CN1055419C

CN1055419C - Aromatization catalyst of waste plastics and preparation process

Info

Publication number: CN1055419C
Application number: CN95107410A
Authority: CN
Inventors: 张庆祥
Original assignee: Individual
Current assignee: Individual
Priority date: 1995-07-04
Filing date: 1995-07-04
Publication date: 2000-08-16
Anticipated expiration: 2015-07-04
Also published as: CN1139591A

Abstract

The present invention absorbs the active constituent of Zncl2 on particulate Al2O3 supporters by an impregnating method to prepare catalysts having surface activity. The catalysts have the advantages of simple preparation method and low cost, are suitable for the technological processes for producing gasoline and diesel oil by waste plastics, and have good aromatization action and olefin superposition action. In the obtained oil products, the aromatic content reaches more than 30%, and the octane value reaches more than 76 (a motor method).

Description

Aromatization catalyst of waste plastics and preparation method thereof

The present invention is a kind of aromatization catalyst of waste plastics and preparation method thereof, the invention belongs to chemical technology field.

With waste plastic produce gasoline, diesel oil is a new technology, just begin in China, normally used catalyzer is a powdered sial series compound, production technique is to drop into powdered catalyzer and plastic waste in the process furnace together, under high temperature more than 700 ℃, carry out catalytic cracking, because the activity of powdery sial series catalysts is lower like this, the aromizing effect is relatively poor, make that to make in the product oil aromaticity content lower, octane value is below 70 (motor methods), institute adds catalyzer can not activate usefulness again with waste residue discharge process furnace, has increased cost.And employed aluminosilicate molecular sieves in large-scale refinery petroleum catalytic cracking at present, aromatization effect is fine, but because its equipment complexity involves great expense, also is not suitable for the technological process that plastic waste is produced gasoline, diesel oil.

The objective of the invention is to prepare a kind of cheap, plastic waste aromatized catalyst that can activating and regenerating is used for plastic waste and produces gasoline, diesel oil process, has aromatization effect preferably, make that aromaticity content reaches more than 30% in the products obtained therefrom oil, octane value reaches more than 76 (motor methods).

The object of the present invention is achieved like this: aromatization catalyst of waste plastics is the active constituent ZnCl with 40-70% ₂Be adsorbed on 100% particulate state Al with pickling process ₂O ₃On the carrier, make and have surface-active catalyzer, wherein ZnCl ₂Be Industrial products, particulate state Al ₂O ₃Carrier is the Industrial products of Φ 4-5mm, and the average aperture of particulate is 50-80 , and pore volume is 0.30-0.80ml/g, and specific surface area is 150-250m ²/ g, tap density is 0.55-0.70g/ml.The Preparation of catalysts method can be used the normal temperature dipping method, boils pickling process and heating, vacuum pickling process.The normal temperature dipping method is under normal temperature condition, with particulate state Al ₂O ₃Carrier places saturated ZnCl ₂In the aqueous solution, flooded 30 minutes, will adsorb ZnCl ₂Reach the particulate state Al of 40-70% ₂O ₃, filter, dry, bake activation through 600～650 ℃ again; Boiling pickling process is with particulate state Al ₂O ₃Carrier places ZnCl ₂Saturated aqueous solution in, boil 30 minutes after, will adsorb ZnCl ₂Reach 40～70% particulate state Al ₂O ₃Filter, dry, bake activation through 600-650 ℃ again; The heating, vacuum pickling process is with particulate state Al ₂O ₃And ZnCl ₂Saturated aqueous solution place vacuum drum, under the heating, vacuum condition dipping 30 minutes, will adsorb ZnCl ₂Reach the particulate state Al of 40-70% ₂O ₃Filter, dry, bake activation through 600-650 ℃ again.

The catalyzer of the present invention's preparation, be applicable to waste plastic production gasoline, diesel oil technological process, be specially adapted to fixed bed catalyst equipment, catalyzer is placed on the fixed bed, plastic waste is placed vapourizing furnace, when the plastic waste steam passes through beds, carry out catalyzed reaction in 270～430 ℃ of condition therapeutic methods to keep the adverse qi flowing downward, solid phase, make in the processed oil, aromaticity content reaches more than 30%, and octane value reaches more than 76 (motor methods).This is catalyst fixed bed under 600～650 ℃ of conditions, can activating and regenerating, and recycle and reach more than 30 times.

The catalyzer of the present invention's preparation is that waste plastic is produced gasoline, the diesel oil technological process is developed the raw catalyst type, the preparation method is simple, with low cost, life cycle is long, have aromizing and alkene oligomerization effect preferably, make the product oil quality stable, aromaticity content reaches more than 30%, and rate alkane value reaches more than 76 (motor methods).

The present invention is further described below in conjunction with embodiment.

Fig. 1 is the sketch of heating, vacuum immersion process for preparing catalyzer of the present invention.

1. rotary drums, 2. charging openings, 3. water baths, 4. vacuum pumps, 5. intake valves among Fig. 1.

The active constituent ZnCl that embodiment 1 usefulness distilled water or deionized water are mixed with ₂Saturated aqueous solution and particulate state Al ₂O ₃Carrier is all put into rotary drum 1, for making particulate state Al ₂O ₃Carrier fully adsorbs, and should make ZnCl ₂Excessive, sealing charging opening 2 rotates rotary drum 1, heated water bath groove 3, open vacuum pump 4, make that vacuum tightness reaches 720mmHg in the rotary drum 1, kept 30 minutes, open intake valve 5, air is slowly fed in the rotary drum 1, to vacuum tightness be 0 o'clock, will adsorb 40-70% active constituent ZnCl ₂Particulate state Al ₂O ₃Filter, oven dry, bake activation through 600-650 ℃ again, because granular size, average aperture, pore volume and specific surface area all directly influence the catalytic effect of catalyzer, so particulate state Al ₂O ₃Carrier is selected the Industrial products of Φ 4-5mm, and the average aperture of particulate is 50-80 , and pore volume is 0.30-0.80ml/g, and specific surface area is 150-250m ²/ g, tap density is 0.55-0.70g/ml, malleation intensity is 9.0-16.0kg/cm ², abrasion loss is the 1.2-2.5% of weight.

Embodiment 2, are mixed with ZnCl with distilled water or deionized water ₂Saturated aqueous solution, the above-mentioned aqueous solution and particulate state Al ₂O ₃Carrier is put into reaction vessel simultaneously, floods at normal temperatures 30 minutes, will adsorb ZnCl ₂Reach the particulate state Al of 40-70% ₂O ₃Filter, oven dry bakes activation through 600-650 ℃ again, makes to have surface-active catalyzer.

Embodiment 3, the ZnCl that is mixed with distilled water or deionized water ₂Saturated aqueous solution is the above-mentioned aqueous solution and particulate state Al ₂O ₃Carrier is put into the reactor with heating unit simultaneously, boils 30 minutes, will adsorb ZnCl ₂Reach the particulate state Al of 40-70% ₂O ₃Filter, oven dry bakes activation again under 600-650 ℃ of condition, makes to have surface-active catalyzer.

Embodiment 4, place plastic waste to produce on the catalyst bed of gasoline, diesel oil conversion unit the catalyzer that makes, under 270-430 ℃ of condition, carry out gas-solid phase reaction with vaporized plastic waste gas, because this catalyzer has aromizing and alkene oligomerization effect preferably, make the steady quality of product oil, aromaticity content reaches more than 30%, and octane value reaches more than 76 (motor methods).Above-mentioned catalyzer in use for some time, can be under 600-650 ℃ of condition activating and regenerating, recycle more than 30 times.

Claims

1. an aromatization catalyst of waste plastics is characterized in that the active ingredient ZnCl with 40-70% (weight) ₂Be adsorbed on 100% particulate state Al ₂O ₃Make on the carrier and have surface-active catalyzer.

2. catalyzer according to claim 1 is characterized in that described ZnCl ₂Be technical grade product.

3. catalyzer according to claim 1 is characterized in that described particulate state Al ₂O ₃Carrier is the Industrial products of Φ 4-5mm, and the average aperture of particulate is 50-80 , and pore volume is 150-250m for the 0.30-0.80ml/g specific surface ²/ g, tap density is 0.55～0.70g/ml.

4. the preparation method of an aromatization catalyst of waste plastics is characterized in that the ZnCl with 40-70% (weight) ₂Be adsorbed on 100% granulated Al with pickling process ₂O ₃On the carrier, bake activation through 600 ℃-650 ℃ again and make and have surface-active catalyzer.

5. method for preparing catalyst according to claim 4 is characterized in that described pickling process has three kinds of embodiments: the normal temperature dipping method, boil pickling process and heating, vacuum pickling process.

6. according to claim 4 and 5 described method for preparing catalyst, it is characterized in that described normal temperature dipping method is with described particulate state Al ₂O ₃Carrier places described ZnCl at normal temperatures ₂Saturated aqueous solution in, flooded 30 minutes, will adsorb ZnCl ₂Reach the particulate state Al of 40-70% (weight) ₂O ₃Filter, dry, bake activation through 600～650 ℃ again.

7. according to claim 4 and 5 described method for preparing catalyst, it is characterized in that the described pickling process of boiling is with described particulate state Al ₂O ₃Carrier places described ZnCl ₂Saturated aqueous solution in boiled 30 minutes, will adsorb ZnCl ₂, reach the particulate state Al of 40-70% (weight) ₂O ₃Filter, dry, bake activation through 600-650 ℃ again.

8. according to claim 4 and 5 described method for preparing catalyst, it is characterized in that described heating, vacuum pickling process is with described particulate state Al ₂O ₃Carrier and described ZnCl ₂Saturated aqueous solution place vacuum drum simultaneously, under the heating, vacuum condition dipping 30 minutes, will adsorb ZnCl ₂Reach the particulate state Al of 40-70% (weight) ₂O ₃Filter, dry, bake activation through 600-650 ℃ again.