CN114570416B - Preparation method and application of molecular sieve supported ruthenium-based catalyst - Google Patents
Preparation method and application of molecular sieve supported ruthenium-based catalyst Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 59
- 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 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 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 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 238000002161 passivation Methods 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
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 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 26
- 239000004033 plastic Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 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 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 22
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- 239000000047 product Substances 0.000 description 10
- 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
- 238000012360 testing method Methods 0.000 description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation 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
- 241000282326 Felis catus Species 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000036541 health Effects 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
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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
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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
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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
- B01J29/08—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
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- 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
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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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a preparation method and application of a molecular sieve supported ruthenium-based catalyst, wherein the method comprises the following steps: mixing ruthenium chloride solution and suspension containing 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 comprises the steps of selecting different molecular sieves and ruthenium chloride solution to be mixed, and then reducing and passivating to obtain the catalyst which 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 molecular sieve supported ruthenium-based catalyst.
Background
In recent years, waste plastics spread worldwide, and their long-term accumulation in the environment has resulted in serious environmental pollution and waste of energy resources. In addition, disposable plastic products used in medical and health and epidemic prevention processes, such as medical surgical masks, protective clothing, gloves, goggles, and the like, have suddenly proliferated. At present, most of waste plastics are not recycled, and serious harm is caused to the ecological environment. It is counted that if the production speed of the existing plastic products and the treatment mode of the waste plastics are unchanged, 120 hundred million tons of plastic waste are buried by 2050, and remain in the natural environment and are not easy to degrade. Therefore, recycling and upgrading of waste plastics is urgent.
At present, most of plastics are very high in regeneration cost, the cost of recycling, classifying and processing the plastics cannot be recovered, and compared with the plastics produced in a large scale in a factory, the traditional mechanical method is poor in performance and higher in cost. A potential alternative to conventional mechanical methods is to depolymerize the plastic using plastic depolymerization techniques to give monomers and then polymerize or selectively decompose the plastic into high value chemicals. Compared with pyrolysis, the hydrogenolysis not only reduces the reaction temperature, but also improves the selectivity of target products, and is focused by scientists. However, since this technology consumes a large amount of hydrogen and is still not economical, there is an urgent need for a sustainable and economically viable process that uses a suitable catalyst under milder conditions than 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 solvent-free, hydrogen-free, degradation technique for selectively decomposing polyethylene into valuable long-chain alkylaromatics and alkylcycloalkanes, termed hydrogenolysis/aromatization tandem, i.e., the hydrogenolysis, hydrogenation and ring-opening steps consume hydrogen produced by ring formation and dehydroaromatization, to replace external hydrogen sources. However, for such a series process, it remains a great challenge to design a catalyst that gives an easily separable product with higher stability.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and application of a molecular sieve supported ruthenium-based catalyst, wherein the catalyst prepared by the method can thermally catalyze polyethylene degradation, and has high selectivity and activity; the catalytic stability is good.
The invention provides a preparation method of a molecular sieve supported ruthenium-based catalyst, which comprises the following steps:
mixing ruthenium chloride solution and suspension containing molecular sieve to obtain 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 being Al=25, HZSM-5 with Si being Al=80, HZSM-5 with Si being Al=200, HZSM-5 with Si being Al=300, USY with Si being Al=10, and USY with Si being Al being P=1:2: 1. SAPO-34 of (a);
the temperature of the reduction is 380-420 ℃ and the time is 110-130 min; the reducing atmosphere is hydrogen.
In the invention, the molecular sieve has proper pore canal structure, acid site type and number, and the catalyst after loading ruthenium has higher activity and selectivity and good catalytic stability.
In the embodiment of the invention, the reduction stability is 400 ℃ and the time is 2h; the flow rate of hydrogen was 50ml/min.
In the present invention, after reduction, the mixture was cooled to room temperature under an argon atmosphere and was cooled to 1vol% O 2 And (3) maintaining the mixture for 55-65 min in Ar atmosphere to form a passivation layer. In particular embodiments, O 2 O in Ar atmosphere 2 And Ar has a volume ratio of 1:99.
the method comprises the steps of filling the dried materials into a quartz reaction tube, placing the quartz reaction tube into a reaction furnace, reducing and passivating to obtain ruthenium-based catalysts loaded by different molecular sieves, and vacuumizing for preservation.
In the invention, the mass ratio of ruthenium chloride to water in the ruthenium chloride solution is (190-210) mg:10mL;
the mass and water volume ratio of the molecular sieve in the molecular sieve-containing suspension is (0.95-1.05) g:35mL.
In the invention, the mixed solution is heated in a water bath; the heating temperature is 75-85 ℃; in a specific embodiment, the temperature of heating is 80 ℃;
the stirring time is 11-13 h; the stirring speed is 400-600 rpm.
In a specific embodiment, the temperature of the mixed solution is 80 ℃; the stirring time was 12h.
In the invention, the molecular sieve is used after pretreatment and calcination;
the temperature of 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 240min.
In the invention, the load of ruthenium in the molecular sieve supported ruthenium-based catalyst is 7-8wt%. In a specific embodiment, the molecular sieve supported ruthenium-based catalyst has a ruthenium loading of 7.4wt%.
The catalyst is preferably stored under vacuum.
The invention provides a polyethylene degradation method, which comprises the following steps:
mixing high-density polyethylene plastic powder with ruthenium-based catalyst supported by molecular sieve, and adding the mixture into N 2 Reacting in He atmosphere, and cooling;
the reaction temperature is 270-290 ℃ and the reaction time is 0.5-48 h;
the molecular sieve supported ruthenium-based catalyst is prepared by the preparation method according to the technical scheme.
In the present invention, the N 2 N in/He 2 And volume ratio of He is 5:95. the N is 2 The atmosphere pressure of the/He is 1.8-2.2 MPa; in a specific embodiment, N 2 The pressure of/He was 2MPa.
The invention applies the ruthenium-based catalyst loaded by different molecular sieves in thermal catalytic polyethylene degradation, wherein metal ruthenium is an active site for plastic dehydrogenation, the number and types of acid sites of different molecular sieves influence dehydrogenation of long-chain molecules and conversion of double bonds to carbon positive active sites, and a pore channel structure influences adsorption capacity between the long-chain molecules and pore channels, wherein the HZSM-5 loaded ruthenium-based catalyst with a silicon-aluminum ratio of 300 has highest cyclic hydrocarbon selectivity, and the HZSM-5 loaded ruthenium-based catalyst with a silicon-aluminum ratio of 25 has highest activity. The invention regulates the acidity and pore canal structure of the molecular sieve to regulate the catalytic activity and selectivity of the molecular sieve supported ruthenium-based catalyst to thermally catalyze the degradation of polyethylene.
In a specific embodiment, the temperature of the reaction is 280 ℃ and the time is 24 hours.
In the present invention, the N 2 The pressure of the/He is 1.5-2.5 MPa. In a specific embodiment, the N 2 The pressure of/He was 2.0MPa.
In the present invention, the polyethylene plastic powder has a particle size of 50 to 100 mesh. The mass ratio of the polyethylene plastic powder to the molecular sieve supported ruthenium-based catalyst is 10:0.9 to 1.1; in a 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 catalyst provided by the invention has the advantages that the time for catalyzing and 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 polyethylene plastic is 0.95-0.96.
The invention discovers that the selectivity of the cyclic hydrocarbon of the molecular sieve supported ruthenium-based catalyst with different pore structures in the thermal catalytic polyethylene degradation follows a trend through regulating the pore structure of the molecular sieve, ru/HZSM-5 (300)>Ru/USY>Ru/SAPO-34, HZSM-5 supported ruthenium-based catalyst with MFI pore structure and silicon-aluminum ratio of 300 shows highest cyclic hydrocarbon selectivity, and 2MPa 5vol% N is filled in a reaction kettle 2 Reaction is carried out for 24 hours at 280 ℃ with the cyclic hydrocarbon selectivity reaching 60.3mol percent.
The invention discovers that the activity of ruthenium-based catalysts loaded by different molecular sieves in thermal catalytic polyethylene degradation follows a trend by regulating the silicon-aluminum ratio of the molecular sieves, ru/HZSM-5 (25)> Ru/HZSM-5(80)>Ru/HZSM-5(200)>Ru/HZSM-5 (300), a ruthenium-based catalyst supported by HZSM-5 and having a silica-alumina ratio of 25, namely Ru/HZSM-5 (25) showed the highest catalytic activity, and a reaction vessel was charged with 2MPa 5vol% N 2 The reaction is carried out for 24 hours at the temperature of 280 ℃ of He, the polyethylene conversion rate reaches 93.0 percent, and the mass activity reaches 385.3mg HDPE g cat -1 h -1 。
The invention provides a preparation method of a molecular sieve supported ruthenium-based catalyst, which comprises the following steps: mixing ruthenium chloride solution and suspension containing molecular sieve to obtain 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 being Al=25, HZSM-5 with Si being Al=80, HZSM-5 with Si being Al=200, HZSM-5 with Si being Al=300, USY with Si being Al=10, SAPO-34 with Si being Al being P=1:2:1; the temperature of the reduction is 380-420 ℃ and the time is 110-130 min; the reducing atmosphere is hydrogen. The method provided by the invention has the advantages that the catalyst obtained by the reduction and passivation treatment after the molecular sieves with different silicon-aluminum ratios are mixed with the ruthenium chloride solution 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 ruthenium-based catalysts supported on different molecular sieves of example 1 of the present invention;
FIG. 2 shows the results of the thermal catalytic high density polyethylene degradation activity and selectivity tests for 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 invention;
FIG. 3 is a thermal catalytic high density polyethylene degradation stability test result of Ru/HZSM-5 (300) of example 3 of the invention;
FIG. 4 shows the results of a test of benzene yield, cyclic hydrocarbon yield and conversion as a function of time for the products of the thermal catalyzed high density polyethylene degradation of Ru/HZSM-5 (300) of example 4 of the present invention.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to illustrate in detail the preparation of a molecular sieve supported ruthenium-based catalyst and its use, but they should not be construed as limiting the scope of the invention.
Example 1
The ruthenium-based catalyst supported by different molecular sieves has an average ruthenium loading of 7.4wt%, and the synthesis method comprises the following steps:
6 different molecular sieves: 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. 200mg of ruthenium chloride hydrate was dissolved in 10ml of deionized water and mixed with 35ml of a suspension containing 1.0g of molecular sieve, the solution was vigorously stirred (400-600 rpm) for 12 hours in a 80℃water bath, evaporated to drynessAfter drying, the obtained sample was filled into a quartz reaction tube, the quartz tube was placed into a reaction furnace, pre-reduced at 400℃for 2 hours, the flow rate of hydrogen was 50ml/min, and after completion of the hydrogen pre-reduction, the reaction tube was cooled to room temperature under an argon atmosphere and at 1vol% O 2 And (3) maintaining the mixture for 1 hour in Ar atmosphere to form a passivation layer, and finally vacuumizing and preserving the obtained catalyst until the catalysis test. The X-ray diffraction patterns of ruthenium-based catalysts with different molecular sieve loadings are shown in figure 1.
Example 2
Thermal catalytic polyethylene degradation performance test of ruthenium-based catalysts with different molecular sieve loadings:
mixing 500mg ruthenium-based catalyst powder loaded by different molecular sieves and 5.0g high-density polyethylene plastic powder uniformly, putting into a hastelloy reaction kettle with the volume of 50ml, and using 5vol% N 2 He washes 10 times, and fills 2MPa 5vol% N in the reaction kettle 2 He, at 280 degrees celsius for 24 hours. Immediately after the reaction was completed, the reaction vessel was cooled in cold water for 1 hour or more, and then the gas-phase product was detected by GC. Then, 1ml of cyclohexane was added as an internal standard and mixed with the liquid phase product uniformly, and after centrifugation, the supernatant and the precipitate were collected at a rotational speed of 13000 rpm for 5 minutes, and the supernatant was quantified by GC and characterized by GC-MS. And (3) drying the precipitate obtained by centrifugation at 80 ℃ overnight by using an oven to obtain solid residues, weighing the solid residues by using an analytical balance, and subtracting the mass of the catalyst added before the reaction from the mass of the solid residues to obtain the mass of the residual undegraded plastic. The application carries out a thermal catalytic high-density polyethylene degradation experiment on 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 other catalysts, and the activity and selectivity test results are shown in figure 2. As can be obtained from fig. 2 a and b (experiments with varying silica alumina ratio), the Ru/HZSM-5 (Si: al=25) catalyst had the highest activity and the Ru/HZSM-5 (Si: al=300) catalyst had the highest selectivity to cyclic hydrocarbons; as can be seen from FIGS. 2 c and d (experiments with varying pore structures), the Ru/HZSM-5 (Si: al=300) catalyst had the highest activity and selectivity to cyclic hydrocarbons.
Example 3
Thermal catalytic 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 baked in a muffle furnace at 200℃for 2 hours, 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 argon atmosphere after the hydrogen pre-reduction is finished, and cooling to 1vol% O 2 After maintaining for 1 hour under an Ar atmosphere to form a passivation layer, the recovered solid was weighed with an analytical balance and high density polyethylene was added to 5.5 g, and the powder was uniformly mixed for a second cycle test. The third cycle test is identical to the second cycle test. The results of the thermal catalytic polyethylene degradation stability test of Ru/HZSM-5 (300) are shown in FIG. 3. As can be seen from fig. 3: the conversion and selectivity of the catalyst are basically unchanged after three cycles.
Example 4
Test of benzene yield, cyclic hydrocarbon yield and conversion trend with reaction time in the products of the thermal catalytic degradation of Ru/HZSM-5 (Si: al=300):
under the reaction conditions of example 2, only the reaction time period was changed, and catalytic performances of 0.5 hours, 1.0 hour, 2.0 hours, 6.0 hours, 12.0 hours, 18.0 hours, 24.0 hours and 48.0 hours were obtained, respectively. The results of the thermal catalytic polyethylene degradation time evolution test of Ru/HZSM-5 (300) are shown in FIG. 4. As can be seen from fig. 4: with the extension of the reaction time, the conversion rate of plastics is continuously improved, and the selectivity of the cyclic hydrocarbon and aromatic hydrocarbon products is obviously improved.
From the above examples, the present invention provides a method for preparing a molecular sieve supported ruthenium-based catalyst, comprising the steps of: mixing ruthenium chloride solution and suspension containing molecular sieve to obtain 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 being Al=25, HZSM-5 with Si being Al=80, HZSM-5 with Si being Al=200, HZSM-5 with Si being Al=300, USY with Si being Al=10, and USY with Si being Al being P=1:2: 1 SAPO-34; the temperature of the reduction is 380-420 ℃ and the time is 110-130 min; the reducing atmosphere is hydrogen. The method provided by the invention has the advantages that the catalyst obtained by the reduction and passivation treatment after the molecular sieves with different silicon-aluminum ratios are mixed with the ruthenium chloride solution 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.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A method of polyethylene degradation comprising the steps of:
mixing polyethylene plastic powder with ruthenium-based catalyst supported by molecular sieve, and adding the mixture into N 2 Reacting in He atmosphere, and cooling; the specific gravity of the polyethylene plastic is 0.95-0.96; the mass ratio of the polyethylene plastic powder to the molecular sieve supported ruthenium-based catalyst is 10:0.9 to 1.1; the load of ruthenium in the molecular sieve supported ruthenium-based catalyst is 7-8wt%;
the reaction temperature is 270-290 ℃ and the reaction time is 0.5-48 h;
the preparation method of the molecular sieve supported ruthenium-based catalyst comprises the following steps:
mixing ruthenium chloride solution and suspension containing molecular sieve to obtain 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 of Al=25, HZSM-5 with Si of Al=80, HZSM-5 with Si of Al=200, HZSM-5 with Si of Al=300, USY with Si of Al=10, or Si with Al: p=1:2: 1 SAPO-34;
the temperature of the reduction is 380-420 ℃ and the time is 110-130 min; the reducing atmosphere is hydrogen.
2. The method according to claim 1, characterized in that the passivation treatment is in particular:
after reduction, the mixture was cooled to room temperature under an argon atmosphere and cooled to 1vol% O 2 And (3) maintaining the mixture for 55-65 min in Ar atmosphere to form a passivation layer.
3. The method according to claim 1, wherein the ruthenium chloride solution has a mass to water volume ratio of (190-210) mg of ruthenium chloride: 10mL;
the mass and water volume ratio of the molecular sieve in the molecular sieve-containing suspension is (0.95-1.05) g:35mL.
4. The method of claim 1, wherein the mixed liquor 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 method of claim 1, wherein the molecular sieve is used after pretreatment calcination;
the temperature of pretreatment calcination is 440-460 ℃ and the time is 220-260 min.
6. The method of claim 1, wherein the N is 2 The pressure of the/He is 1.5-2.5 MPa.
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