CN106890668B - 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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- 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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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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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- 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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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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Abstract
This application discloses a kind of catalyst of Dimethyl ether carbonylation production methyl acetate, which is characterized in that comprising modified EMT molecular sieve, the modified EMT molecular sieve is the EMT molecular sieve after alkali process, then through pyridine and/or the processing of pyridine substituent；The pyridine substituent is that one, two or three on pyridine ring in five H is independently selected from F, Cl, Br, I, CH3、CF3、CH3CH2Or NO2In substituent group substitution be formed by compound.The catalyst has the selectivity of very high stability and methyl acetate.
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, while again
It is energy shortage big country, there is an urgent need to find fungible energy source.Ethyl alcohol has good intersolubility as a kind of clean energy resource,
It can be used as blending component to be spiked into gasoline, part replacing gasoline, and improve the octane number and oxygen content of gasoline, effectively facilitate
The full combustion of gasoline reduces the discharge amount of CO, hydro carbons in vehicle exhaust.Part substitute of the ethyl alcohol as vehicle fuel, can
Make the vehicle fuel in China that the structure feature of diversification be presented.China is mainly developed as raw material using grain especially corn and is fired at present
Expect ethyl alcohol, it has also become Brazil, the third-largest fuel ethanol production in the U.S. and country of consumption are only second to, but according to China's national situation, with grain
Food is that there are many unfavorable factors for raw material progress ethyl alcohol production, and following China's alcohol fuel development is more non-food path
Line.
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 passes 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, and the route of preparation of ethanol by hydrogenating is still to be in
Conceptual phase, but very promising completely new route.Nineteen eighty-three Fujimoto (Appl Catal 1983,7 (3), 361-
368) Dimethyl ether carbonylation gas-solid phase reaction is carried out by catalyst of Ni/AC, within the scope of CO/DME molar ratio 2.4-4, discovery
Dimethyl ether can be reacted in CO generates methyl acetate, and for selectivity between 80-92%, highest yield is 20%.Then, carry out in succession
The research of heteropolyacid salt and MOR, FER, OFF molecular sieve catalytic dimethyl ether carbonylation reaction, and research hotspot is concentrated on
On MOR molecular sieve catalyst, various study on the modification have been carried out to it.Chinese patent CN101613274A utilizes pyridines organic amine
Modified mordenite molecular sieve catalyst, discovery can increase substantially the stability of catalyst.The conversion ratio 10- of dimethyl ether
60%, methyl acetate is selectively greater than 99%, and keeps stablizing in 48 hours rear catalyst activity of reaction.
Dimethyl ether carbonylation disclosed in the prior art produces in the research of methyl acetate, and catalyst easily inactivates, related
It is impossible to meet industrial demands.
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
It is active component to modified EMT molecular sieve, which has the selectivity of very high stability and methyl acetate, when long
Between react after, be still able to maintain high methyl acetate selectivity.
The catalyst of the Dimethyl ether carbonylation production methyl acetate, which is characterized in that include modified EMT molecular sieve, institute
Stating modified EMT molecular sieve is the EMT molecular sieve after alkali process, then through pyridine and/or the processing of pyridine substituent；
The pyridine substituent be one, two or three on pyridine ring in five H independently by selected from F, Cl, Br,
I、CH3、CF3、CH3CH2Or NO2In substituent group substitution be formed by compound.
Preferably, the sial atom Si/Al ratio in the modified EMT molecular sieve is 3~40.It is further preferred that described
Sial atom Si/Al ratio in modified EMT molecular sieve is 3.5~30.It is further preferred that in the modified EMT molecular sieve
Sial atom Si/Al ratio be 4~30.
Preferably, the pyridine substituent is selected from 2- picoline, 3- picoline, 4- picoline, 2,6- dimethyl
Pyridine, 2,4- lutidines, 2,4,6- trimethylpyridine, 2- ethylpyridine, 3-ethylpyridine, 4- ethylpyridine, 3- nitro
Pyridine, 2- chloro-5-nitropyridine, 2- fluorine pyridine, 3- fluorine pyridine and 4- fluorine pyridine, 2- chloropyridine, 3- chloropyridine, 4- chloropyridine,
At least one of 2- bromopyridine, 3- bromopyridine, 4- bromopyridine, 2- iodine pyridine, 3- iodine pyridine, 4- iodine pyridine.
It may include binder in the catalyst, those skilled in the art can urge according to the needs of actual production, selection
The ratio of binder and modified EMT molecular sieve in agent.Preferably, in the catalyst, the weight percent of modified EMT molecular sieve
Content is not less than 50%.
According to the another aspect of the application, the method for preparing the catalyst is provided, which is characterized in that include at least following
Step:
A) EMT molecular sieve is placed in alkaline solution and is handled 1~10 hour at 30~100 DEG C；
B) sample obtained by step a) is washed to neutrality, after adding binder molding, exchanged, filtered with ammonium nitrate solution,
And it is washed with deionized, dries, 350~680 DEG C roasting 1~10 hour in air atmosphere；
C) under the conditions of by sample obtained by step b) under the atmosphere containing pyridine and/or pyridine substituent, 240~400 DEG C
Reason was prepared into the catalyst after 0.5~24 hour after purging.
Preferably, alkaline solution described in step a) is sodium hydroxide and/or potassium hydroxide solution；Sodium hydroxide in solution
And/or the concentration of potassium hydroxide is 0.05~1mol/L.
Preferably, step a) is that EMT molecular sieve is placed in alkaline solution to handle 2~5 hours at 40~90 DEG C.
Preferably, extruded moulding is shaped to described in step b).
Preferably, binder described in step b) is selected from least one of aluminium oxide, silica, titanium oxide.
Preferably, maturing temperature described in the step b) is 400~600 DEG C, the time is 2~6 hours.
Preferably, step c) be by sample obtained by step b) under the atmosphere containing pyridine and/or pyridine substituent, 250~
After handling 2~20 hours under the conditions of 350 DEG C, the catalyst is prepared into after purging.
The atmosphere containing pyridine and/or pyridine substituent refers to pyridine and/or pyridine substituent and non-active gas
Mixture.Those skilled in the art can select the ratio of pyridine and/or pyridine substituent and non-active gas according to actual needs
Example.Preferably, the volume ratio of pyridine and/or pyridine substituent and non-active gas is 0.1~99.9:1.
The non-active gas is selected from least one of nitrogen, inert gas.
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 catalyst, in 150~240 DEG C of reaction temperature, instead
Answering 1.0~10.0MPa of pressure, dimethyl 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: carbon monoxide: hydrogen=
1:1~10:0.5~5；
The catalyst in above-mentioned any catalyst, the catalyst being prepared according to any of the above-described method extremely
Few one kind.
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 by the present application, the selectivity with target product
The advantages that height, catalyst stability is good.The activity and stability for effectively increasing catalyst are reduced, catalyst is reduced
Regeneration times simplify the production technology of Dimethyl ether carbonylation and the production cost of catalyst, reduce production operating cost.
(2) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided by the present application, significantly reduces unit product
Catalyst amount reduces investment.
(3) catalyst of preparing methyl acetate by carbonylating dimethyl ether provided by the present application, be greatly reduced catalyst regeneration,
Activation and handling frequency, reduce the discharge of exhaust gas in catalyst regeneration process, while reducing production maintenance expense.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
In embodiment, the element composition in EMT molecular sieve uses the Magix 2424X type of PHILIPS Co. (Philips)
Ray fluorescence analysis instrument (XRF) measurement.
In embodiment, the object of EMT molecular sieve mutually passes through X-ray powder diffraction material phase analysis (XRD) measurement；Using Dutch pa
Receive X ' the Pert PRO X-ray diffractometer of section (PANalytical) company, Cu target, K α radiation source (λ=0.15418nm), electricity
Press 40KV, electric current 40mA.
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 embodiment 1EMT molecular sieve
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.
By vapor dealuminzation 1 hour, 2 hours, 4 hours, 8 hours at 600 DEG C, sial atomic ratio (Si/Al) point is obtained
Not Wei 10,15,20,30 EMT molecular sieve.
The preparation of 2 catalyst CAT-1 of embodiment
100 grams of EMT molecular sieves (Si/Al=15) are put into the NaOH solution that 1000mL concentration is 0.5mol/L at 80 DEG C
Processing 2 hours, filtration washing to neutrality.EMT molecular sieve after taking out 80g alkali process, 28g boehmite (aqueous 29wt%)
With 10% dust technology extruded moulding after mixing, after roasting, three times (2 hour/time) with the exchange of 0.5mol/L ammonium nitrate, spend
Ion water washing, it is dry, it is roasted 4 hours at 550 DEG C, sample is made in the gas that 300 DEG C, pyridine and nitrogen volume ratio example are 1:5
It is handled 2 hours under atmosphere, is denoted as catalyst CAT-1.
The preparation of 3 catalyst CAT-2~CAT-5 of embodiment
Be respectively adopted silica alumina ratio be Si/Al=4.2, Si/Al=10, Si/Al=20, Si/Al=30 EMT molecular sieve into
Row catalyst preparation, detailed process is as follows:
100 grams of EMT molecular sieves are put into the NaOH solution that 1000ml concentration is 0.5mol/L and are handled 2 hours at 80 DEG C,
Filtration washing is to neutrality.EMT molecular sieve after taking out 80g alkali process, 28g boehmite (aqueous 29wt%) and 10% dilute nitre
Sour extruded moulding after mixing after roasting, three times (2 hour/time) with the exchange of 0.5mol/L ammonium nitrate, is washed with deionized water
It washs, it is dry, it is roasted 4 hours at 550 DEG C, sample is made and handles 2 in the case where 300 DEG C, pyridine and nitrogen volume ratio example are the atmosphere of 1:5
Hour, Dimethyl ether carbonylation catalyst is made.
According to above-mentioned preparation method and condition, it is Si/Al=4.2, Si/Al=10, Si/Al=that silica alumina ratio, which is respectively adopted,
20, the catalyst that the EMT molecular sieve of Si/Al=30 is prepared, is denoted as CAT-2, CAT-3, CAT-4, CAT-5.
The preparation of embodiment 4 catalyst CAT-6 and CAT-7
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, by 0.5mol/L
NaOH solution change the NaOH solution of 0.05mol/L into, gained sample is denoted as catalyst CAT-6.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, by 0.5mol/L
NaOH solution change the NaOH solution of 1mol/L into, gained sample is denoted as catalyst CAT-7.
The preparation of 5 catalyst CAT-8~CAT-10 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, it will be molten in NaOH
Treatment temperature in liquid is changed to 50 DEG C, and gained sample is denoted as catalyst CAT-8.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, it will be molten in NaOH
Treatment temperature in liquid is changed to 70 DEG C, and gained sample is denoted as catalyst CAT-9.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, it will be molten in NaOH
Treatment temperature in liquid is changed to 90 DEG C, and gained sample is denoted as catalyst CAT-10.
The preparation of 6 catalyst CAT-11~CAT-15 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, binder is changed
At silica, gained sample is denoted as catalyst CAT-11, and the weight percentage of binder is 50% in CAT-11.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, binder is changed
At titanium dioxide, gained sample is denoted as catalyst CAT-12, and the weight percentage of binder is 40% in CAT-12.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, binder is changed
At the mixture of silica and aluminium oxide that weight ratio is 1:1, gained sample is denoted as catalyst CAT-13, bonds in CAT-13
The weight percentage of agent is 30%.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, binder is changed
At the mixture of silica and titanium dioxide that weight ratio is 1:1, gained sample is denoted as catalyst CAT-14, glues in CAT-14
The weight percentage for tying agent is 20%.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, binder is changed
At the mixture of aluminium oxide and titanium dioxide that weight ratio is 1:1, gained sample is denoted as catalyst CAT-15, bonds in CAT-15
The weight percentage of agent is 20%.
The preparation of 7 catalyst CAT-16~CAT-18 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, it will be molten in NaOH
The processing time in liquid is changed to 1 hour, and gained sample is denoted as catalyst CAT-16.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, it will be molten in NaOH
The processing time in liquid is changed to 6 hours, and gained sample is denoted as catalyst CAT-17.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, it will be molten in NaOH
The processing time in liquid is changed to 10 hours, and gained sample is denoted as catalyst CAT-18.
The preparation of 8 catalyst CAT-19~CAT-21 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, 0.5mol/ will be used
L ammonium nitrate exchanges three times (2 hour/time), is washed with deionized, and the maturing temperature after drying is changed to 400 DEG C, gained sample note
For catalyst CAT-19.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, 0.5mol/ will be used
L ammonium nitrate exchanges three times (2 hour/time), is washed with deionized, and the maturing temperature after drying is changed to 500 DEG C, gained sample note
For catalyst CAT-20.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, 0.5mol/ will be used
L ammonium nitrate exchanges three times (2 hour/time), is washed with deionized, and the maturing temperature after drying is changed to 650 DEG C, gained sample note
For catalyst CAT-21.
The preparation of 9 catalyst CAT-22~CAT-24 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, 0.5mol/ will be used
L ammonium nitrate exchanges three times (2 hour/time), is washed with deionized, and the calcining time after drying is changed to 2 hours, gained sample note
For catalyst CAT-22.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, 0.5mol/ will be used
L ammonium nitrate exchanges three times (2 hour/time), is washed with deionized, and the calcining time after drying is changed to 6 hours, gained sample note
For catalyst CAT-23.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, 0.5mol/ will be used
L ammonium nitrate exchanges three times (2 hour/time), is washed with deionized, and the calcining time after drying is changed to 10 hours, gained sample
It is denoted as catalyst CAT-24.
The preparation of 10 catalyst CAT-25~CAT-28 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
Air volume ratio is that the treatment temperature under the atmosphere of 1:5 is changed to 240 DEG C, and gained sample is denoted as catalyst CAT-25.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
Air volume ratio is that the treatment temperature under the atmosphere of 1:5 is changed to 280 DEG C, and gained sample is denoted as catalyst CAT-26.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
Air volume ratio is that the treatment temperature under the atmosphere of 1:5 is changed to 350 DEG C, and gained sample is denoted as catalyst CAT-27.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
Air volume ratio is that the treatment temperature under the atmosphere of 1:5 is changed to 400 DEG C, and gained sample is denoted as catalyst CAT-28.
The preparation of 11 catalyst CAT-29~CAT-37 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 2- picoline and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-29。
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 2,4- lutidines and nitrogen volume ratio example is 1:5, gained sample, which is denoted as, urges
Agent CAT-30.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 2,4,6- trimethylpyridines and nitrogen volume ratio example is 1:5, gained sample are denoted as
Catalyst CAT-31.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 2- ethylpyridine and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-32。
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 3- nitropyridine and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-33。
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 2- fluorine pyridine and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-34。
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 3- chloropyridine and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-35。
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 2- bromopyridine and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-36。
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, pyridine and nitrogen
The atmosphere that the atmosphere that volume ratio is 1:5 is changed to 4- iodine pyridine and nitrogen volume ratio example is 1:5, gained sample are denoted as catalyst
CAT-37。
The preparation of 12 catalyst CAT-38~CAT-40 of embodiment
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
The processing time under the atmosphere that air volume ratio is 1:5 is 4 hours, and gained sample is denoted as catalyst CAT-38.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
The processing time under the atmosphere that air volume ratio is 1:5 is 10 hours, and gained sample is denoted as catalyst CAT-39.
Specific preparation method and condition are consistent with catalyst CAT-1 in embodiment 2, the difference is that, in pyridine and nitrogen
The processing time under the atmosphere that air volume ratio is 1:5 is 20 hours, and gained sample is denoted as catalyst CAT-40.
The reaction evaluating of 13 catalyst CAT-1~CAT-40 of embodiment
Catalyst sample 10g is packed into the stainless steel fixed bed reaction pipe that internal diameter is 8.5mm, is passed through carbon monoxide, it will
Reaction system boosts to 5MPa；Then according to molar ratio CO/DME=8, H2/ DME=1, reaction velocity WHSV=3000h-1, it is anti-
The reaction of Dimethyl ether carbonylation production methyl acetate is carried out under conditions of answering 200 DEG C of temperature.Raw material and products obtained therefrom Agilent
7890A gas-chromatography (chromatographic column: HP-PLOT-Q capillary column, Porapak-Q packed column；Detector: FID, TCD) it carries out online
Analysis, the reaction result of catalyst CAT-1~CAT-40 are listed in table 1.
Table 1
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 described comprising modified EMT molecular sieve
Modified EMT molecular sieve is the EMT molecular sieve after alkali process, then through pyridine and/or the processing of pyridine substituent；
The pyridine substituent is that one, two or three on pyridine ring in five H is independently selected from F, Cl, Br, I, CH3、
CF3、CH3CH2Or NO2In substituent group substitution be formed by compound.
2. catalyst according to claim 1, which is characterized in that the sial atomic ratio Si/ in the modified EMT molecular sieve
Al is 3~40.
3. catalyst according to claim 1, which is characterized in that the sial atomic ratio Si/ in the modified EMT molecular sieve
Al is 3.5~30.
4. catalyst according to claim 1, which is characterized in that the pyridine substituent is selected from 2- picoline, 3- first
Yl pyridines, 4- picoline, 2,6- lutidines, 2,4- lutidines, 2,4,6- trimethylpyridine, 2- ethylpyridine,
3-ethylpyridine, 4- ethylpyridine, 3- nitropyridine, 2- chloro-5-nitropyridine, 2- fluorine pyridine, 3- fluorine pyridine and 4- fluorine pyridine,
2- chloropyridine, 3- chloropyridine, 4- chloropyridine, 2- bromopyridine, 3- bromopyridine, 4- bromopyridine, 2- iodine pyridine, 3- iodine pyridine, 4- iodine
At least one of pyridine.
5. the method for preparing catalyst described in claim 1, which is characterized in that at least include the following steps:
A) EMT molecular sieve is placed in alkaline solution and is handled 1~10 hour at 30~100 DEG C；
B) sample obtained by step a) is washed to neutrality, after adding binder molding, with ammonium nitrate solution exchange, filtering, is used in combination
Deionized water washing, drying, 350~680 DEG C roasting 1~10 hour in air atmosphere；
C) 0.5 is handled under the conditions of by sample obtained by step b) under the atmosphere containing pyridine and/or pyridine substituent, 240~400 DEG C
After~24 hours, the catalyst is prepared into after purging.
6. according to the method described in claim 5, it is characterized in that, alkaline solution described in step a) be sodium hydroxide and/or
Potassium hydroxide solution；The concentration of sodium hydroxide and/or potassium hydroxide is 0.05~1mol/L in solution.
7. according to the method described in claim 5, it is characterized in that, step a) is that EMT molecular sieve is placed in alkaline solution
40~90 DEG C are handled 2~5 hours.
8. according to the method described in claim 5, it is characterized in that, being shaped to extruded moulding described in step b).
9. according to the method described in claim 5, it is characterized in that, step c) be by sample obtained by step b) containing pyridine and/
Or under the atmosphere of pyridine substituent, after handling 2~20 hours under the conditions of 250~350 DEG C, the catalysis is prepared into after purging
Agent.
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 catalyst, 150~240 DEG C of reaction temperature, reaction pressure 1.0~
10.0MPa, dimethyl ether mass space velocity are 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: carbon monoxide: hydrogen=1:1~
10:0.5~5；
The catalyst is selected from the described in any item catalyst of Claims 1-4, according to any one of claim 5 to 9 side
At least one of the catalyst that method is prepared.
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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| CN107537551B (en) * | 2017-08-24 | 2020-06-02 | 中国烟草总公司郑州烟草研究院 | Molecular sieve catalyst for carbonylation reaction and preparation method and application thereof |
| 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 |
| CN111517929A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Method for producing acetone |
| CN111514940A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Catalyst for one-step preparation of acetone, preparation method and application thereof |
| CN111517955A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate by dimethyl ether carbonylation |
| CN111514925B (en) * | 2019-02-02 | 2021-06-15 | 中国科学院大连化学物理研究所 | Catalyst for co-production of methyl acetate and acetone from dimethyl ether, preparation method and application thereof |
| CN110694679B (en) * | 2019-10-30 | 2023-04-18 | 上海绿强新材料有限公司 | EMT/FAU core-shell molecular sieve catalyst, and preparation method and application thereof |
| CN112978750B (en) * | 2021-01-26 | 2022-11-25 | 青岛科技大学 | Molecular sieve modification post-treatment method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203479A (en) * | 2005-05-05 | 2008-06-18 | 加利福尼亚大学董事会 | Process for carbonylation of alkyl ethers |
| 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 |
| CN103831124A (en) * | 2012-11-26 | 2014-06-04 | 上海碧科清洁能源技术有限公司 | Phosphorus zeolite catalyst for synthesizing methyl acetate by dimethyl ether carbonylation and method using catalyst |
| CN103896769A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate via carbonylation of dimethyl ether |
| 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 |
-
2015
- 2015-12-18 CN CN201510961959.6A patent/CN106890668B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203479A (en) * | 2005-05-05 | 2008-06-18 | 加利福尼亚大学董事会 | Process for carbonylation of alkyl ethers |
| 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 |
| CN103831124A (en) * | 2012-11-26 | 2014-06-04 | 上海碧科清洁能源技术有限公司 | Phosphorus zeolite catalyst for synthesizing methyl acetate by dimethyl ether carbonylation and method using catalyst |
| CN103896769A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate via carbonylation of dimethyl ether |
| 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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