CN116747898A - Lamellar morphology heteroatom zeolite molecular sieve catalyst for catalyzing polyolefin plastic cracking - Google Patents

Lamellar morphology heteroatom zeolite molecular sieve catalyst for catalyzing polyolefin plastic cracking Download PDF

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CN116747898A
CN116747898A CN202310545850.9A CN202310545850A CN116747898A CN 116747898 A CN116747898 A CN 116747898A CN 202310545850 A CN202310545850 A CN 202310545850A CN 116747898 A CN116747898 A CN 116747898A
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catalyst
lamellar
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王亮
段金娣
肖丰收
王海
吴越新
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract

The invention relates to a polyolefin plastic catalytic pyrolysis technology, and aims to provide a lamellar morphology heteroatom zeolite molecular sieve catalyst for catalyzing polyolefin plastic pyrolysis. The zeolite molecular sieve catalyst adopts a lamellar ZSM-5 zeolite molecular sieve with an MFI type crystal structure, the Si/Al molar ratio is 15-300:1, and the lamellar thickness is 30-300 nanometers. The preparation raw materials are cheap and easy to obtain, noble metals are not used, so that the preparation cost of the catalyst is low, and the large-scale production of the catalyst is facilitated. Compared with the prior art, the catalyst product of the invention is used for carrying out the catalytic pyrolysis of polyolefin plastics, has lower reaction temperature and higher yield, and does not need to additionally add reaction auxiliary agent in the synthesis process. Compared with the traditional zeolite, the lamellar zeolite adopted by the patent has obvious progress in the aspect of carbon deposition resistance, and is beneficial to the long-term use of the catalyst.

Description

Lamellar morphology heteroatom zeolite molecular sieve catalyst for catalyzing polyolefin plastic cracking
Technical Field
The invention relates to a polyolefin plastic catalytic pyrolysis technology, in particular to an MFI type zeolite molecular sieve catalyst with a lamellar crystal structure and application of directly catalyzing and cracking polyolefin plastic into low-carbon alkane and alkene.
Background
The polyolefin plastic brings convenience to life of people and also brings serious pollution problem. The method for preparing the fuel oil and the low-carbon gas by recycling and degrading the waste plastics has very important significance for environmental protection, can obtain great economic benefit and can alleviate the dilemma of petroleum exhaustion.
The catalyst can reduce the reaction temperature, promote the reaction to be rapidly carried out, regulate and control the selectivity of the product and improve the value of the subsequent conversion and utilization of the product. In this process, the controlled cleavage of the C-C bond is an important step. Solid acid catalysts such as zeolite molecular sieves are generally adopted in the current research results, but the reaction is fast deactivated due to the fact that a large amount of carbon deposit is generated in the reaction process. To solve this problem, a relatively advanced method in the current field is to use noble metal Pt to control C-C bond cleavage, and selectively obtain diesel or aromatic components (Science 2020, 370,437-441; nat. Catalyst 2020,3, 893-901). However, noble metals are expensive and are difficult to function in practical applications.
Therefore, the study of non-noble metal, carbon deposition resistant catalysts to achieve controlled degradation of polyolefin plastics is an important challenge.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a method for directly catalyzing and cracking polyolefin plastics into low-carbon alkane and alkene by utilizing an MFI type zeolite molecular sieve with a lamellar crystal structure.
In order to solve the technical problems, the invention adopts the following solutions:
the catalyst adopts a lamellar ZSM-5 zeolite molecular sieve with an MFI type crystal structure, the Si/Al molar ratio is 15-300:1, and the lamellar thickness is 30-300 nanometers.
As a preferable scheme of the invention, the zeolite molecular sieve is also loaded with transition metal elements, and the molar ratio of the transition metal elements to silicon is 0-0.1:1 and is not equal to 0.
As a preferable mode of the present invention, the transition metal element is any one or a combination of any two or more of the following: ni, cu, co, mo, fe, zn or Mn.
The invention further provides a preparation method of the zeolite molecular sieve catalyst, which comprises the steps of dissolving a silicon source, an aluminum source, a template agent and urea in a certain amount of water to form a mixed solution; alternatively, a metal salt is further added to the mixed solution; then carrying out hydrothermal crystallization reaction, and roasting the reaction product to obtain a powdery catalyst product;
wherein the metal salt is a salt compound of transition metal elements of nickel, copper, cobalt, molybdenum, iron, zinc or manganese; in the mixed solution, siO 2 Al template agent urea metal salt H 2 The molar ratio relationship of O is 1:0.003-0.067:0.1-0.5:0.1-2.5:0-0.1:20.0-33.5; the hydrothermal crystallization reaction is carried out in a closed container, the reaction temperature is 120-200 ℃, and the reaction time is 24-120 hours; the condition of the roasting treatment is that the air roasting is carried out for 4 hours at 550 ℃.
As a preferred embodiment of the present invention, the silicon source is any one of the following: silica, tetraethyl silicate, white carbon black; the aluminum source is sodium metaaluminate, aluminum sulfate or boehmite; the template agent is any one of the following: tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), triethylamine; the metal salt is any one of the following: nickel nitrate, nickel sulfate, copper nitrate, copper chloride, copper sulfate, cobalt nitrate, cobalt sulfate, ammonium molybdate, ferric nitrate, ferric chloride, ferric sulfate, zinc nitrate, zinc chloride, zinc sulfate, manganese nitrate, manganese chloride, and manganese sulfate.
The invention also provides an application method of the lamina morphology heteroatom zeolite molecular sieve catalyst in catalyzing polyolefin plastic cracking reaction, which comprises the steps of mixing polyolefin plastic with the catalyst in a reducing atmosphere or an inert atmosphere, directly carrying out catalytic cracking reaction after heating and melting, and finally converting into light alkane and alkene; wherein the mass of the catalyst accounts for 0.01-50% of the mass of the polyolefin plastic; the reaction temperature of catalytic cracking is 200-650 ℃, the reaction time is 0.1-500 h, and the reaction mode is a fixed bed, a slurry bed or a fluidized bed.
As a preferable scheme of the invention, the reducing atmosphere means that carrier gas CO or H is continuously introduced in the reaction process 2 The method comprises the steps of carrying out a first treatment on the surface of the The inert atmosphere is that carrier gas N is continuously introduced in the reaction process 2 Or methane gas.
As a preferable scheme of the invention, the polyolefin plastic is any one or a mixture of the following materials: high density polyethylene, low density polyethylene, polypropylene, polyvinyl chloride, polystyrene, or plastics having the aforementioned polyolefin as a main component.
Description of the inventive principles:
the MFI zeolite has wide application in the catalytic cracking reaction of hydrocarbons due to its unique acidity and pore structure. However, the traditional ZSM-5 molecular sieve has the problems of low molecular diffusion efficiency and easy formation of carbon deposition and rapid inactivation due to small micropore diameter and long diffusion path. In molecular sieve-catalyzed plastic cracking reactions, deactivation of carbon deposition of molecular sieves has always been a major technical hurdle impeding the intensive research by those skilled in the art.
The invention takes the zeolite molecular sieve with MFI structure as the basis, prepares the lamellar ZSM-5 zeolite with different thickness by adjusting the morphology of the molecular sieve, and can prepare the low-carbon olefin compounds by the catalytic pyrolysis of polyolefin plastics. As the zeolite crystal with the lamellar structure has a shorter b-axis thickness and a higher 010 crystal face exposure proportion, the rapid diffusion and desorption of product molecules are greatly promoted, the diffusion efficiency is improved, and the carbon deposition is effectively inhibited. The whole process can be realized at a lower temperature, so that the use of noble metal or addition of auxiliary agents is avoided, toxic and harmful byproducts are not generated in the reaction process, and the method is environment-friendly.
For the prior art, the invention has the beneficial effects that:
1. the preparation raw materials related by the invention are cheap and easy to obtain, and noble metals are not used; the preparation cost of the catalyst is lower, and the catalyst is beneficial to realizing the large-scale production of the catalyst.
2. Compared with the prior art, the catalyst provided by the invention has the advantages of lower reaction temperature and higher yield, and no need of adding additional reaction auxiliary agent in the synthesis process.
3. Compared with the traditional zeolite, the lamellar zeolite adopted by the invention has obvious progress in the aspect of carbon deposition resistance, and is beneficial to the long-term use of the catalyst.
Drawings
FIG. 1 is a comparison of the olefins in the gas product of example 1;
FIG. 2 is a FID spectrum of the gas product of example 3;
FIG. 3 is an SEM image of a platelet ZSM-5 molecular sieve of example 9;
FIG. 4 is an XRD pattern of the platelet ZSM-5 molecular sieve of example 10;
FIG. 5 is a graph showing the adsorption of nitrogen by the platelet ZSM-5 of example 12;
FIG. 6 is a photograph of a reaction residue of the catalytic cracking of polyethylene by the platelet ZSM-5 in example 15;
FIG. 7 is an SEM image of the conventional ZSM-5 of example 11;
FIG. 8 is a photograph of a reaction residue of a conventional ZSM-5 catalytic cracking polyethylene of example 11.
Detailed Description
The invention is described in further detail below in connection with specific embodiments. The examples will allow a person skilled in the art to more fully understand the invention and are not intended to limit it in any way.
In various embodiments, the method for preparing the catalyst comprises: firstly, dissolving a silicon source, an aluminum source, a template agent and urea in a certain amount of water to form a mixed solution; alternatively, a metal salt is further added to the mixed solution; siO in the raw materials 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.003-0.067:0.1-0.5:0.1-2.5:0-0.1:20.0-33.5. Then carrying out hydrothermal crystallization reaction in a closed container, wherein the reaction temperature is 120-200 ℃ and the reaction time is 24-120 hours. And roasting the product after the reaction is finished, wherein the condition is that the air roasting is carried out for 4 hours at 550 ℃. Finally, the powdery ZSM-5 zeolite molecular sieve product is obtained, and the particles of the product have lamellar MFI crystal structure.
In the preparation of the zeolite molecular sieve catalyst in the embodiments of the invention, the silicon source used can be selected from silicon dioxide, tetraethyl silicate or white carbon black; the aluminum source is sodium metaaluminate, aluminum sulfate or boehmite; the template agent can be tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH) or triethylamine; the metal salt can be nickel nitrate, nickel sulfate, copper nitrate, copper chloride, copper sulfate, cobalt nitrate, cobalt sulfate, ammonium molybdate, ferric nitrate, ferric chloride, ferric sulfate, zinc nitrate, zinc chloride, zinc sulfate, manganese nitrate, manganese chloride or manganese sulfate.
The zeolite molecular sieve catalyst can be used for catalyzing the cracking reaction of polyolefin plastics, which is characterized in that the polyolefin plastics and the catalyst are mixed in a reducing atmosphere or an inert atmosphere, and are directly subjected to the catalytic cracking reaction after being heated and melted, and finally converted into low-carbon alkane and olefin. Wherein the mass of the catalyst accounts for 0.01-50% of the mass of the polyolefin plastic; the reaction temperature of catalytic cracking is 200-650 ℃, the reaction time is 0.1-500 h, and the reaction mode can be fixed bed, slurry bed or fluidized bed.
Example 1
Preparation of platelet ZSM-5 (Si/Al molar ratio=40, platelet thickness 100 nm) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25wt%, i.e. mass fraction of TPAOH in aqueous solution, the same applies hereinafter), 14g of TEOS, 350mg of NaAlO 2 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0:32. Crystallizing at 180 deg.c for 24 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm, SEM (shown in figure 3) and 010 crystal face exposure ratio of about 70%.
Application of the catalyst: mixing 500mg polyethylene with 100mg lamellar ZSM-5 (Si/Al molar ratio=40, lamellar thickness 100 nm) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, and introducing H 2 Carrier gas, fixed bed 300 deg.c reaction for 7 hr, and the product is mainly C 2 -C 7 Lower olefins, C 2 -C 12 The product yield of the lower alkane and alkene products is 60.4%, and the product distribution is shown in figure 1.
Example 2
Preparation of a platelet ni@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 And 0.20g Ni (NO) 3 ) 2 ·6H 2 O is uniformly mixed, stirred for 6 hours, 2.83g of urea is added, stirred for 1 hour, siO is added into the reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.01:32. Crystallizing at 200 ℃ for 48h and roasting at 550 ℃ for 4h. The prepared lamellar Ni@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and 010 crystal face exposure ratio of about 70%, and the element analysis result is shown in Table 1.
Application of the catalyst: 500mg of polyethylene plastic was reacted with 100mg of a platelet Ni@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/Si=0.01) zeolite catalyst (catalyst massAccounting for 20 percent of the mass of the polyolefin plastic) are evenly mixed and grinded, and H is introduced 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The product yield of the lower alkane and alkene products was 72.7%.
Example 3
Preparation of a platelet ni@zsm-5 (Si/Al molar ratio=15, platelet thickness 120nm, ni/si=0.01) catalyst: will be 20g H 2 O, 27.3g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 934mg of NaAlO 2 And 0.20g Ni (NO) 3 ) 2 ·6H 2 O is uniformly mixed, stirred for 6 hours, 2.03g of urea is added, stirred for 1 hour, siO is added into the reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.50:0.5:0.01:33.5. Crystallizing at 200 ℃ for 48h and roasting at 550 ℃ for 4h. The prepared lamellar Ni@ZSM-5 molecular sieve has Si/Al molar ratio=15, lamellar thickness of 120nm and 010 crystal face exposure ratio of about 67%, and the element analysis result is shown in Table 1.
Application of the catalyst: mixing polyethylene plastic 500mg with zeolite catalyst (catalyst mass 20% of polyolefin plastic mass) 100mg of lamellar Ni@ZSM-5 (Si/Al molar ratio=15, lamellar thickness 120nm, ni/Si=0.01), grinding uniformly, and introducing N 2 The carrier gas and the slurry bed react for 14 hours at 400 ℃, C 2 -C 12 The product yield of the lower alkane and alkene products was 95.7%.
Example 4
Preparation of a platelet nicu@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/si=0.09, cu/si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、1.80g Ni(NO 3 ) 2 ·6H 2 O and 0.12g Cu (NO) 3 ) 2 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.1:32. Crystallizing 120h at 120 ℃, and roasting 4h at 550 ℃ in air. The prepared lamellar NiCu@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis resultSee Table 1 with a 010 crystal face exposure of about 70%.
Application of the catalyst: 500mg of polyethylene and 100mg of lamellar NiCu@ZSM-5 (molar ratio of Si/Al=40, lamellar thickness of 100nm, ni/Si=0.09, cu/Si=0.01) zeolite catalyst (catalyst mass accounting for 20% of the mass of polyolefin plastic) are mixed and ground uniformly, and H is introduced 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The product yield of the lower alkane and alkene products is 73.5%, and the FID detection spectrum of the gas products is shown in figure 2.
Example 5
Preparation of a platelet nicu@zsm-5 (Si/Al molar ratio=15, platelet thickness 80nm, ni/si=0.09, cu/si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 934mg of NaAlO 2 、1.80g Ni(NO 3 ) 2 ·6H 2 O and 0.12g Cu (NO) 3 ) 2 Uniformly mixing, stirring for 6 hours, adding 3.03g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.46:0.75:0.1:32. Crystallizing 120h at 120 ℃, and roasting 4h at 550 ℃ in air. The prepared lamellar NiCu@ZSM-5 molecular sieve has Si/Al molar ratio=15, lamellar thickness of 80nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 72%.
Application of the catalyst: mixing 500mg polyethylene with 100mg NiCu@ZSM-5 (Si/Al molar ratio=15, sheet thickness 80nm, ni/Si=0.09, cu/Si=0.01) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, introducing N 2 Carrier gas, fluidized bed 650 ℃ reaction for 500 hours, C 2 -C 12 The product yield of the lower alkane and alkene products was 98.5%.
Example 6
Preparation of a platelet como@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, co/si=0.05, mo/si=0.05) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.99g Co(NO 3 ) 2 ·6H 2 O and 0.41g (NH) 4 ) 2 MoO 4 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.1:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar CoMo@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: mixing 500mg of polyethylene and 100mg of lamellar CoMo@ZSM-5 (Si/Al molar ratio=40, lamellar thickness is 100nm, co/Si=0.05, mo/Si=0.05) zeolite catalyst (catalyst mass is 20% of polyolefin plastic mass), grinding uniformly, introducing CO carrier gas, reacting for 7 hours at 300 ℃ in a fixed bed, and reacting for C 2 -C 12 The product yield of the lower alkane and alkene products was 75.5%.
Example 7
Preparation of a platelet como@zsm-5 (Si/Al molar ratio=15, platelet thickness 300nm, co/si=0.05, mo/si=0.05) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 934mg of NaAlO 2 、0.99g Co(NO 3 ) 2 ·6H 2 O and 0.41g (NH) 4 ) 2 MoO 4 Uniformly mixing, stirring for 6h, adding 0.40g of urea, stirring for 1h, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.46:0.1:0.1:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar CoMo@ZSM-5 molecular sieve has Si/Al molar ratio=15, lamellar thickness of 300nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 55%.
Application of the catalyst: mixing 500mg polyethylene with 100mg lamellar CoMo@ZSM-5 (Si/Al molar ratio=15, lamellar thickness 300nm, co/Si=0.05, mo/Si=0.05) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, introducing N 2 Carrying gas and reacting at 300 ℃ for 50 hours by using a slurry bed, C 2 -C 12 The product yield of the lower alkane and alkene products was 88.5%.
Example 8
Preparation of a platelet znmn@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, zn/si=0.01, mn/si=0.05) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.18g Zn(NO 3 ) 2 ·6H 2 O and 0.91gMn (NO) 3 ) 2 ·4H 2 O is uniformly mixed, stirred for 6 hours, 2.83g of urea is added, stirred for 1 hour, siO is added into the reaction system 2 ︰
Al-template agent-urea-metal salt-H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.06:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar ZnMn@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: 500mg of polyethylene and 100mg of a platelet ZnMn@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, zn/Si=0.01, mn/Si=0.05) zeolite catalyst (catalyst mass 20% of the polyolefin plastic mass) were mixed and ground uniformly, and H was introduced 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The product yield of the lower alkane and alkene products was 72.8%.
Example 9
Preparation of a platelet znmn@zsm-5 (Si/Al molar ratio=80, platelet thickness 100nm, zn/si=0.01, mn/si=0.05) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 175mg of NaAlO 2 、0.18g Zn(NO 3 ) 2 ·6H 2 O and 0.91gMn (NO) 3 ) 2 ·4H 2 O is uniformly mixed, stirred for 6 hours, 2.83g of urea is added, stirred for 1 hour, siO is added into the reaction system 2 ︰
Al-template agent-urea-metal salt-H 2 The molar ratio of O is 1:0.013:0.46:0.7:0.06:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar ZnMn@ZSM-5 molecular sieve has Si/Al molar ratio=80, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: mixing 500mg polyethylene with 100mg sheet ZnMn@ZSM-5 (Si/Al molar ratio=80, sheet thickness 100nm, zn/Si=0.01, mn/Si=0.05) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, introducing CH 4 The carrier gas and the slurry bed react for 0.1 hour at 400 ℃, C 2 -C 12 The product yield of the lower alkane and alkene products was 20.8%.
Example 10
Preparation of a platelet fe@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, fe/si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 And 0.17g Fe (NO) 3 ) 3 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.01
32. Crystallizing 72h at 180 ℃ and roasting 4h at 550 ℃. The prepared lamellar Fe@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: mixing 500mg polyethylene plastic with 0.05mg lamellar Fe@ZSM-5 (Si/Al molar ratio=40, lamellar thickness 100nm, fe/Si=0.01) zeolite catalyst (catalyst mass 0.01% of polyolefin plastic mass), grinding uniformly, and introducing H 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The product yield of the lower alkane and alkene products was 61.9%.
Example 11
Preparation of a platelet fe@zsm-5 (Si/Al molar ratio=300, platelet thickness 30nm, fe/si=0.01) catalyst: will be 20g H 2 O, 5.4g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 46.7mg of NaAlO 2 And 0.17g Fe (NO) 3 ) 3 Uniformly mixing, stirring for 6 hours, adding 10.1g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.003:0.10:2.5:0.01:20. Crystallization 72h at 120 ℃ and empty at 550 DEG CAnd roasting for 4 hours. The prepared lamellar Fe@ZSM-5 molecular sieve has Si/Al molar ratio=300, lamellar thickness of 30nm and elemental analysis results shown in Table 1, and 010 crystal face exposure ratio of about 78%.
Application of the catalyst: 500mg of polyethylene plastic and 0.05mg of a platelet Fe@ZSM-5 (Si/Al molar ratio=300, platelet thickness of 30nm, fe/Si=0.01) zeolite catalyst (catalyst mass accounting for 0.01% of the polyolefin plastic mass) are mixed and ground uniformly, and N is introduced 2 Carrying gas, reacting for 50 hours at 200 ℃ in a fluidized bed, C 2 -C 12 The product yield of the lower alkane and alkene products was 15.9%.
Example 12
Preparation of a platelet FeZn@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, fe/Si=0.01, zn/Si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.18g Zn(NO 3 ) 2 ·6H 2 O and 0.17g Fe (NO) 3 ) 3 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.02:32. Crystallizing 72h at 180 ℃ and roasting 4h at 550 ℃. The prepared lamellar FeZn@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: 500mg of polypropylene plastic and 100mg of lamellar FeZn@ZSM-5 (Si/Al molar ratio=40, lamellar thickness is 100nm, fe/Si=0.01, zn/Si=0.01) zeolite catalyst (catalyst mass accounts for 20% of the polyolefin plastic mass) are mixed and ground uniformly, and H is introduced 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The yield of the products of the low-carbon alkane and alkene products is 78.8%, and the elemental analysis results of the used lamellar FeZn@ZSM-5 molecular sieve are shown in Table 1.
Example 13
Preparation of a platelet FeZn@ZSM-5 (Si/Al molar ratio=40, platelet thickness 30nm, fe/Si=0.01, zn/Si=0.01) catalyst: will be 20g H 2 O, 5.4g of tetrapropylammonium hydroxide aqueous solution (TPAOH，25wt％)、14gTEOS、350mg NaAlO 2 、0.18g Zn(NO 3 ) 2 ·6H 2 O and 0.17g Fe (NO) 3 ) 3 Uniformly mixing, stirring for 6 hours, adding 10.1g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.1:2.5:0.02:20. Crystallizing for 72h at 120 ℃ and roasting for 4h at 550 ℃. The prepared lamellar FeZn@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 30nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 78%.
Application of the catalyst: 500mg of polypropylene plastic and 250mg of lamellar FeZn@ZSM-5 (Si/Al molar ratio=40, lamellar thickness is 30nm, fe/Si=0.01, zn/Si=0.01) zeolite catalyst (catalyst mass is 50% of polyolefin plastic mass) are mixed and ground uniformly, and N is introduced 2 The carrier gas and the slurry bed react for 50 hours at 400 ℃, C 2 -C 12 The yield of the products of the low-carbon alkane and alkene products is 98.8%, and the elemental analysis results of the used lamellar FeZn@ZSM-5 molecular sieve are shown in Table 1.
Example 14
Preparation of a platelet nimn@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/si=0.01, mn/si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.20g Ni(NO 3 ) 2 ·6H 2 O and 0.18g Mn (NO) 3 ) 2 ·4H 2 O is uniformly mixed, stirred for 6 hours, 2.83g of urea is added, stirred for 1 hour, siO is added into the reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.02:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar NiMn@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: 500mg of a polyethylene and polypropylene plastic mixture (polyethylene and polypropylene ratio 1:1) was reacted with 100mg of a platelet nimn@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/si=0.01, mn/si=0.01) zeolite catalyst (catalyticThe agent mass is 20 percent of the polyolefin plastic mass), and the mixture is evenly ground and is filled with H 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The product yield of the lower alkane and alkene products was 68.2%.
Example 15
Preparation of a platelet nimn@zsm-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/si=0.01, mn/si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.20g Ni(NO 3 ) 2 ·6H 2 O and 0.18g Mn (NO) 3 ) 2 ·4H 2 O is uniformly mixed, stirred for 6 hours, 2.83g of urea is added, stirred for 1 hour, siO is added into the reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.02:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar NiMn@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: 500mg of a polyethylene and polypropylene plastic mixture (polyethylene and polypropylene ratio 1:1) was mixed with 100mg of a platelet NiMn@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, ni/Si=0.01, mn/Si=0.01) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass) and milled uniformly, and N was introduced 2 The carrier gas and the slurry bed react for 30 hours at 400 ℃, C 2 -C 12 The product yield of the lower alkane and alkene products was 94.2%.
Example 16
Preparation of platelet ZSM-5 (Si/Al molar ratio=40, platelet thickness 30 nm) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 Uniformly mixing, stirring for 6 hours, adding 10.1g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:2.5:0:32. Crystallizing for 100h at 120 ℃, and roasting for 4h at 550 ℃. The prepared lamellar ZSM-5 molecular sieve has Si/Al molar ratio=40 and lamellar thickness of 30nmThe 010 crystal face exposure proportion was about 78%.
Application of the catalyst: mixing 500mg polystyrene plastic with 100mg lamellar ZSM-5 (Si/Al molar ratio=40, lamellar thickness 30 nm) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, and introducing H 2 Carrier gas and fluidized bed at 650 deg.C for 30 hr 2 -C 12 The product yield of the lower alkane and alkene products was 94.6%.
Example 17
Preparation of platelet ZSM-5 (Si/Al molar ratio=15, platelet thickness of 30 nm) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 934mg of NaAlO 2 Uniformly mixing, stirring for 6 hours, adding 10.1g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.46:2.5:0:32. Crystallizing 120h at 120 ℃, and roasting 4h at 550 ℃ in air. The prepared lamellar ZSM-5 molecular sieve has Si/Al molar ratio=15, lamellar thickness of 30nm, XRD shown in figure 4 and 010 crystal face exposure ratio of about 78%.
Application of the catalyst: mixing 500mg polyethylene with 5mg lamellar ZSM-5 (Si/Al molar ratio=15, lamellar thickness 30 nm) zeolite catalyst (catalyst mass 1% of polyolefin plastics mass), grinding uniformly, introducing CH 4 The carrier gas and the slurry bed react for 14 hours at 400 ℃, C 2 -C 12 The product yield of the lower alkane and alkene products was 90.4%.
Example 18
Preparation of a platelet CuZn@ZSM-5 (Si/Al molar ratio=15, platelet thickness 100nm, zn/Si=0.01, cu/Si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%) 14g TEOS, 934mg NaAlO 2 、0.08g ZnCl 2 And 0.08g CuCl 2 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.46:0.7:0.02:32. Crystallizing 72h at 180 ℃ and roasting 4h at 550 ℃. The prepared lamellar CuZn@ZSM-5 molecular sieve has the molar ratio of Si/Al=15, the thickness of the platelet was 100nm, and the elemental analysis results are shown in table 1, with 010 crystal face exposure ratios of about 70%.
Application of the catalyst: mixing 500mg of polyethylene and polystyrene mixture (the ratio of polyethylene to polystyrene is 5:1) and 100mg of zeolite catalyst (catalyst mass is 20% of polyolefin plastic mass) of lamellar CuZn@ZSM-5 (Si/Al molar ratio=15, lamellar thickness is 100nm, zn/Si=0.01, cu/Si=0.01) and grinding uniformly, introducing N 2 Carrying gas, reacting at 400 ℃ for 7 hours by using a slurry bed, and C 2 -C 12 The product yield of the lower alkane and alkene products was 85.7%.
Example 19
Preparation of a platelet CuZn@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, zn/Si=0.01, cu/Si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.08g ZnCl 2 And 0.08g CuCl 2 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.02:32. Crystallizing 72h at 180 ℃ and roasting 4h at 550 ℃. The prepared lamellar CuZn@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: 500mg of a mixture of polyethylene and polystyrene (the ratio of polyethylene to polystyrene is 5:1) was mixed with 100mg of a platelet CuZn@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, zn/Si=0.01, cu/Si=0.01) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass) and milled uniformly, and H was introduced 2 Carrier gas, fixed bed 300 ℃ reaction for 7 hours, C 2 -C 12 The product yield of the lower alkane and alkene products was 72.7%.
Example 20
Preparation of platelet ZSM-5 (Si/Al molar ratio=15, platelet thickness 100 nm) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 934mg of NaAlO 2 Uniformly mixing, stirring for 6 hours,2.83g of urea is added and stirred for 1h, siO in the reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.46:0.7:0:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar ZSM-5 molecular sieve has Si/Al molar ratio=15, lamellar thickness of 100nm, BET shown in figure 5 and 010 crystal face exposure ratio of about 70%.
Application of the catalyst: mixing and grinding 500mg of mixture of polyethylene and polystyrene (the ratio of polyethylene to polystyrene is 2:1) and 100mg of zeolite catalyst (catalyst mass is 20% of polyolefin plastic mass) of lamellar ZSM-5 (Si/Al molar ratio=15, lamellar thickness is 100 nm), and introducing N 2 The carrier gas and the fluidized bed react for 0.1 hour at 650 ℃, C 2 -C 12 The product yield of the lower alkane and alkene products was 82.9%.
Example 21
Preparation of platelet ZSM-5 (Si/Al molar ratio=80, platelet thickness 120 nm) catalyst: will be 20g H 2 O、25.1g TPAOH(25％)、14g TEOS、175mg NaAlO 2 Uniformly mixing, stirring for 6h, adding 2.03g of urea, stirring for 1h, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.013:0.46:0.5:0:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar ZSM-5 molecular sieve has Si/Al molar ratio=80, lamellar thickness of 120nm and 010 crystal face exposure ratio of about 67%.
Application of the catalyst: mixing 500mg polyethylene with 100mg lamellar ZSM-5 (Si/Al molar ratio=80, lamellar thickness 120 nm) zeolite catalyst (catalyst mass 20% of polyolefin plastics mass), grinding uniformly, introducing N 2 Carrying gas, reacting for 7 hours at 650 ℃ in a fluidized bed, C 2 -C 12 The product yield of the lower alkane and alkene products was 93.4%.
Example 22
Preparation of a platelet FeCo@ZSM-5 (Si/Al molar ratio=80, platelet thickness 30nm, fe/Si=0.01, co/Si=0.01) catalyst: will be 20g H 2 O, 5.4g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 175mg of NaAlO 2 、0.16g CoCl 2 ·6H 2 O and 0.12g FeCl 3 Uniformly mixing, stirring for 6 hours, adding 10.1g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.013:0.1:2.5:0.02:20. Crystallizing for 72h at 120 ℃ and roasting for 4h at 550 ℃. The prepared lamellar FeCo@ZSM-5 molecular sieve has Si/Al molar ratio=80, lamellar thickness of 30nm and elemental analysis results shown in Table 1, and the 010 crystal face exposure ratio is about 78%.
Application of the catalyst: mixing 500mg polypropylene with 100mg FeCo@ZSM-5 (Si/Al molar ratio=80, sheet thickness of 30nm, fe/Si=0.01, co/Si=0.01) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, introducing CH 4 The carrier gas and slurry bed were reacted at 400℃for 14 hours with a product yield of 88.3% and elemental analysis results of the platelet FeCo@ZSM-5 molecular sieves used were shown in Table 1.
Example 23
Preparation of a platelet FeCo@ZSM-5 (Si/Al molar ratio=40, platelet thickness 100nm, fe/Si=0.01, co/Si=0.01) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 、0.16g CoCl 2 ·6H 2 O and 0.12g FeCl 3 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0.7:0.02:32. Crystallizing 72h at 180 ℃ and roasting 4h at 550 ℃. The prepared lamellar FeCo@ZSM-5 molecular sieve has Si/Al molar ratio=40, lamellar thickness of 100nm, and elemental analysis results are shown in Table 1, wherein the 010 crystal face exposure ratio is about 70%.
Application of the catalyst: 500mg of polypropylene and 100mg of lamellar FeCo@ZSM-5 (Si/Al molar ratio=40, lamellar thickness is 100nm, fe/Si=0.01, co/Si=0.01) zeolite catalyst (catalyst mass accounting for 20% of the polyolefin plastic mass) are mixed and ground uniformly, and CH is introduced 4 The carrier gas was reacted at 300℃for 7 hours in a fixed bed with a yield of 71.3% and elemental analysis of the used platelet FeCo@ZSM-5 molecular sieve was as shown in Table 1.
Example 24
Preparation of platelet ZSM-5 (Si/Al molar ratio=15, platelet thickness 100 nm) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 934mg of NaAlO 2 Uniformly mixing, stirring for 6 hours, adding 2.83g of urea, stirring for 1 hour, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.067:0.46:0.7:0:32. Crystallizing at 180 deg.c for 24 hr and roasting at 550 deg.c in air for 4 hr. The prepared lamellar ZSM-5 molecular sieve has Si/Al molar ratio=15, lamellar thickness of 100nm and 010 crystal face exposure ratio of about 70%.
Application of the catalyst: 500mg of polyethylene and 100mg of a lamellar ZSM-5 (Si/Al molar ratio=15, lamellar thickness 100 nm) zeolite catalyst (catalyst mass is 20% of the polyolefin plastic mass) are mixed and ground uniformly, CO carrier gas is introduced, and the fluidized bed reacts for 7 hours at 650 ℃, and the product yield is 91.7%. Under the reaction conditions, the carbon deposition amount of the catalyst is less than 1% of the mass of the catalyst, and the photo of the residue after the reaction is shown in FIG. 6.
EXAMPLE 25%Comparative examples of carbon deposition)
Preparation of a conventional ZSM-5 (Si/Al molar ratio=40) catalyst: will be 20g H 2 O, 25.1g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 25 wt%), 14g of TEOS, 350mg of NaAlO 2 Uniformly mixing, stirring for 6h, and adding SiO in a reaction system 2 Al template agent urea metal salt H 2 The molar ratio of O is 1:0.025:0.46:0:0:32. Crystallizing at 180 deg.c for 48 hr and roasting at 550 deg.c in air for 4 hr. The prepared common ZSM-5 molecular sieve has Si/Al molar ratio=40 and 010 crystal face exposure ratio of about 40 percent.
Application of the catalyst: mixing 500mg polyethylene with 100mg common ZSM-5 zeolite (Si/Al molar ratio=15) zeolite catalyst (catalyst mass 20% of polyolefin plastic mass), grinding uniformly, and introducing H 2 The carrier gas was reacted at 300℃for 7 hours with a fixed bed, and the product yield was 21.3%. Under the reaction conditions, the carbon deposition of the catalyst is about 18% of the mass of the catalyst, the SEM of the common ZSM-5 is shown in FIG. 7, and the photo of the residue after the reaction is shown in FIG. 8.
TABLE 1 ICP test results for various elements of different catalysts
TABLE 2 summary of catalytic data for different heteroatom molecular sieves
As can be seen from table 1, table 2 and the accompanying drawings:
the anti-carbon deposition performance of the lamellar ZSM-5 molecular sieve prepared by the invention is obviously superior to that of a common ZSM-5 molecular sieve, and the feasibility of reducing carbon deposition by regulating diffusion in the process of catalytically cracking polyolefin plastics by using the ZSM-5 molecular sieve is fully illustrated. Meanwhile, the transition metal element Zn, co, ni, fe has obvious promotion effect on the catalytic performance, and the transition metal elements Mn, mo and Cu have no obvious influence on the catalytic performance. Along with the improvement of the reaction temperature, the extension of the reaction time and the improvement of the catalyst proportion, the reaction performance is obviously improved.
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.

Claims (8)

1. The catalyst is characterized in that the catalyst adopts a lamellar ZSM-5 zeolite molecular sieve with an MFI type crystal structure, the molar ratio of Si/Al is 15-300:1, and the lamellar thickness is 30-300 nanometers.
2. The zeolite molecular sieve catalyst of claim 1, wherein the zeolite molecular sieve is further loaded with a transition metal element in a molar ratio to silicon of 0 to 0.1:1 and not equal to 0.
3. The zeolite molecular sieve catalyst of claim 2, wherein the transition metal element is any one or a combination of any two or more of the following: ni, cu, co, mo, fe, zn or Mn.
4. The method for preparing zeolite molecular sieve catalyst of claim 1, wherein the silicon source, the aluminum source, the template agent and urea are dissolved in a certain amount of water to form a mixed solution; alternatively, a metal salt is further added to the mixed solution; then carrying out hydrothermal crystallization reaction, and roasting the reaction product to obtain a powdery catalyst product;
wherein the metal salt is a salt compound of transition metal elements of nickel, copper, cobalt, molybdenum, iron, zinc or manganese; in the mixed solution, siO 2 Al template agent urea metal salt H 2 The molar ratio relationship of O is 1:0.003-0.067:0.1-0.5:0.1-2.5:0-0.1:20.0-33.5; the hydrothermal crystallization reaction is carried out in a closed container, the reaction temperature is 120-200 ℃, and the reaction time is 24-120 hours; the condition of the roasting treatment is that the air roasting is carried out for 4 hours at 550 ℃.
5. The method of claim 4, wherein the silicon source is any one of: silica, tetraethyl silicate, white carbon black; the aluminum source is sodium metaaluminate, aluminum sulfate or boehmite; the template agent is any one of the following: tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), triethylamine; the metal salt is any one of the following: nickel nitrate, nickel sulfate, copper nitrate, copper chloride, copper sulfate, cobalt nitrate, cobalt sulfate, ammonium molybdate, ferric nitrate, ferric chloride, ferric sulfate, zinc nitrate, zinc chloride, zinc sulfate, manganese nitrate, manganese chloride, and manganese sulfate.
6. The method for using the catalyst of the heteroatomic zeolite molecular sieve with lamellar morphology in catalyzing polyolefin plastic cracking reaction, which is characterized in that polyolefin plastic and the catalyst are mixed in a reducing atmosphere or an inert atmosphere, and are directly subjected to catalytic cracking reaction after being heated and melted, and finally converted into light alkane and alkene; wherein the mass of the catalyst accounts for 0.01-50% of the mass of the polyolefin plastic; the reaction temperature of catalytic cracking is 200-650 ℃, the reaction time is 0.1-500 h, and the reaction mode is a fixed bed, a slurry bed or a fluidized bed.
7. The method according to claim 6, wherein the reducing atmosphere is continuously fed with carrier gas CO or H during the reaction 2 The method comprises the steps of carrying out a first treatment on the surface of the The inert atmosphere is that carrier gas N is continuously introduced in the reaction process 2 Or methane gas.
8. The method of claim 6, wherein the polyolefin plastic is any one or a mixture of the following: high density polyethylene, low density polyethylene, polypropylene, polyvinyl chloride, polystyrene, or plastics having the aforementioned polyolefin as a main component.
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Citations (4)

* Cited by examiner, † Cited by third party
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