Catalyst for catalytic cracking mixed waste plastic and preparation method thereof

Abstract

The invention discloses a catalyst for manufacturing fuel oil through catalytic pyrolysis of mixed-waste plastics, and a preparation method thereof, and relates to catalytic thermal cracking for manufacturing the fuel oil through waste plastic cracking and a second stage catalyst in thermal cracking catalytic reforming. A first stage catalyst comprises a metallic oxide of 2.0wt percent to 30.0wt percent and carclazyte or montmorillonite of 70.0wt percent to 98.0wt percent; the first stage catalyst is innoxious and cheap, increases the reaction velocity of plastic cracking, reduces the temperature in the scission reaction, improves the selectivity of decomposition products, and is dechlorinated and transformed into innocuous substances. The second stage catalyst is composed of ferric oxide, molybdenum oxide, zinc oxide, cerium oxide, lanthana, nickel oxide or copper oxide, and ZSM-5, MCM-22, USY, REY, Beta or MOR molecular sieves; the second stage catalyst performs the second catalytic pyrolysis and isomerization and the aromatization reversion reactions on pyrolysis gas in the first stage, to increase the distillate rate of pyrolysis gasoline and gas oil. The catalyst and the preparation method thereof have good selectivity, and the raw material does not need classification, washing and drying; the operation is flexible, and the running cost is low; the method is particularly applied to the fuel oil manufacture through the cracking of the mixed-waste plastics in the urban and rural domestic refuse, the composition is complicated; the oil yield of the qualified fuel oil can reach up to more than 70 percent calculated on the basis of the waste plastic.

Description

technical field

[0001] The invention relates to a second-stage catalyst for catalytic thermal cracking and thermal cracking catalytic modification for producing fuel oil by cracking waste plastics. The catalytic cracking catalyst of the invention has good controllability, and the oil yield of qualified fuel oil can be as high as 70% based on waste plastics. Above, the oil quality is good, the gasoline is No. 90, and the diesel oil is No. O to minus 20. Background technique

[0002] A large amount of waste and old plastics produced in daily garbage seriously endanger the living environment of human beings, and are called "white garbage". White garbage is also the most troublesome environmental governance problem for governments of all countries. In the past ten years, there have been many reports on the method of using waste plastics to crack fuel oil, and many waste plastics cracking and fuel oil plants have been established in China. In the gap or semi-gap kettle operation...

Examples

Embodiment 1

[0019] Preparation of the catalyst for the first stage of waste plastic cracking: Add 150 parts of ferric nitrate aqueous solution with an iron content of 3.0wt% to 100 parts of acid white powder, soak for 2 hours at 60 ° C, leave it standing after soaking and pour out the supernatant, and pour the supernatant at 120 After drying at 480°C for 4 hours, and then activating at 480°C for 5 hours, it was determined that the iron oxide content was 2.2 wt%, so that the iron oxide-modified Baishi catalyst was obtained.

[0020] The preparation of the catalyst for catalytic cracking and upgrading of the second stage of crude oil: add 150 parts of lanthanum nitrate aqueous solution containing 1.5wt% lanthanum to 100 parts of hydrogen ZSM-5, soak for 2 hours at 80 ° C, let stand and pour after soaking The supernatant was taken out, dried at 120°C for 4 hours, and then activated at 500°C for 5 hours, and the content of lanthanum oxide was determined to be 1.3 wt%, that is, the lanthanum ox...

Embodiment 2

[0024] Preparation of the catalyst for the cracking of waste plastics in the first stage: Add 150 parts of ferric nitrate aqueous solution containing 6.0 wt% magnesium to 100 parts of acid white powder, soak for 2 hours at 60°C, let stand after soaking and pour out the supernatant, and pour the supernatant at 120 After drying at 480°C for 4 hours, and then activating at 480°C for 5 hours, the content of magnesium oxide was determined to be 6.7wt%, and the magnesium oxide-modified Baishi catalyst was obtained.

[0025] Preparation of the catalytic cracking and upgrading catalyst of the second stage of crude oil: Add 150 parts of cerium nitrate aqueous solution containing 4.0wt% cerium to 100 parts of hydrogen-type USY, soak at 80°C for 2 hours, let stand after soaking and pour out the upper layer The clear liquid was dried at 120°C for 4 hours, and then activated at 500°C for 5 hours, and the content of cerium oxide was determined to be 3.9 wt%, that is, the cerium oxide-modifie...

Embodiment 3

[0029] Preparation of the catalyst for the first stage of waste plastic cracking: add 150 parts of lanthanum nitrate aqueous solution containing 12.0 wt% of lanthanum to 100 parts of montmorillonite, soak at 60 ° C for 2 hours, let stand after soaking and pour out the supernatant, Dry at 120° C. for 4 hours, and then activate at 480° C. for 5 hours. The content of lanthanum oxide is determined to be 13.5 wt %, and the lanthanum oxide-modified montmorillonite catalyst is obtained.

[0030]The preparation of the catalyst of the second stage crude oil catalytic cracking upgrading: in 100 parts of commercially available hydrogen type MCM-22 (silicon-aluminum ratio 32), add 150 parts of zinc nitrate aqueous solution of zinc content 10.0wt%, in 80 ℃ impregnate After soaking for 2 hours, let it stand still and pour out the supernatant, dry it at 120°C for 4 hours, and then activate it at 500°C for 5 hours. The zinc oxide content is determined to be 8.6wt%, and the zinc oxide modified ...

technical field

[0001] The invention relates to a second-stage catalyst for catalytic thermal cracking and thermal cracking catalytic modification for producing fuel oil by cracking waste plastics. The catalytic cracking catalyst of the invention has good controllability, and the oil yield of qualified fuel oil can be as high as 70% based on waste plastics. Above, the oil quality is good, the gasoline is No. 90, and the diesel oil is No. O to minus 20. Background technique

[0002] A large amount of waste and old plastics produced in daily garbage seriously endanger the living environment of human beings, and are called "white garbage". White garbage is also the most troublesome environmental governance problem for governments of all countries. In the past ten years, there have been many reports on the method of using waste plastics to crack fuel oil, and many waste plastics cracking and fuel oil plants have been established in China. In the gap or semi-gap kettle operation...

Examples

Embodiment 1

[0019] Preparation of the catalyst for the first stage of waste plastic cracking: Add 150 parts of ferric nitrate aqueous solution with an iron content of 3.0wt% to 100 parts of acid white powder, soak for 2 hours at 60 ° C, leave it standing after soaking and pour out the supernatant, and pour the supernatant at 120 After drying at 480°C for 4 hours, and then activating at 480°C for 5 hours, it was determined that the iron oxide content was 2.2 wt%, so that the iron oxide-modified Baishi catalyst was obtained.

[0020] The preparation of the catalyst for catalytic cracking and upgrading of the second stage of crude oil: add 150 parts of lanthanum nitrate aqueous solution containing 1.5wt% lanthanum to 100 parts of hydrogen ZSM-5, soak for 2 hours at 80 ° C, let stand and pour after soaking The supernatant was taken out, dried at 120°C for 4 hours, and then activated at 500°C for 5 hours, and the content of lanthanum oxide was determined to be 1.3 wt%, that is, the lanthanum ox...

Embodiment 2

[0024] Preparation of the catalyst for the cracking of waste plastics in the first stage: Add 150 parts of ferric nitrate aqueous solution containing 6.0 wt% magnesium to 100 parts of acid white powder, soak for 2 hours at 60°C, let stand after soaking and pour out the supernatant, and pour the supernatant at 120 After drying at 480°C for 4 hours, and then activating at 480°C for 5 hours, the content of magnesium oxide was determined to be 6.7wt%, and the magnesium oxide-modified Baishi catalyst was obtained.

[0025] Preparation of the catalytic cracking and upgrading catalyst of the second stage of crude oil: Add 150 parts of cerium nitrate aqueous solution containing 4.0wt% cerium to 100 parts of hydrogen-type USY, soak at 80°C for 2 hours, let stand after soaking and pour out the upper layer The clear liquid was dried at 120°C for 4 hours, and then activated at 500°C for 5 hours, and the content of cerium oxide was determined to be 3.9 wt%, that is, the cerium oxide-modifie...

Embodiment 3

[0029] Preparation of the catalyst for the first stage of waste plastic cracking: add 150 parts of lanthanum nitrate aqueous solution containing 12.0 wt% of lanthanum to 100 parts of montmorillonite, soak at 60 ° C for 2 hours, let stand after soaking and pour out the supernatant, Dry at 120° C. for 4 hours, and then activate at 480° C. for 5 hours. The content of lanthanum oxide is determined to be 13.5 wt %, and the lanthanum oxide-modified montmorillonite catalyst is obtained.

[0030]The preparation of the catalyst of the second stage crude oil catalytic cracking upgrading: in 100 parts of commercially available hydrogen type MCM-22 (silicon-aluminum ratio 32), add 150 parts of zinc nitrate aqueous solution of zinc content 10.0wt%, in 80 ℃ impregnate After soaking for 2 hours, let it stand still and pour out the supernatant, dry it at 120°C for 4 hours, and then activate it at 500°C for 5 hours. The zinc oxide content is determined to be 8.6wt%, and the zinc oxide modified ...