CN100434142C - The method of using ethanol to realize the direct denitrification of flue gas dry method - Google Patents
The method of using ethanol to realize the direct denitrification of flue gas dry method Download PDFInfo
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- CN100434142C CN100434142C CNB2006100266655A CN200610026665A CN100434142C CN 100434142 C CN100434142 C CN 100434142C CN B2006100266655 A CNB2006100266655 A CN B2006100266655A CN 200610026665 A CN200610026665 A CN 200610026665A CN 100434142 C CN100434142 C CN 100434142C
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003546 flue gas Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003517 fume Substances 0.000 claims 3
- 238000002485 combustion reaction Methods 0.000 abstract description 24
- 238000005516 engineering process Methods 0.000 abstract description 18
- 239000000446 fuel Substances 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
一种环保技术领域的利用乙醇实现烟气干法直接脱硝的方法。本发明利用乙醇与烟气中的一氧化氮、氧气发生化学反应生成氮气、水蒸汽和二氧化碳从而实现烟气干法直接脱硝，乙醇射入时，烟气温度为750℃-1100℃。本发明的优点在于：第一、射入燃料燃烧过程结束后烟气区域的乙醇直接与烟气中的一氧化氮反应生成氮气。第二、由于乙醇被射入燃烧设备中烟气温度为区域的烟道内与烟气中的一氧化氮直接迅速反应而生成氮气，因此不需另外布置脱硝反应器、脱硝副产物分离装置及催化剂，具有实施容易的特点。第三、由于是在燃料燃烧过程完成后的烟气区域通过乙醇实现烟气干法直接脱硝，因此不受具体燃烧设备和燃料特性限制，有着广阔的应用前景。
The invention relates to a method of utilizing ethanol to realize the direct denitrification of flue gas dry method in the field of environmental protection technology. The invention uses ethanol to react with nitric oxide and oxygen in flue gas to generate nitrogen, water vapor and carbon dioxide to realize direct denitrification of flue gas by dry method. When ethanol is injected, the flue gas temperature is 750°C-1100°C. The advantages of the present invention are: firstly, the ethanol injected into the flue gas area after the fuel combustion process is finished directly reacts with the nitric oxide in the flue gas to generate nitrogen. Second, since the ethanol is injected into the flue of the combustion equipment where the temperature of the flue gas is the highest, it reacts directly and rapidly with the nitric oxide in the flue gas to generate nitrogen, so there is no need to arrange additional denitrification reactors, denitrification by-product separation devices and catalysts , which is easy to implement. Third, since the dry flue gas denitrification is achieved through ethanol in the flue gas area after the fuel combustion process is completed, it is not limited by specific combustion equipment and fuel characteristics, and has broad application prospects.
Description
技术领域 technical field
本发明涉及环保技术领域的方法，具体是一种利用乙醇实现烟气干法直接脱硝的方法。The invention relates to a method in the technical field of environmental protection, in particular to a method for realizing direct denitrification of flue gas by using ethanol.
背景技术 Background technique
燃料燃烧过程中，由于其本身含有氮元素，加之燃烧过程的高温，使得燃烧后气体中含有高浓度一氧化氮有毒气体，对环境造成污染。现有烟气干法脱硝技术中，主要包括高温燃烧过程中采取的空气分级燃烧技术、燃料分级再燃技术及选择性非催化还原技术，燃烧过程结束后的尾部低温选择性催化还原及非选择性催化还原脱硝技术。除空气分级燃烧脱硝技术外，燃料分级再燃脱硝技术、选择性非催化还原脱硝技术、选择性催化还原脱硝技术及非选择性催化还原脱硝技术，均需要脱硝添加剂。其中，燃料分级再燃脱硝技术是在高温还原气氛区域加入脱硝添加剂，选择性非催化还原脱硝技术是在燃料高温燃尽区域加入脱硝添加剂，选择性催化还原脱硝技术和非选择性催化还原脱硝技术是在燃料燃烧结束后的较低温度区域加入脱硝添加剂，实现烟气在高温和较低温度区域的脱硝目的。能否在介于燃烧过程中的高温和燃烧结束后的低温间的中温区域实现干法直接脱硝，一直是一个待解决的难题，因为燃烧过程中的高温脱硝总是和提高燃烧效率相矛盾，燃烧结束后的低温选择性催化还原和非选择性催化还原脱硝技术需要专门的脱硝装置和催化剂，投资和运行费用高。烟气中温干法直接脱硝，既可解决燃料燃烧与烟气脱硝的矛盾，又不需要专门的脱硝装置和催化剂。During the fuel combustion process, due to the nitrogen element itself and the high temperature of the combustion process, the gas after combustion contains a high concentration of nitrogen monoxide poisonous gas, which pollutes the environment. The existing flue gas dry denitrification technology mainly includes air staged combustion technology, fuel staged reburning technology and selective non-catalytic reduction technology adopted in the high-temperature combustion process. Catalytic reduction denitrification technology. In addition to air staged combustion denitrification technology, fuel staged reburning denitrification technology, selective non-catalytic reduction denitrification technology, selective catalytic reduction denitrification technology and non-selective catalytic reduction denitrification technology all require denitrification additives. Among them, fuel graded reburning denitrification technology is to add denitrification additives in the high-temperature reducing atmosphere area, selective non-catalytic reduction denitrification technology is to add denitrification additives to fuel high-temperature burnout areas, selective catalytic reduction denitrification technology and non-selective catalytic reduction denitrification technology are Add denitrification additives in the lower temperature area after fuel combustion to achieve the purpose of denitrification of flue gas in high temperature and lower temperature areas. It has always been a difficult problem to be solved whether to achieve direct denitrification by dry method in the medium temperature region between the high temperature during the combustion process and the low temperature after the combustion, because the high temperature denitrification during the combustion process is always contradictory to improving the combustion efficiency. The low-temperature selective catalytic reduction and non-selective catalytic reduction denitrification technologies after combustion require special denitrification devices and catalysts, and the investment and operation costs are high. The medium-temperature dry method of flue gas direct denitrification can not only solve the contradiction between fuel combustion and flue gas denitrification, but also does not require special denitrification devices and catalysts.
经对现有技术文献的检索发现，中国专利申请号：CN03125332.6，专利名称为：同时脱硫脱硝的干法烟气洁净工艺及其系统，该专利自述为：本发明公开了一种同时脱硫脱硝的干法烟气洁净工艺及其系统，所公开的烟气脱硝工艺为采用双氧水或甲醇作为添加剂，将其喷射到从燃烧设备所排放出的温度为350～700℃烟气中，使烟气中的一氧化氮气体与双氧水或甲醇发生化学反应生成二氧化氮气体，采用氨水或尿素作为脱硝剂，将其喷射到经过脱硫处理的烟气中进行脱硝处理，使烟气中的二氧化氮气体与氨水或尿素发生化学反应生成脱硝副产物硝酸氨。上述发明没能实现烟气直接脱硝，而是在烟气经过脱硫后的较低温度区域通过加入氨水或尿素与之前依靠加入双氧水或甲醇生成的二氧化氮气体生成脱硝副产物硝酸氨实现烟气脱硝目的。同时，由于增加了脱硝反应塔和脱硝产物分离装置，导致系统阻力增大、能耗上升。After searching the existing technical documents, it is found that the Chinese patent application number: CN03125332.6, the patent name is: dry flue gas cleaning process and system for simultaneous desulfurization and denitrification, and the patent self-statement is: the present invention discloses a simultaneous desulfurization and denitrification process. The dry flue gas cleaning process and system for denitrification, the disclosed flue gas denitrification process uses hydrogen peroxide or methanol as an additive, and sprays it into the flue gas discharged from the combustion equipment at a temperature of 350-700°C, so that the flue gas The nitrogen monoxide gas in the gas reacts with hydrogen peroxide or methanol to generate nitrogen dioxide gas. Using ammonia water or urea as a denitrification agent, it is sprayed into the desulfurized flue gas for denitrification treatment, so that the carbon dioxide in the flue gas Nitrogen gas reacts with ammonia water or urea to produce denitrification by-product ammonium nitrate. The above-mentioned invention fails to realize the direct denitrification of flue gas, but in the lower temperature area after the flue gas has been desulfurized, by adding ammonia water or urea and the nitrogen dioxide gas generated by adding hydrogen peroxide or methanol to generate denitrification by-product ammonium nitrate to realize flue gas The purpose of denitrification. At the same time, due to the addition of a denitrification reaction tower and a denitrification product separation device, the system resistance increases and energy consumption increases.
发明内容 Contents of the invention
本发明的目的在于克服现有烟气干法脱硝技术存在的不足，提供一种利用乙醇实现烟气干法直接脱硝的方法，使其利用乙醇实现烟气干法直接脱硝目的，具有实施容易的特点。The purpose of the present invention is to overcome the deficiencies in the existing flue gas dry denitrification technology, and provide a method for using ethanol to realize the direct denitrification of flue gas dry method, so that it can use ethanol to achieve the purpose of direct denitrification of flue gas dry method, which is easy to implement features.
本发明是通过以下技术方案实现的，在燃料燃烧过程结束后的烟气区域，将乙醇喷入含有一氧化氮气体的烟气中，使烟气中的一氧化氮、氧气与乙醇发生化学反应生成氮气、水蒸汽和二氧化碳从而实现烟气干法直接脱硝。The present invention is achieved through the following technical proposals. In the flue gas area after the fuel combustion process, ethanol is sprayed into the flue gas containing nitric oxide gas, so that the nitric oxide, oxygen and ethanol in the flue gas undergo a chemical reaction Generate nitrogen, water vapor and carbon dioxide to achieve direct denitrification of flue gas dry method.
本发明利用乙醇实现烟气干法直接脱硝的化学反应方程式如下：The present invention utilizes ethanol to realize the chemical reaction equation of dry flue gas denitrification directly as follows:
2C2H5OH+2NO+5O2→N2+4CO2+6H2O2C 2 H 5 OH+2NO+5O 2 →N 2 +4CO 2 +6H 2 O
另外，乙醇与烟气中燃料燃烧后剩余氧气发生的化学反应方程式如下：In addition, the chemical reaction equation between ethanol and the remaining oxygen after fuel combustion in the flue gas is as follows:
C2H5OH+3O2→2CO2+3H2OC 2 H 5 OH+3O 2 →2CO 2 +3H 2 O
由上述化学反应方程式可知，喷入烟气中的乙醇，除与烟气中的一氧化氮产生化学反应外，还与烟气中燃料燃烧后剩余的氧气发生化学反应，这样喷入的乙醇量就与烟气中一氧化氮及氧气量有关。在烟气中的一氧化氮及氧气量一定条件下，脱硝效率随一氧化氮与乙醇摩尔百分比值的减小而增大。It can be seen from the above chemical reaction equation that the ethanol injected into the flue gas not only reacts with the nitric oxide in the flue gas, but also reacts with the remaining oxygen after the fuel is burned in the flue gas, so the amount of ethanol injected It is related to the amount of nitric oxide and oxygen in the flue gas. Under the condition of certain amount of nitric oxide and oxygen in the flue gas, the denitrification efficiency increases with the decrease of the molar percentage of nitric oxide and ethanol.
与现有干法脱硝技术相比，本发明的优点在于：第一、射入燃料燃烧过程结束后烟气区域的乙醇直接与烟气中的一氧化氮反应生成氮气。第二、由于乙醇被射入燃烧设备中烟气温度为区域的烟道内与烟气中的一氧化氮直接迅速反应而生成氮气，因此不需另外布置脱硝反应器、脱硝副产物分离装置及催化剂，具有实施容易的特点。第三、由于本发明是在燃料燃烧过程完成后的烟气区域通过乙醇实现烟气干法直接脱硝，因此本发明不受具体燃烧设备和燃料特性限制，有着广阔的应用前景。Compared with the existing dry denitrification technology, the present invention has the following advantages: first, the ethanol injected into the flue gas area after the fuel combustion process is completed directly reacts with the nitric oxide in the flue gas to generate nitrogen. Second, since the ethanol is injected into the flue of the combustion equipment where the temperature of the flue gas is the highest, it reacts directly and rapidly with the nitric oxide in the flue gas to generate nitrogen, so there is no need to arrange additional denitrification reactors, denitrification by-product separation devices and catalysts , which is easy to implement. Third, since the present invention realizes direct denitrification of flue gas through ethanol in the flue gas area after the fuel combustion process is completed, the present invention is not limited by specific combustion equipment and fuel characteristics, and has broad application prospects.
附图说明 Description of drawings
图1为本发明实施例采用的装置示意图Fig. 1 is the device schematic diagram that the embodiment of the present invention adopts
图2为图1所示A-A剖视图Fig. 2 is A-A sectional view shown in Fig. 1
具体实施方式 Detailed ways
下面以一台燃煤电站锅炉为例，结合图1和图2对本发明利用乙醇实现烟气干法直接脱硝进行详细描述。Taking a coal-fired power plant boiler as an example, the present invention will describe in detail the direct denitrification of flue gas by using ethanol in combination with FIG. 1 and FIG. 2 .
燃煤在电站锅炉炉膛1内燃烧生成的含有一氧化氮的高温烟气，在完成与炉膛四周水冷壁的辐射换热后、依次流入水平烟道2、尾部竖井烟道4后排出。表1为烟气中各组分及射入乙醇的摩尔百分比，表2为表1条件下射入乙醇在不同烟气温度下的脱硝效率。The high-temperature flue gas containing nitric oxide generated by burning coal in the furnace 1 of the power plant boiler flows into the horizontal flue 2 and the tail shaft flue 4 in sequence after completing the radiation heat exchange with the water-cooled walls around the furnace. Table 1 shows the molar percentages of each component in the flue gas and injected ethanol, and Table 2 shows the denitrification efficiency of injected ethanol at different flue gas temperatures under the conditions of Table 1.
表1烟气中各组分及射入乙醇的摩尔百分比Table 1 Mole percentage of each component in flue gas and injected ethanol
表2乙醇在不同烟气温度下的脱硝效率Table 2 The denitrification efficiency of ethanol at different flue gas temperatures
由表2可知，在烟气温度为760～870℃间，射入的乙醇具有相对较高的脱硝效率。根据燃煤电站锅炉热力计算和实际运行结果，烟气温度为760～870℃间的区域为水平烟道2的后部，因此利用乙醇喷射装置3将乙醇射入水平烟道2烟气温度为760～870℃间的区域，与烟气中的一氧化氮反应生成氮气而实现干法直接脱硝，具有相对较高的脱硝效率。It can be seen from Table 2 that the injected ethanol has a relatively high denitrification efficiency when the flue gas temperature is between 760 and 870 °C. According to the thermal calculation and actual operation results of coal-fired power plant boilers, the area where the flue gas temperature is between 760 and 870 °C is the rear part of the horizontal flue 2, so the ethanol injection device 3 is used to inject ethanol into the horizontal flue 2. The flue gas temperature is In the area between 760 and 870°C, it reacts with nitric oxide in the flue gas to generate nitrogen to realize direct denitrification by dry method, and has a relatively high denitrification efficiency.
另外，在烟气中的一氧化氮及氧气量一定条件下，脱硝效率随烟气中一氧化氮与加入的乙醇摩尔百分比值的减小而升高。为保证乙醇在烟气中的均匀分布，乙醇喷射装置3既可可布置于水平烟道2的顶部、下部及左右两侧墙上，也可布置于水平烟道2内。In addition, under certain conditions of nitrogen monoxide and oxygen in the flue gas, the denitrification efficiency increases with the decrease of the molar percentage of nitric oxide in the flue gas and the added ethanol. In order to ensure the uniform distribution of ethanol in the flue gas, the ethanol spraying device 3 can be arranged on the top, bottom and left and right walls of the horizontal flue 2, and can also be arranged in the horizontal flue 2.
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| CN102302893B (en) * | 2011-06-20 | 2014-10-29 | 中国华能集团清洁能源技术研究院有限公司 | Selective non-catalytic reduction and denitration method for circulating fluidized bed boiler |
| CN111514738A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | A new type of composite biomass denitrification water agent for dry process cement kiln, its use method and denitration system |
| CN111514726B (en) * | 2019-02-02 | 2024-01-26 | 广东万引科技发展有限公司 | Novel composite biomass denitration agent for dry-method cement kiln, application method of novel composite biomass denitration agent and denitration system |
| CN112742205B (en) * | 2019-10-31 | 2024-01-23 | 广东万引科技发展有限公司 | Novel biomass denitration agent for dry-method cement kiln, application method of novel biomass denitration agent and denitration system |
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| JPS63205140A (en) * | 1987-02-19 | 1988-08-24 | Hidefumi Hirai | Adsorbent for nitrogen monoxide and method for separating and removing nitrogen monoxide |
| CN1032548A (en) * | 1987-10-14 | 1989-04-26 | 燃料技术有限公司 | Reduce the method for nitrogen oxide in the waste gas |
| CN1084098A (en) * | 1992-09-12 | 1994-03-23 | 中国科学院福建物质结构研究所 | Eliminate the new method of nitrogen oxide gas contaminated environment |
| CN1589954A (en) * | 2003-08-26 | 2005-03-09 | 武汉凯迪电力股份有限公司 | Dry smoke cleaning process for desulfurizing and denitrating simultaneously and its system |
| US20050126159A1 (en) * | 2003-12-11 | 2005-06-16 | Cho Byong K. | Method of reducing NOx in diesel engine exhaust |
-
2006
- 2006-05-18 CN CNB2006100266655A patent/CN100434142C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63205140A (en) * | 1987-02-19 | 1988-08-24 | Hidefumi Hirai | Adsorbent for nitrogen monoxide and method for separating and removing nitrogen monoxide |
| CN1032548A (en) * | 1987-10-14 | 1989-04-26 | 燃料技术有限公司 | Reduce the method for nitrogen oxide in the waste gas |
| CN1084098A (en) * | 1992-09-12 | 1994-03-23 | 中国科学院福建物质结构研究所 | Eliminate the new method of nitrogen oxide gas contaminated environment |
| CN1589954A (en) * | 2003-08-26 | 2005-03-09 | 武汉凯迪电力股份有限公司 | Dry smoke cleaning process for desulfurizing and denitrating simultaneously and its system |
| US20050126159A1 (en) * | 2003-12-11 | 2005-06-16 | Cho Byong K. | Method of reducing NOx in diesel engine exhaust |
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