In-situ preparation method for catalyst for preparing at least one of toluene, para-xylene and light olefins, and reaction process

Abstract

Disclosed is an in-situ preparation method for a catalyst for Reaction I: methanol and/or dimethyl ether with toluene are used to prepare light olefins and co-produce para-xylene and/or Reaction II: methanol and/or dimethyl ether with benzene are used to prepare at least one of toluene, para-xylene and light olefins, comprising: contacting at least one of a phosphorus reagent, a silylation reagent and water vapor with a molecular sieve in a reactor to prepare, in situ, the catalyst for the Reaction I and/or the Reaction II, wherein the reactor is a reactor of the Reaction I and/or the Reaction II. By directly preparing a catalyst in a reaction system, the entire chemical production process is simplified, the catalyst preparation and transfer steps are saved, and the operation thereof is easy. The catalyst prepared in situ can be directly used for in situ reactions.

Claims

1. A method for carrying out Reaction I, wherein a raw material comprising methanol and/or dimethyl ether and toluene is contacted with a catalyst obtained by an in-situ and on-line preparation method in a reactor to prepare light olefins and co-produce para-xylene; Reaction I is to prepare light olefins from methanol and/or dimethyl ether and toluene and co-produce para-xylene; wherein; a material stream I is contacted with the catalyst in a reaction system to obtain a material stream II, a C.sub.4 olefin or a C.sub.5+ chain hydrocarbon is separated from the material stream II and returned to the reaction system, and light olefins and para-xylene separated from the material stream II are used as products; the material stream I comprises methanol and/or dimethyl ether and toluene; wherein the reaction system comprises: a first reaction zone containing a Catalyst A; and a second reaction zone containing a Catalyst B; and wherein the Catalyst A is a HZSM-5 molecular sieve catalyst modified by a phosphorus reagent and a silylation reagent, the specific preparation steps are as follows: (A1) a mixture of the phosphorus reagent, the silylation reagent and toluene is fed into the first reaction zone with the HZSM-5 molecular sieve at the temperature ranging from 130° C. to 500° C.; and (A2) the temperature is raised to above 500° C., and calcined in an air atmosphere for a period of time ranging from 1 hour to 6 hours to obtain the Catalyst A; and wherein the Catalyst B is a HZSM-5 molecular sieve catalyst modified by a silylation reagent, the specific preparation steps are as follows: (B1) a mixture of the silylation reagent and methanol is fed into the second reaction zone with the HZSM-5 molecular sieve at the temperature ranging from 120° C. to 250° C.; and (B2) the temperature is raised to above 500° C., and calcined in an air atmosphere for a period of time ranging from 1 hour to 6 hours to obtain the Catalyst B.

2. The method of claim 1, wherein the raw material is contacted with the catalyst at a reaction temperature ranging from 350° C. to 650° C.; in the raw material containing methanol and/or dimethyl ether and toluene, the ratio of methanol and/or dimethyl ether to toluene is as follows: the number of carbon atoms of methanol and dimethyl ether: moles of toluene=0.5 to 10.

3. The method of claim 1, wherein the phosphorus reagent is selected from compounds having the following formula (I): ##STR00003## R.sub.1, R.sub.2 and R.sub.3 are independently selected from C.sub.1-10 alkyl and C.sub.1-10 alkoxy, wherein the phosphorus reagent is at least one selected from trimethoxyphosphine, triethoxyphosphine, tripropoxyphosphine, tributoxyphosphine and methyldiethoxyphosphine.

4. The method of claim 3, wherein at least one of R.sub.1, R.sub.2 and R.sub.3 in the formula (I) is selected from C.sub.1-10 alkoxy.

5. The method of claim 3, wherein the phosphorus reagent is at least one selected from trimethoxyphosphine, triethoxyphosphine, tripropoxyphosphine, tributoxyphosphine and methyldiethoxyphosphine.

6. The method of claim 1, wherein the material stream I is contacted with the catalyst in the first reaction zone to obtain a material stream II-A, the material stream II-A is fed to a separation system and the C.sub.4 olefin or the C.sub.5+ chain hydrocarbon, light olefins and para-xylene are separated; the C.sub.4 olefin or the C.sub.5+ chain hydrocarbon separated in the separation system is fed into the second reaction zone to contact the catalyst to obtain a material stream II-B, the material stream II-B is fed into the separation system; and light olefins and para-xylene separated in the separation system are used as products.

7. The method of claim 1, wherein the reaction system comprises one reactor or a plurality of reactors connected by series and/or parallel; the reactor is at least one of a fixed bed reactor, a fluidized bed reactor or a moving bed reactor.

8. The method of claim 1, wherein the first reaction zone comprises one reactor or a plurality of reactors connected by series and/or parallel, and the second reaction zone comprises one reactor or a plurality of reactors connected by series and/or parallel; the total weight space velocity of the raw material is in a range from 0.1 h.sup.−1 to 10 h.sup.−1.

9. The method of claim 8, wherein the total weight space velocity of the raw material is in a range from 0.8 h.sup.−1 to 3 h.sup.−1.

10. The method of claim 8, wherein the molar content of toluene in the raw material is in a range from 5 mol % to 50 mol %.

11. The method of claim 1, wherein the silylation reagent is at least one selected from the compounds having the following formula (II): ##STR00004## R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are independently selected from C.sub.1-10 alkyl and C.sub.1-10 alkoxy.

12. The method of claim 11, wherein at least one of R.sub.4, R.sub.5, R.sub.6 and R.sub.7 in the formula (II) is selected from C.sub.1-10 alkoxy.

13. The method of claim 11, wherein the silylation reagent is at least one selected from tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a process flow diagram of an embodiment of the application of the present application.

(2) FIG. 2 is a process flow diagram of an embodiment of the application of the present application.

(3) FIG. 3 is a process flow diagram of an embodiment of the application of the present application.

(4) FIG. 4 is a process flow diagram of an embodiment of the application of the present application.

(5) FIG. 5 is a process flow diagram of an embodiment of the application of the present application.

(6) FIG. 6 is a process flow diagram of an embodiment of the application of the present application.

DETAILED DESCRIPTION OF THE EMBODIMENT

(7) The present application will be described in detail below with reference to the embodiments, but the application is not limited to these embodiments.

(8) Unless otherwise specified, the raw materials and reagents used in this application are all commercially available and used without treatment. The equipment used is based on the manufacturer's recommended scheme and parameters.

(9) In the examples, the wear index of the catalyst was measured on an MS-C type wear indexer of Shenyang Hexing Machinery & Electronics Co., Ltd.

(10) In the examples, the fixed bed reactor has an inner diameter of 1.5 cm; the fixed fluidized bed reactor has an inner diameter of 3 cm; and the circulating fluidized bed reactor has an inner diameter of 12 cm.

Example 1: Preparation of HZSM-5 Formed Molecular Sieve Sample For Fixed Bed

(11) 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si/Al=30) was calcined in an air atmosphere at 550° C. for 4 hours, then tableted and crushed, and sieved to obtain formed molecular sieve particles with particle size of 40 to 60 mesh, recorded as FXHZSM-5-A.

(12) 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si/Al=5) was calcined in an air atmosphere at 550° C. for 4 hours, then tableted and crushed, and sieved to obtain formed molecular sieve particles with particle size of 40 to 60 mesh, recorded as FXHZSM-5-B.

(13) 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si/Al=10) was calcined in an air atmosphere at 550° C. for 4 hours, then tableted and crushed, and sieved to obtain formed molecular sieve particles with particle size of 40 to 60 mesh, recorded as FXHZSM-5-C.

Example 2: Preparation of HZSM-11 Formed Molecular Sieve Sample for Fixed Bed

(14) 100 g of HZSM-11 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si/Al=35) was calcined in an air atmosphere at 550° C. for 4 hours, then tableted and crushed, and sieved to obtain formed molecular sieve particles with particle size of 40 to 60 mesh, recorded as FXHZSM-11-A.

(15) 100 g of HZSM-11 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si/Al=12) was calcined in an air atmosphere at 550° C. for 4 hours, then tableted and crushed, and sieved to obtain formed molecular sieve particles with particle size of 40 to 60 mesh, recorded as FXHZSM-11-B.

Example 3: Preparation of HZSM-5 Formed Molecular Sieve Sample for Fluidized Bed

(16) 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si/Al=30) was spray-dried with aluminum- or silicon-containing amorphous binder. The specific steps were as follows:

(17) HZSM-5 zeolite molecular sieve raw powder, pseudo-boehmite, silica sol, xanthan gum (bio-gel) and water were uniformly mixed, and the slurry was obtained by beating, grinding and defoaming; the parts by weight of each component in the slurry was:

(18) TABLE-US-00001 HZSM-5 40 parts by weight Al.sub.2O.sub.3 20 parts by weight SiO.sub.2 40 parts by weight H.sub.2O 240 parts by weight Xanthan gum 1 part by weight

(19) The obtained slurry was spray-dried to obtain a sample of microsphere particles having a particle size distribution of 20 to 100 jam; and the sample of the microsphere particles was calcined at 550° C. for 3 hours in a muffle furnace to obtain a HZSM-5 formed molecular sieve having a wear index of 1.2, recorded as FLHZSM-5-A.

Example 4: Preparation of HZSM-5 Formed Molecular Sieve Sample for Fluidized Bed

(20) The specific preparation conditions and steps were the same as those in Example 3, except that the raw material HZSM-5 zeolite molecular sieve raw powder is used in an amount of 10 kg, and the obtained microsphere particle sample has a particle size distribution of 20 to 120 m and a wear index of 1.2, recorded as FLHZSM-5-B.

(21) The specific preparation conditions and steps were the same as those in Example 3, except that the raw material HZSM-5 zeolite molecular sieve raw powder has a silicon-aluminum ratio Si/Al=10, and the obtained microsphere particle sample has a particle size distribution of 20 to 100 m and a wear index of 1.2, recorded as FLHZSM-5-C.

Example 5: Preparation and Reaction Evaluation of Catalyst FXCAT-1 for Fixed Bed

(22) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(23) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-1. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 1.

(24) TABLE-US-00002 TABLE 1 Catalyst FXCAT-1 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 36.09 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.64 Product Distribution (wt %) Chain Hydrocarbon 77.74 Benzene 0.06 Ethylbenzene 0.25 Para-xylene 19.26 M-xylene 0.04 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.61 Distribution of chain hydrocarbon products (wt %) CH.sub.4 1.26 C.sub.2H.sub.4 39.84 C.sub.2H.sub.6 0.1 C.sub.3H.sub.6 35.32 C.sub.3H.sub.8 0.89 C.sub.4 11.99 C.sub.5 5.06 C.sub.6+ 5.53 C.sub.2H.sub.4 + C.sub.3H.sub.6 75.16

Example 6: Preparation and Reaction Evaluation of Catalyst FXCAT-2 for Fixed Bed

(25) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(26) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=10:40:50. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 45 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-2. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 2.

(27) TABLE-US-00003 TABLE 2 Catalyst FXCAT-2 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (% ) 36.68 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.64 Product Distribution (wt %) Chain Hydrocarbon 77.59 Benzene 0.08 Ethylbenzene 0.29 Para-xylene 19.18 M-xylene 0.04 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.79 Distribution of chain hydrocarbon products (wt %) CH.sub.4 1.23 C.sub.2H.sub.4 39.76 C.sub.2H.sub.6 0.13 C.sub.3H.sub.6 35.25 C.sub.3H.sub.8 0.96 C.sub.4 12.06 C.sub.5 5.11 C.sub.6+ 5.5 C.sub.2H.sub.4 + C.sub.3H.sub.6 75.01

Example 7: Preparation and Reaction Evaluation of Catalyst FXCAT-3 for Fixed Bed

(28) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(29) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=2:8:90. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 225 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-3. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 3.

(30) TABLE-US-00004 TABLE 3 Catalyst FXCAT-3 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 35.59 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.69 Product Distribution (wt %) Chain Hydrocarbon 77.9 Benzene 0.06 Ethylbenzene 0.21 Para-xylene 19.19 M-xylene 0.03 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.58 Distribution of chain hydrocarbon products (wt %) CH.sub.4 1.31 C.sub.2H.sub.4 39.91 C.sub.2H.sub.6 0.09 C.sub.3H.sub.6 35.46 C.sub.3H.sub.8 0.83 C.sub.4 11.91 C.sub.5 5.01 C.sub.6+ 5.48 C.sub.2H.sub.4 + C.sub.3H.sub.6 75.37

Example 8: Preparation and Reaction Evaluation of Catalyst FXCAT-4 for Fixed Bed

(31) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(32) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-4. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 4.

(33) TABLE-US-00005 TABLE 4 Catalyst FXCAT-4 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 35.20 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.90 Product Distribution (wt %) Chain Hydrocarbon 77.58 Benzene 0.09 Ethylbenzene 0.35 Para-xylene 20.33 M-xylene 0.01 O-xylene 0.01 C.sub.9+ Aromatic Hydrocarbon 1.63 Distribution of chain hydrocarbon products (wt %) CH.sub.4 1.11 C.sub.2H.sub.4 41.57 C.sub.2H.sub.6 0.1 C.sub.3H.sub.6 36.98 C.sub.3H.sub.8 1.18 C.sub.4 12.21 C.sub.5 3.43 C.sub.6+ 3.42 C.sub.2H.sub.4 + C.sub.3H.sub.6 78.55

Example 9: Preparation and Reaction Evaluation of Catalyst FXCAT-5 for Fixed Bed

(34) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(35) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 450° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-5. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 5.

(36) TABLE-US-00006 TABLE 5 Catalyst FXCAT-5 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 C onversi on Rate of Toluene (%) 35.80 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.63 Product Distribution (wt %) Chain Hydrocarbon 75.29 Benzene 0.07 Ethylbenzene 0.35 Para-xylene 21.32 M-xylene 0.05 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.89 Distribution of Chain Hydrocarbon Products (wt %) CH.sub.4 1.08 C.sub.2H.sub.4 40.96 C.sub.2H.sub.6 0.11 C.sub.3H.sub.6 36.49 C.sub.3H.sub.8 1.41 C.sub.4 12.65 C.sub.5 3.76 C.sub.6+ 3.54 C.sub.2H.sub.4 + C.sub.3H.sub.6 77.45

Example 10: Preparation and Reaction Evaluation of Catalyst FXCAT-6 for Fixed Bed

(37) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(38) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 150° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-6. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 6.

(39) TABLE-US-00007 TABLE 6 Catalyst FXCAT-6 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 34.79 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.95 Product Distribution (wt %) Chain Hydrocarbon 78.37 Benzene 0.08 Ethylbenzene 0.21 Para-xylene 19.98 M-xylene 0 O-xylene 0.01 C.sub.9+ Aromatic Hydrocarbon 1.35 Distribution of Chain Hydrocarbon Products (wt %) CH.sub.4 0.96 C.sub.2H.sub.4 41.03 C.sub.2H.sub.6 0.11 C.sub.3H.sub.6 37.96 C.sub.3H.sub.8 1.03 C.sub.4 11.01 C.sub.5 4.08 C.sub.6+ 3.82 C.sub.2H.sub.4 + C.sub.3H.sub.6 78.99

Example 11: Preparation and Reaction Evaluation of Catalyst FXCAT-7 for Fixed Bed

(40) The reaction performance of on-line preparing fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene in a fixed bed microreactor was evaluated.

(41) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-11-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-7. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60

(42) TABLE-US-00008 TABLE 7 Catalyst FXCAT-7 Reaction Temperature (° C.) 450 C onversi on Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 33.58 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.90 Product Distribution (wt %) Chain Hydrocarbon 77.79 Benzene 0.07 Ethylbenzene 0.28 Para-xylene 19.88 M-xylene 0.01 O-xylene 0.01 C.sub.9+ Aromatic Hydrocarbon 1.96 Distribution of chain hydrocarbon products (wt %) CH.sub.4 0.85 C.sub.2H.sub.4 40.51 C.sub.2H.sub.6 0.11 C.sub.3H.sub.6 37.79 C.sub.3H.sub.8 0.83 C.sub.4 10.57 C.sub.5 4.53 C.sub.6+ 4.81 C.sub.2H.sub.4 + C.sub.3H.sub.6 78.30

Example 12: Preparation and Reaction Evaluation of Catalyst FLCAT-1 for Fluidized Bed

(43) The reaction performance of on-line preparing fluidized bed catalyst for preparing para-xylene from methanol and toluene and co-producing light olefins in a fixed fluidized bed reactor was evaluated.

(44) The conditions for preparing the catalyst on-line were as follows: 10 g of the formed molecular sieve sample FLHZSM-5-A prepared in Example 3 was loaded into the fixed fluidized bed reactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fluidized bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FLCAT-1. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 60 min. The reaction results were shown in Table 8.

(45) TABLE-US-00009 TABLE 8 Catalyst FLCAT-1 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 31.33 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.61 Product Distribution (wt %) Chain Hydrocarbon 76.56 Benzene 0.09 Ethylbenzene 0.31 Para-xylene 20.25 M-xylene 0.05 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.71 Distribution of chain hydrocarbon products (wt %) CH.sub.4 1.37 C.sub.2H.sub.4 40.78 C.sub.2H.sub.6 0.12 C.sub.3H.sub.6 35.72 C.sub.3H.sub.8 1.5 C.sub.4 11.94 C.sub.5 4.52 C.sub.6+ 4.05 C.sub.2H.sub.4 + C.sub.3H.sub.6 76.50

Example 13: Preparation and Reaction Evaluation of Catalyst FXCAT-8 for Fixed Bed

(46) A fixed bed microreactor was used to produce light olefins and co-produce para-xylene using methanol and toluene as the raw material.

(47) The conditions for preparing the catalyst in-situ were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed microreactor, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-8. Then, the temperature was lowered to a reaction temperature of 450° C. under a nitrogen atmosphere, and the reaction of preparing light olefins and co-producing para-xylene from methanol and toluene was carried out. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 9.

(48) TABLE-US-00010 TABLE 9 Catalyst FXCAT-8 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 35.20 Selectivity of (C.sub.2H.sub.4 + C.sub.3H.sub.6) in Chain Hydrocarbon 73.55 Products (wt %) Selectivity of Para-xylene in Xylene Isomers 99.71 (wt %) Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.84 C.sub.2H.sub.4 30.09 C.sub.2H.sub.6 0.08 C.sub.3H.sub.6 25.84 C.sub.3H.sub.8 0.90 C.sub.4 olefin 9.25 C.sub.4 alkane 1.55 C.sub.5+ Chain Hydrocarbon 7.49 Benzene 0.09 Ethylbenzene 0.35 Para-xylene 20.33 M-xylene 0.04 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 3.14

Example 14: Preparation and Reaction of Catalyst FXCAT-9 for Fixed Bed

(49) According to one embodiment of the present application, as shown in FIG. 1, material stream I comprises methanol and toluene, and methanol and toluene were used as the raw material to prepare light olefins and co-produce para-xylene.

(50) The reaction system was charged with 5 g (40 to 60 mesh) of the formed molecular sieve sample FXHZSM-5-A prepared in Example 1, which was first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-9.

(51) The material stream I was fed to the reaction system and contacted with the catalyst FXCAT-9 and reacted. The material stream II containing the product deviated from the reaction system, and entered into the separation system. The light olefins (ethylene and propylene), C.sub.4 olefins, para-xylene and other components were separated. Among them, C.sub.4 olefins were returned to the reaction system, and light olefins (ethylene and propylene) and para-xylene were used as products. Other components were used as by-products.

(52) The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the material stream I=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, and the reaction temperature was 450° C., at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, as shown in Table 10.

(53) TABLE-US-00011 TABLE 10 Catalyst FXCAT-9 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 37.01 Selectivity of (C.sub.2H.sub.4 + C.sub.3H.sub.6) in Chain Hydrocarbon 82.19 Products (wt %) Selectivity of Para-xylene in Xylene Isomers (wt %) 99.62 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.99 C.sub.2H.sub.4 31.87 C.sub.2H.sub.6 0.19 C.sub.3H.sub.6 27.54 C.sub.3H.sub.8 1.87 C.sub.4 alkane 1.62 C.sub.5+ Chain Hydrocarbon 8.2 Benzene 0.58 Ethylbenzene 0.46 Para-xylene 23.1 M-xylene 0.05 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 3.5

Example 15: Preparation and Reaction of Catalyst FXCAT-10 for Fixed Bed

(54) According to one embodiment of the present application, as shown in FIG. 2, the material stream I comprises dimethyl ether and toluene, and dimethyl ether and toluene were used as the raw material to prepare light olefins and co-produce para-xylene.

(55) The difference from Example 14 was the separation system, and the rest was the same as in Example 14. The fixed bed catalyst was named FXCAT-10. C.sub.1˜3 chain hydrocarbons, C.sub.4 olefins, C.sub.4 alkanes, C.sub.5+ chain hydrocarbons and aromatic hydrocarbons was separated from the separation system of this Example. C.sub.4 olefins were returned to the reaction system. Ethylene and propylene as light olefins products were separated from C.sub.1˜3 chain hydrocarbons. Para-xylene as a product was separated from the aromatic hydrocarbons. Other components were used as by-products. The reaction results were consistent with Example 14 (the deviation was not more than ±1%).

Example 16: Preparation and Reaction of Catalyst FXCAT-11 for Fixed Bed and Catalyst FLCAT-12 for Fluidized Bed

(56) According to one embodiment of the present application, according to the process flow diagram shown in FIG. 3, the material stream I comprises methanol and toluene, and methanol and toluene were used as the raw material to prepare light olefins and co-produce para-xylene.

(57) The first reaction zone contained 10 fixed beds in parallel, and the second reaction zone was a fluidized bed.

(58) 50 g (40 to 60 mesh) of the formed molecular sieve sample FXHZSM-5-A prepared in Example 1 was loaded into 10 fixed beds in the first reaction zone, and each fixed bed was filled with 5 g, and each fixed bed was firstly treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-11.

(59) 50 g (40 to 60 mesh) of the formed molecular sieve sample FLHZSM-5-B prepared in Example 4 was loaded into the fluidized bed in the second reaction zone, first treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of tetraethyl silicate and methanol was fed with a micro feed pump, vaporized and then fed into the fluidized bed of the second reaction zone, tetraethyl silicate:methanol (weight ratio)=40:60. The total weight space velocity of tetraethyl silicate and methanol was 2 h.sup.−1, at atmospheric pressure. After feeding for 3 hours, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FLCAT-12.

(60) The first reaction zone was subjected to a conversion reaction of methanol and an alkylation reaction of toluene with methanol, under the following conditions: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, and the reaction temperature was 450° C., at atmospheric pressure. The material stream I was fed to the fixed bed of the first reaction zone and contacted with catalyst FXCAT-11 to obtain the material stream II-A, the material stream II-A deviated from the first reaction zone and entered the separation system. Ethylene, propylene, C.sub.4 olefins and para-xylene were separated from the separation system. C.sub.4 olefins separated from the separation system was fed into the fluidized bed of the second reaction zone to be contacted with the catalyst FXCAT-12, and the second reaction zone is subjected to the shape-selective aromatization reaction for the fluidized bed at a reaction temperature of 450° C. The material stream II-B was obtained in the second reaction zone, and the material stream II-B deviated from the second reaction zone and entered the separation system. Ethylene and propylene separated from the separation system were used as light olefins products and para-xylene was used as the product. Other components were used as by-products.

(61) The hydrocarbon product of the second reaction zone was analyzed by on-line Agilent 7890 gas chromatography as shown in Table 11; the product distribution after deducting the component of C.sub.4 olefins was shown in Table 12. The mixed hydrocarbon products from first reaction zone and the second reaction zone were analyzed by on-line Agilent 7890 gas chromatography, and the product distribution after deducting the component of C.sub.4 olefins was shown in Table 13.

(62) TABLE-US-00012 TABLE 11 Conversion Rate of C.sub.4 olefin (%) 83.25 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.56 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.74 C.sub.2H.sub.4 0.60 C.sub.2H.sub.6 1.02 C.sub.3H.sub.6 0.26 C.sub.3H.sub.8 9.55 C.sub.4 olefin 16.76 C.sub.4 alkane 0.04 C.sub.5+ 0.23 Benzene 4.94 Toluene 35.74 Ethylbenzene 0.90 Para-xylene 27.07 M-xylene 0.07 O-xylene 0.05 C.sub.9+ Aromatic Hydrocarbon 2.03

(63) TABLE-US-00013 TABLE 12 Conversion Rate of C.sub.4 olefin (%) 83.25 Selectivity of Para-xylene in Xylene Isomers (wt %) 99.56 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.89 C.sub.2H.sub.4 0.72 C.sub.2H.sub.6 1.22 C.sub.3H.sub.6 0.31 C.sub.3H.sub.8 11.47 C.sub.4 alkane 0.05 C.sub.5+ Chain Hydrocarbon 0.28 Benzene 5.93 Toluene 42.94 Ethylbenzene 1.08 Para-xylene 32.52 M-xylene 0.08 O-xylene 0.06 C.sub.9+ Aromatic Hydrocarbon 2.44

(64) TABLE-US-00014 TABLE 13 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 38.08 Selectivity of (C.sub.2H.sub.4 + C.sub.3H.sub.6) in Chain Hydrocarbon 82.44 Products (wt %) Selectivity of Para-xylene in Xylene Isomers 99.69 (wt %) Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.94 C.sub.2H.sub.4 31.68 C.sub.2H.sub.6 0.19 C.sub.3H.sub.6 27.18 C.sub.3H.sub.8 1.85 C.sub.4 alkane 1.64 C.sub.5+ Chain Hydrocarbon 7.90 Benzene 0.58 Ethylbenzene 0.46 Para-xylene 24.00 M-xylene 0.05 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 3.50

Example 17: Preparation and Reaction of Catalyst FXCAT-13 and Catalyst FLCAT-14

(65) According to one embodiment of the present application, as shown in FIG. 4, the material stream I comprises dimethyl ether, methanol and toluene, and dimethyl ether, methanol and toluene were used as the raw material to prepare light olefins and co-produce para-xylene.

(66) The difference from Example 16 was that the first reaction zone contained one fixed bed filled with 50 g of molecular sieve sample FXHZSM-5-A. The difference was also the separation system. C.sub.1˜3 chain hydrocarbons, C.sub.4 olefins, C.sub.4 alkanes, C.sub.5+ chain hydrocarbons and aromatic hydrocarbons were separated from the separation system of this Example. C.sub.4 olefins were returned to the second reaction zone. Ethylene and propylene as light olefins products were separated from C.sub.1˜3 chain hydrocarbons. Para-xylene as a product was separated from the aromatic hydrocarbons. Other components were used as by-products. The rest was the same as in Example 23, and the fixed bed catalyst was designated as FXCAT-13, and the fluidized bed catalyst was designated as FLCAT-14. The reaction results were consistent with that of Example 16 (the deviation was not more than ±1%).

Example 18: Preparation and Reaction of Catalyst FXCAT-15 for Fixed Bed

(67) According to one embodiment of the present application, as per the process flow diagram shown in FIG. 5, methanol and toluene were used as the raw material to prepare light olefins and co-produce para-xylene. The material stream I comprises methanol and toluene.

(68) The reaction system was two fixed beds. As shown in FIG. 5, parts of the reaction system were arranged in series above and below. Using a staged feed, the material stream I was fed from the upper fixed bed and the recirculated C.sub.5+ chain hydrocarbons entered the lower fixed bed.

(69) 10 g (40 to 60 mesh) of the formed molecular sieve sample FXHZSM-5-A prepared in Example 1 was separately loaded into two fixed beds, and the two fixed bed loadings were the same, both being 5 g. The preparation process of catalyst was as follows: each fixed bed was firstly treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to prepare a fixed bed catalyst in-situ for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-15.

(70) The material stream I entered the fixed bed reactor in the upper part of the reaction system, contacted with the catalyst FXCAT-15, and was subjected to a conversion reaction of methanol and a shape-selective alkylation reaction of toluene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, and the reaction temperature was 450° C., at atmospheric pressure.

(71) The material stream II containing product deviated from the reaction system and entered the separation system to separate C.sub.1˜4 chain hydrocarbons, C.sub.5+ chain hydrocarbons and aromatic hydrocarbons. Among them, the C.sub.5+ chain hydrocarbons were returned to the fixed bed in the lower part of the reaction system, and was contacted with the catalyst FXCAT-15 to carry out a reaction such as pyrolysis and shape-selective aromatization, and the reaction temperature of the fixed bed in the lower part of the reaction system was 630° C. Ethylene and propylene as light olefins products were separated from C.sub.1˜4 chain hydrocarbons. Para-xylene as a product was separated from the aromatic hydrocarbon. Other components were used as by-products.

(72) The product was analyzed by on-line Agilent 7890 gas chromatography as shown in Table 14.

(73) TABLE-US-00015 TABLE 14 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 36.55 Selectivity of (C.sub.2H.sub.4 + C.sub.3H.sub.6) in Chain 80.83 Hydrocarbon Products Selectivity of Para-xylene in Xylene 99.70 Isomers (wt %) Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.11 C.sub.2H.sub.4 33.02 C.sub.2H.sub.6 0.31 C.sub.3H.sub.6 27.25 C.sub.3H.sub.8 1.17 C.sub.4 11.7 Benzene 0.65 Ethylbenzene 0.39 Para-xylene 21.05 M-xylene 0.04 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 3.29

Example 19: Preparation and Reaction of Catalyst FXCAT-16 for Fixed Bed

(74) According to one embodiment of the present application, according to the process flow diagram shown in FIG. 6, methanol and toluene were used as the raw material to prepare light olefins and co-produce para-xylene. The material stream I comprises methanol and toluene.

(75) The first reaction zone contained one fixed bed, and the second reaction zone contained one fixed bed.

(76) 5 g (40 to 60 mesh) of the formed molecular sieve sample FXHZSM-5-A prepared in Example 1 was separately loaded into a fixed bed of the first reaction zone and a fixed bed of the second reaction zone. The preparation process of the catalyst was the same: the catalyst in each fixed bed was treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine, tetraethyl silicate and toluene was fed with a micro feed pump, trimethoxyphosphine:tetraethyl silicate:toluene (weight ratio)=5:20:75. The total weight space velocity of trimethoxyphosphine, tetraethyl silicate and toluene was 1 h.sup.−1, at atmospheric pressure. After feeding for 90 minutes, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. According to the above process, the fixed bed catalyst for preparing light olefins from methanol and toluene and co-producing para-xylene, was in-situ prepared in the first fixed bed reaction zone and the second fixed bed reaction zone, respectively, and recorded as FXCAT-16.

(77) The material stream I entered the fixed bed of the first reaction zone and contacted with the catalyst FXCAT-16, and was subjected to a conversion reaction of methanol and a shape-selective alkylation reaction of toluene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Methanol: toluene (molar ratio) in the raw material=10:1, the total weight space velocity of methanol and toluene was 2 h.sup.−1, and the reaction temperature was 450° C., at atmospheric pressure. The material stream II-A containing product deviated from the fixed bed of the first reaction zone and entered the separation system to separate C.sub.1˜4 chain hydrocarbons, C.sub.5+ chain hydrocarbons and aromatic hydrocarbons from the separation system.

(78) The C.sub.5+ chain hydrocarbons separated from the separation system were returned to the fixed bed of the second reaction zone, and were contacted with the catalyst FXCAT-16 to carry out a reaction such as pyrolysis and shape-selective aromatization, and the reaction temperature of the fixed bed of the second reaction zone was 630° C. The material stream II-B containing the product exited the fixed bed of the second reaction zone and entered the separation system. Ethylene and propylene, as light olefins products, from the separation system, were separated from C.sub.1˜4 chain hydrocarbons. Para-xylene as a product was separated from the aromatic hydrocarbon. Other components were used as by-products.

(79) The hydrocarbon product of the second reaction zone was analyzed by on-line Agilent 7890 gas chromatography as shown in Table 15; the product distribution after deducting the component of C.sub.5+ chain hydrocarbons was shown in Table 16. The mixed hydrocarbon products from first reaction zone and the second reaction zone were analyzed by on-line Agilent 7890 gas chromatography, and the product distribution after deducting the component of C.sub.5+ chain hydrocarbons was shown in Table 17.

(80) TABLE-US-00016 TABLE 15 Conversion Rate of C.sub.5+ Chain Hydrocarbon (%) 93.92 Selectivity of Para-xylene in Xylene Isomers 99.70 (wt %) Distribution of Hydrocarbon Products (wt %) CH.sub.4 4.32 C.sub.2H.sub.4 20.83 C.sub.2H.sub.6 3.02 C.sub.3H.sub.6 23.37 C.sub.3H.sub.8 3.45 C.sub.4 8.51 C.sub.5+ 6.08 Benzene 7.46 Toluene 11.07 Ethylbenzene 0.52 Para-xylene 9.96 M-xylene 0.03 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 1.36

(81) TABLE-US-00017 TABLE 16 Conversion Rate of C.sub.5+ Chain Hydrocarbon (%) 93.92 Selectivity of Para-xylene in Xylene Isomers 99.70 (wt %) Distribution of Hydrocarbon Products (wt %) CH.sub.4 4.60 C.sub.2H.sub.4 22.18 C.sub.2H.sub.6 3.22 C.sub.3H.sub.6 24.88 C.sub.3H.sub.8 3.67 C.sub.4 9.06 Benzene 7.94 Toluene 11.79 Ethylbenzene 0.55 Para-xylene 10.60 M-xylene 0.03 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 1.45

(82) TABLE-US-00018 TABLE 17 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 37.11 Selectivity of (C.sub.2H.sub.4 + C.sub.3H.sub.6) in Chain 80.81 Hydrocarbon Products Selectivity of Para-xylene in Xylene 99.70 Isomers (wt %) Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.18 C.sub.2H.sub.4 32.06 C.sub.2H.sub.6 0.31 C.sub.3H.sub.6 27.95 C.sub.3H.sub.8 1.17 C.sub.4 11.59 Benzene 0.65 Ethylbenzene 0.39 Para-xylene 21.35 M-xylene 0.04 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 3.29

Example 20: Preparation and Reaction of Catalyst FXCAT-17 for Fluidized Bed

(83) According to one embodiment of the present application, the flowchart was the same as that of Example 19, as shown in FIG. 6. The difference was in the raw materials and reactors.

(84) The material stream I in this Example comprises dimethyl ether, methanol and toluene, and dimethyl ether, methanol and toluene were used as the raw material to prepare light olefins and co-produce para-xylene.

(85) In the Example, the first reaction zone was one fluidized bed packed with 1 kg of the molecular sieve sample FLHZSM-5-C in Example 4. The second reaction zone was one fluidized bed packed with 1 kg of the same molecular sieve sample FLHZSM-5-C in Example 4. The preparation process of catalyst was as follows: the catalyst in each fluidized bed reactor was treated with 50 mL/min of nitrogen at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. The rest was the same as in Example 19, and the fixed bed catalyst was designated as FLCAT-17. The reaction results were consistent with Example 19 (the deviation was not more than ±1%).

Example 21: Preparation and Reaction Evaluation of Catalyst FXCAT-18 for Fixed Bed

(86) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(87) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-18. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 18.

(88) TABLE-US-00019 TABLE 18 Catalyst FXCAT-18 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 35.93 Selectivity of Para-xylene in Xylene 99.63 Products (wt %) Selectivity of Para-xylene in C.sub.8 91.06 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 94.16 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.72 Toluene 53.09 Ethylbenzene 2.57 Para-xylene 27.21 M-xylene 0.06 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.31

Example 22: Preparation and Reaction Evaluation of Catalyst FXCAT-19 for Fixed Bed

(89) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(90) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 2 hours, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-19. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 19.

(91) TABLE-US-00020 TABLE 19 Catalyst FXCAT-19 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 35.43 Selectivity of Para-xylene in Xylene Products (wt %) 99.78 Selectivity of Para-xylene in C.sub.8 Aromatic Products 91.33 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 94.37 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.81 Toluene 53.32 Ethylbenzene 2.51 Para-xylene 27.07 M-xylene 0.04 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 2.23

Example 23: Preparation and Reaction Evaluation of Catalyst FXCAT-20 for Fixed Bed

(92) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(93) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.4 h.sup.−1, at atmospheric pressure. After feeding for 0.5 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-20. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 20.

(94) TABLE-US-00021 TABLE 20 Catalyst FXCAT-20 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 36.37 Selectivity of Para-xylene in Xylene Products (wt %) 99.67 Selectivity of Para-xylene in C.sub.8 Aromatic Products 90.95 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 93.99 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.61 Toluene 52.92 Ethylbenzene 2.63 Para-xylene 27.34 M-xylene 0.05 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.41

Example 24: Preparation and Reaction Evaluation of Catalyst FXCAT-21 for Fixed Bed

(95) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(96) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-21. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump.

(97) Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 21.

(98) TABLE-US-00022 TABLE 21 Catalyst FXCAT-21 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.37 Selectivity of Para-xylene in Xylene Products (wt %) 99.70 Selectivity of Para-xylene in C.sub.8 Aromatic Products 90.48 (wt %) Selectivity of (Toluene +Para-xylene) in Aromatic 93.09 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 13.62 Toluene 53.41 Ethylbenzene 2.76 Para-xylene 26.99 M-xylene 0.04 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 3.13

Example 25: Preparation and Reaction Evaluation of Catalyst FXCAT-22 for Fixed Bed

(99) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(100) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 450° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-22. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 22.

(101) TABLE-US-00023 TABLE 22 Catalyst FXCAT-22 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 36.71 Selectivity of Para-xylene in Xylene Products (wt %) 99.63 Selectivity of Para-xylene in C.sub.8 Aromatic Products 90.28 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 92.88 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 13.33 Toluene 53.65 Ethylbenzene 2.79 Para-xylene 26.85 M-xylene 0.06 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 3.28

Example 26: Preparation and Reaction Evaluation of Catalyst FXCAT-23 for Fixed Bed

(102) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(103) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 800° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 2 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-23. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 23.

(104) TABLE-US-00024 TABLE 23 Catalyst FXCAT-23 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rat eof Benzene (%) 33.26 Selectivity of Para-xylene in Xylene Products (wt %) 99.65 Selectivity of Para-xylene in C.sub.8 Aromatic Products 91.19 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 93.68 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.57 Toluene 54.35 Ethylbenzene 2.39 Para-xylene 25.68 M-xylene 0.05 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.92

Example 27: Preparation and Reaction Evaluation of Catalyst FXCAT-24 for Fixed Bed

(105) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(106) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 600° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 8 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-24. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump.

(107) Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 24.

(108) TABLE-US-00025 TABLE 24 Catalyst FXCAT-24 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 36.97 Selectivity of Para-xylene in Xylene Products (wt %) 99.70 Selectivity of Para-xylene in C.sub.8 Aromatic Products 91.48 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 93.42 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.07 Toluene 53.96 Ethylbenzene 2.37 Para-xylene 26.31 M-xylene 0.05 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 3.20

Example 28: Preparation and Reaction Evaluation of Catalyst FXCAT-25 for Fixed Bed

(109) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(110) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-11-B was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-25. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was anal zed at 120 min. The

(111) TABLE-US-00026 TABLE 25 Catalyst FXCAT-25 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.56 Selectivity of Para-xylene in Xylene Products (wt %) 99.82 Selectivity of Para-xylene in C.sub.8 Aromatic Products 91.40 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 94.39 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 15.31 Toluene 52.72 Ethylbenzene 2.51 Para-xylene 27.22 M-xylene 0.03 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 2.19

Example 29: Preparation and Reaction Evaluation of Catalyst FXCAT-26 for Fixed Bed

(112) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(113) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 150° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-26. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 26.

(114) TABLE-US-00027 TABLE 26 Catalyst FXCAT-26 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.87 Selectivity of Para-xylene in Xylene Products (wt %) 99.89 Selectivity of Para-xylene in C.sub.8 Aromatic Products 91.38 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 94.44 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 15.11 Toluene 52.91 Ethylbenzene 2.54 Para-xylene 27.26 M-xylene 0.02 O-xylene 0.01 C.sub.9+ Aromatic Hydrocarbon 2.15

Example 30: Preparation and Reaction Evaluation of Catalyst FLCAT-27 for Fluidized Bed

(115) A fluidized bed catalyst for preparing p-toluene and co-producing para-xylene from benzene and methanol by alkylation was prepared on-line in a fixed bed reactor.

(116) The conditions for preparing the catalyst on-line were as follows: 10 g of the formed molecular sieve sample FLHZSM-5-C was loaded into the fixed fluidized bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FLCAT-27. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 27.

(117) TABLE-US-00028 TABLE 27 Catalyst FLCAT-27 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 32.71 Selectivity of Para-xylene in Xylene Products (wt %) 99.66 Selectivity of Para-xylene in C.sub.8 Aromatic Products 90.79 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 94.03 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 17.41 Toluene 51.05 Ethylbenzene 2.61 Para-xylene 26.61 M-xylene 0.05 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.23

Example 31: Preparation and Reaction Evaluation of Catalyst FXCAT-28 for Fixed Bed

(118) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene in a fixed bed microreactor was evaluated.

(119) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-C was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.2 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene by alkylation from methanol and/or dimethyl ether and benzene, which was named FXCAT-28. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene by alkylation from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 28.

(120) TABLE-US-00029 TABLE 28 Catalyst FXCAT-28 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 38.01 Selectivity of Para-xylene in Xylene Products (wt %) 93.60 Selectivity of Para-xylene in C.sub.8 Aromatic Products 80.64 (wt %) Selectivity of (Toluene + Para-xylene) in Aromatic 82.91 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.06 Toluene 44.92 Ethylbenzene 4.52 Para-xylene 26.33 M-xylene 0.99 O-xylene 0.81 C.sub.9+ Aromatic Hydrocarbon 8.37

Example 32: Preparation and Reaction Evaluation of Catalyst FXCAT-29 for Fixed Bed

(121) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(122) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-29. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 29.

(123) TABLE-US-00030 TABLE 29 Catalyst FXCAT-29 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.51 Selectivity of Para-xylene in Xylene 99.74 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.31 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.20 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 16.81 Toluene 52.17 Ethylbenzene 1.56 Para-xylene 27.03 M-xylene 0.04 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.36 Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.03 C.sub.2H.sub.4 39.66 C.sub.2H.sub.6 0.12 C.sub.3H.sub.6 31.63 C.sub.3H.sub.8 1.92 C.sub.4 13.43 C.sub.5 7.07 C.sub.6+ 5.13 C.sub.2H.sub.4+ C.sub.3H.sub.6 71.29

Example 33: Preparation and Reaction Evaluation of Catalyst FXCAT-30 for Fixed Bed

(124) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(125) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=4. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1.5 hours, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-30. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 30.

(126) TABLE-US-00031 TABLE 30 Catalyst FXCAT-30 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 36.01 Selectivity of Para-xylene in Xylene 99.66 Products (wt %) Selectivity of Para-xylene in C.sub.8 93.24 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 94.58 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 16.57 Toluene 52.31 Ethylbenzene 1.84 Para-xylene 26.60 M-xylene 0.05 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.59 Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.12 C.sub.2H.sub.4 37.13 C.sub.2H.sub.6 0.16 C.sub.3H.sub.6 33.02 C.sub.3H.sub.8 2.17 C.sub.4 14.52 C.sub.5 7.14 C.sub.6+ 4.74 C.sub.2H.sub.4+ C.sub.3H.sub.6 70.15

Example 34: Preparation and Reaction Evaluation of Catalyst FXCAT-31 for Fixed Bed

(127) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(128) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=1. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1.5 hours, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-31. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 31.

(129) TABLE-US-00032 TABLE 31 Catalyst FXCAT-31 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 33.68 Selectivity of Para-xylene in Xylene 99.71 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.72 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.35 in Aromatic (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 17.64 Toluene 51.46 Ethylbenzene 1.43 Para-xylene 27.07 M-xylene 0.04 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.32 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.91 C.sub.2H.sub.4 38.18 C.sub.2H.sub.6 0.11 C.sub.3H.sub.6 34 C.sub.3H.sub.8 1.75 C.sub.4 12.97 C.sub.5 6.82 C.sub.6+ 5.26 C.sub.2H.sub.4+ C.sub.3H.sub.6 72.18

Example 35: Preparation and Reaction Evaluation of Catalyst FXCAT-32 for Fixed Bed

(130) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(131) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 250° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-32. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 32.

(132) TABLE-US-00033 TABLE 32 Catalyst FXCAT-32 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.32 Selectivity of Para-xylene in Xylene 99.82 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.60 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.39 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 17.15 Toluene 52.05 Ethylbenzene 1.49 Para-xylene 26.98 M-xylene 0.03 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 2.28 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.97 C.sub.2H.sub.4 37.92 C.sub.2H.sub.6 0.1 C.sub.3H.sub.6 33.95 C.sub.3H.sub.8 1.83 C.sub.4 13.07 C.sub.5 6.93 C.sub.6+ 5.23 C.sub.2H.sub.4+ C.sub.3H.sub.6 71.87

Example 36: Preparation and Reaction Evaluation of Catalyst FXCAT-33 for Fixed Bed

(133) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(134) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 300° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-33. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 33.

(135) TABLE-US-00034 TABLE 33 Catalyst FXCAT-33 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.95 Selectivity of Para-xylene in Xylene 99.63 Products (wt %) Selectivity of Para-xylene in C.sub.8 93.09 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 94.18 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 16.39 Toluene 51.94 Ethylbenzene 1.89 Para-xylene 26.80 M-xylene 0.06 O-xylene 0.04 C.sub.9+ Aromatic Hydrocarbon 2.88 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.95 C.sub.2H.sub.4 36.92 C.sub.2H.sub.6 0.18 C.sub.3H.sub.6 33.39 C.sub.3H.sub.8 2.22 C.sub.4 13.57 C.sub.5 6.95 C.sub.6+ 5.82 C.sub.2H.sub.4+ C.sub.3H.sub.6 70.31

Example 37: Preparation and Reaction Evaluation of Catalyst FXCAT-34 for Fixed Bed

(136) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(137) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 800° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 2 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-34. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 34.

(138) TABLE-US-00035 TABLE 34 Catalyst FXCAT-34 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 32.17 Selectivity of Para-xylene in Xylene 99.88 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.69 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.50 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 18.23 Toluene 52.05 Ethylbenzene 1.43 Para-xylene 26.04 M-xylene 0.02 O-xylene 0.01 C.sub.9+ Aromatic Hydrocarbon 2.22 Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.09 C.sub.2H.sub.4 39.52 C.sub.2H.sub.6 0.11 C.sub.3H.sub.6 32.09 C.sub.3H.sub.8 1.83 C.sub.4 13.19 C.sub.5 6.95 C.sub.6+ 5.22 C.sub.2H.sub.4+ C.sub.3H.sub.6 71.61

Example 38: Preparation and Reaction Evaluation of Catalyst FXCAT-35 for Fixed Bed

(139) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(140) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 600° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 8 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-35. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 35.

(141) TABLE-US-00036 TABLE 35 Catalyst FXCAT-35 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 35.59 Selectivity of Para-xylene in Xylene 99.74 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.23 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.07 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 16.15 Toluene 52.94 Ethylbenzene 1.57 Para-xylene 26.78 M-xylene 0.04 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.49 Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.01 C.sub.2H.sub.4 39.25 C.sub.2H.sub.6 0.13 C.sub.3H.sub.6 31.55 C.sub.3H.sub.8 1.93 C.sub.4 13.51 C.sub.5 7.27 C.sub.6+ 5.35 C.sub.2H.sub.4+ C.sub.3H.sub.6 70.80

Example 39: Preparation and Reaction Evaluation of Catalyst FXCAT-36 for Fixed Bed

(142) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(143) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-11-A catalyst was tableted and crushed into 40-60 mesh, 5 g of (40 to 60 mesh) catalyst was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-36. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 36.

(144) TABLE-US-00037 TABLE 36 Catalyst FXCAT-36 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 34.17 Selectivity of Para-xylene in Xylene 99.85 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.49 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.46 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 18.13 Toluene 51.89 Ethylbenzene 1.49 Para-xylene 26.26 M-xylene 0.03 O-xylene 0.01 C.sub.9+ Aromatic Hydrocarbon 2.19 Distribution of Hydrocarbon Products (wt %) CH.sub.4 0.91 C.sub.2H.sub.4 38.61 C.sub.2H.sub.6 0.09 C.sub.3H.sub.6 34.07 C.sub.3H.sub.8 1.6 C.sub.4 12.23 C.sub.5 6.85 C.sub.6+ 5.64 C.sub.2H.sub.4+ C.sub.3H.sub.6 72.68

Example 40: Preparation and Reaction Evaluation of Catalyst FXCAT-37 for Fixed Bed

(145) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(146) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-37. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 37.

(147) TABLE-US-00038 TABLE 37 Catalyst FXCAT-37 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 33.86 Selectivity of Para-xylene in Xylene 99.85 Products (wt %) Selectivity of Para-xylene in C.sub.8 94.59 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 95.51 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 18.67 Toluene 51.46 Ethylbenzene 1.46 Para-xylene 26.22 M-xylene 0.02 O-xylene 0.02 C.sub.9+ Aromatic Hydrocarbon 2.15 Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.05 C.sub.2H.sub.4 37.59 C.sub.2H.sub.6 0.1 C.sub.3H.sub.6 34.03 C.sub.3H.sub.8 1.69 C.sub.4 13.02 C.sub.5 6.77 C.sub.6+ 5.75 C.sub.2H.sub.4+ C.sub.3H.sub.6 71.62

Example 41: Preparation and Reaction Evaluation of Catalyst FLCAT-38 for Fluidized Bed

(148) A fluidized bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol was prepared on-line in a fixed bed reactor.

(149) The conditions for preparing the catalyst on-line were as follows: 10 g of the formed molecular sieve sample FLHZSM-5-A was loaded into the fixed fluidized bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and the temperature was raised to 550° C. and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fluidized bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FLCAT-38. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from methanol and/or dimethyl ether and benzene by alkylation. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 38.

(150) TABLE-US-00039 TABLE 38 Catalyst FLCAT-38 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 30.18 Selectivity of Para-xylene in Xylene 99.70 Products (wt %) Selectivity of Para-xylene in C.sub.8 93.30 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 94.56 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 17.43 Toluene 51.48 Ethylbenzene 1.83 Para-xylene 26.60 M-xylene 0.05 O-xylene 0.03 C.sub.9+ Aromatic Hydrocarbon 2.58 Distribution of Hydrocarbon Products (wt %) CH.sub.4 1.01 C.sub.2H.sub.4 36.73 C.sub.2H.sub.6 0.11 C.sub.3H.sub.6 34.09 C.sub.3H.sub.8 1.93 C.sub.4 13.55 C.sub.5 7.20 C.sub.6+ 5.38 C.sub.2H.sub.4+ C.sub.3H.sub.6 70.82

Example 42: Preparation and Reaction Evaluation of Catalyst FXCAT-39 for Fixed Bed

(151) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(152) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethyl silicate was fed with a micro feed pump, tetraethyl silicate:trimethoxyphosphine (mass ratio)=2. The total weight space velocity of trimethoxyphosphine and tetraethyl silicate was 0.1 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-39. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 39.

(153) TABLE-US-00040 TABLE 39 Catalyst FXCAT-39 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 37.97 Selectivity of Para-xylene in Xylene 95.28 Products (wt %) Selectivity of Para-xylene in C.sub.8 83.25 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 88.45 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 15.91 Toluene 48.53 Ethylbenzene 3.92 Para-xylene 25.85 M-xylene 0.71 O-xylene 0.57 C.sub.9+ Aromatic Hydrocarbon 4.51 Distribution of Chain Hydrocarbon Products (wt %) CH.sub.4 0.98 C.sub.2H.sub.4 33.21 C.sub.2H.sub.6 0.23 C.sub.3H.sub.6 31.15 C.sub.3H.sub.8 2.62 C.sub.4 16.99 C.sub.5 8.94 C.sub.6+ 5.88 C.sub.2H.sub.4+ C.sub.3H.sub.6 64.36

Example 43: Preparation and Reaction Evaluation of Catalyst FXCAT-40 for Fixed Bed

(154) The reaction performance of on-line preparing fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol in a fixed bed microreactor was evaluated.

(155) The conditions for preparing the catalyst on-line were as follows: 5 g of (40 to 60 mesh) formed molecular sieve sample FXHZSM-5-A was loaded into the fixed bed reactor, first treated with 50 mL/min of air at 550° C. for 1 hour, and then cooled to 200° C. under a nitrogen atmosphere. Tetraethyl silicate was fed with a micro feed pump. The weight space velocity of tetraethyl silicate was 0.067 h.sup.−1, at atmospheric pressure. After feeding for 1 hour, the feed was stopped, and after nitrogen purge, the temperature was raised to 550° C., and calcined in an air atmosphere for 4 hours. The temperature was raised to 700° C. under a nitrogen atmosphere, and the water was fed with a micro feed pump, at a water weight space velocity of 2 h.sup.−1 and atmospheric pressure. After feeding for 4 hours, the feed was stopped to obtain a fixed bed catalyst for preparing toluene and co-producing para-xylene and light olefins from benzene and methanol, which was named FXCAT-40. Then, the reaction temperature was cooled to 450° C. under a nitrogen atmosphere to test the reaction of preparing toluene and co-producing para-xylene and light olefins from benzene and methanol. The reaction conditions were as follows: the raw materials were fed with a micro feed pump. Benzene:methanol (molar ratio) in the raw material=1:1, the total weight space velocity of benzene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the sample was analyzed at 120 min. The reaction results were shown in Table 40.

(156) TABLE-US-00041 TABLE 40 Catalyst FXCAT-40 Reaction Temperature (° C.) 450 Conversion Rate of Methanol (%) 100 Conversion Rate of Toluene (%) 35.93 Selectivity of Para-xylene in Xylene 99.49 Products (wt %) Selectivity of Para-xylene in C.sub.8 90.93 Aromatic Products (wt %) Selectivity of (Toluene + Para-xylene) 94.11 in Aromatic Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 14.72 Toluene 53.09 Ethylbenzene 2.57 Para-xylene 27.17 M-xylene 0.09 O-xylene 0.05 C.sub.9+ Aromatic Hydrocarbon 2.31 Distribution of Chain Hydrocarbon Products (wt %) CH.sub.4 1.31 C.sub.2H.sub.4 11.73 C.sub.2H.sub.6 0.98 C.sub.3H.sub.6 20.65 C.sub.3H.sub.8 11.31 C.sub.4 29.13 C.sub.5 14.86 C.sub.6+ 10.03 C.sub.2H.sub.4+ C.sub.3H.sub.6 32.38

Example 44: Preparation and Reaction Evaluation of Catalyst FXCAT-41 for Fixed Bed

(157) The apparatus, operation and conditions were the same as those in Example 5 except that the trimethoxyphosphine was replaced with methyldiethoxyphosphine, during the preparation of the catalyst, and the others were unchanged to prepare the fixed bed catalyst for preparing light olefins and co-producing para-xylene from methanol and toluene, which was named FXCAT-41. The reaction evaluation conditions were the same as in Example 5, the reaction results were consistent with Example 5 (the deviation was not more than ±1%).

Example 45: Preparation and Reaction Evaluation of Catalyst FLCAT-42 for Fluidized Bed

(158) The reaction performance of on-line preparing fluidized bed catalyst for preparing para-xylene from toluene and methanol by alkylation in a fixed fluidized bed reactor was evaluated.

(159) The conditions for preparing the catalyst on-line were as follows: 1 kg of the formed molecular sieve sample FLHZSM-5-B was loaded into the fixed fluidized bed reactor at the reactor temperature of 300° C., the content of tetraethyl silicate in a mixture of tetraethyl silicate, toluene and methanol was 10% by weight, and toluene:methanol (molar ratio)=2:1, and the total weight space velocity of a mixture of tetraethyl silicate, toluene and methanol was 2 h.sup.−1. After feeding for 10 hours, the feed was stopped to obtain the catalyst for preparing para-xylene from toluene and methanol by alkylation, which was named FLCAT-42.

(160) After preparing FLCAT-42 on-line, it was switched to toluene and methanol alkylation reaction. The reaction conditions were as follows: at the reaction temperature of 450° C., toluene:methanol (molar ratio) in the raw material=2:1, the total weight space velocity of toluene and methanol was 2 h.sup.−1, at atmospheric pressure. The reaction product was analyzed by on-line Agilent 7890 gas chromatography. The reaction results were shown in Table 41.

(161) TABLE-US-00042 TABLE 41 Catalyst FLCAT-42 Reaction Temperature (° C.) 450 Feeding Time (min) 120 Conversion Rate of Methanol (%) 100 Conversion Rate of Benzene (%) 27.15 Selectivity of Para-xylene in Xylene 95.08 Products (wt %) Distribution of Products (wt %) C.sub.1-C.sub.6+ Chain Hydrocarbon 17.22 Benzene 0.51 Ethylbenzene 0.18 Para-xylene 73.85 M-xylene 2.03 O-xylene 1.79 C.sub.9+ Aromatic Hydrocarbon 4.42

(162) The above description is only a few embodiments of the present application, and is not intended to limit the application in any way. While the present application has been described above with reference to preferred embodiments, but these embodiments are not intended to limit the present application. Without departing from the spirit of the present application, one skilled in the art will be able to make several possible variations and modifications and thus the protection scope shall be determined by the scope as defined in the claims.