CN108203588B - Method for treating waste tire by nitrogen atmosphere low-temperature pyrolysis - Google Patents
Method for treating waste tire by nitrogen atmosphere low-temperature pyrolysis Download PDFInfo
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- CN108203588B CN108203588B CN201810091652.9A CN201810091652A CN108203588B CN 108203588 B CN108203588 B CN 108203588B CN 201810091652 A CN201810091652 A CN 201810091652A CN 108203588 B CN108203588 B CN 108203588B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a method for treating waste tires by low-temperature pyrolysis in a nitrogen atmosphere. The method mainly comprises the following steps: (1) uniformly mixing the waste tire powder crushed to 60-100 meshes and the oil according to a certain proportion to prepare oil cement; (2) conveying the oil cement slurry to a pyrolysis reactor by a pump, wherein the reaction pressure is 0.01-4 Mpa; (3) the reaction temperature is 230-350 ℃, and the retention time is 30-120 min; (4) pyrolysis gas can be used as heat required by a fuel gas supply device after separation and purification, and liquid-solid products are separated to obtain pyrolysis oil and pyrolysis carbon black; (5) continuously using heavy components in the pyrolysis oil as the oil distribution for recycling; (6) pyrolytic carbon black is used to provide the heat required by the device or is modified for use as a tire reinforcing carbon black. The method uses the oil as the pulping solvent, the oil cement can realize the continuous feeding and discharging of the waste tire pyrolysis device, the process operation is greatly simplified, and the method has the advantages of low pyrolysis temperature, low pyrolysis gas yield, high pyrolysis oil yield, good pyrolysis carbon black quality and the like.
Description
Technical Field
The invention belongs to the technical field of rubber thermal cracking, and particularly relates to a method for treating waste tires through low-temperature pyrolysis in a nitrogen atmosphere.
Background
By the end of 2016, the quantity of motor vehicles in China reaches 2.9 million, wherein 1.94 million vehicles are kept, and meanwhile, about 3 million waste tires are generated in 2016 all year round, and the weight of the waste tires is over 1000 million tons. The waste rubber is difficult to degrade under natural conditions, and long-term accumulation not only occupies land, but also is easy to cause fire and environmental pollution due to breeding of mosquitoes, and is a typical black pollution source. At present, the waste tires are mainly treated by the following modes: (1) the method is used for dock guardrails, river and sea dams, amusement facilities and the like, but the tire retreading is extremely low in treatment capacity (2), the requirements on waste tires are high, the retreading times are limited (3), the rubber powder is prepared by crushing, the energy consumption is high, the treatment capacity is small (4), the pyrolysis is performed, the waste tires can be pyrolyzed to obtain products with higher economic values such as pyrolysis oil, pyrolysis gas, carbon black and steel wires, and the method is a new technology capable of maximizing resource utilization of the waste tires. Application publication No. CN 104212471a, title of the invention: the comprehensive utilization method of the waste tires comprises the following steps: the waste tire powder is heated at a speed of about 106K/s under the action of the plasma, and is subjected to pyrolysis gasification reaction, the collected gas can be used as mixed combustion gas, and the residual solid can be used as carbon black. The comprehensive utilization method of the waste tire adopts the plasma pyrolysis gasification principle to treat the waste tire to obtain two usable products of combustible gas and carbon black. The method of the invention has simple operation and low cost, not only eliminates pollution, but also recycles high-quality energy and resources. Application publication No. CN 103695021a, title of the invention: a method for preparing pyrolytic oil by co-pyrolysis liquefaction of biomass and waste tires comprises the steps of crushing and drying a biomass raw material and a waste tire raw material respectively, carrying out a thermal cracking reaction on the two raw materials respectively to obtain thermal cracking steam, mixing the two thermal cracking steam in a certain proportion, carrying out a co-pyrolysis reaction on the two thermal cracking steam through a zeolite solid catalyst under the action of the catalyst to generate co-thermal cracking steam, and carrying out primary condensation and secondary condensation on the co-thermal cracking steam to obtain the pyrolytic oil. The method controls the mixing proportion of the two thermal cracking steam by adjusting the flow rate of the two thermal cracking steam, effectively solves the problems of insufficient co-thermal cracking and poor pyrolysis effect caused by different specific gravity and thermal weight loss intervals of the biomass and the waste tire, improves the co-thermal cracking effect of the biomass and the waste tire, and improves the quality of the co-thermal cracking product pyrolysis oil. However, the existing pyrolysis process has the problems of high pyrolysis temperature, large energy consumption, high pyrolysis gas yield, incapability of continuous production and the like.
Disclosure of Invention
The invention aims to provide a method for preparing pyrolysis gas, pyrolysis oil and pyrolysis carbon black by rapidly pyrolyzing and treating waste tires at a lower temperature and enabling the device to continuously operate. The method has mild process conditions and low energy consumption, can realize continuous production, can improve the yield of pyrolysis oil and reduce the yield of pyrolysis gas.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for treating waste tires by nitrogen atmosphere low-temperature pyrolysis comprises the following steps:
(1) mixing the waste tire powder and the oil in a certain proportion to obtain oil cement slurry;
(2) conveying the oil cement paste to a pyrolysis reactor through a pump for pyrolysis reaction, wherein the reaction temperature is 230-350 ℃;
(3) separating and purifying the pyrolysis gas to be used as fuel gas, and separating liquid-solid products to obtain pyrolysis oil and pyrolysis carbon black;
(4) continuously using heavy components in the pyrolysis oil as the oil distribution for recycling;
(5) pyrolytic carbon black is used to provide the heat required by the device or is modified for use as a tire reinforcing carbon black.
Further, a preferred embodiment of the present invention: the mesh number of the waste tire powder is 60-100 meshes.
Further, a preferred embodiment of the present invention: the oil used for preparing the oil cement paste is one of catalytic cracking oil paste, coal tar and residual oil.
Further, a preferred embodiment of the present invention: the reaction pressure of the pyrolysis reaction is 0.01-4 Mpa.
Further, a preferred embodiment of the present invention: the residence time of the pyrolysis reaction is 30-120 min.
The invention has the beneficial effects that:
according to the invention, the waste tire is subjected to low-temperature pyrolysis treatment in a nitrogen atmosphere, the reaction temperature is lower, the temperature is reduced by about 100 ℃ compared with the conventional single pyrolysis of the waste tire, the energy consumption of the device is reduced, the secondary reaction is relieved, the yield of pyrolysis gas is reduced, and the yield of pyrolysis oil is improved; the tyre rubber powder and the oil are prepared into the rubber cement, so that the device can continuously feed and discharge materials, and the process operation is greatly simplified.
The invention has simple process flow and mild conditions, effectively separates and utilizes the pyrolysis gas, the oil and the carbon black, does not pollute the environment, maximizes the resource utilization of the waste tire and has great industrial popularization value.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and the described examples are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
As shown in fig. 1, a method for low-temperature pyrolysis treatment of waste tires in nitrogen atmosphere comprises the following steps:
(1) mixing the waste tire powder and the oil in a certain proportion to obtain oil cement slurry;
(2) conveying the oil cement paste to a pyrolysis reactor through a pump for pyrolysis reaction, wherein the reaction temperature is 230-350 ℃;
(3) separating and purifying the pyrolysis gas twice as fuel gas stripping, and separating liquid-solid products to obtain pyrolysis oil and pyrolysis carbon black;
(4) continuously using heavy components in the pyrolysis oil as the oil distribution for recycling;
(5) pyrolytic carbon black is used to provide the heat required by the device or is modified for use as a tire reinforcing carbon black.
The proportion of the oil cement in the examples is waste tire powder: the catalytic cracking slurry oil is 1:3, and the mesh number of the waste tire rubber powder is 60 meshes and 100 meshes.
Example 1
The method comprises the steps of uniformly mixing waste tire powder crushed to 60 meshes with catalytic cracking slurry oil according to a ratio of 1:3 to prepare slurry oil, conveying the slurry oil to a pyrolysis reactor through a pump to perform pyrolysis reaction, wherein the reaction pressure is 2Mpa, the reaction temperature is 230 ℃, the retention time is 120min, pyrolysis gas is separated and purified to obtain fuel gas, liquid and solid products can be separated to obtain pyrolysis oil and pyrolysis carbon black, heavy components in the pyrolysis oil are continuously used as blending oil to be recycled, and the pyrolysis carbon black can be used for providing heat required by a device or used as tire reinforcing carbon black through modification. The yield of pyrolysis products of the waste tires was: 1.30% of pyrolysis gas, 53.57% of pyrolysis oil and 45.13% of pyrolysis carbon black.
Example 2
The method comprises the steps of uniformly mixing waste tire powder crushed to 100 meshes with catalytic cracking slurry oil according to a ratio of 1:3 to prepare slurry oil, conveying the slurry oil to a pyrolysis reactor through a pump to perform pyrolysis reaction, wherein the reaction pressure is 0.01Mpa, the reaction temperature is 350 ℃, the retention time is 120min, pyrolysis gas is separated and purified to obtain fuel gas, liquid and solid products can be separated to obtain pyrolysis oil and pyrolysis carbon black, heavy components in the pyrolysis oil are continuously used as oil, and the pyrolysis carbon black can be used for providing heat required by a device or used as tire reinforcing carbon black through modification. The yield of pyrolysis products of the waste tires was: 13.12% of pyrolysis gas, 46.35% of pyrolysis oil and 40.53% of pyrolysis carbon black.
Example 3
The method comprises the steps of uniformly mixing waste tire powder crushed to 60 meshes with catalytic cracking slurry oil according to a ratio of 1:3 to prepare slurry oil, conveying the slurry oil to a pyrolysis reactor through a pump to perform pyrolysis reaction, wherein the reaction pressure is 2Mpa, the reaction temperature is 350 ℃, the retention time is 30min, pyrolysis gas is separated and purified to obtain fuel gas, liquid and solid products can be separated to obtain pyrolysis oil and pyrolysis carbon black, heavy components in the pyrolysis oil are continuously used as blending oil to be recycled, and the pyrolysis carbon black can be used for providing heat required by a device or used as tire reinforcing carbon black through modification. The yield of pyrolysis products of the waste tires was: 8.29 percent of pyrolysis gas, 53.01 percent of pyrolysis oil and 38.71 percent of pyrolysis carbon black.
Example 4
The method comprises the steps of uniformly mixing waste tire powder crushed to 60 meshes with catalytic cracking slurry oil according to a ratio of 1:3 to obtain slurry oil, conveying the slurry oil and nitrogen together through a pump to a pyrolysis reactor for pyrolysis reaction, wherein the reaction pressure is 4Mpa, the reaction temperature is 330 ℃, the retention time is 60min, pyrolysis gas is separated and purified to obtain fuel gas, liquid and solid products can be separated to obtain pyrolysis oil and pyrolysis carbon black, heavy components in the pyrolysis oil are continuously used as oil, and the pyrolysis carbon black can be used for providing heat required by a device or used as tire reinforcing carbon black through modification. The yield of pyrolysis products of the waste tires was: pyrolysis gas 6.66%, pyrolysis oil 54.84%, and pyrolysis carbon black 38.49%.
Example 5
The method comprises the steps of uniformly mixing waste tire powder crushed to 60 meshes with coal tar according to a ratio of 1:3 to prepare oil cement, conveying the oil cement and nitrogen to a pyrolysis reactor through a pump for pyrolysis reaction, wherein the reaction pressure is 4Mpa, the reaction temperature is 330 ℃, the retention time is 60min, pyrolysis gas is separated and purified to obtain fuel gas, liquid and solid products can be separated to obtain pyrolysis oil and pyrolysis carbon black, heavy components in the pyrolysis oil are continuously used as oil, and are recycled, and the pyrolysis carbon black can be used for providing heat required by a device or used as tire reinforcing carbon black through modification. The yield of pyrolysis products of the waste tires was: 8.47% of pyrolysis gas, 52.01% of pyrolysis oil and 39.52% of pyrolysis carbon black.
Example 6
The method comprises the steps of uniformly mixing waste tire powder crushed to 60 meshes with residual oil according to a ratio of 1:3 to prepare oil cement, conveying the oil cement and nitrogen to a pyrolysis reactor through a pump for pyrolysis reaction, wherein the reaction pressure is 4Mpa, the reaction temperature is 330 ℃, the retention time is 60min, pyrolysis gas is separated and purified to obtain fuel gas, liquid and solid products can be separated to obtain pyrolysis oil and pyrolysis carbon black, heavy components in the pyrolysis oil are continuously used as oil, and are recycled, and the pyrolysis carbon black can be used for providing heat required by a device or used as tire reinforcing carbon black through modification. The yield of pyrolysis products of the waste tires was: 9.82% of pyrolysis gas, 49.25% of pyrolysis oil and 40.93% of pyrolysis carbon black.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (1)
1. The method for treating the waste tire by the low-temperature pyrolysis in the nitrogen atmosphere is characterized by comprising the following steps of:
(1) mixing the waste tire powder and the oil in a certain proportion to obtain oil cement slurry;
(2) conveying the oil cement paste to a pyrolysis reactor through a pump for pyrolysis reaction, wherein the reaction temperature is 230-350 ℃;
(3) separating and purifying the pyrolysis gas to be used as fuel gas, and separating liquid-solid products to obtain pyrolysis oil and pyrolysis carbon black;
(4) continuously using heavy components in the pyrolysis oil as the oil distribution for recycling;
(5) pyrolytic carbon black is used to provide the heat required by the device or modified for use as tire reinforcing carbon black;
the mesh number of the waste tire powder is 60-100 meshes;
the oil used for preparing the oil cement paste is one of catalytic cracking oil paste, coal tar and residual oil;
the reaction pressure of the pyrolysis reaction is 2-4 Mpa;
the residence time of the pyrolysis reaction is 30-120 min.
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| CN109628130A (en) * | 2019-01-29 | 2019-04-16 | 中国石油大学(华东) | A kind of pretreating process refined altogether for heavy oil and tire glue powder |
| CN110075793A (en) * | 2019-04-16 | 2019-08-02 | 江苏大学 | A kind of nano-carbon material and its preparation method and use of damaged tire preparation |
| CN113293023A (en) * | 2021-06-24 | 2021-08-24 | 南京林业大学 | Method for preparing high-quality oil from waste tires |
| CN114106592A (en) * | 2021-11-05 | 2022-03-01 | 航天环境工程有限公司 | High-temperature plasma purification treatment method for waste tire pyrolysis carbon black |
| CN115404089A (en) * | 2022-08-30 | 2022-11-29 | 光大绿色环保技术服务(江苏)有限公司 | Waste tire cracking device adopting molten salt and carbon black for synergistic heating and application |
| CN115851301A (en) * | 2022-11-04 | 2023-03-28 | 中国科学院广州能源研究所 | Method for preparing low-oxygen high-quality pyrolysis oil by co-pyrolysis of waste tires and waste polyolefin plastics |
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| DE4311034A1 (en) * | 1993-04-03 | 1994-10-06 | Veba Oel Ag | Process for the extraction of chemical raw materials and fuel components from old or waste plastic |
| CN1034739C (en) * | 1993-07-23 | 1997-04-30 | 陈黄传 | Pyrolysis process for waste tyre rubber |
| JPH08120113A (en) * | 1994-10-26 | 1996-05-14 | Nippon Steel Corp | Method for carrying out oiling treatment of waste plastic containing polyesters |
| JPH10292177A (en) * | 1997-04-16 | 1998-11-04 | Tohoku Electric Power Co Inc | Conversion of plastic into oil, and apparatus therefor |
| US7692050B2 (en) * | 2003-03-28 | 2010-04-06 | Ab-Cwt, Llc | Apparatus and process for separation of organic materials from attached insoluble solids, and conversion into useful products |
| DE102006061217B3 (en) * | 2006-12-22 | 2008-06-05 | Buchert, Jürgen | Processing clarified sludge to produce fuel, e.g. for electricity generation, by mixing with biomass, thermally cracking and fluidizing, gasifying and condensing gasified product |
| CN101812314B (en) * | 2009-02-20 | 2013-06-19 | 上海金匙环保科技股份有限公司 | Low-temperature catalytic cracking method with high-value utilization of waste tire |
| CA2783608A1 (en) * | 2012-07-23 | 2014-01-23 | Lucie Wheeler | Environmental process to transform contaminated or uncontaminated feed materials into useful products, uses of the process, products thereby obtained and uses thereof, manufacturing of the corresponding plant |
| CN104073003A (en) * | 2014-06-21 | 2014-10-01 | 太原科技大学 | Road asphalt modifier and preparation method thereof |
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