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WO2014008702A1 - Method for treating nox-containing waste gas and system thereof - Google Patents

Method for treating nox-containing waste gas and system thereof Download PDF

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Publication number
WO2014008702A1
WO2014008702A1 PCT/CN2012/080083 CN2012080083W WO2014008702A1 WO 2014008702 A1 WO2014008702 A1 WO 2014008702A1 CN 2012080083 W CN2012080083 W CN 2012080083W WO 2014008702 A1 WO2014008702 A1 WO 2014008702A1
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WO
WIPO (PCT)
Prior art keywords
nox
ammonia
leachate
molar ratio
exhaust gas
Prior art date
Application number
PCT/CN2012/080083
Other languages
French (fr)
Chinese (zh)
Inventor
杭鹏志
Original Assignee
Hang Pengzhi
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Publication date
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Publication of WO2014008702A1 publication Critical patent/WO2014008702A1/en

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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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/402—Dinitrogen oxide
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

  • the present invention relates to a NOx-containing exhaust gas treatment method in a low temperature section (5 - 15 CTC) and a system using the same, and in particular to an ECR denitration group ammonium nitrate method and a system therefor. Background technique
  • Nitrogen oxides (5% N0 2 and 95% NO) are gases produced by the oxidation of nitrogen during the combustion process. They not only stimulate the human respiratory system, damage animals and plants, destroy the ozone layer, but also One of the main substances causing greenhouse effect, acid rain and photochemical reactions. The demand for NOx emission limits has become stricter around the world, and thermal power plants, waste incineration plants and cement plants are the most important sources of NOx emissions, and their emission reductions have received special attention.
  • SCR is mainly used in large-scale coal-fired boilers.
  • the denitration efficiency can reach 70-90%. It has the advantages of small floor space, high denitration efficiency and no secondary pollution.
  • Humidity, dust, and temperature are high, and their investment and operating costs are relatively high.
  • the SCR is mainly in the middle temperature section (2 30-45 0 °C).
  • the reduction of N0 X to N 2 (nitrogen) and H 2 0 (water) by adding a reducing agent NH 3 (ammonia) completes the denitration.
  • the mechanism is as follows:
  • SNCR is mainly used for NOx emission control of medium and small boilers such as waste incineration plants.
  • the utility model has the advantages of small occupied area, small system investment, simple system and convenient operation, but the denitration efficiency is 25-5 0%, which belongs to the high temperature out-of-sale process, and is only applicable to the process requirements of the transformation of the old unit or the low denitration efficiency.
  • SNCR is mainly in the high temperature section (760-1060 ° C) by adding ⁇ 3 (ammonia) or
  • Leachate is a kind of liquid with high concentration of organic or inorganic components produced by biochemical degradation such as compaction and fermentation during the process of stacking and landfilling. Because it contains malodorous gases, it must be deodorized.
  • Conventional deodorization processes mainly use biofilters, but biofilters have poor deodorization efficiency, large floor space, high construction and operation costs, and complicated operation.
  • the denitration process route realizes low-temperature denitration in the tail gas of power plants, cement kiln, glass kiln, thermal power plant, coal-fired boiler, cement kiln, glass kiln, etc., and directly obtains ammonium salt and deodorizes, which has very realistic environmental protection and economic significance.
  • the technical problem to be solved by the present invention is to provide a NOx-containing exhaust gas and NH 3 (ammonia) in the presence of leachate as a compounding agent at a low temperature (5-150 ° C), using ECRR (electrochemical recovery reactor).
  • ECRR electrochemical recovery reactor
  • the leachate preferably contains an alcohol, an aldehyde or an organic acid as a complexing agent, and the alcohol is preferably methyl mercaptan, dimethyl alcohol, ethanethiol or the like.
  • the main components of the leachate of the present invention are CH 4 S (methyl mercaptan), (CH 3 ) 2 S (dimethyl alcohol), C 2 H 5 HS (ethanethiol), CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde), (CH 3 ) 2 CHCH0 (isobutyraldehyde), CH 3 CH 2 CH 2 C00H (butyric acid), C 4 H 9 C00H (pentanoic acid), NH 3 (ammonia) and RX (other or The remainder of the mixture.
  • the present invention uses the following technical solutions:
  • NOx in the NOx exhaust gas is oxidized to N0 2 , N 2 0 5 , HN0 2 by strong oxidizing active radicals at a temperature of 5 -1 50 ° C, and finally HN0 3 is generated by multiple reactions.
  • N 2 0 5 + H 2 0 ⁇ 2 draws 3 .
  • the strong oxidizing active radical may be a high-energy electron, a plasma, and a 0H-active oxidizing substance generated by a DC high-voltage narrow-pulse discharge field formed by a plasma discharge device.
  • plasma discharges such as blocking dielectric discharge, glow discharge, and corona discharge.
  • glow discharge is widely used in the lighting tube industry because it is suitable for low-voltage environment. It also has certain applications for blocking dielectric discharge, but because of its own structural reasons, once it is absolutely If the media of the edge is clogged or contaminated, it will easily cause the medium to creep, resulting in short circuit of the discharge circuit, and the equipment is unstable.
  • Corona discharge has DC and AC discharge types, but for many reasons, only 10KV-15KV discharge power supply has been developed. Achieving stable narrow pulse discharge limits industrial applications; and AC discharge, because of its high voltage, has a certain amount of radiation, because it has great safety hazards and cannot be popularized.
  • the plasma discharge device in the present invention is an ECRR discharge device (electrochemical recovery reactor), the input voltage is a standard AC voltage (220V or 380V), the discharge frequency is 900 times/second, and the output pulse power is greater than 5 MW, preferably DC. The pulse power is 5-6 MW, and the discharge is stable.
  • ECRR discharge device electrochemical recovery reactor
  • the input voltage is a standard AC voltage (220V or 380V)
  • the discharge frequency is 900 times/second
  • the output pulse power is greater than 5 MW, preferably DC.
  • the pulse power is 5-6 MW, and the discharge is stable.
  • the ECRR discharge device can generate strong oxidizing active radicals, for example, high energy electrons, ultraviolet light, high temperature vacuoles, and 0H, 0 3 , 0, N.
  • the NOx-containing exhaust gas is continuously introduced for reaction in an ECRR (electrochemical recovery reactor) (DC pulse power 5-6 MW, discharge frequency 900 times/second) at a temperature of 5-15 CTC. .
  • ECRR electrochemical recovery reactor
  • the method of the present invention continuously introducing NOx-containing exhaust gas and NH 3 at an ECRR (electrochemical recovery reactor) (DC pulse power 5-6 MW, discharge frequency 900 times/second) at a temperature of 5-15 CTC .
  • the molar ratio between the introduction of the NOx-containing exhaust gas and NH 3 (ammonia) is from 0.8 to 1, more preferably from 0.8 to 0.9.
  • High-energy electrons, ultraviolet light, high-temperature cavities and strong oxidizing active radicals such as 0H, 0 3 , 0, N, etc. in the ECRR discharge field can be used to treat NOx (5% N0 2 and 95% NO) in the exhaust gas.
  • the strong oxidizing active radical denitrates the NOx in the NOx-containing exhaust gas and further reacts with NH 3 to form ammonium nitrate.
  • the NOx-containing exhaust gas is introduced into the ECRR (electrochemical recovery reactor) simultaneously with ammonia (low-concentration ammonia water) and leachate, and the strong oxidizing active radical is firstly NOx-containing.
  • DeNOx in the exhaust gas is then reacted with NH 3 histamine to form ammonium nitrate.
  • the leachate preferably contains an alcohol, an aldehyde, or an organic acid as a complexing agent, and the alcohol is preferably methyl mercaptan, dimethyl alcohol, ethyl mercaptan or the like.
  • the leachate used in accordance with one embodiment of the present invention the main components of which are CH 4 S (methyl mercaptan), (CH 3 ) 2 S (dimethyl alcohol), C 2 H 5 HS (B Mercaptan)), CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde), (CH 3 ) 2 CHCH0 (isobutyraldehyde), CH 3 CH 2 CH 2 C00H (butyric acid), C 4 H 9 C00H (pentyl) Acid), NH 3 (ammonia).
  • the leachate can unexpectedly improve the salt formation efficiency of ammonium nitrate, increase the rate of ammonium nitrate formation and the action of free radicals, and crack into carbon dioxide and water, thereby realizing denitration of NOx-containing waste gas and nitric acid.
  • the ammonium group salt and leachate deodorization are carried out in one process, and the reaction mechanism is as follows:
  • continuous introduction is carried out in an ECRR (Electrochemical Recovery Reactor) (DC20-50KV, 500-1000 times/S electrochemical recovery reactor) at a temperature of 5-150 °C.
  • the NOx exhaust gas, NH 3 (ammonia), leachate as a compounding agent is added according to the ratio of NOx and ammonia detected in the reactor, and preferably, the ratio of NOx to ammonia and the total amount of ammonia contained in the leachate is 0.8. -1, the ratio is preferably from 0.8 to 0.9.
  • leachate accelerates the synthesis amount and synthesis rate of ammonium nitrate, and generates NH 4 N0 3 (ammonium nitrate) which can be used for chemical and agricultural production in a very short time; the compounding agent is preferably an alcohol gas.
  • the leachate itself acts as an organic macromolecule and is also cleaved by strong oxidative active radicals produced by ECRR (electrochemical recovery reactor) after group salt to C0 2 (carbon dioxide) and H 2 0 (water).
  • the molar ratio of NOx to ammonia is preferably selected from 0.8 to 0.9. If the amount of ammonia in the leachate is sufficient, it is not necessary to add ammonia, because too much ammonia will regenerate N0x.
  • the method of the present invention may further comprise the step of temperature-reducing ammonium nitrate in water. According to the difference in solubility of nitrate in water at different temperatures, the precipitation of crystallization of ammonium nitrate is increased to realize the recovery and utilization of ammonium nitrate.
  • Ammonium salt capture devices are known in the art.
  • the invention provides an ECR denitration group ammonium nitrate salt system according to the above method, the system comprising: an electrochemical recovery reactor, an ammonium salt trapping device, a control device; and a pulse power output by the electrochemical recovery reactor More than 5 MW, and continuous discharge is stable; the ammonium salt trapping device is in fluid connection with the electrochemical recovery reactor; the control device is in communication with the electrochemical recovery reactor and the ammonium salt trapping device.
  • the control device is coupled to the electrochemical recovery reactor, the ammonium salt trap, and the circulation pump, respectively, to control the entire process system.
  • a further preferred embodiment of the present invention resides in: further comprising a circulating pump in fluid connection with the ammonium salt capture device for alternately controlling temperature, said control device being in communication with the circulation pump.
  • the circulation pump is in fluid connection with the ammonium salt trap, and can alternately control the temperature to control the solubility of the ammonium salt in water to realize the recovery and capture of ammonium nitrate.
  • the NOx removal efficiency is high, up to 80%;
  • the leachate deodorization efficiency is high, reaching more than 90%
  • the ammonium nitrate group has high salt efficiency of over 85%;
  • the system has no additives and will not cause secondary pollution
  • FIG. 2 is a structural schematic diagram of a process flow chart of an ammonium nitrate salt of the ECR denitration group of the present invention.
  • the NOx-containing exhaust gas and leachate and NH 3 are introduced into the electrochemical recovery reactor 001 to complete the denitration, group salt, and deodorization processes, and then enter the ammonium salt trap 002 to recover the ammonium nitrate formed by the reaction.
  • the structural diagram of the present invention mainly comprises an electrochemical recovery reactor 001, an ammonium salt trap 002, a control unit 003, and a circulation pump 004.
  • Electrochemical recovery reactor 001 is a combination of standard AC voltage (22 0V or 38 0V), which is rapidly superimposed by electromagnetic energy and AC/DC modules and control systems, and outputs more than 5MW of pulse power. Electrochemical recovery reactor 001 has a consistently stable discharge demand.
  • the electrochemical recovery reactor 001 is a large amount of strong oxidizing active particles such as ⁇ 0 ⁇ , ⁇ 0, 0 3 , ⁇ , strong ultraviolet rays, high temperature vacuoles, especially under the action of high-energy electrons generated by the ECRR discharge field. Oxidation and chemical reactivity of 0 ⁇ , ⁇ 0, can be used for the instantaneous oxidation of organic matter in exhaust gas, NO oxidation in NOx to N0 2 , HN0 2 , ⁇ 2 0 5 and introduction of leachate and ⁇ 3 with HN0 2 , HN0 3 Denitrification, group salt, and deodorization processes.
  • 001 ECRR electrochemical recovery reactor
  • the base fully converts NO to N0 2 , N 2 0 5 , HN0 2 , and finally generates HN0 3 (nitric acid) by multiple reactions.
  • the leachate is introduced and reacted with NH 3 and nitric acid to form ammonium nitrate.
  • alcohols such as methyl mercaptan, dimethyl alcohol and ethanethiol and n-butyraldehyde, isobutyraldehyde, butyric acid and valeric acid Wait
  • the rate of formation and production of ammonium nitrate is increased, and then, after strong oxidation, the organic macromolecular molecules of the alcohol gas as a complexing agent are cleaved into carbon dioxide and water.
  • the NOx gas and the NH 3 are used as a complexing agent with the alcohol, the aldehyde, and the organic acid gas in the leachate, thereby achieving the three functions of denitration, ammonium nitrate salt, and deodorization.
  • the ammonium salt of the electrochemical recovery reactor 001 is captured by the ammonium salt trap 002.
  • the circulation pump 004 is used to achieve temperature alternation, thereby affecting the solubility of ammonium nitrate, and the ammonium nitrate is precipitated by precipitation of ammonium nitrate.
  • control unit 003 The entire process system is controlled by control unit 003.
  • the ratio is between 0.8-0.9.
  • the NOx outlet concentration is 110mg/m 3
  • the NOx removal efficiency is 78%
  • the salt salt efficiency is over 65%.
  • the ammonium salt trap uses a secondary cooling recovery system to recover 197.9 kg of ammonium nitrate particles per day.
  • the NOx outlet concentration is 70mg/m 3 and the NOx removal efficiency is 86%.
  • the rate is over 85% and the deodorization efficiency is over 93.2%.
  • the exhaust gas with a volume of 10,000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 ° C is introduced; a certain amount of leachate overflow gas is injected, and the components thereof mainly include: CH 4 S (methyl mercaptan) 19 mg/m ⁇ (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/m 3 , NH 3 (ammonia gas) 230 mg/m 3 , and introduce 170 mg/m 3 of NH 3
  • the NOx outlet concentration is 71mg/m 3
  • the NOx removal efficiency is 85.8%
  • the salt salt efficiency is over 85.2%.
  • the deodorization efficiency is over 93.2%.
  • the molar ratio is between 0.8 and 0.9.
  • the NOx outlet concentration is 109mg/m 3
  • the NOx removal efficiency is 78.2%
  • the salt salt efficiency is over 65.2%.
  • the deodorization efficiency is over 93.2%.
  • the NOx outlet concentration is 72mg/m 3
  • the NOx removal efficiency is 85.6%
  • the salt salt efficiency is above 84.7%.
  • the deodorization efficiency is over 92.4%.
  • the air volume introduced in the ECRR is 10000 m 3 /h, the NOx inlet concentration is 500 mg/m 3 , and the temperature Exhaust gas at 150 °C; inject a certain amount of leachate overflow gas, the main components are: CH 4 S (methyl mercaptan) 19 mg / m ⁇ ( CH 3 ) 2 S (dimethyl alcohol) 27 mg / m 3 , C 2 H 5 HS (ethanethiol)) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/ m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/m 3 , NH 3 (ammonia gas) 230 mg/m 3 , simultaneously introduced into 170 mg / m
  • the NOx outlet concentration is 71 mg/m 3 , the NOx removal efficiency is 85.8%, and the salt-to-salt efficiency is 85.
  • the NOx outlet concentration is 71 mg/m 3 and the NOx removal efficiency is 85.8%.
  • an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 °C in the ECRR; introduce 400 mg/m 3 of NH 3 (ammonia gas) to ensure NOx and NH 3 (ammonia gas) 2 ⁇ Molar ratio between 0. 8-1.
  • the NOx outlet concentration is 108 mg/m 3
  • the NOx removal efficiency is 78. 4%
  • the salt-to-salt efficiency is 65.
  • the NOx outlet concentration is 108 mg/m 3 and the NOx removal efficiency is 78. 4%. 1% or more.
  • the pulsating power is 5-6 MW and the discharge frequency is 900 times/second
  • the NOx outlet concentration is 73 mg/m 3
  • the NOx removal efficiency is 85.4%
  • the salt efficiencies are 84. 5% ⁇ More than 5%, the deodorization efficiency of 93.2% or more.
  • the NOx outlet concentration is 227 mg/m 3
  • the NOx removal efficiency is 45.4%
  • the salt efficiencies are up to 84.
  • the NOx outlet concentration is 227 mg/m 3 and the NOx removal efficiency is 45. 4%. More than 5%, the deodorization efficiency is more than 92.8%.
  • the NOx outlet concentration is 225 mg/m 3
  • the NOx removal efficiency is 45%
  • the salt salt efficiency is 84.
  • the NOx outlet concentration is 225 mg/m 3
  • the NOx removal efficiency is 45%
  • the NOx emission efficiency is 45%.
  • the deodorization efficiency is more than 92.8%.
  • the NOx outlet concentration is 228 mg/m 3
  • the NOx removal efficiency is 45.6%
  • the salt efficiencies are up to 84.
  • the NOx outlet concentration is 228 mg/m 3
  • the NOx removal efficiency is 45.6%
  • the NOx removal efficiency is 84. More than 7%, the deodorization efficiency is over 92.7%.
  • An exhaust gas having an air volume of 10,000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 150 ° C was introduced into the ECRR.
  • the pulsing power is 5-6 MW, and the discharge frequency is 900 times/second.
  • the NOx outlet concentration is 110 mg/m 3
  • the NOx removal efficiency is 78%
  • 70% of the nitric acid is produced. /d (kg/day).
  • the temperature in the present invention has little effect on the denitration and deodorization efficiency, but has a certain influence on the recovered ammonium nitrate.

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Abstract

A method for treating NOx-containing waste gas and a system thereof. The method comprises: under 5-150°C, using a free radical of strong oxidation activity to oxidize the NOx-containing waste gas into NO2, N2O5, and HNO2 which then perform a histamine reaction with ammonia gas to generate ammonium nitrate. Leachate can be input as a compounding agent, to increase salification efficiency of the ammonium nitrate and raise the generation rate and yield of the ammonium nitrate, and at the same time, organic macromolecules in the leachate decompose under the effect of the free radical of strong oxidation activity. The system applied for the method comprises an electrochemical recycling reactor (001), an ammonium salt trapping device (002), and a control device (003).

Description

含 NOx废气处理方法及其系统 技术领域  NOx-containing exhaust gas treatment method and system thereof
本发明涉及一种在低温段（ 5 -1 5 CTC )含 NOx废气处理方法及使用该 方法的系统， 具体涉及 ECR脱硝组硝酸铵盐方法及用于该方法的系统。 背景技术  The present invention relates to a NOx-containing exhaust gas treatment method in a low temperature section (5 - 15 CTC) and a system using the same, and in particular to an ECR denitration group ammonium nitrate method and a system therefor. Background technique
氮氧化物 （NOx ) ( 5 %的 N02和 95 %的 NO )是在燃烧工艺过程中由于 氮的氧化而产生的气体， 它不仅刺激人的呼吸系统， 损害动植物， 破坏 臭氧层， 而且也是引起温室效应、 酸雨和光化学反应的主要物质之一 。 世界各地对 NOx的排放限制要求都趋于严格， 而火电厂、 垃圾焚烧厂和 水泥厂等作为 NOx气体排放的最主要来源，其减排更是受到格外的重视。 Nitrogen oxides (NOx) (5% N0 2 and 95% NO) are gases produced by the oxidation of nitrogen during the combustion process. They not only stimulate the human respiratory system, damage animals and plants, destroy the ozone layer, but also One of the main substances causing greenhouse effect, acid rain and photochemical reactions. The demand for NOx emission limits has become stricter around the world, and thermal power plants, waste incineration plants and cement plants are the most important sources of NOx emissions, and their emission reductions have received special attention.
目前电厂、 水泥窑、 玻璃窑、 燃煤锅炉、 发电厂等脱除 NOx最常用 的方法有： SCR (选择性催化还原技术）、 SNCR (选择性非催化还原技术）、 SCR (选择性催化还原技术） + SNCR (选择性非催化还原技术）组合工艺。  At present, the most common methods for removing NOx from power plants, cement kilns, glass kilns, coal-fired boilers, power plants, etc. are: SCR (Selective Catalytic Reduction Technology), SNCR (Selective Non-Catalytic Reduction Technology), SCR (Selective Catalytic Reduction) Technology) + SNCR (Selective Non-Catalytic Reduction Technology) combination process.
SCR主要用于大型燃煤锅炉， 脱硝效率可达 70-90%以上，它具有占 地面积小、 脱硝效率高、 不产生二次污染等优势， 但因其系统复杂、 属 中温脱硝工艺， 对湿度、 粉尘、 温度要求高， 其投资和运行成本相对较 高。  SCR is mainly used in large-scale coal-fired boilers. The denitration efficiency can reach 70-90%. It has the advantages of small floor space, high denitration efficiency and no secondary pollution. However, due to its complicated system, it is a medium-temperature denitration process. Humidity, dust, and temperature are high, and their investment and operating costs are relatively high.
SCR主要是在中温段 （ 2 30-45 0 °C ) , 通过添加还原剂 NH3 (氨） 将 N0X还原为 N2 (氮气） 和 H20 (水） ， 从而完成脱硝， 机理如下： The SCR is mainly in the middle temperature section (2 30-45 0 °C). The reduction of N0 X to N 2 (nitrogen) and H 2 0 (water) by adding a reducing agent NH 3 (ammonia) completes the denitration. The mechanism is as follows:
4N0 + 4NH3 + 02 → 4N2 + 6 H20 4N0 + 4NH 3 + 0 2 → 4N 2 + 6 H 2 0
2N02 + 4NH3 + 02 → 3N2 + 6H20 2N0 2 + 4NH 3 + 0 2 → 3N 2 + 6H 2 0
6N02 + 4NH3 → 7N2 + 1 2H20 6N0 2 + 4NH 3 → 7N 2 + 1 2H 2 0
SNCR主要用于垃圾焚烧厂等中、 小型锅炉的 NOx的排放控制。 它具 有占地面积小、 系统投资小、 系统简单、 操作方便等优势， 但其脱硝效 率为 25-5 0% , 属于高温脱销工艺， 仅适用于老机组的改造或脱硝效率不 高的工艺要求。 SNCR主要是在高温段 （ 760-1060°C ) , 通过添加 ΝΗ3 (氨） 或 SNCR is mainly used for NOx emission control of medium and small boilers such as waste incineration plants. The utility model has the advantages of small occupied area, small system investment, simple system and convenient operation, but the denitration efficiency is 25-5 0%, which belongs to the high temperature out-of-sale process, and is only applicable to the process requirements of the transformation of the old unit or the low denitration efficiency. . SNCR is mainly in the high temperature section (760-1060 ° C) by adding ΝΗ 3 (ammonia) or
(NH2C0)2C0 (尿素）， 将 N0X还原为 Ν2(氮气）、 Η20 (水）及 C02(二氧化碳）， 从而完成脱硝， 机理如下： (NH 2 C0) 2 C0 (urea), reducing N0 X to Ν 2 (nitrogen), Η 2 0 (water) and C0 2 (carbon dioxide) to complete denitration, the mechanism is as follows:
4N0 + 4NH3 + 02 → 4N2 + 6H20 4N0 + 4NH 3 + 0 2 → 4N 2 + 6H 2 0
4N02 + 2 (NH2C0) 2C0 + 02 → 2N2 + 2H20 + C02 4N0 2 + 2 (NH 2 C0) 2 C0 + 0 2 → 2N 2 + 2H 2 0 + C0 2
常规的 SCR、 SNCR脱 NOx工艺温度通常都在 150°C中高温以上的工 况条件， 都是通过添加 NH3 (氨）、 或尿素将 NOx转化为 N2 (氮气）和水, 属于只在中高温工矿下进行的单纯脱硝工艺。 Conventional SCR, SNCR deNOx process temperatures are usually above 150 ° C high temperature conditions, are by adding NH 3 (ammonia), or urea to convert NOx into N 2 (nitrogen) and water, belongs to only The simple denitration process carried out under medium and high temperature industrial and mining.
渗滤液是垃圾在堆放和填埋过程中由于压实、 发酵等生物化学降解 作用下， 产生的一种高浓度的有机或无机成份的液体， 因含有恶臭气体, 必须对其进行除臭治理。 常规的除臭工艺主要釆用生物滤池， 但是生物 滤池除臭效率较差， 且占地面积大、 建设及运行成本较高、 操作性比较 复杂。  Leachate is a kind of liquid with high concentration of organic or inorganic components produced by biochemical degradation such as compaction and fermentation during the process of stacking and landfilling. Because it contains malodorous gases, it must be deodorized. Conventional deodorization processes mainly use biofilters, but biofilters have poor deodorization efficiency, large floor space, high construction and operation costs, and complicated operation.
如何在低温段 （ 5-15CTC ) 利用 NOx和 NH3 (氨） 、 渗滤液直接合成 得到高附加价值硝酸铵盐、 同时具备铵盐捕集回收系统且兼备渗滤液的 除臭、 含 NOx尾气的脱硝的工艺路线， 实现电厂、 水泥窑、 玻璃窑、 热 电厂、 燃煤锅炉、 水泥窑、 玻璃窑等尾气中实现低温脱硝， 直接得到铵 盐， 除臭， 具有很现实的环保和经济意义。 How to use NOx and NH 3 (ammonia) and leachate to synthesize high-value-added ammonium nitrate in the low temperature section ( 5-15CTC), and have an ammonium salt capture and recovery system, and also have leachate deodorization and NOx-containing exhaust gas. The denitration process route realizes low-temperature denitration in the tail gas of power plants, cement kiln, glass kiln, thermal power plant, coal-fired boiler, cement kiln, glass kiln, etc., and directly obtains ammonium salt and deodorizes, which has very realistic environmental protection and economic significance.
在低温段 （5-15CTC ) 下， 为实现高效脱硝、 组盐， 以 NOx废气和 NH3 (氨）为原料， 渗滤液作为配合剂， 直接在 ECRR (电化学回收反应器) 内实施快速组盐工艺， 组盐 （硝酸铵） 效率， 达到 95%以上， 并通过组 盐捕集回收系统回收硝酸铵盐， 回收硝酸铵盐率达到 80%以上， 成为一 种备受关注的节能减排、 资源回收、 废物处置的资源化回收处置技术， 目前在国内外还没有研究应用案例。 发明内容  In the low temperature section (5-15CTC), in order to achieve high-efficiency denitrification, salt formation, NOx exhaust gas and NH3 (ammonia) as raw materials, leachate as a compounding agent, directly implement fast salt in ECRR (electrochemical recovery reactor) Process, group salt (ammonium nitrate) efficiency, more than 95%, and recovery of ammonium nitrate by group salt capture and recovery system, recovery of ammonium nitrate rate of more than 80%, has become a concern for energy-saving emission reduction, resources There are no research applications at home and abroad for resource recycling and disposal technologies for recycling and waste disposal. Summary of the invention
本发明所要解决的技术问题是在低温下 （5-150°C ) 提供一种将含 NOx废气、 NH3(氨）在渗滤液作为配合剂的参与下， 利用 ECRR (电化学回 收反应器）来实现电厂、 水泥窑、 玻璃窑、 热电厂、 燃煤锅炉等焚烧含 NOx废气低温脱硝、 组盐、 及渗滤液除臭的三重功效， 将全部废物合成 为高附加价值硝酸铵的新型脱硝、 组盐、 除臭工艺路线， 且该工艺不会 产生任何环境污染因子。 The technical problem to be solved by the present invention is to provide a NOx-containing exhaust gas and NH 3 (ammonia) in the presence of leachate as a compounding agent at a low temperature (5-150 ° C), using ECRR (electrochemical recovery reactor). To achieve incineration of power plants, cement kilns, glass kilns, thermal power plants, coal-fired boilers, etc. The triple effect of low-temperature denitrification, group salt, and leachate deodorization of NOx waste gas combines all waste into a new denitrification, group salt and deodorization process route of high value-added ammonium nitrate, and the process does not produce any environmental pollution factors.
本发明中渗滤液作为配合剂， 优选地含有醇、 醛、 有机酸类物质， 该醇类物质优选为甲硫醇、 二甲基醇、 乙硫醇等。 本发明渗滤液的主要 成份为 CH4S (甲硫醇)、（CH3 )2S (二甲基醇 )、C2H5HS (乙硫醇) ) , CH3 (CH2) 2CH0 (正丁醛） 、 (CH3) 2CHCH0 (异丁醛） 、 CH3CH2CH2C00H (丁酸） 、 C4H9C00H (戊酸） 、 NH3 (氨） 及 RX (其它或剩余） 等的混合物。 In the present invention, the leachate preferably contains an alcohol, an aldehyde or an organic acid as a complexing agent, and the alcohol is preferably methyl mercaptan, dimethyl alcohol, ethanethiol or the like. The main components of the leachate of the present invention are CH 4 S (methyl mercaptan), (CH 3 ) 2 S (dimethyl alcohol), C 2 H 5 HS (ethanethiol), CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde), (CH 3 ) 2 CHCH0 (isobutyraldehyde), CH 3 CH 2 CH 2 C00H (butyric acid), C 4 H 9 C00H (pentanoic acid), NH 3 (ammonia) and RX (other or The remainder of the mixture.
为了解决上述技术问题， 本发明釆用如下的技术方案：  In order to solve the above technical problems, the present invention uses the following technical solutions:
根据本发明的方法， 在 5 -1 5 0 °C的温度下， 利用强氧化活性自由基 将 NOx废气中的 NOx氧化为 N02 、 N205、 HN02 ,最终通过多重反应生成 HN03 According to the method of the present invention, NOx in the NOx exhaust gas is oxidized to N0 2 , N 2 0 5 , HN0 2 by strong oxidizing active radicals at a temperature of 5 -1 50 ° C, and finally HN0 3 is generated by multiple reactions.
(硝酸） ， 反应机理如下： (nitric acid), the reaction mechanism is as follows:
02 + e → 20 + e 0 2 + e → 20 + e
N2 + e → 2N + e N 2 + e → 2N + e
NO + N + e→ N2 + 0 + e NO + N + e→ N 2 + 0 + e
H20 + e → 2H + 0 + e H 2 0 + e → 2H + 0 + e
02 + 0 + e → 03 + e 0 2 + 0 + e → 0 3 + e
NO + 0 → N02 NO + 0 → N0 2
NO + 03 → N02 + 02 NO + 0 3 → N0 2 + 0 2
2N02 + 03 → N205 + 02 2N0 2 + 0 3 → N 2 0 5 + 0 2
NO + OH → 画 2 NO + OH → draw 2
N02 + NO + H20 → 2画 2 N0 2 + NO + H 2 0 → 2 draw 2
3HN02—— ^画 3+2N0+H20  3HN02——^Draw 3+2N0+H20
N205 + H20 → 2画 3。 N 2 0 5 + H 2 0 → 2 draws 3 .
该强氧化活性自由基可以为等离子体放电装置形成的直流高压窄脉 冲放电场产生的高能电子、 等离子体和 0H-活性氧化物质等。  The strong oxidizing active radical may be a high-energy electron, a plasma, and a 0H-active oxidizing substance generated by a DC high-voltage narrow-pulse discharge field formed by a plasma discharge device.
等离子体放电类型较多有阻挡介质放电、 辉光放电、 电暈放电等多 种内容。 其中， 辉光放电因适用于低压环境中， 广泛用于照明灯管行业； 阻挡介质放电， 也有一定的应用， 但是因为其自身的结构原因， 一旦绝 缘的介质堵塞或者污染， 极易引起介质爬电， 导致放电回路短路， 而且 装备运行不稳定； 电暈放电有直流和交流放电类型， 但是目前诸多原因 仅开发出 10KV-15KV的放电电源， 难以实现稳定的窄脉冲放电， 限制了 工业化应用； 而交流放电， 因其电压较高， 具有一定的辐射， 因为具有 极大的安全隐患， 不能推广应用。 There are many types of plasma discharges, such as blocking dielectric discharge, glow discharge, and corona discharge. Among them, glow discharge is widely used in the lighting tube industry because it is suitable for low-voltage environment. It also has certain applications for blocking dielectric discharge, but because of its own structural reasons, once it is absolutely If the media of the edge is clogged or contaminated, it will easily cause the medium to creep, resulting in short circuit of the discharge circuit, and the equipment is unstable. Corona discharge has DC and AC discharge types, but for many reasons, only 10KV-15KV discharge power supply has been developed. Achieving stable narrow pulse discharge limits industrial applications; and AC discharge, because of its high voltage, has a certain amount of radiation, because it has great safety hazards and cannot be popularized.
本发明中的等离子体放电装置为 ECRR放电装置 （电化学回收反应 器） ， 其输入电压为标准交流电压 （ 220V或者 380V) , 放电频率 900 次 /秒， 输出的脉冲功率大于 5MW, 优选为直流脉冲功率 5-6MW, 并且持 续稳定放电，具体可以参见申请号为 201210116858.5号中国发明专利申 请中的 "直流高压窄脉冲放电系统" 。  The plasma discharge device in the present invention is an ECRR discharge device (electrochemical recovery reactor), the input voltage is a standard AC voltage (220V or 380V), the discharge frequency is 900 times/second, and the output pulse power is greater than 5 MW, preferably DC. The pulse power is 5-6 MW, and the discharge is stable. For details, see "DC High Voltage Narrow Pulse Discharge System" in Chinese Patent Application No. 201210116858.5.
该 ECRR放电装置可以产生强氧化活性自由基， 例如， 高能电子、 紫 外光、 高温空泡和 0H、 03、 0、 N。 The ECRR discharge device can generate strong oxidizing active radicals, for example, high energy electrons, ultraviolet light, high temperature vacuoles, and 0H, 0 3 , 0, N.
根据本发明方法的另一方面， 在 5-15CTC的温度下， 在 ECRR(电化学 回收反应器） （直流脉冲功率 5-6MW, 放电频率 900次 /秒） 内， 连续导 入含 NOx废气进行反应。  According to another aspect of the method of the present invention, the NOx-containing exhaust gas is continuously introduced for reaction in an ECRR (electrochemical recovery reactor) (DC pulse power 5-6 MW, discharge frequency 900 times/second) at a temperature of 5-15 CTC. .
根据本发明方法的一个方面， 在 5-15CTC的温度下， 在 ECRR(电化学 回收反应器） （直流脉冲功率 5-6MW, 放电频率 900次 /秒） 内， 连续导 入含 NOx废气和 NH3。 优选地， 导入含 NOx废气和 NH3(氨）之间的摩尔比 为 0.8-1, 更有优选地为 0.8-0.9。 ECRR放电场中产生高能电子、 紫外 光、 高温空泡及 0H、 03、 0、 N等强氧化活性自由基， 可将废气中的 NOx ( 5%的 N02和 95%的 NO ) 中尤其是 NO充分氧化为 N02 、 N205、 HN02; 强氧 化活性自由基对含 NOx废气中的 NOx进行脱硝后的产物进一步与 NH3进 行组胺反应生成硝酸铵。 According to one aspect of the method of the present invention, continuously introducing NOx-containing exhaust gas and NH 3 at an ECRR (electrochemical recovery reactor) (DC pulse power 5-6 MW, discharge frequency 900 times/second) at a temperature of 5-15 CTC . Preferably, the molar ratio between the introduction of the NOx-containing exhaust gas and NH 3 (ammonia) is from 0.8 to 1, more preferably from 0.8 to 0.9. High-energy electrons, ultraviolet light, high-temperature cavities and strong oxidizing active radicals such as 0H, 0 3 , 0, N, etc. in the ECRR discharge field can be used to treat NOx (5% N0 2 and 95% NO) in the exhaust gas. It is NO sufficiently oxidized to N0 2 , N 2 0 5 , HN0 2 ; the strong oxidizing active radical denitrates the NOx in the NOx-containing exhaust gas and further reacts with NH 3 to form ammonium nitrate.
根据本发明方法的再一个方面， 在 5-15CTC的温度下， 含 NOx废气 与氨（低浓度氨水）及渗滤液同时导入 ECRR (电化学回收反应器）， 强氧 化活性自由基先对含 NOx废气中的 NOx脱硝然后与 NH3组胺反应生成硝 酸铵。 渗滤液作为配合剂， 优选地含有醇、 醛、 有机酸类物质， 该醇类 物质优选为甲硫醇、 二甲基醇、 乙硫醇等。 根据本发明的一个实施例使 用的渗滤液，其主要成份为 CH4S (甲硫醇）、（ CH3 )2S(二甲基醇）、 C2H5HS (乙 硫醇） )、 CH3(CH2)2CH0 (正丁醛）、 (CH3)2CHCH0 (异丁醛）、 CH3CH2CH2C00H (丁酸） 、 C4H9C00H (戊酸） 、 NH3 (氨） 。 在硝酸铵组盐过程中， 渗滤 液可出人意料地提高了硝酸铵成盐效率， 提高了硝酸铵的生成速率及生 性自由基的作用下， 裂解为二氧化碳和水， 从而实现含 NOx废气脱硝、 硝酸铵组盐、 及渗滤液除臭在一个工艺中进行， 反应机理如下： According to still another aspect of the method of the present invention, at a temperature of 5-15 CTC, the NOx-containing exhaust gas is introduced into the ECRR (electrochemical recovery reactor) simultaneously with ammonia (low-concentration ammonia water) and leachate, and the strong oxidizing active radical is firstly NOx-containing. DeNOx in the exhaust gas is then reacted with NH 3 histamine to form ammonium nitrate. The leachate preferably contains an alcohol, an aldehyde, or an organic acid as a complexing agent, and the alcohol is preferably methyl mercaptan, dimethyl alcohol, ethyl mercaptan or the like. The leachate used in accordance with one embodiment of the present invention, the main components of which are CH 4 S (methyl mercaptan), (CH 3 ) 2 S (dimethyl alcohol), C 2 H 5 HS (B Mercaptan)), CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde), (CH 3 ) 2 CHCH0 (isobutyraldehyde), CH 3 CH 2 CH 2 C00H (butyric acid), C 4 H 9 C00H (pentyl) Acid), NH 3 (ammonia). In the ammonium nitrate salt process, the leachate can unexpectedly improve the salt formation efficiency of ammonium nitrate, increase the rate of ammonium nitrate formation and the action of free radicals, and crack into carbon dioxide and water, thereby realizing denitration of NOx-containing waste gas and nitric acid. The ammonium group salt and leachate deodorization are carried out in one process, and the reaction mechanism is as follows:
N02 + H20 → 画 2 N0 2 + H 2 0 → draw 2
画 2 + 0 → 画 3 Painting 2 + 0 → painting 3
画 2 + 0 + e +NH3 → NH4N03 Draw 2 + 0 + e + NH 3 → NH 4 N0 3
总的反应式为 4N0 + 4NH3 + 302 + 2H20 → 4NH4N03o The overall reaction formula is 4N0 + 4NH 3 + 30 2 + 2H 2 0 → 4NH 4 N0 3o
CH4 + 0, OH + e → C02 + H20 CH4 + 0, OH + e → C0 2 + H 2 0
H2S + 0, OH + e → S0X + H20 H 2 S + 0, OH + e → S0 X + H 2 0
CH4S + 0, OH + e→ S0X + C02 + H20 CH 4 S + 0, OH + e→ S0 X + C0 2 + H 2 0
( CH3) 2S + 0, OH + e → S0X + C02 + H20 ( CH 3 ) 2 S + 0, OH + e → S0 X + C0 2 + H 2 0
C2H5HS + 0, OH + e → S0X + C02 + H20 C 2 H 5 HS + 0, OH + e → S0 X + C0 2 + H 2 0
根据本发明方法的又一个方面， 在 5-150°C的温度下， 在 ECRR (电化 学回收反应器） （DC20-50KV、 500-1000次 /S电化学回收反应器） 内， 连 续导入含 NOx废气、 NH3(氨）、 根据反应器中所检测的 NOx和氨的比例加 入作为配合剂的渗滤液， 优选地， 使 NOx与氨以及渗滤液中所含的氨之 总和的比率为 0.8-1,该比率优选为 0.8-0.9。 渗滤液的加入会加快硝酸 铵的合成量及合成速率， 在极短的时间生成可用于化工、 农业生产的 NH4N03(硝酸铵）； 配合剂优选为醇类气体。渗滤液本身作为有机大分子也 在组盐后经 ECRR (电化学回收反应器）产生的强氧化活性自由基裂解为 C02(二氧化碳）和 H20 (水） 。 According to still another aspect of the method of the present invention, continuous introduction is carried out in an ECRR (Electrochemical Recovery Reactor) (DC20-50KV, 500-1000 times/S electrochemical recovery reactor) at a temperature of 5-150 °C. The NOx exhaust gas, NH 3 (ammonia), leachate as a compounding agent is added according to the ratio of NOx and ammonia detected in the reactor, and preferably, the ratio of NOx to ammonia and the total amount of ammonia contained in the leachate is 0.8. -1, the ratio is preferably from 0.8 to 0.9. The addition of leachate accelerates the synthesis amount and synthesis rate of ammonium nitrate, and generates NH 4 N0 3 (ammonium nitrate) which can be used for chemical and agricultural production in a very short time; the compounding agent is preferably an alcohol gas. The leachate itself acts as an organic macromolecule and is also cleaved by strong oxidative active radicals produced by ECRR (electrochemical recovery reactor) after group salt to C0 2 (carbon dioxide) and H 2 0 (water).
由于脱硝组盐过程中， 部分 NOx转化成 N2逸出， 因此， NOx与氨的 摩尔比优先选择 0.8-0.9。 如渗滤液中的氨足量的话， 无须再添加氨进 去， 因为过多的氨会再度生成 N0x。 Due to the partial conversion of NOx to N 2 during the denitrification process, the molar ratio of NOx to ammonia is preferably selected from 0.8 to 0.9. If the amount of ammonia in the leachate is sufficient, it is not necessary to add ammonia, because too much ammonia will regenerate N0x.
根据本发明方法的又一个方面， 在 5-15CTC的温度下， 在 ECRR (电化 学回收反应器） （DC20-50KV、 500-1000次 /S电化学回收反应器） 内， 连 续导入含 NOx废气、 渗滤液， 优选地， 调节 NOx与渗滤液中所含氨的比 例为 0. 8-1 , 该比例优选为 0. 8-0. 9。 According to still another aspect of the method of the present invention, in an ECRR (electrochemical recovery reactor) (DC20-50KV, 500-1000 times/s electrochemical recovery reactor) at a temperature of 5-15 CTC 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。.
本发明的方法还可以进一步包括将硝酸铵在水中变温析出的步骤。 根据硝酸盐在不同温度下， 在水中溶解度的差异， 提高硝酸铵析出结晶 量， 实现硝酸铵的回收利用。 铵盐捕收装置是本领域的现有技术。  The method of the present invention may further comprise the step of temperature-reducing ammonium nitrate in water. According to the difference in solubility of nitrate in water at different temperatures, the precipitation of crystallization of ammonium nitrate is increased to realize the recovery and utilization of ammonium nitrate. Ammonium salt capture devices are known in the art.
本发明提供了一种用于根据上述方法的 ECR脱硝组硝酸铵盐系统， 该系统包括： 电化学回收反应器、 铵盐捕集装置、 控制装置； 所述电化 学回收反应器输出的脉冲功率大于 5MW, 并且持续稳定放电； 所述铵盐 捕集装置与所述电化学回收反应器呈流体连接； 所述控制装置与电化学 回收反应器和铵盐捕集装置通信连接。 所述控制装置分别与所述电化学 回收反应器、 铵盐捕集装置、 循环泵相连接， 从而控制整个工艺系统。  The invention provides an ECR denitration group ammonium nitrate salt system according to the above method, the system comprising: an electrochemical recovery reactor, an ammonium salt trapping device, a control device; and a pulse power output by the electrochemical recovery reactor More than 5 MW, and continuous discharge is stable; the ammonium salt trapping device is in fluid connection with the electrochemical recovery reactor; the control device is in communication with the electrochemical recovery reactor and the ammonium salt trapping device. The control device is coupled to the electrochemical recovery reactor, the ammonium salt trap, and the circulation pump, respectively, to control the entire process system.
本发明进一步优选技术方案在于： 还包括循环泵与铵盐捕集装置呈 流体连接， 能交替控制温度， 所述控制装置与循环泵通信连接。  A further preferred embodiment of the present invention resides in: further comprising a circulating pump in fluid connection with the ammonium salt capture device for alternately controlling temperature, said control device being in communication with the circulation pump.
该循环泵与铵盐捕集装置呈流体连接， 能交替控制温度从而控制铵 盐在水中溶解度， 来实现硝酸铵的回收捕集。  The circulation pump is in fluid connection with the ammonium salt trap, and can alternately control the temperature to control the solubility of the ammonium salt in water to realize the recovery and capture of ammonium nitrate.
由于含 NOx废气、 和渗滤液都属于有害废物， 且渗滤液溢出混气体 中的醇、 醛、 有机酸类物质对 NOx废气和氨的组盐 （硝酸铵） 效率、 组 盐量具有协同效应的提高作用。 所以， 在 ECRR (电化学回收反应器）内快 速、 高效合成高附加价值的硝酸铵产品的工艺， 将在以往的 SCR、 SNCR 等脱销工艺以外， 提供一条具有重要意义的节能减排、 变废为宝， 直接 合成硝酸铵的 ECR资源回收处置工艺路线。  Since NOx-containing waste gas and leachate are all hazardous wastes, the alcohol, aldehyde and organic acid substances in the leachate overflow mixed gas have a synergistic effect on the NOx exhaust gas and ammonia group salt (ammonium nitrate) efficiency and salt content. Improve the role. Therefore, the process of rapidly and efficiently synthesizing high value-added ammonium nitrate products in ECRR (Electrochemical Recovery Reactor) will provide an important energy saving, emission reduction and waste reduction in addition to the previous SCR, SNCR and other out-of-stock processes. As a treasure, directly synthesize the route of ECR resource recovery and disposal of ammonium nitrate.
本发明的 ECR脱硝组硝酸铵盐方法具有以下几个优点：  The ECR denitration group ammonium nitrate method of the present invention has the following advantages:
1、 在低温段， 脱除 NOx效率高， 达 80%以上；  1. In the low temperature section, the NOx removal efficiency is high, up to 80%;
2、 在低温段， 渗滤液除臭效率高， 达 90%以上；  2. In the low temperature section, the leachate deodorization efficiency is high, reaching more than 90%;
3、 硝酸铵组盐效率高， 达 85%以上；  3. The ammonium nitrate group has high salt efficiency of over 85%;
4、 系统无添加物， 不会造成二次污染；  4. The system has no additives and will not cause secondary pollution;
5、 自动化程度高， 无需专人看管；  5, high degree of automation, no need to take care of;
6、 耗电量小， 处理成本低；  6. Low power consumption and low processing cost;
7、 恶臭及废气处理量大； 8、 结构紧凑， 占地面积小， 如处理 3000- 1 000M3/h风量的含 NOx废 气和渗滤液装置， 占地仅 3-5M2 , 非常适合工业化应用。 附图说明 7. The amount of malodor and exhaust gas treatment is large; 8. Compact structure and small footprint, such as NOx-containing exhaust gas and leachate unit for processing 3000-1 000 M 3 /h air volume, covering only 3-5 M 2 , very suitable for industrial applications. DRAWINGS
下面结合附图和具体实施方式本发明进行详细说明：  The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments:
图 1是本发明 ECR脱硝组硝酸铵盐工艺流程图；  1 is a flow chart of the process of ammonium nitrate in the ECR denitration group of the present invention;
图 2是本发明 ECR脱硝组硝酸铵盐工艺流程图中结构原理图。  2 is a structural schematic diagram of a process flow chart of an ammonium nitrate salt of the ECR denitration group of the present invention.
具体实施方式 detailed description
如图 1所示， 含 NOx废气和渗滤液及 NH3导入到电化学回收反应器 001完成脱硝、 组盐、 及除臭过程后， 进入铵盐捕集装置 002 , 回收反应 生成的硝酸铵。 As shown in Fig. 1, the NOx-containing exhaust gas and leachate and NH 3 are introduced into the electrochemical recovery reactor 001 to complete the denitration, group salt, and deodorization processes, and then enter the ammonium salt trap 002 to recover the ammonium nitrate formed by the reaction.
如图 2所示， 本发明的结构图主要包括电化学回收反应器 001、 铵 盐捕集装置 002、 控制装置 003和循环泵 004组成。  As shown in Fig. 2, the structural diagram of the present invention mainly comprises an electrochemical recovery reactor 001, an ammonium salt trap 002, a control unit 003, and a circulation pump 004.
电化学回收反应器 001 由输入的标准交流电压 （ 22 0V或者 38 0V ) , 通过电磁能和 AC/ DC模块及控制系统等快速叠加的核心模块多重组合， 输出大于 5MW的脉冲功率， 从而能够满足电化学回收反应器 001的持续 稳定放电需求。  Electrochemical recovery reactor 001 is a combination of standard AC voltage (22 0V or 38 0V), which is rapidly superimposed by electromagnetic energy and AC/DC modules and control systems, and outputs more than 5MW of pulse power. Electrochemical recovery reactor 001 has a consistently stable discharge demand.
电化学回收反应器 001即是，在 ECRR放电场产生的高能电子的作用 下， 产生大量如 · 0Η、 · 0、 03、 Ν等强氧化活性粒子、 强紫外线、 高温 空泡， 特别是 · 0Η、 · 0的强氧化性和化学反应活性， 可用于废气中有 机物的瞬间氧化、 NOx中 NO氧化为 N02, HN02、 Ν205及导入渗滤液及 ΝΗ 3 与 HN02, HN03的脱硝、 组盐、 及除臭过程。 The electrochemical recovery reactor 001 is a large amount of strong oxidizing active particles such as · 0 Η, · 0, 0 3 , Ν, strong ultraviolet rays, high temperature vacuoles, especially under the action of high-energy electrons generated by the ECRR discharge field. Oxidation and chemical reactivity of 0Η, · 0, can be used for the instantaneous oxidation of organic matter in exhaust gas, NO oxidation in NOx to N0 2 , HN0 2 , Ν 2 0 5 and introduction of leachate and ΝΗ 3 with HN0 2 , HN0 3 Denitrification, group salt, and deodorization processes.
为了将 NOx中的 NO转化为 N02、 N205、 HN02 , 首先要利用 001 ECRR (电 化学回收反应器）在放电场产生的高能电子、紫外光、 高温空泡及强氧化 活性自由基将 NO充分转化为 N02、 N205、 HN02 ,最终通过多重反应生成 HN03 (硝酸） 。 In order to convert NO in NOx into N0 2 , N 2 0 5 , HN0 2 , firstly, 001 ECRR (electrochemical recovery reactor) is used to generate high-energy electrons, ultraviolet light, high-temperature vacuoles and strong oxidation activity in the discharge field. The base fully converts NO to N0 2 , N 2 0 5 , HN0 2 , and finally generates HN0 3 (nitric acid) by multiple reactions.
接下来导入渗滤液与 NH3与硝酸反应， 生成硝酸铵， 与此同时， 甲 硫醇、 二甲基醇、 乙硫醇等醇类物质及正丁醛、 异丁醛、 丁酸、 戊酸等 在硝酸铵组盐过程中充当配合剂， 提高了硝酸铵的生成速率及生成量， 之后经过强氧化， 作为配合剂的醇类气体的有机大分子分子裂解为二氧 化碳和水。 Next, the leachate is introduced and reacted with NH 3 and nitric acid to form ammonium nitrate. At the same time, alcohols such as methyl mercaptan, dimethyl alcohol and ethanethiol and n-butyraldehyde, isobutyraldehyde, butyric acid and valeric acid Wait As a compounding agent in the ammonium nitrate salt process, the rate of formation and production of ammonium nitrate is increased, and then, after strong oxidation, the organic macromolecular molecules of the alcohol gas as a complexing agent are cleaved into carbon dioxide and water.
如上所述， 本发明即是将 NOx气体及 NH3, 以渗滤液中的醇、 醛、 有 机酸类气体为配合剂， 从而实现脱硝、 硝酸铵组盐、 除臭三重功效。 As described above, in the present invention, the NOx gas and the NH 3 are used as a complexing agent with the alcohol, the aldehyde, and the organic acid gas in the leachate, thereby achieving the three functions of denitration, ammonium nitrate salt, and deodorization.
另外， 因为醇类气体量极其少， 在整个过程中会有少量的  In addition, because the amount of alcohol gas is extremely small, there will be a small amount in the whole process.
(NH4)2S04(硫酸铵）生产， 但不影响硝酸铵合成速率及合成量， 在此说明。 (NH 4 ) 2 S0 4 (ammonium sulfate) production, but does not affect the ammonium nitrate synthesis rate and the amount of synthesis, as described herein.
通过铵盐捕集装置 002捕集电化学回收反应器 001的铵盐结晶。 主 要是根据不同温度下， 硝酸铵在水中溶解度的不同， 利用循环泵 004实 现温度交替， 从而影响硝酸铵的溶解度， 通过析出硝酸铵结晶， 来实现 硝酸铵的捕集。  The ammonium salt of the electrochemical recovery reactor 001 is captured by the ammonium salt trap 002. Mainly according to the different solubility of ammonium nitrate in water at different temperatures, the circulation pump 004 is used to achieve temperature alternation, thereby affecting the solubility of ammonium nitrate, and the ammonium nitrate is precipitated by precipitation of ammonium nitrate.
由控制装置 003控制整个工艺系统。  The entire process system is controlled by control unit 003.
下面对本发明进行具体举例说明：  The present invention is specifically illustrated below:
实施例 1:  Example 1:
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60°C的废气； 导入 400 mg/m3的 NH3 (氨） ， 保证 NOx与 NH3 (氨）摩尔 比在 0.8-0.9之间。直流脉冲功率 5-6MW,放电频率 900次 /秒的工况下， 混合气体通过工艺系统后， NOx出口浓度为 110mg/m3, NOx脱除效率为 78%, 组盐效率达 65%以上， 铵盐捕集装置釆用二级冷却回收系统， 每天 可回收 197.9kg的硝酸铵颗粒。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 ° C in the ECRR; introduce 400 mg/m 3 of NH 3 (ammonia) to ensure NOx and NH 3 (ammonia) moles The ratio is between 0.8-0.9. Under the condition of DC pulse power 5-6MW and discharge frequency 900 times/second, after the mixed gas passes through the process system, the NOx outlet concentration is 110mg/m 3 , the NOx removal efficiency is 78%, and the salt salt efficiency is over 65%. The ammonium salt trap uses a secondary cooling recovery system to recover 197.9 kg of ammonium nitrate particles per day.
实施例 2:  Example 2:
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60°C的废气； 注入一定量的渗滤液， 其成分主要有： CH4S (甲硫醇） 19 mg/m3、 ( CH3 )2S(二甲基醇）27mg/m3、 C2H5HS (乙硫醇) )27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 170 mg/m3的 NH3(氨气 )，保证 NOx与 NH3 (氨气）摩尔比在 0.8-0.9 之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况下， 混合气体通 过工艺系统后， NOx出口浓度为 70mg/m3, NOx脱除效率为 86%, 组盐效 率达 85%以上， 除臭效率达 93.2%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 ° C in the ECRR; inject a certain amount of leachate, the main components of which are: CH 4 S (methyl mercaptan) 19 mg /m 3 , (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 Mg/m 3 , NH 3 (ammonia) 230 mg/m 3 , and introduce 170 mg/m 3 of NH 3 (ammonia gas) to ensure a molar ratio of NOx to NH 3 (ammonia) between 0.8 and 0.9. Under the condition of DC pulse power 5-6MW and discharge frequency 900 times/second, after the mixed gas passes through the process system, the NOx outlet concentration is 70mg/m 3 and the NOx removal efficiency is 86%. The rate is over 85% and the deodorization efficiency is over 93.2%.
实施例 3  Example 3
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60°C的废气； 注入一定量的渗滤液溢出气体， 其成分主要有： CH4S (甲 硫醇） 19 mg/m\ (CH3)2S (二甲基醇） 27mg/m3、 C2H5HS (乙硫醇）） 27mg/m3、 CH3(CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 170 mg/m3的 NH3 (氨气） , 保证 NOx与 NH3 (氨气) 摩尔比在 0.8-0.9之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工 况下， 混合气体通过工艺系统后， NOx出口浓度为 71mg/m3, NOx脱除效 率为 85.8%, 组盐效率达 85.2%以上， 除臭效率达 93.2%以上。 In the ECRR, the exhaust gas with a volume of 10,000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 ° C is introduced; a certain amount of leachate overflow gas is injected, and the components thereof mainly include: CH 4 S (methyl mercaptan) 19 mg/m\(CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/m 3 , NH 3 (ammonia gas) 230 mg/m 3 , and introduce 170 mg/m 3 of NH 3 (ammonia gas) to ensure a molar ratio of NOx to NH 3 (ammonia) between 0.8 and 0.9 . Under the condition of DC pulse power 5-6MW and discharge frequency 900 times/second, after the mixed gas passes through the process system, the NOx outlet concentration is 71mg/m 3 , the NOx removal efficiency is 85.8%, and the salt salt efficiency is over 85.2%. The deodorization efficiency is over 93.2%.
实施例 4  Example 4
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60°C的废气； 导入 400 mg/m3的 NH3 (氨气 ) , 保证 NOx与 NH3(氨气） 摩尔比在 0.8-0.9之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工 况下， 混合气体通过工艺系统后， NOx出口浓度为 109mg/m3, NOx脱除效 率为 78.2%, 组盐效率达 65.2%以上， 除臭效率达 93.2%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 ° C in the ECRR; introduce 400 mg/m 3 of NH 3 (ammonia gas) to ensure NOx and NH 3 (ammonia gas) The molar ratio is between 0.8 and 0.9. Under the condition of DC pulse power 5-6MW and discharge frequency 900 times/second, after the mixed gas passes through the process system, the NOx outlet concentration is 109mg/m 3 , the NOx removal efficiency is 78.2%, and the salt salt efficiency is over 65.2%. The deodorization efficiency is over 93.2%.
实施例 5  Example 5
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60°C的废气； 注入一定量的渗滤液， 其成分主要有： CH4S (甲硫醇） 19 mg/m3、 ( CH3 )2S(二甲基醇）27mg/m3、 C2H5HS (乙硫醇) )27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 170 mg/m3的 NH3(氨气 )，保证 NOx与 NH3 (氨气）摩尔比在 0.8-0.9 之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况下， 混合气体通 过工艺系统后， NOx出口浓度为 72mg/m3, NOx脱除效率为 85.6%, 组盐 效率达 84.7%以上， 除臭效率达 92.4%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 ° C in the ECRR; inject a certain amount of leachate, the main components of which are: CH 4 S (methyl mercaptan) 19 mg /m 3 , (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 Mg/m 3 , NH 3 (ammonia) 230 mg/m 3 , and introduce 170 mg/m 3 of NH 3 (ammonia gas) to ensure a molar ratio of NOx to NH 3 (ammonia) between 0.8 and 0.9. Under the condition of DC pulse power 5-6MW and discharge frequency 900 times/second, after the mixed gas passes through the process system, the NOx outlet concentration is 72mg/m 3 , the NOx removal efficiency is 85.6%, and the salt salt efficiency is above 84.7%. The deodorization efficiency is over 92.4%.
实施例 6  Example 6
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 150 °C的废气；注入一定量的渗滤液溢出气体，其成分主要有： CH4S (甲 硫醇） 19 mg/m\ ( CH3 ) 2S (二甲基醇） 27mg/m3、 C2H5HS (乙硫醇）） 27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 170 mg/m3的 NH3 (氨气） , 保证 NOx与 NH3 (氨气) 摩尔比在 0. 8-0. 9之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工 况下， 混合气体通过工艺系统后， NOx出口浓度为 71mg/m3, NOx脱除效 率为 85. 8%, 组盐效率达 85. 2%以上， 除臭效率达 93. 2%以上。 The air volume introduced in the ECRR is 10000 m 3 /h, the NOx inlet concentration is 500 mg/m 3 , and the temperature Exhaust gas at 150 °C; inject a certain amount of leachate overflow gas, the main components are: CH 4 S (methyl mercaptan) 19 mg / m \ ( CH 3 ) 2 S (dimethyl alcohol) 27 mg / m 3 , C 2 H 5 HS (ethanethiol)) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/ m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/m 3 , NH 3 (ammonia gas) 230 mg/m 3 , simultaneously introduced into 170 mg / m NH 3 (ammonia) 3, to ensure that the molar ratio between NOx and NH 3 (ammonia) at 0. 8-0. 9. The NOx outlet concentration is 71 mg/m 3 , the NOx removal efficiency is 85.8%, and the salt-to-salt efficiency is 85. The NOx outlet concentration is 71 mg/m 3 and the NOx removal efficiency is 85.8%. 2%以上。 More than 2%, deodorization efficiency of 93.2% or more.
实施例 7  Example 7
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60 °C的废气； 导入 400 mg/m3的 NH3 (氨气 ) , 保证 NOx与 NH3 (氨气） 摩尔比在 0. 8-1之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况 下， 混合气体通过工艺系统后， NOx出口浓度为 108mg/m3, NOx脱除效率 为 78. 4%, 组盐效率达 65. 1%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 °C in the ECRR; introduce 400 mg/m 3 of NH 3 (ammonia gas) to ensure NOx and NH 3 (ammonia gas) 2之间之间。 Molar ratio between 0. 8-1. The NOx outlet concentration is 108 mg/m 3 , the NOx removal efficiency is 78. 4%, and the salt-to-salt efficiency is 65. The NOx outlet concentration is 108 mg/m 3 and the NOx removal efficiency is 78. 4%. 1% or more.
实施例 8  Example 8
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 60 °C的废气； 注入一定量的渗滤液， 其成分主要有： CH4S (甲硫醇） 19 mg/m3、 ( CH3 )2S(二甲基醇）27mg/m3、 C2H5HS (乙硫醇) )27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 170 mg/m3的 NH3(氨气），保证 NOx与 NH3 (氨气）摩尔比在 0. 8-1 之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况下， 混合气体通 过工艺系统后， NOx出口浓度为 73mg/m3, NOx脱除效率为 85. 4% , 组盐 效率达 84. 5%以上， 除臭效率达 92. 7%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 60 °C in the ECRR; inject a certain amount of leachate, the main components of which are: CH 4 S (methyl mercaptan) 19 mg /m 3 , (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg / m 3, NH 3 (ammonia) 230 mg / m 3, while introducing 170 mg / m 3 in NH 3 (ammonia), to ensure that the molar ratio of NOx and NH 3 (ammonia) in the 0. 8-1 between. When the pulsating power is 5-6 MW and the discharge frequency is 900 times/second, the NOx outlet concentration is 73 mg/m 3 , the NOx removal efficiency is 85.4%, and the salt efficiencies are 84. 5%以上。 More than 5%, deodorization efficiency of 92.7% or more.
实施例 9  Example 9
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 150 °C的废气；注入一定量的渗滤液溢出气体，其成分主要有： CH4S (甲 硫醇） 19 mg/m\ ( CH3 ) 2S (二甲基醇） 27mg/m3、 C2H5HS (乙硫醇）） 27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 170 mg/m3的 NH3 (氨） ， 保证 NOx与 NH3 (氨）摩尔 比在 0. 8-1之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况下， 混合气体通过工艺系统后， NOx出口浓度为 73mg/m3, NOx脱除效率为 85. 4% , 组盐效率达 84. 5%以上， 除臭效率达 93. 2%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 150 °C in the ECRR; inject a certain amount of leachate overflow gas, the main components of which are: CH 4 S (methyl mercaptan) 19 mg/m\ (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/m 3 , NH 3 (ammonia) 230 mg/m 3 , simultaneously introduced with 170 mg/m 3之间之间。 The NH 3 (ammonia), the NOx and NH 3 (ammonia) molar ratio between 0. 8-1. When the pulsating power is 5-6 MW and the discharge frequency is 900 times/second, the NOx outlet concentration is 73 mg/m 3 , the NOx removal efficiency is 85.4%, and the salt efficiencies are 84. 5%以上以上。 More than 5%, the deodorization efficiency of 93.2% or more.
实施例 10  Example 10
在 ECRR中导入风量为 10000m3/h , NOx入口浓度为 500mg/m3 , 温度 为 150 °C的废气；注入一定量的渗滤液，其成分主要有： CH4S (甲硫醇） 19 mg/m3、 ( CH3 )2S(二甲基醇）27mg/m3、 C2H5HS (乙硫醇) )27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 370 mg/m3的 NH3(氨气 )，保证 NOx与 NH3 (氨气）摩尔比在 1. 0-1. 3 之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况下， 混合气体通 过工艺系统后， NOx出口浓度为 227mg/m3, NOx脱除效率为 45. 4%, 组盐 效率达 84. 5%以上， 除臭效率达 92. 8%以上。 Introduce an exhaust gas with an air volume of 10000 m3/h, a NOx inlet concentration of 500 mg/m3 and a temperature of 150 °C in the ECRR; inject a certain amount of leachate, the main components of which are: CH 4 S (methyl mercaptan) 19 mg/m 3 , (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg /m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/ m 3, NH 3 (ammonia) 230 mg / m 3, while introducing 370 mg / m NH 3 (ammonia) 3, to ensure that the molar ratio of NOx and NH 3 (ammonia) at 1. 0-1. 3 of between. The NOx outlet concentration is 227 mg/m 3 , the NOx removal efficiency is 45.4%, and the salt efficiencies are up to 84. The NOx outlet concentration is 227 mg/m 3 and the NOx removal efficiency is 45. 4%. More than 5%, the deodorization efficiency is more than 92.8%.
实施例 11  Example 11
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 150 °C的废气；注入一定量的渗滤液溢出气体，其成分主要有： CH4S (甲 硫醇） 19 mg/m\ ( CH3 ) 2S (二甲基醇） 27mg/m3、 C2H5HS (乙硫醇）） 27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 370 mg/m3的 NH3 (氨气） , 保证 NOx与 NH3 (氨气) 摩尔比在 1. 0-1. 3之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工 况下， 混合气体通过工艺系统后， NOx出口浓度为 225mg/m3, NOx脱除效 率为 45% , 组盐效率达 84. 4%以上， 除臭效率达 92. 8%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 150 °C in the ECRR; inject a certain amount of leachate overflow gas, the main components of which are: CH 4 S (methyl mercaptan) 19 mg/m\ (CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg / m 3, NH 3 ( ammonia) 230 mg / m 3, while introducing 370 mg / m 3 in NH 3 (ammonia), to ensure that the molar ratio of NOx and NH 3 (ammonia) at 1. 0-1 Between 3. The NOx outlet concentration is 225 mg/m 3 , the NOx removal efficiency is 45%, and the salt salt efficiency is 84. 4%, the NOx outlet concentration is 225 mg/m 3 , the NOx removal efficiency is 45%, and the NOx emission efficiency is 45%. The above, the deodorization efficiency is more than 92.8%.
实施例 12  Example 12
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 150 °C的废气；注入一定量的渗滤液溢出气体，其成分主要有： CH4S (甲 硫醇） 19 mg/m\ ( CH3 ) 2S (二甲基醇） 27mg/m3、 C2H5HS (乙硫醇）） 27mg/m3、 CH3 (CH2) 2CH0 (正丁醛） 21 mg/m3、 (CH3) 2CHCH0 (异丁醛） 27 mg/m3、 CH3CH2CH2C00H (丁酸） 40 mg/m3、 C4H9C00H (戊酸） 5 mg/m3、 NH3 (氨气） 230 mg/m3, 同时导入 370 mg/m3的 NH3 (氨气） , 保证 NOx与 NH3 (氨气) 摩尔比在 1. 0-1. 3之间。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工 况下， 混合气体通过工艺系统后， NOx出口浓度为 228mg/m3, NOx脱除效 率为 45. 6%, 组盐效率达 84. 7%以上， 除臭效率达 92. 7%以上。 Introduce an exhaust gas with an air volume of 10000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 150 °C in the ECRR; inject a certain amount of leachate overflow gas, the main components of which are: CH 4 S (methyl mercaptan) 19 mg/m\(CH 3 ) 2 S (dimethyl alcohol) 27 mg/m 3 , C 2 H 5 HS (ethanethiol) 27 mg/m 3 , CH 3 (CH 2 ) 2 CH0 (n-butyraldehyde) 21 mg/m 3 , (CH 3 ) 2 CHCH0 (isobutyraldehyde) 27 mg/m 3 , CH 3 CH 2 CH 2 C00H (butyric acid) 40 mg/ m 3 , C 4 H 9 C00H (pentanoic acid) 5 mg/m 3 , NH 3 (ammonia gas) 230 mg/m 3 , and introduce 370 mg/m 3 of NH 3 (ammonia gas) to ensure NOx and NH 3 0-1之间之间。 (Ammonia) molar ratio between 1. 0-1. 3. The NOx outlet concentration is 228 mg/m 3 , the NOx removal efficiency is 45.6%, and the salt efficiencies are up to 84. The NOx outlet concentration is 228 mg/m 3 , the NOx removal efficiency is 45.6%, and the NOx removal efficiency is 84. More than 7%, the deodorization efficiency is over 92.7%.
实施例 1 3  Example 1 3
在 ECRR中导入风量为 10000m3/h, NOx入口浓度为 500mg/m3, 温度 为 150 °C的废气。 直流脉冲功率 5-6MW, 放电频率 900次 /秒的工况下， 混合气体通过工艺系统后， NOx出口浓度为 110mg/m3, NOx脱除效率为 78% , 生成 70%的硝酸 200. lkg/d (公斤 /日 ) 。 An exhaust gas having an air volume of 10,000 m 3 /h, a NOx inlet concentration of 500 mg/m 3 and a temperature of 150 ° C was introduced into the ECRR. The pulsing power is 5-6 MW, and the discharge frequency is 900 times/second. After the mixed gas passes through the process system, the NOx outlet concentration is 110 mg/m 3 , the NOx removal efficiency is 78%, and 70% of the nitric acid is produced. /d (kg/day).
由以上实施例可以看到， 本发明中温度对脱硝、 除臭效率几乎没什 么影响， 但是对回收的硝酸铵由一定的影响， 温度越低， 硝酸铵结晶越 多， 反之， 越少。  It can be seen from the above examples that the temperature in the present invention has little effect on the denitration and deodorization efficiency, but has a certain influence on the recovered ammonium nitrate. The lower the temperature, the more crystallized ammonium nitrate, and conversely, the less.
但是， 以上的实施例仅是用来说明本发明， 而并非用作为对本发明 的限定， 只要在本发明的实质精神范围内， 对以上所述实施例的变化、 变型都将落在本发明的权利要求书范围内。  However, the above embodiments are only intended to illustrate the invention, and are not intended to limit the invention, and variations and modifications of the above-described embodiments will fall within the scope of the invention. Within the scope of the claims.

Claims

权 利 要 求 书 claims
1、 一种含 NOx废气处理方法， 其包括， 在 5-150°C温度下， 用强氧 化活性自由基将 NOx废气氧化为 N02 、 N205、 画 2。 1. A method for treating NOx exhaust gas, which includes using strong oxidizing active free radicals to oxidize NOx exhaust gas into N0 2 , N 2 0 5 , and 2 at a temperature of 5-150°C.
2、 根据权利 1所述的方法， 其特征在于， 所述强氧化活性自由基为 高能电子、 紫外光、 高温空泡及 0H、 03、 0、 N。 2. The method according to claim 1, characterized in that the strongly oxidizing active free radicals are high-energy electrons, ultraviolet light, high-temperature cavitation and OH, 0 3 , 0, N.
3、 根据权利要求 1所述的方法， 最终生成硝酸。 3. According to the method of claim 1, nitric acid is finally generated.
4、 根据前述权利要求中任一项所述的方法， 所述强氧化活性自由基 由电化学回收反应器产生。 4. The method according to any one of the preceding claims, wherein the strongly oxidizing active free radicals are generated by an electrochemical recovery reactor.
5、 根据前述权利要求中任一项所述的方法， 所述含 NOx废气与氨一 起导入到电化学回收反应器进行反应， 其中， NOx与氨的摩尔比为 5. According to the method according to any one of the preceding claims, the NOx-containing exhaust gas and ammonia are introduced into an electrochemical recovery reactor for reaction, wherein the molar ratio of NOx to ammonia is
0.8-1. 3。 0.8-1.3.
6、 根据权利要求 5所述的方法， 其中 NOx与氨的摩尔比为 0.8-1。 6. The method according to claim 5, wherein the molar ratio of NOx to ammonia is 0.8-1.
7、 根据权利要求 5所述的方法，其中 NOx与氨的摩尔比为 0.8-0.9。7. The method according to claim 5, wherein the molar ratio of NOx to ammonia is 0.8-0.9.
8. 根据前述权利要求中任一项所述的方法， 其中， 渗滤液导入到所 述电化学回收反应器中， 所述渗滤液含有醇类、 醛类和有机酸类物质。 8. The method according to any one of the preceding claims, wherein leachate is introduced into the electrochemical recovery reactor, and the leachate contains alcohols, aldehydes and organic acids.
9. 根据权利要求 8所述的方法， 其中， 所述渗滤液的主要成份为 CH4S (甲硫醇)、 ( CH3) 2S (二甲基醇 ) 、 C2H5HS (乙硫醇) ) 、 CH3 (CH2) 2CH0 9. The method according to claim 8, wherein the main components of the leachate are CH 4 S (methyl mercaptan), (CH 3 ) 2 S (dimethyl alcohol), C 2 H 5 HS (ethyl alcohol). Thiol) ), CH 3 (CH 2 ) 2 CH0
(正丁醛） 、 (CH3) 2CHCH0 (异丁醛） 、 CH3CH2CH2C00H (丁酸） 、 C4H9C00H (戊酸） 、 NH3 (氨） 。 (n-butyraldehyde), (CH 3 ) 2 CHCHO (isobutyraldehyde), CH 3 CH 2 CH 2 C00H (butyric acid), C 4 H 9 C00H (valeric acid), NH 3 (ammonia).
10. 根据权利要求 8所述的方法， 其中， 所述渗滤液是与 NOx废气 与氨同时导入的。 10. The method according to claim 8, wherein the leachate is introduced simultaneously with the NOx exhaust gas and ammonia.
11. 根据权利要求 10所述的方法， 其中， NOx与氨和渗滤液所含氨 的总和之摩尔比为 0.8-1. 3。 11. The method according to claim 10, wherein the molar ratio of NOx to the sum of ammonia and ammonia contained in the leachate is 0.8-1.3.
12. 根据权利要求 11所述的方法， 其中， 所述摩尔比为 0.8-1。 12. The method according to claim 11, wherein the molar ratio is 0.8-1.
13. 根据权利要求 11所述的方法， 其中， 所述摩尔比为 0.8-0.9。13. The method according to claim 11, wherein the molar ratio is 0.8-0.9.
14. 根据权利要求 8所述的方法，其中，根据反应器后所检测的 NOx 和氨的比例加入所述渗滤液， 使得 NOx与氨和渗滤液所含氨的总和之摩 尔比为 0.8-1. 3。 14. The method according to claim 8, wherein the leachate is added according to the ratio of NOx and ammonia detected after the reactor, so that the molar ratio of NOx to the sum of ammonia and ammonia contained in the leachate is 0.8-1 .3.
15. 根据权利要求 14所述的方法， 其中， 所述摩尔比为 0. 8-1。15. The method according to claim 14, wherein the molar ratio is 0.8-1.
16. 根据权利要求 14所述的方法， 其中， 所述摩尔比为 0. 8-0. 9。16. The method according to claim 14, wherein the molar ratio is 0.8-0.9.
17. 根据前述权利要求中任一项所述的方法， 还进一步包括铵盐捕 收步骤。 17. The method of any one of the preceding claims, further comprising an ammonium salt capture step.
18. 根据权利要求 17所述的方法，其中所述铵盐捕收步骤是在二级 冷却回收系统中进行的。 18. The method of claim 17, wherein the ammonium salt capture step is performed in a secondary cooling recovery system.
19. 用于根据上述权利要求方法的系统， 其包括： 电化学回收反应 器（001 ) 、 铵盐捕集装置（ 002 ) 、 控制装置（ 003 ) ； 所述电化学回收 反应器（001 )输出的脉冲功率大于 5MW, 并且持续稳定放电； 所述铵盐 捕集装置 （ 002 ) 与所述电化学回收反应器 （001 ) 呈流体连接； 所述控 制装置（ 003 )与电化学回收反应器（001 )和铵盐捕集装置（ 002 )通信 连接。 19. A system for the method according to the above claims, which includes: an electrochemical recovery reactor (001), an ammonium salt capture device (002), a control device (003); the output of the electrochemical recovery reactor (001) The pulse power is greater than 5MW, and the discharge continues stably; the ammonium salt capture device (002) is fluidly connected to the electrochemical recovery reactor (001); the control device (003) is connected to the electrochemical recovery reactor (001) 001) is communicated with the ammonium salt capture device (002).
20. 如权利要求 19所述的系统， 其特征在于： 还包括循环泵（ 004 ) 与铵盐捕集装置（ 002 )呈流体连接，能交替控制温度，所述控制装置（ 003 ) 与循环泵 （ 004 ) 通信连接。 20. The system according to claim 19, characterized in that: it further includes a circulation pump (004) fluidly connected to an ammonium salt capture device (002), which can alternately control the temperature, and the control device (003) and the circulation pump (004) Communication connection.
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