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CN116463136A - Pyrolysis process of dangerous waste - Google Patents

Pyrolysis process of dangerous waste Download PDF

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Publication number
CN116463136A
CN116463136A CN202310427568.0A CN202310427568A CN116463136A CN 116463136 A CN116463136 A CN 116463136A CN 202310427568 A CN202310427568 A CN 202310427568A CN 116463136 A CN116463136 A CN 116463136A
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CN
China
Prior art keywords
pyrolysis
oil
temperature
gradually
treatment
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Pending
Application number
CN202310427568.0A
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Chinese (zh)
Inventor
宋曦雷
陈晓敏
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Nantong Haizhiyang Environmental Protection Engineering Technology Co ltd
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Nantong Haizhiyang Environmental Protection Engineering Technology Co ltd
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Priority to CN202310427568.0A priority Critical patent/CN116463136A/en
Publication of CN116463136A publication Critical patent/CN116463136A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0208Separation of non-miscible liquids by sedimentation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D36/00Filter circuits or combinations of filters with other separating devices
    • B01D36/04Combinations of filters with settling tanks
    • B01D36/045Combination of filters with centrifugal separation devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D5/00Condensation of vapours; Recovering volatile solvents by condensation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G7/00Distillation of hydrocarbon oils

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention discloses a pyrolysis treatment process of dangerous wastes, which comprises the following steps: drying, and sending the dangerous waste into a pyrolysis furnace through a feeding device, and gradually volatilizing moisture in the material from the material; dry distillation and continuous heating are carried out, and the pyrolysis furnace keeps micro-positive pressure; the substances are heated and condensed into colloid, and simultaneously, the volatile matters which are separated out are gradually reduced, and the colloid is gradually solidified and carbonized, and the heating time is prolonged along with the rise of the temperature; opening the pyrolysis furnace to discharge carbon black after cooling; condensing pyrolysis gas by a condenser, and then enabling non-condensable gas to enter a combustion chamber of the hot blast stove for combustion; oil treatment and separation of pyrolysis oil and water are realized through an oil-water separation device; the separated wastewater enters a sewage treatment station; and delivering the residues into a pyrolysis furnace for secondary pyrolysis. The invention has simple treatment mode and high treatment efficiency, realizes the secondary utilization of waste, does not generate secondary pollution, saves energy, reduces emission and realizes the recycling of energy.

Description

Pyrolysis process of dangerous waste
Technical Field
The invention belongs to the technical field of heat treatment of solid wastes, and particularly relates to a pyrolysis process of dangerous wastes.
Background
Hazardous waste, also referred to as hazardous waste, refers to waste that presents a real or potential hazard to human health or the environment, or refers to waste that is listed in the national hazardous waste list or has hazardous characteristics identified according to the national regulatory hazardous waste identification standards and methods.
Including paint slag, waste resin, oily sludge, waste activated carbon, etc., for solid waste (residues), common physical treatment processes include: compacting, crushing and sorting; the physical and chemical treatment process of the common hazardous waste comprises the following steps: heat treatment (incineration, pyrolysis), curing/stabilization;
the pyrolysis method is a process of utilizing the thermal instability of organic matters in the hazardous waste, heating and distilling the hazardous waste to crack the organic matters, condensing the hazardous waste to form various new gases, liquids and solids, and extracting fuel oil and combustible gas from the hazardous waste. With this treatment method, tar and other substances are produced, and the treatment is complicated.
Because hazardous waste produces source dispersion, output is big, the constitution is complicated, form and nature are changeable, probably contain toxicity, combustibility, explosiveness, radioactivity, corrosivity, reactivity, infectivity and pathogenicity harmful waste or pollutant, even contain pollutant enriched organism, and some substances are difficult to degrade or difficult to handle, the emission has uncertainty and disguise, and these factors lead to the solid waste to produce secondary pollution to resources, ecological environment etc. in its production, emission and treatment process.
Disclosure of Invention
The present invention is directed to a pyrolysis treatment process for hazardous waste, which solves the problems set forth in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a process for the pyrolysis treatment of hazardous waste, the process comprising the steps of:
s1: drying, namely conveying the paint slag, waste resin, oily sludge, waste activated carbon and other dangerous wastes into a pyrolysis furnace through a feeding device, sealing a feeding port after 10-15 tons of the dangerous wastes are filled once, gradually heating for 2-3 hours by using natural gas for combustion in initial production, gradually volatilizing moisture in the materials, and separating out the moisture in the materials only in a physical evaporation mode; heating is continued by utilizing the non-condensable gas generated in pyrolysis;
s2: dry distillation is carried out, heating is carried out continuously, the temperature of the materials is 350-500 ℃, and the pyrolysis furnace is kept at micro positive pressure; the carbonization process is divided into three stages:
(1) Dehydration and decomposition stage: at the initial stage of carbonization operation, the temperature is relatively low, organic matters firstly remove intrinsic water, and gradually decompose to generate low-molecular volatile matters along with the temperature rise;
(2) Cracking stage: with the continuous rising of the carbonization temperature to 220-270 ℃, the macromolecules in the organic matters are broken, namely cracked, so as to obtain liquid organic matters;
(3) Condensation and carbonization stage: when the temperature is further increased to 330-370 ℃, the remainder is thermally condensed into colloid along with the precipitation of water and organic vapor, meanwhile, the volatile matters which are precipitated gradually decrease, the colloid is gradually solidified and carbonized, the carbon content in the generated solid product gradually increases along with the temperature increase to 430-470 ℃ and the heating time is prolonged to 2-3 hours, and the contents of other elements such as hydrogen, oxygen, nitrogen, sulfur and the like gradually decrease;
the main equation for cleavage is as follows:
(-CH 2 -CH 2 ) n →n[C+H 2 +CH 4 +C 2 H 6 +C 3 H 8 +···+C 12 H 26 +···]
s3: cooling, stopping heating and naturally cooling after pyrolysis of materials in the pyrolysis furnace is finished, cooling for 3-5 hours, starting the pyrolysis furnace when the temperature is reduced to below 100 ℃, and discharging carbon black;
s4: condensing, namely enabling gas phase generated by pyrolysis to enter a condensing device, condensing the pyrolysis gas by a condenser (secondary water cooling, water temperature is 25 ℃), enabling generated non-condensable gas to subsequently enter a combustion chamber of a hot blast stove for combustion, generating hot air for supplying heat to the pyrolysis furnace, treating the flue gas after heat supply by a flue gas purification system, discharging the flue gas after the heat supply reaches the standard, and enabling pyrolysis liquid to enter an oil product treatment system;
s5: oil treatment, wherein pyrolysis gas is condensed by a condenser, and generated pyrolysis liquid firstly enters an oil-water separation device, and the oil-water separation device realizes separation of pyrolysis oil and water by utilizing the characteristic of poor intersolubility of an organic phase and water and the action of gravity;
the separated wastewater enters a sewage treatment station; the separated pyrolysis oil enters an automatic deslagging centrifugal sedimentation type filter, and waste residues in the pyrolysis oil are separated by utilizing the action of gravity and centrifugal force respectively;
the liquid enters a distillation tower for distillation, and the light components and the non-condensable gas obtained by the distillation tower are regenerated and burned in a hot blast furnace; the heavy component is used as fuel oil (the fuel oil can be sold) for the furnace, the wastewater enters a sewage treatment station, and the distilled residue remained after distillation is collected and then is sent into a pyrolysis furnace for secondary pyrolysis.
Preferably, in the step S5, the operation temperature of the distillation column is 150-250 ℃, and the operation pressure is normal pressure.
Preferably, the working temperature of the hot blast stove in the step S4 is 850-1150 ℃, the working pressure is-500 Pa to-100 Pa, and the residence time of the non-condensable gas entering the combustion chamber of the hot blast stove is more than 2 seconds.
The invention has the technical effects and advantages that:
1. the pyrolysis process is suitable for pyrolysis of paint slag, waste resin, oily sludge, waste activated carbon and the like, is simple in process and convenient to operate, and can be used for discharging carbon black, fuel oil, non-condensable gas, waste residues and the like after pyrolysis, and the carbon black can be used in the industries of rubber, paint, printing ink and the like, and the fuel oil can be collected for later use.
2. The non-condensable gas enters a hot air combustion furnace, hot air is generated to supply heat for a pyrolysis furnace, waste residues are put into the pyrolysis furnace again for pyrolysis, and waste water and waste gas are discharged after reaching the standard after being treated.
3. The pyrolysis cost is reduced as a whole, secondary pollution is avoided, energy is saved, emission is reduced, and the recycling of energy is realized.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 shows a specific embodiment of a pyrolysis process for hazardous waste according to the present invention:
a process for the pyrolysis treatment of hazardous waste, the process comprising the steps of:
s1: drying, namely conveying the paint slag, waste resin, oily sludge, waste activated carbon and other dangerous wastes into a pyrolysis furnace through a feeding device, sealing a feeding port after 10-15 tons of the dangerous wastes are filled once, gradually heating for 2-3 hours by using natural gas for combustion in initial production, gradually volatilizing moisture in the materials, and separating out the moisture in the materials only in a physical evaporation mode; heating is continued by utilizing the non-condensable gas generated in pyrolysis;
s2: dry distillation is carried out, heating is carried out continuously, the temperature of the materials is 350-500 ℃, and the pyrolysis furnace is kept at micro positive pressure; the carbonization process is divided into three stages:
(1) Dehydration and decomposition stage: at the initial stage of carbonization operation, the temperature is relatively low, organic matters firstly remove intrinsic water, and gradually decompose to generate low-molecular volatile matters along with the temperature rise;
(2) Cracking stage: with the continuous increase of the carbonization temperature to 250 ℃, the macromolecules in the organic matters are broken, namely cracked, so as to obtain liquid organic matters (including tar);
(3) Condensation and carbonization stage: when the temperature is further increased by 350 ℃, the residual substances are thermally condensed into colloid along with the precipitation of water and organic vapor, meanwhile, the volatile substances which are precipitated gradually decrease, the colloid is gradually solidified and carbonized, the carbon content in the generated solid product gradually increases along with the heating of the temperature to 450 ℃ for 2-3 hours (the heating time is specifically determined according to the total amount of materials), and the contents of other elements such as hydrogen, oxygen, nitrogen, sulfur and the like gradually decrease;
the main equation for cleavage is as follows:
(-CH2-CH2)n→n[C+H2+CH4+C2H6+C3H8+·+C12H26+·]
s3: cooling, stopping heating and naturally cooling after pyrolysis of materials in the pyrolysis furnace is finished, cooling for 3-5 hours, starting the pyrolysis furnace when the temperature is reduced to below 100 ℃, and discharging carbon black;
s4: condensing, namely enabling gas phase generated by pyrolysis to enter a condensing device, condensing the pyrolysis gas by a condenser (secondary water cooling, water temperature is 25 ℃), enabling generated non-condensable gas to subsequently enter a combustion chamber of a hot blast stove for combustion, generating hot air for supplying heat to the pyrolysis furnace, treating the flue gas after heat supply by a flue gas purification system, discharging the flue gas after the heat supply reaches the standard, and enabling pyrolysis liquid to enter an oil product treatment system; the working temperature of the hot blast stove is 850-1150 ℃, the working pressure is-500 Pa to-100 Pa, and the residence time of the non-condensable gas entering the combustion chamber of the hot blast stove is more than 2 seconds.
S5: oil treatment, wherein pyrolysis gas is condensed by a condenser, and generated pyrolysis liquid firstly enters an oil-water separation device, and the oil-water separation device realizes separation of pyrolysis oil and water by utilizing the characteristic of poor intersolubility of an organic phase and water and the action of gravity;
the separated wastewater enters a sewage treatment station; the separated pyrolysis oil enters an automatic deslagging centrifugal sedimentation type filter, and waste residues in the pyrolysis oil are separated by utilizing the action of gravity and centrifugal force respectively;
the liquid enters a distillation tower for distillation, the working temperature of the distillation tower is 150-250 ℃, the working pressure is normal pressure, and the light components and the non-condensable gas obtained by the distillation tower are combusted in a regenerative air furnace; the heavy component is used as fuel oil (the fuel oil can be sold) for the furnace, the wastewater enters a sewage treatment station, and the distilled residue remained after distillation is collected and then is sent into a pyrolysis furnace for secondary pyrolysis.
The pyrolysis of organic matters is to utilize the thermal instability of the organic matters, heat the organic matters under the anaerobic condition to thermally crack the organic matters, and crack the organic matters according to the hydrocarbon proportion to form a gas phase (pyrolysis gas) and a solid phase (regenerated carbon) with higher utilization value. Factors influencing the pyrolysis process and yield and composition include pyrolysis temperature, heating rate, gas-solid phase residence time, material size and the like, wherein pyrolysis temperature is a main influencing factor.
Low temperature anaerobic pyrolysis is a complex continuous chemical reaction process, not a simple mechanical bond breaking process from large to small, and there are two kinds of variation trends in intermediate products in the pyrolysis process: firstly, a cracking process from a large molecule to a small molecule; and secondly, a polycondensation process of polymerizing small molecules into larger molecules. A series of secondary reactions also occur during pyrolysis, which in turn undergo two stages: a drying stage and a carbonization stage. The moisture in the materials is separated out only in a physical evaporation mode in a drying stage, and the carbonization stage is a complex chemical reaction process comprising dehydration, cracking, thermal condensation and other reactions; the carbon content in the generated solid product is gradually increased, and the contents of other elements such as hydrogen, oxygen, nitrogen, sulfur and the like are gradually reduced.
The applicant has further stated that the present invention is described by the above examples as to the implementation method and apparatus structure of the present invention, but the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention must be implemented by the above methods and structures. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the implementation method selected for the present invention, addition of steps, selection of specific modes, etc., fall within the scope of the present invention and the scope of the disclosure.
The present invention is not limited to the above embodiments, and all modes of achieving the object of the present invention by adopting the structure and method similar to those of the present invention are within the scope of the present invention.

Claims (3)

1. A pyrolysis treatment process for hazardous wastes is characterized in that: the treatment process comprises the following steps:
s1: drying, namely sending the dangerous waste into a pyrolysis furnace through a feeding device, sealing a feeding hole, gradually heating for 2-3 hours, gradually volatilizing the moisture in the material from the material, and separating out the moisture in the material only in a physical evaporation mode;
s2: dry distillation is carried out, heating is carried out continuously, the temperature of the materials is 350-500 ℃, and the pyrolysis furnace is kept at micro positive pressure; the carbonization process is divided into three stages:
(1) Dehydration and decomposition stage: at the initial stage of carbonization operation, the temperature is relatively low, organic matters firstly remove intrinsic water, and gradually decompose to generate low-molecular volatile matters along with the temperature rise;
(2) Cracking stage: with the continuous rising of the carbonization temperature to 220-270 ℃, the macromolecules in the organic matters are broken, namely cracked, so as to obtain liquid organic matters;
(3) Condensation and carbonization stage: when the temperature is further increased to 330-370 ℃, the remainder is thermally condensed into colloid along with the precipitation of water and organic vapor, meanwhile, the volatile matters which are precipitated gradually decrease, the colloid is gradually solidified and carbonized, the carbon content in the generated solid product gradually increases along with the temperature increase to 430-470 ℃ and the heating time is prolonged to 2-3 hours, and the contents of other elements such as hydrogen, oxygen, nitrogen, sulfur and the like gradually decrease;
the main equation for cleavage is as follows:
(-CH 2 -CH 2 ) n →n[C+H 2 +CH 4 +C 2 H 6 +C 3 H 8 +···+C 12 H 26 +···]
s3: cooling, stopping heating and naturally cooling after pyrolysis of materials in the pyrolysis furnace is finished, cooling for 3-5 hours, starting the pyrolysis furnace when the temperature is reduced to below 100 ℃, and discharging carbon black;
s4: condensing, namely enabling gas phase generated by pyrolysis to enter a condensing device, condensing pyrolysis gas by a condenser, enabling generated non-condensable gas to subsequently enter a combustion chamber of a hot blast stove for combustion, generating hot air for supplying heat to a pyrolysis furnace, treating the flue gas after heat supply by a flue gas purification system, discharging the flue gas after heat supply reaches the standard, and enabling pyrolysis liquid to enter an oil product treatment system;
s5: oil treatment, wherein pyrolysis gas is condensed by a condenser, and generated pyrolysis liquid firstly enters an oil-water separation device, and the oil-water separation device realizes separation of pyrolysis oil and water by utilizing the characteristic of poor intersolubility of an organic phase and water and the action of gravity;
the separated wastewater enters a sewage treatment station; the separated pyrolysis oil enters an automatic deslagging centrifugal sedimentation type filter, and waste residues in the pyrolysis oil are separated by utilizing the action of gravity and centrifugal force respectively;
the liquid enters a distillation tower for distillation, and the light components and the non-condensable gas obtained by the distillation tower are regenerated and burned in a hot blast furnace; the heavy component is used as fuel oil for the furnace, the wastewater enters a sewage treatment station, and the distilled residue remained after distillation is collected and then sent into a pyrolysis furnace for secondary pyrolysis.
2. A process for the pyrolysis treatment of hazardous waste according to claim 1, characterized in that: in the step S5, the working temperature of the distillation tower is 150-250 ℃ and the working pressure is normal pressure.
3. A process for the pyrolysis treatment of hazardous waste according to claim 1, characterized in that: the working temperature of the hot blast stove in the step S4 is 850-1150 ℃, the working pressure is-500 Pa to-100 Pa, and the residence time of the non-condensable gas entering the combustion chamber of the hot blast stove is more than 2 seconds.
CN202310427568.0A 2023-04-20 2023-04-20 Pyrolysis process of dangerous waste Pending CN116463136A (en)

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Application Number Priority Date Filing Date Title
CN202310427568.0A CN116463136A (en) 2023-04-20 2023-04-20 Pyrolysis process of dangerous waste

Publications (1)

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CN116463136A true CN116463136A (en) 2023-07-21

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020093110A1 (en) * 2018-11-08 2020-05-14 Hermal Bio Energy International Pty Ltd Production of products from bio-energy
CN111996019A (en) * 2020-07-13 2020-11-27 南通天地和环保科技有限公司 Paint-containing waste cracking process for harmless and recycling treatment
CN113546946A (en) * 2021-07-23 2021-10-26 浙江中蓝环境科技有限公司 Anaerobic dry distillation treatment method for medical waste
CN114196425A (en) * 2021-12-17 2022-03-18 上海秦鄠工程技术有限公司 Process method and device for preparing charcoal by biomass pyrolysis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020093110A1 (en) * 2018-11-08 2020-05-14 Hermal Bio Energy International Pty Ltd Production of products from bio-energy
CN111996019A (en) * 2020-07-13 2020-11-27 南通天地和环保科技有限公司 Paint-containing waste cracking process for harmless and recycling treatment
CN113546946A (en) * 2021-07-23 2021-10-26 浙江中蓝环境科技有限公司 Anaerobic dry distillation treatment method for medical waste
CN114196425A (en) * 2021-12-17 2022-03-18 上海秦鄠工程技术有限公司 Process method and device for preparing charcoal by biomass pyrolysis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
戴钧樑: "《废润滑油再生》", 31 March 1999, 中国石化出版社, pages: 370 *

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