CN117983261A - Catalyst for preparing benzene by cyclohexane dehydrogenation and preparation method and application thereof - Google Patents
Catalyst for preparing benzene by cyclohexane dehydrogenation and preparation method and application thereof Download PDFInfo
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- CN117983261A CN117983261A CN202211362269.5A CN202211362269A CN117983261A CN 117983261 A CN117983261 A CN 117983261A CN 202211362269 A CN202211362269 A CN 202211362269A CN 117983261 A CN117983261 A CN 117983261A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a catalyst for preparing benzene by cyclohexane dehydrogenation, a preparation method and application thereof, wherein the catalyst comprises an oxide and a carbide, the oxide is gamma-Al 2O3, and the carbide is Ta 3C2. The application also discloses a preparation method of the catalyst, which comprises the steps of adopting a high-temperature calcination method and preparing Ta 3AlC2, soaking Ta 3AlC2 in hydrofluoric acid solution, mixing, carrying out hydrothermal reaction, washing for a plurality of times, and drying to obtain Ta 3C2. And mixing carbide and oxide, and calcining to obtain the catalyst. The application also discloses a method for preparing benzene by cyclohexane dehydrogenation reaction by using the catalyst.
Description
Technical Field
The application relates to a catalyst for preparing benzene by cyclohexane dehydrogenation and a preparation method and application thereof, belonging to the field of chemical industry.
Background
Along with the large-scale popularization and application of the process for preparing the cyclohexanol by using the cyclohexene hydration method, the cyclohexane productivity is improved year by year, the cyclohexane consumption pressure is increased, and the process for preparing benzene by using the cyclohexane dehydrogenation method becomes possible on a process route. In this case, if a plant for producing adipic acid or caprolactam is provided with both cyclohexene hydration and cyclohexane oxidation production facilities, then the cyclohexane byproduct of the cyclohexene hydration production facility is directly consumed by the cyclohexane oxidation production facility, which is technically quite perfect. However, the cyclohexane oxidation method is gradually eliminated because of high safety risk and outstanding environmental protection problem of by-product waste lye treatment. Cyclohexane productivity is continuously increased, and the production capacity of adipic acid and caprolactam by using cyclohexane as a raw material is limited, so that the market pressure of cyclohexane sales is increased year by year, and even benzene and cyclohexane price reverse hanging occurs. Then, cyclohexane is dehydrogenated, and the benzene and hydrogen produced are used as raw materials of a cyclohexene hydration device, and become options related to factory decision.
In the cyclohexane dehydrogenation reaction process, the active component of the catalyst is noble metal such as platinum, the acidic component is mainly halogen (chlorine or fluorine), the carrier is alumina, and the noble metal forms a dehydrogenation active center. Raney nickel or other non-noble metal catalysts are also useful. In operating units, bimetallic or multimetal catalysts are often employed, with multimetal components as cocatalysts to improve catalyst performance. In existing catalysts, ni, ir, pd and Pt are often used as the active components of dehydrogenation catalysts. Wherein Pt has high activity on naphthene dehydrogenation due to high activation capacity on C-H bond. The higher the dispersity of the metal, the higher the activity of the catalyst under the same content of active component. However, the use of noble metals for the catalyst is difficult and expensive.
Disclosure of Invention
The metal carbide is prepared in the patent and then mixed with the alumina, the cost is low, the preparation method is simple, the carbide and the alumina are tightly combined, and the interaction is strong. The catalyst is applied to the reaction of preparing benzene by dehydrogenating cyclohexane, and has good catalyst activity, high cyclohexane conversion rate and benzene selectivity and good stability.
According to one aspect of the present application, there is provided a catalyst for preparing benzene by dehydrogenation of cyclohexane, capable of improving the conversion rate of cyclohexane and the selectivity of benzene;
The catalyst comprises Ta 3C2 and gamma-Al 2O3;
In the catalyst, the mass ratio of the Ta 3C2 to the gamma-Al 2O3 is 1: (10-30).
According to another aspect of the present application, there is provided a method for preparing the above catalyst, comprising the steps of:
1) Preparing Ta 3AlC2 by a high-temperature calcination method;
2) Immersing the Ta 3AlC2 obtained in 1) in a solution containing hydrofluoric acid to obtain Ta 3C2;
3) Mixing Ta 3C2 obtained in 2) with gamma-Al 2O3, and roasting to obtain the catalyst.
The preparation of Ta 3AlC2 by the high-temperature calcination method comprises the following steps:
And mixing and calcining a raw material containing a tantalum source, an aluminum source and carbon powder to obtain the Ta 3AlC2.
The tantalum source is selected from tantalum powder;
The aluminum source is selected from aluminum powder;
Optionally, the molar ratio of the tantalum source, the aluminum source and the carbon powder is 3: (0.9-1): 2;
Optionally, the molar ratio of the tantalum source, the aluminum source and the carbon powder is 3:0.9: 2. 3:0.95: 2. 3:1:2 or a range value between any two.
Optionally, the temperature of the calcination is 1000-1400 ℃;
Optionally, the temperature of the calcination is any value or range of values between any two of 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃.
Optionally, the calcination time is 1-6 hours.
Optionally, the calcination time is any value or range of values between any two of 1h, 2h, 3h, 4h, 5h, 6 h.
The concentration of hydrofluoric acid in the solution containing hydrofluoric acid is 30-50wt%;
optionally, the concentration of hydrofluoric acid in the solution containing hydrofluoric acid is any value or a range of values between any two of 30wt%, 35wt%, 40wt%, 45wt%, 50 wt%.
Optionally, the solid-to-liquid ratio of Ta 3AlC2 to the solution containing hydrofluoric acid obtained in 1) is 1: (10-30) g/ml;
Optionally, the solid-to-liquid ratio of Ta 3AlC2 to the solution containing hydrofluoric acid obtained in 1) is 1:10g/ml, 1:15g/ml, 1:20g/ml, 1:25g/ml, 1: any value in 30g/ml or a range of values between any two.
The temperature of the impregnation is 40-80 ℃;
Optionally, the temperature of the impregnation is any value or a range of values between any two of 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃.
The soaking time is 28-112 h;
Optionally, the time of the impregnation is any value or a range of values between any two of 28h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h, 112 h. Preferably, the Ta 3C2 is dried;
Optionally, the drying temperature is 60-100 ℃;
Optionally, the temperature of the drying is any value or a range of values between any two of 60 ℃, 70 ℃,80 ℃, 90 ℃, 100 ℃.
Optionally, the drying time is 12-36 h.
Optionally, the drying time is any value or range of values between any two of 12h, 18h, 24h, 30h, 36 h.
The mass ratio of Ta 3C2 to gamma-Al 2O3 obtained in the step 2) is 1: (10-30);
Optionally, the mass ratio of Ta 3C2 obtained in 2) to γ -Al 2O3 is 1: 10. 1: 20. 1:30 or a range of values therebetween.
The mixing comprises a mechanical mixing method or a wet mixing method;
The roasting temperature is 500-600 ℃;
optionally, the firing temperature is any value or range of values between any two of 500 ℃, 550 ℃, 600 ℃.
The roasting time is 4-8 hours.
Optionally, the firing time is any value or range of values between any two of 4h, 5h, 6h, 7h, 8 h.
Washing the Ta 3C2 and the catalyst before drying;
optionally, the washing solvent is selected from water and/or ethanol.
According to another aspect of the present application, there is provided a method for preparing benzene by dehydrogenating cyclohexane, comprising the steps of:
Introducing a material containing hydrogen and cyclohexane into a reactor, and contacting the material with a catalyst to react to obtain a benzene-containing product;
Wherein the catalyst is selected from the catalysts described above or the catalysts prepared by the preparation method described above.
The flow rate of the hydrogen is 5-10 ml/min;
The flow rate of the hydrogen gas is any value or range of values between any two of 5ml/min, 6ml/min, 7ml/min, 8ml/min, 9 ml/min, 10 ml/min.
The mass airspeed of the material is 2-4 h -1.
Optionally, the mass space velocity of the material is any value or a range of values between any two of 2h -1、3h-1、4h-1.
The temperature of the reaction is 280-340 ℃;
Alternatively, the temperature of the reaction is any value or range of values between any two of 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃.
The reaction time is 2-3 h;
alternatively, the reaction time is any value or range of values between any two of 2h, 2.5h, 3 h.
The pressure of the reaction is 0.1-0.4 MPa.
Alternatively, the pressure of the reaction is any value or range of values between any two of 0.1MPa, 0.2MPa, 0.3MPa, 0.4 MPa.
The reactor is a fixed bed reactor.
The application has the beneficial effects that:
1) The catalyst provided by the application can be applied to cyclohexane dehydrogenation reaction to prepare benzene and improve the conversion rate of cyclohexane and the selectivity of the generated benzene.
2) The preparation method of the catalyst provided by the application is stable, controllable and good in reproducibility.
3) The method for preparing benzene by cyclohexane dehydrogenation reaction provided by the application adopts the catalyst provided by the application, has high reaction speed and high yield, and can be applied to large-scale production.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of Ta 3C2 in catalyst 1 #.
Fig. 2 is a scanning electron microscope image of Ta 3C2 in catalyst 1 #.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified. Wherein the gas chromatograph is 7890B type gas chromatograph of Agilent company.
Examples 1 to 28
Preparation of the catalyst
Taking the number 1 in tables 1 to 2 as an example, the molar ratio is 3: (0.9-1): 2, grinding the tantalum powder, the aluminum powder and the carbon powder to obtain a mixture; calcining for 2h in an open tubular furnace at 1400 ℃ to obtain Ta 3AlC2. Then, soaking Ta 3AlC2 in 40wt% hydrofluoric acid solution for mixing (the solid-to-liquid ratio of Ta 3AlC2 to the hydrofluoric acid solution is 1:20 g/ml), and soaking at 60 ℃ for 56h; washing with ethanol for several times, drying at 70deg.C for 24h to obtain Ta 3C2.Ta3C2 and gamma-Al 2O3, mixing with wet mixing method (mass ratio of Ta 3C2 to gamma-Al 2O3 is 1:20), and calcining at 550deg.C under argon atmosphere for 4h. Catalyst Ta 3C2/γ-Al2O3 was obtained and was designated as catalyst 1 #.
The kinds, amounts and reaction parameters of the respective raw materials were adjusted as follows to obtain a series of catalysts having the numbers 2 to 28, which were designated as catalysts 2 # to 28 #, as shown in the following table 1:
TABLE 1
TABLE 2
The following are listed in tables 1-2 above:
The mixing method comprises the following steps: mechanical mixing method (method 1), wet mixing method (method 2).
Washing solvent: deionized water (solution 1), ethanol (solution 2), deionized water and ethanol mixed solution (solution 3)
XRD characterization
And adopting a Miniflex 600 type X-ray diffractometer and a Cu target to diffract the catalyst 1 # powder to obtain a Ta 3C2 diffraction peak in the catalyst 1 #, wherein the Ta 3C2 characteristic peak is consistent with the Ta (shown in figure 1).
SEM characterization
The morphology of Ta 3C2 in catalyst 1 # (shown in fig. 2) was performed by Scanning Electron Microscopy (SEM) (JSM-7800F).
Characterization by gas chromatography
The composition of the cyclohexane dehydrogenation reaction product was analyzed using Agilent 7890B gas chromatography (FID detector, HP-5 capillary column).
Application example 1
The catalyst is used for preparing benzene by cyclohexane dehydrogenation.
Catalysts 1 # to 28 prepared in example 1, catalyst 28 and # are used for preparing benzene by cyclohexane dehydrogenation, and raw materials are contacted with the catalyst in a reactor and react for 3 hours under the condition of 310 ℃ and the pressure of 0.2Mpa to obtain a product containing benzene; the mass space velocity was 3h -1,H2 and the flow rate was 8 ml/min. The raw materials are introduced into a fixed bed reactor loaded with 3g of the catalyst, and the dehydrogenation reaction is carried out to prepare benzene.
After the reaction is stable, the reaction raw materials and the products are analyzed by gas online chromatography. The reaction results are shown in Table 3.
TABLE 3 Table 3
As can be seen from the table, the prepared catalyst is used in the reaction of preparing benzene by dehydrogenation, and has high catalytic activity.
Application example 2
The catalyst 1 # prepared in Table 1 was used for cyclohexane dehydrogenation to prepare benzene, and after the reaction was stabilized, the reaction materials and the products were analyzed by gas online chromatography. The reaction results are shown in Table 4.
TABLE 4 Table 4
It can be seen from the table that the reaction temperature and the H 2 flow rate have a large influence on the conversion of the reaction cyclohexane.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. A catalyst for preparing benzene by cyclohexane dehydrogenation is characterized in that,
The catalyst comprises Ta 3C2 and gamma-Al 2O3;
In the catalyst, the mass ratio of the Ta 3C2 to the gamma-Al 2O3 is 1: (10-30).
2. A process for preparing a catalyst according to claim 1, wherein,
The method comprises the following steps:
1) Preparing Ta 3AlC2 by a high-temperature calcination method;
2) Immersing the Ta 3AlC2 obtained in 1) in a solution containing hydrofluoric acid to obtain Ta 3C2;
3) Mixing Ta 3C2 obtained in 2) with gamma-Al 2O3, and roasting to obtain the catalyst.
3. The method according to claim 2, wherein,
The preparation of Ta 3AlC2 by the high-temperature calcination method comprises the following steps:
And mixing and calcining a raw material containing a tantalum source, an aluminum source and carbon powder to obtain the Ta 3AlC2.
4. A process according to claim 3, wherein,
The tantalum source is selected from tantalum powder;
The aluminum source is selected from aluminum powder;
Preferably, the molar ratio of the tantalum source to the aluminum source to the carbon powder is 3: (0.9-1): 2;
preferably, the temperature of the calcination is 1000-1400 ℃;
Preferably, the calcination time is 1 to 6 hours.
5. The method according to claim 2, wherein,
The concentration of hydrofluoric acid in the solution containing hydrofluoric acid is 30-50wt%;
Preferably, the solid-to-liquid ratio of Ta 3AlC2 to the solution containing hydrofluoric acid obtained in 1) is 1: (10-30) g/ml;
Preferably, the temperature of the impregnation is 40-80 ℃;
Preferably, the time of the impregnation is 28-112 hours;
Preferably, the Ta 3C2 is dried;
preferably, the drying temperature is 60-100 ℃;
preferably, the drying time is 12-36 hours.
6. The method according to claim 2, wherein,
The mass ratio of Ta 3C2 to gamma-Al 2O3 obtained in the step 2) is 1: (10-30);
The mixing comprises a mechanical mixing method or a wet mixing method;
The roasting temperature is 500-600 ℃;
The roasting time is 4-8 hours.
7. The method according to claim 5, wherein,
Washing the Ta 3C2 and the catalyst before drying;
preferably, the washing solvent is selected from water and/or ethanol.
8. A method for preparing benzene by cyclohexane dehydrogenation is characterized in that,
The method comprises the following steps:
Introducing a material containing hydrogen and cyclohexane into a reactor, and contacting the material with a catalyst to react to obtain a benzene-containing product;
Wherein the catalyst is selected from the group consisting of the catalyst of claim 1 or the catalyst prepared by the preparation method of any one of claims 2 to 7.
9. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
The flow rate of the hydrogen is 5-10 ml/min;
The mass airspeed of the material is 2-4 h -1.
10. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
The temperature of the reaction is 280-340 ℃;
the reaction time is 2-3 h;
the pressure of the reaction is 0.1-0.4 MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211362269.5A CN117983261A (en) | 2022-11-02 | 2022-11-02 | Catalyst for preparing benzene by cyclohexane dehydrogenation and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211362269.5A CN117983261A (en) | 2022-11-02 | 2022-11-02 | Catalyst for preparing benzene by cyclohexane dehydrogenation and preparation method and application thereof |
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