CN113813961A - Preparation method of carbon-coated plastic hydrogenolysis catalyst - Google Patents
Preparation method of carbon-coated plastic hydrogenolysis catalyst Download PDFInfo
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- CN113813961A CN113813961A CN202110979635.0A CN202110979635A CN113813961A CN 113813961 A CN113813961 A CN 113813961A CN 202110979635 A CN202110979635 A CN 202110979635A CN 113813961 A CN113813961 A CN 113813961A
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- coated plastic
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000004033 plastic Substances 0.000 title claims abstract description 40
- 229920003023 plastic Polymers 0.000 title claims abstract description 40
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 150000003839 salts Chemical class 0.000 claims abstract description 12
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000002243 precursor Substances 0.000 claims description 4
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 3
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 3
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- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 claims description 3
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
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- 230000008569 process Effects 0.000 description 11
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 9
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- 230000001276 controlling effect Effects 0.000 description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 4
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- 238000000576 coating method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000000366 colloid method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
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- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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Abstract
The invention discloses a preparation method of a carbon-coated plastic hydrogenolysis catalyst, which comprises the following steps of S1, dissolving one or more acetylacetone salts or carbonyl compounds of specific transition metals into a three-neck round-bottom flask containing mixed liquid; s2, under the protection of inert gases such as high-purity argon or nitrogen, placing the three-neck flask in the step S1 in an oil bath at the temperature of 80 ℃ and preserving the temperature until the metal salt is completely dissolved to form a uniform solution; s3, heating the system obtained in the step S2 to 150-350 ℃ and keeping the temperature for a period of time to ensure that the metal salt is completely converted to form the metal-based nano particles. Compared with other methods, the preparation method of the carbon-coated catalyst has the advantages of simple operation, convenience, practicability, easy expansion and the like, the structural parameters of the metal-based core and the carbon coating layer can be accurately regulated, the gradual cracking of the polyolefin macromolecules can be realized, and the activity, the selectivity and the service life of the catalyst are improved.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a carbon-coated plastic hydrogenolysis catalyst.
Background
Energy and environment are the focus of common concern in the world today. In recent years, the development of new energy and low-carbon industries is highly concerned by the nation, and the resource utilization of solid wastes, particularly plastics, is an important part in the recycling economy. According to the reports of McKensin, the annual plastic waste production amount is increased from 2.6 million tons to 4.6 million tons by 2030, and the global half-plastic recycling brings about 600 million dollar industrial profit, but the current recovery rate is only 16%, and the enhancement of the plastic recycling and upgrading utilization are imminent. Currently, the mainstream treatment mode of plastics is still incineration and landfill, and the mass of carbon dioxide generated when plastics are incinerated is three times of the mass of the carbon dioxide, so that the current treatment mode undoubtedly brings bad and long-term negative effects on the ecological environment. With the successive issuance of "forbidden plastic orders" in many developing countries, the european union also plans to improve the plastic recycling rate to 55% in 2030 years, and the plastic recycling is receiving more and more research attention, especially the upgrading and utilization of chemical methods for producing fuel oil, hydrogen and carbon materials by plastic cracking.
In the existing plastic products, more than 60 percent of the products are made of olefin polymers only containing C and H elements, such as polyethylene, polypropylene and polystyrene. Such plastics are consistent with petroleum in terms of elemental composition. Although the components are simple, the molecular weight of the olefin monomer for preparing plastics after polymerization tends to be large, and a solid high molecular polymer is formed. Therefore, cracking these high molecular weight polymers into smaller molecular weight hydrocarbons is an important way to recycle plastics.
The chemical upgrading method of the plastic mainly comprises catalytic hydrogenolysis (ACS Central Science 2019,5, 1795-. In many biological enzymes' decomposition mechanisms of macromolecular compounds, straight-chain macromolecules pass through pores to reach internal hydrogenolysis active sites. One end of the chain molecule passes through the pore channel, and is firstly broken to form small molecules and released from the pore channel. Meanwhile, the cut molecules continuously pass through the pore and are subjected to hydrogenolysis, and after repeated hydrogenolysis, the chain-shaped macromolecules can be completely hydrogenolyzed into micromolecular compounds with narrower carbon number distribution. By simulating the principle of the mechanism, researchers propose that the core-shell catalyst with the mesoporous silica coated beam metal platinum nanoparticles is constructed for hydrogenolysis of low-temperature plastics, and the control of the carbon number distribution of hydrogenolysis products can be realized by adjusting and controlling the size of the mesoporous. However, the use of noble metal platinum limits the scale test and application of the catalyst, and the silica shell is rich in hydroxide, and the surface hydrophilicity of the silica shell can be unfavorable for mass transfer of hydrocarbons in the pore channels, so that the hydrogenolysis efficiency is influenced.
In view of the defects of the prior art, the invention aims to design and prepare a high-performance catalyst for the hydrogenolysis of carbon-coated plastics so as to solve the technical problems of low activity, poor selectivity, short service life and the like of the catalyst in the hydrogenolysis process of the plastics.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a carbon-coated plastic hydrogenolysis catalyst.
The invention provides a preparation method of a carbon-coated plastic hydrogenolysis catalyst, which comprises the following steps:
s1, dissolving acetylacetone salt or carbonyl compound of the specific transition metal into a three-neck round-bottom flask containing the mixed liquid;
s2, under the protection of inert gases such as high-purity argon or nitrogen, placing the three-mouth flask in the step S1 in an oil bath at the temperature of 80 ℃ and preserving the temperature until the metal salt is completely dissolved to form a uniform solution;
s3, heating the system obtained in the step S2 to 150-350 ℃ and keeping the temperature for a period of time to ensure that the metal salt is completely converted to form the metal-based nano particles;
s4: after the system obtained in the step S3 is naturally cooled, adding a mixed solution of ethanol and n-hexane, and performing precipitation on the formed nanoparticles by using a mechanical centrifuge;
s5: repeating the system obtained in the step S4 for 8-10 times according to the step S4;
S6: drying the nanoparticles obtained in the step S5 at a low temperature of 40-80 ℃ in a low vacuum degree environment to form dry powder;
s7, transferring the dried powder obtained in the step S6 to a high-temperature resistant quartz boat, placing the quartz boat in a tube furnace, and roasting the quartz boat at the temperature of 800 ℃ under the conditions of low vacuum degree and 300-800 ℃ and inert gas such as high-purity argon or nitrogen to obtain the carbon-coated metal-based catalyst.
Preferably, the mixed liquid in the step S1 is a tri-n-octylphosphine reducing agent and an oleylamine organic solvent.
Preferably, the mixed liquid in step S1 is tributylphosphine, triphenylphosphine, and organic reagents containing N, P, such as hexadecylamine, octadecylamine, dioctylamine, and the like.
Preferably, the mixed liquid in step S1 is an organic reagent such as 1, 2-hexadecanediol, 1, 2-dodecanediol, etc.
Preferably, the mixed liquid in step S1 is a high-boiling organic solvent such as n-octadecane, octadecene, dioctyl ether, and dibenzyl ether.
Preferably, in step S1, in addition to the precursor of the metal salt, elemental sulfur is further added for preparing the metal sulfide nanoparticles with organic ligands on the surface.
Preferably, in the step S1, the volume ratio of the reducing agent to the organic solvent in the mixed liquid is 0 to 75%.
Preferably, in the step S3, the reaction temperature is 230 ℃.
Preferably, the reaction temperature in the step S3 is 330 ℃.
Preferably, in the step S7, the temperature for powder calcination is 400 ℃.
The invention has the beneficial effects that:
1. the invention adopts a mature wet colloid method to prepare the metal-based nano-particles with the surfaces containing the organic ligands, and is easy to realize the controllable synthesis and the batch production of the nano-structure catalyst.
2. The invention creatively adopts a roasting carbonization method to construct the carbon-coated catalyst, directly carbonizes the surface ligand which is usually difficult to remove, and activates the metal-based nano particles, and the obtained core-shell material has the characteristics of sintering resistance, oxidation resistance, uniform size and simple structure.
3. Due to the unique core-shell structure, the carbon-coated catalyst has unique advantages in the plastic hydrogenolysis process, and mainly comprises the following steps: (a) the carbon coating layer is porous, so that the chain-like high-molecular polymer can orderly enter the kernel and generate hydrogenolysis reaction, and the selectivity of the product is improved; (b) the carbon coating physically separates the metal-based nanoparticles in the carbon coating, so that the metal-based nanoparticles are prevented from being inactivated by sintering and agglomeration in the high-temperature hydrogenolysis process; (c) the abundant surface chemistry and potential hydrogenolysis activity of the carbon coating layer provide more powerful tools for improving the hydrogenolysis activity and selectivity of the plastic.
4. Due to the universality of synthesis by a colloid method, the metal-based core can be composed of different components such as metal monomers, alloys, metal compounds and the like, the types of metal elements are not restricted, and the preparation of the specified catalyst can be realized according to the specific hydrogenolysis reaction target of the plastic.
Drawings
Fig. 1 is a schematic diagram of a preparation process of a first embodiment of a preparation method of a carbon-coated plastic hydrogenolysis catalyst provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, refer to orientations or positional relationships based on those shown in the drawings, and are used only for the purpose of facilitating the description of the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present invention.
A preparation method of a carbon-coated plastic hydrogenolysis catalyst comprises the following steps:
s1, dissolving one or more kinds of acetylacetone salt or carbonyl compound of specific transition metal into a three-neck round-bottom flask containing mixed liquid;
precursor metals in the present invention include, but are not limited to, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, W, Ir, Pt, Au, and other transition metals, alloy species include binary, ternary, quaternary, and high entropy alloys, and metal compound species include, but are not limited to, nitrides, phosphides, sulfides, and the like.
S2, under the protection of inert gases such as high-purity argon or nitrogen, placing the three-mouth flask in the step S1 in an oil bath at the temperature of 80 ℃ and preserving the temperature until the metal salt is completely dissolved to form a uniform solution;
s3, heating the system obtained in the step S2 to 150-350 ℃ and keeping the temperature for a period of time to ensure that the metal salt is completely converted to form the metal-based nano particles;
s4: after the system obtained in the step S3 is naturally cooled, adding a mixed solution of ethanol and n-hexane, and performing precipitation on the formed nanoparticles by using a mechanical centrifuge;
s5: repeating the system obtained in the step S4 for a certain number of times according to the step S4;
respectively repeating the system obtained in the step S4 for zero times, one time, two times and three times to prepare metal-based nanoparticles with different contents of organic ligands on the surface;
S6: drying the nanoparticles obtained in the step S5 at a low temperature of 40-80 ℃ in a low vacuum degree environment to form dry powder;
s7, transferring the dried powder obtained in the step S6 to a high-temperature resistant quartz boat, placing the quartz boat in a tube furnace, and roasting the quartz boat at the temperature of 800 ℃ under the conditions of low vacuum degree and 300-800 ℃ and inert gas such as high-purity argon or nitrogen to obtain the carbon-coated metal-based catalyst.
Wherein, the carbon coating layer can be derived into a carbon material doped with heterogeneous elements from heteroatom groups in the organic ligand, thereby improving the physical and chemical properties of the carbon coating layer material. Because the organic ligands are uniformly distributed on the surface of the nearly spherical nano-particles, a onion-like carbon layer with uniform thickness is formed on the surface of the nano-particles after the ligands are carbonized, and structural parameters such as the thickness of the carbon layer, the size of a pore channel, the graphitization degree, the surface property and the like provide a powerful path for regulating and controlling the activity and selectivity in the hydrogenolysis process of plastics.
Wherein, in step S1, carbon-coated metal alloy nanoparticles are prepared by adding two or more metal salts;
wherein the mixed liquid in the step S1 is a tri-n-octylphosphine reducing agent and an oleylamine organic solvent;
wherein, in step S1, the preparation of metal-based nanoparticles with different sizes is realized by controlling the molar ratio of the metal ions, the reducing agent and the solvent
Wherein the mixed liquid in the step S1 is organic reagents containing N, P, such as tributyl phosphine, triphenylphosphine, hexadecylamine, octadecylamine, dioctylamine and the like, and is used for preparing nanoparticles with different types of ligands on the surface;
the mixed liquid in the step S1 is organic reagents such as 1, 2-hexadecanediol, 1, 2-dodecanediol and the like, and is used for preparing nanoparticles with different types of ligands on the surface;
the mixed liquid in the step S1 is a high-boiling-point organic solvent such as n-octadecane, octadecene, dioctyl ether, and dibenzyl ether, and is used for preparing nanoparticles with different types of ligands on the surface;
in step S1, in addition to the precursor of the transition metal, elemental sulfur is added to prepare metal sulfide nanoparticles with surfaces containing organic ligands;
in step S1, the volume ratio of the reducing agent to the solvent in the mixed liquid is 0-75%;
in step S3, by controlling different reaction temperatures, the preparation of metal-based nanoparticles with different sizes is realized;
wherein, in the step S3, the reaction temperature is 230 ℃ for preparing the metal simple substance nano-particles;
wherein the reaction temperature in the step S3 is 330 ℃ for preparing metal phosphide nano-particles;
In the step S7, the roasting temperature of the powder is 400 ℃;
therefore, the carbon-coated plastic hydrogenolysis catalyst provided by the invention has very high activity, selectivity and stability. The quality of the hydrogen decomposition product is improved by optimizing the key structural parameters of the catalyst. The preparation method of the carbon-coated metal-based catalyst is simple and efficient, is easy to operate, has high expansibility, opens up an efficient conversion method for resource utilization of waste plastics, and has great application and development values.
Specifically, the following embodiments of the present invention are illustrated by specific examples:
example 1:
10 ml of oleylamine and 6 ml of tri-n-octylphosphine were added to a round-bottom three-necked flask having a volume of 250 ml to form a homogeneous solution, and then 1 mmol of nickel acetylacetonate was added to the solution. High-purity nitrogen is continuously introduced into the three-neck flask, a condenser pipe is connected above the three-neck flask, and circulating cooling water flows in the condenser pipe. And immersing the bottom of the flask in an oil bath at the temperature of 80 ℃, and keeping the temperature for at least 30 minutes to completely dissolve the nickel acetylacetonate in the mixed solution. Then, the three-neck flask is quickly immersed into another oil bath pan heated to 230 ℃ and is kept for 1 hour, so that the nickel acetylacetonate is completely converted into nickel nanoparticles. The reaction apparatus is schematically shown in FIG. 1. And after the reaction is finished, taking the three-neck flask out of the oil bath pan, and placing the three-neck flask in the air for natural cooling. After cooling, n-hexane and ethanol were mixed in a volume ratio of 1: 5 the mixed solution prepared is used for washing the three-neck flask, the suspension containing the nano particles is completely transferred to a centrifuge tube with the volume of 50 ml, the centrifuge tube is centrifuged for 5 minutes at the rotating speed of 8000 rpm, the precipitated nickel nano particles are obtained, and the cleaning process is repeated three times. Finally, drying the nickel nano particles obtained by separation in an electronic oven with low vacuum degree and 40 ℃ to obtain powder;
The dried powder was loaded into a quartz boat and placed at the end of a tube furnace into which 5 ml/min of high purity nitrogen was introduced to protect the powder from air oxidation. Heating to 400 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the heat for 1 hour, and then naturally cooling the tubular furnace to obtain the catalyst of the carbon-coated nickel nanoparticles;
example 2
A round bottom three-necked flask having a volume of 250 ml was charged with 12 ml of 1, 2-dichlorobenzene, 0.1 g of trioctylphosphine oxide and 0.2 ml of oleic acid to form a homogeneous solution A. High-purity nitrogen is continuously introduced into the three-neck flask, a condenser pipe is connected above the three-neck flask, and circulating cooling water flows in the condenser pipe. The bottom of the flask was immersed in an oil bath at a temperature of about 200 ℃ and held for at least 30 minutes. 0.54 g of dicobalt octacarbonyl was dissolved in 3 ml of 1, 2-dichlorobenzene to form a homogeneous solution B and was quickly poured into solution A. The reaction was held for 20 minutes to completely convert the cobaltocene octacarbonyl into cobalt nanoparticles. And after the reaction is finished, taking the three-neck flask out of the oil bath pot, and naturally cooling the three-neck flask in the air. After cooling, n-hexane and ethanol were mixed in a volume ratio of 1: 5 the prepared mixed solution washes the three-neck flask, the suspension containing the nano-particles is completely transferred to a centrifuge tube with the volume of 50 ml, and the suspension is centrifuged for 5 minutes at the rotating speed of 6000 rpm per minute to obtain precipitated nickel nano-particles, and the cleaning process is repeated three times. And finally, drying the cobalt nanoparticles obtained by separation in an electronic oven with low vacuum degree and 40 ℃ to obtain powder.
The dried powder was loaded into a quartz boat and placed at the end of a tube furnace into which 5 ml/min of high purity nitrogen was introduced to protect the powder from air oxidation. Heating to 400 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the heat for 1 hour, and then cooling the tubular furnace to obtain the catalyst of the carbon-coated cobalt nanoparticles.
Example 3
A round-bottom three-neck flask with a volume of 250 ml was charged with 10 ml of oleylamine and 5 ml of tri-n-octylphosphine to form a homogeneous solution, and then 0.9 mmol of nickel acetylacetonate and 0.3 mmol of copper acetylacetonate were added to the solution. High-purity nitrogen is continuously introduced into the three-neck flask, a condenser pipe is connected above the three-neck flask, and circulating cooling water flows in the condenser pipe. The bottom of the flask was immersed in an oil bath at 80 ℃ and kept at that temperature for at least 30 minutes to completely dissolve the acetylacetonate in the mixed solution. Then, the three-neck flask is quickly immersed into another oil bath pan heated to 230 ℃ and is kept for 1 hour, so that the acetylacetone salt is completely converted into the nickel-copper alloy nanoparticles. And after the reaction is finished, taking the three-neck flask out of the oil bath pot, and naturally cooling the three-neck flask in the air. After cooling, n-hexane and ethanol were mixed in a volume ratio of 1: 5, the mixed solution prepared in the step 5 is used for flushing the three-neck flask, the suspension containing the nano particles is completely transferred to a centrifugal tube with the volume of 50 ml, the centrifugal tube is centrifuged for 5 minutes at the rotating speed of 8000 revolutions per minute, the precipitated nickel-copper alloy nano particles are obtained, and the cleaning process is repeated three times. And finally, drying the nickel-copper alloy nanoparticles obtained by separation in an electronic oven with low vacuum degree and 40 ℃ to obtain powder.
The dried powder was loaded into a quartz boat and placed at the end of a tube furnace into which 5 ml/min of high purity nitrogen was introduced to protect the powder from air oxidation. Heating to 400 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the heat for 1 hour, and then cooling the tubular furnace to obtain the catalyst of the carbon-coated nickel-copper alloy nanoparticles.
Example 4
10 ml of oleylamine and 6 ml of tri-n-octylphosphine were added to a round-bottom three-necked flask having a volume of 250 ml to form a homogeneous solution, and then 1 mmol of nickel acetylacetonate was added to the solution. High-purity nitrogen is continuously introduced into the three-neck flask, a condenser pipe is connected above the three-neck flask, and circulating cooling water flows in the condenser pipe. And immersing the bottom of the flask in an oil bath at the temperature of 80 ℃, and keeping the temperature for at least 30 minutes to completely dissolve the nickel acetylacetonate in the mixed solution. Thereafter, the oil bath was rapidly heated to 330 ℃ over 5 minutes and held for 1 hour to completely convert the nickel acetylacetonate to nickel phosphide nanoparticles. And after the reaction is finished, taking the three-neck flask out of the oil bath pot, and naturally cooling the three-neck flask in the air. After cooling, n-hexane and ethanol were mixed in a volume ratio of 1: 5 the prepared mixed solution washes the three-neck flask, the suspension containing the nano-particles is completely transferred to a centrifuge tube with the volume of 50 ml, the centrifuge tube is centrifuged for 5 minutes at the rotating speed of 8000 rpm to obtain the precipitated nickel phosphide nano-particles, and the cleaning process is repeated three times. And finally, drying the separated nickel phosphide nano-particles in an electronic oven with low vacuum degree and 40 ℃ to obtain powder.
The dried powder was loaded into a quartz boat and placed at the end of a tube furnace into which 5 ml/min of high purity nitrogen was introduced to protect the powder from air oxidation. Heating to 400 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the heat for 1 hour, and then obtaining the catalyst of the carbon-coated nickel phosphide nano-particles after the tubular furnace is naturally cooled.
Example 5
15 ml of oleylamine was added to a round-bottom three-necked flask having a volume of 250 ml, and then 0.1 mmol of nickel acetylacetonate, 1 mmol of cobalt acetylacetonate and 2 mmol of elemental sulfur were added to the solution. High-purity nitrogen is continuously introduced into the three-neck flask, a condenser pipe is connected above the three-neck flask, and circulating cooling water flows in the condenser pipe. The bottom of the flask was immersed in an oil bath at 80 ℃ and kept at that temperature for at least 30 minutes to completely dissolve the acetylacetonate in the mixed solution. Then, the three-neck flask is covered by a heating cover and heated to 350 ℃ within 5 minutes, and the temperature is kept for 1 hour, so that the acetylacetone salt is completely converted into spinel-type nickel-cobalt sulfide nanoparticles. And after the reaction is finished, taking the three-neck flask out of the heating cover, and naturally cooling the three-neck flask in the air. After cooling, n-hexane and ethanol were mixed in a volume ratio of 1: 5 the prepared mixed solution washes the three-neck flask, the suspension containing the nanoparticles is completely transferred to a centrifuge tube with the volume of 50 ml, the centrifuge tube is centrifuged for 5 minutes at the rotating speed of 8000 rpm to obtain precipitated nickel cobalt sulfide nanoparticles, and the cleaning process is repeated three times. And finally, drying the nickel-cobalt sulfide nano particles obtained by separation in an electronic oven with low vacuum degree and 40 ℃ to obtain powder.
The dried powder was loaded into a quartz boat and placed at the end of a tube furnace into which 5 ml/min of high purity nitrogen was introduced to protect the powder from air oxidation. Heating to 400 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the heat for 1 hour, and then cooling the tubular furnace to obtain the catalyst of the carbon-coated nickel cobalt sulfide nano-particles.
Example 6
20 ml of oleylamine was added to a round-bottom three-necked flask having a volume of 250 ml, and then 1.6 mmol of molybdenum octacarbonyl, 0.4 mmol of nickel acetylacetonate and 4 mmol of elemental sulfur were added to the solution. High-purity nitrogen is continuously introduced into the three-neck flask, a condenser pipe is connected above the three-neck flask, and circulating cooling water flows in the condenser pipe. The bottom of the flask was immersed in an oil bath at 80 ℃ and kept for at least 30 minutes to completely dissolve the metal salt in the mixed solution. And then, covering the three-neck flask with a heating cover, heating to 300 ℃ within 5 minutes, and preserving the heat for 1 hour to completely convert the acetylacetone salt into spinel nickel-doped monolayer molybdenum disulfide nanosheets. And after the reaction is finished, taking the three-neck flask out of the heating cover, and naturally cooling the three-neck flask in the air. After cooling, n-hexane and ethanol were mixed in a volume ratio of 1: 3, flushing the three-neck flask by the prepared mixed solution, completely transferring the suspension containing the nano-sheets to a centrifugal tube with the volume of 50 ml, centrifuging for 5 minutes at the rotating speed of 9000 revolutions per minute to obtain the precipitated molybdenum disulfide nano-sheets, and repeating the cleaning process for three times. And finally, drying the separated molybdenum disulfide nanosheets in an electronic oven with a low vacuum degree and a temperature of 60 ℃ to obtain powder.
The dried powder was loaded into a quartz boat and placed at the end of a tube furnace into which 5 ml/min of high purity nitrogen was introduced to protect the powder from air oxidation. Heating to 400 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the heat for 1 hour, and then naturally cooling the tubular furnace to obtain the catalyst of the carbon-coated molybdenum disulfide nanosheet.
Compared with other methods, the preparation method of the carbon-coated catalyst has the advantages of simple operation, convenience, practicability, easy expansion and the like, and the structural parameters of the core metal and the carbon coating layer can be accurately regulated and controlled. Nanoparticles of single metals, alloys, metal compounds are prepared in organic solvents using widely used metallo-organic thermal decomposition methods. The metal-based nanoparticles remain uniformly dispersed due to the surface coating of the organic ligands. After the nano-particles containing the ligand are obtained through centrifugal separation, the organic ligand is directly carbonized and forms a carbon coating layer on the surface of the nano-particles through roasting treatment in inert atmosphere. On one hand, the physical separation brought by the carbon coating layer can effectively prevent the sintering of the metal-based nano particles; on the other hand, the carbon coating layer is porous due to the formation of a gas product in the ligand carbonization process, which is beneficial to the mass transfer of polyolefin macromolecules and the direct contact with the inner core metal, and the abundant surface chemistry of the carbon material is beneficial to promoting the mass transfer of high molecular polymers, and even the carbon material can have active sites for catalyzing the cracking of hydrocarbon.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-coated plastic hydrogenolysis catalyst is characterized by comprising the following steps:
s1, dissolving acetylacetone salt or carbonyl compound of the specific transition metal into a three-neck round-bottom flask containing mixed liquid;
s2, under the protection of inert gases such as high-purity argon or nitrogen, placing the three-neck flask in the step S1 in an oil bath at the temperature of 80 ℃ and preserving the temperature until the metal salt is completely dissolved to form a uniform solution;
s3, heating the system obtained in the step S2 to 150-350 ℃ and keeping the temperature for a while to ensure that the metal salt is completely converted to form metal-based nano particles;
s4: after the system obtained in the step S3 is naturally cooled, adding a mixed solution of ethanol and n-hexane, and performing precipitation on the formed nanoparticles by using a mechanical centrifuge;
s5: repeating the system obtained in the step S4 for 8-10 times according to the step S4;
s6: drying the nanoparticles obtained in the step S5 at a low temperature of 40-80 ℃ in a low vacuum degree environment to form dry powder;
S7, transferring the dried powder obtained in the step S6 to a high-temperature resistant quartz boat, placing the quartz boat in a tube furnace, and roasting the quartz boat at the temperature of 800 ℃ under the conditions of low vacuum degree and 300-800 ℃ and inert gas such as high-purity argon or nitrogen to obtain the carbon-coated metal-based catalyst.
2. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein the mixed liquid in the step S1 is tri-n-octylphosphine reducer and oleylamine organic solvent.
3. The method of claim 1, wherein the mixed liquid in step S1 is organic reagent containing N, P, such as tributyl phosphine, triphenyl phosphine, hexadecyl amine, octadecyl amine, and dioctyl amine.
4. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein the mixed liquid in step S1 is an organic reagent such as 1, 2-hexadecanediol, 1, 2-dodecanediol, etc.
5. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 4, wherein the mixed liquid in step S1 is a high boiling point organic solvent such as n-octadecane, octadecene, dioctyl ether, and dibenzyl ether.
6. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein in step S1, in addition to the precursor of the metal salt, elemental sulfur is added to prepare the metal sulfide nanoparticles with organic ligands on the surface.
7. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein the volume ratio of the reducing agent to the organic solvent in the mixed liquid in step S1 is 0-75%.
8. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein the reaction temperature in step S3 is 230 ℃.
9. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein the reaction temperature in step S3 is 330 ℃.
10. The method for preparing a carbon-coated plastic hydrogenolysis catalyst as claimed in claim 1, wherein the calcination temperature of the powder in step S7 is 400 ℃.
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