A method for preparing aromatic hydrocarbons

Abstract

The present application discloses a method for preparing aromatic hydrocarbons, the method comprising contacting a raw gas containing methyl halide and carbon monoxide with a solid acid catalyst to react and obtain aromatic hydrocarbons; the solid acid catalyst comprises an acidic zeolite molecular sieve. The method of the present application adds carbon monoxide during the conversion of methyl halide, which can significantly improve the selectivity of aromatic hydrocarbons (especially BTX); accordingly, the method has low production and separation energy consumption, and therefore has broad application prospects.

Description

Technical Field

[0001] The invention belongs to the field of multiphase catalytic conversion, and specifically relates to a method for preparing aromatic hydrocarbons, in which methyl halide and carbon monoxide are used to prepare aromatic hydrocarbons through a catalyst loaded with an acidic zeolite molecular sieve. Background Art

[0002] The continuous growth of energy demand and the urgent desire to improve environmental quality have made global energy development face unprecedented challenges. "Efficient conversion and clean utilization" of energy is an inevitable choice in the process of energy development. Methane is the main component of natural gas, shale gas, and combustible ice. As an important component of energy consumption, the efficient conversion of methane continues to attract the attention of researchers. The spatial structure of methane molecules is a regular tetrahedron with Td four-fold symmetry; the average bond energy of its four CH bonds is 414kJ / mol, and the dissociation energy of the first CH bond is as high as 435kJ / mol, which leads to extremely high chemical stability of methane and is difficult to activate. However, it is thermodynamically favorable for methane to be further converted into chemicals through methyl halides. Taking the conversion of monochloromethane as an example, at normal pressure and 400°C, the ΔH and ΔG of monochloromethane to produce ethylene are 36.368KJ / mol and -54.571KJ / mol, respectively. Therefore, the preparation of high value-added compounds from methane through methyl halides has attracted the attention of researchers.

[0003] Aromatics, especially benzene, toluene and xylene (collectively referred to as BTX), are important organic chemical raw materials second only to ethylene and propylene in terms of output and scale. Their derivatives are widely used in fuel, petrochemical, chemical fiber, plastic, rubber and other chemical products and fine chemicals. At present, aromatics are mainly produced from petroleum as raw materials, of which 70% of BTX aromatics in the world come from the catalytic reforming process unit of refineries. Catalytic reforming technology uses naphtha as raw material and adopts semi-regenerative and continuous regenerative reforming process types. Catalytic reforming generally uses platinum-containing catalysts. Typical catalytic reforming process representatives are UOP's CCRplatformer process and IFP's Aromizer process. In addition, the production process of aromatics in the petroleum route also includes gasoline hydrogenation technology, aromatics extraction technology, heavy aromatics lightening technology and light hydrocarbon aromatization technology. With the continuous development of society, the demand for aromatics in the world is growing. However, the increasingly tight petroleum resources have caused the price of aromatics, especially BTX, to remain high. In view of China's energy resource endowment, it is of great significance to develop new aromatics production routes.

[0004] The conversion of methyl halides to produce high value-added aromatics, especially BTX, is an important research direction. The prior art has disclosed the preparation of aromatics from methyl halides under the catalytic action of molecular sieve catalysts. However, the selectivity of aromatics prepared by this method is very low and it is difficult to meet the requirements of industrialization. How to prepare aromatics, especially BTX, with high selectivity remains a difficult problem in this field. Summary of the invention

[0005] In order to solve the above technical problems, the inventors of the present application provide a method for preparing aromatic hydrocarbons, which can directly generate aromatic hydrocarbons on a catalyst containing a zeolite molecular sieve based on methyl halides as raw materials. The methyl halides in the present method come from methane, and methane is the main component of natural gas, shale gas, and combustible ice. The methyl halides are reacted to generate aromatic hydrocarbons under the conditions of a zeolite molecular sieve catalyst, which overcomes the shortcomings of harsh methane conversion conditions and low product selectivity. The method for producing aromatic hydrocarbons provided by the present application is in the gas-solid phase and uses non-precious metals as catalysts. The process is simple, the catalyst is easy to obtain and low in price, and has important industrial application prospects.

[0006] The catalyst used in this method does not contain precious metals, and no iodine-containing compounds are added; the reaction system is a gas-solid phase reaction, the process is simple, and it has broad application prospects.

[0007] According to one aspect of the present application, a method for preparing aromatic hydrocarbons is provided, characterized in that the method comprises contacting a raw gas containing methyl halide and carbon monoxide with a solid acid catalyst to react to obtain aromatic hydrocarbons; the solid acid catalyst comprises an acidic zeolite molecular sieve.

[0008] Optionally, the methyl halide is monohalomethane, dihalomethane or a mixture thereof.

[0009] Optionally, the methyl halide is at least one of methyl chloride, methyl bromide and methyl iodide.

[0010] Optionally, the methyl chloride includes methyl chloride and dichloromethane.

[0011] Optionally, the methyl bromide includes monobromomethane and dibromomethane.

[0012] Optionally, the iodomethane includes monoiodomethane and diiodomethane.

[0013] Optionally, the mass content of the acidic zeolite molecular sieve in the solid acid catalyst is 50-100%.

[0014] Optionally, the acidic zeolite molecular sieve is a hydrogen-type zeolite molecular sieve.

[0015] Optionally, the solid acid catalyst further comprises a matrix, and the matrix comprises at least one of aluminum oxide, silicon oxide, kaolin and magnesium oxide.

[0016] A person skilled in the art can prepare the acidic zeolite molecular sieve according to any suitable method in the prior art, and the present application does not limit the preparation method. The following is a preferred preparation method of the acidic zeolite molecular sieve: place the Na-type zeolite molecular sieve in a 0.5-1 mol / L NH4NO3 aqueous solution, perform ion exchange at room temperature to 90°C for 0.5-10 hours, wash with deionized water, repeat the above steps 1-3 times, dry at 80-150°C, and calcine at 500-600°C to obtain the acidic zeolite molecular sieve.

[0017] A person skilled in the art can prepare a solid acid catalyst containing a matrix according to any suitable method in the prior art, and the present application does not limit the preparation method thereof. The following is a preferred preparation method for preparing a solid acid catalyst containing a matrix: an acidic zeolite molecular sieve, a matrix, and sesbania powder are mixed in a certain proportion, nitric acid with a concentration of 10% is added and kneaded, and the solid acid catalyst containing the matrix is ​​obtained by extrusion molding and calcination at 500-600°C.

[0018] Optionally, the acidic zeolite molecular sieve comprises at least one channel defined by a 10-membered ring.

[0019] Optionally, the acidic zeolite molecular sieve is selected from at least one of an acidic zeolite molecular sieve having an AEL structure, an acidic zeolite molecular sieve having an FER structure, an acidic zeolite molecular sieve having an MEL structure, an acidic zeolite molecular sieve having an MFI structure, an acidic zeolite molecular sieve having an MWW structure, an acidic zeolite molecular sieve having an MTT structure, an acidic zeolite molecular sieve having an NES structure, and an acidic zeolite molecular sieve having a TON structure.

[0020] Optionally, the silicon-aluminum atomic ratio of the acidic zeolite molecular sieve is 0.5-200.

[0021] Optionally, the silicon-aluminum atomic ratio of the acidic zeolite molecular sieve is 0.5-150.

[0022] Optionally, the silicon-aluminum atomic ratio of the acidic zeolite molecular sieve is 0.5-120.

[0023] Optionally, the acidic zeolite molecular sieve is selected from one or more of SAPO-11, ZSM-35, ZSM-11, SSZ-46, ZSM-5, MCM-22, ITQ-2, ZSM-23, SSZ-32, NU-87, ZSM-22 and NU-10 molecular sieves.

[0024] Optionally, the reaction conditions are: reaction temperature is 300-550°C; reaction pressure is 0.1-25MPa; the mass space velocity of the methyl halide is 0.01-20.0h -1 ; The molar ratio of carbon monoxide to methyl halide is 0.05:1 to 100:1.

[0025] Optionally, the reaction temperature is 350-500°C.

[0026] Optionally, the reaction temperature is selected from any value of 300°C, 350°C, 400°C, 450°C, 550°C, or a range determined by any two values.

[0027] Optionally, the reaction pressure is 0.2-20 MPa.

[0028] Optionally, the reaction pressure is 2.0-15 MPa.

[0029] Optionally, the reaction pressure is selected from any value of 0.2 MPa, 1 MPa, 2 MPa, 3 MPa, 5 MPa, 8 MPa, 12 MPa, 15 MPa, 20 MPa, 25 MPa, or a range determined by any two values.

[0030] Optionally, the mass space velocity of the methyl halide is 0.02 to 6 h -1 .

[0031] Optionally, the mass space velocity of the methyl halide is 0.05 to 3.0 h -1 .

[0032] Optionally, the mass space velocity of the methyl halide is selected from 0.01h -1 、0.02h -1 , 0.05h -1 , 0.1h -1 、0.3h -1 , 0.5h -1 , 1h -1 , 1.5h -1 , 2h -1 , 3h -1 , 4h -1 , 6h -1 , 20h -1 Any value in , or a range of values ​​determined by any two values.

[0033] Optionally, the molar ratio of carbon monoxide to methyl halide is 2:1 to 90:1.

[0034] Optionally, the molar ratio of carbon monoxide to methyl halide is selected from any value of 0.05:1, 1:1, 2:1, 6:1, 10:1, 20:1, 40:1, 50:1, 60:1, 80:1, 90:1, 100:1, or a range determined by any two values.

[0035] Optionally, the raw gas further comprises gas I; the gas I is selected from at least one of hydrogen, nitrogen, helium and argon.

[0036] Optionally, the volume content of carbon monoxide in the raw gas consisting of the gas I and carbon monoxide is 50% to 100%.

[0037] Optionally, the raw gas consists of methyl halide and a gas II containing carbon monoxide; the gas II also includes at least one of hydrogen, nitrogen, helium, argon, and carbon dioxide; the volume content of the carbon monoxide in the gas II is 50-100%.

[0038] Optionally, the volume content of carbon monoxide in the gas II is selected from any value of 50%, 80%, 95%, 97.4%, 100%, or a range determined by any two values.

[0039] Optionally, the reaction is carried out in a reactor, and the reactor includes at least one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.

[0040] In the present application, the coupled conversion of CO and methyl halides to produce aromatics refers to the reaction of CO as a reaction raw material with methyl halides to produce aromatics.

[0041] The beneficial effects of this application include:

[0042] 1) The present application provides a method for producing aromatics. The addition of carbon monoxide during the conversion of methyl halides can significantly improve the selectivity of aromatics (especially BTX). Accordingly, the method has low production and separation energy consumption, and therefore has broad application prospects.

[0043] 2) Using the method of the present application, the method for producing aromatics provided by the present application adopts a method that, compared with the existing method, the catalyst does not contain metal additives, and the catalyst can be repeatedly regenerated after deactivation without a significant decrease in activity. The catalyst production cost is low, the processing steps are few, and the three wastes are less discharged. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is the XRD pattern of some hydrogen-type molecular sieve samples prepared in Example 1. DETAILED DESCRIPTION

[0045] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0046] The endpoints and any values ​​of the range disclosed in this application are not limited to the precise range or value, and these ranges or values ​​should be understood to include close to these ranges or values. For numerical ranges, the endpoint values ​​and individual point values ​​of each range can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0047] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0048] Unless otherwise specified, the raw materials in the examples of the present application are purchased from commercial sources or prepared by known methods. The zeolite molecular sieve raw powder in the examples was purchased from the Catalyst Factory of Nankai University.

[0049] Unless otherwise specified, the analysis methods in the examples all adopt conventional settings and conventional analysis methods of instruments or equipment.

[0050] The analysis method in the examples of this application is as follows:

[0051] In the examples, the conversion of methyl halide is calculated by the internal standard method, and the selectivity of the product is calculated by the normalization method:

[0052] Methyl halide conversion rate = [(mole number of carbon halides in the feed gas) - (mole number of carbon halides in the product)] ÷ (mole number of carbon halides in the feed gas) × (100%)

[0053] Product selectivity = product carbon mole number ÷ total carbon mole of product organic matter × 100%

[0054] Source of molecular sieve raw materials: some of the molecular sieve raw materials used in the experiment were directly purchased from commercial sources, and some were synthesized according to literature. The specific sources and the nomenclature of the molecular sieve carriers are shown in Table 1.

[0055] The phase of the sample was analyzed by a PANalytical X'Pert PRO X-ray diffractometer from the Netherlands. Sample analysis conditions: Cu, Kα radiation Graphite monochromator, Ni filter, tube voltage 40kV, tube current 40mA, scanning speed 5° / min, scanning range 5-60°.

[0056] Table 1 Sources and silicon-aluminum ratios of different catalysts

[0057]

[0058] Example 1 Catalyst Preparation

[0059] Preparation of acidic zeolite molecular sieves

[0060] The Na-type molecular sieve in Table 1 was subjected to NH4NO3 ion exchange, drying and calcination to obtain the hydrogen-type molecular sieve.

[0061] Preparation of HZSM-5: NaZSM-5 molecular sieve powder was added to a pre-prepared 1 mol / L NH4NO3 aqueous solution with a solid-liquid mass ratio of 1:10. The mixture was exchanged at 80°C for 2 hours under stirring, and then vacuum filtered and washed with water. After three consecutive exchange reactions, the mixture was dried at 120°C overnight and calcined at 550°C for 4 hours to obtain the desired catalyst sample HZSM-5.

[0062] The steps for preparing the other Na-type molecular sieves in Table 1 into acidic zeolite molecular sieves are the same as the reaction conditions and steps for preparing HZSM-5 molecular sieves from NaZSM-5 molecular sieves, and only the corresponding molecular sieve raw materials need to be changed. The XRD spectra of HZSM-5, HZSM-35, HMCM-22, and HZSM-22 show that the prepared hydrogen-type samples all maintain typical characteristic peaks, indicating that the topological structure of the molecular sieve is not destroyed during the preparation process.

[0063] For the sake of brevity, the present application omits the XRD spectra of other hydrogen-type molecular sieves, whose topological structures are consistent with the topological structures of the corresponding Na-type molecular sieves.

[0064] Preparation of samples containing matrix

[0065] The matrix-containing shaped hydrogen-type samples were prepared by extrusion molding.

[0066] This embodiment uses HZSM-5 (Si / Al=73) sample as a representative to prepare hydrogen-type samples containing a matrix. The preparation methods of the samples containing a matrix of other hydrogen-type molecular sieves in Table 1 are similar to the preparation methods of the HZSM-5 (Si / Al=73) sample, which will not be repeated here.

[0067] Preparation of HZSM-5 molecular sieve containing alumina matrix: 50g raw material sample HZSM-5 and 50g alumina were fully mixed, 10%wt nitric acid was added and kneaded, and the sample kneaded into a mass was extruded into strips by an extruder. The extruded sample was dried at 120°C and calcined at 550°C for 4h to obtain an acidic zeolite molecular sieve containing a matrix, and the sample was labeled HZ5-AO5.

[0068] Preparation of HZSM-5 molecular sieve containing kaolin matrix: 80g HZSM-5 was mixed with 20g kaolin. 5-15%wt nitric acid was added and kneaded, and the sample kneaded into a mass was extruded into strips by an extruder. The extruded sample was dried at 120°C and calcined at 550°C for 4h to obtain an acidic zeolite molecular sieve containing a matrix, and the sample was labeled HZ8-K2.

[0069] Preparation of HZSM-5 molecular sieve containing magnesium oxide matrix: 80g HZSM-5 is mixed with 20g magnesium oxide. 5-15%wt nitric acid is added and kneaded, and the sample kneaded into a mass is extruded into strips by an extruder. The extruded sample is dried at 120°C and calcined at 550°C for 4h to obtain an acidic zeolite molecular sieve containing a matrix, and the sample is labeled as HZ8-MO2.

[0070] Preparation of HZSM-5 molecular sieve containing a mixed matrix of silica, alumina and magnesia: 80g HZSM-5 was mixed with 20g of a mixture containing silica, alumina and magnesia. The mass ratio of silica: alumina: magnesia was 2:2:1. 5-15%wt nitric acid was added and kneaded, and the sample kneaded into a mass was extruded into strips by an extruder. The extruded sample was dried at 120°C and calcined at 550°C for 4h to obtain an acidic zeolite molecular sieve containing a matrix, and the sample was labeled HZ8-SAM2.

[0071] For the preparation of other acidic zeolite molecular sieves containing matrix samples, they can be prepared according to the above method according to actual needs. The typical samples prepared are shown in Table 2.

[0072] Table 2 Sample number and sample composition

[0073]

[0074]

[0075] Example 2 Preparation of Aromatics from Methyl Chloride over Different Catalysts

[0076] 1g of each solid acid catalyst in Table 2 was loaded into a fixed bed reactor with an inner diameter of 10mm and a quartz tube liner (quartz tube inner diameter 6mm), and the temperature was raised to 550°C at 5°C / min under a nitrogen atmosphere, maintained for 4 hours, and then lowered to a reaction temperature of 400°C under a nitrogen atmosphere, and the pressure of the reaction system was raised to 5MPa with all the raw gas. In this embodiment, all the raw gas consisted of methyl chloride and carbon monoxide. The reaction raw materials were passed through the catalyst bed from top to bottom. Among them, the mass space velocity of the methyl chloride feed was 0.15h -1 ; The molar ratio of carbon monoxide to methyl chloride is 90:1, and the reaction temperature is 400°C. The catalytic reaction is run for 1 hour. The reaction results are shown in Table 3.

[0077] Table 3 Reaction results on different catalysts

[0078]

[0079]

[0080] As shown in Table 3, the catalyst with acidic zeolite molecular sieve as the active component can achieve the purpose of converting methyl chloride and CO into highly selective aromatics.

[0081] Comparative Example 1

[0082] When N2 was used to replace CO in Example 2 and other conditions were the same as in Example 2, the reaction results of methyl chloride on different catalysts are shown in Table 4.

[0083] Table 4 Reaction results of methyl chloride on different catalysts without CO

[0084]

[0085]

[0086] It can be seen from Table 4 that when CO is not used as a raw material, the selectivity of aromatics and BTX decreases significantly, which further illustrates that CO is used as a raw material rather than as a diluent.

[0087] Example 3 Direct conversion of methyl chloride to produce aromatics at different reaction temperatures

[0088] The catalyst used was sample H-7#, the reaction temperature was 300-550°C, and the other reaction conditions were the same as those in Example 2. The results of the catalytic reaction for 1 hour are shown in Table 5.

[0089] Table 5 Reaction results at different reaction temperatures

[0090] Reactor temperature (℃) 300 350 450 550 Methyl chloride conversion rate (%) 14.15 94.52 100 100 Aromatic selectivity (%) 74.82 83.58 77.75 60.37 BTX selectivity (%) 9.40 39.21 54.10 50.29 Selectivity of other compounds (%) 25.18 16.42 22.25 39.63

[0091] Example 4 Direct conversion of methyl chloride to produce aromatics at different reaction pressures

[0092] The catalyst used was H-7# sample, the reaction pressures were 0.2 MPa, 3.0 MPa, 15 MPa, and 20 MPa, respectively, and the other conditions were the same as in Example 2. The reaction was run for 1 hour and the results are shown in Table 6.

[0093] Table 6 Reaction results at different reaction pressures

[0094] Reaction pressure (MPa) 0.2 3 15 20 Methyl chloride conversion rate (%) 28.54 93.77 100 100 Aromatic selectivity (%) 34.31 76.24 85.56 87.14 BTX selectivity (%) 16.76 42.86 66.59 70.88 Selectivity of other compounds (%) 65.69 23.76 14.44 12.86

[0095] It can be seen from Table 6 that the increase in reaction pressure is helpful to promote the conversion of methyl chloride to aromatics. The higher the reaction pressure, the higher the conversion rate, and the higher the selectivity of mixed aromatics and BTX.

[0096] Example 5 Direct conversion of methyl chloride to prepare aromatics at different mass space velocities of methyl chloride

[0097] The catalyst used was H-7# sample, and the mass space velocity of methyl chloride was 0.02, 0.1, 0.5, 1, and 4 h-1, respectively. -1 , other conditions were the same as in Example 2, and the reaction was run for 1 hour. The results are shown in Table 7.

[0098] Table 7 Reaction results at different methyl chloride mass space velocity

[0099] <![CDATA[Mass space velocity of methyl chloride (h -1 )]]> 0.02 0.1 0.5 1 4 Methyl chloride conversion rate (%) 100 100 98.06 78.56 4.15 Aromatic selectivity (%) 83.15 81.59 74.25 70.68 68.54 BTX selectivity (%) 54.29 55.98 52.18 46.99 41.78 Selectivity of other compounds (%) 16.85 18.41 25.75 29.32 31.46

[0100] Example 6 Direct conversion of methyl chloride to produce aromatics under different carbon monoxide and methyl chloride molar ratios

[0101] The catalyst used was H-7# sample, the molar ratios of CO and methyl chloride were 0.05:1, 1:1, 6:1, 40:1, 80:1 and 100:1, respectively, and the mass space velocity of methyl chloride feed was 0.15h -1 , wherein helium is used as the balance atmosphere to maintain the total gas space velocity when the molar ratio of CO to methyl chloride is 0.05:1, 1:1, 6:1, 40:1, and 80:1 respectively, consistent with the molar ratio of CO to methyl chloride being 100:1. Other conditions are the same as those in Example 2. The catalytic reaction is run for 1 hour. The results are shown in Table 8.

[0102] Table 8 Reaction results of different carbon monoxide, methyl chloride and equilibrium atmosphere He molar ratio

[0103]

[0104] It can be seen from Table 8 that the ratio of carbon monoxide to methyl chloride has an important influence on the conversion of methyl chloride. The higher the ratio, the higher the conversion of methyl chloride and the higher the selectivity of mixed aromatics, especially BTX.

[0105] Example 7 Direct conversion of methyl chloride to produce aromatic hydrocarbons when the carbon monoxide feed gas contains any one or a mixture of hydrogen, nitrogen, helium, argon, etc.

[0106] The catalyst used was H-7# sample, CO raw gas was used instead of CO, other conditions were the same as in Example 2, other gases contained in the CO raw gas were shown in Table 9, and the results of the reaction were shown in Table 9 after running for 1 hour.

[0107] Table 9 Reaction results when CO raw gas contains other gases

[0108]

[0109] It can be seen from Table 9 that the increase of impurity gases in carbon monoxide directly leads to a decrease in the ratio of carbon monoxide to methyl chloride, thereby resulting in a decrease in aromatic selectivity, especially BTX selectivity, which further illustrates that CO is used as a raw material.

[0110] Example 8 Preparation of Aromatics by Conversion of Different Methyl Halides as Raw Materials

[0111] When the catalyst used was sample H-7#, and the methyl halides were methyl bromide, methyl iodide, and a mixture thereof, other conditions were the same as in Example 2, and the reaction was run for 1 hour. The results are shown in Table 10.

[0112] Table 10 Reaction results of different methyl halides as raw materials

[0113]

[0114] It can be seen from Table 10 that when acidic zeolite molecular sieve is used as a catalyst, monohalomethane or dihalomethane can be directed to generate aromatic hydrocarbons with high added value.

[0115] Example 9 Direct preparation of aromatic hydrocarbons from methyl halides in different reactors

[0116] The catalyst used was H-7# sample, and fixed bed, fluidized bed and moving bed were used respectively. Other conditions were the same as in Example 2. The reaction was run for 1 hour. The results are shown in Table 11.

[0117] Table 11 Reaction results of different reactors

[0118]

[0119] It can be seen from Table 11 that the purpose of converting methyl halides into aromatic hydrocarbons can be achieved by using different reactor types.

[0120] Example 10 Performance Evaluation of Fresh and Regenerated Catalysts

[0121] The catalyst sample H-14# after deactivation in Example 2 was treated with a mixed gas of 2% oxygen and 98% nitrogen by volume at 550°C for 4 hours to regenerate the catalyst once, and the catalytic reaction was carried out under the conditions of Example 2. The catalyst was regenerated five times in the same manner, and the catalytic activity data after each reaction for 1 hour were selected for comparison, and the results are shown in Table 12.

[0122] Table 12 Reaction results of fresh catalyst and regenerated catalyst

[0123]

[0124] It can be seen from Table 12 that the deactivated catalyst can be regenerated repeatedly without a significant decrease in activity.

[0125] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing aromatic hydrocarbons, characterized in that: The method comprises contacting a raw material gas containing methyl halide and carbon monoxide with a solid acid catalyst to react and obtain aromatic hydrocarbons; The solid acid catalyst comprises an acidic zeolite molecular sieve; The molar ratio of carbon monoxide to methyl halide is 2:1 to 100:1; The silicon-aluminum atomic ratio of the acidic zeolite molecular sieve is 0.5-200; The aromatic hydrocarbon is selected from at least one of benzene, toluene and xylene; The methyl halide is a monohalomethane, a dihalomethane or a mixture thereof; The reaction conditions are: reaction temperature of 300-550°C; reaction pressure of 0.1-25 MPa; mass space velocity of the methyl halide of 0.01-20.0h -1 .

2. The method according to claim 1, characterized in that The methyl halide is at least one of methyl chloride, methyl bromide and methyl iodide.

3. The method according to claim 1, characterized in that: The mass content of the acidic zeolite molecular sieve in the solid acid catalyst is 50-100%.

4. The method according to claim 1, characterized in that The acidic zeolite molecular sieve is a hydrogen-type zeolite molecular sieve.

5. The method according to claim 1, characterized in that The solid acid catalyst further comprises a matrix, and the matrix is ​​selected from at least one of aluminum oxide, silicon oxide, kaolin and magnesium oxide.

6. The method according to claim 1, characterized in that The acidic zeolite molecular sieve comprises at least one channel defined by a 10-membered ring.

7. The method according to claim 1, characterized in that The acidic zeolite molecular sieve is selected from at least one of an acidic zeolite molecular sieve having an AEL structure, an acidic zeolite molecular sieve having an FER structure, an acidic zeolite molecular sieve having an MEL structure, an acidic zeolite molecular sieve having an MFI structure, an acidic zeolite molecular sieve having an MWW structure, an acidic zeolite molecular sieve having an MTT structure, an acidic zeolite molecular sieve having an NES structure, and an acidic zeolite molecular sieve having a TON structure.

8. The method according to claim 1, characterized in that The silicon-aluminum atomic ratio of the acidic zeolite molecular sieve is 0.5-150.

9. The method according to claim 1, characterized in that: The acidic zeolite molecular sieve is selected from one or more of SAPO-11, ZSM-35, ZSM-11, SSZ-46, ZSM-5, MCM-22, ITQ-2, ZSM-23, SSZ-32, NU-87, ZSM-22 and NU-10 molecular sieves.

10. The method according to claim 1, characterized in that The reaction temperature is 350-500°C.

11. The method according to claim 1, characterized in that: The reaction pressure is 0.2~20 MPa.

12. The method according to claim 1, characterized in that The reaction pressure is 2.0~15MPa.

13. The method according to claim 1, characterized in that The mass space velocity of the methyl halide is 0.02~6h -1 .

14. The method according to claim 1, characterized in that The mass space velocity of the methyl halide is 0.05~3.0h -1 .

15. The method according to claim 1, characterized in that The molar ratio of carbon monoxide to methyl halide is 2:1~90:

1.

16. The method according to claim 1, characterized in that The raw gas also contains gas I; The gas I is selected from at least one of hydrogen, nitrogen, helium and argon.

17. The method according to claim 1, characterized in that The reaction is carried out in a reactor; The reactor is selected from at least one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.

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