CN1155571A - Method for producing gasoline, diesel oil and carbon black from waste rubber - Google Patents
Method for producing gasoline, diesel oil and carbon black from waste rubber Download PDFInfo
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- CN1155571A CN1155571A CN 96109172 CN96109172A CN1155571A CN 1155571 A CN1155571 A CN 1155571A CN 96109172 CN96109172 CN 96109172 CN 96109172 A CN96109172 A CN 96109172A CN 1155571 A CN1155571 A CN 1155571A
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- catalyzer
- catalytic cracking
- carbon black
- znnihzsm
- zeolite
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Abstract
A process for producing gasoline, diesel oil and carbon black with waste rubber includes such steps as thermal cracking, removing sulfur and nitrogen, catalytic cracking, removing impurities with inorganic acid, and fractionating. A catalyst used in the process mentioned above is also disclosed in this invention.
Description
The present invention relates to handle the method for waste rubber, relate to particularly with thermo-cracking and catalytic thermal cracking method and handle waste rubber to produce gasoline, diesel oil and sooty method.
Relevant is the method for raw material production gasoline, diesel oil etc. with the waste rubber, existing a lot of reports.
In PCT/US 92/10800 is open, be reflected at vacuum pump and keep under the condition of negative pressure and carry out, the condition harshness, adopt controlled temperature 438 ℃ with interior method, do not allow the sulphur in the rubber vaporize in a large number, do not have actual desulfurization process in the technology.Cause sulphur content height in the product hydrocarbon ils, and unstable (in 0.4-1.5% weight).And the sulphur in the hydrocarbon ils product in use can etching apparatus and a large amount of SO of generation
2, contaminate environment.Because of temperature of reaction can not be higher than 438 ℃, cause the conversion of reactant not thorough, the yield of hydrocarbon ils low (47%), residue content many (43%).Also have quite a few raw material not change into hydrocarbon ils and carbon black.
At US3, in 996,022, rubber and acid halide mix and are molten state and react, and this is laboratory method.Chlorine [Cl in suitability for industrialized production
-] ion severe corrosion equipment at high temperature, production can't be carried out, and is mixed with a large amount of halogenide of not purifying in the residue carbon black, and carbon black has no commercial value.
At US5, in 208,404, rubber and catalyzer mix in reactor and react.Catalyzer is by a large amount of mineral compound such as Wingdale, and calcium oxide and precious metal (Ni, Nb and Ti) are formed, and they are non-volatile in reactor, are blended in the reaction residues carbon black, cause carbon black to be purified at industrial very difficult quilt, have no commercial value.And be reflected at 2kg/cm
2Carry out under the pressure, equipment material and requirement of strength height, big, the severe operational environment of investment, and rubber is low to the transformation efficiency of oil, has only 37%.
US4,108,730 take the fluidisation catalytic bed of complex process to carry out catalyzed reaction.Rubber needs a large amount of heavy oil (heavy oil) to carry out mixed melting, and then carries out catalytic cracking reaction.This must be based upon near the refinery with regard to limit production factory.And the content height (about 1.1%) of sulphur in the product hydrocarbon ils, can produce the SO that exceeds the standard several times in the production application
2, H
2The S contaminate environment.And US4,175,211 and US4,118,281 also is this method, needs a large amount of heavy oil as the fusion agent.
In Japanese kokai publication hei 6-228568, need add the hydrogen treat complex process.And there is not a desulfurization process.
The invention provides by waste rubber (comprising tire) and produce gasoline, diesel oil and sooty method, its operation comprises: at first carry out heat scission reaction, carry out desulfurization, denitrogenation then and carry out catalytic cracking reaction at last.According to the present invention, the waste rubber raw material adds the heat scission reaction still through screw feeder or the reciprocal plug charger of annotating after suitably handling in advance.When material entered, the screw mixer that starts in the heat scission reaction still stirred.The carbon black that generates behind the heat scission reaction 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 jar, enter fixed bed again and further slough the sulphur of surplus, nitrogen, and 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, carbon black reverses out.The present invention has selected unique catalyzer for use and added desulfurization and/or nitrogen rejection facility before catalytic cracking, has guaranteed that catalyzer is not subjected to the pollution of sulphur, has prolonged work-ing life, has enlarged the scope of handling raw material, has overcome the problem that prior art exists.Main chemical cracking reaction of the present invention is as follows:
N[C+H
2+ C
2H
4+ C
2H
6+ C
3H
8+ C
3H
6+ C
4H
8+ C
4H
10+ C
5H
10C
5H
12+ C
6H
6+ C
7H
8+ ... + C
12H
24+ C
12H
26+ ... + C
20H
40+ C
20H
42+ ... + C
25H
52], wherein, C
6H
14～C
12H
24Be gasoline component, C
12H
26-C
20H
42Be diesel component, CH
4-C
4H
10Be incendivity gas.
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 nitrogen rejection facility, 9 for continuing desulfurization and/or nitrogen rejection facility, also be elementary catalytic cracking unit simultaneously, the 10th, catalytic cracking unit, the 25th, separation column.
According to the present invention, with scrap rubber (NR, SR, SBR, BR, IR, CR, NBR, EPM With IIR etc.) anticipate, remove impurity. Heating furnace 1 provides thermal source to thermal cracking Reactor 5 heating, temperature in the kettle is controlled at 350-500 ℃. Useless with what handle well Rubber adds the still 5 from charging aperture 3. When material enters, start Pyrolysis Answer the screw mixer in the still to stir. In this temperature range, rubber raw materials Heat scission reaction takes place, and resolves into more micromolecular hydro carbons gas phase in reactor 5 Material. The scrap rubber residue that is decomposed fully in reactor is carbon black, stirs at spiral Mix under the effect of device 2, carbon black is discharged outside the still from valve 6, can be used as industrial carbon black Sell. More micromolecular gas phase hydrocarbon material enters desulfurization from reactor 5 tops And/or dispose alkaline matter [such as NaOH, KOH] in the nitrogen rejection facility 8,8. NaOH's is molten 318 ℃ of points, 1182 ℃ of boiling points. 350-450 ℃ of temperature range, be molten Attitude, the gas phase hydrocarbon is by being in the fluid alkali of molten condition, and fluid resistance is little, does not send out The angry phase material phenomenon of being obstructed sponges the acidity that most of thermal cracking produces through this Gas such as SO2，SO
3，H
2S ... Deng, enter fixed bed through 8 gaseous substances that come out 9, continue to sponge the sour gas and other gas with foreign flavor that do not absorb fully in 8, Carry out simultaneously elementary catalytic cracking reaction. The catalyst that uses in the fixed bed 9 is this The homemade DL type of inventor catalyst, the gaseous substance of drawing through fixed bed 9 enters Catalytic cracking unit 10,10 adopts fixed bed devices, catalyst be the inventor oneself XL type catalyst processed. Gaseous substance through 9 elementary catalytic cracking has carried out in 10 Full catalytic cracking, and carry out a series of building-up reactions, hydrogen transfer reaction, aromatization Change the reactions such as reaction, generate gasoline, diesel component and other combustible gas as The compounding substances such as gas, the reaction temperature in the fixed bed 9,10 are 250-400 ℃, Pressure is normal pressure or a little higher than normal pressure, and 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, and the inflammable gas that gas-holder 11 is stocked can turn back to burning in the process furnace 1.Gas unnecessary in the gas-holder 11 also can enter the atmospheric combustion emptying through water-sealed tank 12.Mixing liquid oil in the accumulator still 21 through mineral acid (as sulfuric acid, phosphoric acid ... Deng) handle and separating impurity after, with oil pump 23 mixing oil is pumped into heat exchange still 24, be heated to 300-400 ℃ 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 as carrier by the kaolin of 30-60% or atlapulgite, 20-50% zinc oxide (ZnO) or cupric oxide (CuO) are as active constituent, and an amount of silicon or aluminium tackiness agent,, formed in 3-5 hour through the mixing moulding drying as water glass etc. 600 ℃ of calcinings.DL type catalyzer: profile Ф 3 * 4-10mm bulk density 1.0-1.1kg/L crushing strength N/cm ()＞40 applying pressures (MPa) are that normal pressure-0.5 use temperature is used air speed h for ℃ 100-450 ℃
-1For penetrating this catalyzer of Sulfur capacity Wt%＞10,50-2000 can be removed to total sulfur (H
2S+COS)
Content＜0.05PPM
XL type catalyzer in the catalytic cracking unit 10 is made up of ZnNiHZSM-5 and synthetic carrier two portions that the HZSM-5 zeolite obtains after modification.Said ZnNiHZSM-5 zeolite be the HZSM-5 zeolite through zinc (Zn), the nitrate solution of nickel (Ni) or gallium metals such as (Ga) dipping forms, in the ZnNiHZSM-5 catalyzer after metal-modified, contain zinc 1-5%, be preferably 3%, nickeliferous is 0.5-5%, is preferably 1.5%.The spherical particle Hydrogen of HZSM-5 zeolite for having made, silica alumina ratio is 38, contains sodium 16.5PPM, is the catalyst for cracking of using always.Because the existence of nickel has improved dehydrogenation cracked performance, and benzene and content of toluene obviously increase, the ZnNiHZSM-5 zeolite after metal-modified improves the aromizing ability of 20-30% than HZSM-5 zeolite in the ZnNiHZSM-5 catalyzer.The hydrogen of taking off adds the two keys (C=C) in the raw material olefin becomes saturated alkane, the gasoline octane rating height, good stability, inductive phase height.The catalytic conversion reaction of the ZnNiHZSM-5 zeolite after the modification comprises dehydrogenation, polymerization, cyclisation, process such as dehydrogenation again, makes quite a few C
3-C
5Gas reforming is aromatic hydrocarbons and hydrocarbon ils, has improved conversion of raw material.The intensity of the ZnNiHZSM-5 zeolite after metal-modified, stability and life-span metal-modifiedly will be improved 30-50% as ZnHZSM-5 or NiHZSM-5 than a kind of.
Said synthetic vectors is to adopt kaolin to add binding agents such as a certain proportion of silicon-aluminum sol or silicon sol to form: with 20% the sulfuric acid (H of 1374kg
2SO
4) solution joins 0.79M
3(contain Al
2O
3Be 46 grams per liters) Al
2(SO
4)
3Solution stirs and is cooled to room temperature, stirs that adding water glass again (contains SiO down
2Be 120 grams per liters, modulus is 3.2-3.3) 4.9M
3With 1700kg kaolin, stir and promptly get the synthetic vectors slurry.
Preparation XL type catalyzer method is: get synthetic carrier slurry uniform mixing, drying, the moulding of metal-modified ZnNiHZSM-5 catalyzer and the 60-40% of 40-60% by weight proportion, formed in 3 hours 600 ℃ of calcination.
Embodiment
Will be after 1 ton of rubber (tire) removal of impurity pulverize, the magnetization deferrization, 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; Give 5 heat supplies of heat scission reaction still with process furnace 1, make that temperature of charge reaches 350-500 ℃ in the still; Under this temperature, rubber carries out heat scission reaction, resolves into the micro-molecular gas hydrocarbon; The carburet hydrogen introducing device 8 that decomposes in the reactor 5 is to slough sour gas (as SO
2, H
2S gas); The gaseous substance of drawing from 8 is through installing 9, and the DL type catalyzer on fixed bed is wherein further sloughed the sulphur and the nitrogen of surplus, carries out preliminary cracking scission reaction simultaneously; Carry out catalytic cracking reaction from installing the gaseous substance access to plant 10 of drawing 9, the temperature in the device 9,10 remains on 250-400 ℃, and pressure is normal pressure and a little higher than normal pressure.Material behind the catalytic pyrolysis through mineral acid [as sulfuric acid, phosphoric acid ... ] handle back separation, fractionation, condensation, oily water separation obtains gasoline 138kg at last, diesel oil 432kg.Heavy oil at the bottom of the separation column turns back in the heat cracking reaction still and reacts.Wherein the octane value of gasoline (RON) is 93.5, does≤200 ℃, and be 625 (min) inductive phase, and 10% boiling range is 62 ℃, and 50% boiling range is 102 ℃, and 90% boiling range is 180 ℃, and saturated vapor pressure (KPa) is 52.Diesel-fuel cetane number is that 59,10% boiling range is 185 ℃, 220 ℃ of condensation point＜-35 of 50% boiling range ℃, oil product total sulfur content＜0.05PPm.And carbon black 320kg, inflammable gas 110kg.That is: oil is 57%, and carbon black is 32%, and inflammable gas is 11%.Sooty ash content≤0.5% wherein, weight loss on heating≤2.5%, iodine absorption value (mg/g) is 112-130, pulls apart brute force (MPa) 〉=30, elongation % 〉=580.
Claims (9)
1. produce gasoline, diesel oil and sooty method with waste rubber (as tire) 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 stirs with screw mixer in the heat cracking reaction device, before entering catalytic cracking unit through desulfurization and/or nitrogen rejection facility.
2. according to the method for claim 1, it is characterized in that described desulfurization and/or nitrogen rejection facility comprise alkaline absorption unit and fixed bed absorption unit.
3. according to the method for claim 2, it is characterized in that described fixed bed absorption unit also is a catalytic cracking unit simultaneously.
4. according to the method for claim 1, it is characterized in that the catalyzer that uses in the described catalytic cracking unit 10 is following method preparation: ZnNiHZSM-5 uniform mixing, drying, the calcining of weight as 60-40% synthetic vectors and 40-60% formed.
5. according to the method for claim 4, it is characterized in that described synthetic vectors is by 1374kg20% sulfuric acid is added to 0.79M
3(Al
2O
3Content is 46 grams per liters) Al
2(SO
4)
3In the solution, stirring is cooled to room temperature, adds 4.9M again
3Water glass (SiO
2Content is 120 grams per liters) and 1700kg kaolin, stir and get.
6. according to the method for claim 1 or 2, it is characterized in that catalyzer used in the fixed bed 9 is following method preparation:
As carrier, 20-50% zinc oxide (ZnO) or cupric oxide (CuO) are as active constituent, and an amount of silicon or aluminium tackiness agent by the kaolin of 30-60% or atlapulgite,, form in 3-5 hour 600 ℃ of calcinings through the mixing moulding drying as water glass etc.
7. according to the method for claim 4, it is characterized in that the described ZnNiHZSM-5 catalyzer ZnNiHZSM-5 zeolite that to be the HZSM-5 zeolite obtain after metal-modified, that is: with the nitrate solution dipping of HZSM-5 zeolite through zinc, nickel or gallium, with an amount of silicon or aluminium tackiness agent such as water glass etc. through mixing, moulding, drying, calcining forms under 500-700 ℃, wherein contain zinc 1-5%, be preferably 3%; Nickel 0.5-5% is preferably 1.5%; Silica alumina ratio is 20-200, and crystal grain is 0.8-1.6um, and restricted index is 1-12.
8. according to the method for claim 4 or 6, wherein said catalyzer is granular.
9. according to the method for claim 1, when making raw material with rubber, the hydrocarbon ils behind the catalytic pyrolysis needs through mineral acid treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109172 CN1155571A (en) | 1995-08-08 | 1996-08-06 | Method for producing gasoline, diesel oil and carbon black from waste rubber |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107978.6 | 1995-08-08 | ||
| CN 96109172 CN1155571A (en) | 1995-08-08 | 1996-08-06 | Method for producing gasoline, diesel oil and carbon black from waste rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1155571A true CN1155571A (en) | 1997-07-30 |
Family
ID=5120274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96109172 Pending CN1155571A (en) | 1995-08-08 | 1996-08-06 | Method for producing gasoline, diesel oil and carbon black from waste rubber |
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| Country | Link |
|---|---|
| CN (1) | CN1155571A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387664C (en) * | 2006-09-21 | 2008-05-14 | 山西精华科工贸有限公司 | Method of preparing printing ink utilizing waste and old tyre and rubber |
| CN102140357A (en) * | 2011-02-09 | 2011-08-03 | 黄成选 | Environmental friendly waste rubber renewable diesel |
| CN103614159A (en) * | 2013-11-26 | 2014-03-05 | 杨金国 | Tire oil purifying device and method |
| CN105331147A (en) * | 2015-10-28 | 2016-02-17 | 贵州安泰再生资源科技有限公司 | Method of preparing carbon black from junked tires |
| CN110330996A (en) * | 2019-07-19 | 2019-10-15 | 华东理工大学 | The method and device that mineralized waste cracked oil is hydrocracked |
| CN113999546A (en) * | 2021-10-09 | 2022-02-01 | 济南恒誉环保科技股份有限公司 | Secondary treatment process and device for cracked carbon black |
-
1996
- 1996-08-06 CN CN 96109172 patent/CN1155571A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387664C (en) * | 2006-09-21 | 2008-05-14 | 山西精华科工贸有限公司 | Method of preparing printing ink utilizing waste and old tyre and rubber |
| CN102140357A (en) * | 2011-02-09 | 2011-08-03 | 黄成选 | Environmental friendly waste rubber renewable diesel |
| CN103614159A (en) * | 2013-11-26 | 2014-03-05 | 杨金国 | Tire oil purifying device and method |
| CN105331147A (en) * | 2015-10-28 | 2016-02-17 | 贵州安泰再生资源科技有限公司 | Method of preparing carbon black from junked tires |
| CN110330996A (en) * | 2019-07-19 | 2019-10-15 | 华东理工大学 | The method and device that mineralized waste cracked oil is hydrocracked |
| CN110330996B (en) * | 2019-07-19 | 2021-10-29 | 华东理工大学 | Method and device for hydrocracking mineralized refuse pyrolysis oil |
| CN113999546A (en) * | 2021-10-09 | 2022-02-01 | 济南恒誉环保科技股份有限公司 | Secondary treatment process and device for cracked carbon black |
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