CN105694942A - Method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber - Google Patents
Method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber Download PDFInfo
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- CN105694942A CN105694942A CN201610251249.9A CN201610251249A CN105694942A CN 105694942 A CN105694942 A CN 105694942A CN 201610251249 A CN201610251249 A CN 201610251249A CN 105694942 A CN105694942 A CN 105694942A
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- scrap rubber
- liquefaction oil
- aromatic hydrocarbons
- high aromatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention belongs to the technical field of chemical industry, relates to a method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber, in particular to treatment of waste rubber, more particularly a method for preparing high aromatic liquefied oil from waste rubber, and aims to provide a method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber, this method having a short treatment process, high oil yield and short treatment time. The method comprises the following steps: (1), pretreating waste rubber; (2), liquefying slowly at low temperature; (3), pyrolyzing quickly at high temperature; (4), post-treating a pyrolytic product. This method yields 5-10%, 50-56% and 34-38% respectively of pyrolytic gas, aromatic liquefied oil and carbon black, with aromatic content in the aromatic liquefied oil reaching to 40-60%, low ash content in the carbon black and high carbon black quality.
Description
Technical field
The invention belongs to chemical field, particularly relate to scrap rubber and process, the method that particularly scrap rubber produces high aromatic hydrocarbons liquefaction oil。
Background technology
Along with the economic fast development quickly increased with auto industry, damaged tire yield is continuously increased, and enormous amount has caused a series of resource and environmental problem。Junked tire as being difficult to the polymeric solid garbage degraded, long-term air storage, not only cause the waste of land resource, and grow mosquito antibacterial, spread disease, easy initiation fire, be referred to as " black pollution ", the impact for environment is very serious。Therefore, suitable damaged tire processing and utilization method is found, it has also become one of hot issue that people pay close attention to。
At present, waste tyre pyrolytic technology is with its relatively low discharge amount of pollution and higher energy recovery rate, it is increasingly subject to pay attention to, it it is the development in recent years method that processes damaged tire faster, it is possible not only to obtain gas, fuel oil and carbon black product, energy recovery rate is up to more than 80%, and has higher economy and environmental benefit。Patents about producing vapour, diesel oil and white carbon black with scrap rubber for catalytic material pyrolysis has a lot of report。
Prior art generally all adopts specific composite catalyst, such as a kind of method that US Patent No. 5208404 discloses scrap rubber cracking fuel oil and gas, rubber mixes in a kettle. with catalyst and reacts, define catalyst to be made up of limestone, calcium oxide and Ni, Nb and Ti noble metal, and reaction needed under high pressure carries out, not only that equipment material and requirement of strength is higher, add investment and operation easier, and the response time is up to 2h, the oily yield that the method obtains simultaneously is relatively low。
All there is the new catalyst complicated component that scrap rubber is developed in processes at present in prior art, need supporting structure of reactor complicated, the conversion of reaction is not thorough, liquid oil yield is low, residue content is many, and ash content of black is high in product, oil product and carbon black mass are not high, although above-mentioned technology achieves the recycling of scrap rubber simultaneously, but it is all to obtain fuel oil or limonene, product as fuel again with, thus there is the problem that arene content is relatively low, and aromatic hydrocarbons is the important source material of rubber synthesis, rich aromatic hydrocarbons liquefaction oil can recycle as rubber aromatic oil, thus reducing the production cost of rubber。
Summary of the invention
It is desirable to provide a kind of processing procedure is simple, in the liquefaction oil obtained, arene content is high, and the method that high aromatic hydrocarbons liquefaction oil is prepared in the short scrap rubber two-step catalysis pyrolysis of process time。
The present invention provides a kind of method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis, it is characterised in that comprise the steps:
(1) scrap rubber pretreatment, this step is to adopt existing conventional means that waste Crumb rubber is broken into granule, is beneficial to subsequent reactions；
(2) low temperature liquefies at a slow speed: after scrap rubber and catalyst mix, under anaerobic, being warming up to 180-240 DEG C, heating rate is 10-15 DEG C/min, heats up and terminates rear constant temperature 5-20min, is warming up to thermostatic process and all carries out under negative pressure or normal pressure；
(3) high-temperature quick solution: under anaerobic, is warming up to 400-600 DEG C by the reactant of low temperature post liquefaction at a slow speed under-30-20KPa, and heating rate is 15-30 DEG C/min, heats up and terminates rear constant temperature 10-20min；
(4) thermal decomposition product post processing: reaction afterproduct carries out gas-solid and gas-liquid separation, obtains pyrolysis gas, coke and liquefaction oil。
Described step (1) includes scrap rubber cutting, crushes, grinds, sieves and dried so that waste rubber powder particle size range is at 0.1-5.0mm, and moisture content is lower than 2%。
In the present invention, low temperature liquefies at a slow speed and two processes of high-temperature quick solution can carry out in same reactor, it is possible to is divided into two, processes in order to convenient, be typically chosen in a reactor and carry out。
Described dried is under inert gas shielding, dry at 80-130 DEG C。
In described step (2), catalyst adds quality is the 0.1-2% of rubber powder。
In described step (2), negative pressure or normal pressure scope refer to-30-20Kpa。
In described step (4), thermal decomposition product enters cyclone separator and realizes gas solid separation by after white carbon black elimination, and condensed equipment collects liquefaction oil, finally gives pyrolysis gas, coke and liquefaction oil。
Described catalyst is the mixture of one or more in ZSM-5, USY, β, SAPO-11, ZSM-22 molecular sieve。
Described catalyst is Powdered, and silica alumina ratio is 4-80, specific surface area 150-600mm2/ g, 5-8 angstrom of aperture。
Described catalyst mean diameter 50 μm。
There is advantages that
Pyrolysis gas, aromatic hydrocarbons liquefaction oil and white carbon black can be obtained after product that the inventive method obtains is post-treated, pyrolysis gas can use as fuel, coke can as activated carbon or inferior grade white carbon black, liquefaction oil can obtain high aromatic hydrocarbons liquefaction oil after the de-solid process of dehydration, rich aromatic hydrocarbons liquefaction oil can recycle as rubber aromatic oil, thus reducing the production cost of rubber；
Pyrolysis gas, aromatic hydrocarbons liquefaction oil and carbon yield respectively 5-10%, 50-56% and the 34-38% that the present invention obtains, and in aromatic hydrocarbons liquefaction oil, arene content can reach 40-60%, in white carbon black, ash is few, and carbon black mass is high。
Detailed description of the invention
Below by the specific embodiment provided, the present invention will be further described, but not as a limitation of the invention。
Embodiment 1
Damaged tire is cut, crush and after process of milling, make waste rubber powder particle size range at 0.1-5.0mm, it is dried to water content less than 2%, the ZSM-5 catalyst of addition 1% stirs, then render in tank reactor, pass into nitrogen and replace whole response system, system is made to be under oxygen free condition, it is rapidly heated to 180 DEG C with 10 DEG C/min, intensification terminates rear constant temperature 20min, 500 DEG C are risen to afterwards with 15 DEG C/min heating rate, at such a temperature through the catalytic cracking reaction of 20min, the high temperature gas-phase product that cracking generates is discharged through gas outlet, liquid component is collected through a B-grade condensation, reacted residue is piled up in reactor bottom。Product pyrolysis gas 6.1%, liquefaction oil 56.5%, white carbon black 37.4%, after testing, in liquefaction oil, arene content reaches 60.5%。
Embodiment 2
Damaged tire is cut, crush and after process of milling, make waste rubber powder particle size range at 0.1-5.0mm, it is dried to water content less than 2%, the USY catalyst of addition 1% stirs, then render in tank reactor, pass into nitrogen and replace whole response system, system is made to be under oxygen free condition, it is warming up to 200 DEG C with 15 DEG C/min, intensification terminates rear constant temperature 15min, 500 DEG C are risen to afterwards with 20 DEG C/min heating rate, at such a temperature through the catalytic cracking reaction of 15min, the high temperature gas-phase product that cracking generates is discharged through gas outlet, liquid component is collected through a B-grade condensation, reacted residue is piled up in reactor bottom。Product pyrolysis gas 10.2%, liquefaction oil 53.6%, white carbon black 36.2%, after testing, arene content 48.0% in liquefaction oil。
Embodiment 3
Damaged tire is cut, crush and after process of milling, make waste rubber powder particle size range at 0.1-5.0mm, it is dried to water content less than 2%, the beta catalyst of addition 1% stirs, then render in tank reactor, pass into nitrogen and replace whole response system, system is made to be under oxygen free condition, it is warming up to 220 DEG C with 15 DEG C/min, intensification terminates rear constant temperature 5min, 500 DEG C are risen to afterwards with 25 DEG C/min heating rate, at such a temperature through the catalytic cracking reaction of 10min, the high temperature gas-phase product that cracking generates is discharged through gas outlet, liquid component is collected through a B-grade condensation, reacted residue is piled up in reactor bottom。Product pyrolysis gas 8.3%, liquefaction oil 53.2%, white carbon black 38.5%, after testing, arene content 50.0% in liquefaction oil。
Embodiment 4
Damaged tire is cut, crush and after process of milling, make waste rubber powder particle size range at 0.1-5.0mm, it is dried to water content less than 2%, the SAPO-11 catalyst of addition 1% stirs, then render in tank reactor, pass into nitrogen and replace whole response system, system is made to be under oxygen free condition, it is warming up to 200 DEG C with 15 DEG C/min, intensification terminates rear constant temperature 15min, 500 DEG C are risen to afterwards with 30 DEG C/min heating rate, at such a temperature through the catalytic cracking reaction of 10min, the high temperature gas-phase product that cracking generates is discharged through gas outlet, liquid component is collected through a B-grade condensation, reacted residue is piled up in reactor bottom。Product pyrolysis gas 10.6%, liquefaction oil 54.0%, white carbon black 35.4%, after testing, arene content 49.0% in liquefaction。
Above content is the further description present invention done in conjunction with specific embodiment, it is impossible to assert that specific embodiment of the invention is confined to these explanations。For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, it is also possible to make some simple deduction or replace, protection scope of the present invention all should be considered as belonging to。
Claims (8)
1. the method that high aromatic hydrocarbons liquefaction oil is prepared in a scrap rubber two-step catalysis pyrolysis, it is characterised in that comprise the steps:
(1) scrap rubber pretreatment；
(2) low temperature liquefies at a slow speed: after scrap rubber and catalyst mix, being warming up to 180-240 DEG C under anaerobic, heating rate is 10-15 DEG C/min, heats up and terminates rear constant temperature 5-20min, is warming up to thermostatic process and all carries out under negative pressure or normal pressure；
(3) high-temperature quick solution: under anaerobic, is warming up to 400-600 DEG C by the reactant of low temperature post liquefaction at a slow speed under-30～20KPa, and heating rate is 15-30 DEG C/min, heats up and terminates rear constant temperature 10-20min；
(4) thermal decomposition product post processing: reaction afterproduct carries out gas-solid and gas-liquid separation, obtains pyrolysis gas, coke and liquefaction oil。
2. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 1, it is characterized in that: described step (1) includes scrap rubber cutting, crushes, grinds, sieves and dried, making waste rubber powder particle size range at 0.1-5.0mm, moisture content is lower than 2%。
3. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 2, it is characterised in that: described dried is under inert gas shielding, dry at 80-130 DEG C。
4. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 1, it is characterised in that: in described step (4), coke is removed by thermal decomposition product through cyclone separator, the condensed acquisition liquefaction oil of gas。
5. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 1, it is characterised in that: in described step (2), catalyst adds quality is the 0.1-2% of rubber powder。
6. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 5, it is characterised in that: described catalyst is the mixture of one or more in ZSM-5, USY, β, SAPO-11, ZSM-22 molecular sieve。
7. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 6, it is characterised in that: described catalyst is Powdered, and silica alumina ratio is 4-80, specific surface area 150-600mm2/ g, 5-8 angstrom of aperture。
8. the method that high aromatic hydrocarbons liquefaction oil is prepared in scrap rubber two-step catalysis pyrolysis according to claim 7, it is characterised in that: described catalyst mean diameter 50 μm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610251249.9A CN105694942A (en) | 2016-04-21 | 2016-04-21 | Method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610251249.9A CN105694942A (en) | 2016-04-21 | 2016-04-21 | Method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber |
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| CN201610251249.9A Pending CN105694942A (en) | 2016-04-21 | 2016-04-21 | Method for preparing high aromatic liquefied oil by two-step catalytic pyrolysis of waste rubber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916601A (en) * | 2017-03-29 | 2017-07-04 | 山东铂铠环保科技有限公司 | A kind of apparatus and method of the junked tire pyrolysis low ash content low-sulfur carbon black of production |
| CN109943358A (en) * | 2019-04-04 | 2019-06-28 | 福建澳林镁环保科技有限公司 | A kind of macromolecule tiny structure thermal-cracking method for waste tire |
| CN114045523A (en) * | 2021-12-02 | 2022-02-15 | 郑州轻工业大学 | Waste tire pyrolytic carbon catalyst, preparation method and application |
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| CN1117517A (en) * | 1994-08-24 | 1996-02-28 | 中国长江动力公司(集团) | Method and equipment for catalytic cracking waste rubber |
| US20030079664A1 (en) * | 2001-10-26 | 2003-05-01 | Zhian Yu | Tire recycling process |
| CN101089124A (en) * | 2006-06-15 | 2007-12-19 | 任丽娟 | Waste tyre cracking process and apparatus |
| CN104531198A (en) * | 2014-12-19 | 2015-04-22 | 河北科技大学 | Process for thermal cracking of waste tires |
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2016
- 2016-04-21 CN CN201610251249.9A patent/CN105694942A/en active Pending
Patent Citations (4)
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| CN1117517A (en) * | 1994-08-24 | 1996-02-28 | 中国长江动力公司(集团) | Method and equipment for catalytic cracking waste rubber |
| US20030079664A1 (en) * | 2001-10-26 | 2003-05-01 | Zhian Yu | Tire recycling process |
| CN101089124A (en) * | 2006-06-15 | 2007-12-19 | 任丽娟 | Waste tyre cracking process and apparatus |
| CN104531198A (en) * | 2014-12-19 | 2015-04-22 | 河北科技大学 | Process for thermal cracking of waste tires |
Non-Patent Citations (1)
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| 沈伯雄: "《固体废物处理与处置》", 31 August 2010, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916601A (en) * | 2017-03-29 | 2017-07-04 | 山东铂铠环保科技有限公司 | A kind of apparatus and method of the junked tire pyrolysis low ash content low-sulfur carbon black of production |
| CN109943358A (en) * | 2019-04-04 | 2019-06-28 | 福建澳林镁环保科技有限公司 | A kind of macromolecule tiny structure thermal-cracking method for waste tire |
| CN109943358B (en) * | 2019-04-04 | 2021-08-31 | 福建澳林镁环保科技有限公司 | Macromolecule micro-negative pressure thermal cracking method for waste tires |
| CN114045523A (en) * | 2021-12-02 | 2022-02-15 | 郑州轻工业大学 | Waste tire pyrolytic carbon catalyst, preparation method and application |
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Application publication date: 20160622 |