CN106890670A - A kind of catalyst of Dimethyl ether carbonylation production methyl acetate and its application - Google Patents

Abstract

This application discloses the catalyst that a kind of Dimethyl ether carbonylation produces methyl acetate, it is characterised in that contain acidity EMT molecular sieves and mesoporous oxide binding agent in the catalyst；Wherein, acid EMT molecular sieves weight percentage in the catalyst is 30%-95%.The catalyst, with mesoporous oxide as binding agent, greatly improved the selectivity of methyl acetate and the stability of catalyst by using with EMT molecular sieves as active component.

Description

A kind of catalyst of Dimethyl ether carbonylation production methyl acetate and its application

Technical field

The application is related to catalyst and the application of a kind of Dimethyl ether carbonylation production methyl acetate, belonging to Learn 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.By using with EMT molecular sieves as active component, with mesoporous oxide as binding agent, can be big Width improves the selectivity of methyl acetate and the stability of catalyst.

Dimethyl ether carbonylation reaction is typical acid catalyzed reaction, the acidity and pore passage structure of catalyst Property has conclusive influence to catalyst carbonylation performance.EMT zeolites belong to hexagonal crystal system, Space group is P⁶³/ mmc, cell parameter a=b1.7374nm, c=2.8365nm, skeletal density is 12.9 T/nm³.Its skeleton structure is made up of 12 yuan of rings, 6 yuan of rings and 4 yuan of rings, is faujasite FAU A simple six sides analog.As a kind of zeolite better than FAU topological structures, with compared with Strong acid and more acid amount.Meanwhile, EMT has two sets of cross one another vestibules, this some holes Chamber intersects duct and is connected by 2 dimensions, and its superior duct connectivity is more beneficial for absorption and the product of reactant The diffusion of thing molecule.Meanwhile, in dimethyl ether carbonylation reaction, the addition of mesoporous oxide binding agent The intensity of catalyst can not only be effectively improved, at the same can improve catalyst it is active, selective, Stability.

The Dimethyl ether carbonylation produces the catalyst of methyl acetate, it is characterised in that the catalyst In contain acidity EMT molecular sieves and mesoporous oxide binding agent；

Wherein, acid EMT molecular sieves weight percentage in the catalyst is 30%-95%. The acid EMT molecular sieves are calcined after being exchanged by EMT molecular sieves ammonium and obtain.

Preferably, acid EMT molecular sieves weight percentage in the catalyst is 50%~90%.

Preferably, the middle pore specific surface area of the mesoporous oxide binding agent is 1m²/ g~500m²/g。 It is further preferred that the middle pore specific surface area of the mesoporous oxide binding agent is 50m²/g ~200m²/g.It is further preferred that the middle pore specific surface area of the mesoporous oxide binding agent is 50 m²/ g~500m²/g。

Preferably, the mesoporous oxide binding agent is selected from mesoporous aluminas, mesoporous silica, mesopore At least one in titanium oxide, mesopore magnesia, kaolin.It is further preferred that the mesopore oxygen Compound binding agent is selected from least one in mesoporous aluminas, mesoporous silica, mesopore magnesia.

Preferably, the fixed bed catalyst that the catalyst is obtained for extruded moulding.

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 150~200 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 180~200 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 for preparing methyl acetate provided herein, reactivity is high, and stability is obtained To significantly improve, industrial requirement is disclosure satisfy that.

2) catalyst for preparing methyl acetate provided herein, the intensity of catalyst is high, loss It is small.

Specific embodiment

With reference to embodiment in detail the application is described in detail, but the application is not limited to these embodiments.

Using the ratio of the type physical adsorption appearance determination samples of Micromeritics companies of U.S. ASAP 2020 Surface area.Before analysis, sample vacuumizes heat pre-treatment 6h at 350 DEG C, is surveyed by medium of He Amount sample cell free volume.During analysis sample, with nitrogen as adsorbed gas, at liquid nitrogen temperature (77K) Under carry out physical absorption and desorption determine.The specific surface area of material is determined using BET formula；Use Relative pressure (P/P₀) N when being 0.99₂Adsorbance calculate material total pore volume.Use t-plot Method calculates micro pore surface area and Micropore volume.During calculating, N₂Molecular cross-sectional area takes 0.162nm²。

Catalyst solid granule strength is tested：The ZQL-II type intelligence produced using big connection intelligent testing machine factory Energy granule strength test machine determines the mechanical strength of bar shaped catalyst.

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) ÷ is [(in unstripped gas Dimethyl ether carbon molal quantity)-(dimethyl ether carbon molal quantity in product)] × (100%)

Comparative example 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 acid EMT molecular sieves, is designated as sample 1^#。

Embodiment 1

It is from boehmite, silica, magnesia, titanium oxide, kaolin and montmorillonite respectively Binding agent, the mesopore reference area of binding agent is shown in Table 1.

Table 1

Binding agent	Middle pore specific surface area
		Boehmite powder	289
Silica	480
		Magnesia	236
Titanium oxide	189
		Kaolin	38
Montmorillonite	58

Extruded moulding after EMT molecular sieves and binding agent are well mixed with 10% dust technology, after roasting, Three times (2 hour/time) is exchanged with 0.5mol/L ammonium nitrate, is washed with deionized, dried, at 550 DEG C Roasting 4 hours, is obtained catalyst, and gained catalyst numbering is shown in Table with the relation of raw material type and ratio 2。

Table 2

Embodiment 2：The reactivity worth of catalyst

By the gained catalyst fines of embodiment 1 through compressing tablet, pulverize, sieve 40~60 mesh samples for obtaining Reactivity worth for Dimethyl ether carbonylation production methyl acetate is determined.1.0g catalyst is loaded and is reacted Device, by dimethyl ether, hydrogen, carbon monoxide gaseous mixture in 200 DEG C of temperature, pressure 5MPa is empty Pass through reactor under conditions of speed=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 3.

Table 3

Catalyst	Mechanical strength (N/mm)
					0	30.5	99.4
	30	31.8	99.3
					120	29.3	99.2
	200	25.2	98.8
					30	26.3	97.3
	40	21.5	97.5
					50	26.7	98.3
	90	29.3	98.6
					80	25.4	98.0
	85	30.3	97.8
					120	33.8	97.5
	100	20.5	97.6

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 acidity EMT molecular sieves and mesoporous oxide binding agent in agent；

Wherein, acid EMT molecular sieves weight percentage in the catalyst is 30%~95%.

2. catalyst according to claim 1, it is characterised in that the acid EMT molecules Sieve weight percentage in the catalyst is 50%~90%.

3. catalyst according to claim 1, it is characterised in that the mesoporous oxide glues The middle pore specific surface area for tying agent is 1m²/ g~500m²/g。

4. catalyst according to claim 1, it is characterised in that the mesoporous oxide glues The middle pore specific surface area for tying agent is 50m²/ g~200m²/g。

5. catalyst according to claim 1, it is characterised in that the mesoporous oxide glues The middle pore specific surface area for tying agent is 50m²/ g~500m²/g。

6. catalyst according to claim 1, it is characterised in that the mesoporous oxide glues Knot agent is selected from mesoporous aluminas, mesoporous silica, middle pore titanium oxide, mesopore magnesia, kaolin At least one.

7. catalyst according to claim 1, it is characterised in that the mesoporous oxide glues Knot agent is selected from least one in mesoporous aluminas, mesoporous silica, mesopore magnesia.

8. catalyst according to claim 1, it is characterised in that the catalyst is extrusion The fixed bed catalyst that shaping is obtained.

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.