WO2017036199A1 - 一种抑制固体废物焚烧烟气二噁英类物质生成的方法 - Google Patents

一种抑制固体废物焚烧烟气二噁英类物质生成的方法 Download PDF

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WO2017036199A1
WO2017036199A1 PCT/CN2016/084049 CN2016084049W WO2017036199A1 WO 2017036199 A1 WO2017036199 A1 WO 2017036199A1 CN 2016084049 W CN2016084049 W CN 2016084049W WO 2017036199 A1 WO2017036199 A1 WO 2017036199A1
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flue gas
solid waste
inhibiting
reactor
waste incineration
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何品晶
章骅
王思佳
邵立明
吕凡
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Tongji University
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    • 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
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/61—Phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B01D2258/0291—Flue gases from waste incineration plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/124—Liquid reactants

Definitions

  • the invention belongs to the field of solid waste incineration flue gas purification, and particularly relates to a method for suppressing the formation of dioxins in solid waste incineration flue gas.
  • Incineration technology with the advantages of reduction, high decomposition efficiency of organic matter and energy recovery is the main means of solid waste treatment.
  • China Urban Construction Statistical Yearbook in 2013, China's domestic garbage removal volume was 172 million tons, and incineration treatment accounted for 26.9%.
  • incineration is still the main treatment method for industrial hazardous waste and medical waste, which has been built in the past ten years. All provincial hazardous waste treatment centers use incineration as the main treatment facility.
  • Flue gas is one of the main by-products of solid waste incineration and contains a variety of gas and particulate contaminants. Among them, dioxin-like substances are persistent organic pollutants, which are highly toxic and have cumulative effects in the environment.
  • the purification of dioxin in the flue gas is mainly carried out by spraying the powdered activated carbon before the bag filter, and the dioxin-like substance is removed by the activated carbon on the surface of the dust bag, but the removal rate is low, the highest Not more than 50%, it is difficult to fundamentally control dioxin pollution.
  • Dioxins in Solid Waste Incineration Process There are four possible ways to generate: 1) the release of dioxins inherent in solid waste in the furnace, 2) the formation of dioxins in the furnace at high temperatures, and 3) the specific temperature range in which the dioxin is cooled by the flue gas after the furnace.
  • Dioxins are formed by the synthesis of precursors at a specific temperature range in which the flue gas is cooled after the furnace.
  • dioxin is not an industrial product, and the inherent dioxin content in solid waste is extremely low. Therefore, the contribution of pathway 1 to the formation of dioxins in the incineration process is basically negligible; both pathways 2 and 4 are chlorophenol,
  • Organic chlorides such as polychlorinated biphenyls are the raw materials for the synthesis of dioxins, while modern solid waste incinerators have strict temperature, material mixing and gas residence time control measures. These organic chlorides have extremely high conversion rates in the furnace. The content of such substances in the flue gas is extremely low.
  • the route 3 is simple matter (CO in flue gas, HCl, residual carbon in the granules, etc.) are raw materials. Therefore, the raw materials for synthesizing dioxins are not limited. It has been confirmed as the main production route of incineration flue gas dioxins, and should also be the source of flue gas dioxins. The main link of control.
  • Chinese patent CN 101766951A discloses a system for suppressing the formation of dioxin in a waste incineration process, comprising an incinerator, a cooling device, a first separation device, and the incinerator, the cooling device and the first separation device are sequentially connected in sequence, wherein
  • the cooling device is used for partially recovering thermal energy, and reduces the flue gas including fly ash generated in the incinerator to a temperature range of 400 to 800 ° C
  • the first separating device is used for the flue gas from the cooling device after the treatment
  • the fly ash in the process is subjected to treatment for removal of chlorides, organochlorines, heavy metal particles, and transition metal cations as catalysts.
  • This invention merely suppresses or reduces the formation of dioxins by a physical deashing method, but the suppression effect is poor.
  • Chinese patent CN 204478079U discloses a dioxin re-synthesis quenching device for suppressing flue gas in a low-temperature pyrolysis furnace; flue gas enters the flue gas inlet end from the lower part of the quenching device, flows uniformly upward through the grid plate, and then passes through the heat exchange
  • the carrier is discharged to the flue gas discharge end, and the cooling water circulation system is composed of a chiller, a water pump, a cooling water sprinkling device, and a return water tank.
  • the flue gas flow lines are parallel to each other, and the cooling water is sprayed on the heat exchange carrier to cool the smoke.
  • the gas and the cooling water are treated in a reverse manner, so that the rising flue gas temperature is rapidly cooled from 700 ° C to below 200 ° C within 2 s; however, the direct heat exchange and cooling method of the water and the high temperature flue gas used in the quenching treatment is limited by the simultaneous transfer rate of the thermal mass, actually It is difficult to achieve the required cooling rate; at the same time, quenching treatment also makes it possible to carry out flue gas waste heat recovery (power generation), and it cannot be applied to domestic waste incineration that depends on the cost of power generation compensation.
  • CuCl 2 directly decomposes and provides a chlorine atom to a carbon atom to form a C-Cl bond, which is cleaved by a carbon-carbon bond to form a chlorinated aromatic compound, and a tricyclic chloride (dioxin) is formed by a reaction pathway such as condensation.
  • the CuCl 2 present in the incineration flue gas is converted into a catalytically inert substance before it enters a suitable catalytic reaction temperature range (200-450 ° C), which is an effective method for suppressing the formation of dioxins in solid waste incineration flue gas. .
  • the present invention provides a method for suppressing the formation of dioxins in solid waste incineration flue gas.
  • a method for inhibiting the formation of dioxin-like substances in solid waste incineration flue gas introducing flue gas into a suppression reactor in a temperature range in which the incineration flue gas is cooled to 500 ° C to 450 ° C, so that copper chloride in the flue gas particles is The inhibitor mixing reaction is converted to copper metaphosphate.
  • the ceramic honeycomb filler is layered in the suppression reactor, the thickness of each layer of filler is 50-100 mm, the opening ratio of the filler is 75-85%, the height spacing of each layer of filler is 600-800 mm, and the inhibitor is from the reactor between the layers.
  • the nozzle of the wall is sprayed, and the residence time of the flue gas therein is 1.5 to 2.5 s.
  • the inhibitor is ammonium dihydrogen phosphate.
  • ammonium dihydrogen phosphate and water are uniformly mixed into a slurry at a mass ratio of 1:4, and the slurry is used in a standard state volume of 10% to 15 g/ The ratio of Nm 3 is sprayed into the suppression reactor through nozzle atomization.
  • Forming a titanium also confirmed by experiment Cu (PO 3) 2 uncatalyzed; ammonium dihydrogen phosphate (NH 4 H 2 PO 4) by the following reaction process for the partial conversion of CuCl 2 copper phosphate (Cu (PO 3) 2) The ability of dioxin-like substances.
  • the above reaction of converting CuCl 2 into Cu(PO 3 ) 2 can occur instantaneously at a temperature of 200 to 900 ° C, and satisfies the requirements for application in the process of cooling the flue gas.
  • the suppression reactor is cylindrical and has a height to diameter ratio of 4.5:1 to 5.5:1.
  • the shape of the opening of the filler is a regular quadrilateral or a hexagon, and the side of the regular quadrilateral or the hexagonal hole is 50 to 100 mm long.
  • the suppression reactor wall is also provided with a high pressure steam nozzle for blowing off the surface ash of the filler.
  • a gas flow distribution plate is disposed in the suppression reactor near the inlet of the flue gas, and the flue gas is uniformly dispersed.
  • the present invention has the following advantages and beneficial effects:
  • the invention can effectively control the main generation route of dioxins in solid waste incineration flue gas by optimizing the inhibitor and optimizing the reaction conditions.
  • control method of the present invention does not affect the utilization of waste heat of solid waste incineration flue gas, so that it has better Resource utilization effect.
  • the ammonium dihydrogen phosphate inhibitor used in the invention has the advantages of high inhibition efficiency, strong operability, low cost and environmental friendliness, and the technology has good application feasibility.
  • Figure 1 is a schematic view showing the structure of a reactor.
  • 1 is the flue gas inlet
  • 2 is the flue gas outlet
  • 3 is the packing layer
  • 4 is the gas flow distribution plate
  • 5 is the inhibitor nozzle
  • 6 is the high pressure steam nozzle.
  • the domestic waste incinerator has a treatment capacity of 10 t/h and a flue gas flow of about 54,000 Nm 3 /h (15 Nm 3 /s) under steady operation.
  • the average temperature of the incineration flue gas is 850 ° C. After heat exchange between the boiler and the superheater, the flue gas temperature drops to about 480 ° C, and then enters the suppression reactor.
  • the reactor structure was restrained as shown in Fig. 1, which included a cylindrical cylinder which inhibited the reactor diameter of 2.8 m, height of 7 m, and internal volume of 86 m 3 .
  • the flue gas inlet 1 is disposed at the bottom end of the reactor, the flue gas outlet 2 is disposed at the upper end of the reactor, and the upper and lower portions of the reactor are respectively provided with a diversion section having a height of about 1 m, and a frustoconical air distribution plate 4 is disposed above the flue gas inlet 1.
  • the flue gas is uniformly dispersed.
  • One layer of ceramic honeycomb filler layer 3 (thickness: 0.1 m) was set at 0.7 m intervals in the middle of the reactor, and seven layers of filler layer 3 were provided (with a packing height of 4.9 m).
  • the ceramic honeycomb filler has a thickness of 0.1 m and is uniformly opened with a regular hexagonal hole, and the side of the hole is 60 mm long.
  • the reactor wall on the upper part of each layer of packing is provided with an inhibitor nozzle 5 and a high pressure steam nozzle 6; the axis of the inhibitor nozzle 5 is installed 0.35 m above the upper surface of the packing layer 3, and the high pressure steam nozzle 6 is installed 0.15 m above the upper surface of the packing layer.
  • the inhibitor nozzle 5 and the high pressure steam nozzle 6 are mounted on the same vertical line, and each of the layers of the packing has an inhibitor nozzle 5 and a high pressure steam nozzle 6 (each of which is 56 in total), and is evenly distributed along the circumference of the reactor wall.
  • the flue gas passes through the suppression reactor from bottom to top, and the residence time of the flue gas in the reactor is about 2.0s; the amount of inhibitor which is uniformly mixed into a slurry according to the mass ratio of ammonium dihydrogen phosphate to water 1:4 is 64.8kg/h. It is evenly distributed to each nozzle, and is injected into the reactor with a pulse of 0.5 s to react with CuCl 2 in the flue gas to convert it into copper metaphosphate to inhibit the formation of dioxins. High pressure steam (about 0.8 MPa) is also injected into the upper surface of the packing layer at 0.5 s intervals to avoid accumulation of particulate matter in the flue gas, and it also improves the turbulent mixing in the reactor to make the reaction more complete.
  • a method for inhibiting the formation of dioxin-like substances in solid waste incineration flue gas introducing flue gas into a suppression reactor in a temperature range in which the incineration flue gas is cooled to 500 ° C to 450 ° C, so that copper chloride in the flue gas particles is The inhibitor mixing reaction is converted to copper metaphosphate.
  • Example 1 the difference from Example 1 was that the reactor was restrained to have a columnar shape with a height to diameter ratio of 4.5:1.
  • the ceramic honeycomb filler is arranged in the reactor layer, the thickness of each layer is 50mm, the opening ratio of the filler is 75%, the plane shape of the filler opening is a regular hexagon, and the side of the hole is 50mm.
  • the height of each layer of the filler is 600 mm, and the inhibitor is sprayed from the inhibitor nozzle of the reactor wall between the layers of the packing, and the reactor wall is restrained and a high pressure steam nozzle is provided for blowing off the surface ash of the filler.
  • the flue gas passes through the suppression reactor from bottom to top, and the residence time of the flue gas in the reactor is 1.5s; the slurry is uniformly mixed into a slurry according to the mass ratio of ammonium dihydrogen phosphate to water 1:4 to treat the standard volume of the flue gas.
  • the slurry was atomized into the suppression reactor through a nozzle at a ratio of 10 g/Nm 3 .
  • a method for inhibiting the formation of dioxin-like substances in solid waste incineration flue gas introducing flue gas into a suppression reactor in a temperature range in which the incineration flue gas is cooled to 500 ° C to 450 ° C, so that copper chloride in the flue gas particles is The inhibitor mixing reaction is converted to copper metaphosphate.
  • Example 1 the difference from Example 1 was that the reactor was restrained to have a cylindrical shape with a height to diameter ratio of 5:1.
  • the ceramic honeycomb filler was arranged in the reactor layer, the thickness of each layer of packing was 80 mm, the opening ratio of the packing was 80%, the plane shape of the packing opening was a regular quadrilateral, and the side of the hole was 80 mm long.
  • the height of each layer of filler is 700 mm, and the inhibitor is sprayed from the inhibitor nozzle of the reactor wall between the layers of the packing, and the reactor wall is restrained and a high pressure steam nozzle is provided for blowing off the surface ash of the filler.
  • the flue gas passes through the suppression reactor from bottom to top, and the residence time of the flue gas in the reactor is 2.0 s; the slurry is uniformly mixed into a slurry according to the mass ratio of ammonium dihydrogen phosphate to water 1:4 to treat the standard state volume of the flue gas.
  • the slurry was sprayed into the suppression reactor at a ratio of 12 g/Nm 3 through a nozzle.
  • a method for inhibiting the formation of dioxin-like substances in solid waste incineration flue gas introducing flue gas into a suppression reactor in a temperature range in which the incineration flue gas is cooled to 500 ° C to 450 ° C, so that copper chloride in the flue gas particles is The inhibitor mixing reaction is converted to copper metaphosphate.
  • Example 1 the difference from Example 1 was that the reactor was restrained to have a columnar shape with a height to diameter ratio of 5.5:1.
  • the ceramic honeycomb filler is arranged in the reactor layer, the thickness of each layer of packing is 100mm, the opening ratio of the packing is 85%, the plane shape of the packing opening is regular quadrilateral, and the side of the hole is 100mm long.
  • the height of each layer of packing is 800 mm, and the inhibitor is sprayed from the inhibitor nozzle of the reactor wall between the layers of the packing, and the reactor wall is restrained and a high pressure steam nozzle is provided for blowing off the surface ash of the filler.
  • the flue gas passes through the suppression reactor from bottom to top, and the residence time of the flue gas in the reactor is 2.5s; the slurry is uniformly mixed into a slurry according to the mass ratio of ammonium dihydrogen phosphate to water 1:4 to treat the standard state volume of the flue gas.
  • the slurry was atomized into the suppression reactor through a nozzle at a ratio of 15 g/Nm 3 .

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Abstract

一种抑制固体废物焚烧烟气二噁英类物质生成的方法，在焚烧烟气降温至500℃至450℃的温度段，将烟气引入抑制反应器，使烟气颗粒物中的氯化铜与抑制剂混合反应转化为偏磷酸铜，使其失去催化生成二噁英类物质的活性，可源头控制焚烧烟气的二噁英类污染物。

Description

一种抑制固体废物焚烧烟气二噁英类物质生成的方法 技术领域
本发明属于固体废物焚烧烟气净化领域，尤其是涉及一种抑制固体废物焚烧烟气二噁英类物质生成的方法。
背景技术
具有减量化、有机物分解效率高和能源回收等优点的焚烧技术是固体废物处理的主要手段。根据《中国城市建设统计年鉴》，2013年我国生活垃圾清运量为1.72亿吨，焚烧处理量占了26.9％；同时，焚烧还是工业危险废物和医疗废物的主要处理方法，近十年来陆续建成的各个省级危险废物处理中心均以焚烧为主要处理设施。烟气是固体废物焚烧处理的主要副产物之一，含有多种气相和颗粒污染物。其中，二噁英类物质属持久性有机污染物，毒性大、在环境中有累积效应。目前，烟气中二噁英类物质的净化主要采用在袋式除尘器前喷入粉末活性炭的方法，通过活性炭在除尘袋表面成膜吸附去除二噁英类物质，但去除率较低，最高不超过50％，难以根本性地控制二噁英类污染。
由于缺乏高效率的末端净化方法，因此有必要探索烟气中二噁英类物质的源头控制技术。根据近年来的研究(曹玉春，严建华，李晓东，陈彤，岑可法，垃圾焚烧炉中二噁英生成机理的研究进展，热力发电，34(2005)，15-20.)，固体废物焚烧过程二噁英生成的可能途径有4种：1)固体废物中固有的二噁英在炉内释放，2)二噁英在炉内高温气相生成，3)二噁英在炉后烟气降温的特定温度段从头合成生成，4)二噁英在炉后烟气降温的特定温度段通过前驱物合成生成。上述途径中，因二噁英并非工业产物，固体废物中固有的二噁英含量极低，因此，途径1对焚烧过程二噁英生成的贡献基本可以忽略；途径2和4均以氯酚、多氯联苯等有机氯化物为二噁英合成的原料，而现代固体废物焚烧炉有严格的温度、物料混合和气体停留时间的控制措施，这些有机氯化物在炉内的转化率均极高，烟气中此类物质含量极低，这2种途径受到原料量的制约，也不太可能成为焚烧过程二噁英生成的主要贡献者；而途径3以简单的物质(烟气中CO、HCl、颗粒中的残碳等)为原料，因此，合成二噁英的原料不受限制，目前已确认为焚烧烟气二噁英的主要生成途径，也应是烟气二噁英类物质源头控制的主要环节。为此，我国“危险废物集中焚烧处 置工程建设技术规范(HJ/T176-2005)”规定，焚烧废物产生的高温烟气应采取急冷处理，使烟气温度在1.0s内降到200℃以下，减少烟气在200～500℃温区的滞留时间；这个温度范围正是二噁英类物质从头合成的适宜温度区间。但是，急冷处理采用的水与高温烟气直接换热降温方法受热质同时传递速率限制，实际上很难达到要求的降温速率；同时，急冷处理也使烟气余热回收(发电)不可能实施，对于依赖发电补偿成本的生活垃圾焚烧无法应用。
中国专利CN 101766951A公布了一种垃圾焚烧过程中的抑制二噁英生成的系统，包括焚烧炉、降温装置、第一分离装置，并且，焚烧炉、降温装置、第一分离装置依次顺序连接，其中，降温装置用于部分地回收的热能，并将焚烧炉中产生的包括飞灰的烟气降至400～800℃的温度范围，第一分离装置用于将来自于降温装置处理后的烟气中的飞灰进行脱除氯化物、有机氯、重金属颗粒以及作为催化剂的过渡金属阳离子的处理。该发明只是通过物理除灰的方法，抑制或减少了二噁英的生成，但是其抑制效果差。
中国专利CN 204478079U公布了一种低温热解炉的抑制烟气中二噁英再合成急冷装置；烟气从急冷装置的下部进入烟气进入端，经格栅板均匀向上流动，再经换热载体到烟气排出端排出，冷却水循环系统由冷水机、水泵、冷却水喷淋装置、回水槽组成，烟气流流线彼此平行向上，冷却水喷淋在换热载体上使其降温，烟气与冷却水形成逆向方式处理，使上升烟气温度在2s内从700℃迅速冷却到200℃以下；但是急冷处理采用的水与高温烟气直接换热降温方法受热质同时传递速率限制，实际上很难达到要求的降温速率；同时，急冷处理也使烟气余热回收(发电)不可能实施，对于依赖发电补偿成本的生活垃圾焚烧无法应用。
二噁英类物质从头合成是催化过程，大量的研究已经揭示该过程的关键催化剂是氯化铜(CuCl2)，其催化形成二噁英类物质的能力为其它已知具有催化活性物质的数十倍(马洪亭，张于峰，PCDD/F从头合成的影响因素和抑制方法，化工进展，25(2006)，557-562.)，而CuCl2在催化形成二噁英类物质过程中的主要作用是CuCl2直接分解，并为碳原子提供氯原子而形成C-Cl键，经过碳碳键断裂而形成氯化芳香化合物，再由缩合等反应途径生成三环氯化物(二噁英类物质)。可见，将焚烧烟气中存在的CuCl2在其进入适宜的催化反应温度区间(200～450℃)前转化为催化惰性的物质，是抑制固体废物焚烧烟气二噁英类物质生成的有效方法。
发明内容
针对现阶段缺乏固体废物焚烧烟气中二噁英类物质源头控制方法的问题，本发明提供了一种抑制固体废物焚烧烟气二噁英类物质生成的方法。
本发明的目的可以通过以下技术方案来实现：
一种抑制固体废物焚烧烟气二噁英类物质生成的方法，在焚烧烟气降温至500℃至450℃的温度段，将烟气引入抑制反应器，使烟气颗粒物中的氯化铜与抑制剂混合反应转化为偏磷酸铜。
所述的抑制反应器内分层设置陶瓷蜂窝填料，每层填料厚度50～100mm，填料开孔率75～85％，各层填料的高度间距600～800mm，抑制剂从各层填料间反应器壁的喷嘴喷入，烟气在其中的停留时间为1.5～2.5s。
所述的抑制剂为磷酸二氢铵，使用时磷酸二氢铵与水按质量比1:4均匀混合成浆状物，以处理烟气标准状态体积为基准，浆状物以10～15g/Nm3的比例通过喷嘴雾化喷入抑制反应器内。
磷酸二氢铵(NH4H2PO4)可以通过如下反应过程将CuCl2转化为偏磷酸铜(Cu(PO3)2)；同时也通过实验过程确认Cu(PO3)2没有催化形成二噁英类物质的能力。
NH4H2PO4＝NH3+H2O+HPO3
2HPO3+CuCl2＝Cu(PO3)2+HCl
上述CuCl2转化为Cu(PO3)2的反应在200～900℃的温度条件下均可瞬时发生，满足在烟气降温过程中应用的要求。
所述的抑制反应器为圆柱状，高度与直径比为4.5:1～5.5:1。
所述的填料开孔平面形状为正四边形或六边形，正四边形或六边形孔边长50～100mm。
所述的抑制反应器壁同时设高压蒸汽喷嘴用于吹除填料表面积灰。
所述的抑制反应器内靠近烟气入口处设置有气流分布板，对烟气进行均布分散。
与现有技术相比，本发明具有以下优点及有益效果：
1)本发明通过优化抑制剂，同时对反应条件进行优化，可以实现对固体废物焚烧烟气中二噁英类物质主要生成途径的有效控制。
2)本发明的控制方法不影响固体废物焚烧烟气的余热利用，使其具有较好的 资源利用效应。
3)本发明采用的磷酸二氢铵抑制剂具有抑制效率高、可操作性强、成本低廉、环境友好等优点，使技术具有良好的应用可行性。
附图说明
图1为抑制反应器的结构示意图。
图中，1为烟气入口，2为烟气出口，3为填料层，4为气流分布板，5为抑制剂喷嘴，6为高压蒸汽喷嘴。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
生活垃圾焚烧炉，处理能力为10t/h，稳定运行状态下烟气流量约54000Nm3/h(15Nm3/s)。焚烧烟气出炉平均温度为850℃，经过锅炉、过热器换热后，烟气温度降至约480℃，然后进入抑制反应器。
抑制反应器结构如图1所示，其包括一圆柱形筒体，抑制反应器直径2.8m、高度7m，内部容积86m3。烟气入口1设置在反应器底端，烟气出口2设置在反应器上端，反应器上下部各设高度约1m的导流段，在烟气入口1上方设置有截锥形气流分布板4对烟气进行均布分散。抑制反应器内中段间隔0.7m设1层陶瓷蜂窝填料层3(厚度0.1m)，填料层3共设7层(设填料高度共4.9m)。陶瓷蜂窝填料厚度0.1m，均匀开具正六边形孔，孔边长60mm。每层填料上部的反应器壁面设抑制剂喷嘴5和高压蒸汽喷嘴6；抑制剂喷嘴5轴线高于填料层3上表面0.35m安装，高压蒸汽喷嘴6高于填料层上表面0.15m安装。抑制剂喷嘴5和高压蒸汽喷嘴6安装于同一垂直线，每层填料上部安装抑制剂喷嘴5和高压蒸汽喷嘴6各8个(反应器总共各56个)，沿反应器壁面周长均匀分布。
烟气从下至上通过抑制反应器，烟气在反应器内的停留时间约2.0s；按磷酸二氢铵与水质量比1:4均匀混合成浆状物的抑制剂用量为64.8kg/h，均匀分配至各个喷嘴，间隔0.5s脉冲喷入反应器，与烟气中的CuCl2反应，使其转化为偏磷酸铜以抑制二噁英类物质的生成。高压蒸汽(约0.8MPa)同样以0.5s间隔脉冲喷入填料层上表面以避免烟气中颗粒物在填料上积存，同时也可以改善反应器内的湍流混 合，使反应更为完全。
经试验测定，经过反应器的烟气飞灰中未检出CuCl2，烟气中二噁英类物质从头合成中间体(氯苯、氯酚)的含量比对照降低80％以上。
实施例2
一种抑制固体废物焚烧烟气二噁英类物质生成的方法，在焚烧烟气降温至500℃至450℃的温度段，将烟气引入抑制反应器，使烟气颗粒物中的氯化铜与抑制剂混合反应转化为偏磷酸铜。
其中，与实施例1不同之处在于，抑制反应器为圆柱状，高度与直径比为4.5:1。抑制反应器内分层设置陶瓷蜂窝填料，每层填料厚度50mm，填料开孔率75％，填料开孔平面形状为正六边形，孔边长50mm。各层填料的高度间距600mm，抑制剂从各层填料间反应器壁的抑制剂喷嘴喷入，抑制反应器壁同时设高压蒸汽喷嘴用于吹除填料表面积灰。
烟气从下至上通过抑制反应器，烟气在反应器内的停留时间为1.5s；按磷酸二氢铵与水质量比1:4均匀混合成浆状物，以处理烟气标准状态体积为基准，浆状物以10g/Nm3的比例通过喷嘴雾化喷入抑制反应器内。
经试验测定，经过反应器的烟气飞灰中未检出CuCl2，烟气中二噁英类物质从头合成中间体(氯苯、氯酚)的含量比对照降低81.5％。
实施例3
一种抑制固体废物焚烧烟气二噁英类物质生成的方法，在焚烧烟气降温至500℃至450℃的温度段，将烟气引入抑制反应器，使烟气颗粒物中的氯化铜与抑制剂混合反应转化为偏磷酸铜。
其中，与实施例1不同之处在于，抑制反应器为圆柱状，高度与直径比为5:1。抑制反应器内分层设置陶瓷蜂窝填料，每层填料厚度80mm，填料开孔率80％，填料开孔平面形状为正四边形，孔边长80mm。各层填料的高度间距700mm，抑制剂从各层填料间反应器壁的抑制剂喷嘴喷入，抑制反应器壁同时设高压蒸汽喷嘴用于吹除填料表面积灰。
烟气从下至上通过抑制反应器，烟气在反应器内的停留时间为2.0s；按磷酸二氢铵与水质量比1:4均匀混合成浆状物，以处理烟气标准状态体积为基准，浆状物以12g/Nm3的比例通过喷嘴雾化喷入抑制反应器内。
经试验测定，经过反应器的烟气飞灰中未检出CuCl2，烟气中二噁英类物质从 头合成中间体(氯苯、氯酚)的含量比对照降低83％。
实施例4
一种抑制固体废物焚烧烟气二噁英类物质生成的方法，在焚烧烟气降温至500℃至450℃的温度段，将烟气引入抑制反应器，使烟气颗粒物中的氯化铜与抑制剂混合反应转化为偏磷酸铜。
其中，与实施例1不同之处在于，抑制反应器为圆柱状，高度与直径比为5.5:1。抑制反应器内分层设置陶瓷蜂窝填料，每层填料厚度100mm，填料开孔率85％，填料开孔平面形状为正四边形，孔边长100mm。各层填料的高度间距800mm，抑制剂从各层填料间反应器壁的抑制剂喷嘴喷入，抑制反应器壁同时设高压蒸汽喷嘴用于吹除填料表面积灰。
烟气从下至上通过抑制反应器，烟气在反应器内的停留时间为2.5s；按磷酸二氢铵与水质量比1:4均匀混合成浆状物，以处理烟气标准状态体积为基准，浆状物以15g/Nm3的比例通过喷嘴雾化喷入抑制反应器内。
经试验测定，经过反应器的烟气飞灰中未检出CuCl2，烟气中二噁英类物质从头合成中间体(氯苯、氯酚)的含量比对照降低85％。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (8)

  1. 一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，在焚烧烟气降温至500℃至450℃的温度段，将烟气引入抑制反应器，使烟气颗粒物中的氯化铜与抑制剂混合反应转化为偏磷酸铜。
  2. 根据权利要求1所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的抑制反应器内分层设置陶瓷蜂窝填料，每层填料厚度50～100mm，填料开孔率75～85％，各层填料的高度间距600～800mm，抑制剂从各层填料间反应器壁的喷嘴喷入，烟气在其中的停留时间为1.5～2.5s。
  3. 根据权利要求1或2所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的抑制剂为磷酸二氢铵，使用时磷酸二氢铵与水按质量比1:4均匀混合成浆状物，以处理烟气标准状态体积为基准，浆状物以10～15g/Nm3的比例通过喷嘴雾化喷入抑制反应器内。
  4. 根据权利要求2所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的抑制反应器为圆柱状，高度与直径比为4.5:1～5.5:1。
  5. 根据权利要求2所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的填料开孔平面形状为正四边形或六边形，正四边形或六边形孔边长50～100mm。
  6. 根据权利要求2所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的抑制反应器壁同时设高压蒸汽喷嘴用于吹除填料表面积灰。
  7. 根据权利要求2所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的烟气由下至上通过抑制反应器。
  8. 根据权利要求2所述的一种抑制固体废物焚烧烟气二噁英类物质生成的方法，其特征在于，所述的抑制反应器内靠近烟气入口处设置有气流分布板，对烟气进行均布分散。
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