CN106866328B - Method for preparing aromatic hydrocarbon with high selectivity by using methanol - Google Patents
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Abstract
A method for preparing aromatic hydrocarbon with high selectivity by using methanol relates to pretreatment of aromatic hydrocarbon and a catalyst, wherein the catalytic reaction comprises the steps of introducing reaction raw materials into the catalyst after the pretreatment to obtain methanol and a hydrogen capturing-removing agent, carrying out a reaction on the catalyst through a solid catalyst bed layer at an airspeed of 500-10000h -1 to obtain a product aromatic hydrocarbon, adding a salt compound of a metal element into a solvent for ultrasonic dispersion, adding a modified acidic zeolite molecular sieve, continuing the ultrasonic dispersion to obtain a mixture, carrying out suction filtration and washing on the mixture, drying an obtained filter cake, roasting a dried sample, and reducing to obtain the catalyst.
Description
Technical Field
The invention relates to aromatic hydrocarbon, in particular to a method for preparing aromatic hydrocarbon with high selectivity by using methanol.
Background
Aromatic hydrocarbons are important chemical basic raw materials, and benzene, toluene and xylene (namely BTX) in light aromatic hydrocarbons are the most important basic chemicals of petrochemical products. At present, the production of aromatic hydrocarbon mainly comes from petroleum routes, including catalytic reforming, naphtha hydrogenation, pyrolysis gasoline hydrogenation, aromatic hydrocarbon conversion and the like. Because the problems of resource exhaustion, environmental pollution and the like caused by the heavy use of petroleum are increasingly severe, the development of a method for producing aromatic hydrocarbons by a non-petroleum route is particularly urgent. On the other hand, the technology for preparing methanol from coal is quite mature, and important chemical raw materials including olefin and aromatic hydrocarbon can be obtained by acid catalytic conversion of methanol. Therefore, the development of the technology for preparing aromatic hydrocarbon from methanol can provide a good way for efficiently and cleanly utilizing coal resources, can replace or partially replace petroleum resource routes, and is a sustainable development strategy according with the national conditions of China.
The research difficulty of the direct preparation of the aromatic hydrocarbon by the methanol mainly lies in the research of a high-selectivity and high-stability catalyst, Weifei et al discovers that the selectivity of the aromatic hydrocarbon on an Ag-loaded H-ZSM-5 catalyst is 55%, and mainly uses xylene, the aromatic hydrocarbon yield on the H-ZSM-5 catalyst modified by Zn and P is improved to 75% (Acta phys. -Chim.sin.,2013,29,1281), Freeman et al examines the performance of the aromatic hydrocarbon prepared by physically mixing 13 groups of oxides and the H-ZSM-5 molecular sieve, the addition of gallium oxide issued can obviously improve the yields of C 8 and C 9 aromatic hydrocarbons (Catal Lett.,2002,82,217), Ono et al also discovers that Ga/H-Cheo et al is a better methanol aromatization catalyst, the yields are 48% and 67% (Faraday Transactions,1988,84,1091), thos study on the loading capacity of Mo carbide, 2, and the like are respectively 48% and the yield of the C 8 and C-ZSM-5 aromatic hydrocarbon modified by Ca-Cl-Cu 80%, and the selectivity of a catalyst is also reported that when the catalyst is converted into a high-Zr-ZSM-60, the selectivity of the catalyst, the same as a high-Zr-ZSM-60% and the yield of the molybdenum-60-Zr-60-Cu-Zr-Cu-Zr-Al-60, the molybdenum-Cu-7-Cu-Al-7-Cu-Mo-7-Mo-Cu-7-Cu-Mo-7-Mo-7.
Although relatively high aromatic selectivity can be obtained on part of catalysts, C 9+ aromatic content is high, light aromatic BTX selectivity is not high, and most of the research is experimental data obtained in a short reaction time (generally less than 10 h). in most reactions, carbon deposition occurs on the catalysts along with the reaction, acid active centers on the catalysts are covered, so that the activity of the catalysts is reduced, even a catalyst promoter metal sintering phenomenon occurs, the stability of the catalysts is poor, and the service life is shortened.
Disclosure of Invention
The invention aims to provide a method for preparing aromatic hydrocarbon with high selectivity by using methanol.
The method for preparing the aromatic hydrocarbon with high selectivity by using the methanol comprises the following steps:
1) Pretreating a catalyst, wherein the catalyst is a metal oxide/acidic zeolite molecular sieve compound;
In step 1), the preparation method of the metal oxide/acidic zeolite molecular sieve composite can be as follows:
(1) Adding a salt compound of a metal element into a solvent for ultrasonic dispersion, adding a modified acidic zeolite molecular sieve, and continuing ultrasonic dispersion to obtain a mixture;
In the step (1), the mass ratio of the salt compound of the metal element to the solvent can be 1: 0-100; the salt compound can be at least one selected from nitrate, hydrochloride, acetylacetone salt, acetate, bromide and the like; the ultrasonic dispersion time can be 0.5-10 h; the time for continuing the ultrasonic dispersion can be 0.5-10 h.
(2) After the mixture obtained in the step (1) is filtered and washed, drying the obtained filter cake;
in the step (2), the drying can be vacuum drying, the drying temperature can be 40-100 ℃, and the drying time can be 1-48 h.
(3) And (3) roasting the sample dried in the step (2), and reducing to obtain the catalyst.
In the step (3), the roasting method comprises the steps of transferring a dried sample into a tube furnace, and roasting with NO/Ar mixed gas containing NO at the heating rate of 0.5-2 ℃/min at the temperature of 300-650 ℃ for 1-24H, wherein the volume percentage of NO in the NO/Ar mixed gas can be 5-20%, the reduction can be carried out in the atmosphere containing H 2, the volume percentage of H 2 can be 5-50%, the heating rate is 0.5-5 ℃/min, the temperature is 250-500 ℃, and the reduction time is 0.5-10H.
The specific method of the catalyst pretreatment can be as follows: heating the catalyst to 300-650 ℃ from room temperature at a heating rate of not higher than 20 ℃/min in inert gas of nitrogen, argon or helium, and keeping the temperature for 10-300 min.
2) and (3) catalytic reaction, namely introducing reaction raw materials into the pretreated catalyst to form methanol and a hydrogen capturing-removing agent, and reacting the mixture through a solid catalyst bed layer at the space velocity of 500-10000h -1 to obtain the product aromatic hydrocarbon.
In the step 2), the molar ratio of methanol to the hydrogen trapping-removing agent in the methanol and hydrogen trapping-removing agent may be (0.05-100): 1; the hydrogen capture-removal agent can be selected from at least one of carbon monoxide, carbon dioxide, sulfur dioxide, unsaturated olefin, unsaturated alkyne, nitrogen oxide, aldehyde compound, ketone compound and the like; the unsaturated olefin may be selected from at least one of ethylene, propylene, butene, pentene, hexene, etc.; the unsaturated alkyne is one or more of acetylene, propyne and butyne, the nitrogen oxide is at least one of nitric oxide, nitrogen dioxide, nitrous oxide and the like, the aldehyde compound is at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde and the like, and the ketone compound can be at least one of acetone, butanone, pentanone, cyclohexanone and the like; the unsaturated olefin may be selected from at least one of ethylene, propylene, butene, pentene, hexene, etc.; the unsaturated alkyne can be selected from at least one of acetylene, propyne, butyne and the like, the nitrogen oxide can be selected from at least one of nitrogen monoxide, nitrogen dioxide, dinitrogen monoxide and the like, the aldehyde compound can be selected from at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde and the like, and the ketone compound can be selected from at least one of acetone, butanone, pentanone, cyclohexanone and the like. The solid catalyst is a mixture of metal and a modified acidic zeolite molecular sieve or a mixture of metal oxide and the modified acidic zeolite molecular sieve, wherein the mass percent of the metal or the metal oxide can be 0.5-40%, and the balance is the modified acidic zeolite molecular sieve; the metal may be selected from at least one of Cu, Fe, Ni, Co, Ru, Au, Pt, Pd, Ir, Zn, Zr, Ga, Cr, M, Ti, W, etc., and the metal oxide may be selected from at least one of Cu, Fe, Ni, Co, Ru, Au, Pt, Pd, Ir, Zn, Zr, Ga, Cr, M, Ti, W, etc., metal oxide, etc.; the modified acidic zeolite molecular sieve can be selected from zeolite molecular sieves modified by at least one element of Zn, Zr, Mn, Mo, Cu, Cr, Ga and the like by methods of ion exchange and the like, wherein the mass percentage of the modified element can be 0.1-10.0%, and the balance is the acidic zeolite molecular sieve; the acidic zeolite molecular sieve can be selected from at least one of H-MCM-22, H-Beta, H-Y, H-X, H-ZSM-5, H-MOR, H-SSZ-13 and the like; the reaction temperature can be 300-600 ℃, and the reaction pressure can be 0.1-5.0 MPa.
Compared with the prior art, the invention has the following technical effects:
(1) The invention shows excellent catalytic performance of preparing aromatic hydrocarbon from methanol, namely, the selectivity of the aromatic hydrocarbon is remarkably promoted by adding the hydrogen capture-removal agent, the product distribution is characterized by low methane, low heavy alkane and high aromatic hydrocarbon selectivity, and the aromatic hydrocarbon selectivity can reach more than 90 percent.
(2) The reaction raw material hydrogen trapping-removing agent can perform further hydrogenation reaction with hydrogen removed by methanol aromatization under the action of a catalyst, so that hydrogen transfer reaction is inhibited, and the selectivity of aromatic hydrocarbon is improved.
(3) the adopted catalyst is a novel catalyst with multifunction cooperative coupling, the modified zeolite molecular sieve is responsible for preparing aromatic hydrocarbon by aromatizing methanol, and the metal or metal oxide promotes dehydrogenation reaction in the aromatization process, so that the selectivity of the aromatic hydrocarbon is further improved.
(4) Because a large amount of hydrogen removal reaction exists in the reaction process, the carbon deposition on the catalyst can be eliminated by the hydrogen under the reaction condition, and the reaction life is prolonged.
(5) the preparation process of the adopted catalyst is simple and controllable, and the preparation method is easy to carry out amplification preparation.
In conclusion, the method can obtain high selectivity of the aromatic hydrocarbon product, has good stability and has better industrial application prospect.
Detailed Description
The method for producing aromatics with high selectivity from methanol provided by the present invention is further described in detail below, but the present invention is not limited thereto.
Example 1
Weighing 2.0g of Cu (NO 3) 2 & 3H 2 O, adding the weighed 2.0g of Cu (NO 3) 2 & 3H 2 O into 30g of absolute ethyl alcohol for ultrasonic dispersion for 4 hours, weighing 3.0g of Zn ion modified H-beta zeolite molecular sieve (the Zn content is 0.5 wt%), adding the weighed 3.0g of Zn ion modified H-beta zeolite molecular sieve into the solution, continuing to perform ultrasonic dispersion for 5 hours, performing suction filtration and washing on the mixture subjected to ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying box for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tubular furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating to 550 ℃ at the speed of 2 ℃/min for calcination for 6 hours, and reducing the calcined sample for 4 hours at the temperature rise speed of 1 ℃/min by adopting the atmosphere containing 10% of H 2/Ar, wherein the obtained sample is the catalyst.
Taking 1.0g of catalyst, heating the catalyst to 550 ℃ from room temperature at a heating rate of 5 ℃/min in a nitrogen atmosphere, keeping the temperature for 60min, introducing methanol and carbon monoxide (the molar ratio of the methanol to the carbon monoxide is 10:1), reacting the catalyst by a catalyst bed under the conditions that the reaction pressure is 0.5MPa, the space velocity is 4000h -1 and the reaction temperature is 500 ℃, the time is 50h, and analyzing a reaction product and a feed gas on line by using a gas chromatography, wherein the specific reaction performance results are listed in Table 1.
TABLE 1
Note that C 2-4 is C 2 -C 4 hydrocarbon, aromatic is aromatic hydrocarbon (benzene and multi-methyl substituted benzene), Other C 5+ is alkane and alkene with carbon number more than or equal to 5.
Example 2
Weighing 3.5g of Fe (NO 3) 3.9H 2 O, adding the weighed mixture into 50g of water for ultrasonic dispersion for 4 hours, weighing 3.0g of Zr ion modified H-MOR zeolite molecular sieve (the Zr content is 0.5 wt%), adding the weighed mixture into the solution, continuing ultrasonic dispersion for 5 hours, carrying out suction filtration and washing on the mixture after ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying box for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tubular furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating the mixture to 550 ℃ at the speed of 2 ℃/min for calcination for 6 hours, and reducing the calcined sample for 4 hours at the temperature of 400 ℃ (the heating rate of 1 ℃/min) by adopting the atmosphere containing 10% of H 2/Ar, wherein the obtained sample is the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1 except that methanol and ethylene (feed molar ratio 10:1) were used as the raw materials, and the reaction performance was as shown in Table 1.
Example 3
Weighing 3.0g of Co (NO 3) 2.6H 2 O, adding the mixture into 45g of water and ethanol mixed solution (the mass ratio of water to ethanol is 1:1) for ultrasonic dispersion for 4 hours, weighing 3.0g of Cu ion modified H-MCM-22 zeolite molecular sieve (the Cu content is 0.5 wt%), adding the mixture into the solution, continuing ultrasonic dispersion for 5 hours, carrying out suction filtration and washing on the mixture after ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying oven for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tubular furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating to 550 ℃ at the speed of 2 ℃/min for calcination for 6 hours, and reducing the calcined sample for 4 hours at the temperature rise speed of 400 ℃ for 1 ℃/min by adopting the atmosphere containing 10% of H 2/Ar to obtain the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1 except that methanol and acetaldehyde (feed molar ratio 15:1) were used as the raw materials, and the reaction performance was as shown in Table 1.
Example 4
weighing 5.2g of Zn (NO 3) 2 & 6H 2 O, adding the weighed mixture into 50g of absolute ethyl alcohol for ultrasonic dispersion for 4 hours, weighing 3.0g of Mo ion modified H-ZSM-5 zeolite molecular sieve (the Mo content is 0.5 wt%), adding the weighed mixture into the solution, continuing to perform ultrasonic dispersion for 5 hours, performing suction filtration and washing on the mixture subjected to ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying box for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tubular furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating the mixture to 550 ℃ at the speed of 2 ℃/min, calcining the obtained sample for 6 hours, and reducing the calcined sample for 4 hours at the temperature rise speed of 1 ℃/min by adopting the atmosphere containing 10% of H 2/Ar, wherein the obtained sample is the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1 except that methanol and carbon dioxide (feed molar ratio 8:1) were used as the raw materials, and the reaction performance was as shown in Table 1.
Example 5
Weighing 1.2g of PdCl 2, adding the PdCl 2 into 50g of water for ultrasonic dispersion for 4 hours, weighing 3.0g of Zr ion modified H-Y zeolite molecular sieve (with the Zr content of 0.5 wt%), adding the Zr ion modified H-Y zeolite molecular sieve into the solution, continuing ultrasonic dispersion for 5 hours, carrying out suction filtration and washing on the mixture subjected to ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying oven for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tube furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating to 550 ℃ at the speed of 2 ℃/min for calcination for 6 hours, reducing the calcined sample for 4 hours at 400 ℃ (the heating rate of 1 ℃/min) by adopting the atmosphere containing 10% of H 2/Ar, and obtaining the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1 except that methanol and acetylene (feed molar ratio 15:1) were used as the raw materials, and the reaction performance is shown in Table 1.
example 6
Weighing 5.2g of NiCl 2 & 6H 2 O, adding the NiCl 2 & 6H 2 O into 50g of absolute ethyl alcohol for ultrasonic dispersion for 4 hours, weighing 3.0g of Ga ion modified H-SSZ-13 zeolite molecular sieve (the Ga content is 0.5 wt%), adding the Ga ion modified H-SSZ-13 zeolite molecular sieve into the solution, continuing ultrasonic dispersion for 5 hours, carrying out suction filtration and washing on the mixture subjected to ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying box for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tubular furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating the mixture to 550 ℃ at the speed of 2 ℃/min, calcining the mixture for 6 hours, and reducing the calcined sample for 4 hours at the temperature of 400 ℃ (the heating rate of 1 ℃/min) by adopting an atmosphere containing 10% of H 2/Ar to obtain the catalyst.
the catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1 except that the starting materials were methanol and butanone (feed molar ratio: 10:1), and the reaction properties are shown in Table 1.
Example 7
Weighing 1.8g of RuCl 3, adding the RuCl 3 into 30g of water for ultrasonic dispersion for 4 hours, weighing 3.0g of Cr ion modified H-X zeolite molecular sieve (the Cr content is 0.5 wt%), adding the Cr ion modified H-X zeolite molecular sieve into the solution, continuing to perform ultrasonic dispersion for 5 hours, performing suction filtration and washing on the mixture after ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying oven for drying at 80 ℃ for 24 hours, transferring the obtained sample into a tube furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating to 550 ℃ at the speed of 2 ℃/min, calcining for 6 hours, reducing the calcined sample for 4 hours at 400 ℃ (the heating speed of 1 ℃/min) by adopting the atmosphere containing 10% of H 2/Ar, and obtaining the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1, and the reaction properties are shown in Table 1.
Example 8
Weighing 1.5g of IrCl 3, adding the IrCl 3 into 30g of absolute ethyl alcohol for ultrasonic dispersion for 4 hours, weighing 3.0g of Mn ion modified H-ZSM-5 zeolite molecular sieve (with the Mn content of 0.5 wt%), adding the Mn ion modified H-ZSM-5 zeolite molecular sieve into the solution, continuing to perform ultrasonic dispersion for 5 hours, performing suction filtration and washing on the mixture after the ultrasonic dispersion, transferring the obtained filter cake into a vacuum drying oven for drying for 24 hours at the temperature of 80 ℃, transferring the obtained sample into a tubular furnace, introducing NO/Ar mixed gas containing 10% by volume of NO, heating the mixture to 550 ℃ at the speed of 2 ℃/min for calcination for 6 hours, and reducing the calcined sample for 4 hours at the temperature of 400 ℃ (the heating rate of 1 ℃/min) by adopting the atmosphere containing 10% of H 2/Ar, wherein the obtained sample is the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were as in example 2, and the reaction performance is shown in Table 1.
Comparative example 1
The catalyst preparation was the same as in example 4.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 4 except that only methanol was added to the reaction raw materials, and the reaction properties are shown in Table 1.
Comparative example 2
Weighing 1.0g of H-ZSM-5 molecular sieve, and tabletting to obtain the catalyst.
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were as in example 4, and the reaction performance is shown in Table 1.
Claims (5)
1. A method for preparing aromatic hydrocarbon with high selectivity by methanol is characterized by comprising the following steps:
1) Pre-treating a catalyst, namely heating the catalyst to 300-650 ℃ from room temperature at a heating rate of not higher than 20 ℃/min in inert gas of nitrogen, argon or helium, and keeping the temperature for 10-300 min, wherein the catalyst is a metal oxide/modified acidic zeolite molecular sieve compound, the mass fraction of the metal oxide is 0.5-40%, the metal oxide is selected from at least one of oxides of Cu, Fe, Ni, Co, Ru, Pd, Ir and Zn, the modified acidic zeolite molecular sieve is selected from a zeolite molecular sieve modified by at least one element of metal elements of Zn, Zr, Cu, Mo, Ga, Cr and Mn, and the zeolite molecular sieve is an H-beta zeolite molecular sieve, an H-MOR zeolite molecular sieve, an H-MCM-22 zeolite molecular sieve, an H-ZSM-5 zeolite molecular sieve, an H-Y zeolite molecular sieve, One of H-SSZ-13 zeolite molecular sieve and H-X zeolite molecular sieve, wherein the content of metal elements in the modified acidic zeolite molecular sieve is 0.1-10.0%, and the preparation method of the catalyst comprises the following steps:
(1) Adding metal salts of Cu, Fe, Ni, Co, Ru, Pd, Ir and Zn into water and/or an ethanol solvent for ultrasonic dispersion, then adding the modified acidic zeolite molecular sieve for continuous ultrasonic dispersion to obtain a mixture, wherein the mass ratio of the metal nitrate or hydrochloride to the modified acidic zeolite molecular sieve is 0.4-1.733: 1;
(2) after the mixture obtained in the step (1) is filtered and washed, drying the obtained filter cake;
(3) Roasting the dried sample in the step (2) and reducing to obtain a catalyst metal oxide/modified acidic zeolite molecular sieve compound, wherein the roasting method comprises the steps of transferring the dried sample into a tube furnace, roasting by adopting NO/Ar mixed gas containing NO, the heating rate is 0.5-2 ℃/min, the temperature is 300-650 ℃, and the roasting time is 1-24H, the volume percentage of NO in the NO/Ar mixed gas is 5-20%, reducing by adopting an atmosphere containing H 2, the volume percentage of H 2 is 5-50%, the heating rate is 0.5-5 ℃/min, the temperature is 250-500 ℃, and the reducing time is 0.5-10H;
2) And (2) catalytic reaction, namely introducing the catalyst pretreated in the step 1) into reaction raw materials, wherein the components comprise methanol and a hydrogen capture-removal agent, and the reaction is carried out on the product aromatic hydrocarbon through a solid catalyst bed layer under the condition that the space velocity is 500-10000h -1, wherein the reaction temperature is 300-600 ℃, and the reaction pressure is 0.1-5.0 MPa.
2. The method for preparing aromatic hydrocarbons with high selectivity to methanol according to claim 1, wherein in the step 1), the mass ratio of the salt compound of the metal element to the solvent is 1: 0-100; the salt compound is at least one selected from nitrate, hydrochloride, acetylacetone salt, acetate and bromide; the ultrasonic dispersion time is 0.5-10 h; the time for continuing ultrasonic dispersion is 0.5-10 h.
3. The method for preparing the aromatic hydrocarbon with high selectivity of the methanol as claimed in claim 1, wherein in the step 1) and the step 2, the drying is performed in vacuum at a temperature of 40-100 ℃ for 1-48 h.
4. The method for preparing aromatic hydrocarbons with high selectivity from methanol according to claim 1, wherein in the step 2), the molar ratio of methanol to the hydrogen capturing-removing agent in the methanol and the hydrogen capturing-removing agent is (0.05-100): 1; the hydrogen capture-removal agent is selected from at least one of carbon monoxide, carbon dioxide, sulfur dioxide, unsaturated olefin, unsaturated alkyne, nitrogen oxide, aldehyde compound and ketone compound; the unsaturated olefin is selected from at least one of ethylene, propylene, butene, pentene and hexene; the unsaturated alkyne is selected from at least one of acetylene, propyne and butyne, the nitrogen oxide is selected from at least one of nitric oxide, nitrogen dioxide and dinitrogen monoxide, the aldehyde compound is selected from at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and benzaldehyde, and the ketone compound is selected from at least one of acetone, butanone, pentanone and cyclohexanone; the unsaturated olefin is selected from at least one of ethylene, propylene, butene, pentene and hexene; the unsaturated alkyne is selected from at least one of acetylene, propyne and butyne, the nitrogen oxide is selected from at least one of nitrogen monoxide, nitrogen dioxide and dinitrogen monoxide, the aldehyde compound is selected from at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and benzaldehyde, and the ketone compound is selected from at least one of acetone, butanone, pentanone and cyclohexanone.
5. The method for preparing the aromatic hydrocarbon with high selectivity of the methanol as claimed in claim 1, wherein the modification method adopts an ion exchange method.
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| CN107537548B (en) * | 2017-08-24 | 2020-09-25 | 中国烟草总公司郑州烟草研究院 | Carbon-containing molecular sieve catalyst and preparation method and application thereof |
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| CN110872524B (en) * | 2018-09-04 | 2021-12-17 | 中国科学院大连化学物理研究所 | Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor |
| CN115463685B (en) * | 2022-10-27 | 2023-01-31 | 淄博恒亿化工科技有限公司 | Preparation method and application of composite molecular sieve catalyst for synthesizing nitroaromatic compound |
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