KR20230093899A - Metal deposited zeolite catalyst, method for preparing the same, and method for decomposition and de-chlorination of plastics using the same - Google Patents

Abstract

Disclosed herein is a metal-supported zeolite catalyst, a method for preparing the same, and a plastic decomposition and/or dechlorination reaction method using the same. The catalyst is prepared by supporting a metal precursor on zeolite, and provides an effect of greatly improving plastic decomposition reactivity and/or dechlorination reactivity through metal support on zeolite.

Description

Metal-supported zeolite catalyst, manufacturing method thereof, and plastic decomposition and dechlorination reaction method using the same

The present disclosure discloses a metal-supported zeolite catalyst, a method for preparing the same, and a plastic decomposition and/or dechlorination reaction method using the same.

Plastic waste is a major problem worldwide, and a large amount of carbon dioxide is generated during production, incineration, and disposal, which causes greenhouse gas generation. These plastic wastes can be converted into better low-molecular hydrocarbons through a pyrolysis process and used as alternative fuels for petroleum or petrochemical raw materials. Low-molecular compounds can be produced through the pyrolysis process of plastics, but since the compounds produced are mainly paraffins and olefins, continuous operation is difficult due to high viscosity. There are problems that cause

In order to solve this problem, a reaction technology capable of smoothly removing chlorine compounds while properly decomposing plastic waste is required, and a catalytic chemical reaction of thermal decomposition products can be a useful technology. Specifically, by developing a catalyst that simultaneously possesses active decomposition activity that divides thermal decomposition products into very small molecules and dechlorination activity that can remove chlorine, technology to lower the viscosity of thermal decomposition products and lower the chlorine content contained in the final product need this

KR 10-2257763 B1

In one aspect, the present disclosure aims to provide a catalyst for degradation and/or dechlorination of plastics.

In another aspect, an object of the present disclosure is to provide a method for preparing a catalyst for the plastic decomposition and/or dechlorination reaction.

In another aspect, an object of the present disclosure is to provide a plastic decomposition and/or dechlorination reaction method using a catalyst for the plastic decomposition and/or dechlorination reaction.

In one aspect, the present disclosure provides a zeolite; And it provides a catalyst for decomposition and / or dechlorination of plastics, including the metal supported on the zeolite.

In an exemplary embodiment, the zeolite may be one or more selected from the group consisting of HY, HCHA, HZSM-5, and Hβ.

In an exemplary embodiment, the metal may include at least one selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), cerium (Ce), and cobalt (Co).

In an exemplary embodiment, the metal and zeolite may be mixed in a weight ratio of 1:99 to 10:90.

In one exemplary embodiment, the plastic may include at least one selected from the group consisting of polyethylene, polypropylene, and polyvinyl chloride.

In another aspect, the present disclosure provides a method for preparing a catalyst for decomposition and/or dechlorination of plastics, comprising preparing a mixture by mixing a metal precursor solution and a zeolite; drying the mixture; And it provides a method for producing a catalyst for plastic decomposition and / or dechlorination reaction, comprising the step of calcining the dried product.

In an exemplary embodiment, the drying may include concentrating the mixture to remove moisture and then drying.

In an exemplary embodiment, the drying may be performed by concentrating the mixture under reduced pressure at 20 to 50 °C to remove moisture, and then drying at 90 to 100 °C.

In an exemplary embodiment, the firing may be performed at 400 to 600 °C.

In another aspect, the present disclosure provides a plastic decomposition and/or dechlorination reaction method comprising adding a catalyst for the plastic decomposition and/or dechlorination reaction to the plastic and heating the plastic.

In an exemplary embodiment, the catalyst and the plastic may be mixed and heated in a weight ratio of 1:10 to 1,000.

In an exemplary embodiment, the heating may be performed at 250 to 500 °C.

In one aspect, the technology disclosed in this disclosure has the effect of providing a catalyst for decomposition and/or dechlorination of plastics.

In another aspect, the technology disclosed in the present disclosure has an effect of providing a method for preparing a catalyst for decomposition and/or dechlorination of the plastic.

In another aspect, the technology disclosed in the present disclosure has an effect of providing a plastic decomposition and/or dechlorination reaction method using the plastic decomposition and/or dechlorination reaction catalyst.

1 shows a plastic decomposition and dechlorination reaction system according to an embodiment.

Hereinafter, the present disclosure will be described in detail.

In one aspect, the present disclosure provides a zeolite; And it provides a catalyst for decomposition and / or dechlorination of plastics, including the metal supported on the zeolite.

Zeolite is a high surface area crystalline porous material with a three-dimensional structure based on silicon and aluminum atoms.

In an exemplary embodiment, the zeolite may be one or more selected from the group consisting of HY, HCHA, HZSM-5, and Hβ as zeolite ion-exchanged with hydrogen.

In an exemplary embodiment, the zeolite may be HZSM-5.

In an exemplary embodiment, the metal may be a transition metal.

In an exemplary embodiment, the metal may include at least one selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), cerium (Ce), and cobalt (Co).

In an exemplary embodiment, the metal may include iron (Fe) and/or nickel (Ni).

In an exemplary embodiment, the metal is mixed with the zeolite at a weight ratio of 1:99 to 10:90, 3:97 to 7:93, 4:96 to 6:94, or 5:95. may have been

As used herein, plastic refers to a high molecular compound composed of carbon, hydrogen, oxygen, nitrogen, sulfur, chlorine and/or other elements.

In one exemplary embodiment, the plastic may include at least one selected from the group consisting of polyethylene, polypropylene, and polyvinyl chloride.

The catalyst according to the present disclosure has thermal decomposition reaction activity and dechlorination reaction activity of plastics, thereby providing an effect of enhancing decomposition and/or dechlorination efficiency of plastics in contact with solid, liquid, and gaseous plastics.

In an exemplary embodiment, the catalyst may be in contact with plastic at a reaction temperature of 250 to 500 °C.

In an exemplary embodiment, the catalyst may be for a decomposition reaction of plastics.

In one exemplary embodiment, the decomposition of the plastic may be thermal decomposition.

In an exemplary embodiment, the catalyst may be for dechlorination of plastics.

In an exemplary embodiment, the catalyst may include HZSM-5 zeolite; And it may be a catalyst for the dechlorination reaction of plastics containing iron (Fe) supported on the zeolite.

In an exemplary embodiment, the catalyst may include HZSM-5 zeolite; And it may be a catalyst for the decomposition reaction of plastics containing nickel (Ni) and/or cerium (Ce) supported on the zeolite.

In another aspect, the present disclosure provides a method for preparing a catalyst for decomposition and/or dechlorination of plastics, comprising preparing a mixture by mixing a metal precursor solution and a zeolite; drying the mixture; And it provides a method for producing a catalyst for plastic decomposition and / or dechlorination reaction, comprising the step of calcining the dried product.

In an exemplary embodiment, the metal precursor may be a metal nitroxide.

In an exemplary embodiment, the metal precursor solution may be a metal precursor aqueous solution obtained by dissolving a metal precursor in water.

In an exemplary embodiment, the drying may include concentrating the mixture to remove moisture and then drying.

In an exemplary embodiment, the drying may be performed by concentrating the mixture under reduced pressure at 20 to 50 °C to remove moisture, and then drying at 90 to 100 °C.

In an exemplary embodiment, the drying may include concentrating the mixture under reduced pressure for 10 minutes to 100 minutes to remove moisture, and then drying for 1 to 5 hours.

In an exemplary embodiment, the drying may be performed by concentrating the mixture at 20 to 50 °C under reduced pressure for 20 to 60 minutes to remove moisture, and then drying at 90 to 100 °C for 2 to 4 hours.

In one exemplary embodiment, the firing may be performed under an air atmosphere.

In an exemplary embodiment, the firing may be performed at 400 to 600 °C.

In one exemplary embodiment, the firing may be performed for 1 to 10 hours.

In an exemplary embodiment, the firing may be performed at 400 to 600 °C for 4 to 7 hours.

In another aspect, the present disclosure provides a plastic decomposition and/or dechlorination reaction method comprising adding a catalyst for the plastic decomposition and/or dechlorination reaction to the plastic and heating the plastic.

In one exemplary embodiment, the method includes introducing a plastic reactant into a reactor; and heating by adding a catalyst to the reactor.

In an exemplary embodiment, the catalyst and the plastic may be mixed and heated in a weight ratio of 1:10 to 1,000.

In an exemplary embodiment, the heating may be performed at 250 to 500 °C.

In an exemplary embodiment, the heating may be performed for 30 minutes to 300 minutes.

In an exemplary embodiment, the heating may be performed at 250 to 500 °C for 60 minutes to 120 minutes.

The plastic decomposition and/or dechlorination reaction method according to the present disclosure improves the decomposition reactivity and/or dechlorination reactivity of plastics by increasing the efficiency of a thermal decomposition process that decomposes plastics into smaller molecules and using a catalyst having chlorine removal activity. It provides the effect of lowering the viscosity of the thermal decomposition product and lowering the chlorine content contained in the final product.

1 shows a plastic decomposition and dechlorination reaction system according to an embodiment. For example, the reaction system includes a storage device (1) for inert gas such as nitrogen, a reactor (2) connected with a heating device, a plastic reactant (3), a cooler (4) for cooling and collecting the product after the reaction, and washing the product. It may be one comprising a water trap (5) for pyrolysis oil products (6).

Hereinafter, the present disclosure will be described in more detail through examples. These examples are only for exemplifying the present disclosure, and it will be apparent to those skilled in the art that the scope of the present disclosure is not to be construed as being limited by these examples.

Example 1. Preparation of metal supported zeolite catalyst

A catalyst was prepared by impregnating metal into H-ZSM-5 zeolite as follows using a wet impregnation method. Each iron(III) nitrate nonahydrate (Fe(NO ₃ ) ₃ 9H ₂ O), cobalt(II) nitrate hexahydrate (Co(NO ₃ ) ₂ 6H ₂ O), nickel(II) nitrate hexahydrate ( Ni(NO ₃ ) ₂ 6H ₂ O), copper(II) nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O), cerium(II) nitrate hexahydrate (Ce(NO ₃ ) ₃ 6H ₂ O) ) H-ZSM-5 (Si/Al = 11.5) was mixed with an aqueous solution stirred for 30 minutes by mixing the metal precursor and distilled water and stirred for 3 hours. Thereafter, the aqueous solution was concentrated for 40 minutes under vacuum conditions in a rotary evaporator set at 40 °C to remove all moisture. Thereafter, the catalyst was recovered and dried at 100 °C for 3 hours. Thereafter, the catalyst was put into a furnace, heated to 550 °C at a rate of 1 °C/min under an air atmosphere of 300 mL/min, and then calcined for 6 hours to H-ZSM loaded with 5% by weight of the transition metal. -5 catalyst was obtained. Table 1 below shows the types of metal precursors and the amounts of the metal precursors, the H-ZSM-5 carrier, and distilled water used in preparing the catalyst.

support metal Fe Co Ni Cu Ce metal precursor Fe(NO ₃ ) ₃ 9H ₂ O Co(NO ₃ ) ₂ 6H ₂ O Ni(NO ₃ ) ₂ 6H ₂ O Cu(NO ₃ ) ₂ 3H ₂ O Ce(NO ₃ ) ₃ 6H ₂ O Precursor Amount (g) 1.9038 1.3000 1.3038 1.001 0.8155 H-ZSM-5 (g) 5 5 5 5 5 distilled water (g) 80 80 80 80 80

Example 2. Degradation and dechlorination of plastic mixtures

10 g of a plastic mixture composed of polyethylene (PE), 78 wt %, polypropylene (PP) 20 wt %, and polyvinyl chloride (PVC) 2 wt % was placed in a batch reactor and nitrogen gas was introduced at 100 mL/min. 0.2 g of the catalyst was mixed and heated at 250° C. for 30 minutes and then at 450° C. for 1 hour. As catalysts, Ce/H-ZSM-5, Fe/H-ZSM-5, Cu/H-ZSM-5, Co/H-ZSM-5 and Ni/H-ZSM-5 were used. After the reaction, the product was obtained as a liquid product in a cooler and analyzed. The solid product remaining in the reactor was analyzed separately. The yield of gaseous products was calculated considering the amount of solid and liquid products in the amount of reactants. In addition, the gaseous product was passed through a water trap to measure the chlorine removed through titration. The gas, liquid, and solid products obtained after the reaction and the amount of chlorine measured through titration of the water trap are shown in Table 2 below.

catalyst Yield (% by weight) Chlorine removal rate (%) solid Liquid gas non-catalytic 1.8 52.1 46.1 79.0 Ce/H-ZSM-5 1.5 35.6 62.9 66.7 Fe/H-ZSM-5 1.1 44.2 54.8 100.0 Cu/H-ZSM-5 1.5 42.2 56.2 81.1 Co/H-ZSM-5 8.7 52.3 39.1 88.8 Ni/H-ZSM-5 1.3 36.3 62.3 91.6

The liquid product is mainly heavy oil/high carbon hydrocarbons of C ₆ or more, and the gaseous product mainly includes low carbon hydrocarbons in the naphtha region of C ₁ -C ₅ carbon atoms. As shown in Table 2, Fe/H-ZSM-5 showed a high low-carbon hydrocarbon yield and 100.0% chlorine removal rate, and Ni/H-ZSM-5 had a higher low-carbon yield than Fe/H-ZSM-5. It showed hydrocarbon yield and chlorine removal rate of 91.6%.

In the above, specific parts of the present disclosure have been described in detail, and for those skilled in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present disclosure is not limited thereby. something to do. Accordingly, the substantial scope of the disclosure will be defined by the appended claims and their equivalents.

1: storage device for inert gas such as nitrogen
2: reactor with heating device connected
3: plastic reactant
4: Cooler for cooling and collecting products after reaction
5: water trap for washing product
6: pyrolysis oil product

Claims (12)

zeolite; and
A catalyst for decomposition and/or dechlorination of plastics, comprising a metal supported on the zeolite.
According to claim 1,
The zeolite is at least one selected from the group consisting of HY, HCHA, HZSM-5 and Hβ, a catalyst for decomposition and / or dechlorination of plastics.
According to claim 1,
The metal includes at least one selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), cerium (Ce) and cobalt (Co), decomposition and / or dechlorination reaction of plastics catalyst for use.
According to claim 1,
The metal and the zeolite are mixed in a weight ratio of 1: 99 to 10: 90, a catalyst for decomposition and / or dechlorination of plastics.
According to claim 1,
The plastic comprises at least one selected from the group consisting of polyethylene, polypropylene and polyvinyl chloride, a catalyst for decomposition and / or dechlorination of plastics.
A method for preparing a catalyst for plastic decomposition and/or dechlorination according to any one of claims 1 to 5,
Preparing a mixture by mixing a metal precursor solution and zeolite;
drying the mixture; and
A method for producing a catalyst for plastic decomposition and / or dechlorination reaction, comprising the step of calcining the dried product.
According to claim 6,
The drying is a method for preparing a catalyst for decomposition and / or dechlorination of plastics, in which the mixture is concentrated to remove moisture and then dried.
According to claim 7,
The drying is a method for producing a catalyst for decomposition and / or dechlorination of plastics, in which the mixture is concentrated under reduced pressure at 20 to 50 ° C. to remove moisture and then dried at 90 to 100 ° C.
According to claim 6,
The calcination is carried out at 400 to 600 ° C., a method for producing a catalyst for decomposition and / or dechlorination of plastics.
A plastic decomposition and/or dechlorination reaction method comprising the step of adding the plastic decomposition and/or dechlorination reaction catalyst according to any one of claims 1 to 5 to the plastic and heating the plastic.
According to claim 10,
The catalyst and the plastic are mixed at a weight ratio of 1: 10 to 1,000 and heated, decomposition and / or dechlorination reaction method of plastic.
According to claim 10,
The heating is carried out at 250 to 500 ° C., plastic decomposition and / or dechlorination reaction method.

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