CN112694907B - Method for preparing hydrocarbon compound from methane - Google Patents
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Abstract
The invention provides a method for preparing hydrocarbon compounds from methane, which comprises the following steps: will contain CH4And the raw material gas of CO is contacted with a solid catalyst for reaction to obtain hydrocarbons; the solid catalyst comprises a molecular sieve catalyst; the molecular sieve catalyst comprises a zeolite molecular sieve and metal elements, wherein the metal elements are loaded on the zeolite molecular sieve; the metal elements comprise one or more of vanadium, chromium, manganese, tungsten, zinc and aluminum; the number of carbon atoms in the hydrocarbon compound is not less than 2. The invention passes through CH4And the carbonylation reaction with CO changes the activation and conversion paths of methane in the traditional direct conversion process of methane, reduces the reaction temperature, improves the conversion efficiency of methane, and provides a new method for directly converting methane.
Description
Technical Field
The invention relates to a method for preparing hydrocarbon compounds from methane, and belongs to the field of energy catalytic conversion.
Background
Methane is a main component of natural gas, shale gas and combustible ice, and is an important component of energy consumption, and efficient conversion of methane is continuously concerned by researchers. At present, the research on the utilization of methane conversion mainly comprises two aspects of direct conversion and indirect conversion. The indirect methane conversion method has complex flow, large energy consumption, large investment and high production cost. Compared with an indirect conversion method, the direct conversion of methane can obtain fuel or chemicals with high added value in one step, the process is simple, and the atom economy is good, so that the research on the direct conversion and the efficient utilization of methane has important theoretical significance and industrial application value.
In general, direct conversion of methane is required inUnder severe conditions (e.g. high temperature, strong acid medium, etc.), the intermediate species are extremely unstable: such as CO formation easily under oxygen-containing atmosphere2And H2O, carbon deposition species are easily generated under the oxygen-free condition, and further the selectivity of reaction products is low.
Disclosure of Invention
According to one aspect of the present application, a process for preparing hydrocarbon compounds from methane is provided, which changes the activation path of methane and lowers the reaction temperature through coupling methane and carbon monoxide via carbonylation route, and provides a new method for directly converting methane.
According to one aspect of the present application, there is provided a method for producing hydrocarbon compounds from methane, the method comprising at least: will contain CH4And the raw material gas of CO is contacted with a solid catalyst for reaction to obtain hydrocarbons; the solid catalyst comprises a molecular sieve catalyst; the molecular sieve catalyst comprises a zeolite molecular sieve and a metal element, wherein the metal element is loaded on the zeolite molecular sieve; the metal elements comprise one or more of vanadium, chromium, manganese, tungsten, zinc and aluminum.
Optionally, the number of carbon atoms in the hydrocarbon compound is more than or equal to 2.
Optionally, the hydrocarbon compound comprises at least one of lower hydrocarbon, monocyclic aromatic hydrocarbon and fused ring aromatic hydrocarbon; the carbon atom number n of the low-carbon hydrocarbon is more than or equal to 2 and less than or equal to 5.
Optionally, the CO is with the CH4The molar ratio of (A) to (B) is 0.05 to 100.
Preferably, the CO and the CH4The molar ratio of (A) to (B) is 0.1 to 90.
Preferably, the CO and the CH4The molar ratio of (a) to (b) is 1 to 80.
Optionally, the CO is with the CH4Independently selected from 10: 1. 20: 1. 50: 1. 60: 1. 80: 1. 90: 1. 100, and (2) a step of: 1; the lower limit is independently selected from 0.05: 1. 0.1:1, 0.5:1, 1:1, 2: 1. 10: 1. 20: 1. 50: 1. 60: 1. 80: 1. 90: 1.
optionally, the reaction conditions are: the reaction temperature is350-650 ℃; the reaction pressure is 0.3-20 MPa; the CH4The mass airspeed of the catalyst is 0.01-10 h-1。
Optionally, the reaction conditions are: the reaction temperature is 360-640 ℃; the reaction pressure is 0.5-18 MPa; the CH4The mass airspeed of the reactor is 0.015-9 h-1。
Optionally, the upper limit of the reaction temperature is independently selected from 380 ℃, 400 ℃, 450 ℃, 500 ℃, 530 ℃, 540 ℃, 560 ℃, 580 ℃, 620 ℃, 640 ℃, 650 ℃; the lower limit is independently selected from 350 ℃, 360 ℃, 370 ℃, 450 ℃, 490 ℃, 530 ℃, 580 ℃, 620 ℃, 630 ℃ and 640 ℃.
Optionally, the upper limit of the reaction pressure is independently selected from 0.5MPa, 6MPa, 10MPa, 15MPa, 20 MPa; the lower limits are independently selected from 0.3MPa, 1MPa, 6MPa, 10MPa, 15 MPa.
Alternatively, the upper limit of the methane mass space velocity is independently selected from 0.02h-1、0.04h-1、0.06h-1、0.1h-1、0.2h-1、0.3h-1、0.35h-1、0.5h-1、1h-1、1.50h-1、2.5h-1、3h-1、4h-1、5h-1、10h-1(ii) a The lower limit is independently selected from 0.01h-1、0.02h-1、0.04h-1、0.1h-1、0.35h-1、0.5h-1、1h-1、1.50h-1、2.5h-1、3h-1、4h-1、8h-1。
Optionally, the feed gas comprises feed gas a and feed gas B; the feed gas A contains CH4(ii) a The feed gas B contains CO.
Optionally, in the raw material gas B, the volume content of the CO in the raw material gas B is 15-100%.
Optionally, the feed gas B also comprises a gas I; the gas I is at least one selected from hydrogen, nitrogen, helium, argon, carbon dioxide, ethylene, ethane, methanol, dimethyl ether and acetic acid.
Optionally, the zeolite molecular sieve is a hydrogen-form zeolite molecular sieve; the hydrogen-type zeolite molecular sieve is selected from at least one of a hydrogen-type zeolite molecular sieve with BEA topology, a hydrogen-type zeolite molecular sieve with CDO topology, a hydrogen-type zeolite molecular sieve with CHA topology, a hydrogen-type zeolite molecular sieve with EMT topology, a hydrogen-type zeolite molecular sieve with ETL topology, a hydrogen-type zeolite molecular sieve with FAU topology, a hydrogen-type zeolite molecular sieve with FER topology, a hydrogen-type zeolite molecular sieve with MFI topology, a hydrogen-type zeolite molecular sieve with MFS topology, a hydrogen-type zeolite molecular sieve with MOR topology, a hydrogen-type zeolite molecular sieve with MMW topology and a hydrogen-type zeolite molecular sieve with MTF topology; the zeolite molecular sieve has a silicon-aluminum atomic ratio of 5-400.
Optionally, the loading amount of the metal element in the solid catalyst is 0.005-30 wt%; the mass of the metal element is calculated by the mass of the metal element; the mass of the solid catalyst is based on the mass of the solid catalyst itself.
Optionally, the loading amount of the metal element in the solid catalyst is 0.1-30 wt%.
Optionally, the content of the molecular sieve catalyst in the solid catalyst is 50-100 wt%.
Optionally, a matrix is also included in the solid catalyst; the matrix comprises at least one of alumina, silica, kaolin and magnesia.
Optionally, the reaction is carried out in a reactor comprising one or more of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.
The skilled person can select a suitable reactor according to the actual production needs. Preferably, the reactor is a fixed bed reactor.
The beneficial effects that this application can produce include:
1) the application provides a method for directly generating hydrocarbons through coupling methane and carbon monoxide and a carbonylation process, which changes the traditional methane activation method, reduces the reaction temperature and has the advantages of low energy consumption, simple process and the like;
2) the application provides a method for preparing hydrocarbon compounds from methane, wherein the raw material gas containing carbon monoxide can contain any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, ethylene, ethane, methanol, dimethyl ether and acetic acid besides carbon monoxide, and methane can react with carbon monoxide under the carbon monoxide atmosphere and can also perform coupling reaction with other small molecular compounds under the action of carbon monoxide to realize the purpose of converting methane into hydrocarbons, so that the method has wide application range.
Drawings
FIG. 1 is a transmission electron microscope photograph of catalyst # 14 prepared in example 1 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The analysis method in the examples of the present application is as follows:
in the examples, the conversion of methane was calculated by internal standard method, and the selectivity of the product was calculated by normalization method, the formula is as follows:
methane conversion rate [ (mole of methane carbon in the feed gas) - (mole of methane carbon in the product) ]/(mole of methane carbon in the feed gas) × (100%)
Product selectivity ═ product carbon moles ÷ product organic carbon moles sum × 100%
The hydrocarbons of C2-C5 in the product are classified into low-carbon hydrocarbons, benzene, toluene, xylene and the like are classified into monocyclic aromatic hydrocarbons, and naphthalene, methylnaphthalene and aromatic hydrocarbons with the carbon number more than 11 are classified into condensed ring aromatic hydrocarbons.
The molecular sieve carrier raw material source is as follows: the molecular sieve raw materials used in the experiment are partly directly commercially available and partly synthesized according to the literature, and the specific sources and the nomenclature of the molecular sieve carriers are shown in table 1.
TABLE 1 sources and Si/Al ratios of different catalysts
Synthesis of NaEMT reference Science, 2012356 (6): 70-73 and 'preparation, secondary synthesis and modification of molecular sieve' in 'molecular sieve and porous material chemistry': 2004: 416-466;
the synthesis of SAPO-34 refers to the synthesis method of SAPO-34 in methanol to olefin;
Na-EU-12 synthesis references Angew. chem. int. Ed.2016,55, 7369-7373 and "preparation, secondary synthesis and modification of molecular sieves" in molecular sieves and porous materials chemistry ": 2004: 416-466;
Na-MCM-65 synthesis references J.Phys.chem.B 2004,108, 15216-;
synthesis of Na-ZSM-57 references j.catal.2000,196, 158-166;
Na-MCM-22 synthesis references Zeolite, 1995,15,1, 2-8;
for the synthesis of Na-MCM-35, refer to chem.Mater.1999,11, 2919-2927.
Example 1
Preparation of hydrogen type molecular sieve
Passing the Na-type molecular sieve in Table 1 through NH4NO3Ion exchange, drying and roasting to obtain the hydrogen type molecular sieve.
Preparation of HMOR: in a hydrothermal synthesis kettle, adding NaMOR molecular sieve powder into pre-prepared 1mol/L NH4NO3In the aqueous solution, the solid-liquid mass ratio was 1:10, and the exchange reaction was carried out at 80 ℃ for 2 hours while stirring, vacuum-filtered and washed with water. The reaction was then continued for 2h with stirring at 80 ℃ and after 3 successive exchange reactions, drying at 120 ℃ overnight followed by calcination at 550 ℃ for 4h gave the desired catalyst sample, HMOR.
The steps for preparing the other Na-type molecular sieves in the table 1 into hydrogen-type molecular sieves are similar to the steps for preparing the HMOR molecular sieves by using the NaMOR molecular sieve, and are not described one by one here.
Preparation of matrix-containing samples
The formed hydrogen type sample containing the matrix is prepared by adopting a strip extrusion forming method.
In this example, a substrate-containing hydrogen type sample was prepared, as represented by an HZSM-5(Si/Al ═ 50) sample, and the preparation of the substrate-containing sample using the other hydrogen type molecular sieves in table 1 was similar to that of the HZSM-5(Si/Al ═ 50) sample, and the details thereof are omitted.
Preparation of HZSM-5 molecular sieve containing alumina matrix: fully mixing 50g of raw material sample HZSM-5 with 50g of alumina, adding 10 wt% nitric acid for kneading, and extruding the kneaded dough-shaped sample through a strip extruding machine for strip forming. Drying the extruded sample at 120 ℃, and roasting at 550 ℃ for 4h to obtain the acidic zeolite molecular sieve containing the matrix, wherein the sample is marked as HZ5-AO 5.
Preparation of HZSM-5 molecular sieve containing kaolin matrix: 80g of HZSM-5 was mixed with 20g of kaolin. Adding nitric acid with the concentration of 15 wt% for kneading, and extruding the kneaded dough-shaped sample through a strip extruding machine for strip extrusion molding. The extruded sample is dried at 120 ℃ and roasted at 550 ℃ for 4h to obtain the acidic zeolite molecular sieve containing the matrix, and the sample is marked as HZ 8-K2.
Preparation of HZSM-5 molecular sieve containing magnesium oxide matrix: 80g of HZSM-5 was mixed with 20g of magnesium oxide. Adding nitric acid with the concentration of 15 wt% for kneading, and extruding the kneaded dough-shaped sample through a strip extruding machine for strip extrusion molding. The extruded sample is dried at 120 ℃ and roasted at 550 ℃ for 4h to obtain the acidic zeolite molecular sieve containing the matrix, and the sample is marked as HZ8-MO 2.
Preparing an HZSM-5 molecular sieve containing a mixed matrix of silicon oxide, aluminum oxide and magnesium oxide: 80g of HZSM-5 was mixed with 20g of a mixture containing silica, alumina and magnesia. Wherein, the ratio of silicon oxide: alumina: the mass ratio of magnesium oxide is 2: 2: 1. adding nitric acid with the concentration of 15 wt% for kneading, and extruding the kneaded dough-shaped sample through a strip extruding machine for strip extrusion molding. The extruded sample is dried at 120 ℃ and roasted at 550 ℃ for 4h to obtain the acidic zeolite molecular sieve containing the matrix, and the sample is marked as HZ8-SAM 2.
Preparation of hydrogen type molecular sieve loaded metal catalyst
And drying the prepared hydrogen type molecular sieve, preparing the required metal soluble salt into a solution, and preparing the supported metal catalyst by using a wet impregnation method.
Preparation of HZSM-5(Si/Al ═ 25) molecular sieve supported zinc metal catalyst: 2.7g of Zn (NO)3)2·6H2Dissolving O in 10g of deionized water, then putting 10g of a water-free HZSM-5 (Si/Al-25) molecular sieve into the prepared solution, naturally airing the sample, drying at 110 ℃, then heating to 550 ℃ at the heating rate of 2 ℃/min, and staying at the temperature for 4 hours to prepare a Zn/HZSM-5-25 catalyst sample with the Zn content of 6%. During the preparation of the samples, the amount of soluble metal salt required is adjusted according to the respective supported metal content.
The prepared hydrogen type molecular sieve supported metal catalyst is shown in table 2.
The preparation method of other hydrogen-type molecular sieve supported zinc metal catalysts prepared in the table 1 is similar to the preparation method of a Zn/HZSM-5-25 catalyst sample, and is not described one by one here.
The catalysts 28# to 31# in Table 2 are prepared by HZ5-AO5, HZ8-K2, HZ8-MO2 and HZ8-SAM2 molecular sieves respectively, and the specific methods are as follows:
2.7g of Zn (NO)3)2·6H2Dissolving O in 10g of deionized water, then putting 10g of a water-free HZ5-AO5 molecular sieve into the prepared solution, naturally airing the sample, drying the sample at 110 ℃, then heating to 550 ℃ at the heating rate of 2 ℃/min, and staying at the temperature for 4 hours to prepare a Zn/HZ5-AO5 catalyst sample with the Zn content of 6%, wherein the preparation method of the catalysts 29# to 31# in the table 2 is similar to that of the catalyst 28# and is not repeated.
Morphology characterization of hydrogen type molecular sieve supported metal catalyst
FIG. 1 is a transmission electron micrograph of catalyst # 14 prepared in example 1, and it can be seen from the micrograph of the sample that the metal supported on the sample is uniformly dispersed and the metal particle size is uniform, about 2.8 nm.
The TEM image of the other catalysts prepared in example 1 is similar to that of catalyst # 14 and will not be repeated herein.
Table 2 catalysts prepared according to the above methods, respectively, are as follows
Example 2: production of hydrocarbons from methane over different catalysts
According to the results shown in Table 2, 0.4g of the catalyst was charged into a fixed bed reactor having an inner diameter of 10mm and a quartz tube inner liner (inner diameter of the quartz tube: 6mm), the temperature was raised to 500 ℃ at 5 ℃/min under a helium atmosphere, the reaction was maintained for 2 hours, and a reaction raw material gas was introduced at a reaction pressure of 2.0MPa and a molar ratio of carbon monoxide to methane of 8: 1, methane mass space velocity of 0.22. The reaction temperature is 500 ℃ and the catalyst is reacted for 1h, and the reaction results are shown in Table 3.
TABLE 3 evaluation results of catalysts
As can be seen from Table 3, when methane was reacted over the catalyst # 19, the conversion of methane was the highest and the yields of naphthalene and methylnaphthalene in the product were 54.8%.
Comparative example 1:
when methane was reacted over the catalyst of table 2 without carbon monoxide under otherwise identical conditions as in example 2, the methane conversion was zero.
Example 3: direct conversion of methane to hydrocarbons at different reaction temperatures
The catalyst used was 14# sample, and the reaction temperature was 350 ℃ and 650 ℃ respectively, and other reaction conditions were the same as in example 1. The results of the catalytic reaction for 1 hour are shown in Table 4.
TABLE 4 reaction results at different reaction temperatures
| Reactor temperature (. degree.C.) | 350 | 400 | 450 | 550 | 600 | 650 |
| Methane conversion (%) | 0.82 | 2.46 | 11.89 | 37.31 | 45.92 | 56.99 |
| Selectivity (%) for lower hydrocarbons | 100 | 90.5 | 44.7 | 9.9 | 8.6 | 7.5 |
| Monocyclic aromatic selectivity (%) | 0 | 1.1 | 16.3 | 12.4 | 13.2 | 10.2 |
| Naphthalene and methylnaphthalene Selectivity (%) | 0 | 8.4 | 31.7 | 73.1 | 68 | 69.7 |
| C11+ aromatics selectivity (%) | 0 | 0 | 7.3 | 4.6 | 10.2 | 12.6 |
It can be seen from table 4 that when the catalyst 14# is used for reaction, the conversion rate of methane is the highest at 650 ℃, and it can be seen that the influence of temperature on the reaction rate is still very obvious, at lower temperature, the products are mainly low-carbon hydrocarbons, and at higher temperature, the products are mainly naphthalene and methylnaphthalene.
Example 4: direct conversion of methane to hydrocarbons at different reaction pressures
The results of the reaction carried out under the same conditions as in example 2 for 1 hour using a sample of catalyst # 14 at reaction pressures of 0.1MPa, 1.0MPa, 4.0MPa, 8MPa, 15MPa and 20MPa, respectively, are shown in Table 5.
TABLE 5 results of reactions at different reaction pressures
| Reaction pressure (MPa) | 0.1 | 1 | 4 | 8 | 15 | 20 |
| Methane conversion (%) | 6.56 | 18.45 | 32.39 | 42.23 | 50.02 | 53.3 |
| Selectivity (%) for lower hydrocarbons | 40.2 | 27.1 | 22.3 | 14.4 | 8.5 | 5.4 |
| Monocyclic aromatic selectivity (%) | 36.2 | 17.3 | 14.9 | 10.8 | 8.6 | 4.5 |
| Naphthalene and methylnaphthalene Selectivity (%) | 23.6 | 50.6 | 58.2 | 64.2 | 70.5 | 80 |
| C11+ aromatics selectivity (%) | 0 | 5 | 4.6 | 10.6 | 12.4 | 11.1 |
As can be seen from Table 5, when the catalyst No. 14 sample is used for reaction, the conversion rate of methane is the highest when the methane is at 20MPa, and it can be seen that when the pressure is increased from 0.1MPa to 8MPa, the pressure increase has obvious influence on the methane reaction rate, and the methane reaction rate is not obviously increased when the pressure is continuously increased.
Example 5: direct methane conversion to produce hydrocarbons at different methane mass space velocities
The catalyst used was a 14# sample with a catalyst loading of 0.4g and a mass space velocity of methane of 0.02, 0.1, 0.5, 1, 4 and 8h, respectively-1The reaction temperature is 500 ℃, the pressure is 2.0MPa, and the ratio of carbon monoxide to methane is 8: 1; the reaction results after 1 hour are shown in Table 6.
TABLE 6 results of different methane airspeeds at different times
| Methane mass space velocity (h)-1) | 0.02 | 0.1 | 0.5 | 1 | 4 | 8 |
| Methane conversion (%) | 60.12 | 30.28 | 10.18 | 5.09 | 1.27 | 0.64 |
| Selectivity (%) for lower hydrocarbons | 11.3 | 14.6 | 16.7 | 18.2 | 17.5 | 16.3 |
| Monocyclic aromatic selectivity (%) | 10.2 | 12.8 | 18.4 | 20.4 | 22.4 | 24.2 |
| Naphthalene and methylnaphthalene Selectivity (%) | 70.7 | 68.2 | 59.3 | 55.2 | 50.9 | 51.6 |
| C11+ aromatics selectivity (%) | 7.8 | 4.4 | 5.6 | 6.2 | 9.2 | 7.9 |
As can be seen from Table 6, when the reaction was carried out using the catalyst No. 14 sample, the mass space velocity of methane was 0.02h-1And when the methane conversion rate is highest, the mass space velocity of methane is continuously increased, and the methane conversion rate is reduced.
Example 6: direct conversion of methane to hydrocarbons at different carbon monoxide to methane molar ratios
The catalyst used was 14# sample with a catalyst loading of 0.4g, CO/CH4The molar ratio was 0.05, 1, 6,15, 40, 80, 100, the reaction temperature was 500 ℃, the pressure was 2.0MPa, and the reaction results for 1 hour are shown in table 7.
TABLE 7 reaction results under different molar ratios of carbon monoxide to methane
| CO/CH4 | 0.05:1 | 1:1 | 6:1 | 15:1 | 40:1 | 80:1 | 100:1 |
| Methane conversion (%) | 0.2 | 1.9 | 4.5 | 6.4 | 8.1 | 10.2 | 15.2 |
| Selectivity (%) for lower hydrocarbons | 40.3 | 38.2 | 20.8 | 18.5 | 16.8 | 14.1 | 13.5 |
| Monocyclic aromatic selectivity (%) | 36.8 | 22.7 | 14.7 | 13.2 | 12.1 | 10.5 | 11.2 |
| Naphthalene and methylnaphthalene Selectivity (%) | 15.1 | 29.0 | 60.5 | 64.5 | 64.7 | 62.4 | 63.7 |
| C11+ aromatics Selectivity (%) | 7.8 | 10.1 | 4.0 | 3.8 | 6.4 | 13 | 11.6 |
As can be seen from Table 7, when the reaction was carried out using the catalyst No. 14 sample, CO/CH4100: at 1, the methane conversion is highest, and the main products are naphthalene and methylnaphthalene.
Example 7: when the carbon monoxide raw material gas contains any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, ethylene, ethane, acetic acid, methanol, dimethyl ether and the like, the methane directly prepares hydrocarbons
A sample with catalyst # 14 was used with a feed gas feed ratio of CH4：CO：C2H4: ar ═ 1: 8: 0.5: 0.5, other reaction conditions were the same as in example 2. The results of the catalytic reaction for 1 hour are shown in Table 8.
TABLE 8 reaction results when the carbon monoxide feed gas contains oxygenates or hydrocarbons
As can be seen from table 8, when the reaction was carried out using the catalyst sample No. 14, the conversion of methane was the highest when dimethyl ether was contained in the CO feed gas, and the main product was monocyclic aromatic hydrocarbons.
Example 8: direct production of hydrocarbons from methane in different reactors
The results of the catalytic reaction for 1 hour using the sample of catalyst # 14 under the same reaction conditions as in example 2 are shown in Table 9.
TABLE 9 results of different reactor reactions
As can be seen from table 9, when the reaction was carried out using the catalyst sample No. 14, the conversion of methane was the highest using the fixed bed reactor.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (11)
1. A process for the preparation of hydrocarbons from methane, characterized in that it comprises at least:
will contain CH4And the raw material gas of CO is contacted with a solid catalyst for reaction to obtain a hydrocarbon compound;
the solid catalyst comprises a molecular sieve catalyst;
the molecular sieve catalyst comprises a zeolite molecular sieve and a metal element, wherein the metal element is loaded on the zeolite molecular sieve;
the metal elements comprise one or more of vanadium, chromium, manganese, tungsten, zinc and aluminum;
the hydrocarbon compounds are naphthalene and methylnaphthalene;
the CO and the CH4The molar ratio of (A) to (B) is 1-80;
the zeolite molecular sieve is a hydrogen type zeolite molecular sieve;
the hydrogen-type zeolite molecular sieve is selected from HZSM-5;
the reaction temperature is 450-650 ℃.
2. The method for producing hydrocarbon compounds from methane according to claim 1,
the reaction conditions are as follows: the reaction pressure is 0.3-20 MPa; the CH4The mass airspeed of the catalyst is 0.01-10 h-1。
3. The method for producing hydrocarbon compounds from methane according to claim 1,
the reaction conditions are as follows: the reaction pressure is 0.5-18 MPa; the CH4The mass airspeed of the reactor is 0.015-9 h-1。
4. The method for producing hydrocarbon compounds from methane according to claim 1,
the raw material gas comprises a raw material gas A and a raw material gas B; the feed gas A contains CH4(ii) a The feed gas B contains CO.
5. The method for producing hydrocarbon compounds from methane according to claim 4,
in the feed gas B, the volume content of CO in the feed gas B is 15-100%.
6. The method for producing hydrocarbon compounds from methane according to claim 4,
the feed gas B also comprises a gas I; the gas I is at least one selected from hydrogen, nitrogen, helium, argon, carbon dioxide, ethylene, ethane, methanol, dimethyl ether and acetic acid.
7. The process for producing hydrocarbon compounds from methane according to claim 1,
the zeolite molecular sieve has a silicon-aluminum atomic ratio of 4-400.
8. The method for producing hydrocarbon compounds from methane according to claim 1,
the loading amount of the metal element in the solid catalyst is 0.005-30 wt%;
the mass of the metal element is calculated by the mass of the metal element;
the mass of the solid catalyst is based on the mass of the solid catalyst itself.
9. The method for preparing hydrocarbon compounds from methane according to claim 1, wherein the content of the molecular sieve catalyst in the solid catalyst is 50-100 wt%.
10. The method for producing hydrocarbon compounds from methane according to claim 9,
the solid catalyst also comprises a substrate;
the matrix comprises at least one of alumina, silica, kaolin and magnesia.
11. The method for producing hydrocarbon compounds from methane according to claim 1,
the reaction is carried out in a reactor, wherein the reactor comprises one or more of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor.
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| US6239057B1 (en) * | 1999-01-15 | 2001-05-29 | Uop Llc | Catalyst for the conversion of low carbon number aliphatic hydrocarbons to higher carbon number hydrocarbons, process for preparing the catalyst and process using the catalyst |
| CN101460430A (en) * | 2006-04-21 | 2009-06-17 | 埃克森美孚化学专利公司 | Production of aromatics from methane |
| CN101765575A (en) * | 2007-08-03 | 2010-06-30 | 三井化学株式会社 | Process for producing aromatic hydrocarbon |
| CN101945703A (en) * | 2008-02-21 | 2011-01-12 | 埃克森美孚化学专利公司 | Production of aromatics from methane |
| CN109420517A (en) * | 2017-08-30 | 2019-03-05 | 北京化工大学 | A kind of method that methane low temperature conversion prepares higher hydrocarbon |
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