, it is characterised in that described by silicon tetrachloride
Sial atomic ratio Si/Al in the Hydrogen EMT zeolite molecular sieves of steam dealuminzation is 5~40；Preferably,
Sial atomic ratio Si/Al in the Hydrogen EMT zeolite molecular sieves by silicon tetrachloride steam dealuminzation
It is 6~30.
3. catalyst according to claim 1, it is characterised in that described by silicon tetrachloride
It is 100~900m to contain specific surface area in the Hydrogen EMT zeolite molecular sieves of steam dealuminzation2·g-1, hole body
Product is 0.15~0.30cm3·g-1It is mesoporous.
4. catalyst according to claim 1, it is characterised in that pass through in the catalyst
The weight percentage of the Hydrogen EMT zeolite molecular sieves of silicon tetrachloride steam dealuminzation is not less than 50%.
5. catalyst according to claim 1, it is characterised in that described by silicon tetrachloride
The Hydrogen EMT zeolite molecular sieves of steam dealuminzation are by Hydrogen EMT zeolite molecular sieves and silicon tetrachloride steam
Contacted at 500~700 DEG C and obtained.
6. catalyst according to claim 3, it is characterised in that described by silicon tetrachloride
The Hydrogen EMT zeolite molecular sieves of steam dealuminzation are by Hydrogen EMT zeolite molecular sieves and silicon tetrachloride steam
After being contacted at 500~700 DEG C, expanding agent is added at a temperature of 65~150 DEG C, treatment 5~24 is small
Shi Hou, obtains through drying, roasting.
7. the catalyst according to any one of claim 6, it is characterised in that the expanding agent
Selected from cetrimonium bromide, NaOH, sodium carbonate, TPAOH extremely
Few one kind.
8. catalyst according to claim 1, it is characterised in that the catalyst is also included
Binding agent, by the Hydrogen EMT zeolite molecular sieves weight in the catalyst of silicon tetrachloride steam dealuminzation
Amount percentage composition is 50~90wt%.
9. a kind of method that Dimethyl ether carbonylation produces methyl acetate, it is characterised in that two will be contained
The unstripped gas of methyl ether, carbon monoxide and hydrogen is passed through reactor, with any one of claim 1 to 8 institute
The catalyst contact stated, in 150~240 DEG C of reaction temperature, 1.0~10.0MPa of reaction pressure, diformazan
Ether mass space velocity is 0.01~1.5h-1Under conditions of react, produce methyl acetate；
In the unstripped gas, the molar ratio of dimethyl ether, carbon monoxide and hydrogen is dimethyl ether：One oxygen
Change carbon：Hydrogen=1：1~10：0.5~5.
10. method according to claim 9, it is characterised in that the reactor is by least
Individual fixed bed reactors composition.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586247A (en) * | 2018-07-02 | 2018-09-28 | 中国科学院山西煤炭化学研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| WO2020155143A1 (en) * | 2019-02-02 | 2020-08-06 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate by means of carbonylation of dimethyl ether |
| US11292761B2 (en) * | 2017-09-29 | 2022-04-05 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for directly producing methyl acetate and/or acetic acid from syngas |
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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 |
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| CN101903100A (en) * | 2007-12-19 | 2010-12-01 | 英国石油化学品有限公司 | Carbonylation process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11292761B2 (en) * | 2017-09-29 | 2022-04-05 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for directly producing methyl acetate and/or acetic acid from syngas |
| CN108586247A (en) * | 2018-07-02 | 2018-09-28 | 中国科学院山西煤炭化学研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| WO2020155143A1 (en) * | 2019-02-02 | 2020-08-06 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate by means of carbonylation of dimethyl ether |
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