CN1066482C

CN1066482C - Produce gasoline, diesel oil and sooty method with waste rubber and/or plastic waste

Info

Publication number: CN1066482C
Application number: CN95195757A
Authority: CN
Inventors: 邢力
Original assignee: Individual
Current assignee: Individual
Priority date: 1995-08-08
Filing date: 1995-11-07
Publication date: 2001-05-30
Anticipated expiration: 2015-11-07

Abstract

The invention discloses a kind of waste rubber that utilizes, plastic waste is produced gasoline, diesel oil and sooty method.The inventive method comprises thermo-cracking, decon, catalytic cracking, and compositions such as fractionation the invention also discloses the catalyzer that uses in the inventive method.

Description

Produce gasoline, diesel oil and sooty method with waste rubber and/or plastic waste

TECHNICAL FIELD OF THE INVENTION

The present invention relates to handle the method for waste rubber and/or plastic waste, relate to particularly with thermo-cracking and catalytic thermal cracking method and handle waste rubber and/or plastic waste to produce gasoline, diesel oil and sooty method.

Technical background

About being the method for raw material production gasoline, diesel oil etc., reported a lot with waste rubber and plastic waste.Such as U.S. Pat 5,414,169, US4,851,601 and EP-A-0607862 etc.US5, the method for describing in 414,169 comprises carries out thermo-cracking earlier with plastic waste or waste rubber, then with thermal cracking products liquefaction, and then carries out catalytic pyrolysis with catalyzer in liquid phase.US4, the plastic waste product of then having described thermo-cracking in the liquid phase in 851,601 carries out the gas phase catalysis cracking under catalyzer ZSM-5 effect, and this method is improper to the Halogen polyolefine, in order to avoid make catalyst deactivation.EP-A-0607862 then discloses and a kind ofly material after the thermo-cracking is earlier carried out catalytic cracking with acidic solid catalyst has obtained elementary catalytic cracking production, and then with its refrigerated separation, the reacted gas phase component of gained is again through as H ₃PO ₄Catalyzer obtains the secondary hydrocarbon ils.

Of the present invention open

The invention provides by waste rubber and/or plastic waste and produce gasoline, diesel oil and sooty method.Waste rubber and/or plastic waste raw material add the heat scission reaction still through screw feeder or the reciprocal plug charger of annotating after suitably handling in advance according to the present invention.When material enters, start screw mixer and stir.Behind the heat scission reaction, the carbon black that generates is discharged outside the still under the driving of screw mixer, and the hydro carbons gaseous substance than small molecules that cracking generates, enter desulfurization and/or denitrogenation and/or dechlorination jar, enter fixed bed again and carry out further desulfurization and/or denitrogenation and/or dechlorination, carry out elementary catalytic pyrolysis simultaneously; Thereafter, the material of gas phase enters cat-cracker and carries out catalytic pyrolysis, and the product behind the catalytic pyrolysis separates after condensation and obtains desired product.The screw mixer that is provided with in the heat scission reaction still of the present invention has reduced the coking of material, improves heat transfer efficiency.Clockwise stirring, the counter-rotating discharging.The present invention selected unique catalyzer for use and before catalytic cracking, added desulfurization and/or nitrogen and/or chlorine appliance ensure the work-ing life of catalyzer, enlarged the scope of handling raw material, overcome the problem that prior art exists.

Brief description of drawings

Fig. 1 is a reacting flow chart of the present invention.

In accompanying drawing 1, the 27th, screw feeder or back and forth annotate plug formula charger, the 1st, process furnace, the 5th, the heat scission reaction still, 2 is spiral stirrer, the 8th, desulfurization and/or denitrogenation and/or dechlorination device, 9 for continuing desulfurization and/or nitrogen and/or chlorine device, also be elementary catalytic cracking unit simultaneously, the 10th, catalytic cracking unit, the 25th, separation column.

Detailed description of the present invention

According to the present invention, rubber (NR, SR, SBR, BR, IR, CR, NBR, EPM will give up With IIR etc.) and/or waste plastics (PE, PP, PS, PVC, ABS) anticipate, remove assorted Matter. Heating furnace 1 provides thermal source to 5 heating of heat scission reaction still, and temperature in the kettle is controlled at 350-500 ℃. Useless rubber and/or the waste plastics handled well are added still 5 from reinforced hole 3 In. When material enters, start the spiral mixer and stir. In this temperature scope, Rubber and/or plastics raw material generation heat scission reaction resolve into littler branch in reaction still 5 The hydrocarbon class gaseous substance of son. Be useless rubber such as raw material, it is residual then to be decomposed fully in the reaction still Slag is carbon black, and under the effect of spiral agitator 2, carbon black is discharged from valve 6 outside the still, can As the preparation tire used. The gas phase hydrocarbons of littler molecule advances from reaction still 5 tops Enter the alkaline material of configuration in desulfurization and/or denitrogenation and/or the dechlorination apparatus 8,8, absorb through this The acid gas that most of thermal cracking produces enters fixed bed through 8 gaseous substances that come out 9, continue to absorb acid gas and other gas with foreign flavor that does not absorb fully in 8, simultaneously Carry out elementary catalytic cracking reaction. The catalyst that uses in the fixed bed 9 is homemade as the present invention Catalyst DL, the gaseous substance of drawing through fixed bed 9 enters catalytic cracking unit 10,10 Adopt fixed bed device, catalyst is that the inventor is from controlling catalyst XL. Through 9 elementary urging The gaseous substance of changing cracking carries out completely catalytic cracking in 10, and carries out a series of different The reactions such as structure generate gasoline, and diesel component and other combustible gas such as gas etc. are mixed Compound matter, the reaction temperature in the fixed bed 9,10 is 200-400 ℃, pressure is 0.02-0.08MPa air speed is 1-2000/h.

The crackate of being drawn by catalytic cracking unit 10 enters condenser 19 and is cooled to room temperature, and mixing liquid is vapour, diesel oil.Enter accumulator still 21 through separator 20, gas enters gas-holder 11 through separator 20 tops.Gas unnecessary in the gas-holder 11 enters the atmosphere emptying through water-sealed tank 12.The inflammable gas that gas-holder 11 is stocked can turn back to burning in the process furnace 1.Mixing liquid oil in the accumulator still 21 is behind acid-alkali treatment wherein, with oil pump 23 mixing oil is pumped into heat exchange still 24, be heated to 250-350 ℃ and enter separation column 25, do not coexist according to gasoline, diesel oil boiling range and to separate in the separation column 25, gasoline enters condenser 14 from cat head, enters gasoline storage 18 through water-and-oil separator.Diesel oil enters stripping tower 26 from separation column 25 middle parts, and after the superheated vapour effect, diesel oil enters condenser 13, through water-and-oil separator 15, enters diesel oil storage 17 at last.

DL catalyzer in the fixed bed 9 is formed by category-A and category-B mixing of materials, wherein category-A is by on the high mountain range of 40-70% or atlapulgite, the NaOH of 10-30% or KOH solution (solids content is 10-20%), the ZnO of 10-15% or soluble zinc salt, the CuO of 3-5% or soluble copper salt and an amount of silicon or this area typical binders such as aluminium tackiness agent such as water glass are through mixing washing, drying gets 500-700 ℃ of following calcining.Category-B is then by on the high mountain range of 40-80% or atlapulgite, the NaOH of 10-30% or KOH solution (solids content is 10-20%), 10-20%CaO or CaCO ₃And an amount of silicon or aluminium tackiness agent such as water glass etc., through mixing, moulding, washing, drying, form 500-700 ℃ of calcining.

A and the mutual ratio of category-B blended can suitably be adjusted as required, and this can grasp for those skilled in the art.Preferably, be made into particulate state.

Catalyzer XL in the catalytic cracking unit 10 is by the complete synthesis or semi-synthetic carrier of 10-70%, the HZSM-5 zeolite of 10-50%, the NaOH of 10-20% or KOH solution (solids content is 10-20%), the compound of 3-5%ZnO or Zn, Pt, Fe, Cu and Ni and an amount of silicon or al binder are through mixing, moulding, washing, drying, 500-700 ℃ of following calcining forms.Silicon or al binder preferably use water glass.Described full synthesis carrier is that common glue method or step-by-step precipitation method are made, and wherein contains SiO ₂Be the amorphous aluminum silicide of 20-80%, silicon magnesium etc. for adjusting the heap ratio of catalyzer, also can add an amount of clay and increase weight in full synthesis carrier.Described semi-synthetic carrier is a kaolin, and halloysite or atlapulgite etc. are the clay of matrix and the free Al of being commonly used in cracking catalyst ₂O ₃, SiO ₂, Na ₂SiO ₃And SiO ₂Al ₂O ₃Binding agent form.Catalyzer XL preferably makes particulate state.

Embodiment 1

To pulverize after 1 ton of plastics removal of impurity, then through screw feeder or back and forth annotate plug formula charger and join in the reactor 5 of thermo-cracking by charge cavity 3; Process furnace 1 is given 5 heat supplies of heat scission reaction still, makes that temperature of charge reaches 350-500 ℃ in the still; Under this temperature, plastic waste carries out heat scission reaction, resolves into the micro-molecular gas hydrocarbon; The carburet hydrogen introducing device 8 that decomposes in reactor 5 is to slough sour gas; The gaseous substance of introducing from 8 is through installing 9, and the further desulfurization of DL catalyzer, chlorine and nitrogen on fixed bed wherein carry out preliminary cracking scission reaction simultaneously; Carry out catalytic pyrolysis from installing the air-flow access to plant 10 of drawing 9; Temperature in the device 9,10 remains on 200-400 ℃, and pressure is 0.02-0.08MPa.Material behind the catalytic pyrolysis is through separating, and fractionation obtains gasoline 370kg, 370kg diesel oil.Wherein the RON of gasoline is 90-93, does≤205 ℃; Diesel-fuel cetane number 45-60,95% boiling range is less than 360 ℃ (zero pour≤-20 ℃)

Embodiment 2

With 1 ton of waste rubber is raw material, and other operation obtains: gasoline 320kg, diesel oil 309kg, carbon black 280kg with embodiment 1.Wherein sooty BP absorption value is 47 ± 7cm ²/ 100g, ash≤0.3%, weight loss on heating≤1.0%.Industrial applicibility

According to the inventive method, be that raw material can obtain the stable gasoline of productive rate, diesel oil and carbon black with waste rubber, plastic waste, guaranteed the industrialization continuous production.

Claims

1. produce gasoline, diesel oil and sooty method with waste rubber and/or plastic waste for one kind, comprise: raw material is added the heat cracking reaction device through charger, behind Pintsch process, discharge carbon black, gaseous phase materials enters catalytic cracking unit, then through the separation column fractionation, it is characterized in that material before entering catalytic cracking unit through desulfurization and/or denitrogenation and/or dechlorination device, described desulfurization and/or denitrogenation and/or dechlorination device comprise alkaline absorption unit and fixed bed absorption unit; The catalyzer that uses in the described catalytic cracking unit is following method preparation: with the complete synthesis or semisynthetic carrier of 10-70% (weight), the 10-50%HZSM-5 zeolite, the solids content of 10-20% is NaOH or the KOH solution of 10-20%, the compound of 3-5%ZnO or Zn, Pt, Ni, Cu and Fe and an amount of silicon or al binder are through mixing moulding, washing, drying, calcining or do not calcine and form; And the catalyzer in the described fixed bed mixes by category-A and category-B, wherein

Category-A is by kaolin or the atlapulgite of 40-70%, and the solids content of 10-30% is NaOH or the KOH solution of 10-20%, the ZnO of 10-15% or soluble zinc salt, the CuO of 3-5% or soluble copper salt and an amount of silicon or aluminium tackiness agent are through mixing washing, drying, the calcining and get;

Category-B is by kaolin or the atlapulgite of 40-80%, and the solids content of 10-30% is NaOH or the KOH solution of 10-20%, 10-20%CaO or CaCO ₃With an amount of silicon or aluminium tackiness agent through mixing, drying, calcining and getting.

2. according to the method for claim 1, it is characterized in that described fixed bed absorption unit also is a catalytic cracking unit simultaneously.

3. according to the process of claim 1 wherein that the temperature of reaction in fixed bed absorption unit or the catalytic cracking unit is 200-400 ℃, pressure is 0.02-0.08Mpa.

4. according to the process of claim 1 wherein that described catalyzer is granular.