CN110721740A - Preparation method and application of bifunctional catalyst - Google Patents
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- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The invention discloses a preparation method and application of a bifunctional catalyst, and the preparation method comprises the following steps: step 1, preparing metal M and SiO2Composite M/SiO of carrier2(ii) a Or loading a metal M on the graphene oxide; step 2, mixing M/SiO2Mixing the compound, an aluminum source, a phosphorus source, a microporous template agent and graphene oxide, grinding, and placing in a hydrothermal kettle for crystallization reaction; or SiO2Mixing a carrier, an aluminum source, a phosphorus source, a microporous template agent and graphene oxide loaded with metal M, grinding, and placing in a hydrothermal kettle for crystallization reaction; and 3, washing, drying and roasting the product after the crystallization reaction to obtain the M/SAPO-11 bifunctional catalyst. Compared with the catalyst prepared by the traditional solvent-free method, the prepared M/SAPO-11 catalyst has obviously increased isomer yield which reaches 84 percent to the maximum; compared with a catalyst without the graphene oxide, the catalytic activity is improved.
Description
Technical Field
The invention belongs to the technical field of molecular sieve catalysts, and particularly relates to a preparation method of a bifunctional catalyst.
Background
Based on the increasingly strict requirements of environmental regulations on the continuous enhancement of product performance, the hydroisomerization reaction of alkanes plays an increasingly important role in the chemical process. The reaction can isomerize normal paraffin in fraction oil into branched paraffin, and this can raise the octane number of gasoline, improve the low temperature flowability of diesel oil and lubricating oil and maintain high product yield.
The preparation of the supported metal molecular sieve dual-function catalyst is a core technology of long paraffin isomerization catalytic reaction, wherein hydrogenation-dehydrogenation reaction is carried out on a noble metal active component, and a carbocation rearrangement process is carried out on a molecular sieve carrier. The SAPO-11 molecular sieve has a one-dimensional straight-through pore channel, is suitable for acidity, has a small pore channel size, can limit the formation of double-branched chain and multi-branched chain products, has an excellent shape-selective effect, and can remarkably improve isomerization selectivity. At present, in the preparation of the bifunctional catalyst, the metal load is mainly carried by adopting an impregnation method, the interaction between the obtained catalyst metal and a carrier is weaker, and the hydrogenation performance of the metal is lower. The inventor proposes a new method for preparing a bifunctional catalyst with strong interaction, namely a pre-loading method (application number: 201910305683.4), in the patent, the application of the pre-loading method to the hydroisomerization reaction not only can lead the yield of the product liquid to reach more than 99 percent, but also can greatly increase the yield of isomers, but because Pt blocks the pore passages of the molecular sieve, the acidity of the molecular sieve is reduced, and the catalytic activity is reduced, therefore, the development of an improved pre-loading process for preparing the bifunctional catalyst is particularly important on the premise of ensuring high yield of the isomers. Conventional methods for modifying molecular sieves, including post-treatment and templating methods, typically result in a loss of crystallinity of the molecular sieve. The method for simply prolonging the reaction time has small improvement range of the crystallinity of the molecular sieve in the invention.
Disclosure of Invention
The invention aims to provide a preparation method of a bifunctional catalyst, which is characterized in that graphene oxide is added into a reaction system, so that the crystallinity of a molecular sieve is improved, the acidity of the molecular sieve is improved, the activity of a hydroisomerization reaction is improved, and the catalytic performance is optimized.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a process for preparing a bifunctional catalyst, the process comprising the steps of:
step 1, preparing metal M and SiO2Composite M/SiO of carrier2(ii) a Or loading a metal M on the graphene oxide;
and 3, washing, drying and roasting the product after the crystallization reaction to obtain the M/SAPO-11 bifunctional catalyst.
Preferably, theSiO2The support is fumed silica with different specific surface areas. Further preferably, the SiO2The carrier is white carbon black.
Preferably, the metal M is a combination of one or more of Pt, Pd, Ni.
Preferably, the M/SiO2The mass ratio of the aluminum source to the microporous template to the phosphorus source to the graphene oxide is (0.05-0.3): 1: (0.7-1.2): (0.7-1.2): (0.005-0.5); or, the SiO2The mass ratio of the aluminum source to the microporous template to the phosphorus source to the graphene oxide loaded with the metal M is (0.05-0.3): 1: (0.7-1.2): (0.7-1.2): (0.005-0.5).
Preferably, the graphene oxide has different numbers and distributions of surface functional groups.
Preferably, the crystallization reaction temperature in the step 2 is 140-220 ℃, and the reaction time is 9-72 h.
Preferably, the roasting atmosphere in the step 3 is air, and the roasting temperature is 500-700 ℃.
The invention also provides application of the M/SAPO-11 bifunctional catalyst in long-chain alkane hydroisomerization reaction. Preferably, the long chain alkane has a carbon number between 12 and 30.
Compared with the prior art, the invention has the following beneficial effects:
1, the prepared M/SAPO-11 bifunctional catalyst is applied to the hydroisomerization reaction of long-chain alkane, and compared with the catalyst prepared by the traditional solvent-free method, the isomer yield is obviously increased and reaches 84 percent at most; compared with a system without adding graphene oxide, the catalytic activity is improved, and the reaction conversion rate is improved from 62% to 74% when the temperature is 350 ℃.
2, in order to avoid the phenomenon that the acidity is weakened due to blockage of SAPO-11 pore canals by metal particles, the invention also adopts an impregnation method to load metal on graphene oxide, then the graphene oxide is mixed with the reaction raw material of the SAPO-11, and crystallization reaction is carried out to obtain the confined structure catalyst M/SAPO-11 with the metal positioned in the SAPO-11. The catalyst with the limited domain structure prepared by the method can avoid the blockage of micropores of the molecular sieve caused by the addition of Pt, and the acidity of the molecular sieve can be increased by the addition of graphene oxide, so that the activity is enhanced.
Drawings
FIG. 1 is an XRD pattern of each of the products obtained in examples of the present invention and comparative examples.
FIG. 2 is a graph showing the conversion of n-dodecane in hydroisomerization over temperature for catalysts prepared in examples 1-3 of the present invention and comparative example 1, respectively.
FIG. 3 is a graph showing the isomer yield versus temperature for n-dodecane hydroisomerization reactions for catalysts prepared in examples 1-3 of the present invention and comparative example 1, respectively.
FIG. 4 is a graph showing the temperature dependence of the conversion of n-dodecane in the hydroisomerization over the catalyst prepared in example 3 of the present invention and in comparative example 2, respectively.
FIG. 5 is a graph showing the isomer yield versus temperature for the hydroisomerization of n-dodecane for catalysts prepared in example 3 according to the present invention and in comparative example 2, respectively.
FIG. 6 is a graph showing the conversion of catalysts prepared in comparative example 3 and comparative example 4 of the present invention with respect to n-dodecane hydroisomerization reaction, respectively, as a function of temperature.
FIG. 7 is a graph showing the isomer yield versus temperature for the hydroisomerization of n-dodecane for the catalysts prepared in comparative example 3 and comparative example 4, respectively, according to the present invention.
Fig. 8 is an XRD spectrum of the limited domain catalyst prepared in example 4 of the present invention.
FIG. 9 is a plot of the conversion of the constrained domain catalyst prepared in example 4 of the present invention versus the temperature for the hydroisomerization of n-dodecane.
FIG. 10 is a plot of the isomer yield versus temperature for n-dodecane hydroisomerization over the constrained domain catalyst prepared in example 4 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail with reference to examples.
Example 1
The microporous template agent is di-n-propylamine, di-n-propylamine and reaction raw material phosphoric acid are used for forming di-n-propylamine phosphate before reaction, and the reaction molar ratio of di-n-propylamine to phosphoric acid is 1:1.0-1: 1.2.
1.05mL of H with a concentration of 0.245mol/L2PtCl6Dipping the solution on 0.25g of white carbon black, dipping for 24h at room temperature, drying and sintering to obtain Pt/SiO2. Mixing Pt with SiO2Mixing with 2.912g of pseudo-boehmite, 6.28g of di-n-propylamine phosphate and 0.283g of graphene oxide, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at the temperature of 200 ℃ for 24 hours, carrying out centrifugal washing on the obtained product, drying at the temperature of 80 ℃ and roasting at the temperature of 600 ℃ in air atmosphere for 6 hours to obtain the final catalyst product. The obtained product is named as Pt/SAPO-11-B-0.03 GO.
As can be seen in FIG. 1, the Pt/SAPO-11-B-0.03GO sample crystallized well with a typical AEL structure, which was confirmed to be the SAPO-11 crystalline phase by comparison to a standard card.
Comparative example 1
Weighing 0.25g of white carbon black, 2.912g of pseudo-boehmite and 6.28g of di-n-propylamine phosphate, mixing, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at the temperature of 200 ℃ for 24 hours, carrying out centrifugal washing on the obtained product, drying at the temperature of 80 ℃ and roasting at the temperature of 600 ℃ for 6 hours to obtain SAPO-11. Pt is loaded on the SAPO-11 by adopting an equal-volume impregnation mode, in particular to 1.05mL of H with the concentration of 0.037mol/L2PtCl6Dipping the solution on 1g of SAPO-11, dipping for 24h at room temperature, drying and sintering to obtain the catalyst product Pt/SAPO-11-A. Since this comparative example was different in mass from the sample obtained in example 1, the Pt concentration at the time of carrying out the loading was different; however, elemental analysis of the prepared catalyst products revealed that the Pt loadings of the comparative example and example 1 were the same, both 0.7%.
Comparative example 2
1.05mL of H with a concentration of 0.245mol/L2PtCl6Dipping the solution on 0.25g of white carbon black, dipping for 24h at room temperature, drying and sintering to obtain Pt/SiO2. Mixing Pt with SiO2Mixing with 2.912g of pseudo-boehmite and 6.28g of di-n-propylamine phosphate, grinding for 10 minutes, and charging the obtained powder into a reactorPerforming crystallization reaction at 200 ℃ for 24h in a kettle, centrifugally washing the obtained product, drying at 80 ℃ and roasting at 600 ℃ for 6h to obtain the final catalyst product. The obtained product is named as Pt/SAPO-11-B.
Example 2
1.05mL of H with a concentration of 0.245mol/L2PtCl6Dipping the solution on 0.25g of white carbon black, dipping for 24h at room temperature, drying and sintering to obtain Pt/SiO2. Mixing Pt with SiO2Mixing with 2.912g of pseudo-boehmite, 6.28g of di-n-propylamine phosphate and 0.472g of graphene oxide, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at the temperature of 200 ℃ for 24 hours, carrying out centrifugal washing on the obtained product, drying at the temperature of 80 ℃ and roasting at the temperature of 600 ℃ in air atmosphere for 6 hours to obtain the final product. The obtained product is named as Pt/SAPO-11-B-0.05 GO.
Example 3
1.05mL of H with a concentration of 0.245mol/L2PtCl6Dipping the solution on 0.25g of white carbon black, dipping for 24h at room temperature, drying and sintering to obtain Pt/SiO2. Mixing Pt with SiO2Mixing with 2.912g of pseudo-boehmite, 6.28g of di-n-propylamine phosphate and 0.661g of graphene oxide, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at the temperature of 200 ℃ for 24 hours, carrying out centrifugal washing on the obtained product, drying at the temperature of 80 ℃ and roasting at the temperature of 600 ℃ in air atmosphere for 6 hours to obtain the final product. The obtained product is named as Pt/SAPO-11-B-0.07 GO.
Referring to FIG. 1, XRD patterns of the respective catalyst products obtained in examples 1 to 3 and comparative examples 1 to 2 are shown. As can be seen from FIG. 1, the catalysts obtained in examples 1 to 3 crystallized well and had typical AEL structures.
The catalysts synthesized in examples 1 to 3 and the SAPO-11-A catalyst synthesized in comparative example 1 are respectively subjected to catalytic hydroisomerization reactions under the following reaction conditions: 280 ℃ and 380 ℃, 4.5MPa and WHSV of 1.5h-1，nH215 for nC 12. Referring to FIGS. 2 and 3, the conversion and isomer yield of the hydroisomerization reaction are plotted against temperature for the catalyst products obtained in examples 1-3 and comparative example 1. Can be seen from FIGS. 2 and 3To: the catalyst prepared in the embodiment 1-3 has a remarkably improved isomer yield of 84% at the highest and a liquid yield of more than 99% relative to the SAPO-11-A catalyst in the hydroisomerization reaction of n-dodecane at the temperature of 340-380 ℃. The SAPO-11-A catalyst of the comparative example gave a maximum isomer yield of 71% for the hydroisomerization of n-dodecane. However, the SAPO-11-A catalyst prepared by the post-loading process is superior in conversion to the catalysts of examples 1-3. The reason for this analysis may be: after the catalyst prepared by the pre-loading process loads metal Pt, Pt is easy to block the pore channels of the molecular sieve, so that the acidity of the molecular sieve is reduced, the catalytic activity is reduced, and the conversion rate is reduced.
Referring to fig. 4 and 5, the conversion and isomer yield versus temperature for the n-dodecane hydroisomerization reaction are plotted for the catalysts prepared in example 3 and comparative example 2. Fig. 4 and 5 show that: compared with the bifunctional catalyst prepared by the previous load process (comparative example 2), the catalytic activity is obviously enhanced after the graphene oxide is added into the system, and the reaction conversion rate is improved from 62% to 74% when the temperature is 350 ℃. The reason is that the functional groups on the surface of the graphene oxide and the reaction raw materials form hydrogen bonds and amido bonds, so that the raw materials are gathered on the surface of the graphene oxide, the concentration of reactants is increased, the crystallinity of the molecular sieve is enhanced, and the acidity is improved. Therefore, by adopting a pre-loading process and adding graphene oxide, the high isomer yield can be ensured, and the catalytic activity can be improved to a certain extent.
The catalyst products obtained in the catalytic activity examples 1 to 3 can all realize the isomer yield of more than 80% when catalyzing the hydroisomerization reaction of n-dodecane.
Comparative example 3
1.05mL of H with a concentration of 0.245mol/L2PtCl6Dipping the solution on 0.25g of white carbon black, dipping for 24h at room temperature, drying and sintering to obtain Pt/SiO2. Mixing Pt with SiO2Mixing with 2.912g of pseudo-boehmite and 6.28g of di-n-propylamine phosphate, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at 200 ℃ for 48 hours, centrifuging and washing the obtained product, drying at 80 ℃ and roasting at 600 ℃ for 6 hours to obtain the productAnd (4) a final product. The obtained product is named as Pt/SAPO-11-B-48 h.
Comparative example 4
1.05mL of H with a concentration of 0.245mol/L2PtCl6Dipping the solution on 0.25g of white carbon black, dipping for 24h at room temperature, drying and sintering to obtain Pt/SiO2. Mixing Pt with SiO2Mixing with 2.912g of pseudo-boehmite and 6.28g of di-n-propylamine phosphate, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at 200 ℃ for 72 hours, centrifuging and washing the obtained product, drying at 80 ℃ and roasting at 600 ℃ for 6 hours to obtain the final product. The obtained product is named as Pt/SAPO-11-B-72 h.
Referring to fig. 6 and 7, the conversion and isomer yield versus temperature for the n-dodecane hydroisomerization reaction for the catalysts prepared in comparative examples 3 and 4 are shown. As can be seen from fig. 6 and 7, there was substantially no change in catalyst performance over the extended reaction time to 48h and 72 h. Therefore, the catalytic activity cannot be improved by prolonging the reaction time.
Example 4
1.05mL of H with a concentration of 0.245mol/L2PtCl6The solution is dipped on 0.283g of graphene oxide, dipped for 24h at room temperature, dried and sintered. Then mixing with 0.25g of white carbon black, 2.912g of pseudo-boehmite and 6.28g of di-n-propylamine phosphate, grinding for 10 minutes, putting the obtained powder into a reaction kettle, carrying out crystallization reaction at the temperature of 200 ℃ for 24 hours, carrying out centrifugal washing on the obtained product, drying at the temperature of 80 ℃ and roasting at the temperature of 600 ℃ for 6 hours to obtain a final product, namely a limited-domain catalyst, which is named as Pt/SAPO-11-C.
Referring to FIG. 8, an XRD spectrum diagram of a limited-domain catalyst Pt/SAPO-11-C is shown. The XRD spectrum showed that the confined domain catalyst prepared in example 4 has a typical AEL structure, belongs to the crystalline phase of SAPO-11, and is free of impurity phases. Referring to FIGS. 9 and 10, the conversion and isomer yield versus temperature for a Pt/SAPO-11-C catalyst for n-dodecane hydroisomerization is shown. As can be seen from fig. 9 and 10: Pt/SAPO-11-C had higher activity and isomer yield (72.8%) than the comparative hydrothermal sample Pt/SAPO-11-A. From this, it can be judged that: the catalyst with the confinement structure prepared by the method can avoid the blockage of micropores of the molecular sieve caused by the addition of Pt, and can increase the acidity of the molecular sieve by the addition of graphene oxide, so that the activity of the catalyst is enhanced.
The above description is only a part of the preferred embodiments of the present invention, and the present invention is not limited to the contents of the embodiments. It will be apparent to those skilled in the art that various changes and modifications can be made within the spirit of the invention, and any changes and modifications made are within the scope of the invention.
Claims (10)
1. A method for preparing a bifunctional catalyst, said method comprising the steps of:
step 1, preparing metal M and SiO2Composite M/SiO of carrier2(ii) a Or loading a metal M on the graphene oxide;
step 2, mixing M/SiO2Mixing the compound, an aluminum source, a phosphorus source, a microporous template agent and graphene oxide, grinding, and placing in a hydrothermal kettle for crystallization reaction; or SiO2Mixing a carrier, an aluminum source, a phosphorus source, a microporous template agent and graphene oxide loaded with metal M, grinding, and placing in a hydrothermal kettle for crystallization reaction;
and 3, washing, drying and roasting the product after the crystallization reaction to obtain the M/SAPO-11 bifunctional catalyst.
2. A process for preparing a bifunctional catalyst as claimed in claim 1, characterized in that: the SiO2The support is fumed silica with different specific surface areas.
3. A process for preparing a bifunctional catalyst as claimed in claim 2, characterized in that: the SiO2The carrier is white carbon black.
4. A process for preparing a bifunctional catalyst as claimed in claim 1, characterized in that: the metal M is one or more of Pt, Pd and Ni.
5. A process for preparing a bifunctional catalyst as claimed in claim 1, characterized in that: the M/SiO2The mass ratio of the aluminum source to the microporous template to the phosphorus source to the graphene oxide is (0.05-0.3): 1: (0.7-1.2): (0.7-1.2): (0.005-0.5); the SiO2The mass ratio of the aluminum source to the microporous template to the phosphorus source to the graphene oxide loaded with the metal M is (0.05-0.3): 1: (0.7-1.2): (0.7-1.2): (0.005-0.5).
6. A process for preparing a bifunctional catalyst as claimed in claim 1, characterized in that: the graphene oxide has different numbers and distributions of surface functional groups.
7. A process for preparing a bifunctional catalyst as claimed in claim 1, characterized in that: the crystallization reaction temperature in the step 2 is 140-220 ℃, and the reaction time is 9-72 h.
8. An improved process for preparing a bifunctional catalyst as claimed in claim 1, characterized in that: in the step 3, the roasting atmosphere is air, and the roasting temperature is 500-700 ℃.
9. The use of the M/SAPO-11 bifunctional catalyst of claim 1 in long chain alkane hydroisomerization reactions.
10. The use of an M/SAPO-11 bifunctional catalyst according to claim 9, wherein: the carbon number of the long-chain alkane is between 12 and 30.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113333017A (en) * | 2021-05-18 | 2021-09-03 | 四川泸天化股份有限公司 | Preparation method and application of biomass charcoal-assisted synthesis bifunctional catalyst |
| CN113680381A (en) * | 2021-08-18 | 2021-11-23 | 四川泸天化股份有限公司 | Preparation method and application of bifunctional molecular sieve catalyst |
| CN116328828A (en) * | 2021-12-22 | 2023-06-27 | 中国石油天然气股份有限公司 | Hydroisomerization catalyst and preparation method and application thereof |
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