WO2022170774A1 - Dispositif de traitement de minerai d'ilménite utilisant des produits de pyrolyse de déchets solides - Google Patents

Dispositif de traitement de minerai d'ilménite utilisant des produits de pyrolyse de déchets solides Download PDF

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WO2022170774A1
WO2022170774A1 PCT/CN2021/122980 CN2021122980W WO2022170774A1 WO 2022170774 A1 WO2022170774 A1 WO 2022170774A1 CN 2021122980 W CN2021122980 W CN 2021122980W WO 2022170774 A1 WO2022170774 A1 WO 2022170774A1
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ore
pyrolysis
flue gas
temperature
waste
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PCT/CN2021/122980
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English (en)
Chinese (zh)
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牛小川
张广震
赵建强
苏波
赵凤娇
牛晓璐
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济南恒誉环保科技股份有限公司
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Priority to ZA2021/09510A priority Critical patent/ZA202109510B/en
Publication of WO2022170774A1 publication Critical patent/WO2022170774A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the field of comprehensive utilization of solid waste, and relates to a device for processing ilmenite ore by using a pyrolysis product of solid waste.
  • Solid wastes come from a wide variety of sources and are difficult to handle. They not only pollute the air, water and soil, but also many of these solid wastes contain harmful components, which affect the environment in many ways, including production, transportation, storage, treatment and disposal. Each process may cause greater harm to the environment. In order to control its pollution to the environment, it must be disposed of harmlessly.
  • solid waste pyrolysis is a new treatment method, which mainly uses high temperature environment to promote the pyrolysis of polymer components in solid waste.
  • Ilmenite is an oxide mineral of iron and titanium, also known as titanomagnetite, which is the main ore for refining titanium. Ilmenite is heavy, grey to black with a little metallic sheen. The crystals are generally plate-like, and the crystals are aggregated into blocks or granules.
  • the composition is FeTiO 3 , and the content of TiO 2 is 52.66%. It is the main mineral for extracting titanium and titanium dioxide. How to reduce the impact of Fe on TiO 2 in the smelting process has always been a difficult problem in the field; meanwhile, a large amount of heat energy is consumed in the smelting process, and the recovery and utilization of this part of the heat energy is also one of the problems that have been difficult to solve in the field.
  • the present invention proposes a device for processing ilmenite ore by using solid waste pyrolysis products, including an ore preheating device, a pyrolysis reduction device and a multi-stage cooling device, and a heater is provided on the outer side of the pyrolysis reduction device , the heater is connected with a flue gas heat exchanger; the feed port of the pyrolysis reduction device is connected to the discharge port of the iron ore preheating device, and the discharge port of the pyrolysis reduction device is connected to the multi-stage cooling device.
  • the hot air is sent to the flue gas heat exchanger through the pipeline to adjust the temperature and then sent to the iron ore preheating device; the device with this structure can send waste plastic, waste coke, etc.
  • Pyrolysis reduction device in this device, waste plastics, waste coke, etc. are pyrolyzed to generate reducing gas by increasing the temperature, so that the device is completely in a reducing gas atmosphere, and reacts with ilmenite ore in a high temperature environment to generate elemental iron, which improves the
  • the actual content of FeTiO 3 is then lowered to about 40°C through multi-stage heat exchange, and the high-temperature gas generated by the heat exchange is used as the heat source of the iron ore preheating device, realizing the comprehensive utilization of energy.
  • a device for processing ilmenite ore by using solid waste pyrolysis product comprising an ore preheating device, a pyrolysis reduction device and a multi-stage cooling device connected in sequence;
  • a heater is arranged on the outer side of the pyrolysis reduction device, and the heater is connected with a heating device and a flue gas heat exchanger; the feed inlet of the pyrolysis reduction device is connected with the discharge outlet of the ore preheating device, and the outlet The material port is connected with the multi-stage cooling device;
  • the multi-stage cooling device includes a solid product primary cooler and a solid product secondary cooler, wherein the primary cooler uses ambient air as a heat exchange medium, and the secondary cooler uses cooling water as a heat exchange medium to achieve solid Classified cooling of the product, wherein the hot air after the heat exchange of the primary cooler is sent to the flue gas heat exchanger through the pipeline for temperature adjustment and then sent to the ore preheating device;
  • the flue gas heat exchanger is also connected with a heat recovery fan, so that the hot flue gas after heat exchange can be sent to the heating device, the heat in it can be reused, and the comprehensive recovery and utilization of heat energy can be realized. It is also connected with the heating device through pipelines;
  • the device with this structure first uses the flue gas containing a large amount of waste heat generated in the whole device as a heat source to further heat the hot air obtained from the primary cooler to preheat the ilmenite ore.
  • the mixed hot gas and The direct contact heat exchange of the ore can not only increase the temperature of the ore, but also play the role of purging the impurities on the surface of the ore.
  • This process can generally increase the temperature of the ore to about 300 °C, which is unfavorable for subsequent smelting. The elements will be removed, and the quality of the ore will be high, which is conducive to subsequent processing;
  • waste plastics, waste coke and other wastes that can generate reducing gas can be sent to the pyrolysis reduction device together with the preheated ilmenite ore.
  • the outer side of the pyrolysis reduction device is provided with a heater, which is connected with a heating device.
  • the flue gas heat exchanger the hot flue gas is provided by the heating device as a heat source to supply heat for the pyrolysis reduction device, and the heated flue gas is sent to the flue gas heat exchanger, under the action of the heater, the pyrolysis reduction
  • the device can provide a high temperature above 600 °C, so that waste plastics, waste coke and other pyrolysis generate reducing gas.
  • the entire device is in an oxygen-free environment, which can promote the pyrolysis of waste plastics and waste coke to generate more reduction.
  • it is generally controlled to use a sealed connection between the ore preheating device and the pyrolysis reduction device, and it is preferable to set a material seal or a material seal in the ore preheating device.
  • the gas replacement device replaces the oxygen-containing gas in the ore preheating device with an inert gas.
  • the methods and devices used are conventional technologies in the field, and the inventor will not repeat them here; under the above temperature environment, waste plastics, waste
  • the gas produced by coke pyrolysis is mainly hydrogen and carbon monoxide, and the carbon element contained in the coke itself is a reducing substance, which makes the device completely in a reducing atmosphere;
  • the temperature of the pyrolysis reduction device is controlled to above 600°C is not only to ensure the cracking of the above-mentioned solid wastes such as waste plastics, but also more importantly, at a temperature of about 600°C, the FeTiO 3 -Fe2O 3 solid solution is dissolved and dissolved in titanium. Hematite platelets are precipitated in the iron ore and are arranged in the (0001) orientation. At this time, the precipitation of Fe 2 O 3 is realized.
  • Fe 2 O 3 can be reduced to iron element, which reduces and separates more iron element from ilmenite, increases the actual content of FeTiO 3 , and facilitates subsequent processing to obtain metallic titanium.
  • the residence time of ilmenite per unit volume in the pyrolysis reduction device is generally controlled to be more than 6h, and the amount of waste plastic and waste coke is excessive, that is to say, the amount of this part of the raw material far exceeds that of ilmenite. , so as to ensure that sufficient reducing substances are produced;
  • the ilmenite ore processed by the pyrolysis reduction device also contains a large amount of waste heat.
  • the comprehensive utilization of this part of the waste heat is another important goal of the present invention.
  • the inventor designed a multi-stage cooling device including a primary cooling of solid products.
  • the primary cooler uses ambient air as the heat exchange medium
  • the secondary cooler uses cooling water as the heat exchange medium.
  • the reason for this design is to take advantage of the large ambient air flow and use
  • the solid product primary cooler transfers the waste heat of the treated ilmenite ore to the ambient air as much as possible to make it hot air. If the temperature of this part of the hot air directly meets the temperature requirements of the ore preheating device, it can be passed through the pipe.
  • the temperature If the temperature is insufficient, it can enter the flue gas heat exchanger, conduct secondary heat exchange with the hot flue gas discharged from the heater, and further absorb the heat in it to obtain hot air with a higher temperature.
  • this part of the hot air can be directly sent to the ore preheating device to preheat the ilmenite; if the temperature after heat exchange is too high, it can be passed through the mixing device Mix with ambient air or external exhaust flue gas to reduce its temperature to meet the temperature requirements of the ore preheating device; at the same time, the hot flue gas after heat exchange by the flue gas heat exchanger can enter the regenerative fan, and the processing part of the fan acts as a
  • the air source is sent to the heating device for secondary heating as the heat source of the pyrolysis reduction device, and the remaining part is cooled and sent to the air mixing device as the heat source of the ore preheating device.
  • the subsequent coolers cannot be sent to the heating device for secondary heating as the heat source of the pyrolysis reduction device, and
  • the ilmenite ore After being cooled by the solid product primary cooler, the ilmenite ore still contains a large amount of thermal energy.
  • the inventors used the solid product secondary cooler to force heat exchange to reduce its temperature to about 40°C, and the temperature increased.
  • the resulting cooling water can be used as a heat source for other processes or ambient heating, and continues to be used as cooling water after heat exchange and cooling;
  • the ilmenite ore after this step has been reduced to room temperature, so the elemental iron in it can be separated by conventional means and used for other purposes, and the ilmenite ore obtained by separation can be purified by using the existing technology. Titanium element is obtained to obtain metallic titanium, which avoids the influence of iron on subsequent purification.
  • the ore preheating device is connected with a flue gas dust removal and purification system, so that the hot flue gas or hot air after heat exchange with the ilmenite can be processed by the system to remove the solid dust and reduce its pollution to the environment, And it is directly discharged through the exhaust device;
  • the pyrolysis reduction device is connected with a gas purification system. Since waste plastics, waste coke and other heat are deactivated to generate reducing gas, gas components such as olefins will also be generated. These components can be used as fuel gas, but in order to reduce the Environmental pollution also requires the treatment of the gas components, such as removing harmful impurities through alkali washing and acid washing to obtain purer fuel gas. This part of the fuel gas can be directly sent to the heating device for combustion as fuel gas ; In addition, the gas-phase product generated by the pyrolysis reduction unit can also be recycled back to the pyrolysis reduction unit through the pipeline for secondary cracking in order to obtain more gas products.
  • the reducing gas in this part of the product It can be used as the reducing substance of the above-mentioned reduced iron element, and other gas components can continue the above process to obtain higher purity fuel gas;
  • waste plastics, waste coke, etc. can be sent to the pyrolysis reduction device together with the preheated iron ore, and the waste plastics, waste coke, etc. can be reduced by increasing the temperature in the device.
  • Pyrolysis produces reducing gas, so that the device is completely in a reducing gas atmosphere, reacts with ilmenite ore to generate elemental iron in a high temperature environment, increases the actual content of FeTiO 3 , and then reduces its temperature to 40 ° C through multi-stage heat exchange
  • the high-temperature gas generated by heat exchange is used as the heat source of the iron ore preheating device, realizing the comprehensive utilization of energy.
  • FIG. 1 is a schematic diagram of an apparatus for treating ilmenite ore with a solid waste pyrolysis product according to the present invention.
  • a device for processing ilmenite ore by using solid waste pyrolysis products includes an ore preheating device, a pyrolysis reduction device and a multi-stage cooling device connected in sequence;
  • a heater is arranged on the outside, and the heater is connected with a heating device and a flue gas heat exchanger; the feed port of the pyrolysis reduction device is connected with the discharge port of the ore preheating device, and the discharge port of the pyrolysis reduction device is connected with the multi-stage cooling device ;
  • the multi-stage cooling device includes a solid product primary cooler and a solid product secondary cooler, wherein the primary cooler uses ambient air as a heat exchange medium, and the secondary cooler uses cooling water as a heat exchange medium to achieve solid Classified cooling of the product, wherein the hot air after the heat exchange of the primary cooler is sent to the flue gas heat exchanger through the pipeline for temperature adjustment and then sent to the ore preheating device;
  • the flue gas heat exchanger is also connected with a heat recovery fan, so that the hot flue gas after heat exchange can be sent to the heating device, the heat in it can be reused, and the comprehensive recovery and utilization of heat energy can be realized. It is also connected with the heating device through pipelines;
  • the device with this structure first uses the flue gas containing a large amount of waste heat generated in the whole device as a heat source to further heat the hot air obtained from the primary cooler to preheat the ilmenite ore.
  • the mixed hot gas and The direct contact heat exchange of the ore can not only increase the temperature of the ore, but also play the role of purging the impurities on the surface of the ore.
  • This process can generally increase the temperature of the ore to about 300 °C, which is unfavorable for subsequent smelting. The elements will be removed, and the quality of the ore will be high, which is conducive to subsequent processing;
  • waste plastics, waste coke and other wastes that can generate reducing gas can be sent to the pyrolysis reduction device together with the preheated ilmenite ore.
  • the outer side of the pyrolysis reduction device is provided with a heater, which is connected with a heating device.
  • the flue gas heat exchanger the hot flue gas is provided by the heating device as a heat source to supply heat for the pyrolysis reduction device, and the heated flue gas is sent to the flue gas heat exchanger, under the action of the heater, the pyrolysis reduction
  • the device can provide a high temperature above 600 °C, so that waste plastics, waste coke and other pyrolysis generate reducing gas.
  • the whole device is in an oxygen-free environment, which can promote the pyrolysis of waste plastics and waste coke to generate more reducing gas. gas, and at the same time ensure the safety of the entire device.
  • a sealed connection is generally controlled between the ore preheating device and the pyrolysis reduction device, and a material seal or gas is preferably installed in the ore preheating device.
  • the replacement device replaces the oxygen-containing gas in the ore preheating device with an inert gas.
  • waste plastics under the above temperature environment, waste plastics, waste coke
  • the gas produced by pyrolysis is mainly hydrogen and carbon monoxide, and the carbon element contained in the coke itself is a reducing substance, which makes the device completely in a reducing gas atmosphere;
  • the temperature of the pyrolysis reduction device is controlled to above 600°C is not only to ensure the cracking of the above-mentioned solid wastes such as waste plastics, but also more importantly, the FeTiO3 - Fe2O3 solid solution is dissolved at a temperature of about 600°C. Hematite platelets are precipitated in ilmenite and arranged in the (0001) orientation. At this time, the precipitation of Fe 2 O 3 is realized, and at a temperature above 600 °C, in an atmosphere full of reducing gas, Fe 2 O 3 can be reduced to iron element, so that more iron element is separated from ilmenite, and the actual content of FeTiO 3 is increased, which is convenient for subsequent processing to obtain metal titanium.
  • the continuity of the process is generally controlled that the residence time of ilmenite per unit volume in the pyrolysis reduction device is more than 6h, and the amount of waste plastic and waste coke is excessive, that is to say, the amount of this part of the raw material far exceeds that of titanium. iron ore, thereby ensuring that sufficient reducing substances are produced;
  • the ilmenite ore processed by the pyrolysis reduction device also contains a large amount of waste heat.
  • the comprehensive utilization of this part of the waste heat is another important goal of the present invention.
  • the inventor designed a multi-stage cooling device including a primary cooling of solid products.
  • the primary cooler uses ambient air as the heat exchange medium
  • the secondary cooler uses cooling water as the heat exchange medium.
  • the reason for this design is to take advantage of the large ambient air flow and use
  • the solid product primary cooler transfers the waste heat of the treated ilmenite ore to the ambient air as much as possible to make it hot air. If the temperature of this part of the hot air directly meets the temperature requirements of the ore preheating device, it can be passed through the pipe.
  • the temperature If the temperature is insufficient, it can enter the flue gas heat exchanger, conduct secondary heat exchange with the hot flue gas discharged from the heater, and further absorb the heat in it to obtain hot air with a higher temperature.
  • this part of the hot air can be directly sent to the ore preheating device to preheat the ilmenite; if the temperature after heat exchange is too high, it can be passed through the mixing device Mix with ambient air or external exhaust flue gas to reduce its temperature to meet the temperature requirements of the ore preheating device; at the same time, the hot flue gas after heat exchange by the flue gas heat exchanger can enter the regenerative fan, and the processing part of the fan acts as a
  • the air source is sent to the heating device for secondary heating as the heat source of the pyrolysis reduction device, and the remaining part is cooled and sent to the air mixing device as the heat source of the ore preheating device.
  • the subsequent coolers cannot be sent to the heating device for secondary heating as the heat source of the pyrolysis reduction device, and
  • the ilmenite ore After being cooled by the solid product primary cooler, the ilmenite ore still contains a large amount of thermal energy.
  • the inventors used the solid product secondary cooler to force heat exchange to reduce its temperature to about 40°C, and the temperature increased.
  • the resulting cooling water can be used as a heat source for other processes or ambient heating, and continues to be used as cooling water after heat exchange and cooling;
  • the pyrolysis reduction device is connected with a gas purification system. Since waste plastics, waste coke and other heat are deactivated to generate reducing gas, gas components such as olefins will also be generated. These components can be used as fuel gas, but in order to reduce the Environmental pollution also requires the treatment of the gas components, such as removing harmful impurities through alkali washing and acid washing to obtain purer fuel gas. This part of the fuel gas can be directly sent to the heating device for combustion as fuel gas .
  • the gas-phase product generated by the pyrolysis reduction device can also be recycled back to the pyrolysis reduction device through the pipeline, and then cracked twice to obtain more gas products.
  • the reducing gas in this part of the product can be used as the above-mentioned reduced iron element.
  • the reducing substances are used, and other gas components can continue the above process to obtain higher purity fuel gas;

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Abstract

L'invention concerne un dispositif de traitement de minerai d'ilménite utilisant des produits de pyrolyse de déchets solides, le dispositif comprenant un dispositif de préchauffage de minerai, un dispositif de réduction pyrolytique et un dispositif de refroidissement à étages multiples, un dispositif de chauffage étant disposé sur un côté externe supérieur du dispositif de réduction pyrolytique, et le dispositif de chauffage étant relié à un échangeur de chaleur de gaz de combustion ; un orifice d'alimentation du dispositif de réduction pyrolytique est relié à un orifice d'évacuation du dispositif de préchauffage de minerai, et un orifice d'évacuation du dispositif de réduction pyrolytique est relié au dispositif de refroidissement à étages multiples. Au moyen du dispositif ayant une telle structure, des déchets plastiques, des déchets de coke, etc. et du minerai d'ilménite préchauffé peuvent être introduits conjointement dans le dispositif de réduction pyrolytique, et dans le dispositif, par augmentation de la température, les déchets plastiques, les déchets de coke, etc. sont pyrolysés pour générer un gaz réducteur, de telle sorte que le dispositif se trouve entièrement dans une atmosphère réductrice, le gaz réducteur réagit avec le minerai d'ilménite pour produire du fer élémentaire dans un environnement à haute température pour augmenter la teneur réelle en FeTiO3, puis la température est réduite à environ 40 °C au moyen d'un échange de chaleur à étages multiples, et un gaz à haute température généré au moyen d'un échange de chaleur est utilisé en tant que source de chaleur du dispositif de préchauffage de minerai de fer, ce qui permet d'obtenir l'utilisation complète de l'énergie.
PCT/CN2021/122980 2021-10-09 2021-10-11 Dispositif de traitement de minerai d'ilménite utilisant des produits de pyrolyse de déchets solides WO2022170774A1 (fr)

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ZA2021/09510A ZA202109510B (en) 2021-10-09 2021-11-24 Device for treating ilmenite ore by using pyrolysis products of solid wastes

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CN202111174074.3A CN113981248B (zh) 2021-10-09 2021-10-09 一种利用固废热解产物处理钛铁矿矿石的装置

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CN110903855A (zh) * 2019-12-05 2020-03-24 陕西鼓风机（集团）有限公司 一种物料热解气化工艺、系统及应用
CN110872531A (zh) * 2019-12-12 2020-03-10 青岛理工大学 利用固体颗粒热载体热解气化的梯级余热回收装置及方法
CN112941306A (zh) * 2021-01-28 2021-06-11 东北大学 一种微细粒钛铁矿选择性焙烧-磁选的装置及方法
CN112941305A (zh) * 2021-01-28 2021-06-11 东北大学 微细粒钛铁矿流态化还原焙烧-磁选回收钛的装置及方法

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