METHOD FOR PREPARING P-XYLENE

Abstract

A method for preparing p-xylene is provided. Raw materials containing methanol, naphtha and CO.sub.2 are introduced into a reactor filled with a catalyst for a reaction to produce p-xylene. By adding the methanol, the product distribution is adjusted, and the selectivity of p-xylene is obviously improved. In addition, components containing benzene and toluene in aromatic hydrocarbon products are returned to a reaction system and co-fed with the raw materials for a reaction to produce p-xylene, so that cyclic utilization of the raw materials is achieved, and the method has extremely high economic benefits. The method has a simple process and high feasibility, can greatly improve the selectivity and yield of p-xylene, has an important application value, and provides a new way for large-scale utilization of CO.sub.2.

Claims

1. A method for preparing p-xylene, comprising introducing raw materials containing methanol, naphtha, and CO.sub.2 into a reactor filled with a catalyst for a reaction to produce the p-xylene.

2. The method according to claim 1, wherein conditions for the reaction are as follows: a reaction temperature is in a range from 450? C. to 650? C., a reaction pressure is in a range from 0.1 MPa to 3.5 MPa, a weight hourly space velocity of the naphtha is in a range from 0.1 h.sup.?1 to 5 h.sup.?1, a weight hourly space velocity of the CO.sub.2 is in a range from 0.1 h.sup.?1 to 3 h.sup.?1, and a weight hourly space velocity of the methanol is in a range from 0.1 h.sup.?1 to 5 h.sup.?1.

3. The method according to claim 1, wherein conditions for the reaction are as follows: a reaction temperature is in a range from 500? C. to 600? C., a reaction pressure is in a range from 0.1 MPa to 3 MPa, a weight hourly space velocity of the naphtha is in a range from 0.5 h.sup.?1 to 2 h.sup.?1, a weight hourly space velocity of the CO.sub.2 is in a range from 0.5 h.sup.?1 to 2 h.sup.?1, and a weight hourly space velocity of the methanol is in a range from 0.5 h.sup.?1 to 2 h.sup.?1.

4. The method according to claim 1, wherein an amount ratio of the CO.sub.2, the naphtha, and the methanol is (0.3-2):1:(0.3-2).

5. The method according to claim 1, wherein an amount ratio of the CO.sub.2, the naphtha, and the methanol is (0.3-1.5):1:(0.3-1.5).

6. The method according to claim 1, wherein components containing benzene and toluene in a mixture obtained after the reaction are separated from the mixture, the components are returned to a reaction system and co-fed with the raw materials for the reaction on the catalyst to produce the p-xylene.

7. The method according to claim 1, wherein the catalyst is an acidic molecular sieve.

8. The method according to claim 7, wherein the acidic molecular sieve is an HZSM-5 zeolite molecular sieve.

9. The method according to claim 8, wherein the HZSM-5 zeolite molecular sieve has a silica-alumina ratio (Si/Al ratio) of 10-50.

10. The method according to claim 8, wherein the HZSM-5 zeolite molecular sieve is a metal-modified HZSM-5 zeolite molecular sieve.

11. The method according to claim 10, wherein a metal used for a metal modification is selected from at least one of La, Zn, Ga, Fe, Mo, and Cr.

12. The method according to claim 8, wherein the HZSM-5 zeolite molecular sieve is an HZSM-5 zeolite molecular sieve modified by a metal modification and a silanization reagent modification.

13. The method according to claim 12, wherein a silanization reagent used for the silanization reagent modification is selected from at least one of compounds with the following chemical formula: ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from C.sub.1-10 alkyl and C.sub.1-10 alkoxyl.

14. The method according to claim 13, wherein at least one of the R.sub.1, the R.sub.2, the R.sub.3, and the R.sub.4 is selected from the C.sub.1-10 alkoxyl.

15. The method according to claim 13, wherein the silanization reagent is selected from tetraethyl silicate and/or tetramethyl silicate.

16. The method according to claim 1, wherein before the reaction, the method further comprises a step of preparing the catalyst: placing an HZSM-5 zeolite molecular sieve in a metal salt solution, and carrying out an impregnation, a drying, and a calcination to obtain a metal-modified HZSM-5 zeolite molecular sieve.

17. The method according to claim 16, wherein conditions for the impregnation are as follows: an impregnation temperature is in a range from 60? C. to 100? C., and an impregnation time is in a range from 2 to 10 hours.

18. The method according to claim 16, wherein a solid-liquid ratio of the HZSM-5 zeolite molecular sieve to the metal salt solution is 1:20 to 1:1.

19. The method according to claim 16, wherein a metal salt is a soluble metal salt corresponding to a metal used for a metal modification.

20. The method according to claim 16, wherein before the reaction, a preparation of the catalyst further comprises the following steps: subjecting a material containing a silanization reagent and the metal-modified HZSM-5 zeolite molecular sieve to a contact treatment, and carrying out a purging with an inert gas, followed by the calcination to obtain an HZSM-5 zeolite molecular sieve modified by a metal modification and a silanization reagent modification.

21. The method according to claim 20, wherein the contact treatment is carried out at a temperature of a range from 250? C. to 450? C.

22. The method according to claim 20, wherein a weight hourly space velocity of the silanization reagent is in a range from 0.02 h.sup.?1 to 0.5 h.sup.?1.

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

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0089] FIGURE is a schematic diagram of a process flow for preparing p-xylene.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0090] The present application is described in detail below in conjunction with examples, but the present application is not limited to the examples.

[0091] Unless otherwise specified, raw materials and catalysts used in the examples of the present application are purchased by commercial ways and used directly without treatment, and instruments and equipment are used in accordance with solutions and parameters recommended by manufacturers.

[0092] In the examples, the inner diameter of a fixed bed reactor is 1.5 cm.

[0093] A schematic diagram of a process flow of a method for preparing p-xylene provided by the present application is shown in the figure.

[0094] As shown in the figure, raw materials containing naphtha, CO.sub.2 and methanol are first fed into a reaction system to enable the raw materials containing naphtha, CO.sub.2 and methanol to contact with a catalyst in the reaction system for a reaction so as to obtain a mixture A. The mixture A is sent into a first separation system for separation to obtain other components and C.sub.5+ components. The C.sub.5+ components are sent into a second separation system for separation to obtain products containing components containing benzene and toluene, p-xylene and other C.sub.5+ components. The components containing benzene and toluene are pumped back to the reaction system to produce p-xylene, and finally separated to obtain p-xylene.

[0095] In the examples of the present application, the type of naphtha is direct coal liquefied naphtha, which includes specific components as shown in the following table. Composition of Direct Coal Liquefied Naphtha

TABLE-US-00001 Aromatic Carbon number N-alkanes Isoalkanes Cycloalkanes hydrocarbons 6 0.03 0.00 0.00 0.00 7 3.76 0.71 31.85 1.60 8 9.36 2.62 27.53 1.94 9 2.03 2.44 13.88 0.40 10 0.15 0.75 0.74 0.07 11 0.01 0.03 0.10 0.00 Total 15.34 6.55 74.10 4.01

Example 1 Preparation of an HZSM-5 Molecular Sieve Molded Sample used in a Fixed Bed

[0096] 100 g of an HZSM-5 zeolite molecular sieve (Nankai Catalyst Factory, Si/Al=15) was calcined in an air atmosphere at 550? C. for 4 hours, subjected to pressing molding, crushed and sieved to obtain molded molecular sieve particles with a particle size of 40-60 mesh, recorded as FX-HZSM-5.

Example 2 Preparation of a Zinc-Modified HZSM-5 Molecular Sieve Molded Sample used in a Fixed Bed

[0097] 100 g of an HZSM-5 zeolite molecular sieve (Nankai Catalyst Factory, Si/Al=15) was placed in a 10 wt % zinc nitrate aqueous solution, where the mass ratio (namely solid-liquid ratio) of the HZSM-5 zeolite molecular sieve to the zinc nitrate aqueous solution was 1/10. The molecular sieve was impregnated at 80? C. for 6 hours, drained, dried in an air atmosphere at 120? C. for 4 hours, and then calcined in an air atmosphere at 550? C. for 4 hours to obtain a [Zn]HZSM-5 molecular sieve sample. Then, the sample was subjected to pressing molding, crushed and sieved to obtain molded molecular sieve particles with a particle size of 40-60 mesh, recorded as FX-[Zn]HZSM-5.

Example 3 Preparation of a Gallium-Modified HZSM-5 Molecular Sieve Molded Sample used in a Fixed Bed

[0098] 100 g of an HZSM-5 zeolite molecular sieve (Nankai Catalyst Factory, Si/Al=15) was placed in a 10 wt % gallium nitrate aqueous solution, where the mass ratio (namely solid-liquid ratio) of the HZSM-5 zeolite molecular sieve to the gallium nitrate aqueous solution was 1/10. The molecular sieve was impregnated at 80? C. for 6 hours, drained, dried in an air atmosphere at 120? C. for 4 hours, and then calcined in an air atmosphere at 550? C. for 4 hours to obtain a [Ga]HZSM-5 molecular sieve sample. Then, the sample was subjected to pressing molding, crushed and sieved to obtain molded molecular sieve particles with a particle size of 40-60 mesh, recorded as FX-[Ga]HZSM-5.

Example 4 Preparation of a Lanthanum-Modified HZSM-5 Molecular Sieve Molded Sample used in a Fixed Bed

[0099] 100 g of an HZSM-5 zeolite molecular sieve (Nankai Catalyst Factory, Si/Al=15) was placed in a 10 wt % lanthanum nitrate aqueous solution, where the mass ratio (namely solid-liquid ratio) of the HZSM-5 zeolite molecular sieve to the lanthanum nitrate aqueous solution was 1/10. The molecular sieve was impregnated at 90? C. for 4 hours, drained, dried in an air atmosphere at 120? C. for 4 hours, and then calcined in an air atmosphere at 550? C. for 4 hours to obtain a [La]HZSM-5 molecular sieve sample. Then, the sample was subjected to pressing molding, crushed and sieved to obtain molded molecular sieve particles with a particle size of 40-60 mesh, recorded as FX-[La]HZSM-5.

Example 5 Preparation of an Iron-Modified HZSM-5 Molecular Sieve Molded Sample used in a Fixed Bed

[0100] 100 g of an HZSM-5 zeolite molecular sieve (Nankai Catalyst Factory, Si/Al=15) was placed in a 10 wt % ferric nitrate aqueous solution, where the mass ratio (namely solid-liquid ratio) of the HZSM-5 zeolite molecular sieve to the ferric nitrate aqueous solution was 1/10. The molecular sieve was impregnated at 70? C. for 8 hours, drained, dried in an air atmosphere at 120? C. for 4 hours, and then calcined in an air atmosphere at 550? C. for 4 hours to obtain a [Fe]HZSM-5 molecular sieve sample. Then, the sample was subjected to pressing molding, crushed and sieved to obtain molded molecular sieve particles with a particle size of 40-60 mesh, recorded as FX-[Fe]HZSM-5.

Example 6 Preparation of a Chromium-Modified HZSM-5 Molecular Sieve Molded Sample used in a Fixed Bed

[0101] 100 g of an HZSM-5 zeolite molecular sieve (Nankai Catalyst Factory, Si/Al=15) was placed in a 10 wt % chromium nitrate aqueous solution, where the mass ratio (namely solid-liquid ratio) of the HZSM-5 zeolite molecular sieve to the chromium nitrate aqueous solution was 1/10. The molecular sieve was impregnated at 70? C. for 8 hours, drained, dried in an air atmosphere at 120? C. for 4 hours, and then calcined in an air atmosphere at 550? C. for 4 hours to obtain a [Cr]HZSM-5 molecular sieve sample. Then, the sample was subjected to pressing molding, crushed and sieved to obtain molded molecular sieve particles with a particle size of 40-60 mesh, recorded as FX-[Cr]HZSM-5.

Example 7 Preparation of a Zinc-Modified HZSM-5 Molecular Sieve Molded Sample used in a Fluidized Bed

[0102] 100 g of the [Zn]HZSM-5 molecular sieve sample prepared in Example 2 was mixed with an amorphous binder containing aluminum or silicon for spray drying and molding. Specific steps are as follows.

[0103] The [Zn]HZSM-5 molecular sieve sample, pseudo-boehmite, silica sol, xanthan gum (biological gum) and water were uniformly mixed, followed by beating, milling and defoaming to obtain slurry. The slurry includes the following parts by weight of components:

TABLE-US-00002 [Zn]HZSM-5 35 parts by weight, Al.sub.2O.sub.3 20 parts by weight, SiO.sub.2 45 parts by weight, H.sub.2O 240 parts by weight, and xanthan gum 1 part by weight.

[0104] The obtained slurry was subjected to spray drying and molding to obtain a microsphere particle sample with the particle size distribution of 20-100 ?m. Then, the microsphere particle sample was calcined in a Muffle furnace at 550? C. for 3 hours to obtain a [Zn]HZSM-5 molded molecular sieve with an abrasion index of 1.2, recorded as FL-[Zn]HZSM-5.

Example 8 Reaction Evaluation of Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Aromatic Hydrocarbons

[0105] Reaction evaluation of coupling conversion of methanol, naphtha and CO.sub.2 to produce aromatic hydrocarbons was carried out on a micro-fixed bed reactor. Evaluation conditions are as follows. 5 g of the FX-HZSM-5 catalyst prepared in Example 1 was loaded into a fixed bed reactor, and treated with nitrogen at 50 ml/min at 550? C. for 1 hour. Then, methanol, naphtha and CO.sub.2 were co-fed. The raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of the CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 1:3:2, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.33 h.sup.?1, the weight hourly space velocity of the methanol was 0.67 h.sup.?1, and the reaction pressure was 1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 1.

TABLE-US-00003 TABLE 1 Reaction evaluation results of a catalyst in Example 8 Conversion rate of naphtha (wt %) 89.27 Conversion rate of CO.sub.2 (wt %) 33.24 Conversion rate of methanol (wt %) 100.00 Selectivity of aromatic hydrocarbons in hydrocarbon 68.05 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 2.97 Selectivity of PX in xylene products (wt %) 24.79 Composition of hydrocarbon products (wt %) Methane 4.37 Ethylene 3.96 Ethane 8.41 Propylene 2.96 Propane 7.92 C.sub.4 4.33 Benzene 19.51 Toluene 26.88 Ethylbenzene 0.81 P-xylene 2.97 M-xylene 6.19 O-xylene 2.82 C.sub.8+ aromatic hydrocarbons 8.87

Example 9 Reaction Evaluation of Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Aromatic Hydrocarbons

[0106] Reaction evaluation of coupling conversion of methanol, naphtha and CO.sub.2 to produce aromatic hydrocarbons was carried out on a micro-fixed bed reactor. Evaluation conditions are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, and treated with nitrogen at 50 ml/min at 550? C. for 1 hour. Then, methanol, naphtha and CO.sub.2 were co-fed. The raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of the CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 2.

TABLE-US-00004 TABLE 2 Reaction evaluation results of a catalyst in Example 9 Conversion rate of naphtha (wt %) 92.37 Conversion rate of CO.sub.2 (wt %) 38.21 Conversion rate of methanol (wt %) 100.00 Selectivity of aromatic hydrocarbons in hydrocarbon 77.08 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 6.98 Selectivity of PX in xylene products (wt %) 23.99 Composition of hydrocarbon products (wt %) Methane 4.17 Ethylene 2.91 Ethane 6.05 Propylene 2.69 Propane 6.14 C.sub.4 0.96 Benzene 10.87 Toluene 27.51 Ethylbenzene 0.56 P-xylene 6.98 M-xylene 15.88 O-xylene 6.23 C.sub.8+ aromatic hydrocarbons 9.05

Example 10 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0107] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-1.

[0108] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 3.

TABLE-US-00005 TABLE 3 Reaction evaluation results of a catalyst in Example 10 Conversion rate of naphtha (wt %) 92.23 Conversion rate of CO.sub.2 (wt %) 27.29 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 8.50 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 71.95 Selectivity of aromatic hydrocarbons in hydrocarbon 77.17 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 32.53 Selectivity of PX in xylene products (wt %) 95.84 Composition of hydrocarbon products (wt %) Methane 1.89 Ethylene 3.19 Ethane 2.95 Propylene 5.31 Propane 4.07 C.sub.4 5.43 Benzene 7.69 Toluene 30.31 Ethylbenzene 1.38 P-xylene 32.53 M-xylene 0.96 O-xylene 0.45 C.sub.8+ aromatic hydrocarbons 3.84

Example 11 Preparation of a Catalyst used for Coupling Conversion Of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0109] With same operations as that in Example 10, a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared, named as FXNCC-1.

[0110] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. According to Example 10, components containing benzene and toluene in reaction products of the methanol, the naphtha and the CO.sub.2 were prepared into raw materials, and then fed by a micro-feed pump (equivalent to the operations that benzene and toluene were separated from reaction products of the methanol, the naphtha and the CO.sub.2, and then pumped back to a fixed bed reactor by a micro-feed pump). Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 4.

TABLE-US-00006 TABLE 4 Reaction evaluation results of a catalyst in Example 11 Conversion rate of naphtha (wt %) 91.27 Conversion rate of CO.sub.2 (wt %) 24.13 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 10.94 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 63.03 Selectivity of PX in xylene products (wt %) 96.17 Composition of hydrocarbon products (wt %) Methane 2.18 Ethylene 5.21 Ethane 3.08 Propylene 5.73 Propane 3.83 C.sub.4 7.00 Ethylbenzene 2.13 P-xylene 63.03 M-xylene 1.68 O-xylene 0.83 C.sub.8+ aromatic hydrocarbons 5.30

Example 12 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0111] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Ga]HZSM-5 catalyst prepared in Example 3 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-2.

[0112] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 5.

TABLE-US-00007 TABLE 5 Reaction evaluation results of a catalyst in Example 12 Conversion rate of naphtha (wt %) 89.96 Conversion rate of CO.sub.2 (wt %) 24.09 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 8.98 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 72.39 Selectivity of aromatic hydrocarbons in hydrocarbon 77.15 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 34.30 Selectivity of PX in xylene products (wt %) 96.10 Composition of hydrocarbon products (wt %) Methane 1.43 Ethylene 3.89 Ethane 2.83 Propylene 5.09 Propane 3.92 C.sub.4 5.70 Benzene 7.27 Toluene 29.42 Ethylbenzene 1.25 P-xylene 34.30 M-xylene 0.93 O-xylene 0.46 C.sub.8+ aromatic hydrocarbons 3.51

Example 13 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0113] With same operations as that in Example 12, a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared, named as FXNCC-2.

[0114] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. According to Example 12, components containing benzene and toluene in reaction products of the methanol, the naphtha and the CO.sub.2 were prepared into raw materials, and then fed by a micro-feed pump (equivalent to the operations that benzene and toluene were separated from reaction products of the methanol, the naphtha and the CO.sub.2, and then pumped back to a fixed bed reactor by a micro-feed pump). Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 6.

TABLE-US-00008 TABLE 6 Reaction evaluation results of a catalyst in Example 13 Conversion rate of naphtha (wt %) 85.78 Conversion rate of CO.sub.2 (wt %) 22.01 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 13.77 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 60.41 Selectivity of PX in xylene products (wt %) 95.91 Composition of hydrocarbon products (wt %) Methane 1.97 Ethylene 6.63 Ethane 3.15 Propylene 7.16 Propane 3.62 C.sub.4 7.68 Ethylbenzene 1.67 P-xylene 60.41 M-xylene 1.79 O-xylene 0.78 C.sub.8+ aromatic hydrocarbons 5.14

Example 14 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0115] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[La]HZSM-5 catalyst prepared in Example 4 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene, named as FXNCC-3.

[0116] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 7.

TABLE-US-00009 TABLE 7 Reaction evaluation results of a catalyst in Example 14 Conversion rate of naphtha (wt %) 85.07 Conversion rate of CO.sub.2 (wt %) 20.11 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 10.01 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 70.08 Selectivity of aromatic hydrocarbons in hydrocarbon 74.63 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 31.02 Selectivity of PX in xylene products (wt %) 95.88 Composition of hydrocarbon products (wt %) Methane 2.92 Ethylene 4.57 Ethane 3.43 Propylene 5.44 Propane 3.55 C.sub.4 5.45 Benzene 9.33 Toluene 28.40 Ethylbenzene 1.20 P-xylene 31.02 M-xylene 0.89 O-xylene 0.44 C.sub.8+ aromatic hydrocarbons 3.36

Example 15 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0117] With same operations as that in Example 14, a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared, named as FXNCC-3.

[0118] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. According to Example 14, components containing benzene and toluene in reaction products of the methanol, the naphtha and the CO.sub.2 were prepared into raw materials, and then fed by a micro-feed pump (equivalent to the operations that benzene and toluene were separated from reaction products of the methanol, the naphtha and the CO.sub.2, and then pumped back to a fixed bed reactor by a micro-feed pump). Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 8.

TABLE-US-00010 TABLE 8 Reaction evaluation results of a catalyst in Example 15 Conversion rate of naphtha (wt %) 83.16 Conversion rate of CO.sub.2 (wt %) 18.11 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 14.14 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 60.20 Selectivity of PX in xylene products (wt %) 96.11 Composition of hydrocarbon products (wt %) Methane 2.85 Ethylene 6.78 Ethane 2.66 Propylene 7.36 Propane 4.01 C.sub.4 6.72 Ethylbenzene 1.71 P-xylene 60.20 M-xylene 1.62 O-xylene 0.81 C.sub.8+ aromatic hydrocarbons 5.28

Example 16 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0119] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Fe]HZSM-5 catalyst prepared in Example 5 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene, named as FXNCC-4.

[0120] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 9.

TABLE-US-00011 TABLE 9 Reaction evaluation results of a catalyst in Example 16 Conversion rate of naphtha (wt %) 81.29 Conversion rate of CO.sub.2 (wt %) 22.23 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 13.78 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 67.52 Selectivity of aromatic hydrocarbons in hydrocarbon 71.40 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 26.45 Selectivity of PX in xylene products (wt %) 96.37 Composition of hydrocarbon products (wt %) Methane 1.99 Ethylene 5.40 Ethane 2.40 Propylene 8.38 Propane 3.22 C.sub.4 7.21 Benzene 10.53 Toluene 29.54 Ethylbenzene 1.08 P-xylene 26.45 M-xylene 0.70 O-xylene 0.30 C.sub.8+ aromatic hydrocarbons 2.80

Example 17 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0121] With same operations as that in Example 16, a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared, named as FXNCC-4.

[0122] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. According to Example 16, components containing benzene and toluene in reaction products of the methanol, the naphtha and the CO.sub.2 were prepared into raw materials, and then fed by a micro-feed pump (equivalent to the operations that benzene and toluene were separated from reaction products of the methanol, the naphtha and the CO.sub.2, and then pumped back to a fixed bed reactor by a micro-feed pump). Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 10.

TABLE-US-00012 TABLE 10 Reaction evaluation results of a catalyst in Example 17 Conversion rate of naphtha (wt %) 79.13 Conversion rate of CO.sub.2 20.06 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 18.41 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 55.45 Selectivity of PX in xylene products (wt %) 95.84 Composition of hydrocarbon products (wt %) Methane 2.12 Ethylene 7.24 Ethane 2.58 Propylene 11.17 Propane 3.68 C.sub.4 8.55 Ethylbenzene 1.94 P-xylene 55.45 M-xylene 1.58 O-xylene 0.83 C.sub.8+ aromatic hydrocarbons 4.86

Example 18 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0123] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Cr]HZSM-5 catalyst prepared in Example 6 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene, named as FXNCC-5.

[0124] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 11.

TABLE-US-00013 TABLE 11 Reaction evaluation results of a catalyst in Example 18 Conversion rate of naphtha (wt %) 83.78 Conversion rate of CO.sub.2 (wt %) 23.01 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 9.36 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 66.81 Selectivity of aromatic hydrocarbons in hydrocarbon 70.83 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 26.16 Selectivity of PX in xylene products (wt %) 96.26 Composition of hydrocarbon products (wt %) Methane 2.87 Ethylene 3.91 Ethane 4.16 Propylene 5.45 Propane 4.77 C.sub.4 8.02 Benzene 10.41 Toluene 29.21 Ethylbenzene 1.07 P-xylene 26.16 M-xylene 0.70 O-xylene 0.32 C.sub.8+ aromatic hydrocarbons 2.95

Example 19 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0125] With same operations as that in Example 18, a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared, named as FXNCC-5.

[0126] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. According to Example 18, components containing benzene and toluene in reaction products of the methanol, the naphtha and the CO.sub.2 were prepared into raw materials, and then fed by a micro-feed pump (equivalent to the operations that benzene and toluene were separated from reaction products of the methanol, the naphtha and the CO.sub.2, and then pumped back to a fixed bed reactor by a micro-feed pump). Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 12.

TABLE-US-00014 TABLE 12 Reaction evaluation results of a catalyst in Example 19 Conversion rate of naphtha (wt %) 80.08 Conversion rate of CO.sub.2 (wt %) 21.77 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 13.47 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 55.41 Selectivity of PX in xylene products (wt %) 95.52 Composition of hydrocarbon products (wt %) Methane 2.86 Ethylene 5.79 Ethane 4.36 Propylene 7.69 Propane 5.08 C.sub.4 9.78 Ethylbenzene 1.32 P-xylene 55.41 M-xylene 1.68 O-xylene 0.92 C.sub.8+ aromatic hydrocarbons 5.11

Example 20 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0127] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared on-line in a micro-fixed fluidized bed reactor. Conditions for on-line preparation of the catalyst are as follows. 10 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 7 was loaded into a fixed fluidized bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 200 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 75 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene, named as FLNCC-1.

[0128] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 13.

TABLE-US-00015 TABLE 13 Reaction evaluation results of a catalyst in Example 20 Conversion rate of naphtha (wt %) 86.35 Conversion rate of CO.sub.2 (wt %) 23.66 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 6.14 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 68.53 Selectivity of aromatic hydrocarbons in hydrocarbon 73.87 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 30.21 Selectivity of PX in xylene products (wt %) 96.30 Composition of hydrocarbon products (wt %) Methane 2.96 Ethylene 1.03 Ethane 3.89 Propylene 5.12 Propane 5.01 C.sub.4 8.13 Benzene 7.88 Toluene 29.27 Ethylbenzene 1.11 P-xylene 30.21 M-xylene 0.78 O-xylene 0.38 C.sub.8+ aromatic hydrocarbons 4.23

Example 21 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce P-Xylene and Reaction Evaluation

[0129] With same operations as that in Example 20, a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce p-xylene was prepared, named as FLNCC-1.

[0130] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. According to Example 20, components containing benzene and toluene in reaction products of the methanol, the naphtha and the CO.sub.2 were prepared into raw materials, and then fed by a micro-feed pump (equivalent to the operations that benzene and toluene were separated from reaction products of the methanol, the naphtha and the CO.sub.2, and then pumped back to a fixed bed reactor by a micro-feed pump). Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 14.

TABLE-US-00016 TABLE 14 Reaction evaluation results of a catalyst in Example 21 Conversion rate of naphtha (wt %) 83.26 Conversion rate of CO.sub.2 (wt %) 20.95 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 7.86 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 59.94 Selectivity of PX in xylene products (wt %) 96.06 Composition of hydrocarbon products (wt %) Methane 2.16 Ethylene 1.98 Ethane 4.01 Propylene 5.88 Propane 5.71 C.sub.4 10.43 Ethylbenzene 1.34 P-xylene 59.94 M-xylene 1.63 O-xylene 0.83 C.sub.8+ aromatic hydrocarbons 6.09

Comparative Example 1 Preparation of a Catalyst used for Coupling Conversion of Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0131] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-1.

[0132] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. A raw material, naphtha, was fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2 to the naphtha was 0.8:1, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 15.

TABLE-US-00017 TABLE 15 Evaluation of reaction performance of a catalyst in Comparative Example 1 Conversion rate of naphtha (wt %) 80.12 Conversion rate of CO.sub.2 (wt %) 31.13 Selectivity of ethylene and propylene in hydrocarbon 12.61 products (wt %) Selectivity of benzene, toluene and PX in hydrocarbon 69.06 products (wt %) Selectivity of aromatic hydrocarbons in hydrocarbon 73.73 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 12.31 Selectivity of PX in xylene products (wt %) 95.50 Composition of hydrocarbon products (wt %) Methane 2.29 Ethylene 5.4 Ethane 2.93 Propylene 7.21 Propane 3.26 C.sub.4 5.18 Benzene 19.3 Toluene 37.45 Ethylbenzene 1.34 P-xylene 12.31 M-xylene 0.39 O-xylene 0.19 C.sub.8+ aromatic hydrocarbons 2.75

[0133] As can be seen, the content of p-xylene in composition of hydrocarbon products is 12.31% when methanol is not contained in the raw materials, and compared with Example 10, the content of p-xylene is increased to 32.53% due to the addition of methanol. Therefore, the addition of methanol greatly improves the selectivity of p-xylene.

Example 22 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0134] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-1.

[0135] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:1.2, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 1.2 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 16.

TABLE-US-00018 TABLE 16 Reaction evaluation results of a catalyst in Example 22 Conversion rate of naphtha (wt %) 90.19 Conversion rate of CO.sub.2 (wt %) 25.87 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 6.58 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 69.37 Selectivity of aromatic hydrocarbons in hydrocarbon 77.43 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 44.36 Selectivity of PX in xylene products (wt %) 96.04 Composition of hydrocarbon products (wt %) Methane 1.96 Ethylene 2.35 Ethane 3.76 Propylene 4.23 Propane 5.31 C.sub.4 4.96 Benzene 4.32 Toluene 20.69 Ethylbenzene 1.26 P-xylene 44.36 M-xylene 1.18 O-xylene 0.65 C.sub.8+ aromatic hydrocarbons 4.97

[0136] As can be seen, compared with Example 10, the content of p-xylene in composition of hydrocarbon products is increased from 32.53% to 44.36% when the added amount of methanol is increased. The results further indicate that the addition of methanol improves the selectivity of p-xylene.

Example 23 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0137] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 400? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-6.

[0138] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 17.

TABLE-US-00019 TABLE 17 Reaction evaluation results of a catalyst in Example 23 Conversion rate of naphtha (wt %) 90.03 Conversion rate of CO.sub.2 (wt %) 25.21 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 7.76 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 72.28 Selectivity of aromatic hydrocarbons in hydrocarbon 76.27 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 32.44 Selectivity of PX in xylene products (wt %) 96.85 Composition of hydrocarbon products (wt %) Methane 2.11 Ethylene 3.03 Ethane 3.17 Propylene 4.73 Propane 5.15 C.sub.4 5.55 Benzene 8.42 Toluene 30.36 Ethylbenzene 0.98 P-xylene 32.44 M-xylene 0.69 O-xylene 0.37 C.sub.8+ aromatic hydrocarbons 3.00

Example 24 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0139] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.4 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-7.

[0140] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 18.

TABLE-US-00020 TABLE 18 Reaction evaluation results of a catalyst in Example 24 Conversion rate of naphtha (wt %) 81.35 Conversion rate of CO.sub.2 (wt %) 23.65 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 8.08 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 70.43 Selectivity of aromatic hydrocarbons in hydrocarbon 73.66 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 32.69 Selectivity of PX in xylene products (wt %) 98.02 Composition of hydrocarbon products (wt %) Methane 3.79 Ethylene 4.22 Ethane 5.36 Propylene 3.86 Propane 5.51 C.sub.4 3.60 Benzene 7.70 Toluene 29.37 Ethylbenzene 0.61 P-xylene 32.69 M-xylene 0.43 O-xylene 0.23 C.sub.8+ aromatic hydrocarbons 2.63

Example 25 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0141] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.05 h.sup.?1 at normal pressure. After feeding for 240 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-8.

[0142] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 19.

TABLE-US-00021 TABLE 19 Reaction evaluation results of a catalyst in Example 25 Conversion rate of naphtha (wt %) 91.01 Conversion rate of CO.sub.2 (wt %) 26.85 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 8.01 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 71.62 Selectivity of aromatic hydrocarbons in hydrocarbon 76.20 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 33.01 Selectivity of PX in xylene products (wt %) 96.23 Composition of hydrocarbon products (wt %) Methane 2.12 Ethylene 3.50 Ethane 4.50 Propylene 4.51 Propane 5.50 C.sub.4 3.67 Benzene 8.15 Toluene 29.17 Ethylbenzene 0.98 P-xylene 33.01 M-xylene 0.86 O-xylene 0.44 C.sub.8+ aromatic hydrocarbons 3.59

Example 26 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0143] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-1.

[0144] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 0.8:1:0.6, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 0.8 h.sup.?1, the weight hourly space velocity of the methanol was 0.6 h.sup.?1, and the reaction pressure was 3 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 20.

TABLE-US-00022 TABLE 20 Reaction evaluation results of a catalyst in Example 26 Conversion rate of naphtha (wt %) 93.05 Conversion rate of CO.sub.2 (wt %) 30.59 Conversion rate of methanol (wt %) 100 Selectivity of ethylene and propylene in hydrocarbon 1.70 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 74.72 Selectivity of aromatic hydrocarbons in hydrocarbon 81.44 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 30.39 Selectivity of PX in xylene products (wt %) 86.80 Composition of hydrocarbon products (wt %) Methane 3.62 Ethylene 0.69 Ethane 4.49 Propylene 1.01 Propane 5.48 C.sub.4 3.28 Benzene 8.81 Toluene 30.90 Ethylbenzene 1.05 P-xylene 30.39 M-xylene 3.01 O-xylene 1.61 C.sub.8+ aromatic hydrocarbons 5.66

Example 27 Preparation of a Catalyst used for Coupling Conversion of Methanol, Naphtha and CO.SUB.2 .to Produce Benzene, Toluene and P-Xylene and Reaction Evaluation

[0145] A catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene was prepared on-line in a micro-fixed bed reactor. Conditions for on-line preparation of the catalyst are as follows. 5 g of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 was loaded into a fixed bed reactor, treated with nitrogen at 50 ml/min at 550? C. for 1 hour, and then cooled to 300? C. in a nitrogen atmosphere. In the nitrogen atmosphere (controlled by a mass flow meter, 100 ml/min), tetraethyl silicate was pumped into the reactor at a weight hourly space velocity of 0.2 h.sup.?1 at normal pressure. After feeding for 60 minutes, the feeding was stopped. A resulting mixture was purged with nitrogen, heated to 550? C., and then calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst used for coupling conversion of naphtha and CO.sub.2 to produce benzene, toluene and p-xylene, named as FXNCC-1.

[0146] Then, the temperature was adjusted to a reaction temperature of 550? C. in a nitrogen atmosphere. Raw materials, methanol and naphtha, were fed by a micro-feed pump, and the flow of CO.sub.2 was controlled by a mass flow meter. The mass ratio of the raw material CO.sub.2, the naphtha and the methanol was 1.5:1:1.5, the weight hourly space velocity of the naphtha was 1.0 h.sup.?1, the weight hourly space velocity of the CO.sub.2 was 1.5 h.sup.?1, the weight hourly space velocity of the methanol was 1.5 h.sup.?1, and the reaction pressure was 0.1 MPa. Reaction products were analyzed by on-line Agilent7890 gas chromatography, and sampling was carried out for analysis when a reaction was carried out for 30 minutes. Reaction results are shown in Table 21.

TABLE-US-00023 TABLE 21 Reaction evaluation results of a catalyst in Example 27 Conversion rate of naphtha (wt %) 89.21 Conversion rate of CO.sub.2 (wt %) 23.09 Conversion rate of methanol (wt %) 100.00 Selectivity of ethylene and propylene in hydrocarbon 12.29 products (wt %) Selectivity of BTX in hydrocarbon products (wt %) 70.15 Selectivity of aromatic hydrocarbons in hydrocarbon 74.25 products (wt %) Selectivity of PX in hydrocarbon products (wt %) 28.57 Selectivity of PX in xylene products (wt %) 96.07 Composition of hydrocarbon products (wt %) Methane 1.59 Ethylene 5.24 Ethane 2.71 Propylene 7.05 Propane 3.34 C.sub.4 5.83 Benzene 8.42 Toluene 31.99 Ethylbenzene 1.03 P-xylene 28.57 M-xylene 0.76 O-xylene 0.41 C.sub.8+ aromatic hydrocarbons 3.06

[0147] The above descriptions are only several examples of the present application, and are not intended to limit the present application in any way. Although the present application is disclosed above through preferred examples, the examples are not intended to limit the present application. For any skilled person familiar with the art, various changes or modifications made by using the technical contents disclosed above without departing from the scope of technical schemes of the present application are considered as equivalent examples, which fall within the scope of the technical schemes.