CN114570416A - Preparation method and application of ruthenium-based catalyst loaded by molecular sieve - Google Patents
Preparation method and application of ruthenium-based catalyst loaded by molecular sieve Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000004698 Polyethylene Substances 0.000 claims abstract description 23
- -1 polyethylene Polymers 0.000 claims abstract description 23
- 229920000573 polyethylene Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 238000002161 passivation Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229920003023 plastic Polymers 0.000 claims description 28
- 239000004033 plastic Substances 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000004700 high-density polyethylene Substances 0.000 description 12
- 229920001903 high density polyethylene Polymers 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
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- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- IHICGCFKGWYHSF-UHFFFAOYSA-N C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C Chemical group C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C IHICGCFKGWYHSF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention provides a preparation method and application of a ruthenium-based catalyst loaded by a molecular sieve, wherein the method comprises the following steps: mixing a ruthenium chloride solution and a suspension containing a molecular sieve, stirring the obtained mixed solution, drying, and then carrying out reduction and passivation treatment to obtain a catalyst; the molecular sieve is selected from HZSM-5 with Si: Al: 25, HZSM-5 with Si: Al: 80, HZSM-5 with Si: Al: 200, HZSM-5 with Si: Al: 300, USY with Si: Al: 10 or SAPO-34 with Si: Al: P: 1:2: 1. The method selects different molecular sieves and ruthenium chloride solution to be mixed, and the catalyst obtained through reduction and passivation treatment can be applied to the degradation of polyethylene and has higher selectivity and catalytic activity; the catalytic stability is good. The method has mild reaction conditions and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a ruthenium-based catalyst loaded by a molecular sieve.
Background
In recent years, waste plastics spread worldwide, and their long-term accumulation in the environment has led to serious environmental pollution and waste of energy resources. In addition, disposable plastic articles used in medical hygiene and epidemic prevention processes, such as medical surgical masks, protective clothing, gloves, protective eyepieces, and the like, have suddenly proliferated. At present, most of waste plastics are not recycled and treated, which causes great harm to the ecological environment. According to statistics, if the production speed of the existing plastic products and the treatment mode of waste plastics are not changed, 120 hundred million tons of plastic wastes are buried in 2050 years and remain in the natural environment and are not easy to degrade. Therefore, the recycling of waste plastics is urgently upgraded.
At present, most of plastic recycling cost is very high, the cost of recycling, classifying and processing the plastic cannot be recovered, and compared with the plastic produced in a large scale in a factory, the performance of the traditional mechanical method for recycling the plastic is poorer, and the cost is higher. A potential alternative to the traditional mechanical methods is to depolymerize the plastic to monomers using plastic depolymerization techniques and then polymerize or selectively decompose the plastic to high value chemicals. Hydrogenolysis has received attention from scientists not only to lower reaction temperatures but also to improve selectivity to the desired product as compared to pyrolysis. However, since this technology consumes a large amount of hydrogen and is still not economical enough, there is a strong need for a sustainable and economically feasible process that uses a suitable catalyst under milder conditions compared to pyrolysis and does not consume hydrogen or other solvents to upgrade waste plastics into valuable products such as benzene-toluene-xylene (BTX) and the like. Recently, a solventless, hydrogen-free degradation technique for the selective decomposition of polyethylene into valuable long-chain alkylaromatics and alkylcycloalkanes is called hydrogenolysis/aromatization cascade, i.e. the hydrogenolysis, hydrogenation and ring-opening steps consume the hydrogen produced by the cyclization and dehydroaromatization to replace the external hydrogen source. However, for such a series process, it is still a great challenge to design a catalyst that can obtain easily separated products and has higher stability.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method and an application of a ruthenium-based catalyst loaded by a molecular sieve, wherein the catalyst prepared by the method can be used for thermally catalyzing polyethylene degradation and has high selectivity and activity; the catalytic stability is good.
The invention provides a preparation method of a ruthenium-based catalyst loaded by a molecular sieve, which comprises the following steps:
mixing a ruthenium chloride solution and a suspension containing a molecular sieve to obtain a mixed solution;
stirring the mixed solution, drying, and then carrying out reduction and passivation treatment to obtain a ruthenium-based catalyst loaded by a molecular sieve;
the molecular sieve is selected from HZSM-5 with Si: Al ═ 25, HZSM-5 with Si: Al ═ 80, HZSM-5 with Si: Al ═ 200, HZSM-5 with Si: Al ═ 300, USY with Si: Al ═ 10, and the molecular sieve is selected from the group consisting of HZSM-5 with Si: Al ═ 25, HZSM-5 with Si: Al ═ 300, USY with Si: Al ═ 10, and the molecular sieve is selected from the group consisting of Si: Al: P ═ 1:2: SAPO-34 of 1;
the reduction temperature is 380-420 ℃, and the time is 110-130 min; the reducing atmosphere is hydrogen.
In the invention, the molecular sieve has proper pore channel structure, acid site type and number, and the ruthenium-loaded catalyst has higher activity and selectivity and good catalytic stability.
In the embodiment of the invention, the reduction is stable at 400 ℃ for 2 h; the flow rate of hydrogen was 50 ml/min.
In the present invention, after reduction, it was cooled to room temperature under an argon atmosphere and 1 vol% O2And keeping the temperature in the Ar atmosphere for 55-65 min to form a passivation layer. In a specific embodiment, O2O in an/Ar atmosphere2And Ar in a volume ratio of 1: 99.
according to the invention, the dried material is filled in a quartz reaction tube, the quartz reaction tube is placed in a reaction furnace, and ruthenium-based catalysts loaded by different molecular sieves are obtained through reduction and passivation treatment and are stored in a vacuum-pumping manner.
In the invention, the volume ratio of the mass of the ruthenium chloride to the water in the ruthenium chloride solution is (190-210) mg: 10 mL;
the volume ratio of the mass of the molecular sieve to the volume of water in the molecular sieve-containing suspension is (0.95-1.05) g: 35 mL.
In the present invention, the mixed solution is heated in a water bath; the heating temperature is 75-85 ℃; in a specific embodiment, the heating temperature is 80 ℃;
the stirring time is 11-13 h; the stirring speed is 400-600 rpm.
In a specific embodiment, the temperature for heating the mixed solution is 80 ℃; the stirring time was 12 h.
In the invention, the molecular sieve is used after being pretreated and calcined;
the temperature of the pretreatment calcination is 440-460 ℃, and the time is 220-260 min.
In a specific embodiment, the temperature of the pretreatment calcination is 450 ℃ and the time is 240 min.
In the invention, the load amount of ruthenium in the ruthenium-based catalyst loaded by the molecular sieve is 7-8 wt%. In a specific example, the loading amount of ruthenium in the molecular sieve-supported ruthenium-based catalyst was 7.4 wt%.
The catalyst is preferably stored under vacuum in the present invention.
The invention provides a method for degrading polyethylene, which comprises the following steps:
mixing high-density polyethylene plastic powder and a molecular sieve-supported ruthenium-based catalyst in N2Reacting under the atmosphere of/He, and cooling;
the reaction temperature is 270-290 ℃, and the reaction time is 0.5-48 h;
the ruthenium-based catalyst loaded by the molecular sieve is prepared by the preparation method of the technical scheme.
In the present invention, said N2N in/He2And He in a volume ratio of 5: 95. said N is2The pressure of the atmosphere of the/He is 1.8-2.2 MPa; in a specific embodiment, N2The pressure/He was 2 MPa.
According to the application of the ruthenium-based catalyst loaded by different molecular sieves in the thermal catalysis of polyethylene degradation, metal ruthenium is an active site for plastic dehydrogenation, the number and types of acid sites of different molecular sieves influence long-chain molecule dehydrogenation and conversion of double bonds to carbon positive active sites, and the adsorption capacity between long-chain molecules and pore channels is influenced by the pore channel structure, wherein the HZSM-5-loaded ruthenium-based catalyst with the silicon-aluminum ratio of 300 has the highest cyclic hydrocarbon selectivity, and the HZSM-5-loaded ruthenium-based catalyst with the silicon-aluminum ratio of 25 has the highest activity. The invention adjusts the acidity and the pore structure of the molecular sieve to regulate and control the catalytic activity and the selectivity of the ruthenium-based catalyst loaded by the molecular sieve to the thermal catalytic polyethylene degradation.
In a specific embodiment, the reaction temperature is 280 ℃ and the reaction time is 24 h.
In the present invention, said N2The pressure of the/He is 1.5-2.5 MPa. In a specific embodiment, said N2The pressure/He was 2.0 MPa.
In the invention, the granularity of the polyethylene plastic powder is 50-100 meshes. The mass ratio of the polyethylene plastic powder to the molecular sieve-supported ruthenium-based catalyst is 10: 0.9 to 1.1; in the specific embodiment, the mass ratio of the polyethylene plastic powder to the molecular sieve-supported ruthenium-based catalyst is 10: 1.0.
in the invention, the catalyst provided by the invention can catalyze and degrade both high-density polyethylene and low-density polyethylene, and compared with high-density polyethylene, the time for catalytically degrading low-density polyethylene is shorter and the required temperature is lower. The specific gravity of the low-density polyethylene plastic is 0.910-0.925; in the embodiment of the invention, the specific gravity of the adopted polyethylene plastic is 0.95-0.96.
The invention discovers that the selectivity of cyclic hydrocarbon of ruthenium-based catalyst loaded by molecular sieves with different pore channel structures in the thermal catalysis of polyethylene degradation follows a trend by regulating the pore channel structure of the molecular sieve, and Ru/HZSM-5(300)>Ru/USY>Ru/SAPO-34 HZSM-5 supported ruthenium-based catalyst with MFI pore channel structure and silicon-aluminum ratio of 300 shows highest selectivity of cyclic hydrocarbon, and 2MPa and 5 vol% of N are filled in a reaction kettle2The selectivity of cyclic hydrocarbon reaches 60.3 mol% when the reaction is carried out for 24 hours at 280 ℃ under the condition of/He.
The invention discovers that the activity of ruthenium-based catalysts loaded with different molecular sieves in the thermal catalysis of polyethylene degradation follows a trend by regulating the silicon-aluminum ratio of the molecular sieves, and Ru/HZSM-5(25)> Ru/HZSM-5(80)>Ru/HZSM-5(200)>Ru/HZSM-5(300) and HZSM-5 supported ruthenium-based catalyst with the silicon-aluminum ratio of 25, namely Ru/HZSM-5(25) shows the highest catalytic activity, and 2MPa and 5 vol% of N are filled in a reaction kettle2Reaction at 280 deg.c for 24 hr to reach polyethylene converting rate of 93.0% and mass activity up to 385.3mgHDPE gcat -1h-1。
The invention provides a preparation method of a ruthenium-based catalyst loaded by a molecular sieve, which comprises the following steps: mixing a ruthenium chloride solution and a suspension containing a molecular sieve to obtain a mixed solution; stirring the mixed solution, drying, and then carrying out reduction and passivation treatment to obtain a ruthenium-based catalyst loaded by a molecular sieve; the molecular sieve is selected from HZSM-5 containing 25 parts of Si and Al, HZSM-5 containing 80 parts of Si and Al, HZSM-5 containing 200 parts of Si and Al, HZSM-5 containing 300 parts of Si and Al, USY containing 10 parts of Si and SAPO-34 containing 1 part of Si and Al and P and 2 part of 1; the reduction temperature is 380-420 ℃, and the time is 110-130 min; the reducing atmosphere is hydrogen. The method provided by the invention selects the molecular sieves with different silicon-aluminum ratios to be mixed with the ruthenium chloride solution, and the catalyst obtained through reduction and passivation treatment can be applied to the degradation of polyethylene and has higher selectivity and catalytic activity; the catalytic stability is good. The method has mild reaction conditions and is environment-friendly.
Drawings
FIG. 1 is an X-ray diffraction pattern of a ruthenium-based catalyst supported on different molecular sieves of example 1 of the present invention;
FIG. 2 shows the results of the activity and selectivity tests for the thermocatalytic HDPE degradation of Ru/HZSM-5(25), Ru/HZSM-5(80), Ru/HZSM-5(200), Ru/HZSM-5(300), Ru/USY, Ru/SAPO-34 according to example 2 of the present invention;
FIG. 3 shows the result of the stability test of the degradation of Ru/HZSM-5(300) of example 3 of the present invention in the presence of thermocatalytic HDPE;
FIG. 4 shows the results of the measurement of the reaction time-dependent tendency of benzene yield, cyclic hydrocarbon yield and conversion in the product of the thermal catalytic degradation of high density polyethylene of Ru/HZSM-5(300) according to example 4 of the present invention.
Detailed Description
In order to further illustrate the present invention, the following examples are given to describe in detail the preparation method and application of a molecular sieve-supported ruthenium-based catalyst provided in the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
A ruthenium-based catalyst loaded by different molecular sieves has an average loading of ruthenium of 7.4 wt%, and is synthesized by the following steps:
6 different molecular sieves were: HZSM-5(Si: Al ═ 25), HZSM-5(Si: Al ═ 80), HZSM-5(Si: Al ═ 200), HZSM-5(Si: Al ═ 300), USY (Si: Al ═ 10), SAPO-34 (Si: Al: P ═ 1:2: 1) were calcined in a muffle furnace at 450 degrees celsius for 4 hours. Dissolving 200mg of ruthenium chloride hydrate in 10ml of deionized water, mixing the solution with 35ml of suspension containing 1.0g of molecular sieve, violently stirring the solution at 80 ℃ in water bath for 12 hours (400-600 rpm), evaporating and drying the solution, filling the obtained sample into a quartz reaction tube, placing the quartz reaction tube into a reaction furnace, pre-reducing the quartz reaction tube at 400 ℃ for 2 hours, wherein the hydrogen flow is 50ml/min, cooling the quartz reaction tube to room temperature under the argon atmosphere after the hydrogen pre-reduction is finished, and cooling the quartz reaction tube to 1 vol% of O2Keeping the reaction kettle in a/Ar atmosphere for 1 hour to form a passivation layer, and finally vacuumizing and storing the obtained catalyst until the catalyst is tested. The X-ray diffraction patterns of ruthenium-based catalysts with different molecular sieve loadings are shown in figure 1.
Example 2
The thermal catalysis polyethylene degradation performance test of ruthenium-based catalyst with different molecular sieve loads:
mixing 500mg of ruthenium-based catalyst powder loaded by different molecular sieves and 5.0g of high-density polyethylene plastic powder uniformly, putting the mixture into a Hastelloy reaction kettle with the volume of 50ml, and adding 5 vol% of N2Washing the reaction kettle for 10 times with/He, and filling the reaction kettle with 2MPa 5 vol% N2Reaction at 280 ℃ for 24 hours/He. Immediately after the reaction is finished, the reaction kettle is placed in cold water to be cooled for more than 1 hour, and then a gas phase product is detected by GC.And then opening the kettle, adding 1ml of cyclohexane as an internal standard, uniformly mixing with the liquid phase product, centrifuging, collecting supernate and precipitate, wherein the centrifugal speed is 13000 r/min, the centrifugal time is 5min, and quantifying the supernate by using GC and determining the quantity by using GC-MS. And (3) drying the precipitate obtained by centrifugation overnight at 80 ℃ in an oven to obtain solid residue, weighing the solid residue by using an analytical balance, and subtracting the mass of the added catalyst before the reaction from the mass of the solid residue to obtain the mass of the residual undegraded plastic. The activity and selectivity test results of the thermocatalytic high-density polyethylene degradation experiments are shown in figure 2, wherein the thermocatalytic high-density polyethylene degradation experiments are carried out on catalysts such as Ru/HZSM-5(Si: Al ═ 25), Ru/HZSM-5(Si: Al ═ 80), Ru/HZSM-5(Si: Al ═ 200), Ru/HZSM-5(Si: Al ═ 300), Ru/USY, Ru/SAPO-34 and the like. As can be seen from a and b in fig. 2 (variable silica to alumina ratio experiment), the Ru/HZSM-5(Si: Al ═ 25) catalyst has the highest activity, and the Ru/HZSM-5(Si: Al ═ 300) catalyst has the highest selectivity to cyclic hydrocarbons; from c and d (pore-changing structure experiment) in fig. 2, the Ru/HZSM-5(Si: Al ═ 300) catalyst showed the highest activity and selectivity to cyclic hydrocarbons.
Example 3
Thermal catalyzed polyethylene degradation stability test of Ru/HZSM-5(Si: Al ═ 300):
under the reaction conditions of example 2, the solid residue obtained after 1 reaction was calcined at 200 ℃ for 2 hours in a muffle furnace, then heated to 600 ℃ for 5 hours, and cooled to room temperature. Filling the recovered solid into a quartz reaction tube, placing the quartz tube into a reaction furnace, pre-reducing for 2 hours at 400 ℃, wherein the hydrogen flow is 50ml/min, cooling to room temperature under an argon atmosphere after the hydrogen pre-reduction is finished, and cooling to 1 vol% O2The passivation layer was formed by holding under an Ar atmosphere for 1 hour, and after weighing the recovered solid with an analytical balance and adding high density polyethylene to 5.5 g, the powders were mixed well for the second cycle test. The procedure of the third cycle test was identical to the second. The results of the thermal catalyzed polyethylene degradation stability test of Ru/HZSM-5(300) are shown in FIG. 3. As can be seen from fig. 3: the catalyst is circulated for three times, and the conversion rate and the selectivity of the catalyst are basically unchanged.
Example 4
Testing the benzene yield, cyclic hydrocarbon yield and conversion rate of products of thermal catalytic degradation of high density polyethylene of Ru/HZSM-5(Si: Al ═ 300) according to the reaction time:
under the reaction conditions of example 2, catalytic performances of 0.5 hours, 1.0 hours, 2.0 hours, 6.0 hours, 12.0 hours, 18.0 hours, 24.0 hours and 48.0 hours of reaction were obtained, respectively, with only the length of the reaction time being changed. The results of the time evolution test of the Ru/HZSM-5(300) for the thermocatalytic polyethylene degradation are shown in FIG. 4. As can be seen from fig. 4: as the reaction time is prolonged, the conversion rate of the plastic is continuously improved, and the selectivity of the cyclic hydrocarbon and aromatic hydrocarbon products is obviously increased.
From the above examples, the present invention provides a preparation method of a ruthenium-based catalyst supported by a molecular sieve, comprising the following steps: mixing a ruthenium chloride solution and a suspension containing a molecular sieve to obtain a mixed solution; stirring the mixed solution, drying, and then carrying out reduction and passivation treatment to obtain a ruthenium-based catalyst loaded by a molecular sieve; the molecular sieve is selected from HZSM-5 with Si: Al ═ 25, HZSM-5 with Si: Al ═ 80, HZSM-5 with Si: Al ═ 200, HZSM-5 with Si: Al ═ 300, USY with Si: Al ═ 10, and the molecular sieve is selected from the group consisting of HZSM-5 with Si: Al ═ 25, HZSM-5 with Si: Al ═ 300, USY with Si: Al ═ 10, and the molecular sieve is selected from the group consisting of Si: Al: P ═ 1:2: SAPO-34 of 1; the reduction temperature is 380-420 ℃, and the time is 110-130 min; the reducing atmosphere is hydrogen. The method provided by the invention selects the molecular sieves with different silicon-aluminum ratios to be mixed with the ruthenium chloride solution, and the catalyst obtained through reduction and passivation treatment can be applied to the degradation of polyethylene and has higher selectivity and catalytic activity; the catalytic stability is good. The method has mild reaction condition and is environment-friendly.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a ruthenium-based catalyst loaded by a molecular sieve comprises the following steps:
mixing a ruthenium chloride solution and a suspension containing a molecular sieve to obtain a mixed solution;
stirring the mixed solution, drying, and then carrying out reduction and passivation treatment to obtain a ruthenium-based catalyst loaded by a molecular sieve;
the molecular sieve is selected from HZSM-5 with Si: Al ═ 25, HZSM-5 with Si: Al ═ 80, HZSM-5 with Si: Al ═ 200, HZSM-5 with Si: Al ═ 300, USY with Si: Al ═ 10, or Si: Al: p is 1:2: SAPO-34 of 1;
the reduction temperature is 380-420 ℃, and the time is 110-130 min; the reducing atmosphere is hydrogen.
2. The preparation method according to claim 1, wherein the passivation treatment is specifically:
after reduction, the mixture was cooled to room temperature under an argon atmosphere and 1 vol% O2And keeping the temperature in the Ar atmosphere for 55-65 min to form a passivation layer.
3. The method according to claim 1, wherein the ratio of the mass of ruthenium chloride to the volume of water in the ruthenium chloride solution is (190-210) mg: 10 mL;
the volume ratio of the mass of the molecular sieve to the volume of water in the molecular sieve-containing suspension is (0.95-1.05) g: 35 mL.
4. The method according to claim 1, wherein the mixed solution is heated in a water bath; the heating temperature is 75-85 ℃;
the stirring time is 11-13 h; the stirring speed is 400-600 rpm.
5. The preparation method according to claim 1, wherein the molecular sieve is used after being pretreated and calcined;
the temperature of the pretreatment calcination is 440-460 ℃, and the time is 220-260 min.
6. The preparation method according to claim 1, wherein the loading amount of ruthenium in the molecular sieve-supported ruthenium-based catalyst is 7-8 wt%.
7. A method of polyethylene degradation comprising the steps of:
mixing polyethylene plastic powder and a molecular sieve-supported ruthenium-based catalyst in N2Reacting under the atmosphere of/He, and cooling;
the reaction temperature is 270-290 ℃, and the reaction time is 0.5-48 h;
the ruthenium-based catalyst loaded by the molecular sieve is prepared by the preparation method of any one of claims 1 to 6.
8. The method of claim 7, wherein N is2The pressure of the/He is 1.5-2.5 MPa.
9. The method according to claim 7, wherein the mass ratio of the polyethylene plastic powder to the molecular sieve-supported ruthenium-based catalyst is 10: 0.9 to 1.1.
10. The method of claim 7, wherein the polyethylene plastic has a specific gravity of 0.95 to 0.96.
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