CN109517612B - Continuous, efficient and green waste tire superheated steam energy conversion method - Google Patents
Continuous, efficient and green waste tire superheated steam energy conversion method Download PDFInfo
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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
- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
- C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
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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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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a continuous, efficient and green waste tire superheated steam energy conversion method, which comprises the following steps of: (1) crushing the waste tire into pieces; (2) taking the mass of the waste tire as a reference, adding 0.6-1.4% of a mixture of calcium chloride and calcium oxide into the scrap tire; (3) carrying out pyrolysis reaction at the temperature of 250-400 ℃ in an oxygen-free protective atmosphere; (4) introducing superheated steam into the pyrolysis reaction product at the temperature of 800-900 ℃, performing steam conversion reaction on the pyrolysis reaction product to generate hydrogen-rich combustible gas, and performing separation and purification treatment; the method solves the problems of high energy consumption, low cracking efficiency, difficult comprehensive utilization of cracking products, no environmental protection requirement, low controllability of the cracking treatment process and the like in the cracking process of the waste tire rubber, and realizes energy conversion, cleanness and high-efficiency utilization of the waste tire by pyrolysis and conversion reaction with high-temperature steam under medium-high temperature conditions (800-900 ℃).
Description
Technical Field
The invention relates to a waste tire treatment method, in particular to a continuous, efficient and green waste tire superheated steam energy conversion method.
Background
The tyre is mainly composed of rubber (including natural rubber and synthetic rubber), carbon black and various organic and inorganic auxiliary agents (including plasticizer, anti-aging agent, sulfur, zinc oxide and the like). With the continuous and rapid development of economic society, the automobile holding amount in the world will continue to rapidly increase, the accumulated amount of waste tires reaches 30 hundred million, wherein, the number of discarded tires per year in China exceeds one hundred million, which accounts for one third of the world, and 2000 million tons of waste tires are estimated to be generated in China by 2020. A large amount of waste tires waste precious rubber resources, meanwhile, a large amount of waste tires are accumulated to occupy land, black pollution which is more difficult to treat than plastic pollution (white pollution) is also formed, and the reasonable disposal of the waste tires becomes an urgent global environmental problem.
The waste tires are reusable resources, and the recycling and comprehensive utilization level of the waste tires is one of the important marks of national economic development. The waste tire treatment must accord with the principle of resource, harmlessness and reduction of waste treatment, and the current comprehensive utilization ways of the waste tires mainly comprise renovation, reclaimed rubber and rubber powder, heat energy utilization, pyrolysis and the like.
At present, the retreading rate of the tires in China is only 26:1, and particularly the retreading rate of the tires of a passenger car is almost zero. The reclaimed rubber refers to rubber which is prepared by crushing, heating, mechanically treating and other physical and chemical processes of waste vulcanized rubber, so that the waste vulcanized rubber is changed into rubber which has plasticity and viscosity and can be vulcanized again. The car tire which accounts for nearly half of the production amount of the waste tire has extremely low value when being used for producing reclaimed rubber and rubber powder. Practice shows that the waste rubber is used for producing reclaimed rubber, a large amount of energy is consumed in the production process, various performance indexes of vulcanized rubber in the reclaimed rubber are not as good as those of waste tires before treatment, and meanwhile, the high-temperature high-pressure dynamic desulfurization process in the production process also has the defects of high energy consumption, low additional value, prominent secondary pollution generation problem and the like.
The tires have very high heat value (2937MJ/kg), the heat value per kilogram is 69 percent higher than that of wood, 10 percent higher than that of bituminous coal and 4 percent higher than that of coke, so that a heat energy utilization method (a cement kiln, an industrial boiler, a power generation boiler and the like) directly used as fuel is an important method for comprehensively treating and utilizing the waste tires. However, in the aerobic combustion process, highly toxic carcinogen dioxin is easily generated, so the equipment cost is high, and complicated flue gas treatment equipment is required to be configured in order to meet the requirement of environment protection for emission.
The pyrolysis of the waste tire refers to a process that under the working condition of no oxygen or oxygen deficiency and at a proper temperature, macromolecules with unsaturated bonds in the main chain of rubber are broken, products mainly comprise monomers, dimers and fragments, products are polymerized into a plurality of olefins again, volatile substances are removed, and solid carbon is formed, and the products mainly comprise pyrolysis oil, solid mainly comprising crude carbon black and non-condensable combustible gas. According to the pyrolysis temperature, the method can be divided into high-temperature pyrolysis (1000 ℃), medium-temperature pyrolysis (600-700 ℃) and low-temperature pyrolysis (600 ℃). The pyrolysis process has the advantages that because the oxygen-deficient decomposition is adopted, the secondary pollution to the atmospheric environment is favorably reduced, and the generation and pollution of dioxin can be controlled; most of harmful components such as sulfur, heavy metals and the like in the waste are fixed in the solid black carbon and are effectively recycled.
At present, pyrolysis of waste tires mainly includes three types of processes, i.e., thermal cracking, catalytic degradation, microwave depolymerization, and the like, and the thermal cracking process includes atmospheric inert gas pyrolysis (for example, "a continuous cracking process and apparatus" disclosed in patent document No. CN104910948A, "a continuous steam cracking apparatus label and a cracking furnace for use in the continuous steam cracking apparatus label" disclosed in patent document No. CN101555413A "), vacuum pyrolysis, molten salt pyrolysis: (1) and (3) pyrolyzing the inert gas at normal pressure: the waste rubber is heated to 500 ℃ in an inert gas, and 35% (mass fraction of the waste rubber, the same applies hereinafter) of solid residue (mainly, crude carbon black containing 0.2 mass fraction of sulfur and 0.10 to 0.15 mass fraction of ash), 55% of oil (containing 0.51 mass fraction of aromatic oil and 0.33 mass fraction of crude naphtha) and 3% of gas can be obtained. (2) Vacuum pyrolysis: the vacuum pyrolysis is to decompose under reduced pressure and low temperature, and to crack the waste rubber under the conditions of total pressure of 2-20 kPa and temperature of 510 ℃, so that 50% of oil, 25% of carbon black, 9% of steel, 5% of fiber and 11% of gas can be obtained; under the conditions of total pressure of 0.3kPa and temperature of 420 ℃, 55 percent of oil product, 35 percent of solid and 10 percent of gas can be obtained. (3) Pyrolysis of molten salt: the tyre crumb was dipped into a lithium chloride/potassium chloride eutectic and heated to 500 ℃ to yield 47% oil, 45% solid residue and 12% gas.
At present, thermal cracking equipment mainly comprises a moving bed, a fluidized bed, a fixed bed and a rotary kiln. The thermal cracking equipment for scrap tires not only needs to meet the temperature reaction conditions, but also needs to fully consider the complexity of feeding, the sealing performance of the cracking equipment and supporting facilities so as to meet strict environmental protection requirements. At present, in all cracking processes, substances to be cracked are put into a cracker for cracking, main target products are liquid and solid products, so that the coking in the equipment is easily caused, and pyrolysis products are subjected to multistage condensation separation and filtration, so that the main products of low-temperature pyrolysis in waste tires, namely pyrolysis oil and solid components mainly comprising crude carbon black, are extremely complicated due to extremely complicated pyrolysis equipment and process conditions, the quality is difficult to ensure, the large-scale industrial application cannot be realized, and the obvious defects still exist in the analysis of benefit targets of three major factors, namely environmental protection, social benefit and economy.
The patent document with the publication number of CN105925293A discloses a self-dedusting type waste tire pyrolysis and cracking system, which provides a self-dedusting type waste tire pyrolysis and cracking system based on heat accumulation type radiant tube heating, the system can perform two operations of pyrolysis and cracking, oil gas generated by pyrolysis enters a particle bed dust removal device, the oil gas is filtered and dedusted, clean oil gas enters a cracking chamber, the dedusting pressure of subsequent processes is reduced, macromolecular tar molecules are cracked into micromolecular gaseous hydrocarbons, and the reactor can generate a large amount of cracked gas, so that the problem that the produced pyrolysis oil is difficult to use is solved. However, in the technology, the pyrolysis chamber and the cracking chamber are communicated, and the pyrolysis and the cracking processes are carried out by heating through the heat accumulating type radiation pipe, so that the pyrolysis and the cracking products are easy to coke at the wall of the heat accumulating type radiation pipe to influence the reaction efficiency, and meanwhile, solid products formed by components such as carbon black in the tire are still difficult to utilize.
Disclosure of Invention
The invention aims to provide a continuous, efficient and green method for converting superheated steam energy of waste tires, which aims to solve the problems of high energy consumption, low cracking efficiency, difficulty in comprehensive utilization of cracking products, incapability of meeting the requirement of environmental protection, low controllability of a cracking treatment process and the like in the cracking process of tire rubber.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a continuous high-efficiency green waste tire superheated steam energy conversion method comprises the following steps:
(1) scrap tires are broken into pieces.
(2) Taking the mass of the waste tire as a reference, adding 0.6-1.4% of a mixture of calcium chloride and calcium oxide into the scrap-shaped waste tire, preferably, the mass ratio of the calcium chloride to the calcium oxide is 2: 1.
(3) Carrying out pyrolysis reaction at the temperature of 250-400 ℃ in an oxygen-free protective atmosphere; the oxygen-free protective atmosphere is realized by oxygen discharge treatment by introducing superheated steam.
(4) Introducing superheated steam into a liquid-solid mixture (high-boiling point and macromolecular heavy components, carbon black and the like) after pyrolysis reaction at the temperature of 800-900 ℃ to perform steam conversion reaction, wherein the reaction formulas are shown as formulas (1) and (2), and generating hydrogen-rich combustible gas, and performing separation and purification treatment.
The pyrolysis reaction enables light-component combustible gas such as methane generated by pyrolysis of waste tires to flow to a conversion gas pipeline for collection, and liquid-solid mixture such as carbon black, heavy-component substances with high boiling points and macromolecules in the tire waste (after the pyrolysis reaction) and the like are subjected to conversion reaction with high-temperature water vapor under medium-high temperature conditions (800-900 ℃).
The pyrolytic carbon black component in the tire and high-temperature water vapor perform water gas shift reaction as shown in formula (1), the carbon black is converted into CO, and hydrogen H generated by the water gas shift reaction2To be recycled as a combustible gas:
C+H2O(g)＝CO+H2(1)
high boiling point, macromolecule heavy component further thermal cracking through chain scission and dehydrogenation reaction in the tire after pyrolysis, hydrocarbon such as methane produced simultaneously passes through reforming reaction with vapor again as formula (2), generates rich hydrogen combustible gas:
CxHy+xH2O(g)＝xCO+(x+y/2)H2(2)
x and y are positive integers.
In summary, the waste tire material is converted into clean combustible energy gas such as hydrogen, methane and the like through pyrolysis and conversion reaction with high-temperature water vapor (superheated steam) under medium-high temperature conditions (800 ℃ -900 ℃), so that the energy conversion and clean and efficient utilization of the waste tire are realized, and the problems of high energy consumption, low cracking efficiency, difficulty in comprehensive utilization of cracking products, no environmental protection requirement, low controllability of the cracking treatment process and the like in the cracking process of the waste tire rubber are solved.
The invention has the advantages and beneficial effects that: (1) the waste tires are mainly heated before 250 ℃, the traditional waste tire thermal cracking mode is completed only by heating to 550-600 ℃, the pyrolysis temperature in the technology of the invention is 250-400 ℃, and the pyrolysis process of the temperature section mainly generates combustible light components such as methane and the likeThe escape of gas greatly reduces the generation of products such as high carcinogen-polycyclic aromatic hydrocarbon and the like in a complete cracking chamber, so that high-boiling point and macromolecular heavy components, carbon black and other substances in the tire waste participate in the subsequent water-based gas conversion reaction; (2) gibbs free energy delta from reaction of carbon with steam to carbon monoxide and hydrogenrGm 0It is known that-146.34T +135248J/mol requires a reaction temperature of higher than 924K (651 ℃ C.) and the reaction proceeds more easily at higher temperatures; on the other hand, chain scission and dehydrogenation reactions of high-boiling-point and macromolecular heavy component, hydrocarbon such as methane and the like and steam reforming reactions are strong endothermic reactions, the temperature of the steam reforming reaction provided by the invention is 800-900 ℃, the temperature can ensure the rapid progress of the reforming reaction, and meanwhile, the consumption cost of reaction fuel and the manufacturing cost of the reactor cannot be obviously improved due to overhigh use temperature; (3) the waste tire material has very low thermal conductivity, and the heating temperature rise needs a long time, and the technology of the invention adopts the superheated steam with good heating effect (high specific heat capacity and large diffusion rate) as the heat conduction medium of the pyrolysis and conversion reaction, thereby improving the reaction speed; (4) in the technology, 0.6-1.4% of mixture of calcium chloride and calcium oxide is added into the scrap tire, so that the pyrolysis efficiency of the scrap tire is improved, the dehydrogenation reaction is promoted to improve the relative content of hydrogen, and the calcium chloride and the calcium oxide are combined with sulfur in the tire waste to form calcium sulfide, so that the formation of harmful sulfur-containing atmosphere products is greatly reduced.
Drawings
FIG. 1 is a front view of a continuous, efficient and green system for converting waste tire superheated steam energy.
FIG. 2 is a right side view of a continuous, efficient, green, waste tire superheated steam energy conversion system.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1 and 2, the continuous, efficient and green waste tire superheated steam energy conversion system comprises:
a pyrolysis system comprising two first pyrolysis devices 2 and second pyrolysis devices 6 (the number of pyrolysis devices is not limited in the present invention) connected in series, wherein the pyrolysis devices (the first pyrolysis device 2 and the second pyrolysis device 6) comprise a pyrolysis feed port, a pyrolysis discharge port, a pyrolysis superheated steam inlet, a pyrolysis gas outlet and a pyrolysis heating device, and the pyrolysis feed port of the first pyrolysis device 2 is provided with a hopper 1 for feeding (feeding broken waste tire fragments). The pyrolysis discharge hole of the first pyrolysis device 2 is connected with the pyrolysis feed hole of the second pyrolysis device 6.
The pyrolysis superheated steam inlet is connected with a superheated steam pipeline 4, and superheated steam is introduced into the pyrolysis device (the first pyrolysis device 2 and the second pyrolysis device 6). The introduced superheated steam can exhaust the air in the pyrolysis device.
The pyrolysis gas outlet is connected with a conversion gas pipeline 3 and used for collecting the converted gas. The combustible gas introduced into the conversion gas pipeline 3 is used as clean energy gas for power generation, combustion heat supply and the like after separation and purification treatment.
The pyrolysis heating device is used for heating the pyrolysis device, the pyrolysis heating device selects an electric heater, the pyrolysis heating device heats the waste tire materials in the first pyrolysis device 2 to 250 ℃, the pyrolysis heating device heats the materials in the second pyrolysis device 6 to 400 ℃, light-component combustible gas such as methane generated by pyrolysis of the waste tires flows to a conversion gas pipeline for collection, and liquid-solid mixture such as carbon black and heavy-component materials with high boiling points and macromolecules in the tire waste materials is subjected to conversion reaction with high-temperature water vapor at 800-900 ℃.
A gas conversion system comprising a conversion device 8 and a combustion chamber 12 heating the conversion device 8. The conversion device 8 comprises a conversion feeding hole, a conversion discharging hole and a conversion superheated steam inlet. In order to further utilize a small amount of unconverted solid products, a conversion discharge hole of the conversion device 8 is connected with a blanking device 10, the blanking device 10 comprises a blanking inlet and a blanking outlet, and the conversion discharge hole is connected with the blanking inlet; a blanking conveying device is arranged in the blanking device 10 and conveys materials from a blanking inlet to a blanking outlet; the discharge outlet is arranged in the combustion chamber 12, and the material at the discharge outlet is combusted in the combustion chamber 12 (the combustion can be carried out by adopting the nozzle 13).
The material at the pyrolysis discharge port of the second pyrolysis device 6 is conveyed to the conversion feed port. A conversion conveying device 9 is arranged in the conversion device 8, a screw conveyor is selected as the conversion conveying device 9, and the conversion conveying device 9 conveys materials from a conversion feeding hole to a conversion discharging hole.
The conversion superheated steam inlet is connected with the superheated steam pipeline 4, so that substances such as high-boiling-point and macromolecular heavy components and carbon black after pyrolysis and the like perform conversion reaction with high-temperature water vapor (superheated steam) in the conversion device 8 under medium-high temperature conditions (800-900 ℃). The temperature can ensure the rapid progress of the conversion reaction, and meanwhile, the consumption cost of reaction fuel and the manufacturing cost of the reactor can not be obviously promoted due to overhigh use temperature.
The pyrolytic carbon black component in the tire and high-temperature water vapor perform water gas shift reaction as shown in formula (1), the carbon black is converted into CO, and hydrogen H generated by the water gas shift reaction2To be recycled as a combustible gas:
C+H2O(g)＝CO+H2(1)
high boiling point, macromolecule heavy component thing in the tire after the pyrolysis is through chain scission and dehydrogenation reaction, further thermal cracking, hydrocarbon such as methane of production again passes through reforming reaction with vapor as following formula (2) with steam simultaneously, generates rich hydrogen combustible gas:
CxHy+xH2O(g)＝xCO+(x+y/2)H2(2)
x and y are positive integers.
In order to utilize the gas generated by the conversion, the conversion gas pipeline 3 is connected with a conversion gas branch, and the conversion gas branch is connected with the combustion chamber 12 to provide combustion gas for the combustion chamber 12, so that the conversion reaction can be carried out independently without depending on external energy.
The combustor 12 below is provided with the combustion chamber export, is provided with discharging device 11 below the combustion chamber export, discharging device 11 includes ejection of compact import and ejection of compact export, ejection of compact import and combustion chamber exit linkage, be provided with ejection of compact conveyor in discharging device 11, spiral conveyer is chooseed for use to ejection of compact conveyor, ejection of compact conveyor 11 carries material (residue) to ejection of compact export from ejection of compact import, will burn the residue and discharge.
A superheated steam generator 14, said superheated steam generator 14 generating superheated steam, i.e. to generate superheated steam to participate in the aqueous gas reforming reaction, said superheated steam being fed to the superheated steam line 4.
The working process is as follows:
the method comprises the steps of crushing waste tires into chips, and adding 0.6-1.4% of a mixture of calcium chloride and calcium oxide into the waste tire chips (materials) by taking the mass of the waste tires as a reference, wherein the mass ratio of the calcium chloride to the calcium oxide is 2: 1. The method comprises the steps of adding a mixture of waste tire fragments (materials), calcium chloride and calcium oxide into a first pyrolysis device 2 through a measuring hopper 1, introducing superheated steam for oxygen discharge treatment, heating the materials in the first pyrolysis device 2 to 250 ℃, introducing the materials into a second pyrolysis device 6, introducing the superheated steam, and pyrolyzing the materials in the second pyrolysis device 6 (at 250-400 ℃). The materials are collected by a conversion gas pipeline through light component combustible gas such as methane generated by pyrolysis of the first pyrolysis device 2 and the second pyrolysis device 6, and liquid-solid mixture materials such as carbon black, heavy component substances with high boiling points and macromolecules in the tire waste participate in subsequent conversion reaction with high-temperature water vapor.
The liquid-solid mixture obtained by pyrolysis is conveyed to a conversion device 8 through a pyrolysis discharge port of a second pyrolysis device 6, superheated steam is introduced into the conversion device 8, and the superheated steam and high-temperature water vapor (superheated steam) are subjected to conversion reaction at the temperature of 800-900 ℃ to be converted into hydrogen-rich clean combustible energy gas. The converted gas flows to the first pyrolysis device 2 and the second pyrolysis device 6 in the conversion device 8 and finally flows to the converted gas pipeline 3, and separation and purification treatment are carried out, so that the combustible gas energy conversion and clean and efficient utilization of the waste tires are realized.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (3)
1. A continuous high-efficiency green waste tire superheated steam energy conversion method is characterized by comprising the following steps:
(1) crushing the waste tire into pieces;
(2) taking the mass of the waste tire as a reference, adding 0.6-1.4% of a mixture of calcium chloride and calcium oxide into the scrap tire;
(3) carrying out pyrolysis reaction at the temperature of 250-400 ℃ in an oxygen-free protective atmosphere;
(4) at the temperature of 800-900 ℃, superheated steam is introduced into the liquid-solid mixture after the pyrolysis reaction to carry out the steam conversion reaction, generate the hydrogen-rich combustible gas, and carry out separation and purification treatment.
2. The continuous high-efficiency green waste tire superheated steam energy conversion method according to claim 1, characterized in that: the mass ratio of the calcium chloride to the calcium oxide is 2: 1.
3. The continuous high-efficiency green waste tire superheated steam energy conversion method according to claim 1, characterized in that: the oxygen-free protective atmosphere is realized by oxygen discharge treatment by introducing superheated steam.
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| CN110396418A (en) * | 2019-06-24 | 2019-11-01 | 翁荣周 | A kind of continuous internal heat type damaged tire pyrolysis reactor |
| CN114181747A (en) * | 2021-10-21 | 2022-03-15 | 北京工业大学 | Method for preparing hydrogen-rich gas by carrying out overheat catalytic conversion on waste organic-inorganic composite material |
| CN115591911B (en) * | 2022-10-12 | 2024-05-28 | 昆明理工大学 | Full-recycling treatment method for waste tires |
| CN115746885A (en) * | 2022-11-08 | 2023-03-07 | 光大环境科技（中国）有限公司 | Fly ash molten salt low-temperature pyrolysis device and method |
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| CN1073591C (en) * | 1997-08-18 | 2001-10-24 | 中国科学院山西煤炭化学研究所 | Method for prodn. of gasolene, diesel oil and carbon black from waste tyre, and prodn. equipment therefor |
| CA2430999C (en) * | 2000-12-08 | 2012-01-10 | Foretop Corporation | Process and gas generator for generating fuel gas |
| CN1944581A (en) * | 2006-10-27 | 2007-04-11 | 清华大学 | Method for continuously thermal decomposing waste tire using gas burning kiln |
| CN105001913B (en) * | 2015-08-18 | 2018-03-27 | 青岛理工大学 | Device for producing combustible gas by pyrolyzing carbon black in tire and preparation method |
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