WO2021128658A1 - Hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds - Google Patents

Hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds Download PDF

Info

Publication number
WO2021128658A1
WO2021128658A1 PCT/CN2020/084648 CN2020084648W WO2021128658A1 WO 2021128658 A1 WO2021128658 A1 WO 2021128658A1 CN 2020084648 W CN2020084648 W CN 2020084648W WO 2021128658 A1 WO2021128658 A1 WO 2021128658A1
Authority
WO
WIPO (PCT)
Prior art keywords
volatile organic
hydrolysis
organic compounds
oxidation
chlorine
Prior art date
Application number
PCT/CN2020/084648
Other languages
French (fr)
Chinese (zh)
Inventor
翁小乐
隆云鹏
吴忠标
戴晓霞
Original Assignee
浙江大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江大学 filed Critical 浙江大学
Publication of WO2021128658A1 publication Critical patent/WO2021128658A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/808—Hydrolytic
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to the technical field of waste gas treatment, in particular to a process and device for hydrolysis-oxidation two-stage degradation of chlorine-containing volatile organic compounds.
  • Chlorine-containing volatile organic compounds mainly come from industrial waste gas, and they have received increasing attention due to their persistent damage to the environment.
  • CVOCs generally come from the production and use of vinyl chloride, herbicides, and plastics.
  • CVOCs have high biological toxicity and high persistence, and some CVOCs (such as methylene chloride and tetrachloroethylene) can destroy the ozone layer and exacerbate global warming, causing serious harm to human health.
  • Industrial emissions of CVOCs have been banned by the laws of many countries, so it is more necessary to deal with them properly.
  • the current CVOCs treatment technology is mainly divided into recycling technology and destruction technology.
  • the former includes adsorption method, absorption method, condensation method and membrane separation method, and the latter mainly includes biodegradation method, photocatalysis method, plasma method, and direct combustion method. , Catalytic hydrodeoxygenation method and catalytic combustion method, etc.
  • the catalytic combustion method is considered to be the most promising treatment method at present.
  • the core of catalytic combustion technology is the development of catalysts.
  • the current research is mainly focused on precious metal catalysts, molecular sieve catalysts and transition metal oxide catalysts.
  • the deactivation of the catalyst in the catalytic oxidation process of CVOCs is mainly reflected in two aspects.
  • One is that Cl easily reacts with the active components in the catalytic combustion process to produce metal chlorides and oxychlorides with lower boiling points, which leads to the loss of active components, and the other is Cl. Strong adsorption on the catalyst causes the active sites to be occupied.
  • the Chinese patent document with the publication number CN110404534A discloses a highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds and a preparation method thereof.
  • the catalyst uses RuO 2 as the active component and uses Sn y Ti 1-y O 2 or MO x -Sn y Ti 1-y O 2 mixed metal oxide as the support, this invention realizes the control of the crystal form of the support oxide through the doping of TiO 2 by Sn, and is in the construction of a tin-titanium-based catalyst with high-efficiency activation performance.
  • the dispersion of RuO 2 on the surface of the carrier is greatly improved; the catalyst has the characteristics of high catalytic activity against volatile organic compounds containing chlorine, strong resistance to chlorine poisoning, and high selectivity to CO 2 of the product. Sex organic matter also has a good removal effect.
  • the Chinese patent document with the publication number CN108295852A discloses a Ce-Zr catalyst for the oxidation reaction of chlorine-containing volatile organic compounds.
  • the invention uses Ru to support Ce-Zr.
  • PCDDs polychlorinated dibenzodioxins
  • PCDFs polychlorinated dibenzofurans
  • the invention provides a two-stage hydrolysis-oxidation process for degrading chlorine-containing volatile organic compounds, and at the same time has the advantages of lower investment and operating costs, simple operation, safe operation, fewer high-toxic by-products, and the like.
  • a two-stage hydrolysis-oxidation process for degrading chlorine-containing volatile organic compounds includes the following steps:
  • the invention combines two stages of low-temperature hydrolysis and high-temperature oxidation to process chlorine-containing volatile organic compounds, and the front and back stages are equipped with different catalyst materials, and a dechlorination agent is added between the two stages to absorb the intermediate product.
  • the first stage mainly dechlorinates chlorine-containing volatile organic compounds to reduce the chlorine content in the reaction system; the middle stage mainly removes the intermediate product HCl to prevent it from negatively affecting the reaction effect of the latter stage; the latter stage mainly dechlorination Volatile organic compounds are degraded.
  • the invention first hydrolyzes and dechlorines at low temperature, and then absorbs chlorine to prevent chlorine from entering the high-temperature oxidation section. This can prevent the high-temperature oxidation catalyst from being poisoned by chlorine and lose its activity, and it can also prevent chlorine from generating more toxic chlorine-containing by-products under high-temperature conditions. .
  • the concentration of the chlorine-containing volatile organic compound is 10-10000 ppm; the chlorine-containing volatile organic compound contains 0.1-25% of water vapor.
  • the chlorine-containing volatile organic compound is at least one of chlorobenzene, dichloromethane, monochloromethane and dichloroethylene.
  • the space velocity of the gas in the reactor is 1000-15000 h -1 .
  • the hydrolysis catalyst that catalyzes the hydrolysis and dechlorination is a modified lanthanide-based catalyst; further preferably, the preparation method of the hydrolysis catalyst is: combining a lanthanide metal oxide or oxide with The mixture of additives is immersed in an excess of phosphoric acid solution, adsorbed and saturated, washed with water to neutrality, dried, and then calcined at 300-500°C for 3-10 hours to obtain.
  • the lanthanide-based catalyst is a cerium-based catalyst; the auxiliary agent is zirconia.
  • the dechlorination agent has a good absorption effect on HCl.
  • the dechlorination agent is at least one of alkali, alkali metal and alkaline earth metal oxide; most preferably, the dechlorination agent is CaO.
  • step (3) the dechlorinated volatile organic compounds are subjected to a catalytic deep oxidation reaction at 200-300°C.
  • step (3) oxygen gas needs to be blown into the catalytic deep oxidation reaction of the dechlorinated volatile organic compounds so that the oxygen content is 5-20%.
  • the oxidation catalyst uses a high specific surface material or a high performance rare earth oxygen storage material as a carrier, and uses at least one of Pt, Pd, Mn and Co as the main active component.
  • the oxidation catalyst can be a commercially available oxidation catalyst, such as a commercially available 1% Pt-TiO 2 catalyst or a Ce 0.1 Mn 0.9 O 2 catalyst.
  • the removal rate of chlorine-containing volatile organic compounds by the treatment process of the present invention can reach more than 95%. After testing, the dechlorination effect of the hydrolysis section was good, and after deep oxidation in the oxidation section, no dioxins were detected in the tail gas.
  • the present invention also provides a two-stage hydrolysis-oxidation device for degrading chlorine-containing volatile organic compounds, which includes a catalytic hydrolysis reaction furnace, an HCl removal chamber and a catalytic deep oxidation reaction furnace connected in sequence;
  • the catalytic hydrolysis reaction furnace is provided with a hydrolysis catalyst, and at 100-250°C, the chlorine-containing volatile organic compounds generate HCl and dechlorinated volatile organic compounds under the action of the hydrolysis catalyst;
  • the HCl removal bin is provided with a dechlorination agent for absorbing HCl;
  • An oxidation catalyst is arranged in the catalytic deep oxidation reaction furnace, and the dechlorinated volatile organic compounds are oxidized and degraded under the action of the oxidation catalyst at 200-500°C.
  • the hydrolysis catalyst is a modified lanthanide-based catalyst; the dechlorination agent is at least one of alkali, alkali metal and alkaline earth metal oxide; the oxidation catalyst is a high-performance rare earth oxygen storage material
  • the carrier has at least one of Pt, Pd, Mn and Co as the main active ingredient.
  • the furnace body of the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace is provided with an insulation layer.
  • the catalytic hydrolysis reaction furnace, the HCl removal chamber and the catalytic deep oxidation reaction furnace are connected through a hot gas pipeline; the inner wall and the outer surface of the hot gas pipeline are both provided with a thermal insulation material layer.
  • an electric auxiliary heater is provided in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace.
  • the hydrolysis-oxidation two-stage degradation device for chlorine-containing volatile organic compounds further includes a control system and a temperature sensor that are electrically connected to each other; the temperature sensor is used to collect the inside of the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace
  • the control system drives the electric auxiliary heater to turn off and stop heating; when the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction
  • the control system drives the electric auxiliary heater to turn on for heating.
  • the hydrolysis-oxidation two-stage degradation device for chlorine-containing volatile organic compounds further includes a tail gas detection system for detecting the components of the exhaust tail gas.
  • the process and device of the present invention effectively combine the two stages of hydrolysis and oxidation.
  • the front stage mainly dechlorinates chlorine-containing volatile organic compounds, and removes the intermediate product HCl through the HCl removal bin, thereby reducing the chlorine content in the reaction system and preventing The deactivation of the oxidation catalyst in the latter stage; the latter stage is mainly to further degrade the volatile organic matter after dechlorination, so that the dechlorinated organic matter is further decomposed into CO 2 , H 2 O and other small molecular inorganic substances.
  • the entire process has high removal efficiency for industrial chlorine-containing VOCs, stable treatment effect, and guarantees low by-product emissions.
  • the low catalytic temperature saves costs and is suitable for the treatment of industrial chlorine-containing VOCs with high air volume and low concentration.
  • the required temperature is lower and the energy consumption is less. Since the VOCs processed in the catalytic deep oxidation reactor are mainly dechlorinated, the processing temperature required is lower than that of the chlorine-containing VOCs, which reduces energy consumption;
  • the entire reaction system avoids the generation temperature range of the highly toxic by-product dioxin.
  • the chlorine element in the system is mainly removed from the system in the form of HCl, and the chlorine element rarely enters the subsequent catalytic deep oxidation reaction furnace. , It reduces the production of polychlorinated highly toxic by-products such as dioxins, and is more environmentally friendly.
  • Figure 1 is a schematic diagram of the structure of a two-stage hydrolysis-oxidation device for degradation of chlorine-containing volatile organic compounds.
  • the hydrolysis-oxidation two-stage degrading chlorine-containing volatile organic compound device of the present invention includes a catalytic hydrolysis reaction furnace 1, an HCl removal chamber 2 and a catalytic deep oxidation reaction furnace 3 connected in sequence.
  • the catalytic hydrolysis reaction furnace 1, the HCl removal bin 2 and the catalytic deep oxidation reaction furnace 3 are connected through a hot gas pipeline 5, and an exhaust gas detection system 6 is also provided at the gas outlet of the catalytic deep oxidation reaction furnace 3.
  • the inner wall of the hot gas pipeline 5 is provided with an inner insulating material layer, and the outer surface is provided with an outer insulating material layer.
  • the catalytic hydrolysis reaction furnace 1 and the catalytic deep oxidation reaction furnace 3 are also provided with an electric auxiliary heater and control system 4, and the electric auxiliary heater and control system 4 has a temperature sensor 4-1.
  • the temperature sensor 4-1 is located in the catalytic hydrolysis reaction furnace 1 and the catalytic deep oxidation reaction furnace 3, and collects the temperature in the furnace.
  • the information output terminal of the temperature sensor 4-1 is connected with the control system, and the output terminal of the control system is connected with the electric auxiliary
  • the on/off switch of the heater is connected; when the temperature value transmitted by the temperature sensor 4-1 to the control system exceeds the maximum threshold of the set temperature range, the control system drives the electric auxiliary heater to turn off and stop heating; when the temperature sensor 4-1 transmits When the temperature value of the control system is lower than the minimum threshold value of the set temperature range, the control system drives the electric auxiliary heater to turn on for auxiliary heating.
  • the heating chamber of the catalytic hydrolysis reaction furnace 1 is surrounded by a shell 1-1, and the shell 1-1 is also provided with a heat preservation material 1-2.
  • the heating furnace is provided with hydrolysis catalyst packing layers 1-3.
  • the hydrolysis catalyst is a lanthanide-based catalyst modified by phosphoric acid and then formed into a honeycomb or granular catalyst.
  • the HCl removal chamber 2 is provided with a HCl removal packing layer 2-1.
  • the filler in the HCl removal chamber 2 is CaO or other alkali metal/alkaline earth metal oxides, which can have a good absorption effect on HCl.
  • the structure of the catalytic deep oxidation reaction furnace 3 is similar to that of the catalytic hydrolysis reaction furnace 1, and the heating furnace chamber is surrounded by a shell, and the shell is also provided with insulation materials.
  • An oxidation catalyst packing layer is arranged in the heating furnace.
  • the oxidation catalyst is prepared with high-performance rare earth oxygen storage materials as the carrier, precious metals Pt, Pd or transition metals Mn, Co, etc. as the main active ingredients, and is prepared by a high dispersion rate uniform distribution method.
  • the mass ratio of the active components to the carrier is (0.01 ⁇ 0.1):1.
  • the two-stage hydrolysis-oxidation method for high-efficiency and stable degradation of industrial chlorine-containing volatile organic compounds is as follows: industrial flue gas first passes through a catalytic hydrolysis reactor, and uses the water vapor contained in the flue gas (the best range is 0.1%-25.0%).
  • the hydrolysis and dechlorination reaction produces HCl and dechlorination VOCs, which enter the HCl removal chamber.
  • the HCl is removed by the dechlorinating agent in the HCl removal chamber.
  • the dechlorinated VOCs enter the catalytic deep oxidation reaction furnace. In the catalytic deep oxidation reaction furnace, The dechlorinated VOCs are further deeply oxidized.
  • the temperature in the catalytic hydrolysis reaction furnace is set to 100-250°C, and the temperature in the catalytic deep oxidation reaction furnace is set to 200-500°C.
  • the device and method of the present invention are suitable for the degradation of organic substances such as chlorobenzene, dichloromethane, monochloromethane, and dichloroethylene.
  • the removal rate of these organic substances can reach more than 95%, and no dioxins etc. are detected in the exhaust gas. Toxic by-products.
  • the hydrolysis catalyst is prepared by the impregnation method.
  • the hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
  • the oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
  • CaO is used as the adsorbent in the HCl removal bin.
  • By-products such as benzene and dioxins.
  • the oxidation catalyst uses a commercially available 1% Pt-TiO 2 catalyst.
  • CaO is used as the adsorbent in the HCl removal bin.
  • the hydrolysis catalyst is prepared by the impregnation method, using 1 mol/L phosphoric acid solution and zirconium oxide-cerium oxide as raw materials, dipped in excess phosphoric acid and then dried, and calcined in a muffle furnace at 400°C for 3 hours to obtain the hydrolysis catalyst.
  • the oxidation catalyst uses a commercially available catalyst Ce 0.1 Mn 0.9 O 2 (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
  • CaO is used as the adsorbent in the HCl removal bin.
  • the hydrolysis catalyst is prepared by the impregnation method.
  • the hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
  • the oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
  • CaO is used as the adsorbent in the HCl removal bin.
  • the hydrolysis catalyst is prepared by the impregnation method.
  • the hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
  • the oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
  • CaO is used as the adsorbent in the HCl removal bin.
  • the hydrolysis catalyst is prepared by the impregnation method.
  • the hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
  • the oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
  • CaO is used as the adsorbent in the HCl removal bin.
  • the oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
  • CaO is used as the adsorbent in the HCl removal bin.
  • the removal rate of monochloromethane can reach 92%, and trichloromethane, tetrachloromethane and 65.67 ⁇ g/m 3 methylene chloride are detected in the tail gas.

Abstract

A hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds. The process comprises: (1) performing catalyzed hydrolysis and dechlorination on chlorinated volatile organic compounds at 100-250°C, so as to produce HCl and dechlorinated volatile organic compounds; (2) using a dechlorinating agent on the HCl and the dechlorinated volatile organic compounds to remove the HCl therefrom; and (3) performing catalytic deep oxidation on the dechlorinated volatile organic compounds at 200-500℃. The process can avoid loss of catalytic activity resulting from chlorine poisoning during high temperature oxidation, and can prevent chlorine from producing toxic chlorine-containing by-products at high temperature conditions.

Description

水解-氧化两段式降解含氯挥发性有机物的工艺及装置Process and device for hydrolysis-oxidation two-stage degradation of chlorine-containing volatile organic compounds 技术领域Technical field
本发明涉及废气处理技术领域，尤其涉及一种水解-氧化两段式降解含氯挥发性有机物的工艺及装置。The invention relates to the technical field of waste gas treatment, in particular to a process and device for hydrolysis-oxidation two-stage degradation of chlorine-containing volatile organic compounds.
背景技术Background technique
含氯挥发性有机物(CVOCs)主要来自工业废气，由于其对环境产生持久性的危害而日益受到人们的重点关注。Chlorine-containing volatile organic compounds (CVOCs) mainly come from industrial waste gas, and they have received increasing attention due to their persistent damage to the environment.
CVOCs一般来源于氯乙烯、除草剂、塑料等的生产与使用。CVOCs具有高生物毒性和高持久性，并且一部分CVOCs(如二氯甲烷、四氯乙烯)能够破坏臭氧层和加剧全球变暖，对人类健康造成了严重危害。CVOCs的工业排放已被许多国家的法律明令禁止，因此更需要对其妥善处理。CVOCs generally come from the production and use of vinyl chloride, herbicides, and plastics. CVOCs have high biological toxicity and high persistence, and some CVOCs (such as methylene chloride and tetrachloroethylene) can destroy the ozone layer and exacerbate global warming, causing serious harm to human health. Industrial emissions of CVOCs have been banned by the laws of many countries, so it is more necessary to deal with them properly.
现行的CVOCs处理技术主要分为回收技术和销毁技术，前者包括吸附法、吸收法、冷凝法和膜分离法等，后者则主要包括生物降解法、光催化法、等离子体法、直接燃烧法、催化加氢脱氧法和催化燃烧法等。综合考虑各种方法的使用范围、成本、处理彻底性等多方因素，催化燃烧法被认为是目前最具前景的处理方式。The current CVOCs treatment technology is mainly divided into recycling technology and destruction technology. The former includes adsorption method, absorption method, condensation method and membrane separation method, and the latter mainly includes biodegradation method, photocatalysis method, plasma method, and direct combustion method. , Catalytic hydrodeoxygenation method and catalytic combustion method, etc. Considering various factors such as the scope of application, cost, and thoroughness of treatment, the catalytic combustion method is considered to be the most promising treatment method at present.
催化燃烧技术的核心是催化剂的开发，目前研究主要集中在贵金属催化剂、分子筛催化剂和过渡金属氧化物催化剂。CVOCs催化氧化过程中催化剂的失活主要体现在两方面，一是催化燃烧过程中Cl容易与活性组分反应生成沸点较低的金属氯化物和氯氧化物导致活性组分的流失，二是Cl强吸附在催化剂上导致活性位被占据。The core of catalytic combustion technology is the development of catalysts. The current research is mainly focused on precious metal catalysts, molecular sieve catalysts and transition metal oxide catalysts. The deactivation of the catalyst in the catalytic oxidation process of CVOCs is mainly reflected in two aspects. One is that Cl easily reacts with the active components in the catalytic combustion process to produce metal chlorides and oxychlorides with lower boiling points, which leads to the loss of active components, and the other is Cl. Strong adsorption on the catalyst causes the active sites to be occupied.
公开号为CN110404534A的中国专利文献公开了一种高效抗氯中毒的挥发性有机物催化氧化催化剂及其制备方法，所述催化剂以RuO 2为活性组分，以Sn yTi 1-yO 2或MO x-Sn yTi 1-yO 2混合金属氧化物为载体，该发明通过Sn对TiO 2的掺杂，实现了对载体氧化物晶型的调控，在构建具有高效活化性能的锡钛基催化剂载体的同时，大幅提高了RuO 2在该载体表面的分散度；该催化剂具有对含氯挥发性有机物催化活性高、抗氯中毒性能强和产物对 CO 2选择性高等特点的同时，对普通挥发性有机物也具有较好的脱除效果。 The Chinese patent document with the publication number CN110404534A discloses a highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds and a preparation method thereof. The catalyst uses RuO 2 as the active component and uses Sn y Ti 1-y O 2 or MO x -Sn y Ti 1-y O 2 mixed metal oxide as the support, this invention realizes the control of the crystal form of the support oxide through the doping of TiO 2 by Sn, and is in the construction of a tin-titanium-based catalyst with high-efficiency activation performance. At the same time as the carrier, the dispersion of RuO 2 on the surface of the carrier is greatly improved; the catalyst has the characteristics of high catalytic activity against volatile organic compounds containing chlorine, strong resistance to chlorine poisoning, and high selectivity to CO 2 of the product. Sex organic matter also has a good removal effect.
公开号为CN108295852A的中国专利文献公开了一种针对含氯挥发性有机物的氧化反应的Ce-Zr类催化剂，该发明用Ru负载于Ce-Zr上。The Chinese patent document with the publication number CN108295852A discloses a Ce-Zr catalyst for the oxidation reaction of chlorine-containing volatile organic compounds. The invention uses Ru to support Ce-Zr.
催化燃烧法对特定有机氯化物可以取得理想的处理效果，但是焚烧过程中温度在250-400℃时，容易生成多氯二苯并二噁英(PCDDs)以及多氯二苯呋喃(PCDFs)副产物，而多氯二苯并二噁英和多氯二苯呋喃是一种高毒性、高致癌性以及高持久性的含氯有机污染物。Catalytic combustion can achieve ideal treatment effects on specific organic chlorides, but when the temperature is 250-400℃ during the incineration process, it is easy to produce polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Products, and polychlorinated dibenzodioxins and polychlorinated dibenzofurans are highly toxic, carcinogenic and persistent chlorinated organic pollutants.
发明内容Summary of the invention
本发明提供了一种水解-氧化两段式降解含氯挥发性有机物的工艺，同时具有投资及运行成本较低、操作简单、运行安全及高毒副产物较少等优点。The invention provides a two-stage hydrolysis-oxidation process for degrading chlorine-containing volatile organic compounds, and at the same time has the advantages of lower investment and operating costs, simple operation, safe operation, fewer high-toxic by-products, and the like.
具体技术方案如下：The specific technical solutions are as follows:
一种水解-氧化两段式降解含氯挥发性有机物的工艺，包括以下步骤：A two-stage hydrolysis-oxidation process for degrading chlorine-containing volatile organic compounds includes the following steps:
(1)在100-250℃下，对含氯挥发性有机物进行催化水解脱氯反应，生成HCl和脱氯挥发性有机物；(1) Catalytic hydrolysis and dechlorination of chlorine-containing volatile organic compounds at 100-250°C to generate HCl and dechlorinated volatile organic compounds;
(2)将HCl和脱氯挥发性有机物通过脱氯剂，脱除其中的HCl；(2) Pass HCl and dechlorinated volatile organic compounds through a dechlorinating agent to remove HCl;
(3)在200-500℃下，对脱氯挥发性有机物进行催化深度氧化反应。(3) Catalytic deep oxidation reaction of dechlorinated volatile organic compounds at 200-500°C.
本发明将低温水解和高温氧化两段联合起来对含氯挥发性有机物进行处理，并且前后两段配备不同的催化剂材料，两段中间加有脱氯剂对中间产物进行吸收。前段主要对含氯挥发性有机物进行脱氯，减少反应体系中的氯含量；中段主要对中间产物HCl进行去除，防止其对后段的反应效果产生负面影响；后段主要是对脱氯之后的挥发性有机物进行降解。The invention combines two stages of low-temperature hydrolysis and high-temperature oxidation to process chlorine-containing volatile organic compounds, and the front and back stages are equipped with different catalyst materials, and a dechlorination agent is added between the two stages to absorb the intermediate product. The first stage mainly dechlorinates chlorine-containing volatile organic compounds to reduce the chlorine content in the reaction system; the middle stage mainly removes the intermediate product HCl to prevent it from negatively affecting the reaction effect of the latter stage; the latter stage mainly dechlorination Volatile organic compounds are degraded.
本发明先低温水解脱氯，再将氯吸收，防止氯进入高温氧化段，这样既能防止高温氧化催化剂氯中毒而失去活性，还可以防止氯在高温条件下产生毒性更强的含氯副产物。The invention first hydrolyzes and dechlorines at low temperature, and then absorbs chlorine to prevent chlorine from entering the high-temperature oxidation section. This can prevent the high-temperature oxidation catalyst from being poisoned by chlorine and lose its activity, and it can also prevent chlorine from generating more toxic chlorine-containing by-products under high-temperature conditions. .
所述的含氯挥发性有机物的浓度为10-10000ppm；所述含氯挥发性有机物中含水汽0.1-25％。The concentration of the chlorine-containing volatile organic compound is 10-10000 ppm; the chlorine-containing volatile organic compound contains 0.1-25% of water vapor.
优选的，所述的含氯挥发性有机物为氯苯、二氯甲烷、一氯甲烷和二氯乙烯中的至少一种。Preferably, the chlorine-containing volatile organic compound is at least one of chlorobenzene, dichloromethane, monochloromethane and dichloroethylene.
进一步优选的，步骤(1)-(3)中，反应器内气体的空速为1000-15000h -1。 Further preferably, in steps (1)-(3), the space velocity of the gas in the reactor is 1000-15000 h -1 .
优选的，步骤(1)中，催化水解脱氯的水解催化剂为改性处理的镧系基催化剂；进一步优选的，所述的水解催化剂的制备方法为：将镧系金属氧化物或氧化物与助剂的混合物浸渍于过量的磷酸溶液中，吸附饱和后水洗至中性，烘干，再300-500℃煅烧3-10个小时，即得。Preferably, in step (1), the hydrolysis catalyst that catalyzes the hydrolysis and dechlorination is a modified lanthanide-based catalyst; further preferably, the preparation method of the hydrolysis catalyst is: combining a lanthanide metal oxide or oxide with The mixture of additives is immersed in an excess of phosphoric acid solution, adsorbed and saturated, washed with water to neutrality, dried, and then calcined at 300-500°C for 3-10 hours to obtain.
所述的镧系基催化剂为铈基催化剂；所述的助剂为氧化锆。The lanthanide-based catalyst is a cerium-based catalyst; the auxiliary agent is zirconia.
步骤(2)中，脱氯剂对HCl具有良好的吸收效果。优选的，步骤(2)中，所述的脱氯剂为碱、碱金属和碱土金属氧化物中的至少一种；最优选的，所述的脱氯剂为CaO。In step (2), the dechlorination agent has a good absorption effect on HCl. Preferably, in step (2), the dechlorination agent is at least one of alkali, alkali metal and alkaline earth metal oxide; most preferably, the dechlorination agent is CaO.
优选的，步骤(3)中，在200-300℃下，对脱氯挥发性有机物进行催化深度氧化反应。Preferably, in step (3), the dechlorinated volatile organic compounds are subjected to a catalytic deep oxidation reaction at 200-300°C.
步骤(3)中，对脱氯挥发性有机物催化深度氧化反应时需要通入氧气，使含氧量为5～20％。In step (3), oxygen gas needs to be blown into the catalytic deep oxidation reaction of the dechlorinated volatile organic compounds so that the oxygen content is 5-20%.
优选的，氧化催化剂以高比面材料或高性能稀土储氧材料为载体，以Pt、Pd、Mn和Co中的至少一种为主要活性成份。Preferably, the oxidation catalyst uses a high specific surface material or a high performance rare earth oxygen storage material as a carrier, and uses at least one of Pt, Pd, Mn and Co as the main active component.
所述的氧化催化剂可以选择市售的氧化催化剂，例如市售的1％Pt-TiO 2催化剂或Ce 0.1Mn 0.9O 2催化剂。 The oxidation catalyst can be a commercially available oxidation catalyst, such as a commercially available 1% Pt-TiO 2 catalyst or a Ce 0.1 Mn 0.9 O 2 catalyst.
本发明的处理工艺对含氯挥发性有机物的脱除率可以达到95％以上。经检测，水解段的脱氯效果良好，经氧化段深度氧化后，尾气中未检测到二噁英。The removal rate of chlorine-containing volatile organic compounds by the treatment process of the present invention can reach more than 95%. After testing, the dechlorination effect of the hydrolysis section was good, and after deep oxidation in the oxidation section, no dioxins were detected in the tail gas.
本发明还提供了一种水解-氧化两段式降解含氯挥发性有机物的装置，包括依次连通的催化水解反应炉、HCl脱除仓和催化深度氧化反应炉；The present invention also provides a two-stage hydrolysis-oxidation device for degrading chlorine-containing volatile organic compounds, which includes a catalytic hydrolysis reaction furnace, an HCl removal chamber and a catalytic deep oxidation reaction furnace connected in sequence;
所述催化水解反应炉内设有水解催化剂，在100-250℃下，含氯挥发性有机物在水解催化剂作用下生成HCl和脱氯挥发性有机物；The catalytic hydrolysis reaction furnace is provided with a hydrolysis catalyst, and at 100-250°C, the chlorine-containing volatile organic compounds generate HCl and dechlorinated volatile organic compounds under the action of the hydrolysis catalyst;
所述HCl脱除仓内设置有用于吸收HCl的脱氯剂；The HCl removal bin is provided with a dechlorination agent for absorbing HCl;
所述催化深度氧化反应炉内设置有氧化催化剂，在200-500℃下，脱氯挥发性有机物在氧化催化剂作用下氧化降解。An oxidation catalyst is arranged in the catalytic deep oxidation reaction furnace, and the dechlorinated volatile organic compounds are oxidized and degraded under the action of the oxidation catalyst at 200-500°C.
优选的，所述水解催化剂为改性处理的镧系基催化剂；所述脱氯剂为碱、碱金属和碱土金属氧化物中的至少一种；所述氧化催化剂以高性能稀土储氧材料为载体，以Pt、Pd、Mn和Co中的至少一种为主要活性成份。Preferably, the hydrolysis catalyst is a modified lanthanide-based catalyst; the dechlorination agent is at least one of alkali, alkali metal and alkaline earth metal oxide; the oxidation catalyst is a high-performance rare earth oxygen storage material The carrier has at least one of Pt, Pd, Mn and Co as the main active ingredient.
优选的，所述的催化水解反应炉和催化深度氧化反应炉炉体设有保温 层。Preferably, the furnace body of the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace is provided with an insulation layer.
优选的，所述的催化水解反应炉、HCl脱除仓以及催化深度氧化反应炉通过热气管路连通；所述的热气管路的内壁和外表面均设有隔热材料层。Preferably, the catalytic hydrolysis reaction furnace, the HCl removal chamber and the catalytic deep oxidation reaction furnace are connected through a hot gas pipeline; the inner wall and the outer surface of the hot gas pipeline are both provided with a thermal insulation material layer.
优选的，所述的催化水解反应炉和催化深度氧化反应炉内设有电辅助加热器。Preferably, an electric auxiliary heater is provided in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace.
优选的，所述的水解-氧化两段式降解含氯挥发性有机物的装置还包括相互电连接的控制***和温度传感器；所述温度传感器用于采集催化水解反应炉和催化深度氧化反应炉内的温度并传输给控制***；当催化水解反应炉和催化深度氧化反应炉内的温度大于设定阈值时，控制***驱动电辅助加热器关闭，停止加热；当催化水解反应炉和催化深度氧化反应炉内的温度小于设定阈值时，控制***驱动电辅助加热器开启，进行加热。Preferably, the hydrolysis-oxidation two-stage degradation device for chlorine-containing volatile organic compounds further includes a control system and a temperature sensor that are electrically connected to each other; the temperature sensor is used to collect the inside of the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace When the temperature in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace is greater than the set threshold, the control system drives the electric auxiliary heater to turn off and stop heating; when the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction When the temperature in the furnace is less than the set threshold, the control system drives the electric auxiliary heater to turn on for heating.
优选的，所述的水解-氧化两段式降解含氯挥发性有机物的装置还包括尾气检测***，用于检测排放尾气的成分。Preferably, the hydrolysis-oxidation two-stage degradation device for chlorine-containing volatile organic compounds further includes a tail gas detection system for detecting the components of the exhaust tail gas.
本发明的工艺和装置将水解和氧化两段催化有效结合，前段主要对含氯挥发性有机物进行脱氯，并通过HCl脱除仓对中间产物HCl进行去除，减少反应体系中的氯含量，防止后段氧化催化剂的失活；后段主要是对脱氯之后的挥发性有机物进行进一步降解，使脱氯有机物进一步分解成CO 2、H 2O等小分子无机物。整个工艺对工业含氯VOCs的去除效率高、处理效果稳定，保障了低副产物的排放，另外由于催化温度较低节约了成本，适用于大风量低浓度的工业含氯VOCs的处理。 The process and device of the present invention effectively combine the two stages of hydrolysis and oxidation. The front stage mainly dechlorinates chlorine-containing volatile organic compounds, and removes the intermediate product HCl through the HCl removal bin, thereby reducing the chlorine content in the reaction system and preventing The deactivation of the oxidation catalyst in the latter stage; the latter stage is mainly to further degrade the volatile organic matter after dechlorination, so that the dechlorinated organic matter is further decomposed into CO 2 , H 2 O and other small molecular inorganic substances. The entire process has high removal efficiency for industrial chlorine-containing VOCs, stable treatment effect, and guarantees low by-product emissions. In addition, the low catalytic temperature saves costs and is suitable for the treatment of industrial chlorine-containing VOCs with high air volume and low concentration.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
(1)将工业含氯VOCs的处理工艺分成了水解+氧化两个步骤，利用第一步水解将含氯VOCs的氯元素以HCl的形式脱除，脱氯VOCs进一步被氧化，解决了工业含氯VOCs处理时催化剂稳定性不好的缺点；(1) The treatment process of industrial chlorine-containing VOCs is divided into two steps: hydrolysis + oxidation. The chlorine element of chlorine-containing VOCs is removed in the form of HCl by the first hydrolysis, and the dechlorinated VOCs are further oxidized, which solves the problem of industrial pollution. Disadvantages of poor catalyst stability during chlorine VOCs treatment;
(2)在本发明的水解体系里，所需要的温度较低，能耗消耗较少。由于催化深度氧化反应炉中处理的VOCs主要都已经脱氯，所需要的处理温度较含氯VOCs较低，减少了能耗；(2) In the hydrolysis system of the present invention, the required temperature is lower and the energy consumption is less. Since the VOCs processed in the catalytic deep oxidation reactor are mainly dechlorinated, the processing temperature required is lower than that of the chlorine-containing VOCs, which reduces energy consumption;
(3)整个反应体系避免了高毒性副产物二噁英的生成温度区间，体系中的氯元素主要以HCl的形式从体系中脱除，氯元素很少进入到后段的催化深度氧化反应炉，减少了多氯高毒性副产物如二噁英等的生成，对环 境更友好。(3) The entire reaction system avoids the generation temperature range of the highly toxic by-product dioxin. The chlorine element in the system is mainly removed from the system in the form of HCl, and the chlorine element rarely enters the subsequent catalytic deep oxidation reaction furnace. , It reduces the production of polychlorinated highly toxic by-products such as dioxins, and is more environmentally friendly.
附图说明Description of the drawings
图1为水解-氧化两段式降解含氯挥发性有机物的装置结构示意图。Figure 1 is a schematic diagram of the structure of a two-stage hydrolysis-oxidation device for degradation of chlorine-containing volatile organic compounds.
具体实施方式Detailed ways
下面结合附图和实施例对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be pointed out that the embodiments described below are intended to facilitate the understanding of the present invention and do not have any limiting effect on it.
如图1所示，本发明的水解-氧化两段式降解含氯挥发性有机物的装置包括依次连通的催化水解反应炉1、HCl脱除仓2以及催化深度氧化反应炉3。催化水解反应炉1、HCl脱除仓2和催化深度氧化反应炉3通过热气管路5连通，在催化深度氧化反应炉3的出气口还设有尾气检测***6。热气管路5的内壁设置内隔热材料层，外表面设置外隔热材料层。As shown in FIG. 1, the hydrolysis-oxidation two-stage degrading chlorine-containing volatile organic compound device of the present invention includes a catalytic hydrolysis reaction furnace 1, an HCl removal chamber 2 and a catalytic deep oxidation reaction furnace 3 connected in sequence. The catalytic hydrolysis reaction furnace 1, the HCl removal bin 2 and the catalytic deep oxidation reaction furnace 3 are connected through a hot gas pipeline 5, and an exhaust gas detection system 6 is also provided at the gas outlet of the catalytic deep oxidation reaction furnace 3. The inner wall of the hot gas pipeline 5 is provided with an inner insulating material layer, and the outer surface is provided with an outer insulating material layer.
催化水解反应炉1和催化深度氧化反应炉3还设有电辅助加热器及控制***4，电辅助加热器及控制***4具有温度传感器4-1。温度传感器4-1位于催化水解反应炉1和催化深度氧化反应炉3内，对炉内的温度给予采集，温度传感器4-1的信息输出端与控制***连接，控制***的输出端与电辅助加热器的启闭开关连接；当温度传感器4-1传输至控制***的温度值超过设定温度范围最大阀值时，控制***驱动电辅助加热器关闭，停止加热；当温度传感器4-1传输至控制***的温度值低于设定温度范围最小阀值时，控制***驱动电辅助加热器开启，进行辅助加热。The catalytic hydrolysis reaction furnace 1 and the catalytic deep oxidation reaction furnace 3 are also provided with an electric auxiliary heater and control system 4, and the electric auxiliary heater and control system 4 has a temperature sensor 4-1. The temperature sensor 4-1 is located in the catalytic hydrolysis reaction furnace 1 and the catalytic deep oxidation reaction furnace 3, and collects the temperature in the furnace. The information output terminal of the temperature sensor 4-1 is connected with the control system, and the output terminal of the control system is connected with the electric auxiliary The on/off switch of the heater is connected; when the temperature value transmitted by the temperature sensor 4-1 to the control system exceeds the maximum threshold of the set temperature range, the control system drives the electric auxiliary heater to turn off and stop heating; when the temperature sensor 4-1 transmits When the temperature value of the control system is lower than the minimum threshold value of the set temperature range, the control system drives the electric auxiliary heater to turn on for auxiliary heating.
催化水解反应炉1的加热炉膛由外壳1-1围成，外壳1-1内还设有保温材料1-2。加热炉膛内设有水解催化剂填料层1-3。水解催化剂是磷酸改性处理的镧系基催化剂，然后经过成型制备而成的蜂窝状或者颗粒状催化剂。The heating chamber of the catalytic hydrolysis reaction furnace 1 is surrounded by a shell 1-1, and the shell 1-1 is also provided with a heat preservation material 1-2. The heating furnace is provided with hydrolysis catalyst packing layers 1-3. The hydrolysis catalyst is a lanthanide-based catalyst modified by phosphoric acid and then formed into a honeycomb or granular catalyst.
HCl脱除仓2内设有脱HCl填料层2-1。HCl脱除仓2内的填料为CaO或者其他碱金属/碱土金属氧化物，能对HCl有良好的吸收效果。The HCl removal chamber 2 is provided with a HCl removal packing layer 2-1. The filler in the HCl removal chamber 2 is CaO or other alkali metal/alkaline earth metal oxides, which can have a good absorption effect on HCl.
催化深度氧化反应炉3的结构与催化水解反应炉1的结构相似，其加热炉膛由外壳围成，外壳内还设有保温材料。加热炉膛内设有氧化催化剂填料层。氧化催化剂以高性能稀土储氧材料为载体，以贵金属Pt、Pd或 过渡金属Mn、Co等为主要活性成份，用高分散率均匀分布的方法制备而成，活性组分和载体的质量比为(0.01～0.1):1。The structure of the catalytic deep oxidation reaction furnace 3 is similar to that of the catalytic hydrolysis reaction furnace 1, and the heating furnace chamber is surrounded by a shell, and the shell is also provided with insulation materials. An oxidation catalyst packing layer is arranged in the heating furnace. The oxidation catalyst is prepared with high-performance rare earth oxygen storage materials as the carrier, precious metals Pt, Pd or transition metals Mn, Co, etc. as the main active ingredients, and is prepared by a high dispersion rate uniform distribution method. The mass ratio of the active components to the carrier is (0.01～0.1):1.
水解-氧化两段式高效稳定降解工业含氯挥发性有机物的方法为：工业烟气先通过催化水解反应炉，利用烟气中本身含有的水汽(最佳范围为0.1％-25.0％)，发生水解脱氯反应，生成HCl和脱氯VOCs，进入HCl脱除仓，HCl被HCl脱除仓中的脱氯剂脱除，脱氯VOCs进入催化深度氧化反应炉，在催化深度氧化反应炉中，脱氯VOCs进一步被深度氧化。The two-stage hydrolysis-oxidation method for high-efficiency and stable degradation of industrial chlorine-containing volatile organic compounds is as follows: industrial flue gas first passes through a catalytic hydrolysis reactor, and uses the water vapor contained in the flue gas (the best range is 0.1%-25.0%). The hydrolysis and dechlorination reaction produces HCl and dechlorination VOCs, which enter the HCl removal chamber. The HCl is removed by the dechlorinating agent in the HCl removal chamber. The dechlorinated VOCs enter the catalytic deep oxidation reaction furnace. In the catalytic deep oxidation reaction furnace, The dechlorinated VOCs are further deeply oxidized.
催化水解反应炉内温度设置为100-250℃，催化深度氧化反应炉内温度设置为200-500℃。The temperature in the catalytic hydrolysis reaction furnace is set to 100-250°C, and the temperature in the catalytic deep oxidation reaction furnace is set to 200-500°C.
本发明的装置及方法适用于氯苯、二氯甲烷、一氯甲烷、二氯乙烯等有机物的降解，对这些有机物的脱除率可以达到95％以上，并且尾气中未检测到二噁英等毒副产物。The device and method of the present invention are suitable for the degradation of organic substances such as chlorobenzene, dichloromethane, monochloromethane, and dichloroethylene. The removal rate of these organic substances can reach more than 95%, and no dioxins etc. are detected in the exhaust gas. Toxic by-products.
实施例1Example 1
(1)催化剂：(1) Catalyst:
水解催化剂采用浸渍法制备，以1mol/L磷酸溶液、氧化铈为原料，通过过量浸渍磷酸后烘干，于马弗炉中400℃煅烧3个小时，即得到水解催化剂。The hydrolysis catalyst is prepared by the impregnation method. The hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
氧化催化剂采用市售催化剂1％Pt-TiO 2(江苏博斯纳环境科技有限公司、定制)。 The oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体依次通过催化水解反应炉、HCl脱除仓和催化深度氧化反应炉，初始气体浓度为：[氯苯]＝500ppm，以氮气为载气，10％氧气，0.5％含水量，当含氯挥发性有机物气体空速为10000h -1时，水解段温度为200℃，氧化段温度为250℃时，氯苯的去除率可以达到98％，且尾气中未检测到多氯苯、二噁英等副产物。 Pass the chlorine-containing volatile organic compound gas through the catalytic hydrolysis reaction furnace, the HCl removal chamber and the catalytic deep oxidation reaction furnace in sequence. The initial gas concentration is: [chlorobenzene]=500ppm, using nitrogen as the carrier gas, 10% oxygen, 0.5% containing Water quantity, when the space velocity of the chlorine-containing volatile organic compound gas is 10000h -1 , the temperature of the hydrolysis section is 200℃, and the temperature of the oxidation section is 250℃, the removal rate of chlorobenzene can reach 98%, and no polychlorine is detected in the exhaust gas. By-products such as benzene and dioxins.
对比例1Comparative example 1
(1)催化剂：(1) Catalyst:
氧化催化剂采用市售的1％Pt-TiO 2催化剂。 The oxidation catalyst uses a commercially available 1% Pt-TiO 2 catalyst.
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体通过催化深度氧化反应炉，初始气体浓度为：[氯苯]＝500ppm，以氮气为载气，10％氧气，0.5％含水量，当含氯挥发性有机物气体空速为10000h -1时，氧化段温度为250℃时，氯苯的去除率为83％，尾气中检测到了4.11μg/m 3的对二氯苯以及12种痕量二噁英。 Pass the chlorine-containing volatile organic compound gas through the catalytic deep oxidation reaction furnace. The initial gas concentration is: [chlorobenzene]=500ppm, using nitrogen as the carrier gas, 10% oxygen, 0.5% water content, when the chlorine-containing volatile organic compound gas space velocity When it is 10000h -1 and the oxidation zone temperature is 250°C, the removal rate of chlorobenzene is 83%, and 4.11μg/m 3 p-dichlorobenzene and 12 trace dioxins are detected in the exhaust gas.
实施例2Example 2
(1)催化剂：(1) Catalyst:
水解催化剂采用浸渍法制备，以1mol/L磷酸溶液、氧化锆-氧化铈为原料，通过过量浸渍磷酸后烘干，于马弗炉中400℃煅烧3个小时，即得到水解催化剂。The hydrolysis catalyst is prepared by the impregnation method, using 1 mol/L phosphoric acid solution and zirconium oxide-cerium oxide as raw materials, dipped in excess phosphoric acid and then dried, and calcined in a muffle furnace at 400°C for 3 hours to obtain the hydrolysis catalyst.
氧化催化剂采用市售催化剂Ce 0.1Mn 0.9O 2(江苏博斯纳环境科技有限公司、定制)。 The oxidation catalyst uses a commercially available catalyst Ce 0.1 Mn 0.9 O 2 (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体依次通过催化水解反应炉、HCl脱除仓和催化深度氧化反应炉，初始气体浓度为：[二氯甲烷]＝1000ppm，以氮气为载气，10％氧气，1.0％含水量，当含氯挥发性有机物气体空速为15000h -1时，水解段温度为200℃，氧化段温度为280℃时，二氯甲烷的去除率可以达到96％，且尾气中未检测到三氯甲烷、四氯甲烷、二噁英等多氯副产物。 Pass the chlorine-containing volatile organic compound gas through the catalytic hydrolysis reactor, the HCl removal chamber and the catalytic deep oxidation reactor in sequence. The initial gas concentration is: [dichloromethane]=1000ppm, using nitrogen as carrier gas, 10% oxygen, 1.0% Water content, when the space velocity of the chlorine-containing volatile organic compound gas is 15000h -1 , the temperature of the hydrolysis section is 200℃, and the temperature of the oxidation section is 280℃, the removal rate of dichloromethane can reach 96%, and no detection in the tail gas Polychlorinated by-products such as chloroform, tetrachloromethane, and dioxins.
实施例3Example 3
(1)催化剂：(1) Catalyst:
水解催化剂采用浸渍法制备，以1mol/L磷酸溶液、氧化铈为原料，通过过量浸渍磷酸后烘干，于马弗炉中400℃煅烧3个小时，即得到水解催化剂。The hydrolysis catalyst is prepared by the impregnation method. The hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
氧化催化剂采用市售催化剂1％Pt-TiO 2(江苏博斯纳环境科技有限公司、定制)。 The oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体依次通过催化水解反应炉、HCl脱除仓和催化深度氧化反应炉，初始气体浓度为：[二氯甲烷]＝1000ppm，以氮气为载气，10％氧气，5％含水量，当含氯挥发性有机物气体空速为15000h -1时，水解段温度为200℃，氧化段温度为250℃时，二氯甲烷的去除率可以达到98％，且尾气中未检测到三氯甲烷、四氯甲烷、二噁英等多氯副产物。 Pass the chlorine-containing volatile organic compound gas through the catalytic hydrolysis reactor, the HCl removal chamber and the catalytic deep oxidation reactor in sequence. The initial gas concentration is: [dichloromethane]=1000ppm, using nitrogen as carrier gas, 10% oxygen, 5% Water content, when the space velocity of the chlorine-containing volatile organic compound gas is 15000h -1 , the temperature of the hydrolysis section is 200 ℃, and the temperature of the oxidation section is 250 ℃, the removal rate of methylene chloride can reach 98%, and no detection in the tail gas Polychlorinated by-products such as chloroform, tetrachloromethane, and dioxins.
实施例4Example 4
(1)催化剂：(1) Catalyst:
水解催化剂采用浸渍法制备，以1mol/L磷酸溶液、氧化铈为原料，通过过量浸渍磷酸后烘干，于马弗炉中400℃煅烧3个小时，即得到水解催化剂。The hydrolysis catalyst is prepared by the impregnation method. The hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
氧化催化剂采用市售催化剂1％Pt-TiO 2(江苏博斯纳环境科技有限公司、定制)。 The oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体依次通过催化水解反应炉、HCl脱除仓和催化深度氧化反应炉，初始气体浓度为：[二氯甲烷]＝2000ppm，以氮气为载气，10％氧气，2.0％含水量，当含氯挥发性有机物气体空速为10000h -1时，水解段温度为200℃，氧化段温度为300℃时，二氯甲烷的去除率可以达到95％，且尾气中未检测到三氯甲烷、四氯甲烷、二噁英等多氯副产物。 Pass the chlorine-containing volatile organic compound gas through the catalytic hydrolysis reaction furnace, HCl removal chamber and catalytic deep oxidation reaction furnace in sequence. The initial gas concentration is: [dichloromethane]=2000ppm, using nitrogen as carrier gas, 10% oxygen, 2.0% Water content, when the space velocity of the chlorine-containing volatile organic compound gas is 10000h -1 , the temperature of the hydrolysis section is 200 ℃, and the temperature of the oxidation section is 300 ℃, the removal rate of methylene chloride can reach 95%, and no detection in the tail gas Polychlorinated by-products such as chloroform, tetrachloromethane, and dioxins.
实施例5Example 5
(1)催化剂：(1) Catalyst:
水解催化剂采用浸渍法制备，以1mol/L磷酸溶液、氧化铈为原料，通过过量浸渍磷酸后烘干，于马弗炉中400℃煅烧3个小时，即得到水解催化剂。The hydrolysis catalyst is prepared by the impregnation method. The hydrolysis catalyst is obtained by using 1mol/L phosphoric acid solution and cerium oxide as raw materials, dipping in excess phosphoric acid and drying, and calcining in a muffle furnace at 400°C for 3 hours.
氧化催化剂采用市售催化剂1％Pt-TiO 2(江苏博斯纳环境科技有限公司、定制)。 The oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体依次通过催化水解反应炉、HCl脱除仓和催 化深度氧化反应炉，初始气体浓度为：[一氯甲烷]＝3000ppm，以氮气为载气，10％氧气，1.5％含水量，当含氯挥发性有机物气体空速为10000h -1时，水解段温度为180℃，氧化段温度为250℃时，一氯甲烷的去除率可以达到99％，且尾气中未检测到三氯甲烷、四氯甲烷、二噁英等多氯副产物，仅检测到8.9μg/m 3二氯甲烷。 Pass the chlorine-containing volatile organic compound gas through the catalytic hydrolysis reactor, the HCl removal chamber and the catalytic deep oxidation reactor in sequence. The initial gas concentration is: [monochloromethane]=3000ppm, using nitrogen as carrier gas, 10% oxygen, 1.5% Water content, when the space velocity of the chlorine-containing volatile organic compound gas is 10000h -1 , the temperature of the hydrolysis section is 180℃, and the temperature of the oxidation section is 250℃, the removal rate of monochloromethane can reach 99%, and no detection in the tail gas Among polychlorinated by-products such as chloroform, tetrachloromethane, and dioxins, only 8.9 μg/m 3 methylene chloride was detected.
对比例2Comparative example 2
(1)催化剂：(1) Catalyst:
氧化催化剂采用市售催化剂1％Pt-TiO 2(江苏博斯纳环境科技有限公司、定制)。 The oxidation catalyst used commercially available 1% Pt-TiO 2 catalyst (Jiangsu Perzina Environmental Technology Co., Ltd., customized).
HCl脱除仓中吸附剂采用CaO。CaO is used as the adsorbent in the HCl removal bin.
(2)应用处理：(2) Application processing:
将含氯挥发性有机物气体通过催化深度氧化反应炉，初始气体浓度为：[一氯甲烷]＝3000ppm，以氮气为载气，10％氧气，1.5％含水量，当含氯挥发性有机物气体空速为10000h -1时，氧化段温度为250℃时，一氯甲烷的去除率可以达到92％，尾气中检测到三氯甲烷、四氯甲烷以及65.67μg/m 3二氯甲烷。 Pass the chlorine-containing volatile organic compound gas through the catalytic deep oxidation reaction furnace. The initial gas concentration is: [monochloromethane]=3000ppm, using nitrogen as the carrier gas, 10% oxygen, 1.5% water content, when the chlorine-containing volatile organic compound gas is empty When the speed is 10000h -1 and the temperature of the oxidation section is 250°C, the removal rate of monochloromethane can reach 92%, and trichloromethane, tetrachloromethane and 65.67μg/m 3 methylene chloride are detected in the tail gas.
以上所述的实施例对本发明的技术方案和有益效果进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充和等同替换等，均应包含在本发明的保护范围之内。The above-mentioned embodiments describe in detail the technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Anything within the principle scope of the present invention Any modifications, additions and equivalent replacements made should be included in the protection scope of the present invention.

Claims (10)

  1. 一种水解-氧化两段式降解含氯挥发性有机物的工艺，其特征在于，包括以下步骤：A two-stage hydrolysis-oxidation process for degrading chlorine-containing volatile organic compounds is characterized in that it comprises the following steps:
    (1)在100-250℃下，对含氯挥发性有机物进行催化水解脱氯反应，生成HCl和脱氯挥发性有机物；(1) Catalytic hydrolysis and dechlorination of chlorine-containing volatile organic compounds at 100-250°C to generate HCl and dechlorinated volatile organic compounds;
    (2)将HCl和脱氯挥发性有机物通过脱氯剂，脱除其中的HCl；(2) Pass HCl and dechlorinated volatile organic compounds through a dechlorinating agent to remove HCl;
    (3)在200-500℃下，对脱氯挥发性有机物进行催化深度氧化反应。(3) Catalytic deep oxidation reaction of dechlorinated volatile organic compounds at 200-500°C.
  2. 根据权利要求1所述的水解-氧化两段式降解含氯挥发性有机物的工艺，其特征在于，所述的含氯挥发性有机物的浓度为10-10000ppm；所述含氯挥发性有机物中含水汽0.1-25％。The hydrolysis-oxidation two-stage process for degrading chlorine-containing volatile organic compounds according to claim 1, wherein the concentration of the chlorine-containing volatile organic compounds is 10-10000 ppm; the chlorine-containing volatile organic compounds contain water Steam 0.1-25%.
  3. 根据权利要求1所述的水解-氧化两段式降解含氯挥发性有机物的工艺，其特征在于，步骤(1)中，催化水解脱氯的水解催化剂为改性处理的镧系基催化剂。The hydrolysis-oxidation two-stage process for degradation of chlorine-containing volatile organic compounds according to claim 1, wherein in step (1), the hydrolysis catalyst that catalyzes the hydrolysis and dechlorination is a modified lanthanide-based catalyst.
  4. 根据权利要求3所述的水解-氧化两段式降解含氯挥发性有机物的工艺，其特征在于，所述的水解催化剂的制备方法为：镧系金属氧化物或氧化物与助剂的混合物浸渍于过量的磷酸溶液中，吸附饱和后水洗至中性，烘干，再300-500℃煅烧3-10个小时，即得。The hydrolysis-oxidation two-stage process for degrading chlorine-containing volatile organic compounds according to claim 3, wherein the preparation method of the hydrolysis catalyst is: lanthanide metal oxide or impregnation of a mixture of oxides and additives In the excess phosphoric acid solution, after the adsorption is saturated, the water is washed to neutrality, dried, and then calcined at 300-500°C for 3-10 hours to obtain.
  5. 根据权利要求1所述的水解-氧化两段式降解含氯挥发性有机物的工艺，其特征在于，步骤(2)中，所述的脱氯剂为碱、碱金属和碱土金属氧化物中的至少一种。The hydrolysis-oxidation two-stage process for degrading chlorine-containing volatile organic compounds according to claim 1, wherein in step (2), the dechlorination agent is selected from alkali, alkali metal and alkaline earth metal oxides At least one.
  6. 根据权利要求1所述的水解-氧化两段式降解含氯挥发性有机物的工艺，其特征在于，步骤(3)中，对脱氯挥发性有机物催化深度氧化反应时需要通入氧气，使含氧量为5～20％。The hydrolysis-oxidation two-stage process for degrading chlorine-containing volatile organic compounds according to claim 1, wherein in step (3), oxygen is required to be introduced when the dechlorinated volatile organic compounds are catalyzed and deeply oxidized, so that the The oxygen content is 5-20%.
  7. 一种水解-氧化两段式降解含氯挥发性有机物的装置，其特征在于，包括依次连通的催化水解反应炉、HCl脱除仓和催化深度氧化反应炉；A two-stage hydrolysis-oxidation device for degrading chlorine-containing volatile organic compounds is characterized in that it comprises a catalytic hydrolysis reaction furnace, an HCl removal chamber and a catalytic deep oxidation reaction furnace which are connected in sequence;
    所述催化水解反应炉内设有水解催化剂，在100-250℃下，含氯挥发性有机物在水解催化剂作用下生成HCl和脱氯挥发性有机物；The catalytic hydrolysis reaction furnace is provided with a hydrolysis catalyst, and at 100-250°C, the chlorine-containing volatile organic compounds generate HCl and dechlorinated volatile organic compounds under the action of the hydrolysis catalyst;
    所述HCl脱除仓内设置有用于吸收HCl的脱氯剂；The HCl removal bin is provided with a dechlorination agent for absorbing HCl;
    所述催化深度氧化反应炉内设置有氧化催化剂，在200-500℃下，脱 氯挥发性有机物在氧化催化剂作用下氧化降解。An oxidation catalyst is arranged in the catalytic deep oxidation reaction furnace, and the dechlorinated volatile organic compounds are oxidized and degraded under the action of the oxidation catalyst at 200-500°C.
  8. 根据权利要求7所述的水解-氧化两段式降解含氯挥发性有机物的装置，其特征在于，所述的催化水解反应炉和催化深度氧化反应炉内设有电辅助加热器。The hydrolysis-oxidation two-stage degradation device for chlorine-containing volatile organic compounds according to claim 7, wherein the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace are equipped with electric auxiliary heaters.
  9. 根据权利要求8所述的水解-氧化两段式降解含氯挥发性有机物的装置，其特征在于，所述的水解-氧化两段式降解含氯挥发性有机物的装置还包括相互电连接的控制***和温度传感器；所述温度传感器用于采集催化水解反应炉和催化深度氧化反应炉内的温度并传输给控制***；当催化水解反应炉和催化深度氧化反应炉内的温度大于设定阈值时，控制***驱动电辅助加热器关闭，停止加热；当催化水解反应炉和催化深度氧化反应炉内的温度小于设定阈值时，控制***驱动电辅助加热器开启，进行加热。The device for hydrolysis-oxidation two-stage degradation of chlorine-containing volatile organic compounds according to claim 8, wherein the hydrolysis-oxidation two-stage device for degradation of chlorine-containing volatile organic compounds further comprises an electrical connection control System and temperature sensor; the temperature sensor is used to collect the temperature in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace and transmit it to the control system; when the temperature in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace is greater than the set threshold , The control system drives the electric auxiliary heater to turn off and stops heating; when the temperature in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace is less than the set threshold, the control system drives the electric auxiliary heater to turn on for heating.
  10. 根据权利要求8所述的水解-氧化两段式降解含氯挥发性有机物的装置，其特征在于，所述的水解-氧化两段式降解含氯挥发性有机物的装置还包括尾气检测***，用于检测排放尾气的成分。The device for hydrolysis-oxidation two-stage degradation of chlorine-containing volatile organic compounds according to claim 8, characterized in that the hydrolysis-oxidation two-stage device for degradation of chlorine-containing volatile organic compounds further comprises an exhaust gas detection system. To detect the composition of exhaust gas.
PCT/CN2020/084648 2019-12-25 2020-04-14 Hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds WO2021128658A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911387185.5A CN111001297A (en) 2019-12-25 2019-12-25 Process and device for degrading chlorine-containing volatile organic compounds in two stages of hydrolysis and oxidation
CN201911387185.5 2019-12-25

Publications (1)

Publication Number Publication Date
WO2021128658A1 true WO2021128658A1 (en) 2021-07-01

Family

ID=70118268

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/084648 WO2021128658A1 (en) 2019-12-25 2020-04-14 Hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds

Country Status (2)

Country Link
CN (1) CN111001297A (en)
WO (1) WO2021128658A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113209793A (en) * 2021-05-13 2021-08-06 湖南农业大学 Purification system and purification process for chlorine-containing volatile organic compounds
CN113893581B (en) * 2021-10-28 2022-09-16 南京沿江资源生态科学研究院有限公司 Organic solvent innocent treatment system
CN116371436A (en) * 2023-02-08 2023-07-04 美瑞科技(河南)有限公司 Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101247879A (en) * 2005-06-13 2008-08-20 应用材料股份有限公司 Methods and apparatus for process abatement
CN101559319A (en) * 2009-05-13 2009-10-21 北京化工大学 Vapor phase hydrolysis method for carbon tetrachloride and chloroform
CN109603869A (en) * 2019-01-23 2019-04-12 浙江大学 The cerium oxide catalyst and its preparation method and application of phosphoric acid modification

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108126685A (en) * 2017-11-14 2018-06-08 浙江大学 Two-part catalyst of catalytic degradation VOCs containing chlorine and its preparation method and application
CN109939501A (en) * 2019-04-03 2019-06-28 西安飞机工业（集团）有限责任公司 A kind of milling glue spraying waste gas processing method containing tetrachloro-ethylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101247879A (en) * 2005-06-13 2008-08-20 应用材料股份有限公司 Methods and apparatus for process abatement
CN101559319A (en) * 2009-05-13 2009-10-21 北京化工大学 Vapor phase hydrolysis method for carbon tetrachloride and chloroform
CN109603869A (en) * 2019-01-23 2019-04-12 浙江大学 The cerium oxide catalyst and its preparation method and application of phosphoric acid modification

Also Published As

Publication number Publication date
CN111001297A (en) 2020-04-14

Similar Documents

Publication Publication Date Title
WO2021128658A1 (en) Hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds
CN103638761B (en) A kind of method of low temperature plasma coupling and catalyzing oxidation removal foul gas and device thereof
CN109126773B (en) Catalyst for purifying waste incineration flue gas and preparation method thereof
CN101199885A (en) Method for easy volatility Cl generation aromatic low temperature catalyst burning eliminable
CN109603869B (en) Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof
CN105478136A (en) Industrial organic waste gas catalytic degradation catalyst cooperated with low-temperature plasma, and preparation method and application of catalyst
CN104028087B (en) A kind of method and device thereof removing dioxin in high-temperature flue gas
CN101767011A (en) Low-temperature catalytic combustion eliminating method of volatile chloro aryl hydrocarbons
CN101347723A (en) Catalyst for eliminating chlorinated aromatic hydrocarbons by low-temperature catalytic combustion
CN111330606A (en) Catalyst for efficiently degrading chlorine-containing organic waste gas at low temperature and preparation method and application thereof
CN101185796A (en) Chlorination aromatic hydrocarbon waste gases catalytic purification method
CN101513612A (en) Catalyst for removing nitrogen oxide and organic pollutant discharged in burning and method for preparing same
CN101245916A (en) Method for eliminating chloro-aromatics low temperature catalytic combustion
WO1996020786A1 (en) Catalyst for purifying fumigation exhaust gas and purification method of fumigation exhaust gas
CN203108437U (en) System for performing catalytic degradation on dioxin
CN101637722A (en) Catalyst for removing organic pollutants in incineration gas and preparation method thereof
CN101279253A (en) Catalyst for eliminating chlorinated aromatic hydrocarbons by low-temperature catalytic combustion
CN110465301B (en) Active carbon catalyst and preparation method and application thereof
KR100506813B1 (en) Mn oxide catalyst for decomposing ozone and the method therefor
CN101862593A (en) Low-temperature catalytic combustion elimination method for chlorine-containing volatile organic compounds
CN109261144B (en) Catalyst for chlorine-containing organic waste gas treatment process
CN112473657B (en) Low-vanadium catalyst for synergistically removing dioxin and mercury in flue gas and preparation method and application thereof
CN102353064A (en) Method for eliminating chlorinated aromatic hydrocarbons through low temperature catalytic combustion
CN101693206A (en) Catalyst for removing low concentration benzene series matter in gas at room temperature and application thereof
CN102794107A (en) Method and system for catalyzing and degrading dioxin

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20905292

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20905292

Country of ref document: EP

Kind code of ref document: A1