CN111001431A - Core-shell catalyst for preparing ethanol from dimethyl ether and synthesis gas by one-step method and preparation method and application thereof - Google Patents
Core-shell catalyst for preparing ethanol from dimethyl ether and synthesis gas by one-step method and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a core-shell catalyst for preparing ethanol from dimethyl ether and synthesis gas by a one-step method, and a preparation method and application thereof. The catalyst takes a mercerized molecular sieve subjected to hydrogen ion exchange as a core, a double-layer Cu-based hydrogenation catalyst loaded outside the core as a shell, wherein a first layer of shell close to the mercerized molecular sieve is a CuSi composite material and is obtained by roasting a silica sol shell loaded copper salt in an inert atmosphere, a second layer of shell is a CuAl composite material and is obtained by roasting an aluminum sol loaded copper salt in an inert or reducing atmosphere, and Cu loading amounts in the two layers of shells obtained by roasting are respectively 3-7 wt%. The reactants dimethyl ether and carbon monoxide firstly carry out carbonylation reaction on a silk-screen molecular sieve core to generate methyl acetate, and then the methyl acetate is diffused to a Cu-based double-shell layer to carry out hydrogenation reaction to generate ethanol and methanol. The method can realize the technical route of preparing the ethanol by one-step method of the dimethyl ether and the synthesis gas. The method has the advantages of high selectivity of ethanol, low Cu loading, shortened technical route and the like, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a core-shell catalyst for one-step preparation of ethanol from dimethyl ether and synthesis gas, and a preparation method and application thereof.
Background
With the increasing energy demand and the increasing contradiction of the shortage of petroleum supply and the increasing of the global environmental pressure, the fuel ethanol is generally concerned by countries in the world due to the cleanness and environmental protection of the fuel ethanol, the ethanol is used as an important clean energy source and is mixed with gasoline in a proportion of 10 percent, and the fuel ethanol gasoline can reduce the emission of carbon monoxide and hydrocarbon in automobile exhaust, thereby having important significance for solving the problem of atmospheric pollution in China and realizing sustainable development. After the global fuel ethanol yield is increased rapidly in 2006-2010, the global fuel ethanol yield is influenced by grain consumption disputes, and the global fuel ethanol yield is increased slowly in 2011-2013 and is maintained at the level of 830-857 hundred million liters per year. In 2014, the fuel ethanol market has been recovered to a certain extent, and the fuel ethanol market is increased by 5 percent on a par. The worldwide demand for fuel ethanol will reach 17753 million tons in 2025 as predicted by the united states energy information center.
At present, fuel ethanol is mainly divided into grain ethanol, non-grain ethanol and cellulosic ethanol. Grain ethanol takes corn, wheat and other grains as raw materials, and the production of the grain ethanol and non-grain ethanol occupies more farmlands, so that the grain-competing problem of people and livestock exists, and the grain-competing problem is gradually limited or prohibited by relevant policies of governments of various countries. China is a country rich in coal and less in oil, so that ethanol prepared by coal chemical industry conforms to the basic national conditions of China. Researchers at home and abroad in recent years explore an economic, environment-friendly and green process route of 'synthesis gas → methanol → dimethyl ether → methyl acetate → ethanol'. At present, the total yield of the domestic dimethyl ether device can reach about 1400 million tons, but the operating rate is only 38%, and the problem that the dimethyl ether capacity is seriously excessive is solved by the route.
At present, a technical route of 'dimethyl ether → methyl acetate → ethanol' is developed domestically, dimethyl ether and carbon monoxide are subjected to carbonylation reaction to generate methyl acetate, and methyl acetate and hydrogen are subjected to hydrogenation reaction to generate ethanol, wherein the technology for preparing ethanol by hydrogenating methyl acetate is mature, and industrial application is realized. At present, researchers at home and abroad are all dedicated to developing a process route for preparing ethanol by using dimethyl ether and synthesis gas as raw materials through a one-step method, but two sections of catalysts are required to be filled in a reactor in the process route, the process is equivalent to the series connection of two reactors, the synergistic effect between the activities of the two catalysts is greatly limited, and the process is not beneficial to industrial application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a core-shell catalyst for preparing ethanol by dimethyl ether and synthesis gas in one step, and a preparation method and application thereof. The catalyst of the invention is composed of a double-layer Cu-based shell and an MOR molecular sieve core structure, can realize the one-step preparation of ethanol by dimethyl ether and synthesis gas, has the advantages of high ethanol selectivity, low Cu loading capacity and the like, and has good industrial application prospect.
The technical content of the invention is as follows:
a core-shell catalyst for preparing ethanol by a dimethyl ether and synthesis gas one-step method is characterized in that a mercerized molecular sieve subjected to hydrogen ion exchange is used as a core, a double-layer Cu-based hydrogenation catalyst loaded outside the core is used as a shell, a first layer of shell close to the mercerized molecular sieve is a CuSi composite material, a silica sol shell loaded copper salt is roasted in an inert atmosphere to obtain a second layer of shell, a CuAl composite material is a second layer of shell, an aluminum sol loaded copper salt is roasted in an inert or reducing atmosphere to obtain a second layer of shell, and Cu loading amounts in the two layers of shells obtained by roasting are 3-7 wt% respectively.
According to one embodiment of the Cu-based core-shell catalyst of the present invention, the mordenite loaded shell front channels are pre-adsorbed with pyridine and methyl iodide. The molecular sieve catalyst can effectively inhibit carbon deposition side reaction in the process of preparing methyl acetate by dimethyl ether carbonylation through pre-adsorption modification, improve the conversion rate of dimethyl ether and the selectivity of the product methyl acetate, and greatly prolong the service life of the catalyst.
According to one embodiment of the Cu-based core-shell catalyst, the pre-adsorption treatment temperature of pyridine is 100-300 ℃, and the pre-adsorption treatment temperature of methyl iodide gas is 100-280 ℃.
The invention also provides a preparation method of the Cu-based core-shell catalyst, which comprises the following steps:
1) hydrothermally synthesizing a raw material of the silk-screen molecular sieve by using a template agent, forming the raw material into molecular sieve balls through hydrogen ion exchange, and performing pre-adsorption treatment on pore passages of the silk-screen molecular sieve at a certain temperature by sequentially using pyridine and methyl iodide;
2) dissolving ethyl orthosilicate in water to form colloid, coating the colloid on a molecular sieve sphere, and vacuumizing and drying to form a silica sol shell;
3) spraying a copper salt solution on a silica sol shell, drying, and roasting in inert gas;
4) coating the aluminum sol on a Cu-based shell of a sphere, and vacuumizing and drying to form an aluminum sol shell;
5) and spraying the copper salt solution on an aluminum sol shell, drying, and roasting in a reducing atmosphere to directly obtain the usable dual-Cu-based shell MOR core catalyst CuAl @ CuSi @ MOR. If the calcination is carried out under an inert atmosphere, the reduction is carried out on the apparatus before use.
According to one embodiment of the preparation method of the Cu-based core-shell catalyst, in the step (2), the coating thickness of the tetraethoxysilane colloid is 0.2-0.4 mm, and the drying temperature is controlled to be 40-60 ℃.
According to an embodiment of the preparation method of the Cu-based core-shell catalyst of the present invention, the copper salt sprayed in the steps (3) and (5) is an aqueous ammonia solution of copper salt.
According to an embodiment of the preparation method of the Cu-based core-shell catalyst, in the step (3), the loading amount of Cu is 3-7 wt.%, the calcination temperature is 200-300 ℃, and the inert gas is one or more of nitrogen, helium and argon.
According to one embodiment of the preparation method of the Cu-based core-shell catalyst, in the step (4), the coating thickness of the alumina sol is 0.1-0.3 mm, and the drying temperature is controlled between 50-80 ℃.
According to an embodiment of the preparation method of the Cu-based core-shell catalyst, in the step (5), the loading amount of Cu is 3 to 7 wt.%, the calcination temperature is 250 to 300 ℃, and the reducing gas is one or more of hydrogen and carbon monoxide.
The invention further provides an application of the Cu-based core-shell catalyst, which is characterized in that dimethyl ether and synthesis gas are used as raw material gases, and the raw material gases are reacted in a reactor filled with the Cu-based core-shell catalyst to obtain ethanol, wherein the reaction temperature is 190-250 ℃, the reaction pressure is 1.0-10.0 MPa, and the airspeed of the raw material gases is 1000-10000 h-1The ratio of carbon monoxide to dimethyl ether in the feed gas is 5: 1-20: 1, and the ratio of carbon monoxide to hydrogen is 1: 1-5: 1.
Due to the adoption of the scheme, the invention has the beneficial effects that: Cu/SiO2And Cu/Al2O3The MOR core can convert dimethyl ether and carbon monoxide into methyl acetate, and the methyl acetate diffused from the MOR core passes through the double-layer Cu-based shell and undergoes hydrogenation reaction with hydrogen to generate ethanol. The double-shell catalyst of the invention can realize 100% conversion rate of methyl acetate generated on MOR core and high selectivity of ethanol. Furthermore, the Cu loading on the double shell Cu-based catalyst is low (< 10 wt.%) compared to the Cu-based hydrogenation catalyst alone. The invention realizes the one-step preparation of ethanol by dimethyl ether and synthesis gas by preparing the double Cu-based shell-MOR core, reduces the production cost and shortens the technical route of preparing ethanol by the prior dimethyl ether indirect method.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
In the examples, pyridine pre-treated MOR pellets were prepared according to the method disclosed in CN103896766A, and methyl iodide pre-treated MOR pellets were prepared according to the method disclosed in CN 106311336A.
Example 1
The embodiment provides a Cu-based core-shell catalyst for preparing ethanol by dimethyl ether and synthesis gas through one-step method and a preparation method thereof, and the preparation method comprises the following specific steps:
step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, after H ion exchange forming hydrogen-type mercerized molecular sieve raw powder, and through rolling ball forming
And (3) carrying out pre-adsorption treatment on the pore passages of the silk optical molecular sieve by pyridine gas and methyl iodide gas in sequence. The pretreatment temperature of the pyridine gas is 280 ℃, and the pretreatment temperature of the methyl iodide gas is 250 ℃;
step (2): dissolving TEOS in water to form colloid, coating the colloid on a molecular sieve sphere, vacuumizing and drying (the drying temperature is controlled at 50 ℃) to form a silica sol shell with the thickness of about 0.4 mm;
and (3): spraying an ammonia water solution of copper salt on a silica sol shell, drying, and roasting in nitrogen gas, wherein the roasting temperature is 280 ℃, and the Cu loading capacity is 4.6 wt.%;
and (4): then coating the aluminum sol on a Cu-based shell of the sphere, vacuumizing and drying to form an aluminum sol shell, wherein the drying temperature is controlled to be 65 ℃, and the coating thickness of the aluminum sol is 0.3 mm;
and (5): spraying an ammonia water solution of copper salt on an aluminum sol shell, drying, and roasting in a hydrogen atmosphere at the roasting temperature of 255 ℃, so as to finally obtain the double-Cu-based shell MOR core catalyst named CuAl @ CuSi @ MOR-1, wherein the Cu loading amount is 3.5 wt.%.
This example also provides a catalyst activity test, comprising the following steps:
weighing 10g of CuAl @ CuSi @ MOR catalyst, crushing into 10-20 mesh particles, and using the particles for testing the activity of the dimethyl ether and synthesis gas one-step method ethanol. 5.0g of the sample was weighed into a stainless steel reaction tube having an inner diameter of 20mm, followed by addition of N2Slowly increasing the pressure of the gas to 2.0MPa, controlling the reaction temperature to be 220 ℃, stopping introducing nitrogen, starting introducing raw material gas (carbon monoxide, dimethyl ether and hydrogen in a volume ratio of 8:1:5), and controlling the volume space velocity of the raw material gas to be 3000h-1The recording of the reaction time is started. When reactingAfter 200 hours had elapsed, the reaction product was analyzed on-line by gas chromatography, and the results of the activity test are shown in Table 1.
Example 2
Step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, after H ion exchange forming hydrogen-type mercerized molecular sieve raw powder, and through rolling ball forming
And (3) carrying out pre-adsorption treatment on the pore passages of the silk optical molecular sieve by pyridine gas and methyl iodide gas in sequence. The pretreatment temperature of the pyridine gas is 280 ℃, and the pretreatment temperature of the methyl iodide gas is 250 ℃;
step (2): dissolving TEOS in water to form colloid, coating the colloid on a molecular sieve sphere, vacuumizing and drying (the drying temperature is controlled at 50 ℃) to form a silica sol shell with the thickness of about 0.36 mm;
and (3): spraying an ammonia water solution of copper salt on a silica sol shell, drying, and roasting in nitrogen gas, wherein the roasting temperature is 275 ℃, and the Cu loading is 4.4 wt.%;
and (4): then coating the aluminum sol on a Cu-based shell of the sphere, vacuumizing and drying to form an aluminum sol shell, wherein the drying temperature is controlled to be 65 ℃, and the coating thickness of the aluminum sol is 0.26 mm;
and (5): spraying an ammonia water solution of copper salt on an aluminum sol shell, drying, and roasting in a hydrogen atmosphere at the roasting temperature of 255 ℃, so as to finally obtain the double-Cu-based shell MOR core catalyst named CuAl @ CuSi @ MOR-2, wherein the Cu loading amount is 3.7 wt.%.
This example also provides a catalyst activity test, comprising the following steps:
weighing 10g of CuAl @ CuSi @ MOR catalyst, crushing into 10-20 mesh particles, and using the particles for testing the activity of the dimethyl ether and synthesis gas one-step method ethanol. 5.0g of the sample was weighed into a stainless steel reaction tube having an inner diameter of 20mm, followed by addition of N2Slowly increasing the pressure of the gas to the reaction pressure of 2.0MPa, controlling the reaction temperature to be 220 ℃, stopping introducing the nitrogen and starting introducing the raw material gas (carbon monoxide: two in volume ratio)Hydrogen gas of methyl ether is 8:1:5), and the volume space velocity of the raw material gas is controlled to be 3000h-1The recording of the reaction time is started. When the reaction time reached 200 hours, the reaction product was analyzed on-line by gas chromatography, and the results of the activity test are shown in Table 1.
Example 3
Step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, after H ion exchange forming hydrogen-type mercerized molecular sieve raw powder, and through rolling ball forming
And (3) carrying out pre-adsorption treatment on the pore passages of the silk optical molecular sieve by pyridine gas and methyl iodide gas in sequence. The pretreatment temperature of the pyridine gas is 280 ℃, and the pretreatment temperature of the methyl iodide gas is 250 ℃;
step (2): dissolving TEOS in water to form colloid, coating the colloid on a molecular sieve sphere, vacuumizing and drying (the drying temperature is controlled at 50 ℃) to form a silica sol shell with the thickness of about 0.4 mm;
and (3): spraying an ammonia water solution of copper salt on a silica sol shell, drying, and roasting in nitrogen gas, wherein the roasting temperature is 270 ℃, and the Cu loading is 4.7 wt.%;
and (4): then coating the aluminum sol on a Cu-based shell of the sphere, vacuumizing and drying to form an aluminum sol shell, wherein the drying temperature is controlled to be 67 ℃, and the coating thickness of the aluminum sol is 0.25 mm;
and (5): spraying an ammonia water solution of copper salt on an aluminum sol shell, drying, and roasting in a hydrogen atmosphere at 258 ℃ to finally obtain the dual-Cu-based shell MOR core catalyst named CuAl @ CuSi @ MOR-3, wherein the Cu loading amount is 3.3 wt.%.
This example also provides a catalyst activity test, comprising the following steps:
weighing 10g of CuAl @ CuSi @ MOR catalyst, crushing into 10-20 mesh particles, and using the particles for testing the activity of the dimethyl ether and synthesis gas one-step method ethanol. 5.0g of the sample was weighed into a stainless steel reaction tube having an inner diameter of 20mm, followed by addition of N2The gas is slowly boosted to the reaction pressure of 2.0MPaControlling the reaction temperature to be 220 ℃, stopping introducing nitrogen, starting introducing feed gas (carbon monoxide: dimethyl ether: hydrogen in a volume ratio of 8:1:5), and controlling the volume space velocity of the feed gas to be 3000h-1The recording of the reaction time is started. When the reaction time reached 200 hours, the reaction product was analyzed on-line by gas chromatography, and the results of the activity test are shown in Table 1.
Comparative example 1
The embodiment provides a method for preparing ethanol by a one-step method of dimethyl ether and synthesis gas and an application thereof, and the method comprises the following specific steps:
step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, carrying out H ion exchange to obtain hydrogen-type mercerized molecular sieve raw powder, and carrying out ball rolling molding to obtain the mercerized molecular sieve raw powder
The molecular sieve pellets are subjected to pre-adsorption treatment on a silk optical molecular sieve pore passage by pyridine and methyl iodide gas in sequence, wherein the pyridine pretreatment temperature is 280 ℃, and the methyl iodide gas pretreatment temperature is 250 ℃;
step (2): dissolving TEOS in water to form colloid, coating the colloid on a molecular sieve sphere, vacuumizing and drying to form a silica sol shell, controlling the drying temperature at 50 ℃, and coating the TEOS colloid to a thickness of 0.4 mm;
and (3): spraying an ammonia water solution of copper salt on a silica sol shell, drying, and roasting in hydrogen gas, wherein the roasting temperature is 280 ℃, and the Cu loading is 4.6 wt.%, and finally obtaining the Cu-based shell MOR core catalyst which is named as CuSi @ MOR-1.
This example also provides a catalyst activity test, comprising the following steps:
weighing 10g of CuSi @ MOR-1 catalyst, crushing into 10-20 mesh particles, and using the particles for testing the activity of the dimethyl ether and synthesis gas one-step method ethanol. 5.0g of the sample was weighed into a stainless steel reaction tube having an inner diameter of 20mm, followed by addition of N2Slowly increasing the pressure of the gas to 2.0MPa, controlling the reaction temperature to be 220 ℃, stopping introducing nitrogen and starting introducing raw material gas (carbon monoxide, dimethyl ether and hydrogen in volume ratio)The ratio of the raw material gas to the raw material gas is 8:1:5), and the volume space velocity of the raw material gas is controlled to be 3000h-1The recording of the reaction time is started. When the reaction time reached 200 hours, the reaction product was analyzed on-line by gas chromatography, and the results of the activity test are shown in Table 1.
Comparative example 2
The embodiment provides a method for preparing ethanol by a one-step method of dimethyl ether and synthesis gas and an application thereof, and the method comprises the following specific steps:
step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, carrying out H ion exchange to obtain hydrogen-type mercerized molecular sieve raw powder, and carrying out ball rolling molding to obtain the mercerized molecular sieve raw powder
The molecular sieve pellets are subjected to pre-adsorption treatment on a silk-screen molecular sieve pore passage by pyridine and methyl iodide gas in sequence, wherein the pretreatment temperature of the pyridine gas is 280 ℃, and the pretreatment temperature of the methyl iodide gas is 250 ℃;
step (2): dissolving TEOS in water to form colloid, coating the colloid on a molecular sieve sphere, vacuumizing and drying to form a layer of silica sol shell, controlling the drying temperature at 50 ℃, and coating the colloid to a thickness of 0.4 mm;
and (3): spraying an ammonia water solution of copper salt on a silica sol shell, drying, and roasting in hydrogen gas, wherein the roasting temperature is 280 ℃, and the Cu loading is 10.6 wt.%, and finally obtaining the Cu-based shell MOR core catalyst which is named as CuSi @ MOR-2.
This example also provides a catalyst activity test, comprising the following steps:
weighing 10g of CuSi @ MOR-2 catalyst, crushing into 10-20 mesh particles, and using the particles for testing the activity of the dimethyl ether and synthesis gas one-step method ethanol. 5.0g of the sample was weighed into a stainless steel reaction tube having an inner diameter of 20mm, followed by addition of N2Slowly increasing the pressure of the gas to 2.0MPa, controlling the reaction temperature to be 220 ℃, stopping introducing nitrogen, starting introducing raw material gas (carbon monoxide, dimethyl ether and hydrogen are 8:1:5 in volume ratio), and controlling the volume space velocity of the raw material gas to be 3000h-1The recording of the reaction time is started. After the reaction time reaches 200 hoursThe reaction products were analyzed on-line by gas chromatography, and the results of the activity tests are shown in Table 1.
Comparative example 3
The embodiment provides a method for preparing ethanol by a one-step method of dimethyl ether and synthesis gas and an application thereof, and the method comprises the following specific steps:
step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, carrying out H ion exchange to obtain hydrogen-type mercerized molecular sieve raw powder, and carrying out ball rolling molding to obtain the mercerized molecular sieve raw powder
The molecular sieve pellets are subjected to pre-adsorption treatment on a silk optical molecular sieve pore passage by pyridine and methyl iodide gas in sequence, wherein the pyridine pretreatment temperature is 280 ℃, and the methyl iodide gas pretreatment temperature is 250 ℃;
step (2): then coating the aluminum sol on a Cu-based shell of the sphere, vacuumizing and drying to form an aluminum sol shell, wherein the drying temperature is controlled at 65 ℃, and the coating thickness of the aluminum sol is 0.3 mm;
and (3): spraying an ammonia water solution of copper salt on an aluminum sol shell, drying, and roasting in a hydrogen atmosphere at the roasting temperature of 255 ℃ and the Cu loading of 3.5 wt.% to finally obtain the Cu-based shell MOR core catalyst named CuAl @ MOR.
This example also provides a catalyst activity test, comprising the following steps:
weighing 10g of CuAl @ MOR-3 catalyst, crushing into 10-20 mesh particles, and using the particles for testing the activity of the dimethyl ether and synthesis gas one-step method ethanol. 5.0g of the sample was weighed into a stainless steel reaction tube having an inner diameter of 20mm, followed by addition of N2Slowly increasing the pressure of the gas to 2.0MPa, controlling the reaction temperature to be 220 ℃, stopping introducing nitrogen, starting introducing raw material gas (carbon monoxide, dimethyl ether and hydrogen are 8:1:5 in volume ratio), and controlling the volume space velocity of the raw material gas to be 3000h-1The recording of the reaction time is started. When the reaction time reached 200 hours, the reaction product was analyzed on-line by gas chromatography, and the results of the activity test are shown in Table 1.
Comparative example 4
The embodiment provides a method for preparing ethanol by a two-step method of dimethyl ether and synthesis gas and application thereof, and the method comprises the following specific steps:
step (1): firstly, utilizing hexadecyl trimethyl ammonium bromide (CTAB) template agent to hydrothermally synthesize mercerized molecular sieve raw powder, carrying out H ion exchange to obtain hydrogen-type mercerized molecular sieve raw powder, and carrying out ball rolling molding to obtain the mercerized molecular sieve raw powder
The molecular sieve pellets are subjected to pre-adsorption treatment on a silk optical molecular sieve pore passage by pyridine and methyl iodide gas in sequence, wherein the pyridine pretreatment temperature is 280 ℃, and the methyl iodide gas pretreatment temperature is 250 ℃;
step (2): preparing Cu-based catalyst Cu/SiO by adopting coprecipitation method according to patent CN105749913A2The Cu loading is 31 wt%, and the hydrogenation catalyst Cu/SiO is finally obtained by roasting at 280 ℃ and then carrying out hydrogen reduction treatment at the same temperature2。
This example also provides a catalyst activity test, comprising the following steps:
respectively weighing MOR catalyst and Cu/SiO2And 10g of catalyst is respectively crushed into particles of 10-20 meshes and is used for dimethyl ether carbonylation and methyl acetate hydrogenation activity tests. Respectively weighing the above two catalysts 5.0g and 1.0g, respectively placing into the upper section and the lower section of a stainless steel reaction tube with an inner diameter of 20mm, respectively placing quartz sand with a thickness of 10mm into the middle layer, and adding N2Slowly increasing the pressure of the gas to 2.0MPa, controlling the reaction temperature to be 220 ℃, stopping introducing nitrogen, starting introducing raw material gas (carbon monoxide, dimethyl ether and hydrogen are 8:1:5 in volume ratio), and controlling the volume space velocity of the raw material gas to be 3000h-1The recording of the reaction time is started. When the reaction time reached 200 hours, the reaction product was analyzed on-line by gas chromatography, and the results of the activity test are shown in Table 1.
TABLE 1 results of different catalyst Activity tests
The results of the activity test in Table 1 show that in the reaction of preparing ethanol by a one-step method of dimethyl ether and synthesis gas, the double Cu-based shell MOR nuclear catalyst CuAl @ CuSi @ MOR-1, -2, -3 prepared by the method of the invention has the dimethyl ether conversion rate and the conversion rates of CuSi @ MOR-1, CuSi @ MOR-2, CuAl @ MOR, MOR + Cu/SiO2The catalyst is equivalent, the selectivity of methyl acetate is 0 percent, namely the methyl acetate generated on MOR nucleus is converted by 100 percent, and the selectivity of ethanol reaches 58.3 percent, which are all higher than other catalysts. The method of the invention is proved that the double Cu-based shell MOR core catalyst can realize two-stage MOR + Cu/SiO2The catalyst can not realize 100 percent conversion rate of a methyl acetate intermediate product and high selectivity of a product ethanol, the MOR core single Cu-based shell can not obtain such good effect, and the Cu loading capacity of the catalyst is greatly reduced compared with that of two-stage catalysts. The method for preparing the catalyst is simple and easy to operate, reduces the production cost, shortens the process route, and has good industrial application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A core-shell catalyst for preparing ethanol by a dimethyl ether and synthesis gas one-step method is characterized in that a mercerized molecular sieve subjected to hydrogen ion exchange is used as a core, a double-layer Cu-based hydrogenation catalyst loaded outside the core is used as a shell, wherein a first layer of shell close to the mercerized molecular sieve is a CuSi composite material, the CuSi composite material is obtained by roasting a silica sol shell loaded copper salt in an inert atmosphere, a second layer of shell is a CuAl composite material, the CuAl composite material is obtained by roasting an aluminum sol loaded copper salt in an inert or reducing atmosphere, and Cu loading amounts in the two layers of shells obtained by roasting are respectively 3-7 wt%.
2. The core-shell catalyst according to claim 1, wherein the loading shell front pore channel of the mercerized molecular sieve is subjected to pre-adsorption treatment by pyridine and methyl iodide.
3. The core-shell catalyst according to claim 2, wherein the temperature for pre-adsorption treatment of pyridine is 100 to 300 ℃ and the temperature for pre-adsorption treatment of methyl iodide gas is 100 to 280 ℃.
4. The preparation method of the Cu-based core-shell catalyst is characterized by comprising the following steps of:
1) hydrothermally synthesizing a raw material of the silk-screen molecular sieve by using a template agent, forming the raw material into molecular sieve balls through hydrogen ion exchange, and performing pre-adsorption treatment on pore passages of the silk-screen molecular sieve at a certain temperature by sequentially using pyridine and methyl iodide;
2) coating silica sol on a molecular sieve sphere, and vacuumizing and drying to form a silica sol shell;
3) spraying a copper salt solution on a silica sol shell, drying, and roasting in inert gas to form a first layer of Cu-based shell;
4) coating the aluminum sol on a first layer of Cu-based shell of the sphere, and vacuumizing and drying to form an aluminum sol shell;
5) and spraying the copper salt solution on an aluminum sol shell, drying, and roasting in a reducing atmosphere to finally obtain the dual-Cu-based shell MOR core catalyst CuAl @ CuSi @ MOR.
5. The preparation method according to claim 4, wherein the tetraethoxysilane is dissolved in water to form the silica sol in the step (2), the coating thickness of the silica sol is 0.2-0.4 mm, and the drying temperature is controlled to be 40-60 ℃.
6. The method according to claim 4, wherein the copper salt sprayed in the steps (3) and (5) is an aqueous ammonia solution of a copper salt.
7. The preparation method according to claim 4, wherein the loading amount of Cu in the step (3) is 3-7 wt%, the roasting temperature is 200-300 ℃, and the inert gas is one or more of nitrogen, helium and argon.
8. The method according to claim 4, wherein the thickness of the alumina sol coated in the step (4) is 0.1 to 0.3mm, and the drying temperature is controlled to be 50 to 80 ℃.
9. The preparation method according to claim 4, wherein the loading amount of Cu in the step (5) is 3-7 wt%, the roasting temperature is 250-300 ℃, and the reducing gas is one or more of hydrogen and carbon monoxide.
10. The application of the core-shell catalyst according to any one of claims 1 to 3, wherein dimethyl ether and synthesis gas are used as raw material gases, the raw material gases are reacted by a reactor filled with the core-shell catalyst to obtain ethanol, the reaction temperature is 190-250 ℃, the reaction pressure is 1.0-10.0 MPa, and the airspeed of the raw material gases is 1000-10000 h-1The ratio of carbon monoxide to dimethyl ether in the feed gas is 5: 1-20: 1, and the ratio of carbon monoxide to hydrogen is 1: 1-5: 1.
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