Method for preparing paraxylene

Abstract

This application discloses a method for preparing paraxylene, which comprises injecting a raw material containing methanol, naphtha, and CO2 into a reactor containing a catalyst, reacting the raw material to produce paraxylene. The product distribution is adjusted by adding methanol, and the selectivity of paraxylene is greatly improved. In addition, the components containing benzene and toluene in the aromatic hydrocarbon product are returned to the reaction system and co-fed with the raw material to react and produce paraxylene, which realizes the recycling of raw materials and has a very high economic effect. The method has a simple process, high feasibility, and can greatly improve the selectivity and yield of paraxylene, which has important application value and provides a new method for the large-scale utilization of CO2.

Description

Technical Field

[0001] The present application relates to a method for preparing paraxylene, particularly a method for preparing paraxylene by the coupling conversion of methanol, naphtha and CO on a zeolite molecular sieve-based catalyst, and belongs to the field of the petrochemical industry. 2 by the coupling conversion of methanol, naphtha and CO on a zeolite molecular sieve-based catalyst, and belongs to the field of the petrochemical industry.

Background Art

[0002] With the development of modern industry, the concentration of carbon dioxide (CO 2 ) in the atmosphere as the main greenhouse gas has increased, and as a result, the greenhouse effect has become increasingly prominent. In 2020, the world's CO 2 emissions reached 34 billion tons, and China's CO 2 emissions exceeded 10 billion tons. At the 75th session of the United Nations General Assembly in 2020, China proposed that efforts should be made to peak CO 2 emissions by 2030 and to achieve carbon neutrality by 2060. Therefore, the recovery, fixation and resource utilization of CO 2 have become a major concern for countries around the world. From the perspective of resources, CO 2 is the cheapest carbon resource in the world.

[0003] Aromatic hydrocarbons (benzene, toluene, paraxylene) represented by triphenyl are basic chemical raw materials. Among them, paraxylene is the most popular product among aromatic hydrocarbons, with a large market scale and a high dependence on imports. In 2019, the production volume of paraxylene reached 13.46 million tons, and the import volume reached 15.94 million tons, with a foreign dependence rate of 52%. Industrially, paraxylene is mainly prepared from naphtha by a catalytic reforming unit and an aromatic hydrocarbon complex unit. However, the process is numerous, the process is complex, and the investment is huge. Therefore, most of the aromatic hydrocarbons are obtained by the conversion technology from naphtha to aromatic hydrocarbons. Aromatic hydrocarbons produced by naphtha catalytic reforming account for 80% of the amount of petroleum-based aromatic hydrocarbons. Therefore, CO 2 utilization technology, particularly CO 2Vigorously developing technologies for converting [substance] into aromatic hydrocarbons is of great economic and social significance. It can solve the shortage of chemical products in China. On the other hand, since the market scale of aromatic hydrocarbon products is large, large-scale CO 2 emission reduction can be achieved.

[0004] CN108160104A discloses a catalyst for preparing aromatic hydrocarbons by hydrogenating carbon dioxide, its manufacturing method and uses. When using a nano metal oxide and a ZSM-5 molecular sieve catalyst mixed by mechanical mixing, pulverization mixing, or ball mill pulverization, the C 5+ content of the carbon dioxide hydrogenation product reaches 80%, and the selectivity of aromatic hydrocarbons reaches 70% or more. CN107840778A discloses a method for preparing aromatic hydrocarbons by hydrogenating carbon dioxide under the action of a composite catalyst. The composite catalyst is composed of an iron-based catalyst for hydrogenating carbon dioxide to produce low-carbon olefins as the first component and a metal-modified or unmodified molecular sieve that mainly functions in the aromatization of olefins. Under the action of the composite catalyst, the CO 2 conversion rate is 33%, the selectivity of C 5+ hydrocarbons reaches 65%, and aromatic hydrocarbons account for 63% of C 5+ hydrocarbons. According to research, it is known that CO 2 is first activated under the action of a metal oxide, and then aromatic hydrocarbons are produced through processes such as carbon chain growth, migration, and ring formation of the intermediate components generated by the reaction with hydrogen under the action of the molecular sieve. All of the above research is for preparing liquid hydrocarbons and aromatic hydrocarbons by hydrogenating CO 2 . In addition to technical indicators, the hydrogen supply source has also become an important issue restricting industrial use.

Summary of the Invention

[0005] This application provides a new technical route for preparing aromatic hydrocarbons using CO 2 , that is, using naphtha as a raw material and combining it with CO 2 to prepare aromatic hydrocarbons, thereby preparing aromatic hydrocarbons and CO2 Provide a new method for large-scale utilization.

[0006] According to the first aspect of the present application, a method for preparing paraxylene is provided. In this method, not only paraxylene but also benzene and toluene can be obtained, and benzene and toluene can also be recycled as reaction raw materials.

[0007] A method for preparing paraxylene, comprising injecting a raw material containing methanol, naphtha, and CO 2 into a reactor containing a catalyst, reacting to produce paraxylene.

[0008] Optionally, the reaction conditions are a reaction temperature of 450 to 650 °C, a reaction pressure of 0.1 to 3.5 MPa, a weight hourly space velocity of naphtha of 0.1 to 5 h -1 and a weight hourly space velocity of CO 2 of 0.1 to 3 h -1 and a weight hourly space velocity of methanol of 0.1 to 5 h -1 respectively.

[0009] Optionally, the reaction conditions are a reaction temperature of 500 to 600 °C, a reaction pressure of 0.1 to 3 MPa, a weight hourly space velocity of naphtha of 0.5 to 2 h -1 and a weight hourly space velocity of CO 2 of 0.5 to 2 h -1 and a weight hourly space velocity of methanol of 0.5 to 2 h -1 respectively.

[0010] Optionally, the reaction conditions are a reaction temperature of 500 to 600 °C, a reaction pressure of 0.1 to 1 MPa, a weight hourly space velocity of naphtha of 0.5 to 2 h -1 and a weight hourly space velocity of CO 2 of 0.5 to 2 h -1 and a weight hourly space velocity of methanol of 0.5 to 2 h -1 respectively.

[0011] Optionally, the reaction temperature is independently selected from any value among 450 °C, 480 °C, 500 °C, 520 °C, 550 °C, 570 °C, 600 °C, 620 °C, 650 °C or a range of values between any two of these values.

[0012] Optionally, the reaction pressure is independently selected from any value among 0.1 MPa, 0.15 MPa, 0.2 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3 MPa or a value in the range between any two values.

[0013] Optionally, the weight hourly space velocity of naphtha is 0.1 h -1 , 0.2 h -1 , 0.5 h -1 , 0.7 h -1 , 1 h -1 , 1.2 h -1 , 1.5 h -1 , 2 h -1 , 2.5 h -1 , 3 h -1 , 3.5 h -1 , 4 h -1 , 4.5 h -1 , 5 h -1 and is independently selected from any value among them or a value in the range between any two values.

[0014] Optionally, the weight hourly space velocity of CO 2 is 0.1 h -1 , 0.2 h -1 , 0.5 h -1 , 0.7 h -1 , 1 h -1 , 1.2 h -1 , 1.5 h -1 , 2 h -1 , 2.5 h -1 , 3 h -1 and is independently selected from any value among them or a value in the range between any two values.

[0015] Optionally, the weight hourly space velocity of methanol is 0.1 h -1 , 0.2 h -1 , 0.5 h -1 , 0.7 h -1 , 1 h -1 , 1.2 h -1 , 1.5 h -1 , 2 h -1 , 2.5 h -1 , 3 h -1 , 3.5 h -1, 4 h -1 , 4.5 h -1 , 5 h -1 It is independently selected from any value among them or values in the range between any two values.

[0016] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 0.3 - 2:1:0.3 - 2.

[0017] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 0.3 - 1.5:1:0.3 - 1.5.

[0018] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 0.5 - 1.0:1:0.5 - 1.0.

[0019] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 1:3:2.

[0020] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 0.8:1:0.6.

[0021] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 0.8:1:1.2.

[0022] Optionally, for CO 2 , the ratio of the usage amounts of naphtha and methanol is 1.5:1:1.5.

[0023] Optionally, the components containing benzene and toluene in the mixture obtained by the reaction are separated from the obtained mixture, returned to the reaction system, and co-fed with the raw materials on the catalyst for reaction to produce paraxylene.

[0024] In this application, by separating the components containing benzene or toluene from the mixture obtained by the reaction, that is, by returning the components containing benzene or toluene in the by-products to the reaction system, recycling of the raw materials becomes possible.

[0025] Optionally, the catalyst is an acidic molecular sieve.

[0026] Optionally, the acidic molecular sieve is an HZSM-5 zeolite molecular sieve.

[0027] Optionally, the silica / alumina ratio Si / Al of the HZSM-5 zeolite molecular sieve is 10 to 50.

[0028] Optionally, the silica / alumina ratio Si / Al of the HZSM-5 zeolite molecular sieve is 15.

[0029] In this application, the silica / alumina ratio of the HZSM-5 zeolite molecular sieve is not the main factor affecting the catalytic activity, and it is only necessary to use the generally used silica / alumina ratio Si / Al.

[0030] Optionally, the HZSM-5 zeolite molecular sieve is a metal-modified HZSM-5 zeolite molecular sieve.

[0031] Optionally, the metal used for the metal modification is selected from at least one of La, Zn, Ga, Fe, Mo, and Cr.

[0032] Optionally, the HZSM-5 zeolite molecular sieve is an HZSM-5 zeolite molecular sieve modified with a metal modification and a silanization reagent.

[0033] In this application, the HZSM-5 zeolite molecular sieve modified with a metal and a silanization reagent refers to the modification of the HZSM-5 zeolite molecular sieve with a metal and then with a silanization reagent.

[0034] Optionally, the silanization reagent used for the modification with the silanization reagent is selected from at least one of the compounds having the following chemical formula:

Chemical formula

[0035] Optionally, at least one of the above R 1 , R 2 , R 3 and R 4 is selected from C 1 ~ 10 alkoxy groups.

[0036] Optionally, the silanization reagent is selected from at least one of tetraethyl orthosilicate and / or tetramethyl orthosilicate.

[0037] Optionally, before the reaction, the preparation of the catalyst further includes the step of putting the HZSM-5 zeolite molecular sieve into a metal salt solution, soaking it, drying it, and roasting it to obtain the above-mentioned metal-modified HZSM-5 zeolite molecular sieve.

[0038] Optionally, the method of the metal modification further includes the step of putting the HZSM-5 zeolite molecular sieve into a metal salt solution, soaking it, drying it, and roasting it to obtain the metal-modified HZSM-5 zeolite molecular sieve.

[0039] Optionally, the immersion conditions are an immersion temperature of 60 to 100°C and an immersion time of 2 to 10 hours.

[0040] Optionally, the immersion conditions are an immersion temperature of 70 to 90°C and an immersion time of 4 to 8 hours.

[0041] Optionally, the immersion temperature is independently selected from any value among 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C or a value within the range between any two of these values.

[0042] Optionally, the immersion time is independently selected from any value among 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or a value within the range between any two of these values.

[0043] Optionally, the solid-liquid ratio of the above HZSM-5 zeolite molecular sieve and the metal salt solution is 1:20 to 1:1.

[0044] The solid-liquid ratio refers to the mass ratio.

[0045] Optionally, the solid-liquid ratio of the above HZSM-5 zeolite molecular sieve and the metal salt solution is 1:10 to 1:1.

[0046] Optionally, the solid-liquid ratio of the above HZSM-5 zeolite molecular sieve and the metal salt solution is independently selected from any value among 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1 or a value within the range between any two of these values.

[0047] Optionally, the above metal salt is a soluble metal salt corresponding to the metal used for metal modification.

[0048] In the present application, the soluble metal salt can be a nitrate, sulfate, etc. corresponding to the metal used for metal modification. It is, for example, zinc nitrate, gallium nitrate, lanthanum nitrate, chromium nitrate, etc.

[0049] Optionally, in the method of metal modification, the drying condition is to dry under air atmosphere at 100 - 150 °C.

[0050] Optionally, in the method of metal modification, the calcination condition is to calcine under air atmosphere at 500 - 700 °C.

[0051] Optionally, before the reaction, the preparation of the catalyst further includes a step of contacting a material containing a silanization reagent with a metal - modified HZSM - 5 zeolite molecular sieve, purging with an inert gas, and calcining to obtain an HZSM - 5 zeolite molecular sieve modified with the above - mentioned metal and silanization reagent.

[0052] Optionally, the method of modification with the above - mentioned silanization reagent includes a step of contacting a material containing a silanization reagent with a metal - modified HZSM - 5 zeolite molecular sieve, purging with an inert gas, and calcining to obtain an HZSM - 5 zeolite molecular sieve modified with the above - mentioned metal and silanization reagent.

[0053] Optionally, the temperature of the above - mentioned contact treatment is 250 - 450 °C.

[0054] Optionally, the temperature of the above - mentioned contact treatment is 300 - 400 °C.

[0055] Optionally, the weight hourly space velocity of the above - mentioned silanization reagent is 0.02 - 0.5 h -1 -1.

[0056] Optionally, the weight hourly space velocity of the above - mentioned silanization reagent is 0.05 - 0.4 h -1 -1.

[0057] Optionally, the temperature of the contact treatment is 300 °C.

[0058] Optionally, the weight hourly space velocity of the above - mentioned silanization reagent is 0.2 h -1 -1.

[0059] Optionally, the inert gas is selected from at least one of nitrogen, helium, and argon.

[0060] Optionally, the temperature of the contact treatment is independently selected from any value among 250°C, 270°C, 300°C, 320°C, 350°C, 370°C, 400°C, 420°C, 450°C or a value in the range between any two values.

[0061] Optionally, the weight hourly space velocity of the silanization reagent is 0.02 h -1 , 0.05 h -1 , 0.1 h -1 , 0.15 h -1 , 0.2 h -1 , 0.25 h -1 , 0.3 h -1 , 0.35 h -1 , 0.4 h -1 , 0.45 h -1 , 0.5 h -1 and is independently selected from any value among or a value in the range between any two values.

[0062] Optionally, in the method of modification with the silanization reagent, the roasting condition is to inject air at a temperature of 400°C to 650°C for roasting.

[0063] Optionally, the reactor is a fixed bed reactor, a fluidized bed reactor, or a moving bed reactor.

[0064] Optionally, the naphtha is selected from at least one of hydrocracked naphtha, catalytically cracked naphtha, raffinate, topped crude oil, and direct coal liquefaction naphtha.

[0065] Optionally, the carbon number distribution range of the hydrocarbons in the naphtha is C 4 ~C 12 .

[0066] In another aspect of the present application, a process flow for preparing paraxylene is further provided, which includes the following. Naphtha, CO 2 and a raw material containing methanol are supplied to a reaction system, subjected to a catalytic reaction to obtain a mixture A, and the mixture A enters a first separation system and is separated to obtain a C 5+ component, and the C 5+ component enters a second separation system and paraxylene is obtained by separation.

[0067] Optionally, the C 5+ component enters a second separation system, and a component containing benzene and toluene is obtained by separation, and the component containing benzene and toluene and naphtha, CO 2 and the raw material containing methanol are co-supplied to the reaction system.

[0068] A method for preparing a catalyst for preparing paraxylene using methanol, naphtha and CO 2 as raw materials includes the step of putting HZSM-5 zeolite molecular sieve into a metal salt solution, soaking, drying and calcining to obtain the above metal-modified HZSM-5 zeolite molecular sieve.

[0069]

[0070] A method for preparing a catalyst for preparing paraxylene using methanol, naphtha and CO 2 as raw materials includes the following steps: (1) putting HZSM-5 zeolite molecular sieve into a metal salt solution, soaking, drying and calcining to obtain the above metal-modified HZSM-5 zeolite molecular sieve;

[0071]

[0072]

[0073] (2) contacting a material containing a silanization reagent with the metal-modified HZSM-5 zeolite molecular sieve, purging with an inert gas, and calcining to obtain the HZSM-5 zeolite molecular sieve modified with the above metal and silanization reagent.

[0073] A method for preparing paraxylene, comprising: a catalyst preparation step (S1), comprising: putting HZSM-5 zeolite molecular sieve into a metal salt solution, immersing, drying, and calcining to obtain the metal-modified HZSM-5 zeolite molecular sieve (step S1); injecting a raw material containing methanol, naphtha, and CO 2 into a reactor containing the catalyst prepared in step (S1), reacting to generate paraxylene (step 2).

[0074] Optionally, the catalyst preparation step in step (s1) further comprises: contacting a material containing a silanization reagent with the metal-modified HZSM-5 zeolite molecular sieve, purging with an inert gas, and calcining to obtain the HZSM-5 zeolite molecular sieve modified with the metal and the silanization reagent.

[0075] Specific preparation conditions are as described above.

[0076] In this application, unless otherwise specified, the specified data range is selected from any value within the range and includes the endpoint values of the range.

[0077] In this application, C 1 ~ 10 alkyl group and C 1 ~ 10 in the alkoxy group, C 1 ~ 10 refers to that the total number of carbon atoms in the alkyl group or alkoxy group is 1 to 10.

[0078] The beneficial effects produced by this application are as follows.

[0079] 1) In the method for preparing paraxylene by the combination of naphtha and CO 2 provided by this application, adding methanol can adjust the product distribution and significantly improve the selectivity of paraxylene.

[0080] 2) In the method for preparing paraxylene by the combination of naphtha and CO provided by this application, methanol is added to the raw materials, and the components containing benzene and toluene in the by-products are returned to the reaction system. As a result, the recycling of the raw materials is realized, and the economic effect is very high. 2 2

[0081] 3) In the method for preparing paraxylene provided by this application, the process is simple, highly feasible, can significantly improve the selectivity and yield of paraxylene, has important application value, and provides a new method for the large-scale utilization of CO. 2 2

Brief Description of the Drawings

[0082]

Figure 1

Embodiments for Carrying Out the Invention

[0083] Hereinafter, this application will be described in detail with reference to the embodiments, but this application is not limited to these embodiments.

[0084] Unless otherwise specified, all raw materials and catalysts in the embodiments of this application are purchased from industrial routes and used directly without treatment, and the equipment and devices used incorporate the methods and parameters recommended by the manufacturers.

[0085] In the embodiment, the inner diameter of the fixed-bed reactor is 1.5 cm.

[0086] The process flow of the method for preparing paraxylene provided by this application is shown in FIG. 1.

[0087] Referring to FIG. 1, first, raw materials containing naphtha, CO 2 and methanol are supplied to the reaction system, and naphtha, CO 2A raw material containing methanol is subjected to a catalytic reaction with a catalyst in a reaction system to obtain mixture A. Mixture A enters a first separation system, and through separation, component C is obtained together with other components. 5+ Component C 5+ enters a second separation system, and through separation, components containing benzene and toluene, paraxylene, and other component C 5+ are obtained. The components containing benzene and toluene are pumped back into the reaction system to produce paraxylene, and finally, paraxylene is separated.

[0088] In the examples of this application, the type of naphtha is direct coal liquefaction naphtha, and its specific composition is as shown in the following table.

Table 0

[0089] Example 1 Preparation of a shaped HZSM-5 molecular sieve sample for a fixed bed 100 g of HZSM-5 zeolite molecular sieve raw material powder (Nankai University Catalyst Factory, Si / Al = 15) was calcined at 550 °C for 4 hours in an air atmosphere, then pelletized and formed, crushed, and sieved to obtain shaped molecular sieve particles with a particle size of 40 - 60 mesh, which is denoted as FX-HZSM-5.

[0090] Example 2 Preparation of a shaped sample of zinc-modified HZSM-5 molecular sieve for a fixed bed

[0091] 100 g of HZSM-5 zeolite molecular sieve (Nankai University Catalyst Factory, Si / Al = 15) was put into a 10 wt% zinc nitrate aqueous solution. The mass ratio of the HZSM-5 zeolite molecular sieve to the zinc nitrate aqueous solution (i.e., solid-liquid ratio) was 1 / 10. It was immersed at 80 °C for 6 hours, drained, and then dried at 120 °C for 4 hours under an air atmosphere. After that, it was calcined at 550 °C for 4 hours under an air atmosphere to obtain a [Zn]HZSM-5 molecular sieve sample, which was pelletized, formed, crushed, and sieved to obtain shaped molecular sieve particles with a particle size of 40 - 60 mesh, which was denoted as FX-[Zn]HZSM-5.

[0092] Example 3 Preparation of a shaped sample of gallium-modified HZSM-5 molecular sieve for fixed bed 100 g of HZSM-5 zeolite molecular sieve (Nankai University Catalyst Factory, Si / Al = 15) was put into a 10 wt% gallium nitrate aqueous solution. The mass ratio of the HZSM-5 zeolite molecular sieve to the gallium nitrate aqueous solution (i.e., solid-liquid ratio) was 1 / 10. It was immersed at 80 °C for 6 hours, drained, and then dried at 120 °C for 4 hours under an air atmosphere. After that, it was calcined at 550 °C for 4 hours under an air atmosphere to obtain a [Ga]HZSM-5 molecular sieve sample, which was pelletized, formed, crushed, and sieved to obtain shaped molecular sieve particles with a particle size of 40 - 60 mesh, which was denoted as FX-[Ga]HZSM-5.

[0093] Example 4 Preparation of a shaped sample of lanthanum-modified HZSM-5 molecular sieve for fixed bed

[0094] 100 g of HZSM-5 zeolite molecular sieve (Nankai University Catalyst Factory, Si / Al = 15) was put into a 10 wt% lanthanum nitrate aqueous solution. The mass ratio of the HZSM-5 zeolite molecular sieve to the lanthanum nitrate aqueous solution (i.e., solid-liquid ratio) was 1 / 10. It was immersed for 4 hours under the condition of 90 °C, drained, and then dried under the condition of 120 °C for 4 hours in an air atmosphere. After that, it was calcined at 550 °C for 4 hours in an air atmosphere to obtain a [La]HZSM-5 molecular sieve sample, which was tableted, formed, crushed, and sieved to obtain shaped molecular sieve particles with a particle size of 40 - 60 mesh, which was designated as FX-[La]HZSM-5.

[0095] Example 5 Preparation of a shaped sample of iron-modified HZSM-5 molecular sieve for fixed bed 100 g of HZSM-5 zeolite molecular sieve (Nankai University Catalyst Factory, Si / Al = 15) was put into a 10 wt% iron nitrate aqueous solution. The mass ratio of the HZSM-5 zeolite molecular sieve to the iron nitrate aqueous solution (i.e., solid-liquid ratio) was 1 / 10. It was immersed for 8 hours under the condition of 70 °C, drained, and then dried under the condition of 120 °C for 4 hours in an air atmosphere. After that, it was calcined at 550 °C for 4 hours in an air atmosphere to obtain a [Fe]HZSM-5 molecular sieve sample, which was tableted, formed, crushed, and sieved to obtain shaped molecular sieve particles with a particle size of 40 - 60 mesh, which was designated as FX-[Fe]HZSM-5.

[0096] Example 6 Preparation of a shaped sample of chromium-modified HZSM-5 molecular sieve for fixed bed 100 g of HZSM-5 zeolite molecular sieve (Nankai University Catalyst Factory, Si / Al = 15) was put into an aqueous solution of 10 wt% chromium nitrate. The mass ratio of HZSM-5 zeolite molecular sieve to the aqueous solution of chromium nitrate (i.e., solid-liquid ratio) was 1 / 10. It was immersed for 8 hours at 70 °C, drained, and then dried in an air atmosphere at 120 °C for 4 hours. After that, it was calcined in an air atmosphere at 550 °C for 4 hours to obtain a [Cr]HZSM-5 molecular sieve sample, which was tableted, formed, crushed, and sieved to obtain shaped molecular sieve particles with a particle size of 40 - 60 mesh, denoted as FX-[Cr]HZSM-5.

[0097] Example 7 Preparation of a shaped molecular sieve sample of zinc-modified HZSM-5 for fluidized bed 100 g of the [Zn]HZSM-5 molecular sieve sample prepared in Example 2 was mixed with an amorphous binder containing aluminum or silicon, spray-dried and formed. The specific steps are as follows.

[0098] [Zn]HZSM-5 molecular sieve sample, pseudoboehmite, silica sol, xanthan gum (bacterial polysaccharide), and water were uniformly mixed, beaten, rubber-crushed, and defoamed to obtain a slurry. The weight parts of each component in the slurry are as follows. [Zn]HZSM-5 35 parts by weight Al 2 O 3 20 parts by weight SiO 2 45 parts by weight H 2 O 240 parts by weight Xanthan gum 1 part by weight

[0099] The obtained slurry was spray-dried and formed to obtain a sample of microspherical particles with a particle size distribution of 20 - 100 μm. The sample of microspherical particles was calcined in a muffle furnace at 550 °C for 3 hours to obtain a shaped molecular sieve of [Zn]HZSM-5 with an attrition index of 1.2, denoted as FL-[Zn]HZSM-5.

[0100] Example 8 Preparation of Aromatic Hydrocarbons by the Coupled Conversion of Methanol, Naphtha and CO 2 Reaction Evaluation of the Preparation of Aromatic Hydrocarbons by the Coupled Conversion Evaluate the reaction of preparing aromatic hydrocarbons by the coupled conversion of methanol, naphtha and CO in a micro fixed-bed reactor. The reaction conditions are as follows. Put 5 grams of the FX-HZSM-5 catalyst prepared in Example 1 into the fixed-bed reactor, and first treat it with nitrogen at 550 °C for 1 hour at a flow rate of 50 mL / min. Next, co-feed methanol, naphtha and CO 2 The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 1:3:2, the weight hourly space velocity of naphtha is 1.0 h 2 and the weight hourly space velocity of CO -1 is 0.33 h 2 and the weight hourly space velocity of methanol is 0.67 h -1 The reaction pressure is 1 MPa. Analyze the reaction products by on-line Agilent 7890 gas chromatography and collect samples for analysis after 30 minutes of reaction. The reaction results are shown in Table 1. -1

Table 1

[0101] Example 9 Preparation of Aromatic Hydrocarbons by the Coupled Conversion of Methanol, Naphtha and CO 2 Reaction Evaluation of the Preparation of Aromatic Hydrocarbons by the Coupled Conversion Evaluate the reaction of preparing aromatic hydrocarbons by the coupled conversion of methanol, naphtha and CO in a micro fixed-bed reactor. The reaction conditions are as follows. Put 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 into the fixed-bed reactor, and first treat it with nitrogen at 550 °C for 1 hour at a flow rate of 50 mL / min. Next, co-feed methanol, naphtha and CO 2 The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 1:3:2, the weight hourly space velocity of naphtha is 1.0 h 2 ​: The mass ratio of naphtha to methanol is 0.8:1:0.6, and the weight hourly space velocity of naphtha is 1.0 h -1 and the weight hourly space velocity of CO 2 is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. The reaction products are analyzed by an on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 2.

Table 2

[0102] Example 10 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and p-xylene by the combined conversion of methanol, naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO 2 is prepared on-line in a micro fixed-bed reactor. The conditions for on-line catalyst preparation are as follows. 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 are placed in a fixed-bed reactor, first treated with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cooled to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the pressure is atmospheric. After supplying for 60 minutes, the supply is stopped, purged with nitrogen, the temperature is raised to 550 °C, calcined in an air atmosphere for 4 hours, and a fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO 2 is obtained, and this is named FXNCC-1.

[0103] Next, under a nitrogen atmosphere, the temperature is adjusted to the reaction temperature of 550 °C, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO​2 : The mass ratio of naphtha to methanol is 0.8:1:0.6, and the weight hourly space velocity of naphtha is 1.0 h -1 and the weight hourly space velocity of CO 2 is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. The reaction products are analyzed by an on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 3.

Table 3

[0104] Example 11 Preparation and reaction evaluation of a catalyst for preparing p-xylene by the combined conversion of methanol, naphtha and CO 2 The operation is the same as that in Example 10. A fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO is obtained and named FXNCC-1. 2 Next, the temperature is adjusted to the reaction temperature of 550 °C under a nitrogen atmosphere, and methanol, naphtha and CO

[0105] are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h 2 and the weight hourly space velocity of CO -1 is 0.8 h 2 and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Based on the compositions of benzene and toluene in the reaction products of methanol, naphtha and CO -1 in Example 10, the raw materials are prepared and fed by a micro-feed pump (methanol, naphtha and CO 2 ), and 2 ​Separate benzene and toluene from the reaction product and pump it back to the fixed-bed reactor with a micro-feed pump (equivalent to). Analyze the reaction product by online Agilent 7890 gas chromatography and collect samples for analysis after 30 minutes of reaction. The reaction results are shown in Table 4.

Table 4

[0106] Example 12 Methanol, Naphtha and CO 2 Preparation and Reaction Evaluation of Catalysts for Preparing Benzene, Toluene and p-Xylene by the Combined Conversion of Naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the combined conversion of is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of the FX-[Ga]HZSM-5 catalyst prepared in Example 3 into the fixed-bed reactor, first treat it at 550 °C for 1 hour with nitrogen at 50 mL / min, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the normal pressure is maintained. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine in an air atmosphere for 4 hours, and then obtain a fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO 2 , and name this catalyst FXNCC-2.

[0107] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 . The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6, and the weight hourly space velocity of naphtha is 1.0 h -1 , and the CO 2The weight hourly space velocity is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. The reaction products are analyzed by on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 5. [Table 5]

[0108] Example 13 Preparation and reaction evaluation of a catalyst for preparing paraxylene by the combined conversion of methanol, naphtha and CO 2 The operation is the same as in Example 12, and a fixed-bed catalyst for preparing benzene, toluene and paraxylene by the combined conversion of naphtha and CO 2 is obtained and named FXNCC-2.

[0109] Next, the temperature is adjusted to the reaction temperature of 550 °C under a nitrogen atmosphere, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6. The weight hourly space velocity of naphtha is 1.0 h -1 and the weight hourly space velocity of CO 2 is 0.8 h -1 while the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Based on the compositions of benzene and toluene in the reaction products of methanol, naphtha and CO 2 in Example 12, the raw materials are prepared and fed by a micro-feed pump (equivalent to separating benzene and toluene from the reaction products of methanol, naphtha and CO 2 and pumping them back to the fixed-bed reactor with a micro-feed pump). The reaction products are analyzed by on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 6.​

Table 6

[0110] Example 14 Preparation and reaction evaluation of a catalyst for preparing paraxylene by the combined conversion of methanol, naphtha and CO 2 Naphtha and CO 2 The catalyst for preparing paraxylene by the combined conversion of naphtha and CO is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of the FX-[La]HZSM-5 catalyst prepared in Example 4 into a fixed-bed reactor. First, treat it with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 and the normal pressure. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine for 4 hours under an air atmosphere, and then obtain a fixed-bed catalyst for preparing paraxylene by the combined conversion of naphtha and CO, which is named FXNCC-3. 2

[0111] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 :naphtha:methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h -1 and the weight hourly space velocity of CO 2 is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h -1 , and the reaction pressure is 0.1 MPa. The reaction products are analyzed by an online Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 7. ​​

Table 7

[0112] Example 15 Methanol, Naphtha and CO 2 Preparation and Reaction Evaluation of Catalyst for Preparing p-Xylene by Coupling Conversion of

[0113] The operation is the same as that in Example 14, and a fixed-bed catalyst for preparing p-xylene by coupling conversion of naphtha and CO 2 is obtained and named FXNCC-3.

[0114] Next, under a nitrogen atmosphere, the temperature is adjusted to the reaction temperature of 550 °C, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 :naphtha:methanol (mass ratio) = 0.8:1:0.6. The weight hourly space velocity of naphtha is 1.0 h -1 , the weight hourly space velocity of CO 2 is 0.8 h -1 , and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Based on the compositions of benzene and toluene in the reaction products of methanol, naphtha and CO 2 in Example 14, the raw materials are prepared and fed by a micro-feed pump (equivalent to separating benzene and toluene from the reaction products of methanol, naphtha and CO 2 and pumping them back to the fixed-bed reactor with a micro-feed pump). The reaction products are analyzed by on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 8.

Table 8

[0115] Example 16 Methanol, Naphtha and CO 2Preparation and Reaction Evaluation of Catalyst for Preparing Paraxylene by Coupling Conversion Naphtha and CO 2 The catalyst for preparing paraxylene by the coupling conversion of naphtha and CO is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of FX-[Fe]HZSM-5 catalyst prepared in Example 5 into a fixed-bed reactor, first treat it with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the normal pressure is maintained. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine for 4 hours under an air atmosphere, and then obtain a fixed-bed catalyst for preparing paraxylene by the coupling conversion of naphtha and CO 2 , and name it FXNCC-4

[0116] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 . The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 :naphtha:methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h -1 , the weight hourly space velocity of CO 2 is 0.8 h -1 , and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. The reaction products are analyzed by an online Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 9

Table 9

[0117] Example 17 Methanol, Naphtha and CO 2Preparation and Reaction Evaluation of a Catalyst for Preparing Paraxylene by Coupling Conversion The operation is the same as in Example 16, and a fixed-bed catalyst for preparing paraxylene by the coupling conversion of naphtha and CO 2 is obtained and named FXNCC-4.

[0118] Next, under a nitrogen atmosphere, the temperature is adjusted to the reaction temperature of 550 °C, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8: 1: 0.6, and the weight hourly space velocity of naphtha is 1.0 h -1 and the weight hourly space velocity of CO 2 is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Based on the compositions of benzene and toluene in the reaction products of methanol, naphtha and CO 2 in Example 16, the raw materials are prepared and fed by a micro-feed pump (equivalent to separating benzene and toluene from the reaction products of methanol, naphtha and CO 2 and pumping them back to the fixed-bed reactor with a micro-feed pump). The reaction products are analyzed by on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 10.

Table 10

[0119] Example 18 Preparation and Reaction Evaluation of a Catalyst for Preparing Paraxylene by the Coupling Conversion of Methanol, Naphtha and CO 2 Preparation and Reaction Evaluation of a Catalyst for Preparing Paraxylene by Coupling Conversion

[0120] Naphtha and CO 2The catalyst for preparing paraxylene by the combined conversion is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of the FX-[Cr]HZSM-5 catalyst prepared in Example 6 into a fixed-bed reactor, first treat it with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the pressure is normal pressure. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine for 4 hours under an air atmosphere, and then obtain a fixed-bed catalyst for preparing paraxylene by the combined conversion of naphtha and CO 2 , and name it FXNCC-5.

[0121] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 . The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6. The weight hourly space velocity of naphtha is 1.0 h -1 , and the weight hourly space velocity of CO 2 is 0.8 h -1 , and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. The reaction products are analyzed by an online Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 11.

Table 11

[0122] Example 19 Preparation and reaction evaluation of a catalyst for preparing paraxylene by the combined conversion of methanol, naphtha and CO 2 The operation is the same as that in Example 18, and the combined conversion of naphtha and CO is the same as that in Example 18, and the combined conversion of naphtha and CO 2A fixed-bed catalyst for preparing paraxylene by coupling conversion is obtained and named FXNCC-5.

[0123] Next, under a nitrogen atmosphere, the temperature is adjusted to the reaction temperature of 550 °C, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8: 1: 0.6, and the weight hourly space velocity of naphtha is 1.0 h -1 while the weight hourly space velocity of CO 2 is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Based on the composition of benzene and toluene in the reaction products of methanol, naphtha and CO 2 in Example 18, the raw materials are prepared and fed by a micro-feed pump (equivalent to separating benzene and toluene from the reaction products of methanol, naphtha and CO 2 and pumping them back to the fixed-bed reactor with a micro-feed pump). The reaction products are analyzed by on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 12.

Table 12

[0124] Example 20 Preparation and reaction evaluation of a catalyst for preparing paraxylene by the coupling conversion of methanol, naphtha and CO 2 Naphtha and CO 2The catalyst for preparing paraxylene by the combined conversion is prepared online in a micro fixed fluidized bed reactor. The conditions for online catalyst preparation are as follows. Put 10 grams of the FL-[Zn]HZSM-5 catalyst prepared in Example 7 into a fixed fluidized bed reactor. First, treat it with nitrogen at 50 mL / min at 550 °C for 1 hour, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 200 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the normal pressure is maintained. After supplying for 75 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine for 4 hours under an air atmosphere, and then obtain a fixed bed catalyst for preparing paraxylene by the combined conversion of naphtha and CO 2 , and name this catalyst FLNCC-1.

[0125] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 . The methanol and naphtha raw materials are supplied by a micro feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6. The weight hourly space velocity of naphtha is 1.0 h -1 , the weight hourly space velocity of CO 2 is 0.8 h -1 , and the weight hourly space velocity of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Analyze the reaction products by online Agilent 7890 gas chromatography, and collect samples for analysis after 30 minutes of reaction. The reaction results are shown in Table 13.

Table 13

[0126] Example 21 Preparation and reaction evaluation of a catalyst for preparing paraxylene by the combined conversion of methanol, naphtha and CO 2

[0127] The operation is the same as in Example 20, and a fixed-bed catalyst for preparing paraxylene by the coupling conversion of naphtha and CO 2 is obtained and named FLNCC-1.

[0128] Next, under a nitrogen atmosphere, the temperature is adjusted to the reaction temperature of 550 °C, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8: 1: 0.6, and the weight hourly space velocity of naphtha is 1.0 h -1 while that of CO 2 is 0.8 h -1 and that of methanol is 0.6 h -1 . The reaction pressure is 0.1 MPa. Based on the compositions of benzene and toluene in the reaction products of methanol, naphtha and CO 2 in Example 20, the raw materials are prepared and fed by a micro-feed pump (equivalent to separating benzene and toluene from the reaction products of methanol, naphtha and CO 2 and pumping them back to the fixed-bed reactor with a micro-feed pump). The reaction products are analyzed by on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 14.

Table 14

[0129] Comparative Example 1 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and paraxylene by the coupling conversion of naphtha and CO 2 Naphtha and CO 2 ​The catalyst for preparing benzene, toluene and paraxylene by coupling conversion is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of FX-[Zn]HZSM-5 catalyst prepared in Example 2 into a fixed-bed reactor. First, treat it with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the normal pressure is maintained. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine for 4 hours under an air atmosphere, and then use naphtha and CO 2 to obtain a fixed-bed catalyst for preparing benzene, toluene and paraxylene by coupling conversion, which is named FXNCC-1.

[0130] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere. The naphtha raw material is supplied by a micro feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The ratio of raw material CO 2 : naphtha (mass ratio) = 0.8:1. The weight hourly space velocity of naphtha is 1.0 h -1 , and the weight hourly space velocity of CO 2 is 0.8 h -1 , and the reaction pressure is 0.1 MPa. The reaction products are analyzed by an online Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 15.

Table 15

[0131] When there is no methanol in the raw material, the paraxylene content in the hydrocarbon product composition is 12.31%. However, compared with Example 10, it can be seen that the addition of methanol increases the paraxylene content to 32.53%. Therefore, the addition of methanol significantly improves the selectivity of paraxylene.

[0132] Example 22 Methanol, Naphtha and CO 2 Preparation and Reaction Evaluation of Catalysts for Preparing Benzene, Toluene and p-Xylene by Coupling Conversion of Naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the coupling conversion of naphtha and CO is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 into a fixed-bed reactor. First, treat it with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cool it to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the pressure is normal pressure. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, calcine for 4 hours under an air atmosphere, and then obtain a fixed-bed catalyst for preparing benzene, toluene and p-xylene by the coupling conversion of naphtha and CO 2 , and name it FXNCC-1.

[0133] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 . The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:1.2. The weight hourly space velocity of naphtha is 1.0 h -1 , the weight hourly space velocity of CO 2 is 0.8 h -1 , and the weight hourly space velocity of methanol is 1.2 h -1 . The reaction pressure is 0.1 MPa. Analyze the reaction products by online Agilent 7890 gas chromatography, and collect samples for analysis after 30 minutes of reaction. The reaction results are shown in Table 16.

Table 16

[0134] Comparing with Example 10, it can be seen that when the addition amount of methanol increases, the p-xylene content in the hydrocarbon product composition increases from 32.53% to 44.36%. Furthermore, it shows that the selectivity of p-xylene is significantly improved by the addition of methanol.

[0135] Example 23 Methanol, naphtha and CO 2 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and p-xylene by the combined conversion of Naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO is prepared online in a micro fixed-bed reactor. The conditions for online catalyst preparation are as follows. Put 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 into a fixed-bed reactor. First, treat it with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cool it to 400 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the pressure is normal pressure. After supplying for 60 minutes, stop the supply, purge with nitrogen, raise the temperature to 550 °C, and calcine for 4 hours under an air atmosphere, and then naphtha and CO 2 A fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of is obtained, and this is named FXNCC-6.

[0136] Next, adjust the temperature to the reaction temperature of 550 °C under a nitrogen atmosphere, and co-feed methanol, naphtha and CO 2 . The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h -1 , and the weight hourly space velocity of CO 2 is 0.8 h -1 , and the weight hourly space velocity of methanol is 0.6 h -1The reaction pressure is 0.1 MPa. The reaction products are analyzed by an on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 17.

Table 17

[0137] Example 24 Methanol, naphtha and CO 2 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and paraxylene by the combined conversion of naphtha and CO 2 The catalyst for preparing benzene, toluene and paraxylene by the combined conversion of naphtha and CO is prepared on-line in a micro fixed-bed reactor. The conditions for on-line catalyst preparation are as follows. 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 are placed in a fixed-bed reactor, first treated with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cooled to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.4 h -1 , at atmospheric pressure. After supplying for 60 minutes, the supply is stopped, purged with nitrogen, the temperature is raised to 550 °C, calcined in an air atmosphere for 4 hours, and then a fixed-bed catalyst for preparing benzene, toluene and paraxylene by the combined conversion of naphtha and CO 2 is obtained, and this is named FXNCC-7.

[0138] Next, the temperature is adjusted to the reaction temperature of 550 °C under a nitrogen atmosphere, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are fed by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h -1 , and the weight hourly space velocity of CO 2 is 0.8 h -1 and the weight hourly space velocity of methanol is 0.6 h-1 The reaction pressure is 0.1 MPa. The reaction products are analyzed by an on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 18.

Table 18

[0139] Example 25 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and p-xylene by the combined conversion of methanol, naphtha and CO 2 Naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO is prepared on-line in a micro fixed-bed reactor. The conditions for on-line catalyst preparation are as follows. 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 are placed in a fixed-bed reactor. First, it is treated with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cooled to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.05 h -1 , and the pressure is atmospheric. After supplying for 240 minutes, the supply is stopped, purged with nitrogen, the temperature is raised to 550 °C, and calcined in an air atmosphere for 4 hours, and then a fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO is obtained, which is named FXNCC-8. 2

[0140] Next, the temperature is adjusted to the reaction temperature of 550 °C under a nitrogen atmosphere, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 :naphtha:methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h -1 , and the weight hourly space velocity of CO 2 is 0.8 h -1 ​​and the weight hourly space velocity of methanol is 0.6 h -1 , and the reaction pressure is 0.1 MPa. The reaction products are analyzed by an on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 19.

Table 19

[0141] Example 26 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and p-xylene by the combined conversion of methanol, naphtha and CO 2 Naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the combined conversion of is prepared on-line in a micro fixed-bed reactor. The conditions for on-line catalyst preparation are as follows. 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 are placed in a fixed-bed reactor, first treated with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cooled to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 , and the pressure is normal pressure. After supplying for 60 minutes, the supply is stopped, purged with nitrogen, the temperature is raised to 550 °C, calcined in an air atmosphere for 4 hours, and then a fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO 2 is obtained and named FXNCC-1.

[0142] Next, the temperature is adjusted to the reaction temperature of 550 °C under a nitrogen atmosphere, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 0.8:1:0.6, the weight hourly space velocity of naphtha is 1.0 h -1 and the weight hourly space velocity of CO 2 is 0.8 h​-1 and the weight hourly space velocity of methanol is 0.6 h -1 and the reaction pressure is 3 MPa. The reaction products are analyzed by an on-line Agilent 7890 gas chromatography, and samples are taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 20.

Table 20

[0143] Example 27 Preparation and reaction evaluation of a catalyst for preparing benzene, toluene and p-xylene by the combined conversion of methanol, naphtha and CO 2

[0144] Naphtha and CO 2 The catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO is prepared on-line in a micro fixed-bed reactor. The conditions for on-line catalyst preparation are as follows. 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 are placed in a fixed-bed reactor. First, it is treated with nitrogen at 550 °C for 1 hour at a rate of 50 mL / min, and then cooled to 300 °C under a nitrogen atmosphere. Under a nitrogen atmosphere (controlled by a mass flow meter, 100 ml / min), tetraethyl orthosilicate is pumped into the reactor, and the weight hourly space velocity of tetraethyl orthosilicate is 0.2 h -1 and the pressure is atmospheric. After supplying for 60 minutes, the supply is stopped, purged with nitrogen, the temperature is raised to 550 °C, and after calcining in an air atmosphere for 4 hours, a fixed-bed catalyst for preparing benzene, toluene and p-xylene by the combined conversion of naphtha and CO is obtained, and this is named FXNCC-1. 2

[0145] Next, under a nitrogen atmosphere, the temperature is adjusted to the reaction temperature of 550 °C, and methanol, naphtha and CO 2 are co-fed. The methanol and naphtha raw materials are supplied by a micro-feed pump, and the CO 2 flow rate is controlled by a mass flow meter. The raw material CO 2 : naphtha: methanol (mass ratio) = 1.5:1:1.5, and the weight hourly space velocity of naphtha is 1.0 h​​-1 and the weight hourly space velocity of CO 2 is 1.5 h -1 and the weight hourly space velocity of methanol is 1.5 h -1 , and the reaction pressure is 0.1 MPa. The reaction product is analyzed by an on-line Agilent 7890 gas chromatography, and a sample is taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 21.

Table 21

[0146] The above content is only some examples of this application, and does not impose any formal restrictions on this application. Although this application discloses the above in preferred embodiments, it is not intended to limit this application. Those skilled in the art can, without departing from the scope of the technical solution of this application, use the technical content disclosed above to make minor changes or modifications with equivalent changes in equivalent embodiments, and these belong to the scope of the technical solution.

Claims

1. A method for preparing paraxylene, wherein a raw material containing methanol, naphtha, and CO 2 is passed through a reactor containing a catalyst to cause a reaction to produce paraxylene, The ratio of the usage amounts of CO₂, naphtha, and methanol is 0.3 to 2:1:0.3 to 2, The catalyst is an HZSM-5 zeolite molecular sieve, characterized by the method.

2. The reaction conditions are a reaction temperature of 450 to 650 °C, a reaction pressure of 0.1 to 3.5 MPa, a weight hourly space velocity of naphtha of 0.1 to 5 h -1 , CO 2 with a weight hourly space velocity of 0.1 to 3 h -1 , a weight hourly space velocity of methanol of 0.1 to 5 h -1 , and the method according to claim 1, characterized in that it is so.

3. The reaction conditions are a reaction temperature of 500 to 600 °C, a reaction pressure of 0.1 to 3 MPa, a weight hourly space velocity of naphtha of 0.5 to 2 h -1 , CO 2 with a weight hourly space velocity of 0.5 to 2 h -1 , a weight hourly space velocity of methanol of 0.5 to 2 h -1 , and the method according to claim 1, characterized in that it is so.

4. CO 2 The method according to claim 1, characterized in that the ratio of the amounts of use of CO, naphtha, and methanol is 0.3 to 1.5:1:0.3 to 1.

5.

5. A component containing benzene and toluene in the mixture obtained by the reaction is separated from the obtained mixture, returned to the reaction system, and co-fed with the raw material on the catalyst for reaction to produce paraxylene, characterized by the method according to claim 1.

6. The silica / alumina Si / Al of the HZSM-5 zeolite molecular sieve is 10 to 50, characterized by the method according to claim 1.

7. The HZSM-5 zeolite molecular sieve is a metal-modified HZSM-5 zeolite molecular sieve, characterized by the method according to claim 1.

8. The metal used for the metal modification is selected from at least one of La, Zn, Ga, Fe, Mo, and Cr, characterized by the method according to claim 7.

9. The HZSM-5 zeolite molecular sieve is a HZSM-5 zeolite molecular sieve modified with a metal and a silanization reagent, characterized by the method according to claim 1.

10. The silanization reagent used for the modification with the silanization reagent is selected from at least one of the compounds having the following chemical formula, 【Chemical 1】 wherein R 1 , R 2 , R 3 and R 4 are each independently selected from at least one of C 1 to 10 alkyl groups and C 1 to 10 alkoxy groups, the method according to claim 9.

11. Said R 1 , R 2 , R 3 and R 4 at least one of which is selected from C 1 to 10 an alkoxy group, the method according to claim 10.

12. The silanization reagent is selected from tetraethyl orthosilicate and / or tetramethyl orthosilicate, characterized by the method according to claim 10.

13. Before the reaction, The preparation of the catalyst further includes the step of putting the HZSM-5 zeolite molecular sieve into a metal salt solution, immersing it, drying it, and roasting it to obtain a metal-modified HZSM-5 zeolite molecular sieve, characterized by the method according to claim 1.

14. The immersion conditions are an immersion temperature of 60 to 100°C and an immersion time of 2 to 10 hours, characterized by the method according to claim 13.

15. The solid-liquid ratio of the HZSM-5 zeolite molecular sieve to the metal salt solution is 1:20 to 1:1, characterized by the method according to claim 13.

16. The metal salt is a soluble metal salt corresponding to the metal used for the metal modification, characterized by the method according to claim 13.

17. Before the reaction, the preparation of the catalyst further comprises the step of contacting a material containing a silylating reagent with a metal-modified HZSM-5 zeolite molecular sieve, purging with an inert gas, and calcining to obtain the metal-modified and silylating reagent-modified HZSM-5 zeolite molecular sieve, the method according to claim 13.

18. The method according to claim 17, wherein the temperature of the contacting treatment is 250 to 450 °C.

19. The weight hourly space velocity of the silanization reagent is 0.02 to 0.5 h -1 The method according to claim 17, characterized in that it is as such.

20. The method according to claim 1, wherein the reactor is a fixed-bed reactor, a fluidized-bed reactor, or a moving-bed reactor.

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