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Methyl acetate production method

一种乙酸甲酯、酸性的技术，应用在生产乙酸甲酯及其衍生物领域，能够解决易失活、二甲醚羰基化活性低、不能够满足工业生产的需求等问题，达到稳定性提高、反应活性高的效果

Active Publication Date: 2017-02-01
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In 2006 Berkeley's Enrique Iglesia research group (Angew.Chem, Int.Ed.45(2006) 10, 1617-1620, J.Catal.245(2007) 110, J.Am.Chem.Soc.129(2007) 4919 ) Carry out the carbonylation reaction of dimethyl ether in molecular sieve systems with 8-membered rings and 12-membered rings or 10-membered rings, such as Mordenite (mordenite) and Ferrierite (ferrierite), the result is that the B acid activity in the 8-membered ring The carbonylation reaction is carried out on the center, the selectivity of methyl acetate is very good, reaching 99%, but the carbonylation activity of dimethyl ether is very low
In the publicly reported results, the catalyst has operated stably for less than 100 hours and is easily deactivated, and the related results cannot meet the needs of industrial production

Method used

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Experimental program
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Embodiment

[0030] The present invention is described in detail below through some examples, but the present invention is not limited to these examples.

[0031] In an embodiment, the conversion rate of dimethyl ether and the selectivity of methyl acetate are all calculated based on the number of carbon moles of dimethyl ether:

[0032] The conversion rate of dimethyl ether=[(the number of dimethyl ether carbon moles in the feed gas)-(the number of dimethyl ether carbon moles in the product)]÷(the number of dimethyl ether carbon moles in the feed gas)×(100% )

[0033] The selectivity of methyl acetate=(2 / 3)×(the number of carbon moles of methyl acetate in the product)÷[(the number of carbon moles of dimethyl ether in the feed gas)-(the number of moles of dimethyl ether in the product) ]×(100%)

[0034] The four Na-EMTs with silicon-aluminum atomic molar ratios of 2, 4, 15 and 25, and the Na-EMTs with a silicon-aluminum atomic molar ratio of 4 containing Ga and Fe in the framework were p...

preparation example

[0036] H-EMT catalyst

[0037] 100 grams of roasted Na-EMT zeolite molecular sieves with silicon-aluminum atomic molar ratios of 2, 4, 15 and 25 were exchanged three times with 0.5 mol / L ammonium nitrate, each time for 2 hours, washed with deionized water, and dried. Calcined at 550°C for 4 hours, and respectively prepared 20-40 mesh 1#, 2#, 3# and 4# catalysts by extrusion.

[0038] Ga-EMT catalyst

[0039] 100 g of calcined gallium-containing Na-EMT zeolite molecular sieves (silicon-aluminum atomic molar ratio of 4) were exchanged three times with 0.5 mol / L ammonium nitrate, each time for 2 hours, washed with deionized water, dried, and roasted at 550 ° C After 4 hours, 20-40 mesh 5# catalyst was prepared by extrusion.

[0040] Fe-EMT catalyst

[0041] 100 g of calcined iron-containing Na-EMT zeolite molecular sieve (silicon-aluminum atomic molar ratio is 4) was exchanged three times with 0.5 mol / L ammonium nitrate, each time for 2 hours, washed with deionized water, drie...

Embodiment 1

[0056] According to Table 2, put 10 g of catalyst into a fixed-bed reactor with a tube inner diameter of 28 mm, raise the temperature to 550 °C at 5 °C / min under a nitrogen atmosphere, keep it for 4 hours, and then drop it to a reaction temperature of 190 °C under a nitrogen atmosphere. °C, the pressure of the reaction system was raised to 5 MPa with CO. The reaction raw materials are passed through the catalyst bed from top to bottom. Among them, the dimethyl ether feed space velocity is 0.10h -1 The mol ratio of carbon monoxide and dimethyl ether is 6: 1, under the condition that the mol ratio of the carbon monoxide in the feed gas of carbon monoxide and hydrogen is 2: 1, under the condition of 190 ℃ of reaction temperature, catalytic reaction runs 100 hours, reaction The results are shown in Table 2.

[0057] Table 2 "Evaluation results of dimethyl ether carbonylation catalysts

[0058] catalyst Dimethyl ether conversion rate (%) Methyl acetate selectivity ...

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Abstract

The present invention provides a methyl acetate production method, which comprises that dimethyl ether and raw material gas containing carbon monoxide and hydrogen are subjected to a carbonylation reaction on a catalyst having an acid EMT structure zeolite molecular sieve to obtain the methyl acetate. The invention provides the new methyl acetate production method, wherein the method is performed in the presence of the acid EMT zeolite molecular sieve of the catalyst, such that the reaction activity is high, the stability can be significantly improved, and the industrial production requirements can be met.

Description

technical field [0001] The invention relates to a method for producing methyl acetate and its derivatives by carbonylation of dimethyl ether. Background technique [0002] With the rapid development of modern industry, the contradiction between energy supply and demand has become increasingly prominent. my country, as a big energy consumer and a big energy shortage country, urgently needs to find alternative energy sources. As a clean energy source, ethanol has good miscibility and can be blended into gasoline as a blending component to partially replace gasoline, increase the octane number and oxygen content of gasoline, and effectively promote the complete combustion of gasoline. Reduce carbon monoxide and hydrocarbon emissions in vehicle exhaust. As a partial substitute of vehicle fuel, ethanol can make my country's vehicle fuel present a diversified structural feature. At present, my country mainly develops fuel ethanol with grain, especially corn, and has become the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/37C07C69/14
CPCC07C67/37C07C69/14B01J29/7019B01J29/7438B01J29/7638B01J2229/186B01J2229/42B01J29/7069C07C29/147C07C51/377
Inventor 刘红超朱文良刘勇倪友明刘中民王林英田鹏
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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