CN115814839B - Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof - Google Patents

Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN115814839B
CN115814839B CN202211691294.8A CN202211691294A CN115814839B CN 115814839 B CN115814839 B CN 115814839B CN 202211691294 A CN202211691294 A CN 202211691294A CN 115814839 B CN115814839 B CN 115814839B
Authority
CN
China
Prior art keywords
molecular sieve
catalyst
silicalite
boron
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211691294.8A
Other languages
Chinese (zh)
Other versions
CN115814839A (en
Inventor
孙利
董兆亮
于世君
宋全仁
栾忠凌
王鑫
王贤彬
王炳春
李进
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Catalyst Holding Co ltd
Original Assignee
China Catalyst Holding Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Catalyst Holding Co ltd filed Critical China Catalyst Holding Co ltd
Priority to CN202211691294.8A priority Critical patent/CN115814839B/en
Publication of CN115814839A publication Critical patent/CN115814839A/en
Application granted granted Critical
Publication of CN115814839B publication Critical patent/CN115814839B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Abstract

The invention belongs to the technical field of molecular sieve catalysts, and particularly relates to a boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst, and a preparation method and application thereof. Firstly preparing boron or phosphorus doped Silicalite-1 molecular sieve slurry by adopting a hydrothermal crystallization method, and then drying, dipping and drying until the water content is required, carrying out a dry gel crystallization reaction, roasting under a nitrogen atmosphere, oxidizing and roasting under an air atmosphere and reducing under a hydrogen atmosphere to obtain the boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal low-carbon alkane dehydrogenation catalyst. The preparation method of the catalyst is simple, the dehydrogenation catalyst can be obtained after the crystallization of the dry gel material, drying, molding, roasting and reduction, and the steps of washing, filtering and the like are omitted in the preparation process of the catalyst, so that the emission of a large amount of wastewater containing metal and template agent is reduced, and the industrial scale-up production of the catalyst is facilitated.

Description

Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of molecular sieve catalysts, and particularly relates to a boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst, and a preparation method and application thereof.
Background
The low-carbon olefin (ethylene, propylene, butylene, etc.) is an important bulk organic chemical raw material, and is widely used for producing high-molecular materials such as plastics, resins, rubber, etc., basic organic chemical intermediates and products. Long chain olefins are typically produced by polymerization of small molecular weight lower olefins (C2-C4), and thus efficient synthesis of lower olefins is of great interest in both academia and industry. Ethylene, propylene and butadiene are called industrial triene, are main raw materials for petrochemical development, and in a plurality of synthetic methods such as dehydrogenation, cracking, dehydration and the like, a method for directly dehydrogenating alkane to prepare corresponding alkene by dehydrogenation has been developed into an important way for increasing the yield of low-carbon alkene. The low-carbon alkane direct dehydrogenation technology has the characteristics of high olefin selectivity, byproduct hydrogen in the production process, good atom economy and the like, but the technical process is limited by thermodynamic equilibrium. Taking propane dehydrogenated propylene as an example, the reaction is a strong endothermic reaction, the equilibrium conversion rates are about 18% and 50% respectively at 500 ℃ and 600 ℃, and the precondition for obtaining higher conversion rate is that the reaction needs to be carried out at high temperature, but side reactions such as C-C cracking and the like are obviously aggravated at high temperature, thereby causing the reduction of the selectivity of the catalyst, carbon deposition or coking deactivation. Therefore, in order to increase the life of the low-carbon alkane dehydrogenation catalyst, frequent carbon burning regeneration is often required for the deactivated catalyst.
The catalyst which has better application effect at the present stage and has been commercialized is mainly CrO x /Al 2 O 3 And Pt-Sn/Al 2 O 3 Is a catalyst. However, the toxicity of the Cr catalyst and the problems of cost performance, selectivity, stability and the like of the Pt-based catalyst still remain to be further improved. How to maintain higher conversion and thermal stability of dehydrogenation catalysts at high temperatures remains a very challenging topic. The platinum-based catalysts have a relatively high market share in consideration of factors such as environmental impact. The size of the metal platinum nano particles in the platinum-based catalyst is a key factor influencing dehydrogenation performance, and reducing the particle size is beneficial to exposing more metal active sites, so that the conversion rate of alkane is improved. Al (Al) 2 O 3 、SiO 2 And the like are the most commonly used carriers for supporting Pt nano-particles, but during the dehydrogenation high-temperature conversion process, the small-size Pt nano-particles can be seriously sintered to rapidly reduce the activity. Therefore, the development of a metal dehydrogenation catalyst with excellent catalytic performance, high thermal stability and good coking resistance has very important significance.
The molecular sieve is an ideal metal load carrier because of the characteristics of regular pore channel structure, adjustable acidity, excellent hydrothermal stability, chemical stability and the like. At present, the metal loading molecular sieve mode can be divided into a traditional loading mode mainly comprising an impregnation method, an ion exchange method and the like and a molecular sieve packaging metal mode synthesized by using ligand stable metal ions as raw materials by a one-step method. The metal-loaded molecular sieve prepared by the traditional loading mode is easy to cause uneven particle size of metal nano particles, poor in dispersity and finally poor in catalytic performance. The molecular sieve encapsulated metal catalyst prepared by taking the metal chelate as a raw material can fully utilize the internal microporous structure of the molecular sieve to effectively inhibit aggregation of metal particles, reduce the size of the metal particles, and simultaneously can obviously improve the hydrothermal stability of the metal particles so as to further improve the catalytic reaction performance of the metal particles, but the stability problem of the metal chelate under the conditions of strong alkalinity of molecular sieve synthesis and hydrothermal autogenous pressure reaction at 100-200 ℃ is one of the problems to be solved by the method.
For the dehydrogenation of lower alkanes, the aluminum in the molecular sieve framework has a certain acidity and typically has a negative impact on the selectivity to the corresponding olefin. Therefore, designing a molecular sieve-encapsulated metal catalyst, such as by compositing platinum with various auxiliary metal elements (e.g., tin, gallium, copper, zinc, etc.), to produce a molecular sieve-encapsulated metal catalyst by alloying design is generally considered to be an effective synthetic strategy for improving the stability and olefin selectivity of platinum-based catalysts. The silicalite-1 molecular sieve with the MFI topological structure has the characteristics of good adsorption and separation characteristics, thermal stability, simple synthesis process and the like, and is regarded as an ideal molecular sieve for packaging metals. Patent CN106669768A discloses a method of preparing a metal oxide with noble metal [ M (NH 2 CH 2 CH 2 NH 2 ) 2 ]Cl 2 The (M=Pd, pt or Au) complex is used as a precursor, and the metal@silicalite-1 molecular sieve catalyst loaded with ultra-small noble metal nano particles is prepared by a one-step hydrothermal synthesis method, and can be applied to hydrogen production by formic acid decomposition and shape-selective catalytic reduction reaction of nitrobenzene, wherein the molecular sieve catalyst is in a hexagonal prism shape with nano size, the average diameter of the upper surface and the lower surface of the hexagonal prism is 100-200 nm, and the thickness is 50-100 nm. Patent CN110026230A discloses a process for preparing low-carbon alkane by dehydrogenationThe catalyst for preparing corresponding olefin and its application have chemical composition of noble metal element in 0.3-20%, modifying element in 0.1-50% and carrier. Patent CN110479353A discloses a catalyst and a preparation method and application thereof, wherein the catalyst carrier is a pure silicon molecular sieve comprising a silicalite-1 molecular sieve or a Beta molecular sieve, and the active element in the active component comprises Pt. Wherein Pt is loaded in the carrier in the form of sub-nano Pt clusters, zn is linked with the carrier through Zn-O-Si bonds in the form of single-site +2 valent Zn ions, and is connected with platinum clusters through Zn-O-Pt bonds. In addition, the design of the molecular sieve oxide composite dehydrogenation catalyst can also obviously improve the performance of the oxide-based dehydrogenation catalyst, for example, CN113509955A, CN110614117A, CN113289671A and other patents disclose a preparation method of a series of Co and Zn oxide molecular sieve composite dehydrogenation catalysts.
In summary, pt-based noble metal catalysts are one of the main stream propane dehydrogenation catalysts, but the problems of easy coking and deactivation of the catalyst at high temperature and continuous regeneration are not solved effectively.
Disclosure of Invention
Aiming at the defects of the prior art in the aspect of metal supported molecular sieve catalysts, the invention aims to provide a boron or phosphorus doped Silicalite-1 molecular sieve packaged metal catalyst, a preparation method and application thereof, wherein the boron or phosphorus doped Silicalite-1 molecular sieve is prepared by adopting a one-step hydrothermal method, and then the boron or phosphorus doped Silicalite-1 molecular sieve packaged metal low-carbon alkane dehydrogenation catalyst is obtained after the steps of dipping, drying to the required water content, dry gel crystallization reaction, roasting in nitrogen atmosphere, oxidizing roasting in air atmosphere, hydrogen atmosphere reduction and the like. The invention not only can remarkably improve the utilization rate of metal elements, but also can remarkably improve the catalytic performance of the metal elements in the aspect of low-carbon alkane dehydrogenation application.
The technical scheme for solving the technical problems is as follows:
the invention provides a preparation method of a boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst, which comprises the following steps:
(1) Preparation of boron or phosphorus doped Silicalite-1 molecular sieves: weighing deionized water, boron or phosphorus element compound, template agent, alkali metal source and silicon source, stirring and mixing for 1-6 hours at 25-35 ℃ to obtain mixed sol, transferring the sol into a crystallization kettle, crystallizing and reacting for 24-72 hours at 140-180 ℃ at 50-200 r/min, cooling, and drying the crystallized slurry at 70-90 ℃ for 24-48 hours to obtain boron or phosphorus doped Silicalite-1 molecular sieve carrier;
(2) Preparing an impregnating solution: weighing deionized water, a metal source and a chelating agent, stirring and mixing for 1-3 hours at the temperature of 25-35 ℃ to obtain an impregnating solution;
(3) Dipping the dipping liquid obtained in the step (2) at the temperature of 30-60 ℃ to treat the boron or phosphorus doped Silicate-1 molecular sieve carrier obtained in the step (1), wherein the mass ratio of the dipping liquid to the boron or phosphorus doped Silicalite-1 molecular sieve carrier is 2-5:1, the dipping time is 3-9 hours, drying at 70-90 ℃ to obtain a dry adhesive material, and controlling the water content of the dry adhesive material to be 17-25%;
(4) Transferring the dry glue material obtained in the step (3) into a crystallization kettle, and carrying out dry glue crystallization reaction under the conditions that the reaction temperature is 140-180 ℃ and the reaction time is 24-72 hours;
(5) And (3) drying and forming the crystallized product obtained in the step (4), roasting under nitrogen atmosphere, oxidizing and roasting under air atmosphere and reducing under hydrogen atmosphere to obtain the boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst.
In the above technical scheme, in the step (1), siO in the sol 2 :B OR P:M:ROH:H 2 The molar ratio of O is 100:0.06-0.4:0.43-1.43:17-30:1400-2100, wherein M is alkali metal and ROH is template agent;
the boron or phosphorus element compound is selected from one of boric acid, phosphoric acid, ammonium phosphate and ammonium dihydrogen phosphate;
the template agent is tetrapropylammonium hydroxide aqueous solution with the mass concentration of 25-35%;
the alkali metal source is sodium hydroxide or potassium hydroxide;
the silicon source is selected from one of tetraethoxysilane and gas-phase white carbon black.
In the above technical solution, in the step (2), the metal source includes a noble metal source and a co-active metal source, wherein the noble metal is selected from at least one of Ru, rh, pd, pt, au, and the co-active metal is selected from one of Sc, ti, V, cr, mn, fe, co, ni, cu, zn, Y, zr, nb, mo, W, ga, in, ge, sn, pb, sb, bi, la, ce;
the chelating agent is selected from one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine;
the molar ratio of the chelating agent to the co-active metal in the metal source is 5-20:1.
In the above technical scheme, in the step (2), the noble metal is selected from one of Pt and Pd, and the auxiliary active metal is selected from one of Fe, co, ni, cu, zn, ga, in, sn, la, ce.
In the above technical scheme, in the step (2), the noble metal source is selected from one of hexachloroplatinic acid, ammonium hexachloroplatinate, palladium chloride dihydrate and ammonium chloropalladate, and the auxiliary active metal is selected from one of hydrochloride, nitrate, sulfate or acetate of metal.
In the above technical scheme, in the step (3), the carrier in the dry glue material is SiO 2 The loading amount of noble metal element is SiO 2 0.1 to 0.7 mass percent, siO 2 The mol ratio of the noble metal element to the auxiliary active metal element is 100:0.06-0.4:0.54-1.89, and the mol ratio of the noble metal element to the boron or phosphorus element is 1:1.
In the above technical solution, in the step (3), as is well known to those skilled in the art, the water content of the dry glue material is tested by using a halogen moisture meter, and the test conditions are as follows: the test temperature was 120℃and the test time was 10 minutes.
In the technical scheme, in the step (5), the drying temperature is 90-120 ℃ and the drying time is 12-24 hours;
the nitrogen atmosphere is high-purity nitrogen atmosphere, the roasting temperature is 350-450 ℃, and the roasting time is 3-9 hours;
the oxidizing roasting temperature is 550-600 ℃ and the oxidizing time is 3-9 hours under the air atmosphere;
the hydrogen atmosphere is high-purity hydrogen atmosphere, the reduction temperature is 550-600 ℃, and the reduction time is 3-9 hours.
In the above technical solution, the molding method in step (6) adopts a manner well known to those skilled in the art to process, and the raw powder of the boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal low-carbon alkane dehydrogenation catalyst is mixed with a carrier commonly used in the art (such as diatomite), a commonly used adhesive (such as silica sol) and water according to a conventional method in the art, and is molded by the conventional method and then used, so that the catalyst can be obtained by directly completing the roasting under nitrogen atmosphere, the oxidizing roasting under air atmosphere and the hydrogen atmosphere reduction process on an industrial device.
In another aspect, the invention provides a catalyst prepared by the preparation method.
In a further aspect, the invention provides an application of the catalyst in the dehydrogenation reaction of light alkane.
In the technical scheme, the dehydrogenation reaction of the low-carbon alkane is carried out in a tubular reactor; the low-carbon alkane is selected from one of ethane, propane and butane; the reaction conditions are as follows: the reaction pressure is 0.05-0.3 MPa, the reaction temperature is 500-650 ℃, and the Weight Hourly Space Velocity (WHSV) of the low-carbon alkane feed is 2-100 h -1 。
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method, the boron or phosphorus doped Silicalite-1 molecular sieve is prepared by a hydrothermal method and used as a carrier, and the non-metal element boron or phosphorus is doped, so that the acid position of the Silicalite-1 molecular sieve is increased, the molecular sieve has better noble metal anchoring and dispersing effects, and the obtained catalyst has better thermal stability and circulation stability;
2. the Silicate-1 molecular sieve loaded with active metal is subjected to secondary crystallization by adopting a dry gel conversion method, so that the metal coating rate, the dispersibility and the utilization rate are improved, and the loss of metal along with crystallization mother liquor in the liquid phase crystallization process is avoided;
3. the preparation method of the catalyst is simple, the dehydrogenation catalyst can be obtained after the crystallization of the dry gel material, drying, molding, roasting under nitrogen atmosphere, oxidizing roasting under air atmosphere and reducing under hydrogen atmosphere, the obtained catalyst has no steps of washing, filtering and the like, the emission of a large amount of wastewater containing metal and template agent is reduced, the preparation process technology of the catalyst is relatively mature, and the industrial scale-up production of the catalyst is very facilitated.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a powder X-ray diffraction pattern of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal lower alkane dehydrogenation catalyst prepared in example 1;
FIG. 2 is a scanning electron microscope image of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst prepared in example 1;
FIG. 3 is a powder X-ray diffraction pattern of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal lower alkane dehydrogenation catalyst prepared in example 2;
FIG. 4 is a scanning electron microscope image of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal light alkane dehydrogenation catalyst prepared in example 2;
FIG. 5 is a powder X-ray diffraction pattern of a boron doped Silicalite-1 molecular sieve encapsulated metal lower alkane dehydrogenation catalyst prepared in example 7;
FIG. 6 is a scanning electron microscope image of a boron doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst prepared in example 7.
Detailed Description
The following detailed description of the technical solution of the present invention is given by way of examples, but the present invention is not limited to the following description.
The technique of the present invention will be further described by the evaluation of the dehydrogenation reaction performance of propane.
Example 1
A preparation method of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst comprises the following steps:
(1) Preparation of phosphorus doped Silicalite-1 molecular sieves: 6483.06g of deionized water, 3.08g of ammonium phosphate hydrate, 3494.08g of tetrapropylammonium hydroxide water solution with the mass fraction of 25%, 4.43g of sodium hydroxide and 5263.92g of tetraethoxysilane are weighed at the temperature range of 25-35 DEG CStirring and mixing for 6 hours to obtain uniform mixed sol, transferring the sol into a crystallization kettle, crystallizing at the stirring rotation speed of 50 r/min and the temperature of 180 ℃ for 24 hours, cooling, drying the crystallized slurry at the temperature of 70 ℃ for 48 hours to obtain phosphorus doped Silicalite-1 molecular sieve raw powder, wherein SiO in the sol 2 :P:Na:TPAOH:H 2 O molar ratio is 100.0:0.06:0.43:17.0:2000.0;
(2) Preparing an impregnating solution: weighing 3323.80g of deionized water, 3.23g of palladium chloride dihydrate, 55.13g of ferric nitrate nonahydrate and 164.00g of chelating agent ethylenediamine, stirring and mixing for 1 hour at the temperature of 25-35 ℃ to obtain an impregnating solution, wherein the molar ratio of the chelating agent ethylenediamine to Fe is 20:1;
(3) Dipping the dipping liquid obtained in the step (2) at 30 ℃ to treat the phosphorus doped Silicalite-1 molecular sieve carrier obtained in the step (1), wherein the mass ratio of the dipping liquid to the Silicalite-1 molecular sieve carrier is 2:1, the dipping time is 9 hours, drying at 70 ℃ to obtain a dry gel material, controlling the water content of the dry gel material to be 17-25%, and the carrier in the dry gel material is SiO 2 The loading amount of noble metal Pd is SiO 2 0.1% by mass of SiO 2 The molar ratio of the noble metal element to the auxiliary active metal element is 100.0:0.06:0.54;
(4) Transferring the dry glue material obtained in the step (3) into a crystallization kettle, and carrying out dry glue crystallization reaction under the conditions that the reaction temperature is 180 ℃ and the reaction time is 24 hours;
(5) Drying the crystallized product obtained in the step (4) for 24 hours at a drying temperature of 90 ℃ to obtain Silicalite-1 molecular sieve encapsulated metal catalyst raw powder;
(6) The boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst raw powder prepared in the step (5) is subjected to tabletting molding by a tablet press, and then is crushed and screened to obtain a 10-20-mesh sample;
(7) Mixing 1.0g of the sample with 3.0g of quartz sand, filling the mixture into a tubular reactor, filling the mixture into a high-purity nitrogen atmosphere with the height of 30mm, heating the mixture to 400 ℃ in a high-purity nitrogen atmosphere with the temperature of 200ml/min, roasting the mixture for 6 hours, switching the mixture into an air atmosphere with the temperature of 200ml/min, heating the mixture to 580 ℃ and oxidizing the mixture for 6 hours, switching the mixture into a high-purity nitrogen atmosphere with the temperature of 200ml/min, purging the mixture for 30 minutes at the temperature of 580 ℃, and finally reducing the mixture in a high-purity hydrogen atmosphere with the temperature of 200ml/min for 6 hours at the temperature of 580 ℃ to obtain the Silicalite-1 molecular sieve packaged metal catalyst.
After the reduction of the high-purity hydrogen atmosphere is completed, the performance evaluation of the dehydrogenation reaction of the catalyst is carried out, the catalyst is switched to the high-purity nitrogen atmosphere of 200ml/min for purging for 30 minutes, the reaction temperature is maintained at 580 ℃, the atmosphere is switched to the propane gas of 72.9ml/min, the dehydrogenation reaction is carried out, and the product is analyzed by a gas chromatograph.
Further, the method for evaluating the regeneration of the catalyst comprises the following steps:
a. after the catalyst is deactivated, the reaction atmosphere is switched to a high-purity nitrogen atmosphere of 200ml/min, the reaction temperature is reduced to 500 ℃, then the reaction atmosphere is switched to an air atmosphere of 200ml/min for 3 hours of oxidation, then the reaction temperature is increased to 550 ℃ for 3 hours of oxidation, and finally the reaction temperature is increased to 580 ℃ for 3 hours of oxidation;
b. switching to a high-purity nitrogen atmosphere of 200ml/min, purging for 30 minutes at 580 ℃, and then reducing for 6 hours at 580 ℃ in a high-purity hydrogen atmosphere of 200 ml/min;
c. after the reduction of the high-purity hydrogen atmosphere is finished, the reaction temperature is maintained at 580 ℃ by switching to the high-purity nitrogen atmosphere of 200ml/min for purging for 30 minutes, and the dehydrogenation reaction is carried out by switching the atmosphere to the propane gas of 72.9ml/min, and the product is analyzed by a gas chromatograph.
FIG. 1 is a powder X-ray diffraction diagram of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst, wherein the crystallized product is still of an MFI structure and has no metal peak, which indicates that the metal has better dispersity; the scanning electron microscope of fig. 2 shows that the grain size of the obtained catalyst sample ranges from 0.1 to 0.4 micrometers. The propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1.
Example 2
A preparation method of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst comprises the following steps:
(1) Preparation of phosphorus doped Silicalite-1 molecular sieves: weighing 5664.62g of deionized water, 18.97g of ammonium dihydrogen phosphate and the mass7185.98g of tetrapropylammonium hydroxide aqueous solution with the fraction of 35%, 24.06g of sodium hydroxide and 2527.80g of fumed silica (model HM150, dry basis of 98% measured by roasting at 850 ℃ C. For 2 hours, the same applies hereinafter) are stirred and mixed for 1 hour at the temperature of 25-35 ℃ to obtain uniform mixed sol, the sol is transferred into a crystallization kettle, the stirring speed is 200 r/min, the crystallization reaction is carried out for 72 hours at 140 ℃, the temperature is reduced, the crystallization slurry is dried at 90 ℃ for 24 hours to obtain phosphorus doped Silicalite-1 molecular sieve raw powder, and SiO in the sol 2 :P:Na:TPAOH:H 2 O molar ratio is 100.0:0.40:1.43:30.0:1400.0;
(2) Preparing an impregnating solution: weighing 12777.63g of deionized water, 58.57g of ammonium chloropalladate, 219.02g of cobalt sulfate heptahydrate and 737.48g of chelating agent tetraethylenepentamine, stirring and mixing for 3 hours at the temperature of 25-35 ℃ to obtain an impregnating solution, wherein the molar ratio of the chelating agent tetraethylenepentamine to Co is 5:1;
(3) Dipping the dipping liquid obtained in the step (2) at the temperature of 60 ℃ to treat the phosphorus doped Silicalite-1 molecular sieve carrier obtained in the step (1), wherein the mass ratio of the dipping liquid to the Silicalite-1 molecular sieve carrier is 5:1, the dipping time is 3 hours, drying at the temperature of 90 ℃ to obtain a dry gel material, controlling the water content of the dry gel material to be 17-25%, and the carrier in the dry gel material is SiO 2 The loading amount of noble metal Pd is SiO 2 0.7% by mass of SiO 2 The molar ratio of the noble metal element to the auxiliary active metal element is 100.0:0.40:1.89;
(4) Transferring the dry glue material obtained in the step (3) into a crystallization kettle, and carrying out dry glue crystallization reaction under the conditions that the reaction temperature is 140 ℃ and the reaction time is 72 hours;
(5) Drying the crystallized product obtained in the step (4) for 12 hours at a drying temperature of 120 ℃ to obtain Silicalite-1 molecular sieve encapsulated metal catalyst raw powder;
(6) Tabletting the catalyst raw powder prepared in the step (5) by a tablet press, heating to 400 ℃ in a high-purity nitrogen atmosphere of 200ml/min, roasting for 6 hours, switching to an air atmosphere of 200ml/min, heating to 580 ℃ for oxidation for 6 hours, switching to a high-purity nitrogen atmosphere of 200ml/min, purging for 30 minutes at 580 ℃, and finally reducing in a high-purity hydrogen atmosphere of 200ml/min for 6 hours at 580 ℃ to obtain the phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst.
FIG. 3 is a powder X-ray diffraction diagram of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst, wherein the crystallized product is still of an MFI structure and has no metal peak, indicating that the metal has better dispersity; FIG. 4 is a scanning electron microscope image showing that the grain size of the resulting catalyst sample ranges from 0.4 to 0.7 microns.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 3
A preparation method of a phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst comprises the following steps:
(1) Preparation of phosphorus doped Silicalite-1 molecular sieves: weighing 7778.70g of deionized water, 5.68g of concentrated phosphoric acid, 5392.39g of tetrapropylammonium hydroxide aqueous solution with the mass fraction of 30%, 19.52g of potassium hydroxide and 2322.71g of gas-phase white carbon black, stirring and mixing for 3 hours at the temperature of 25-35 ℃ to obtain uniform mixed sol, transferring the sol into a crystallization kettle, crystallizing at the temperature of 160 ℃ for 48 hours at the stirring rotation speed of 120 r/min, cooling, drying the crystallized slurry at 80 ℃ for 36 hours to obtain phosphorus doped Silicalite-1 molecular sieve raw powder, and drying SiO in the sol 2 :P:K:TPAOH:H 2 O molar ratio is 100.0:0.13:0.90:21.0:1700.0;
(2) Preparing an impregnating solution: weighing 8191.32g of deionized water, 21.86g of ammonium hexachloroplatinate, 72.53g of nickel acetate tetrahydrate and 262.95g of chelating agent ethylenediamine, stirring and mixing for 2 hours at the temperature of 25-35 ℃ to obtain an impregnating solution, wherein the molar ratio of the chelating agent ethylenediamine to Ni is 15:1;
(3) Dipping the dipping liquid obtained in the step (2) at 45 ℃ to treat the gallium-doped Silicalite-1 molecular sieve carrier obtained in the step (1), wherein the mass ratio of the dipping liquid to the Silicalite-1 molecular sieve carrier is 3.3:1, the dipping time is 6 hours, drying at 80 ℃ to obtain a dry gel material, controlling the water content of the dry gel material to be 17-25%, and drying the dry gel materialCarrier in material is SiO 2 The loading amount of the noble metal Pt is SiO 2 0.42% by mass of SiO 2 The molar ratio of the noble metal element to the auxiliary active metal element is 100.0:0.13:0.77;
(4) Transferring the dry glue material obtained in the step (3) into a crystallization kettle, and carrying out dry glue crystallization reaction under the conditions that the reaction temperature is 160 ℃ and the reaction time is 48 hours;
(5) Drying the crystallized product obtained in the step (4) for 16 hours at a drying temperature of 100 ℃ to obtain Silicalite-1 molecular sieve encapsulated metal catalyst raw powder;
(6) Tabletting the catalyst raw powder prepared in the step (5) by a tablet press, heating to 400 ℃ in a high-purity nitrogen atmosphere of 200ml/min, roasting for 6 hours, switching to an air atmosphere of 200ml/min, heating to 580 ℃ for oxidation for 6 hours, switching to a high-purity nitrogen atmosphere of 200ml/min, purging for 30 minutes at 580 ℃, and finally reducing in a high-purity hydrogen atmosphere of 200ml/min for 6 hours at 580 ℃ to obtain the phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 4
The preparation method of the phosphorus-doped Silicalite-1 molecular sieve-encapsulated metal catalyst is the same as that of the embodiment 3, except that: the auxiliary active metal source in the impregnating solution in the step (2) is 72.82g of copper sulfate pentahydrate.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 5
The preparation method of the phosphorus-doped Silicalite-1 molecular sieve-encapsulated metal catalyst is the same as that of example 3, except that: the auxiliary active metal source in the impregnating solution in the step (2) is 86.76g of zinc nitrate hexahydrate.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 6
The preparation method of the phosphorus-doped Silicalite-1 molecular sieve-encapsulated metal low-carbon alkane dehydrogenation catalyst is the same as that of the embodiment 3, and the specific preparation method is as follows: the auxiliary active metal source in the impregnating solution in the step (2) is 74.58g of gallium nitrate hydrate.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 7
The preparation method of the boron doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst is the same as that of the embodiment 3, except that: a, the step (1) is a boron doped Silicalite-1 molecular sieve, and the consumption of boron source boric acid is 3.04g; b, the auxiliary active metal source in the impregnating solution in the step (2) is 85.46g of indium trichloride tetrahydrate.
FIG. 5 is a powder X-ray diffraction diagram of a boron doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst, wherein the crystallized product is still of an MFI structure and has no metal peak, indicating that the metal has better dispersity; FIG. 6 shows a scanning electron microscope plot showing that the grain size range of the resulting catalyst samples is 0.7-1.5 microns.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 8
A boron doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst and a preparation method thereof are the same as in example 3, except that: a, the step (1) is a boron doped Silicalite-1 molecular sieve, and the consumption of boron source boric acid is 3.04g; b, the auxiliary active metal source in the impregnating solution in the step (2) is 102.16g of tin tetrachloride pentahydrate.
The Pt content was 0.41% by mass of the silica and the Sn content was 1.55% by mass of the silica as measured by X-ray fluorescence spectroscopy (XRF).
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 9
A boron doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst and a preparation method thereof are the same as in example 3, except that: a, the step (1) is a boron doped Silicalite-1 molecular sieve, and the consumption of boron source boric acid is 3.04g; b, the auxiliary active metal source in the impregnating solution in the step (2) is 102.93g of lanthanum trichloride hexahydrate.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Example 10
A boron doped Silicalite-1 molecular sieve encapsulated metal low carbon alkane dehydrogenation catalyst and a preparation method thereof are the same as in example 3, except that: a, the step (1) is a boron doped Silicalite-1 molecular sieve, and the consumption of boron source boric acid is 3.04g; b, the auxiliary active metal source in the impregnating solution in the step (2) is 103.32g of cerium trichloride hexahydrate.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Comparative example 1
The preparation method of the boron doped Silicalite-1 molecular sieve encapsulated metal catalyst adopts a two-step hydrothermal synthesis method, and the raw materials are the same as those in example 8.
(1) Preparation of boron doped Silicalite-1 molecular sieves: weighing 7778.70g of deionized water, 3.04g of boric acid, 5392.39g of tetrapropylammonium hydroxide aqueous solution with the mass fraction of 30%, 19.52g of potassium hydroxide and 2322.71g of fumed silica, stirring and mixing for 3 hours at the temperature of 25-35 ℃ to obtain uniform mixed sol, transferring the sol into a crystallization kettle, crystallizing at the stirring rotation speed of 120 r/min and the temperature of 160 ℃ for 48 hours, and cooling to obtain boron doped Silicalite-1 molecular sieve crystallization slurry, wherein SiO in the sol 2 :B:K:TPAOH:H 2 O molar ratio is 100.0:0.13:0.90:21.0:1700.0;
(2) Preparing a metal source: weighing 8191.32g of deionized water, 21.86g of ammonium hexachloroplatinate, 102.16g of tin tetrachloride pentahydrate and 262.95g of chelating agent ethylenediamine, stirring and mixing for 2 hours at the temperature of 25-35 ℃ to obtain a metal source solution, wherein the molar ratio of the chelating agent ethylenediamine to Sn is 15:1;
(3) Adding the metal source solution obtained in the step (2) into the boron doped Silicalite-1 molecular sieve crystallization slurry obtained in the step (1), and stirring and mixing for 3 hours at the temperature of 25-35 ℃ to obtain uniform mixed slurry;
(4) Transferring the mixed slurry obtained in the step (3) into a crystallization kettle, and crystallizing at 160 ℃ for 48 hours at the stirring rotation speed of 120 revolutions per minute;
(5) Filtering and washing the crystallized product obtained in the step (4) to pH 7-8, and drying for 16 hours at a drying temperature of 100 ℃ to obtain the boron doped Silicalite-1 molecular sieve encapsulated metal catalyst raw powder.
As can be seen from the comparison of the X-ray fluorescence spectrum (XRF) test that the Pt content is 0.33% of the mass of the silicon dioxide and the Sn content is 0.80% of the mass of the silicon dioxide, the metal in the product obtained by adopting the hydrothermal crystallization method has more loss along with crystallization mother liquor and water washing water.
Catalyst dehydrogenation performance evaluation the propane dehydrogenation performance of the catalyst prepared in this example is shown in table 1 as in example 1.
Table 1 activity evaluation data for the propane dehydrogenation catalyst application of the catalysts prepared in examples 1-10 and comparative example 1
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (9)

1. A method for preparing a boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst, which is characterized by comprising the following steps:
(1) Preparation of boron or phosphorus doped Silicalite-1 molecular sieves: weighing deionized water, boron or phosphorus element compound, template agent, alkali metal source and silicon source, stirring and mixing for 1-6 hours at 25-35 ℃ to obtain mixed sol, transferring the sol into a crystallization kettle, crystallizing and reacting for 24-72 hours at 140-180 ℃ at 50-200 r/min, cooling, and drying the crystallized slurry at 70-90 ℃ for 24-48 hours to obtain boron or phosphorus doped Silicalite-1 molecular sieve carrier;
(2) Preparing an impregnating solution: weighing deionized water, a metal source and a chelating agent, stirring and mixing for 1-3 hours at the temperature of 25-35 ℃ to obtain an impregnating solution;
(3) Dipping the dipping liquid obtained in the step (2) at the temperature of 30-60 ℃ to treat the boron or phosphorus doped Silicate-1 molecular sieve carrier obtained in the step (1), wherein the mass ratio of the dipping liquid to the boron or phosphorus doped Silicalite-1 molecular sieve carrier is 2-5:1, the dipping time is 3-9 hours, drying at 70-90 ℃ to obtain a dry adhesive material, and controlling the water content of the dry adhesive material to be 17-25%;
(4) Transferring the dry glue material obtained in the step (3) into a crystallization kettle, and carrying out dry glue crystallization reaction under the conditions that the reaction temperature is 140-180 ℃ and the reaction time is 24-72 hours;
(5) And (3) drying and forming the crystallized product obtained in the step (4), roasting under nitrogen atmosphere, oxidizing and roasting under air atmosphere and reducing under hydrogen atmosphere to obtain the boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst.
2. The method according to claim 1, wherein in the step (1), siO in the sol is as follows 2 :BOR P:M:ROH:H 2 The molar ratio of O is 100:0.06-0.4:0.43-1.43:17-30:1400-2100, wherein M is alkali metal and ROH is mouldA plate agent;
the boron or phosphorus element compound is selected from one of boric acid, phosphoric acid, ammonium phosphate and ammonium dihydrogen phosphate;
the template agent is tetrapropylammonium hydroxide aqueous solution with the mass concentration of 25-35%;
the alkali metal source is sodium hydroxide or potassium hydroxide;
the silicon source is selected from one of tetraethoxysilane and gas-phase white carbon black.
3. The method of claim 1, wherein in step (2), the metal source comprises a noble metal source and a co-active metal source, wherein the noble metal is selected from at least one of Ru, rh, pd, pt, au and the co-active metal is selected from one of Sc, ti, V, cr, mn, fe, co, ni, cu, zn, Y, zr, nb, mo, W, ga, in, ge, sn, pb, sb, bi, la, ce;
the chelating agent is selected from one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine;
the molar ratio of the chelating agent to the co-active metal in the metal source is 5-20:1.
4. The method according to claim 3, wherein in the step (2), the noble metal is selected from one of Pt and Pd, and the auxiliary active metal is selected from one of Fe, co, ni, cu, zn, ga, in, sn, la, ce.
5. The method according to claim 1, wherein in the step (2), the noble metal source is selected from one of hexachloroplatinic acid, ammonium hexachloroplatinate, palladium chloride dihydrate, ammonium chloropalladate, and the co-active metal is selected from one of metal hydrochloride, nitrate, sulfate, and acetate.
6. The method according to claim 1, wherein in the step (3), the carrier in the dry gel material is SiO 2 The loading amount of noble metal element is SiO 2 0.1 to 0.7 mass percent, siO 2 Noble metal element and assistantThe molar ratio of the active metal elements is 100:0.06-0.4:0.54-1.89, and the molar ratio of the noble metal elements to the boron or phosphorus elements is 1:1.
7. The method according to claim 1, wherein in the step (5), the drying temperature is 90 to 120 ℃ and the drying time is 12 to 24 hours;
the nitrogen atmosphere is high-purity nitrogen atmosphere, the roasting temperature is 350-450 ℃, and the roasting time is 3-9 hours;
the oxidizing roasting temperature is 550-600 ℃ and the oxidizing time is 3-9 hours under the air atmosphere;
the hydrogen atmosphere is high-purity hydrogen atmosphere, the reduction temperature is 550-600 ℃, and the reduction time is 3-9 hours.
8. A catalyst prepared by the method of any one of claims 1-7.
9. Use of the catalyst of claim 8 in a dehydrogenation reaction of light alkanes.
CN202211691294.8A 2022-12-27 2022-12-27 Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof Active CN115814839B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211691294.8A CN115814839B (en) 2022-12-27 2022-12-27 Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211691294.8A CN115814839B (en) 2022-12-27 2022-12-27 Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115814839A CN115814839A (en) 2023-03-21
CN115814839B true CN115814839B (en) 2024-03-22

Family

ID=85518776

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211691294.8A Active CN115814839B (en) 2022-12-27 2022-12-27 Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115814839B (en)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009082785A (en) * 2007-09-28 2009-04-23 Kyuchaku Gijutsu Kogyo Kk Method and apparatus for treating gas containing harmful substance
CN102553632A (en) * 2010-12-15 2012-07-11 中国石油化工股份有限公司 Low carbon alkane dehydrogenation catalyst, preparation method and application thereof
CN103068774A (en) * 2010-08-12 2013-04-24 三井化学株式会社 Method for manufacturing unsaturated hydrocarbon, and dehydrogenation catalyst used in said method
CN103204517A (en) * 2012-01-16 2013-07-17 湖北大学 Method for synthesizing microporous molecular sieve with methylene doped in skeleton without template
CN106187661A (en) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 A kind of C8aromatics isomerization-separation coupling reaction method
CN106669768A (en) * 2017-01-09 2017-05-17 吉林大学 Metal@Sillicalite-1 molecular sieve loading super-small noble metal particles, preparation method and application
CN107346821A (en) * 2016-05-06 2017-11-14 苏州汉瀚储能科技有限公司 A kind of preparation method of boron doping porous carbon ball
WO2018188532A1 (en) * 2017-04-10 2018-10-18 武汉凯迪工程技术研究总院有限公司 High-nitrogen crude oil hydrorefining catalyst and preparation method therefor, and preparation method for carrier thereof
CN109261199A (en) * 2018-09-27 2019-01-25 太原理工大学 A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications
CN110614117A (en) * 2019-09-10 2019-12-27 中国石油大学(北京) Co-Silicalite-1 catalyst, and preparation method and application thereof
CN110980756A (en) * 2019-11-22 2020-04-10 中触媒新材料股份有限公司 Method for preparing SSZ-39 molecular sieve by taking phosphorus modified Y-type molecular sieve as raw material
CN113694960A (en) * 2021-08-20 2021-11-26 常州工学院 ZrCu-MOR zeolite for synthesizing 5-ethoxymethylfurfural and preparation method thereof
CN114453017A (en) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 Hydrocracking catalyst, and preparation method and application thereof
CN115430460A (en) * 2022-09-22 2022-12-06 浙江大学 Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111408370B (en) * 2019-01-08 2022-03-22 天津大学 Supported PtZn intermetallic alloy catalyst and preparation method and application thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009082785A (en) * 2007-09-28 2009-04-23 Kyuchaku Gijutsu Kogyo Kk Method and apparatus for treating gas containing harmful substance
CN103068774A (en) * 2010-08-12 2013-04-24 三井化学株式会社 Method for manufacturing unsaturated hydrocarbon, and dehydrogenation catalyst used in said method
CN102553632A (en) * 2010-12-15 2012-07-11 中国石油化工股份有限公司 Low carbon alkane dehydrogenation catalyst, preparation method and application thereof
CN103204517A (en) * 2012-01-16 2013-07-17 湖北大学 Method for synthesizing microporous molecular sieve with methylene doped in skeleton without template
CN106187661A (en) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 A kind of C8aromatics isomerization-separation coupling reaction method
CN107346821A (en) * 2016-05-06 2017-11-14 苏州汉瀚储能科技有限公司 A kind of preparation method of boron doping porous carbon ball
CN106669768A (en) * 2017-01-09 2017-05-17 吉林大学 Metal@Sillicalite-1 molecular sieve loading super-small noble metal particles, preparation method and application
WO2018188532A1 (en) * 2017-04-10 2018-10-18 武汉凯迪工程技术研究总院有限公司 High-nitrogen crude oil hydrorefining catalyst and preparation method therefor, and preparation method for carrier thereof
CN109261199A (en) * 2018-09-27 2019-01-25 太原理工大学 A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications
CN110614117A (en) * 2019-09-10 2019-12-27 中国石油大学(北京) Co-Silicalite-1 catalyst, and preparation method and application thereof
CN110980756A (en) * 2019-11-22 2020-04-10 中触媒新材料股份有限公司 Method for preparing SSZ-39 molecular sieve by taking phosphorus modified Y-type molecular sieve as raw material
CN114453017A (en) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 Hydrocracking catalyst, and preparation method and application thereof
CN113694960A (en) * 2021-08-20 2021-11-26 常州工学院 ZrCu-MOR zeolite for synthesizing 5-ethoxymethylfurfural and preparation method thereof
CN115430460A (en) * 2022-09-22 2022-12-06 浙江大学 Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Acidity and catalyst performance of two shape-selective HZSM-5 catalysts for alkylation of toluene with methanol;Li G.X.;《Reaction Kinetics Mechanisms and Catalysis》;20200218;第129卷(第2期);第963-974页 *
Effects of dopants in PtSn/M-Silicate-1 on structure property and on catalytic propane dehydrogenation performance;Zhou S. et al.;《Chemistryselect》;20200514;第5卷(第14期);第4175-4185页 *
Pt、Mg助剂对Co/Silicalite-1催化剂丙烷脱氢性能影响的研究;于雪;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20230315;B014-254 *
Silicalite-1催化剂上重整汽油富苯馏分甲醇烷基化反应研究;蒋玉鑫;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20200715;B017-34 *
吴志杰.《能源转化催化原理》.东营: 中国只有大学出版社,2018,第13-138页. *
多级孔分子筛Silicalite-1的制备及其在合成气直接制低碳烯烃反应中的应用;冯英杰等;《石油化工》;20180815(第08期);第7-13页 *
无模板剂法合成ZSM-35分子筛研究;高晓坤等;《硅酸盐通报》;20200615;第39卷(第06期);第1965-1969页 *

Also Published As

Publication number Publication date
CN115814839A (en) 2023-03-21

Similar Documents

Publication Publication Date Title
Wang et al. Cr doped mesoporous silica spheres for propane dehydrogenation in the presence of CO2: Effect of Cr adding time in sol-gel process
JP5483114B2 (en) A method for producing a multicomponent bismuth molybdate catalyst with pH adjustment and a method for producing 1,3-butadiene using the same.
CN107840778A (en) A kind of method of hydrogenation of carbon dioxide preparing aromatic hydrocarbon
CN107265478B (en) A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof
WO2018010358A1 (en) Method for preparing styrene from side-chain alkylation of methylbenzene and synthesis gas
CN107303512A (en) A kind of bifunctional catalyst and its application in benzene hydrogenation alkylated reaction
WO2020125487A1 (en) Method for the preparation of low-carbon olefin in high selectivity from synthesis gas catalyzed by heteroatom-doped molecular sieve
WO2017031635A1 (en) Iron-based catalyst prepared by using coprecipitation-melting method, preparation method therefor, and application thereof
CN113751052A (en) Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof
Wu et al. Effective synthesis of vanadium-doped mesoporous silica nanospheres by sol-gel method for propane dehydrogenation reaction
CN115814839B (en) Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof
CN117443434A (en) Ball-like non-noble metal doped Silicalite-1 catalyst and preparation method and application thereof
JP7007763B2 (en) A method for producing ethylene by a composite catalyst modified with an organic alkali and hydrogenation of carbon monoxide.
CN112221493A (en) Noble metal modified gallium oxide catalyst and preparation method and application thereof
CN113860324B (en) Synthesis method and application of morphology-controllable KL molecular sieve
CN104549444B (en) The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application
CN104549295B (en) Olefin isomerization catalyst
CN105582933B (en) Catalyst for double-bond isomerization
CN115805097B (en) Large-grain Zn@Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN113856743B (en) Catalyst for propylene production and environment-friendly process for propylene production
CN114433220B (en) Preparation method of benzene and synthesis gas alkylation catalyst
CN107021504B (en) A kind of preparation method of mesoporous IM-5 molecular sieve
CN117482982A (en) Gallium or indium doped S-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof
CN117443433A (en) S-1 molecular sieve encapsulated metal low-carbon alkane dehydrogenation catalyst and preparation method and application thereof
CN115920947A (en) Co @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant