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WO2017128943A1 - Anaerobic catalytic thermal cracking method for solid waste - Google Patents

Anaerobic catalytic thermal cracking method for solid waste Download PDF

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Publication number
WO2017128943A1
WO2017128943A1 PCT/CN2017/070473 CN2017070473W WO2017128943A1 WO 2017128943 A1 WO2017128943 A1 WO 2017128943A1 CN 2017070473 W CN2017070473 W CN 2017070473W WO 2017128943 A1 WO2017128943 A1 WO 2017128943A1
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WO
WIPO (PCT)
Prior art keywords
cracking
waste
garbage
gas
anaerobic
Prior art date
Application number
PCT/CN2017/070473
Other languages
French (fr)
Chinese (zh)
Inventor
王志成
Original Assignee
王志成
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Publication date
Application filed by 王志成 filed Critical 王志成
Publication of WO2017128943A1 publication Critical patent/WO2017128943A1/en

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Classifications

    • 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
    • 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
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/18—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge
    • C10B47/22—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge in dispersed form
    • C10B47/24—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge in dispersed form according to the "fluidised bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • C10B49/04—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
    • C10B49/08—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
    • C10B49/10—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
    • 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
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C10B57/10—Drying
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a process method for garbage disposal, in particular to a treatment method for non-toxic catalytic thermal cracking of solid waste to achieve harmless discharge.
  • garbage Human activities will inevitably produce all kinds of garbage, including domestic garbage, industrial waste, agricultural and forestry waste, electronic waste and medical waste.
  • Most of the garbage exists in the form of a mixture.
  • organic substances and environmental impacts are relatively large, and the varieties are very wide. It mainly includes synthetic polymer materials that are difficult to degrade in nature, such as plastics, adhesives, fibers, paints, etc.; also includes naturally degradable biomass such as food, straw, paper products, wood products, etc.; It is industrial waste containing precious metals, heavy metals and specific chemicals, such as electroplating sludge, electronic waste, and special chemical waste.
  • the above three categories can be classified into non-degradable organic matter, degradable biomass and chemical electronic waste.
  • the hazard of burning garbage is that the oxidation process has newly produced many complicated and pollutants. If the purification is not strict, it will cause secondary pollution. As a means of replacing landfills, the related technologies are also constantly improving.
  • the improved multi-stage incinerators including fluidized bed incinerators, have improved combustion efficiency and reduced pollutant emissions to a certain extent, but additional equipment and High operation to remove harmful substances generated by incineration, and the degree of recycling and efficiency of waste is still very low.
  • the biodegradation method is a treatment method for a class of degradable substances. First, the source classification is required, and then only the degradable portion can be processed, and the treatment cycle is too long. Therefore, this method does not have a basis for widespread application.
  • the anaerobic fermentation method can use the produced biogas as a resource product to a certain extent, but it still needs to be strictly purified along with the formation of sulfides and nitrides.
  • the biogas residue as an organic fertilizer must have no limitation on the premise that the source of the garbage is not polluted. .
  • aerobic fermentation can shorten the treatment cycle, in addition to the biogas residue, there are not many grams of products used, and the process of discharging carbon dioxide in large quantities requires solving carbon emission problems.
  • the widely used grate furnace and fluidized bed furnace have more complete combustion and higher furnace temperature than the traditional incinerator.
  • the new multi-stage or multi-chamber combustion structure makes the combustion more complete and can also control the main burning.
  • the chamber is depleted of oxygen or anaerobic combustion to achieve partial gasification or partial cracking.
  • the combustion conditions are difficult to control and the working state is unstable. Due to the unevenness of the garbage and the change of composition, the process conditions such as the furnace temperature vary greatly, and the fluctuation of the working conditions makes the operation very difficult.
  • the gas generated by partial cracking or gasification has a low calorific value, and it is difficult to directly use a gas engine to generate electricity, and the widely used steam turbine is not efficient in power generation, which limits the resource disposal level of garbage disposal.
  • the gas calorific value was not significantly improved.
  • the existing rotary kiln type plastic and rubber cracking refining technology achieves the purpose of cracking by external heating method.
  • the process and equipment can be cracked at a lower temperature for a single plastic or rubber to produce a liquid-based product. Not suitable for other materials or complex mixtures, such as household waste.
  • the dry carbonization process such as straw is used for the special single material such as straw, and the reaction kettle is used to generate gas and carbon by batch cracking and carbonization.
  • the calorific value of the gas is low and the carbon quality is not high.
  • the overall resource level is low and the energy consumption is high, which is not suitable for the disposal of the mixture.
  • the present invention proposes a continuous, high-efficiency and environmentally friendly method for anaerobic thermal cracking of solid waste.
  • the method for anaerobic catalytic thermal cracking of solid waste comprises the following steps:
  • Step 1 Garbage pretreatment
  • the external garbage After the external garbage is put into the garbage pool to remove the waste water, it is coarsely crushed, dehydrated and pulverized into garbage particles of less than 3 cm in turn; the waste heat and regenerated combustible gas and/or external heating are used to heat the garbage particles, and evaporated. And air drying to reduce the moisture content of the garbage particles to 10 Within 30% of the range, dry granules are obtained;
  • Step 2 Decomposition of garbage cracking
  • the dried refuse granules are put into a fluidized cracking furnace, and the fluidization is heated by using waste heat and regenerating combustible gas and/or external heating under anaerobic conditions.
  • the cracking furnace makes the temperature of the cracking and the heating rate reach the process design requirements, and the catalyst is added to decompose the organic substances in the dry garbage particles into inorganic substances, combustible gas, bio-carbon and liquid compounds;
  • Step 3 Reprocessing of the product after cracking and decomposition
  • the inorganic substances, combustible gas, bio-carbon and liquid compounds are separated, purified, and synthesized into a building material, a gas, a finished fertilizer, and a fuel by a process.
  • the invention can process complex mixed garbage under medium and low temperature (400-850 degrees Celsius), catalysis and completely without oxygen, such as unsorted domestic garbage, continuous feeding, high-efficiency thermal cracking, gas and carbon, etc.
  • the generated tar is subjected to secondary cracking to eliminate pipe blockage and increase the calorific value of the gas.
  • this invention can realize the harmless resource disposal of unclassified garbage, and can treat all garbage containing organic substances harmlessly.
  • the process does not require the use of an additional inert gas protection.
  • the whole system is complete, concise and efficient.
  • the system is optimized, the unit energy consumption is low, and no secondary pollutants are generated or discharged.
  • the pyrolysis gas of the product has a high calorific value and a low tar content, which can be directly connected to the internal combustion engine to generate electricity.
  • the carbon structure of the product is controllable and the activity is high.
  • the material waste of the invention does not need to be sorted and sorted, the system structure is reasonable and simple, and the unit energy consumption is low. It can be used for the anaerobic cracking of almost all solid wastes for the purpose of harmless resource disposal.
  • the product carbon and cracked gas are of high quality and controllable, and have a larger product development space. Product carbon has a wide range of applications and can be further processed. The entire process is free of pollutants and can achieve near zero emissions.
  • the figure is a schematic diagram of a process flow of a preferred embodiment of the present invention.
  • the invention adopts a solid waste anoxic cracking technology, which is a process of decomposing organic solid waste under anaerobic conditions.
  • This process is a complex chemical reaction reduction process. Including macromolecular bond cleavage, isomerization and polymerization of small molecules, and finally generate a variety of smaller molecules, including: (1) flammability based on low molecular hydrocarbons such as hydrogen, carbon monoxide and methane gas; (2) organic substances including compounds such as acetone and acetone which are liquid at normal temperature; (3) Solid bio-carbon, glass, metal, earth sand, and the like. The result is that all organic matter, including plastics, man-made fibers, paper, animal and plant waste, is broken down into water, liquefied gas fuels and specialty carbon.
  • FIG. 1 shows a process flow of a preferred embodiment of the present invention.
  • the solid waste non-oxygen catalytic thermal cracking method comprises the following steps:
  • Step 1 Garbage pretreatment
  • the waste After the waste is put into the garbage pool to remove the waste water, it is coarsely broken, recovered, mechanically dehydrated, and pulverized into garbage particles of less than 3 cm.
  • the waste system is further heated by the drying system using residual heat and regenerated combustible gas and/or external heating, and the moisture content of the garbage particles is reduced to 10 by evaporation and air drying. Within 30% of the range, dry granules are obtained to ensure efficient cleavage.
  • Step 2 Decomposition of garbage cracking
  • the cracking furnace makes the cracking temperature and heating rate reach the process design requirements, and the catalyst is added, so that the organic matter in the dry garbage particles can be quickly and efficiently decomposed into inorganic substances, combustible gas, bio-carbon and organic carbon, liquid compounds, such as , tar, etc.
  • the temperature of the waste cracking decomposition is maintained in the range of 400-850 degrees Celsius. The heat generated when the waste is cracked and decomposed is exchanged by a heat exchanger and reused as waste heat.
  • the solidification cracking of the garbage is carried out by using solid particles pulverized by the mixed garbage as a fluidization medium.
  • the waste cracking decomposition requires fluidized gas and oxygen-free protective gas. These two gases use their own generated cracking gas to achieve process oxygen-free fluidization conditions through circulation.
  • the biochar is subjected to high-temperature jet pulverization in a cracking furnace, and the particle size reaches a micro-nano scale; the inorganic substance is automatically separated from other cracking products under fluidization conditions by utilizing gravity difference in the furnace.
  • Step 3 Reprocessing of the product after cracking and decomposition
  • Products that are cracked by combustible gas, bio-carbon and liquid compounds are designed, separated, purified, and synthesized into building materials, gas, finished fertilizer, fuel oil and other products.
  • the waste water generated during the pretreatment of the garbage and the cracking of the waste is collected and purified, and the heat in the treated water is exchanged for heat and reused as waste heat. It is also possible to use purified water as reclaimed water for process, greening or irrigation.
  • the odor gas generated during the pretreatment of the garbage and the decomposition of the waste is subjected to purification treatment, and the heat in the purified exhaust gas is exchanged for heat and reused as waste heat. It is also possible to use the purified exhaust gas as a clean fuel or as a raw material for the production of downstream products.
  • Garbage disposal The thermal cracking, production, and purification steps are completed under continuous conditions.
  • the invention adopts fluidized bed continuity to carry out anaerobic cracking of complex mixed garbage.
  • an oxygen scavenging device is set inside the system to remove the oxygen initially entering the system and control the reaction conditions, thereby avoiding the generation of harmful substances and the explosion risk of the system.
  • the purpose of heat transfer and pulverization of carbon is achieved by using the unclassified garbage itself and the inert material carried therein as the fluidization medium. Under the action of the catalyst, the thermal cracking is directed to the reaction, and the existing pollutants are effectively eliminated, and the product quality is stable. control.
  • the gravity principle is used to control the fluidization intensity, and the inert substance, carbon and cracking gas are automatically separated in the projection kettle.
  • the reduction characteristics of the cracking gas itself are used as a heating and fluidization carrier to circulate back to the system, and the oxides such as heavy metals are effectively reduced to achieve chemical degradation.
  • the reformer is implanted into the cracking process, and the heat of the system is fully utilized to remove substances such as tar which are easily condensed and settled, thereby avoiding problems such as blockage of the pipeline and improving the calorific value and carbon activity of the cracked gas.
  • the invention can process complex mixed garbage under medium and low temperature (400-850 degrees Celsius), catalysis and completely without oxygen, such as unsorted domestic garbage, continuous feeding, high-efficiency thermal cracking, gas and carbon, etc.
  • the generated tar is subjected to secondary cracking to eliminate pipe blockage and increase the calorific value of the gas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

An anaerobic catalytic thermal cracking method for solid waste, the steps thereof comprising: waste pre-treatment: putting transported waste into a garbage pool and removing waste water, then implementing in turn coarse breaking, dehydration, and crushing into waste pellets of less than 3 cm; heating the waste pellets using surplus heat and renewable combustible gas and/or external heating; and drying to reduce the water content of the waste particles to 10-30% to obtain dry waste particles. Waste cracking and decomposition: placing the dry waste pellets into a fluidised cracking furnace, and in anaerobic conditions, heating the fluidised cracking furnace using surplus heat and renewable combustible gas and/or external heating, such that the cracking temperature and heating rate meet requirements, and adding a catalyst, such that the organic matter in the dry waste pellets is decomposed into inorganic matter, combustible gas, biochar, and liquid compounds. Post-cracking and post-decomposition product processing: separation, purification, synthesis, and processing of the inorganic matter, combustible gas, biochar, and liquid compounds into buildings materials, fuel gas, finished fertiliser, and fuel oil. The present method can process complex mixed waste and continuously feed in material in mid and low temperature, catalytic, and entirely anaerobic conditions, in order to implement highly efficient thermal cracking to produce fuel gas and carbon, and additionally implementing secondary cracking and decomposition of the produced tar to eliminate pipeline blockages and improve the calorific value of the fuel gas.

Description

一种固体垃圾无氧催化热裂解方法Anaerobic catalytic thermal cracking method for solid waste 技术领域Technical field
本发明涉及垃圾处理的工艺方法，尤其涉及一种固体垃圾无氧催化热裂解达到无害排放的处理方法。 The invention relates to a process method for garbage disposal, in particular to a treatment method for non-toxic catalytic thermal cracking of solid waste to achieve harmless discharge.
背景技术Background technique
人类活动必然会产生各种垃圾，包括生活垃圾、工业垃圾、农林垃圾、电子垃圾和医疗垃圾等等。绝大部分垃圾以混合物形式存在，其中对人类健康和环境影响较大的是有机物质一类，品种十分广泛。主要包括自然界难以降解的人工合成高分子材料，如塑料、粘合剂、纤维、油漆等等；另外也包括自然可降解的生物质，如食物、秸秆、纸制品、木制品等；第三部分是含有贵金属、重金属、特定化学品的工业垃圾，如电镀污泥、电子垃圾、特种化工废料。以上三类可归纳为不可降解有机物、可降解生物质和化工电子垃圾。 Human activities will inevitably produce all kinds of garbage, including domestic garbage, industrial waste, agricultural and forestry waste, electronic waste and medical waste. Most of the garbage exists in the form of a mixture. Among them, organic substances and environmental impacts are relatively large, and the varieties are very wide. It mainly includes synthetic polymer materials that are difficult to degrade in nature, such as plastics, adhesives, fibers, paints, etc.; also includes naturally degradable biomass such as food, straw, paper products, wood products, etc.; It is industrial waste containing precious metals, heavy metals and specific chemicals, such as electroplating sludge, electronic waste, and special chemical waste. The above three categories can be classified into non-degradable organic matter, degradable biomass and chemical electronic waste.
随着人类生活水平的提高，垃圾产量也在不断上升。仅生活垃圾，年增长率均在 5%-8% ，少数大城市垃圾的年增长率达到 8%-10%, 人均日产垃圾量已超过 1 千克。我国城市垃圾 2015 产生量就达 2.6 亿吨，接近中等发达工业国家水平，且增长越来越快的趋势。 With the improvement of human living standards, garbage production is also rising. Domestic garbage only, annual growth rate is 5%-8% The annual growth rate of garbage in a few large cities has reached 8%-10%, and the per capita daily garbage production has exceeded 1 kg. China's urban waste production in 2015 reached 2.6 It is close to the level of medium-developed industrial countries and is growing faster and faster.
垃圾的大量产生和处理技术的不完善，已经对国家的经济发展、人民的生活质量和自然环境造成了日益严峻的负面影响。 世界各国在充分认识到这一发展瓶颈的同时，正积极集中力量开发可实现无害化和资源化处置垃圾的有效技术。 The incompleteness of the mass production and treatment of garbage has caused an increasingly serious negative impact on the country's economic development, people's quality of life and the natural environment. While fully recognizing this development bottleneck, countries around the world are actively focusing on developing effective technologies that can achieve harmless and resource-based disposal of waste.
传统的垃圾填埋技术，虽仍然是全世界垃圾处理的主要手段之一，但因是转移性处置、永久性占用土地资源、存在对地下水的和大气污染的潜在风险，且填埋后需要长期维护、最终仍然需要彻底处理， 这一技术方法已显现出长期环境危害忧患，已逐渐成为过渡性方法，势必会被取代。 Although traditional landfill technology is still one of the main means of waste disposal in the world, it is a potential risk of transfer disposal, permanent occupation of land resources, groundwater and atmospheric pollution, and long-term after landfill. Maintenance, and ultimately still need to be thoroughly processed, This technical method has shown long-term environmental hazards and has gradually become a transitional method, which is bound to be replaced.
焚烧垃圾的危害在于氧化过程新生成许多复杂又还污染物，如果净化不严格，就会造成二次污染。焚烧作为取代填埋的手段，相关技术也在不断提高，改进后的多段焚烧炉，包括流化床焚烧炉，虽然提高了燃烧效率，一定程度地降低了污染物排放，但仍需附加设备和高运行来清除焚烧所产生的有害物质，且垃圾的资源化程度和效率仍然很低。 The hazard of burning garbage is that the oxidation process has newly produced many complicated and pollutants. If the purification is not strict, it will cause secondary pollution. As a means of replacing landfills, the related technologies are also constantly improving. The improved multi-stage incinerators, including fluidized bed incinerators, have improved combustion efficiency and reduced pollutant emissions to a certain extent, but additional equipment and High operation to remove harmful substances generated by incineration, and the degree of recycling and efficiency of waste is still very low.
生物降解法是对可降解一类物质的处理方法， 首先要求源头分类，再就是只能处理可降解部分，处理周期过长， 因此这种方法不具备广泛应用的基础。 厌氧发酵法可一定程度地利用产生的沼气做为资源化产物，但伴随生成硫化物和氮化物仍需严格净化，沼渣作为有机肥须在垃圾源头没有污染的前提下，局限性很大。 好氧发酵虽然可缩短处理周期，但除沼渣外，没有多少克利用的产物，其过程大量排放二氧化碳， 需解决碳排放问题。 The biodegradation method is a treatment method for a class of degradable substances. First, the source classification is required, and then only the degradable portion can be processed, and the treatment cycle is too long. Therefore, this method does not have a basis for widespread application. The anaerobic fermentation method can use the produced biogas as a resource product to a certain extent, but it still needs to be strictly purified along with the formation of sulfides and nitrides. The biogas residue as an organic fertilizer must have no limitation on the premise that the source of the garbage is not polluted. . Although aerobic fermentation can shorten the treatment cycle, in addition to the biogas residue, there are not many grams of products used, and the process of discharging carbon dioxide in large quantities requires solving carbon emission problems.
广泛使用的炉排炉和流化床炉，和传统的焚烧炉相比，燃烧更加充分，炉温得到提高，新增的多段或多室燃烧结构，使得燃烧也更加充分，也可以控制主烧室贫氧或少氧燃烧，达到部分气化或部分裂解的作用。在垃圾不分类的前提条件下，燃烧条件控制困难，工作状态不稳定。 由于垃圾的不均匀和成分的变化，炉温等工艺条件变化幅度较大，工况波动使得操作十分困难。部分裂解或气化所产生的气体，其热值很低，难以直接采用燃气机发电，而广泛使用的蒸汽涡轮发电效率不高，使得垃圾处置资源化水平受到限制。通过冷凝脱水和喷淋，虽然消除了一些污染物，减少了后期的腐蚀和排放，但气体热值没有明显改善。 The widely used grate furnace and fluidized bed furnace have more complete combustion and higher furnace temperature than the traditional incinerator. The new multi-stage or multi-chamber combustion structure makes the combustion more complete and can also control the main burning. The chamber is depleted of oxygen or anaerobic combustion to achieve partial gasification or partial cracking. Under the premise that the garbage is not classified, the combustion conditions are difficult to control and the working state is unstable. Due to the unevenness of the garbage and the change of composition, the process conditions such as the furnace temperature vary greatly, and the fluctuation of the working conditions makes the operation very difficult. The gas generated by partial cracking or gasification has a low calorific value, and it is difficult to directly use a gas engine to generate electricity, and the widely used steam turbine is not efficient in power generation, which limits the resource disposal level of garbage disposal. By condensing dehydration and spraying, although some pollutants were eliminated and later corrosion and emissions were reduced, the gas calorific value was not significantly improved.
目前存在的转窑式塑料、橡胶裂解炼油技术，通过外加热方法，达到裂解目的。其工艺和设备，对于单一的塑料或者橡胶可以在较低温度下裂解，生成以液体为主的产物， 不适合其它材料的或者复杂混合物质，例如生活垃圾。 The existing rotary kiln type plastic and rubber cracking refining technology achieves the purpose of cracking by external heating method. The process and equipment can be cracked at a lower temperature for a single plastic or rubber to produce a liquid-based product. Not suitable for other materials or complex mixtures, such as household waste.
秸秆等干馏碳化工艺，针对秸秆等特殊的单一物料，采用反应釜，批次裂解和碳化生成燃气和碳，燃气热值偏低，碳质量也不高。整体资源化水平低，能耗较高，不适合混合物的处置。 The dry carbonization process such as straw is used for the special single material such as straw, and the reaction kettle is used to generate gas and carbon by batch cracking and carbonization. The calorific value of the gas is low and the carbon quality is not high. The overall resource level is low and the energy consumption is high, which is not suitable for the disposal of the mixture.
如何采取一种连续、高效和环保的处理固体垃圾的方法，是业界亟待解决的技术问题。 How to adopt a continuous, efficient and environmentally friendly method for handling solid waste is a technical problem that needs to be solved in the industry.
发明内容Summary of the invention
本发明为了解决现有固体垃圾处理存在的技术问题，提出一种连续、高效和环保的固体垃圾无氧催化热裂解方法。 In order to solve the technical problems existing in the existing solid waste treatment, the present invention proposes a continuous, high-efficiency and environmentally friendly method for anaerobic thermal cracking of solid waste.
本发明提供的固体垃圾无氧催化热裂解方法，其包括如下步骤： The method for anaerobic catalytic thermal cracking of solid waste provided by the invention comprises the following steps:
步骤1：垃圾预处理 Step 1: Garbage pretreatment
将外运垃圾放入垃圾池除去废水后，依次进行粗破、脱水、粉碎成小于3厘米的垃圾颗粒；再利用余热和再生可燃气和/或外加热来加热所述的垃圾颗粒，通过蒸发和风干将垃圾颗粒的水分含量降低到10 ~ 30% 范围内，得到干燥垃圾颗粒； After the external garbage is put into the garbage pool to remove the waste water, it is coarsely crushed, dehydrated and pulverized into garbage particles of less than 3 cm in turn; the waste heat and regenerated combustible gas and/or external heating are used to heat the garbage particles, and evaporated. And air drying to reduce the moisture content of the garbage particles to 10 Within 30% of the range, dry granules are obtained;
步骤2：垃圾裂化分解 Step 2: Decomposition of garbage cracking
将所述的干燥垃圾颗粒投入 流化 裂解炉，在无氧的条件下，利用余热和再生可燃气和/或外加热来加热所述的 流化 裂解炉，使得裂解的温度和升温速度达到工艺设计要求，并添加催化剂，使得干燥垃圾颗粒中的有机物质分解成无机物、可燃气、生物碳和液体化合物； The dried refuse granules are put into a fluidized cracking furnace, and the fluidization is heated by using waste heat and regenerating combustible gas and/or external heating under anaerobic conditions. The cracking furnace makes the temperature of the cracking and the heating rate reach the process design requirements, and the catalyst is added to decompose the organic substances in the dry garbage particles into inorganic substances, combustible gas, bio-carbon and liquid compounds;
步骤3：裂化分解后的产物再加工 Step 3: Reprocessing of the product after cracking and decomposition
将所述的无机物、可燃气、生物碳和液体化合物，通过工艺分离、净化、合成加工成建材、燃气、成品肥料、燃油。 The inorganic substances, combustible gas, bio-carbon and liquid compounds are separated, purified, and synthesized into a building material, a gas, a finished fertilizer, and a fuel by a process.
本发明在中低温（400-850摄氏度）、催化、完全没有氧气条件下，可以处理复杂的混合垃圾，如未分选的生活垃圾，连续进料，实现高效热裂解，产生燃气和碳等，同时，对产生的焦油进行二次裂解，消除管道堵塞和提高燃气热值等。 The invention can process complex mixed garbage under medium and low temperature (400-850 degrees Celsius), catalysis and completely without oxygen, such as unsorted domestic garbage, continuous feeding, high-efficiency thermal cracking, gas and carbon, etc. At the same time, the generated tar is subjected to secondary cracking to eliminate pipe blockage and increase the calorific value of the gas.
本发明 可以实现不分类垃圾的无害化资源化处置，可对几乎所有含有机物质的垃圾进行无害化处理。连续处理，操作简单，自动化程度高，无需人工参与分选或者直接接触垃圾。工艺无需采用外加惰性气体保护。整个系统完整、简洁，效率高。系统优化，单位能耗低，无二次污染物生成或排出。产品裂解气热值高，焦油含量很低,可直接接内燃机发电。产品碳结构可控，活性高。 this invention It can realize the harmless resource disposal of unclassified garbage, and can treat all garbage containing organic substances harmlessly. Continuous processing, simple operation, high degree of automation, no need to manually participate in sorting or direct contact with garbage. The process does not require the use of an additional inert gas protection. The whole system is complete, concise and efficient. The system is optimized, the unit energy consumption is low, and no secondary pollutants are generated or discharged. The pyrolysis gas of the product has a high calorific value and a low tar content, which can be directly connected to the internal combustion engine to generate electricity. The carbon structure of the product is controllable and the activity is high.
本发明物料垃圾无需分类分选，系统结构合理简捷，单位能耗低。可用于几乎所有固体废弃物的无氧裂解，达到无害化资源化处置的目的。产物碳和裂解气质量高、可控，有更大的产品开发空间。产品碳具有广泛的应用市场，可进一步加工。整个过程无污染物生成，可做到近零排放。 The material waste of the invention does not need to be sorted and sorted, the system structure is reasonable and simple, and the unit energy consumption is low. It can be used for the anaerobic cracking of almost all solid wastes for the purpose of harmless resource disposal. The product carbon and cracked gas are of high quality and controllable, and have a larger product development space. Product carbon has a wide range of applications and can be further processed. The entire process is free of pollutants and can achieve near zero emissions.
附图说明DRAWINGS
图为本发明较佳实施例的工艺流程示意图。  The figure is a schematic diagram of a process flow of a preferred embodiment of the present invention.
具体实施方式detailed description
本发明采用的是一种固体废弃物无氧裂解技术，该技术是一将有机固体废弃物在无氧条件下加热分解的过程。该过程是一个复杂的化学反应还原过程。包括大分子的键断裂，异构化和小分子的聚合等反应，最后生成各种较小的分子，主要包括：(1)以氢气、一氧化碳、甲烷等低分子碳氢化合物为主的可燃性气体； (2)在常温下为液态的包括乙酸丙酮等化合物在内的有机类； (3)固体生物碳、玻璃、金属、土砂等。结果就是将所有的有机物，包括塑料、人造纤维、纸张、动植物垃圾等，均被分解成水、类似液化气燃料和特种碳。 The invention adopts a solid waste anoxic cracking technology, which is a process of decomposing organic solid waste under anaerobic conditions. This process is a complex chemical reaction reduction process. Including macromolecular bond cleavage, isomerization and polymerization of small molecules, and finally generate a variety of smaller molecules, including: (1) flammability based on low molecular hydrocarbons such as hydrogen, carbon monoxide and methane gas; (2) organic substances including compounds such as acetone and acetone which are liquid at normal temperature; (3) Solid bio-carbon, glass, metal, earth sand, and the like. The result is that all organic matter, including plastics, man-made fibers, paper, animal and plant waste, is broken down into water, liquefied gas fuels and specialty carbon.
如图1所示为本发明一较佳实施例的工艺流程。所述固体垃圾无氧催化热裂解方法，其包括如下步骤： FIG. 1 shows a process flow of a preferred embodiment of the present invention. The solid waste non-oxygen catalytic thermal cracking method comprises the following steps:
步骤1：垃圾预处理 Step 1: Garbage pretreatment
将外运垃圾放入垃圾池除去废水后，依次进行粗破、回收金属、机械脱水、粉碎成小于3厘米的垃圾颗粒。再由干燥系统利用余热和再生可燃气和/或外加热来加热所述的垃圾颗粒，通过蒸发和风干将垃圾颗粒的水分含量降低到10 ~ 30% 范围内，得到干燥垃圾颗粒，以保证裂解的高效进行。 After the waste is put into the garbage pool to remove the waste water, it is coarsely broken, recovered, mechanically dehydrated, and pulverized into garbage particles of less than 3 cm. The waste system is further heated by the drying system using residual heat and regenerated combustible gas and/or external heating, and the moisture content of the garbage particles is reduced to 10 by evaporation and air drying. Within 30% of the range, dry granules are obtained to ensure efficient cleavage.
步骤2：垃圾裂化分解 Step 2: Decomposition of garbage cracking
将干燥垃圾颗粒投入 流化 裂解炉，在完全没有空气--无氧的条件下，利用余热和再生可燃气和/或外加热来加热所述的 流化 裂解炉，使得裂解的温度和升温速度达到工艺设计要求，并添加催化剂，从而能够快速高效地将干燥垃圾颗粒中的有机物质分解成无机物、可燃气、生物碳和有机碳、液体化合物,如，焦油等。 垃圾裂化分解的温度保持在400-850摄氏度范围内。将垃圾裂化分解时产生的热量经热交换器进行交换，当作余热再利用。 所述垃圾裂化分解是利用混合垃圾粉碎后的固体颗粒作为流化介质的。垃圾裂化分解需要流化气体和无氧保护气体，这两种气体采用自身产生的裂解气体，通过循环实现工艺无氧流化条件。所述的生物碳在裂解炉中进行高温气流粉碎，粒度达到微纳米级；所述无机物在炉中利用重力差异，在流化条件下与其他裂解产物自动分离。 Put dry garbage particles into fluidization a cracking furnace that uses residual heat and regenerated combustible gas and/or external heating to heat the fluidization in the absence of air-free oxygen The cracking furnace makes the cracking temperature and heating rate reach the process design requirements, and the catalyst is added, so that the organic matter in the dry garbage particles can be quickly and efficiently decomposed into inorganic substances, combustible gas, bio-carbon and organic carbon, liquid compounds, such as , tar, etc. The temperature of the waste cracking decomposition is maintained in the range of 400-850 degrees Celsius. The heat generated when the waste is cracked and decomposed is exchanged by a heat exchanger and reused as waste heat. The solidification cracking of the garbage is carried out by using solid particles pulverized by the mixed garbage as a fluidization medium. The waste cracking decomposition requires fluidized gas and oxygen-free protective gas. These two gases use their own generated cracking gas to achieve process oxygen-free fluidization conditions through circulation. The biochar is subjected to high-temperature jet pulverization in a cracking furnace, and the particle size reaches a micro-nano scale; the inorganic substance is automatically separated from other cracking products under fluidization conditions by utilizing gravity difference in the furnace.
步骤3：裂化分解后的产物再加工 Step 3: Reprocessing of the product after cracking and decomposition
将可燃气、生物碳和液体化合物等裂解出的产物，通过工艺参数设计，分离、净化、合成加工成建材、燃气、成品肥料、燃油等产品。 Products that are cracked by combustible gas, bio-carbon and liquid compounds are designed, separated, purified, and synthesized into building materials, gas, finished fertilizer, fuel oil and other products.
在上述垃圾处理的同时， 将垃圾预处理和垃圾裂化分解时产生的废水收集后进行净化处理，将处理后的中水中的热量进行热交换，当作余热再利用。还可以将净化后的水作为再生水用于工艺、绿化或灌溉等。将垃圾预处理和垃圾裂化分解时产生的异味气体进行净化处理，将净化后的废气中的热量进行热交换，当作余热再利用。还可以将净化后的废气，做为洁净燃料或者做为再生原料生产下游产品。垃圾处理 是在连续条件完成热裂解、产出和净化步骤的。 At the same time as the above garbage disposal, The waste water generated during the pretreatment of the garbage and the cracking of the waste is collected and purified, and the heat in the treated water is exchanged for heat and reused as waste heat. It is also possible to use purified water as reclaimed water for process, greening or irrigation. The odor gas generated during the pretreatment of the garbage and the decomposition of the waste is subjected to purification treatment, and the heat in the purified exhaust gas is exchanged for heat and reused as waste heat. It is also possible to use the purified exhaust gas as a clean fuel or as a raw material for the production of downstream products. Garbage disposal The thermal cracking, production, and purification steps are completed under continuous conditions.
本发明采用流化床连续性进行无氧裂解复杂混合垃圾。利用裂解气的还原特性，设定一个除氧装置于系统内部，将初进入系统的氧气脱除，并控制反应条件，可避免有害物质的生成和系统的爆炸危险。利用不分类垃圾本身和其中携带的惰性物质作为流化介质，达到传热和粉碎生成的碳的目的，在催化剂作用下，热裂解定向反应，并有效地消除存在的污染物，产品质量稳定可控。利用重力原理，控制流化强度，在放映釜内自动分出惰性物质、碳和裂解气。利用裂解气本身的还原特性，做为加热和流化载体循环回系统，并有效地还原重金属等氧化物，达到化学降解作用。把重整器植入裂解工艺内，充分利用系统热量，除去焦油等容易凝结沉降的物质，避免了管道堵赛等问题，同时可提高裂解气的热值和碳的活性。 The invention adopts fluidized bed continuity to carry out anaerobic cracking of complex mixed garbage. By using the reducing characteristics of the cracking gas, an oxygen scavenging device is set inside the system to remove the oxygen initially entering the system and control the reaction conditions, thereby avoiding the generation of harmful substances and the explosion risk of the system. The purpose of heat transfer and pulverization of carbon is achieved by using the unclassified garbage itself and the inert material carried therein as the fluidization medium. Under the action of the catalyst, the thermal cracking is directed to the reaction, and the existing pollutants are effectively eliminated, and the product quality is stable. control. The gravity principle is used to control the fluidization intensity, and the inert substance, carbon and cracking gas are automatically separated in the projection kettle. The reduction characteristics of the cracking gas itself are used as a heating and fluidization carrier to circulate back to the system, and the oxides such as heavy metals are effectively reduced to achieve chemical degradation. The reformer is implanted into the cracking process, and the heat of the system is fully utilized to remove substances such as tar which are easily condensed and settled, thereby avoiding problems such as blockage of the pipeline and improving the calorific value and carbon activity of the cracked gas.
本发明在中低温（400-850摄氏度）、催化、完全没有氧气条件下，可以处理复杂的混合垃圾，如未分选的生活垃圾，连续进料，实现高效热裂解，产生燃气和碳等，同时，对产生的焦油进行二次裂解，消除管道堵塞和提高燃气热值等。 The invention can process complex mixed garbage under medium and low temperature (400-850 degrees Celsius), catalysis and completely without oxygen, such as unsorted domestic garbage, continuous feeding, high-efficiency thermal cracking, gas and carbon, etc. At the same time, the generated tar is subjected to secondary cracking to eliminate pipe blockage and increase the calorific value of the gas.
以上结合具体实施例描述了本发明的技术原理。这些描述只是为了解释本发明的原理，而不能以任何方式解释为对本发明保护范围的限制。基于此处的解释，本领域的技术人员不需要付出创造性的劳动即可联想到本发明的其它具体实施方式，这些方式都将落入本发明的保护范围之内。 The technical principles of the present invention have been described above in connection with specific embodiments. The descriptions are merely illustrative of the principles of the invention and are not to be construed as limiting the scope of the invention. Based on the explanation herein, those skilled in the art can devise various other embodiments of the present invention without departing from the scope of the invention.

Claims (10)

  1. 一种固体垃圾无氧催化热裂解方法，其包括如下步骤： An organic waste anaerobic catalytic thermal cracking method comprising the following steps:
    步骤 1 ：垃圾预处理Step 1: Garbage pretreatment
    将外运垃圾放入垃圾池除去废水后，依次进行粗破、脱水、粉碎成小于 3 厘米的垃圾颗粒；再利用余热和再生可燃气和 / 或外加热来加热所述的垃圾颗粒，通过蒸发和风干将垃圾颗粒的水分含量降低到 10-30% 范围内，得到干燥垃圾颗粒；After the waste is put into the garbage pool to remove the waste water, it is coarsely crushed, dehydrated and pulverized into garbage particles of less than 3 cm in turn; reuse waste heat and regenerate combustible gas and / Or heating to heat the garbage particles, and reducing the moisture content of the garbage particles to 10-30% by evaporation and air drying to obtain dry garbage particles;
    步骤 2 ：垃圾裂化分解Step 2: Decomposition of garbage cracking
    将所述的干燥垃圾颗粒投入流化裂解炉，在无氧的条件下，利用余热和再生可燃气和 / 或外加热来加热所述的流化裂解炉，使得裂解的温度和升温速度达到工艺设计要求，并添加催化剂，使得干燥垃圾颗粒中的有机物质分解成无机物、可燃气、生物碳和液体化合物；The dried garbage particles are put into a fluidized cracking furnace to utilize waste heat and regenerate combustible gas and/or under anaerobic conditions. Or external heating to heat the fluidized cracking furnace, so that the temperature and temperature rising rate of the cracking meet the process design requirements, and the catalyst is added to decompose the organic matter in the dried garbage particles into inorganic matter, combustible gas, bio-carbon and liquid compound. ;
    步骤 3 ：裂化分解后的产物再加工Step 3: Reprocessing of the product after cracking and decomposition
    将所述的无机物、可燃气、生物碳和液体化合物，通过工艺分离、净化、合成加工成建材、燃气、成品肥料、燃油。 The inorganic substances, combustible gas, bio-carbon and liquid compounds are separated, purified, and synthesized into a building material, a gas, a finished fertilizer, and a fuel by a process.
  2. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，所述垃圾裂化分解的温度保持在 400-850 摄氏度范围内。 The method of anaerobic catalytic thermal cracking of solid waste according to claim 1, wherein the temperature of the cracking decomposition of the garbage is maintained at 400-850 Within the Celsius range.
  3. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，所述垃圾裂化分解需要流化气体和无氧保护气体，这两种气体采用自身产生的裂解气体，通过循环实现工艺无氧流化条件。 Claims 1 The method for anaerobic catalytic pyrolysis of solid waste is characterized in that the waste cracking decomposition requires a fluidized gas and an anaerobic protective gas, and the two gases adopt a self-generated cracking gas to realize a process of oxygen-free fluidization through circulation. condition.
  4. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，所述的生物碳在裂解炉中进行高温气流粉碎，粒度达到微纳米级；所述的无机物在炉中利用重力差异，在流化条件下与其他裂解产物自动分离。 Claims 1 The method for anaerobic catalytic pyrolysis of solid waste is characterized in that the biochar is subjected to high-temperature jet pulverization in a cracking furnace, and the particle size reaches a micro-nano scale; the inorganic substance is utilized in the furnace by gravity difference, in the flow It is automatically separated from other cleavage products under the conditions of the reaction.
  5. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，所述垃圾裂化分解是在连续条件完成热裂解、产出和净化步骤的。 Claims 1 The method for anaerobic thermal cracking of solid waste is characterized in that the cracking decomposition of the garbage is performed in a thermal cracking, production and purification step under continuous conditions.
  6. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，所述垃圾裂化分解是利用混合垃圾粉碎后的固体颗粒作为流化介质的。 Claims 1 The method for anaerobic thermal cracking of solid waste is characterized in that the solidification of the waste is carried out by using solid particles pulverized by mixed garbage as a fluidization medium.
  7. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，将所述垃圾裂化分解时产生的热量经热交换器进行交换，当作所述的余热再利用。 Claims 1 The method for anaerobic catalytic thermal cracking of solid waste is characterized in that heat generated during cracking and decomposition of the garbage is exchanged by a heat exchanger and reused as the residual heat.
  8. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，将所述垃圾预处理和垃圾裂化分解时产生的废水收集后进行净化处理，将处理后的中水中的热量进行热交换，当作余热再利用，净化后的水作为再生水用于工艺、绿化或灌溉。 Claims 1 The method for anaerobic catalytic thermal cracking of solid waste is characterized in that the waste water generated by the waste pretreatment and the waste cracking decomposition is collected and purified, and the heat in the treated water is exchanged as The waste heat is reused, and the purified water is used as reclaimed water for the process, greening or irrigation.
  9. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，将所述垃圾预处理和垃圾裂化分解时产生的异味气体进行净化处理，将处理后的废气中的热量进行热交换，当作余热再利用。Claims 1 The method for anaerobic catalytic pyrolysis of solid waste is characterized in that the odor gas generated during the pretreatment of the garbage and the cracking of the garbage is purified, and the heat in the treated exhaust gas is exchanged for heat. Reuse.
  10. 如权利要求 1 所述的固体垃圾无氧催化热裂解方法，其特征在于，将所述垃圾预处理和垃圾裂化分解时产生的异味气体进行净化处理，将处理后的废气经过净化后，做为洁净燃料或者做为再生原料生产下游产品。Claims 1 The method for anaerobic catalytic thermal cracking of solid waste is characterized in that the odor gas generated during the pretreatment of the garbage and the cracking of the garbage is purified, and the treated exhaust gas is purified and used as a clean fuel or Production of downstream products for recycled raw materials.
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