CN109465023B - Preparation method of isomerization catalyst with MTT-type structure molecular sieve as carrier - Google Patents
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- 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
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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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Abstract
The invention discloses a preparation method of an isomerization catalyst taking an MTT type structure molecular sieve as a carrier. The preparation method of the catalyst comprises the following specific steps: firstly, carrying out partial demoulding treatment on the molecular sieve raw powder with the MTT-type structure at the temperature of 100-400 ℃; then loading the VIII group noble metal active component on the treated molecular sieve; then reducing in hydrogen atmosphere to obtain the target catalyst. The method realizes effective regulation and control of metal property, acid property and pore canal property of the catalyst by controlling the removal mode of the template agent in the molecular sieve carrier. Compared with the catalyst prepared by the prior art, the catalyst prepared by the method of the invention has high reaction activity and isomer yield in the normal paraffin isomerization reaction.
Description
Technical Field
The invention belongs to the fields of petrochemical industry, fine chemical industry and molecular sieve catalysts, and particularly relates to a preparation method and application of an isomerization catalyst taking an MTT-type structure molecular sieve as a carrier.
Technical Field
The alkane isomerization reaction plays an important role in the quality improvement process of oil products. The hydroisomerization of light paraffins can produce gasoline blending components of high octane number, while the hydroisomerization of long-chain paraffins is mainly used to improve the low-temperature flow properties of aviation kerosene, diesel fuel and lubricating oils. At present, the most advanced catalyst applied to the reaction is a bifunctional catalyst taking a molecular sieve as a carrier and loading a metal component with a (de) hydrogenation performance. The preparation of catalysts for isomerization of alkanes using molecular sieves as carriers is reported in patent documents US4710485, 5135638, 5282598, CN1792451, 1788844, 101245260, etc.
During the isomerization reaction of the alkane, the metal site mainly provides hydrogenation/dehydrogenation performance, the acid site of the molecular sieve carrier provides isomerization/cracking performance, and the pore structure of the molecular sieve provides shape-selective function. The isomerization performance of the catalyst is determined by its metals, acidity and pore channels.
Generally, the acidity and pore channels of molecular sieve supported isomerization catalysts result from the removal of the templating agent from the molecular sieve. The method for removing the template agent from the molecular sieve is generally to roast in an air atmosphere at a temperature of not less than 500 ℃. For example, Liu et al roasting treatment at 600 ℃ for 6h in an air atmosphere removes the template dipropylamine in SAPO-11 (J.colloid Interf.Sci.2014,418, 193.); philippaerts and the like are roasted at 550 ℃ in an air atmosphere for 24h to remove a template agent tetrapropylammonium bromide (J.Catal.2010,270, 172) in the ZSM-5; liu et al calcined at 550 ℃ for 8h in an air atmosphere to remove the template hexamethylenediamine (J.Catal.2016,335,11.) from ZSM-22.
In the roasting and demolding process, the water vapor generated by the oxidation combustion reaction of the template agent and the caused local high temperature and high pressure can damage the framework structure of the molecular sieve, and the pore canal property and the acid property of the molecular sieve are influenced. Corma et al found that 540 ℃ calcination de-molding resulted in molecular sievesDealumination occurs and affects the surface acidity of the sieve (J.Catal.1994,148, 569.). Ward et al found that calcination at a demolding temperature higher than 500 ℃ causes destruction of the hydroxyl groups of the Y molecular sieve structure, so that the molecular sieve has
The amount of acid (B acid) decreased and the amount of Lewis acid (L acid) increased (j.catal.1968,11,251.).
The MTT type molecular sieve has unique one-dimensional ten-membered ring channel with about the size of the pore opening
The supported catalyst taking the supported catalyst as the carrier shows excellent performance in the hydroisomerization reaction of long-chain alkane. Similar to the demolding method, the MTT type molecular sieve supported catalyst is usually prepared by removing the template agent from the molecular sieve at a higher temperature (not lower than 500 ℃). For example, Wang et al calcined at 550 deg.C for 3h in an air atmosphere to remove the template pyrrolidine from ZSM-23 to produce a Pt/ZSM-23 isomerization catalyst (Ind. Eng. chem. Res.2016,55,6069.). The roasting and demoulding process influences the distribution and quantity of acid sites and the micropore volume on the MTT type molecular sieve, so that the acid quantity and the micropore volume are reduced. Therefore, the method realizes the regulation and control of the acid property and the pore channel property of the molecular sieve with the MTT-type structure by controlling the demoulding mode in the molecular sieve by a new means, and is necessary for preparing the hydroisomerization catalyst with high isomer yield.
Studies have shown that the metal performance (hydrogenation/dehydrogenation performance) of a catalyst is related to the loading location of the metal. Generally, the closer the distance between the metal site and the acid site, the better the hydrogenation/dehydrogenation performance of the catalyst. Due to the unique one-dimensional straight pore channel structure and the narrow pore size of the MTT type molecular sieve, the acid sites which play a role in the isomerization process are mainly positioned near the pores on the outer surface of the molecular sieve. On the catalyst taking the MTT type molecular sieve as the carrier, the metal site on the outer surface is closer to the acid site which acts, so that better hydrogenation/dehydrogenation performance can be provided. And the conventional preparation method at present has difficulty in controlling the loading position of the metal component. Therefore, it is important to develop a method for controlling the metal component supported on the outer surface of the molecular sieve having the MTT-type structure.
The invention provides a preparation method of an isomerization catalyst taking an MTT type structure molecular sieve as a carrier. The template agent in the molecular sieve is removed by roasting firstly, then the metal active component is loaded, and the template agent in the molecular sieve is completely removed by utilizing the reduction process of the catalyst. Firstly, the template agent in the molecular sieve generates active carbon species through Hofmann elimination and other reactions by roasting at the relative low temperature of 100-400 ℃, and the process is an endothermic process. Then, loading a hydrogenation metal component on the molecular sieve, and reducing in hydrogen or hydrogen-containing atmosphere; in the process, active carbon species in the molecular sieve are removed by catalytic hydrogenation into hydrocarbons. The invention fully utilizes the reduction process of the catalyst for demoulding, and compared with the conventional preparation method, the carbon species in the molecular sieve is removed by hydrogenation, the heat release of the oxidation removal is small, no steam is generated, and the damage effect on the framework structure of the molecular sieve is small.
Meanwhile, the method can also control the loading position of the metal component. Roasting at a relatively low temperature of 50-400 ℃, blocking the generated active carbon species in the pore canal of the molecular sieve, removing organic matters and impurities adsorbed on the outer surface, and exposing the hydroxyl on the outer surface of the molecular sieve. Therefore, in the process of loading the metal component, the metal component cannot enter the pore channels of the molecular sieve due to the blockage of the pore channels of the molecular sieve and only can interact with the hydroxyl on the outer surface of the molecular sieve, and finally the catalyst with the metal component only distributed on the outer surface of the molecular sieve carrier is obtained.
In conclusion, compared with the catalyst prepared by the conventional method, the catalyst prepared by the method has higher acid content and micropore volume, the metal component of the catalyst is distributed on the outer surface of the molecular sieve, and the catalyst shows higher reaction activity and isomer yield in the isomerization process.
Disclosure of Invention
The invention aims to provide a preparation method of an isomerization catalyst taking an MTT type structure molecular sieve as a carrier.
Specifically, the invention provides a preparation method of an isomerization catalyst taking an MTT type structure molecular sieve as a carrier, which is characterized by comprising the following steps: firstly, roasting to remove partial template agent in the molecular sieve, then loading metal active component, completely removing the template agent in the molecular sieve by utilizing the catalyst reduction process to prepare the isomerization catalyst, comprising the following steps,
(1) roasting the molecular sieve raw powder containing the template agent and having the MTT-type structure at the temperature of 100 ℃ and 400 ℃ for 0.5-18h, wherein the content of carbon deposition and organic matters in the roasted molecular sieve is 0.5-10 wt% of the weight of the molecular sieve;
(2) loading the molecular sieve calcined in the step (1) with a VIII group noble metal active component, wherein the content of the VIII group noble metal component is 0.05-10 wt.%;
(3) reducing the sample loaded with the metal component in the step (2) for 0.5-12h at the temperature of 150-450 ℃ in a reducing atmosphere to prepare the isomerization catalyst.
The treatment temperature in the step (1) of the method is 150-400 ℃, and the treatment time is 1-12 h;
in the method provided by the invention, the content of carbon deposition and organic matters in the calcined molecular sieve in the step (1) is 0.5-8 wt% of the weight of the molecular sieve;
the calcination treatment process described in step (1) of the method provided by the present invention is generally performed in an oxygen-containing atmosphere (e.g., air, oxygen, ozone, etc.), and may also be performed in an inert atmosphere (e.g., nitrogen, argon, etc.) or a reducing atmosphere (e.g., hydrogen sulfide, carbon monoxide, etc.);
the reduction temperature in the step (3) of the method is 200-400 ℃, and the reduction time is 1-8 h;
the reducing atmosphere in the step (3) of the method provided by the invention is hydrogen or a mixed gas of hydrogen and other gases (such as inert gases, alkane, alkene and the like);
in the method provided by the invention, the VIII group noble metal active component in the step (2) or the step (3) is one or more of elements such as Pt, Pd, Ir and the like;
the content of the VIII group noble metal in the step (2) of the method provided by the invention is 0.05-5.0 wt.%;
the molecular sieve with the MTT-type structure in the method provided by the invention is one or more of ZSM-23, Me-ZSM-23(Me ═ Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd or Ni and the like), EU-13, KZ-1, ISI-4 and the like.
The loading of the metal component in the step (2) of the method provided by the invention adopts operation methods conventional in the art, including but not limited to impregnation, precipitation, deposition, adhesive bonding or mechanical pressing, etc., so that the group VIII noble metal precursor is dispersed on the carrier to realize the combination of the group VIII noble metal and the carrier; the metal precursors used include, but are not limited to, metal acids, metal acid salts, chlorides, ammonia complexes, carbonyl complexes, or mixtures thereof;
in the invention, active carbon species react with hydrogen in the reduction process of the catalyst to mainly generate hydrocarbon or nitrogen-hydrogen compounds; in the conventional roasting process, the template in the molecular sieve is mainly oxidized and combusted with oxygen to mainly generate carbon oxygen or oxynitride;
the template agent is organic amine in the pore channels and on the outer surface of the MTT-type molecular sieve, is derived from the self-synthesis process of the MTT-type structure molecular sieve, and comprises but is not limited to dimethylamine, N, N-dimethylformamide, tetramethylammonium ions and other organic amines or the mixture of the organic amines;
the metal component is loaded on the treated molecular sieve in the step (2) of the method provided by the invention and then needs to be dried by adopting the conventional operation methods in the field, including but not limited to heating drying, freeze drying, supercritical drying and the like, and the common method is to carry out drying at 40-300 ℃ in an air atmosphere, preferably at 60-200 ℃; drying for 0.5-24h, preferably for 1-8 h;
the catalyst provided by the invention can be widely applied to the processing processes of petroleum fractions, biomasses and Fischer-Tropsch synthesis products, such as the processes of isomerization pour point depression, isomerization dewaxing and the like.
Compared with the conventional preparation method, the preparation method of the catalyst taking the MTT-type structure molecular sieve as the carrier has the following advantages:
1. the roasting and demolding temperature of the molecular sieve carrier is reduced, and the energy consumption in the preparation process of the catalyst is reduced;
2. the template agent in the molecular sieve is removed by fully utilizing the reduction process, the damage to the framework structure of the molecular sieve in the demolding process is reduced, and the prepared catalyst has high micropore volume and acid content;
3. the prepared isomerization catalyst has high activity and isomer yield in the isomerization reaction of the alkane.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, and do not mean that the conditions must be met for achieving the purpose.
The measurement of the acid amount of the catalyst was carried out on a Micromeritics AutoChem2920 chemisorption instrument. The sample is treated in situ for 60min under the condition of introducing He at 350 ℃ on an adsorption instrument, then the temperature of the sample tube is reduced to 100 ℃, and NH is introduced3Introducing He to purge for 60min after adsorption saturation, raising the temperature to 700 ℃ at 10 ℃/min after the baseline of the TCD detector is stable, and recording NH3Desorption profile. Acid amount of sample according to NH3Concentration calibration curve and NH3And calculating the desorption peak area.
And determining the carbon deposition and organic matter content of the sample according to the thermogravimetric analysis result. The samples were subjected to thermogravimetric measurements using an instrument of type STA 449F 3, NETZSCH company, germany. The measurement conditions were as follows: the sample loading was 10mg and the temperature was raised from 40 ℃ to 900 ℃ at a rate of 10 ℃/min in an air atmosphere (flow 20 ml/min). The carbon deposition and organic matter content of the sample are weight loss amounts of more than 200 ℃ in the thermogravimetric result of the sample.
Pore volume measurements of the catalysts were performed on a Micromeritics ASAP2420 physisorption instrument. Before testing, the samples were subjected to a vacuum treatment at 200 ℃ for 6h and then to N at liquid nitrogen temperature2And (4) measuring adsorption and desorption isotherms. The micropore volume of the sample was calculated by the t-plot method.
The evaluation of the catalyst is carried out in a stainless steel fixed bed reactor, 1.0mL of the prepared catalyst is taken to be filled in the reactor, the temperature is raised to the reaction temperature under the atmosphere of hydrogen, raw oil n-dodecane is introduced for reaction,the product was analyzed by gas chromatography. Reaction conditions are as follows: the reaction temperature is 200 ℃ and 300 ℃, the normal pressure is realized, and the hourly space velocity of n-dodecane liquid is 1.0h-1The hydrogen-oil ratio (mol/mol) was 15.
Comparative example
20g of ZSM-23 molecular sieve raw powder containing the template (the content of the template is 6.2 wt.% of the weight of the molecular sieve) is placed in a quartz tube, roasted for 24h at 560 ℃ in an air atmosphere, and naturally cooled to room temperature to obtain a ZSM-23 molecular sieve carrier completely removed by the template, wherein the content of carbon deposit and organic matters in the molecular sieve carrier is 0. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 400 ℃ in a hydrogen atmosphere for 4h to give 0.5 wt.% Pt/ZSM-23 catalyst. The catalyst has carbon deposit and organic matter content of 0, acid content of 0.43mmol/g, and micropore volume of 0.024cm3/g。
Example 1
20g of ZSM-23 molecular sieve raw powder (the content of the template agent is 6.2 wt% of the weight of the molecular sieve) which is the same as that of the comparative example is placed in a quartz tube, the temperature is raised to 150 ℃ at 5 ℃/min in the air atmosphere, the roasting is carried out for 4h at the temperature, and then the roasting is naturally cooled to the room temperature, so as to obtain the treated ZSM-23 molecular sieve carrier, wherein the content of carbon deposition and organic matters in the molecular sieve carrier is 3.0 wt%. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 300 ℃ for 4h in a hydrogen atmosphere to give 0.5 wt.% Pt/ZSM-23 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the acid content is 0.66mmol/g, and the micropore volume is 0.055cm3/g。
Example 2
20g of Co-ZSM-23 molecular sieve raw powder containing a template (the content of the template is 6.2 wt% of the weight of the molecular sieve, and the content of Co is 0.5 wt%) is placed in a quartz tube, the temperature is raised to 230 ℃ at the rate of 5 ℃/min in the air atmosphere, the mixture is roasted for 12 hours at the temperature, and then the mixture is naturally cooled to the room temperature, so that the treated Co-ZSM-23 molecular sieve carrier is obtained, wherein the content of carbon deposition and organic matters in the molecular sieve carrier is 2.4 wt%. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6Solution impregnation 5g of the above fractionAnd (4) a sub-sieve carrier. The impregnated sample was dried at 120 ℃ for 2h and reduced at 400 ℃ in a hydrogen atmosphere for 4h to give 0.5 wt.% Pt/Co-ZSM-23 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the acid content is 0.62mmol/g, and the micropore volume is 0.042cm3/g。
Example 3
20g of Fe-ZSM-23 molecular sieve raw powder containing a template (the content of the template is 6.8 wt% of the weight of the molecular sieve, and the content of Fe is 1.5 wt%) is placed in a quartz tube, the temperature is raised to 300 ℃ at the speed of 5 ℃/min in the air atmosphere, the mixture is roasted for 2 hours at the temperature, and then the mixture is naturally cooled to the room temperature, so that the treated Fe-ZSM-23 molecular sieve carrier is obtained, wherein the content of carbon deposition and organic matters in the molecular sieve carrier is 1.6 wt%. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 400 ℃ in a hydrogen atmosphere for 2h to give 0.5 wt.% Pt/Fe-ZSM-23 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the acid content is 0.59mmol/g, and the micropore volume is 0.041cm3/g。
Example 4
20g of Sn-ZSM-23 molecular sieve raw powder containing a template (the content of the template is 6.5 wt% of the weight of the molecular sieve, and the content of Sn is 1.1 wt%) is placed in a quartz tube, the temperature is raised to 400 ℃ at the speed of 5 ℃/min in the air atmosphere, the raw powder is roasted for 1h at the temperature, and then the raw powder is naturally cooled to the room temperature, so that the treated Sn-ZSM-23 molecular sieve carrier is obtained, wherein the content of carbon deposition and organic matters in the molecular sieve carrier is 0.9 wt%. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 200 ℃ for 8h in a hydrogen atmosphere to give 0.5 wt.% Pt/Sn-ZSM-23 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the acid content is 0.48mmol/g, and the micropore volume is 0.038cm3/g。
Example 5
20g of Mn-ZSM-23 molecular sieve raw powder containing a template (the content of the template is 6.1 wt.% of the weight of the molecular sieve, and the content of Mn is 0.8 wt.%) is put into a quartz tube, heated to 150 ℃ at 5 ℃/min in a nitrogen atmosphere, roasted for 8h at the temperature, and then dried by the microwave ovenAnd then cooling to room temperature to obtain the treated Mn-ZSM-23 molecular sieve carrier, wherein the carbon deposition and organic matter content in the molecular sieve carrier is 3.1 wt.%. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 400 ℃ in a hydrogen atmosphere for 4h to give 0.5 wt.% Pt/Mn-ZSM-23 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the acid content is 0.65mmol/g, and the micropore volume is 0.052cm3/g。
Example 6
20g of ZSM-23 molecular sieve raw powder (the content of the template agent is 6.2 wt% of the weight of the molecular sieve) which is the same as that of the comparative example is placed in a quartz tube, heated to 200 ℃ at the temperature of 5 ℃/min in a hydrogen atmosphere, roasted for 6h at the temperature, and naturally cooled to room temperature to obtain a treated ZSM-23 molecular sieve carrier, wherein the content of carbon deposition and organic matters in the molecular sieve carrier is 2.8 wt%. With 5.0mL of H containing 0.001g/mL of Pt2PtCl6The solution was impregnated with 5g of the above molecular sieve support. The impregnated sample was dried at 120 ℃ for 2h and reduced at 400 ℃ for 1h in a hydrogen atmosphere to give 0.5 wt.% Pt/ZSM-23 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the acid content is 0.63mmol/g, and the micropore volume is 0.054cm3/g。
TABLE 1 characterization results of molecular sieves and catalysts in comparative examples and examples
TABLE 2 reaction evaluation results of catalysts in comparative examples and examples
a, when the reaction temperature is 240 ℃, the conversion rate of n-dodecane on the catalyst is increased;
b maximum isomer yield of catalyst in n-dodecane isomerization reaction.
As can be seen from Table 1, the content of carbon deposition and organic matters in the molecular sieve obtained by demolding by the conventional method in the comparative example is 0, and the molecular sieves obtained by calcining the molecular sieve raw powder at the temperature of 150-400 ℃ in the examples 1-6 contain a certain amount of carbon deposition and organic matters. But the carbon deposit and organic matter contained in the catalyst are completely removed after the catalyst is reduced. The effect is: examples 1-6 using the process of the present invention, catalysts having high acid content and large micropore volume were obtained compared to the catalysts prepared by the conventional process in the comparative example.
As can be seen from table 2, the catalysts prepared in examples 1 to 6 by the method of the present invention showed high reactivity and isomer yield in the hydroisomerization reaction of paraffins, as compared to the catalysts prepared by the conventional method of the comparative example.
Claims (8)
1. A preparation method of an isomerization catalyst taking an MTT type structure molecular sieve as a carrier is characterized in that: the method comprises the following steps of roasting MTT type structure molecular sieve raw powder at the temperature of 100-400 ℃, then loading a metal active component, and then preparing an isomerization catalyst by reduction,
(1) roasting the molecular sieve raw powder containing the template agent and having an MTT-type structure at the temperature of 100 ℃ and 400 ℃ for 0.5 to 18 hours, controlling the content of carbon deposition and organic matters in the roasted molecular sieve to be 0.5 to 10wt percent of the weight of the molecular sieve,
(2) loading the calcined molecular sieve in the step (1) with a VIII group noble metal active component, wherein the content of the VIII group noble metal component is 0.05-10 wt.%,
(3) reducing the sample loaded with the VIII group noble metal component in the step (2) for 0.5-12h at the temperature of 150-450 ℃ in a reducing atmosphere to prepare an isomerization catalyst;
wherein, the molecular sieve with MTT type structure is one or more than two of ZSM-23, Me-ZSM-23, EU-13, KZ-1 and ISI-4, and Me ═ Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd and Ni, and the mass content is 0.05-5 wt.%.
2. The method of claim 1, wherein: the treatment temperature in the step (1) is 150-400 ℃, and the treatment time is 1-12 h.
3. The method of claim 1, wherein: and (2) controlling the content of carbon deposition and organic matters in the roasted molecular sieve to be 0.5-8 wt% of the weight of the molecular sieve in the step (1).
4. The method of claim 1, wherein: the reduction temperature in the step (3) is 200-400 ℃, and the reduction time is 1-8 h.
5. The method of claim 1, wherein: the reducing atmosphere in the step (3) is hydrogen or hydrogen and nitrogen, helium, neon, argon, C1-C4Alkane, C1-C4The hydrogen gas is 5-100% by volume of one or more than two kinds of olefin mixed gas.
6. The method of claim 1, wherein: the active component of the VIII group noble metal in the step (2) or the step (3) is one or more than two of Pt, Pd and Ir elements.
7. The method of claim 2, wherein: the group VIII noble metal content in step (2) is 0.05-5.0 wt.%.
8. The method of claim 1, wherein: the template agent in the molecular sieve raw powder in the step (1) is one or more than two of dimethylamine, N-dimethylformamide and tetramethylammonium ions, and the content of the template agent is 0.5-20 wt% of the weight of the molecular sieve.
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