Shape-selective isomerization catalyst and preparation method and application thereof

Abstract

The invention discloses a shape-selective isomerization catalyst as well as a preparation method and application thereof. The catalyst comprises a ten-membered ring aluminum phosphate molecular sieve, a noble metal active component and a metal oxide auxiliary active component. The ten-membered ring aluminum phosphate molecule is selected from at least one of SAPO-11, MeAPO-11, SAPO-41 and MeAPO-41, and the ten-membered ring aluminum phosphate molecule is selected from at least one of SAPO-11, the noble metal active component is selected from at least one of Pt and Pd; the metal oxide auxiliary agent is selected from at least one of CeO2, Nb2O5 and Ta2O5. Compared with the catalyst prepared in the prior art, the catalyst prepared by the method provided by the invention has higher activity and isomer yield in the isomerization reaction of long-chain n-alkanes.

Description

Technical Field

[0001] The present application relates to a shape-selective isomerization catalyst, a preparation method and an application thereof, and belongs to the technical field of fine chemical industry. Background Art

[0002] Bifunctional solid catalysts are widely used in the alkane hydroisomerization process and consist of two parts: a hydrogenation-dehydrogenation component and an acidic support. Among them, the hydrogenation-dehydrogenation component is mainly Group VIII metals such as Pt, Pd, Rh, Ir, and Ni, etc.; the acidic support can be divided into the following three categories: 1. Amorphous single metal oxides or composite oxides, such as Al2O3 treated with halides, SiO2 / Al2O3, superacid ZrO2 / SO4 2- 、WO3 / ZrO2, etc.; 2. Zeolite series of silicon-aluminum, such as Y, Beta, ZSM-5, etc.; 3. Zeolite series of aluminum phosphate, such as SAPO-5, SAPO-11, SAPO-31, and SAPO-41, etc. Compared with amorphous oxides and superacids, zeolites show excellent performance in terms of shape-selective selectivity, stability, anti-poisoning, and anti-coking ability. Therefore, isomerization catalysts with zeolites as carriers are widely used. Patent documents such as US5882505, US20040138051A1, US20050077209A1, CN1792451, CN1788844A, and CN101245260A have all described in detail the preparation methods of alkane hydroisomerization catalysts with zeolites as carriers.

[0003] Tenne-ring aluminophosphate zeolites are a class of synthetic zeolites, and their typical representatives are SAPO-11, MeAPO-11 (Me = Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni), SAPO-41, MeAPO-41 (Me = Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni), which have the characteristics of moderate acidity and one-dimensional straight channels and are ideal carriers for shape-selective isomerization catalysts of long-chain alkanes.

[0004] According to the reaction mechanism of n-alkanes on bifunctional catalysts, the conversion of n-alkanes on the catalyst surface mainly undergoes three chemical reaction steps and two diffusion steps. The chemical reaction steps include alkane dehydrogenation reaction and olefin hydrogenation reaction on metal centers and isomerization / cracking reaction on acidic centers. The diffusion steps include the diffusion of n-olefins from metal centers to acidic centers and the diffusion of iso-olefins from acidic centers to metal centers. From the perspective of chemical reaction steps, the isomerization performance of bifunctional catalysts is affected by factors such as the metallicity (electronic properties, loading, and dispersion, etc.) of the catalyst, acidity (acid type, acid amount, and acid strength, etc.), and pore structure. In the alkane isomerization reaction, the metallicity of the catalyst can not only ensure the progress of alkane dehydrogenation reaction and olefin hydrogenation reaction, improve the reaction activity and isomer selectivity of the catalyst, but also inhibit the formation of carbon deposition and improve the stability of the catalyst. When the metallicity is insufficient to balance the acidity, the isomerization carbocations on acidic centers are prone to further isomerization or even cracking reactions, resulting in a lower isomer selectivity of the catalyst. For a long time, people often increase the number of metal active sites by increasing the metal loading and improving the dispersion, so as to maintain the balance with acidic sites, while little attention has been paid to improving the intrinsic activity of metal sites. Summary of the Invention

[0005] The object of the present invention is to provide a shape-selective isomerization catalyst based on ten-membered ring aluminophosphate molecular sieve and its preparation method.

[0006] Specifically, the present invention provides a shape-selective isomerization catalyst using a ten-membered ring aluminophosphate molecular sieve as a carrier, which can improve the hydrogenation / dehydrogenation performance of noble metals based on metal oxide promoters CeO2, Nb2O5, Ta2O5, so as to obtain excellent hydroisomerization performance.

[0007] According to one aspect of the present application, there is provided a shape-selective isomerization catalyst, which includes a ten-membered ring aluminophosphate molecular sieve, an active component, a promoter, and a binder;

[0008] The active component is loaded on the promoter;

[0009] The ten-membered ring aluminophosphate molecular sieve is selected from at least one of SAPO-11, MeAPO-11, SAPO-41, and MeAPO-41;

[0010] Among them, Me in MeAPO-11 and MeAPO-41 is selected from at least one of Zn, Mg, Mn, Co, Cr, Cu, Cd, and Ni;

[0011] The active component is selected from Pt and / or Pd;

[0012] The promoter is a metal oxide, and the metal oxide is selected from at least one of CeO2, Nb2O5, and Ta2O5;

[0013] The binder is alumina.

[0014] Optionally, the acid amount of the ten-membered ring aluminophosphate molecular sieve is 0.8 - 2.0 mmol(NH3) / g.

[0015] Optionally, the acid amount of the ten-membered ring aluminophosphate molecular sieve independently selects any value from 0.8 mmol(NH3) / g, 1.0 mmol(NH3) / g, 1.2 mmol(NH3) / g, 1.4 mmol(NH3) / g, 1.6 mmol(NH3) / g, 1.8 mmol(NH3) / g, 2.0 mmol(NH3) / g or the range value between any two of the above.

[0016] Optionally, the acid amount of the ten-membered ring aluminophosphate molecular sieve is 1.2 - 1.8 mmol(NH3) / g.

[0017] Optionally, in the shape-selective isomerization catalyst, the content of the active component is 0.05 wt.% - 0.3 wt.%.

[0018] Optionally, in the shape-selective isomerization catalyst, the content of the active component independently selects any value from 0.05 wt.%, 0.1 wt.%, 0.15 wt.%, 0.2 wt.%, 0.25 wt.%, 0.3 wt.% or the range value between any two of the above.

[0019] Optionally, in the shape-selective isomerization catalyst, the content of the ten-membered ring aluminophosphate molecular sieve is 30 wt.% - 75 wt.%.

[0020] Optionally, in the shape-selective isomerization catalyst, the content of the ten-membered ring aluminophosphate molecular sieve independently selects any value from 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.% or the range value between any two of the above.

[0021] Optionally, in the shape-selective isomerization catalyst, the content of the ten-membered ring aluminophosphate molecular sieve is 50 wt.% - 70 wt.%.

[0022] Optionally, in the shape-selective isomerization catalyst, the content of the promoter is 5 wt.% - 50 wt.%.

[0023] Optionally, in the shape-selective isomerization catalyst, the content of the promoter is independently selected from any value among 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.% or a range value between any two of the above.

[0024] Optionally, in the shape-selective isomerization catalyst, the content of the promoter is 5 wt.% to 15 wt.%.

[0025] Optionally, in the shape-selective isomerization catalyst, the content of the binder is 20 wt.% to 50 wt.%.

[0026] Optionally, in the shape-selective isomerization catalyst, the content of the binder is independently selected from any value among 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.% or a range value between any two of the above.

[0027] Optionally, in the MeAPO-11 and MeAPO-41, the mass content of Me is 0.05 to 5 wt.%.

[0028] Optionally, in the MeAPO-11 and MeAPO-41, the mass content of Me is independently selected from any value among 0.05 wt.%, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.% or a range value between any two of the above.

[0029] According to another aspect of the present application, a preparation method of the above-mentioned shape-selective isomerization catalyst is provided, and the preparation method includes the following steps:

[0030] (1) Immerse the metal oxide in a solution containing the active component precursor, dry I, and calcine I to obtain the metal oxide loaded with the active component;

[0031] (2) Mix, knead, extrude, dry II, calcine II, and reduce the mixture containing the metal oxide loaded with the active component, the ten-membered ring aluminophosphate molecular sieve, and the binder to obtain the shape-selective isomerization catalyst.

[0032] Optionally, in the step (1), the active component precursor is selected from at least one of platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, dichlorotetraammineplatinum, dichlorodiammineplatinum, dinitrodiammineplatinum, palladium chloride, ammonium chloropalladate, dichlorotetraamminepalladium, dichlorodiamminepalladium, and dinitrodiamminepalladium.

[0033] Optionally, in the step (1), the temperature of the dry I is 50 to 200 °C, and the time of the dry I is 0.5 to 24 h.

[0034] Optionally, in the step (1), the atmosphere for the first calcination is an oxygen-containing atmosphere.

[0035] Optionally, the oxygen content in the oxygen-containing atmosphere is 10-100%.

[0036] Optionally, in the step (1), the oxygen-containing atmosphere is selected from one of pure oxygen, oxygen-nitrogen mixture or oxygen-argon mixture.

[0037] Optionally, in the step (1), the temperature of the first calcination is 400-1200 °C, and the time of the first calcination is 0.1-48 h.

[0038] Optionally, the temperature of the first calcination is 500-900 °C, and the time of the first calcination is 0.5-24 h.

[0039] Optionally, in the step (2), the temperature of the second drying is 50-200 °C, and the time of the second drying is 0.5-24 h.

[0040] Optionally, in the step (2), the temperature of the second calcination is 350-550 °C, and the time of the second calcination is 0.5-24 h.

[0041] Optionally, in the step (2), the atmosphere for the reduction is hydrogen, and the gas flow rate of hydrogen is 5-30 mL / min / g 催化剂 。

[0042] Optionally, the temperature of the reduction is 200-400 °C, and the time of the reduction is 2-8 h.

[0043] Optionally, the temperature of the reduction is 250-350 °C, and the time of the reduction is 4-8 h.

[0044] According to another aspect of the present application, there is provided an application of the shape-selective isomerization catalyst as described above in the isomerization reaction of long-chain alkanes.

[0045] Optionally, the conditions for the isomerization reaction of long-chain alkanes are as follows:

[0046] The reaction temperature is 200-400 °C, the reaction pressure is 0.1-10 MPa, the feed volume space velocity is 0.5-5 h -1 , and the hydrogen-oil ratio (mol / mol) is 5-50.

[0047] Optionally, the reaction temperature is 280-350 °C.

[0048] Optionally, the long-chain alkane is a C8-C50 long-chain alkane.

[0049] The catalyst provided by this application can be widely used in the processing of petroleum fractions, biomass, and Fischer-Tropsch synthesis products, such as isomerization for dewaxing, isodewaxing, and other processes.

[0050] The preparation method of the above catalyst provided by this application is as follows: First, a noble metal active component is loaded on a metal oxide promoter, and after calcination, it is mixed with a ten-membered ring aluminophosphate molecular sieve in a certain proportion, and a binder is added for kneading, forming, and calcining, and the target catalyst is obtained after reduction, including the following steps:

[0051] (1) A noble metal precursor is loaded on a metal oxide promoter by an impregnation method, and after drying, the metal oxide promoter containing the noble metal precursor is calcined in an oxygen-containing atmosphere to obtain a metal oxide promoter loaded with a noble metal;

[0052] (2) The metal oxide promoter loaded with a noble metal obtained in step (1) is mixed with a ten-membered ring aluminophosphate molecular sieve and an alumina binder in a certain proportion, kneaded, extruded, dried, calcined, and reduced in a reducing atmosphere to prepare the shape-selective isomerization catalyst.

[0053] Optionally, the noble metal precursor in step (1) is selected from at least one of platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, dichlorotetraammineplatinum, dichlorodiammineplatinum, dinitrodiammineplatinum, palladium chloride, ammonium chloropalladate, dichlorotetraamminepalladium, dichlorodiamminepalladium, and dinitrodiamminepalladium.

[0054] Optionally, in step (1), a noble metal precursor is loaded on a metal oxide promoter by an impregnation method, and the operation method is to prepare an aqueous solution or ammonia aqueous solution of a certain concentration of the noble metal precursor, and then impregnate it on the metal oxide promoter.

[0055] The beneficial effects that this application can produce include:

[0056] 1) The noble metal content in the shape-selective isomerization catalyst provided by this application is 0.05 wt% - 0.3 wt%, which is greatly reduced compared with the noble metal loading of about 0.5 wt% in traditional hydroisomerization catalysts.

[0057] 2) The shape-selective isomerization catalyst provided by this application has higher activity and isomer yield in the alkane isomerization reaction.

[0058] 3) The preparation process of the shape-selective isomerization catalyst provided by this application is simple and easy to implement. Specific Embodiments

[0059] The following describes this application in detail with reference to embodiments, but this application is not limited to these embodiments.

[0060] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0061] Conversion rate (Conv) = C 所有产物 / (C 所有产物 + C 剩余正十六烷 ) × 100%;

[0062] Selectivity (S) = C 异十六烷 / C 所有产物 × 100%;

[0063] Yield (Y) = Conv × S × 100%.

[0064] Comparative Example 1

[0065] Take 50 g of template-removed SAPO-11 molecular sieve, and its acid amount is 1.5 mmol(NH3) / g. Impregnate 50 g of the above carrier with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry naturally and dry at 120 °C for 4 h, calcine at 500 °C for 4 h, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce at 400 °C for 4 h to obtain 0.5 wt% Pt / SAPO-11 catalyst. The catalytic reaction evaluation results are shown in Table 1.

[0066] Comparative Example 2

[0067] Take 50 g of template-removed MgAPO-11 molecular sieve, and its acid amount is 1.7 mmol(NH3) / g. Impregnate 50 g of the above carrier with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry naturally and dry at 120 °C for 4 h, calcine at 500 °C for 4 h, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce at 400 °C for 4 h to obtain 0.5 wt% Pt / MgAPO-11 catalyst. The catalytic reaction evaluation results are shown in Table 1.

[0068] Comparative Example 3

[0069] Take 50 g of template-removed SAPO-41 molecular sieve, and its acid amount is 1.3 mmol(NH3) / g. Impregnate 50 g of the above carrier with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry naturally and dry at 120 °C for 4 h, calcine at 500 °C for 4 h, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce at 400 °C for 4 h to obtain 0.5 wt% Pt / SAPO-41 catalyst. The catalytic reaction evaluation results are shown in Table 1.

[0070] Comparative Example 4

[0071] Take 50 g of the template-removed CoAPO-41 molecular sieve, and its acid amount is 1.4 mmol(NH3) / g. Impregnate 50 g of the above carrier with 25 mL of an H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, calcine it at 500 °C for 4 h, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce it at 400 °C for 4 h to obtain a 0.5 wt% Pt / CoAPO-41 catalyst. The catalytic reaction evaluation results are shown in Table 1.

[0072] Comparative Example 5

[0073] Take 40 g of the template-removed SAPO-11 molecular sieve, and its acid amount is 1.5 mmol(NH3) / g. Then take 20 g of pseudoboehmite, mix the SAPO-11 molecular sieve with pseudoboehmite and add 10 ml of 10 wt% nitric acid to knead and extrude into pellets, dry it at 120 °C for 4 h, calcine it at 550 °C for 12 h, and crush the obtained carrier into 20-40 mesh particles for standby. Impregnate 50 g of the above 20-40 mesh carrier with 25 mL of an H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, calcine it at 500 °C for 4 h, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce it at 400 °C for 4 h to obtain a 0.5 wt% Pt / SAPO-11 catalyst containing an alumina binder. The catalytic reaction evaluation results are shown in Table 1.

[0074] Comparative Example 6

[0075] Take 40 g of the template-removed SAPO-41 molecular sieve, and its acid amount is 1.3 mmol(NH3) / g. Then take 20 g of pseudoboehmite, mix the SAPO-41 molecular sieve with pseudoboehmite and add 10 ml of 10 wt% nitric acid to knead and extrude into pellets, dry it at 120 °C for 4 h, calcine it at 550 °C for 12 h, and crush the obtained carrier into 20-40 mesh particles for standby. Impregnate 50 g of the above carrier with 25 mL of an H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, calcine it at 500 °C for 4 h, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce it at 400 °C for 4 h to obtain a 0.5 wt% Pt / SAPO-41 catalyst containing an alumina binder. The catalytic reaction evaluation results are shown in Table 1.

[0076] Example 1

[0077] Take 50 g of CeO2 (particle size 20 - 40 nm), impregnate it with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, and calcine it at 600 °C for 4 h under air flow to obtain 0.5 wt% Pt / CeO2 supported; take 20 g of the above 0.5 wt% Pt / CeO2, 10 g of pseudo-boehmite, and 20 g of SAPO-11 molecular sieve in Comparative Example 1, mix them evenly, add 10 mL of 10 wt% nitric acid for kneading and extrusion molding, dry at 120 °C for 4 h, calcine at 500 °C for 12 h, crush into 20 - 40 mesh particles, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce at 400 °C for 4 h to obtain a 0.2 wt% Pt / CeO2 - SAPO-11 catalyst containing CeO2 promoter. The catalytic reaction evaluation results are shown in Table 1.

[0078] Example 2

[0079] Take 50 g of Nb2O5 (particle size 20 - 40 nm), impregnate it with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, and calcine it at 630 °C for 4 h under air flow to obtain 0.5 wt% Pt / Nb2O5 supported; take 10 g of the above 0.5 wt% Pt / Nb2O5, 10 g of pseudo-boehmite, and 30 g of MgAPO-11 molecular sieve in Comparative Example 2, mix them evenly, add 10 mL of 10 wt% nitric acid for kneading and extrusion molding, dry at 120 °C for 4 h, calcine at 500 °C for 12 h, crush into 20 - 40 mesh particles, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce at 400 °C for 4 h to obtain a 0.1 wt% Pt / Nb2O5 - MgAPO-11 catalyst containing Nb2O5 promoter. The catalytic reaction evaluation results are shown in Table 1.

[0080] Example 3

[0081] Take 50 g of Ta2O5 (particle size 30 - 50 nm), impregnate it with 16 mL of H2PtCl6 solution containing 0.025 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, and calcine it at 600 °C for 4 h under air flow to obtain 0.8 wt% Pt / Ta2O5 supported; take 10 g of the above 0.8 wt% Pt / Ta2O5, 10 g of pseudo-boehmite, and 20 g of SAPO-41 molecular sieve in Comparative Example 3, mix them evenly, add 8 mL of 10 wt% nitric acid for kneading and extrusion molding, dry at 120 °C for 4 h, calcine at 500 °C for 12 h, crush into 20 - 40 mesh particles, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂Hydrogen gas was used to reduce it at 400 °C for 4 h to prepare a 0.2 wt% Pt / Ta2O5-SAPO-41 catalyst containing Nb2O5 promoter. The catalytic reaction evaluation results are shown in Table 1.

[0082] Example 4

[0083] Take 50 g of Nb2O5 (particle size 20 - 40 nm), impregnate it with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, and calcine it at 650 °C for 4 h under a stream of air to obtain 0.5 wt% Pt / Nb2O5 supported; take 10 g of the above 0.5 wt% Pt / Nb2O5, 10 g of pseudo-boehmite, and 30 g of CoAPO-41 molecular sieve in Comparative Example 4, mix them evenly, add 10 ml of 10 wt% nitric acid, knead and extrude into pellets, dry at 120 °C for 4 h, calcine at 500 °C for 12 h, crush into 20 - 40 mesh particles, and then use hydrogen gas with a flow rate of 20 mL / min / g 催化剂 to reduce it at 400 °C for 4 h to prepare a 0.1 wt% Pt / Nb2O5-CoAPO-41 catalyst containing Nb2O5 promoter. The catalytic reaction evaluation results are shown in Table 1.

[0084] Example 5

[0085] Take 50 g of Ta2O5 (particle size 30 - 50 nm), impregnate it with 16 mL of H2PtCl6 solution containing 0.025 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, and calcine it at 700 °C for 4 h under a stream of air to obtain 0.8 wt% Pt / Ta2O5 supported; take 10 g of the above 0.8 wt% Pt / Ta2O5, 10 g of pseudo-boehmite, and 20 g of SAPO-11 molecular sieve in Comparative Example 1, mix them evenly, add 8 ml of 10 wt% nitric acid, knead and extrude into pellets, dry at 120 °C for 4 h, calcine at 500 °C for 12 h, crush into 20 - 40 mesh particles, and then use hydrogen gas with a flow rate of 25 mL / min / g 催化剂 to reduce it at 400 °C for 4 h to prepare a 0.2 wt% Pt / Ta2O5-SAPO-11 catalyst containing Nb2O5 promoter. The catalytic reaction evaluation results are shown in Table 1.

[0086] Example 6

[0087] Take 50 g of CeO2 (particle size 20 - 40 nm), impregnate it with 25 mL of H2PtCl6 solution containing 0.01 g / mL of Pt, air-dry it naturally and dry it at 120 °C for 4 h, and calcine it at 750 °C for 4 h under flowing air to obtain 0.5 wt% Pt / CeO2 supported; take 10 g of the above 0.5 wt% Pt / CeO2, 10 g of pseudo-boehmite, and 30 g of the SAPO-41 molecular sieve in Comparative Example 3, mix them evenly, add 10 ml of nitric acid with a concentration of 10 wt%, knead and extrude into pellets, dry at 120 °C for 4 h, calcine at 500 °C for 12 h, crush into 20 - 40 mesh particles, and then use hydrogen with a flow rate of 20 mL / min / g 催化剂 to reduce it at 400 °C for 4 h to obtain a 0.1 wt% Pt / CeO2 - SAPO-41 catalyst containing a CeO2 promoter. The catalytic reaction evaluation results are shown in Table 1.

[0088] Catalyst evaluation in Example 7

[0089] The catalyst evaluation was carried out in a stainless steel tube fixed-bed reactor. Take 10 mL of the prepared catalyst and load it into the reactor. Heat it to the reaction temperature under a hydrogen atmosphere, and pass the raw material oil n-hexadecane for reaction. The products were analyzed by gas chromatography. Reaction conditions: reaction temperature 280 - 350 °C, 3 MPa, n-hexadecane feed volume space velocity 1.0 h -1 , and the hydrogen-oil ratio (mol / mol) was 15. The specific reaction results are shown in Table 1..

[0090] Table 1. Catalyst evaluation results in comparative examples and examples

[0091]

[0092]

[0093] As can be seen from Table 1, compared with the catalysts prepared by the conventional method in the comparative examples, the catalysts prepared by the present method in Examples 1 - 6 can obtain higher activity, higher isomer selectivity and isomer yield in the hydroisomerization reaction of long-chain alkanes.

[0094] The above are only several embodiments of the present application, and do not impose any form of limitation on the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, within the scope of the technical solution of the present application, making some changes or modifications using the disclosed technical content is equivalent to equivalent implementation cases and all belong to the scope of the technical solution.

Claims

1. A shape-selective isomerization catalyst, characterized in that, The shape-selective isomerization catalyst includes a ten-membered ring aluminophosphate molecular sieve, an active component, a promoter, and a binder; The active component is loaded on the promoter; The ten-membered ring aluminophosphate molecular sieve is selected from at least one of SAPO-11, MeAPO-11, SAPO-41, and MeAPO-41; Among them, Me in MeAPO-11 and MeAPO-41 is selected from at least one of Zn, Mg, Mn, Co, Cr, Cu, Cd, and Ni; The active component is selected from Pt and / or Pd; The promoter is a metal oxide, and the metal oxide is selected from at least one of CeO2, Nb2O5, and Ta2O5; The binder is alumina.

2. The shape-selective isomerization catalyst according to claim 1, characterized in that, The acid amount of the ten-membered ring aluminophosphate molecular sieve is 0.8 - 2.0 mmol(NH3) / g; Preferably, the acid amount of the ten-membered ring aluminophosphate molecular sieve is 1.2 - 1.8 mmol(NH3) / g; Preferably, in the shape-selective isomerization catalyst, the content of the active component is 0.05 wt.% - 0.3 wt.%; Preferably, in the shape-selective isomerization catalyst, the content of the ten-membered ring aluminophosphate molecular sieve is 30 wt.% - 75 wt.%; Preferably, in the shape-selective isomerization catalyst, the content of the ten-membered ring aluminophosphate molecular sieve is 50 wt.% - 70 wt.%; Preferably, in the shape-selective isomerization catalyst, the content of the promoter is 5 wt.% - 50 wt.%; Preferably, in the shape-selective isomerization catalyst, the content of the promoter is 5 wt.% - 15 wt.%; Preferably, in the shape-selective isomerization catalyst, the content of the binder is 20 wt.% - 50 wt.%; Preferably, in MeAPO-11 and MeAPO-41, the mass content of Me is 0.05 - 5 wt.%.

3. A method for preparing the shape-selective isomerization catalyst according to any one of claims 1 to 2, characterized in that, The preparation method includes the following steps: (1) Immerse the metal oxide in a solution containing an active component precursor, dry I, and calcine I to obtain a metal oxide loaded with the active component; (2) Mix, knead, extrude, dry II, calcine II, and reduce a mixture containing the metal oxide loaded with the active component, the ten-membered ring aluminophosphate molecular sieve, and the binder to obtain the shape-selective isomerization catalyst.

4. The preparation method according to claim 3, characterized in that, In the step (1), the active component precursor is selected from at least one of platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, dichlorotetraammineplatinum, dichlorodiammineplatinum, dinitrodiammineplatinum, palladium chloride, ammonium chloropalladate, dichlorotetraamminepalladium, dichlorodiamminepalladium, and dinitrodiamminepalladium.

5. The preparation method according to claim 3, characterized in that, In the step (1), the temperature of dry I is 50 - 200 °C, and the time of dry I is 0.5 - 24 h; Preferably, in the step (1), the atmosphere of calcine I is an oxygen-containing atmosphere; Preferably, the oxygen content in the oxygen-containing atmosphere is 10 - 100%; 6. The preparation method according to claim 3, characterized in that, In the step (1), the temperature of calcine I is 400 - 1200 °C, and the time of calcine I is 0.1 - 48 h; Preferably, the temperature of calcine I is 500 - 900 °C, and the time of calcine I is 0.5 - 24 h.

7. The preparation method according to claim 3, characterized in that, In the step (2), the temperature of the second drying is 50 to 200 °C, and the time of the second drying is 0.5 to 24 h; Preferably, in the step (2), the temperature of the second calcination is 350 to 550 °C, and the time of the second calcination is 0.5 to 24 h; Preferably, in the step (2), the reducing atmosphere is hydrogen, and the gas flow rate of hydrogen is 5 - 30 mL / min / g 催化剂 ; Preferably, the temperature of the reduction is 200 to 400 °C, and the time of the reduction is 2 to 8 h; Preferably, the temperature of the reduction is 250 to 350 °C, and the time of the reduction is 4 to 8 h.

8. Application of the shape-selective isomerization catalyst according to any one of claims 1 to 2 in the isomerization reaction of long-chain alkanes.

9. The application according to claim 8, wherein The conditions for the long-chain alkane isomerization reaction are as follows: The reaction temperature is 200 to 400 °C, the reaction pressure is 0.1 to 10 MPa, and the feed volume space velocity is 0.5 to 5 h -1 , and the hydrogen-oil ratio (mol / mol) is 5 to 50.

10. The application according to claim 9, wherein The reaction temperature is 280 to 350 °C; Preferably, the long-chain alkane is a C8-C50 long-chain alkane.

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