CN113941360A - Catalyst for oxygen-free aromatization of methane and preparation method and application thereof - Google Patents
Catalyst for oxygen-free aromatization of methane and preparation method and application thereof Download PDFInfo
- Publication number
- CN113941360A CN113941360A CN202111217410.8A CN202111217410A CN113941360A CN 113941360 A CN113941360 A CN 113941360A CN 202111217410 A CN202111217410 A CN 202111217410A CN 113941360 A CN113941360 A CN 113941360A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methane
- oxygen
- molecular sieve
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
Abstract
The invention discloses a catalyst for oxygen-free aromatization of methane, a preparation method and application thereof, wherein the preparation process adopts a sequential impregnation method, an auxiliary agent Ga and an active component metal Mo are respectively impregnated on an HZSM-5 molecular sieve, the steps are simple and convenient, the operation is easy, and the catalyst has good application prospect. The catalyst prepared by the method has excellent stability, and through doping of the additive Ga, the dispersion of metal Mo is increased, the sintering of Mo is effectively inhibited, and the catalytic stability of the catalyst is improved. The invention also discloses the application of the catalyst in the anaerobic aromatization reaction of methane, and the catalyst can be continuously used for 50 h without obvious inactivation, thereby obtaining good application effect.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for oxygen-free aromatization of methane, and a preparation method and application thereof.
Background
Methane is a main component of natural gas, shale gas, combustible ice and the like, is an abundant natural resource, is not only used as fuel supply in large quantity, but also is a source raw material of a plurality of industrial chemicals. The methane conversion pathways are primarily indirect and direct. The methane oxygen-free aromatization reaction is an important reaction in the direct conversion process of natural gas, and the reaction avoids the defect of low aromatic selectivity caused by deep oxidation of methane. The main product benzene of the reaction is a chemical raw material with large demand, is in a liquid state at normal temperature, and is easy to separate from gas-phase substances, so that the production process is simplified, and the utilization value of natural resources such as natural gas is improved.
The catalyst used for the anaerobic aromatization reaction of methane at present has the best effect of Mo/HZSM-5, the molecular sieve is produced industrially in large scale, and the catalyst carrier has the characteristic of simple and easy preparation. However, the oxygen-free aromatization reaction of methane is a strong endothermic reaction, and a high-temperature condition is required in the reaction process, so that the catalyst is inactivated because active metal is sintered to block the pore channels of the molecular sieve, and the using effect of the catalyst in the reaction is greatly reduced. Therefore, the development of the catalyst with good carbon deposition resistance and excellent thermal stability has important significance for the industrial application of methane oxygen-free aromatization reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a catalyst for methane oxygen-free aromatization reaction and a preparation method thereof, the preparation process adopts a sequential impregnation method, and the obtained active components of the catalyst are uniformly dispersed on a molecular sieve carrier, so that the distribution of acid sites of the catalyst is improved, and the reaction stability of the catalyst is effectively improved.
The invention also provides the application of the catalyst for the methane oxygen-free aromatization reaction in the methane oxygen-free aromatization.
The invention is realized by the following technical scheme
A preparation method of a catalyst for methane oxygen-free aromatization reaction is characterized in that an auxiliary metal solution is used for modifying a molecular sieve, then a metal salt is used as a precursor solution for loading an active metal component on the modified molecular sieve, and the catalyst for the methane oxygen-free aromatization reaction is obtained through post-treatment.
Further, the mass ratio of the molecular sieve carrier to the active metal in the catalyst is 1: 0.03 to 0.05.
Further, the mass ratio of the active metal component to the auxiliary metal in the catalyst is 1: 0.1 to 0.35.
Further, the active component precursor is (NH)4)6Mo7O24 The metal promoter precursor is selected from GaCl3. The carrier is HZSM-5 molecular sieve, SiO of molecular sieve carrier2/Al2O3 =25。
Further, the post-treatment comprises the steps of sequentially stirring, drying and roasting the loaded modified molecular sieve.
Further, the loaded modified molecular sieve is stirred for 20-40 min at room temperature, then is placed for 12 h at room temperature, and is dried and roasted.
Further, the drying temperature is 110-130 ℃, and the time is 11-13 h; the roasting temperature is 450-550 ℃ and the roasting time is 1.5-2.5 h.
The catalyst for methane oxygen-free aromatization prepared by the method.
Further, the particle diameter of the catalyst particles is preferably 20 to 60 mesh.
The catalyst for the methane oxygen-free aromatization reaction is applied to methane oxygen-free aromatization.
Further, the application of the catalyst in the oxygen-free aromatization of methane comprises the following steps:
placing the catalyst in a fixed bed quartz tube, and heating the catalyst to 650-750 ℃ from room temperature under Ar purging; then introducing reaction gas, and reacting under the condition that the pressure is 0.08-0.12 MPa.
Further, the heating rate is 10 ℃/min when the temperature is raised from the room temperature to 650-750 ℃; the gas inlet ratio during the reaction is as follows: CH (CH)4/N2=9/1, reaction space velocity 12000 mL/(g · h).
Further, the application of the catalyst in the oxygen-free aromatization of methane specifically comprises the following steps:
0.1g of the catalyst prepared above was placed in a fixed bed quartz tube, and the temperature was raised from room temperature to a temperature of 10 ℃/min under Ar purging at a rate of temperature rise of 10 ℃/minAnd introducing reaction gas at 700 ℃, wherein the gas inlet ratio is as follows: CH (CH)4/N2=9/1, the reaction space velocity was 12000 mL/(g.h), and the reaction pressure was 0.1 MPa.
Compared with the prior art, the invention has the beneficial effect that
The catalyst for the anaerobic methane aromatization reaction is prepared by a sequential impregnation method, and the auxiliary Ga and the active component metal Mo are sequentially impregnated on the HZSM-5 molecular sieve, so that the acid sites of the carrier are effectively controlled, the control of the acid sites is favorable for the generation of products, the generation of carbon deposition is reduced (the carbon deposition is the main reason of catalyst deactivation), and the stability of the catalyst is obviously improved. The preparation method is simple and easy to operate, and has good application prospect. The catalyst increases the dispersion of metal Mo through the doping of the additive Ga, effectively inhibits the sintering of the Mo, improves the catalytic stability of the catalyst, and has good carbon deposition resistance. Experiments prove that the catalyst can be continuously used for 50 hours without obvious inactivation in the application of methane oxygen-free aromatization reaction, effectively solves the problems of the catalyst for methane oxygen-free aromatization in the prior art, and obtains good industrial application effect.
Drawings
FIG. 1 is a TEM image of catalysts obtained in examples 1 to 4 of the present invention and comparative examples 1 to 2; FIGS. (a) to (d) are TEM images of catalysts shown in examples 1 to 4 in this order;
FIG. 2 is a graph showing the partial physicochemical properties of catalysts obtained in examples 1 to 4 of the present invention and comparative examples 1 to 2, wherein FIG. 2(a) is an XPS spectrum and FIG. 2(b) is NH3TPD spectrum 2(c) is H2-a TPR map;
FIG. 3 is a graph of methane conversion versus benzene production rate for catalysts prepared in examples 1 through 4 of the present invention and comparative example 1; in the figure, 3 (a) shows the change in the conversion of methane with time in 21 hours, 3 (b) shows the change in the formation rate of benzene with time in 21 hours, 3 (c) shows the change in the conversion of methane with time in 50 hours with the catalyst prepared in example 1, and 3 (d) shows the change in the formation rate of benzene with time in 50 hours with the catalyst prepared in example 1.
Detailed Description
The invention is further described below in conjunction with the drawings and the detailed description to facilitate understanding of the technical solutions of the invention. It should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The carrier used in the following examples is HZSM-5 molecular sieve, molecular sieve carrier SiO2/Al2O3 = 25, from southern catalytic plant. Precursor (NH)4)6Mo7O24And the metal promoter precursor is selected from GaCl3(this may be achieved by a method known to those skilled in the art).
Example 1
A catalyst for methane oxygen-free aromatization reaction comprises an active component of metal Mo, a metal additive Ga and a carrier HZSM-5 molecular sieve, wherein the metal Mo and the metal Ga are loaded on the HZSM-5 molecular sieve carrier;
the preparation method of the catalyst for the oxygen-free aromatization reaction of methane comprises the following steps:
(1) 5g of HZSM-5 molecular sieve is weighed and heated to 550 ℃ from room temperature at the heating rate of 5 ℃/min in the air atmosphere (a muffle furnace is adopted), and the carrier for the catalyst is obtained by roasting at the temperature for 4 h.
(2) Modifying the carrier obtained in the step (1):
0.2001 g of GaCl were weighed out3 Adding into a beaker containing 5 mL of pure water, stirring with a glass rod, transferring into a 10 mL volumetric flask, washing, transferring, and diluting to a constant volume to obtain 0.00011 mol/mL GaCl3A solution; weighing 1g of the carrier obtained in the step (1), placing the carrier in a 25 ml crucible, and transferring 500 microliters of GaCl by using a liquid transfer gun3Dropwise adding the solution into a crucible containing the carrier while stirring, completing the step within 30min, and then placing the obtained sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; finally heating the mixture from room temperature to 500 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃ to obtain the modified molecular sieve, which is named0.4% Ga/HZSM-5.
(3) Loading of active components:
weighing 3.8350g (NH)4)6Mo7O24Adding into a beaker containing 20 mL of pure water, stirring uniformly with a glass rod, transferring into a 25 mL volumetric flask, washing, transferring, and fixing volume to obtain 0.000124 mol/mL (NH)4)6Mo7O24 A solution; remove 500. mu.l of the above (NH) with a pipette4)6Mo7O24Dropwise adding the solution into the modified molecular sieve obtained in the step (2), stirring while dropwise adding, completing the step within 30min, and then placing the prepared sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; finally, heating the mixture from room temperature to 500 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃; and cooling to room temperature, tabletting, forming, crushing and screening to obtain 20-60-mesh particles, thereby obtaining the catalyst for the methane oxygen-free aromatization reaction, which is named as 4% Mo-0.4% Ga/HZSM-5.
Example 2
A catalyst for oxygen-free aromatization reaction of methane comprises an active component of metal Mo, a metal additive Ga and a carrier HZSM-5 molecular sieve, wherein the metal Mo and the metal Ga are loaded on the HZSM-5 molecular sieve carrier.
The preparation method of the catalyst for the oxygen-free aromatization reaction of methane comprises the following steps:
(1) 5g of HZSM-5 molecular sieve is weighed and heated to 550 ℃ from room temperature at the heating rate of 5 ℃/min in the air atmosphere (a muffle furnace is adopted), and the carrier for the catalyst is obtained by roasting at the temperature for 4 h.
(2) Modifying the carrier obtained in the step (1):
0.3530 g of GaCl were weighed out3 Adding into a beaker containing 5 mL of pure water, stirring with a glass rod, transferring into a 10 mL volumetric flask, washing, transferring, and diluting to constant volume to obtain 0.00019 mol/mL GaCl3A solution; weighing 1g of the carrier obtained in the step (1), placing the carrier in a 25 ml crucible, and transferring 500 microliters of GaCl by using a liquid transfer gun3The solution is added into a crucible containing the carrier dropwise while stirringCompleting the step within 30min, and placing the obtained sample at room temperature for 12 h; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; and finally, heating the mixture to 500 ℃ from room temperature at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃ to obtain the modified molecular sieve, wherein the modified molecular sieve is named as 0.7 percent Ga/HZSM-5.
(3) Loading of active components:
weighing 3.8350g (NH)4)6Mo7O24Adding into a beaker containing 20 mL of pure water, stirring uniformly with a glass rod, transferring into a 25 mL volumetric flask, washing, transferring, and fixing volume to obtain 0.000124 mol/mL (NH)4)6Mo7O24 A solution; remove 500. mu.l of the above (NH) with a pipette4)6Mo7O24Dropwise adding the solution into the modified molecular sieve obtained in the step (2), stirring while dropwise adding, completing the step within 30min, and then placing the prepared sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; finally, heating the mixture from room temperature to 500 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃; and cooling to room temperature, tabletting, molding, crushing and screening to obtain 20-60-mesh particles, thus obtaining the catalyst for methane oxygen-free aromatization reaction, which is named as 4% Mo-0.7% Ga/HZSM-5.
Example 3
A catalyst for oxygen-free aromatization reaction of methane comprises an active component of metal Mo, a metal additive Ga and a carrier HZSM-5 molecular sieve, wherein the metal Mo and the metal Ga are loaded on the HZSM-5 molecular sieve carrier.
The preparation method of the catalyst for the oxygen-free aromatization reaction of methane comprises the following steps:
(1) 5g of HZSM-5 molecular sieve is weighed and heated to 550 ℃ from room temperature at the heating rate of 5 ℃/min in the air atmosphere (a muffle furnace is adopted), and the carrier for the catalyst is obtained by roasting at the temperature for 4 h.
(2) Modifying the carrier obtained in the step (1):
0.5043 g of GaCl were weighed out3 Adding into a beaker containing 5 mL of pure water, stirring with a glass rod, transferring to a 10 mL containerIn a measuring flask, washing, transferring and preparing GaCl with constant volume of 0.00027 mol/ml3A solution; weighing 1g of the carrier obtained in the step (1), placing the carrier in a 25 ml crucible, and transferring 500 microliters of GaCl by using a liquid transfer gun3Dropwise adding the solution into a crucible containing the carrier while stirring, completing the step within 30min, and then placing the obtained sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; and finally, heating the mixture to 500 ℃ from room temperature at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃ to obtain the modified molecular sieve, wherein the modified molecular sieve is named as 1% Ga/HZSM-5.
(3) Loading of active components:
weighing 3.8350g (NH)4)6Mo7O24Adding into a beaker containing 20 mL of pure water, stirring uniformly with a glass rod, transferring into a 25 mL volumetric flask, washing, transferring, and fixing volume to obtain 0.000124 mol/mL (NH)4)6Mo7O24 A solution; remove 500. mu.l of the above (NH) with a pipette4)6Mo7O24Dropwise adding the solution into the modified molecular sieve obtained in the step (2), stirring while dropwise adding, completing the step within 30min, and then placing the prepared sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; finally, heating the mixture from room temperature to 500 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃; and cooling to room temperature, tabletting, molding, crushing and screening to obtain 20-60-mesh particles, thus obtaining the catalyst for the methane oxygen-free aromatization reaction, which is named as 4% Mo-1% Ga/HZSM-5.
Example 4
A catalyst for oxygen-free aromatization reaction of methane comprises an active component of metal Mo, a metal additive Ga and a carrier HZSM-5 molecular sieve, wherein the metal Mo and the metal Ga are loaded on the HZSM-5 molecular sieve carrier.
The preparation method of the catalyst for the oxygen-free aromatization reaction of methane comprises the following steps:
(1) 5g of HZSM-5 molecular sieve is weighed and heated to 550 ℃ from room temperature at the heating rate of 5 ℃/min in the air atmosphere (a muffle furnace is adopted), and the carrier for the catalyst is obtained by roasting at the temperature for 4 h.
(2) Modifying the carrier obtained in the step (1):
0.7060 g of GaCl were weighed out3 Adding into a beaker containing 5 mL of pure water, stirring with a glass rod, transferring into a 10 mL volumetric flask, washing, transferring, and diluting to a constant volume to obtain 0.00038 mol/mL GaCl3A solution; weighing 1g of the carrier obtained in the step (1), placing the carrier in a 25 ml crucible, and transferring 500 microliters of GaCl by using a liquid transfer gun3Dropwise adding the solution into a crucible containing the carrier while stirring, completing the step within 30min, and then placing the obtained sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; and finally, heating the mixture to 500 ℃ from room temperature at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃ to obtain the modified molecular sieve, wherein the modified molecular sieve is named as 1.4% Ga/HZSM-5.
(3) Loading of active components:
weighing 3.8350g (NH)4)6Mo7O24Adding into a beaker containing 20 mL of pure water, stirring uniformly with a glass rod, transferring into a 25 mL volumetric flask, washing, transferring, and fixing volume to obtain 0.000124 mol/mL (NH)4)6Mo7O24 A solution; remove 500. mu.l of the above (NH) with a pipette4)6Mo7O24Dropwise adding the solution into the modified molecular sieve obtained in the step (2), stirring while dropwise adding, completing the step within 30min, and then placing the prepared sample for 12 h at room temperature; then placing the mixture in a drying oven to be dried for 12 hours at 120 ℃; finally, heating the mixture from room temperature to 500 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and roasting the mixture for 2 hours at the temperature of 500 ℃; and cooling to room temperature, tabletting, molding, crushing and screening to obtain 20-60-mesh particles, thereby obtaining the catalyst for the methane oxygen-free aromatization reaction, which is named as 4% Mo-1.4% Ga/HZSM-5.
Comparative example 1
Comparative example 1 differs from example 1 in that: comparative example 1 the same procedure as in example 1 was repeated except that the metallic Ga precursor in step (1) of example 1 was omitted to obtain a metal promoter-free catalyst designated as 4% Mo/HZSM-5.
Comparative example 2
Comparative example 2 differs from example 1 in that: in comparative example 2, the metal Ga precursor and the active metal Mo precursor in step (2) and step (3) of example 1 were omitted, and the rest was the same as in example 1, to obtain a pure supported HZSM-5 molecular sieve, which was named HZSM-5.
The catalysts prepared in the above examples were characterized with the following results:
physicochemical property characterization was performed on the catalysts obtained in examples 1 to 4 and comparative examples 1 to 3, and the results were as follows:
TEM characterization of the catalysts obtained in examples 1-4 is shown in FIG. 1. The figure shows that the active metals are uniformly dispersed on the support after the catalyst sample is modified by the additive Ga.
XPS and NH were performed on the catalyst samples obtained in examples 1 to 4 and comparative examples 1 to 23TPD and H2TPR analysis, the results are shown in FIG. 2. In fig. 2(a), it is seen from the peak shift that doping with gallium changes the chemical environment of the molybdenum species and thus has some effect on its chemical state; after the metal additives with different contents are doped, the peak intensity of the molybdenum species is lower, which shows that the molybdenum species is more inside the carrier than the catalyst sample without doping, which also shows that after the metal additives Ga are doped, the active metal molybdenum species and the molecular sieve are combined more tightly, and the stability is improved; in fig. 2(b), compared with the comparative example, the addition of the auxiliary agent Ga in the example promotes more active metal molybdenum to occupy the position of the strong acid, and the amount of the weak acid is increased or kept unchanged, which shows that the metal is more prone to occupy the strong acid site, the high-temperature desorption peak is reduced along with the increase of the doping amount of the auxiliary agent, and the proper acid strength is favorable for the stability of the catalyst; in FIG. 2(c), the results of comparative example 1 show that two reduction peaks, which are attributed to H absorbed by molybdenum trioxide reduced to molybdenum dioxide, are located at about 467 ℃ and at about 672 ℃ respectively2The latter is attributed to H consumed by further reducing molybdenum dioxide into elemental metal2In examples 1 to 4, the reduction peak of the active metal Mo species still existed, and the position of the first reduction peak remained unchanged, but the peak width was broadened, as shown in TableDoping with the promoter Ga changes the reduction properties of the molybdenum species.
The application of the prepared catalyst for the anaerobic aromatization reaction of methane in the anaerobic aromatization of methane
Respectively weighing 0.1g of the catalyst prepared in the embodiments 1-4 and the comparative example 1 of the invention, placing the catalyst in a quartz tube of a fixed bed reactor, introducing pure Ar gas at a flow rate of 20 mL/min, starting to heat the quartz tube, raising the temperature of a catalyst bed layer from room temperature to 700 ℃ at a temperature rise rate of 10 ℃/min, and then switching to introduce 90% (the content of methane is 90%) of CH4/N2And (3) reaction gas. The catalyst was carbonized for 5 min. The reaction product was then quantitatively analyzed by an on-line gas chromatograph, and the data was recorded every 1 h as shown in fig. 3.
The activity and stability of the catalysts prepared in examples 1 to 4 and comparative example 1 of the present invention are shown in fig. 3, and it can be seen from the figure that compared with the catalyst without metal promoter, the activity of the catalysts prepared in examples 1 to 4 is higher, the instantaneous methane conversion rate at 700 ℃ can reach 25%, the generation rate of the target product benzene can reach 35 μmol/g/min at most, and the catalyst in example 1 can be reacted for 50 h without deactivation, so that the catalyst has excellent stability.
In conclusion, the preparation method of the catalyst with excellent stability for the oxygen-free aromatization reaction of methane, which is disclosed by the invention, has the advantages that the auxiliary agent Ga and the active component metal Mo are respectively impregnated on the HZSM-5 molecular sieve carrier, the steps are simple and convenient, the operation is easy, and the application prospect is good. The catalyst prepared by the preparation method takes metal Mo as an active component, is doped with a metal additive Ga, and the acid sites of the molecular sieve carrier are regulated and controlled by the aid Ga, so that the active metal Mo occupies proper acid sites after being loaded, is uniformly dispersed, effectively prevents Mo from sintering and agglomerating at high temperature, and has good carbon deposit resistance. The catalyst prepared by the invention continuously reacts for 50 hours at 700 ℃ and 0.1 Mpa at an airspeed of 12000 mL/(g.h), and the activity of the catalyst is not obviously reduced, so that the catalyst has good stability.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for methane oxygen-free aromatization reaction is characterized in that an auxiliary metal solution is used for modifying a molecular sieve, then a metal salt is used as a precursor solution for loading an active metal component on the modified molecular sieve, and the catalyst for the methane oxygen-free aromatization reaction is obtained through post-treatment.
2. The process for preparing a catalyst for oxygen-free aromatization of methane according to claim 1 wherein the mass ratio of molecular sieve to active metal in the catalyst is from 1: 0.03 to 0.05.
3. The method of claim 1 for preparing a catalyst for oxygen-free aromatization of methane according to the mass ratio of active metal component to promoter metal in the catalyst of 1: 0.1 to 0.35.
4. The method of claim 2 or 3 for preparing a catalyst for oxygen-free aromatization of methane wherein the active component precursor is (NH)4)6Mo7O24 The metal promoter precursor is selected from GaCl3。
5. The method of claim 1, wherein the post-treatment comprises sequentially stirring, drying and calcining the loaded modified molecular sieve; wherein the loaded modified molecular sieve is stirred for 20-40 min at room temperature, then is placed for 11-13 h at room temperature, and is dried and roasted.
6. The method for preparing a catalyst for oxygen-free aromatization of methane according to claim 5, wherein the drying temperature is 110-130 ℃ and the time is 11-13 h; the roasting temperature is 450-550 ℃ and the roasting time is 1.5-2.5 h.
7. A catalyst for oxygen-free aromatization of methane prepared according to any one of claims 1-6.
8. Use of a catalyst for an oxygen-free aromatization of methane according to claim 7 and any one of claims 1 to 6 in the oxygen-free aromatization of methane.
9. The application of claim 8, wherein the application comprises the steps of: placing the catalyst of claim 1 in a fixed bed quartz tube, and increasing the temperature from room temperature to 650-750 ℃ under Ar purging; then introducing reaction gas, and reacting under the condition that the pressure is 0.08-0.12 MPa.
10. The use according to claim 9, wherein the rate of temperature rise from room temperature to 650-750 ℃ is 10 ℃/min; the gas inlet ratio during the reaction is as follows: CH (CH)4/N2=9/1, reaction space velocity 12000 mL/(g · h).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111217410.8A CN113941360A (en) | 2021-10-19 | 2021-10-19 | Catalyst for oxygen-free aromatization of methane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111217410.8A CN113941360A (en) | 2021-10-19 | 2021-10-19 | Catalyst for oxygen-free aromatization of methane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113941360A true CN113941360A (en) | 2022-01-18 |
Family
ID=79331404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111217410.8A Pending CN113941360A (en) | 2021-10-19 | 2021-10-19 | Catalyst for oxygen-free aromatization of methane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113941360A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114367305A (en) * | 2022-01-27 | 2022-04-19 | 郑州大学 | Hollow structure catalyst for methane oxygen-free aromatization and preparation method and application thereof |
| CN115672387A (en) * | 2022-10-26 | 2023-02-03 | 中国石油大学(北京) | Methane oxygen-free aromatization catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190032A (en) * | 1997-02-04 | 1998-08-12 | 中国科学院大连化学物理研究所 | Hetero-atom molecular-sieve catalyst for oxygen-free dehydrogenating aromatization of methane and its use |
| JPH1147606A (en) * | 1997-07-31 | 1999-02-23 | Osaka Sekiyu Kagaku Kk | Catalyst for aromatizing lower hydrocarbon and production of aromatic compound using the same |
| CN1593761A (en) * | 2004-07-14 | 2005-03-16 | 汕头大学 | Fe modified Mo based molecular sieve catalyst and preparation method thereof |
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
| WO2015058636A1 (en) * | 2013-10-21 | 2015-04-30 | 北京化工大学 | Method for preparing aromatic hydrocarbon by direct conversion of methane |
| CN106540742A (en) * | 2015-09-18 | 2017-03-29 | 北京化工大学 | Multi-stage porous methane non oxidative aromatization and alkylating aromatic hydrocarbon coupled catalyst of a kind of high catalytic activity and its preparation method and application |
| WO2019039749A1 (en) * | 2017-08-21 | 2019-02-28 | 서울대학교산학협력단 | Method for producing metal oxide catalyst supported on mesoporous hzsm-11 for direct dehydrogenation and aromatization reaction of methane and propane co-reactant, and method for producing btx using catalyst |
-
2021
- 2021-10-19 CN CN202111217410.8A patent/CN113941360A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190032A (en) * | 1997-02-04 | 1998-08-12 | 中国科学院大连化学物理研究所 | Hetero-atom molecular-sieve catalyst for oxygen-free dehydrogenating aromatization of methane and its use |
| JPH1147606A (en) * | 1997-07-31 | 1999-02-23 | Osaka Sekiyu Kagaku Kk | Catalyst for aromatizing lower hydrocarbon and production of aromatic compound using the same |
| CN1593761A (en) * | 2004-07-14 | 2005-03-16 | 汕头大学 | Fe modified Mo based molecular sieve catalyst and preparation method thereof |
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
| WO2015058636A1 (en) * | 2013-10-21 | 2015-04-30 | 北京化工大学 | Method for preparing aromatic hydrocarbon by direct conversion of methane |
| CN106540742A (en) * | 2015-09-18 | 2017-03-29 | 北京化工大学 | Multi-stage porous methane non oxidative aromatization and alkylating aromatic hydrocarbon coupled catalyst of a kind of high catalytic activity and its preparation method and application |
| WO2019039749A1 (en) * | 2017-08-21 | 2019-02-28 | 서울대학교산학협력단 | Method for producing metal oxide catalyst supported on mesoporous hzsm-11 for direct dehydrogenation and aromatization reaction of methane and propane co-reactant, and method for producing btx using catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 董群等: "甲烷芳构化Mo/HZSM-5催化剂上添加第二组分的研究" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114367305A (en) * | 2022-01-27 | 2022-04-19 | 郑州大学 | Hollow structure catalyst for methane oxygen-free aromatization and preparation method and application thereof |
| CN115672387A (en) * | 2022-10-26 | 2023-02-03 | 中国石油大学(北京) | Methane oxygen-free aromatization catalyst and preparation method and application thereof |
| CN115672387B (en) * | 2022-10-26 | 2024-03-19 | 中国石油大学(北京) | Methane anaerobic aromatization catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113941360A (en) | Catalyst for oxygen-free aromatization of methane and preparation method and application thereof | |
| JP5726323B2 (en) | Methane synthesis catalyst, method for producing the precursor, and catalyst precursor | |
| CN110961138B (en) | Nitrogen-doped graphene grown in situ by self-assembled denitration sulfur-resistant catalyst and preparation method thereof | |
| CN110773218A (en) | Nitrogen-doped biochar-loaded metal nickel catalyst and application thereof | |
| CN115041188B (en) | Modification method of supported platinum-copper alloy catalyst and application of supported platinum-copper alloy catalyst in propylene preparation by propane dehydrogenation | |
| CN109772393A (en) | A kind of preparation method and applications of sulfur doping hydrogenation catalyst | |
| CN113117712B (en) | Methane dry reforming reaction under microwave condition and catalyst thereof | |
| CN110801828A (en) | Catalyst for preparing olefin by oxidative dehydrogenation of ethane chemical chain and application of catalyst in oxidative dehydrogenation reaction of ethane | |
| CN111974441B (en) | Three-dimensional porous structure nickel modified HY molecular sieve oxygen carrier and preparation and application thereof | |
| CN112892569B (en) | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by hydrogen sulfide selective oxidation under medium-high temperature condition by adopting same | |
| CN114789064A (en) | Catalyst for preparing methanol by partial oxidation of coal bed gas and preparation method and application thereof | |
| JP2009028710A (en) | Catalyst for aromatization of lower hydrocarbon | |
| CN114308043A (en) | Preparation method of acidified two-dimensional layered vermiculite supported nickel-based catalyst | |
| CN109590001B (en) | Anti-carbon deposition catalyst for preparing synthesis gas by methane reforming and preparation method thereof | |
| CN112808294A (en) | Boron nitride/nickel oxide composite material and preparation method and application thereof | |
| JP6794811B2 (en) | Steam reforming catalyst, methane reforming catalyst, catalyst production method and hydrogen production method | |
| CN113546620B (en) | Palladium oxide supported zinc-based catalyst and preparation method and application thereof | |
| CN107790169B (en) | Isobutane oxidative dehydrogenation catalyst, preparation method and application thereof | |
| KR100413635B1 (en) | Catalyst for producing carbon and method of producing carbon | |
| Chen et al. | PtZn/ZnO intermetallic catalyst prepared by reactive metal-support interaction for the semi-hydrogenation of 1, 4-butynediol | |
| CN116571260A (en) | Supported molybdenum carbide catalyst and preparation method and application thereof | |
| CN111790391A (en) | Synthesis of Ni/Zn bimetallic oxide catalyst and application thereof in oxidative dehydrogenation reaction of n-butane | |
| CN113355123A (en) | Method for catalytic pyrolysis of lignin | |
| CN115090280A (en) | Supported cluster molybdenum oxide catalyst, preparation method thereof and application thereof in propane dehydrogenation | |
| CN116924390A (en) | Method for preparing nitrogen and fluorine co-doped hollow carbon nanocages in one step |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |