CN104197319B - A low-emission coal combustion method and device - Google Patents
A low-emission coal combustion method and device Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 62
- 238000009841 combustion method Methods 0.000 title claims abstract description 13
- 238000002485 combustion reaction Methods 0.000 claims abstract description 50
- 238000000197 pyrolysis Methods 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011280 coal tar Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 230000008520 organization Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol amine Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Abstract
本发明涉及一种低排放的煤燃烧方法及装置，先将部分煤或全部煤进行高温热解，热解过程中煤中的部分硫以H2S析出，热解后的煤以及煤焦油送入燃烧装置中燃烧，煤中剩余的硫元素在燃烧过程中生成SO2，或者将剩余部分煤与热解后的煤以及煤焦油送入燃烧装置中一块燃烧生成SO2，生产的SO2与析出的H2S被送入反应器中反应生产单质硫，生成的部分硫单质与烟气中的Hg反应生成HgS，剩余的硫单质通过硫冷凝器生成液态硫，净化后的气体再次通入燃烧装置合适位置进行燃烧。本发明仅通过煤燃烧过程的调整与组织，实现低SO2、NOx、Hg排放的煤燃烧方法，从燃烧过程的源头上降低SO2、NOx、Hg排放浓度。
The invention relates to a low-emission coal combustion method and device. First, part or all of the coal is pyrolyzed at high temperature. During the pyrolysis process, part of the sulfur in the coal is precipitated as H 2 S. Combustion in the combustion device, the remaining sulfur in the coal generates SO 2 during the combustion process, or send the remaining part of coal, pyrolyzed coal and coal tar into the combustion device to burn together to generate SO 2 , the produced SO 2 and The precipitated H 2 S is sent to the reactor to react to produce elemental sulfur, and part of the generated elemental sulfur reacts with Hg in the flue gas to form HgS, and the remaining elemental sulfur passes through the sulfur condenser to generate liquid sulfur, and the purified gas is passed into the The combustion device is in a suitable position for combustion. The invention realizes the coal combustion method with low SO 2 , NO x , and Hg emissions only through the adjustment and organization of the coal combustion process, and reduces the emission concentrations of SO 2 , NO x , and Hg from the source of the combustion process.
Description
技术领域technical field
本发明涉及一种新型的低SO2、NOx、Hg排放的煤燃烧方法及装置，特别是通过煤燃烧过程的调整与合理组织实现燃煤污染物燃烧过程中控制的新方法，属于环境保护技术领域。The invention relates to a new coal combustion method and device with low SO 2 , NO x , and Hg emissions, especially a new method for controlling the combustion process of coal-burning pollutants through the adjustment and rational organization of the coal combustion process, which belongs to environmental protection technology field.
背景技术Background technique
据统计，目前我国每年煤炭消耗量近四十亿吨，其中近50％用于各种燃烧装置。煤燃烧后生成的SO2、NOx、粉尘等是影响空气中PM2.5浓度的主要污染物。2013年我国这三项污染物排放总量分别约2044万吨、2227万吨和1500万吨，均位居世界第一，同时排放了数百万吨的汞。燃煤锅炉是大气污染主要源头之一，随着国家对环保的日益重视和污染物排放标准的逐步提高，控制燃煤锅炉排放的任务将越来越艰巨，污染物控制成本越来越高。According to statistics, my country's annual coal consumption is nearly 4 billion tons, of which nearly 50% is used in various combustion devices. SO 2 , NO x , and dust generated after coal combustion are the main pollutants that affect the concentration of PM2.5 in the air. In 2013, my country’s total emissions of these three pollutants were about 20.44 million tons, 22.27 million tons, and 15 million tons, respectively, ranking first in the world, while emitting millions of tons of mercury. Coal-fired boilers are one of the main sources of air pollution. With the country's increasing emphasis on environmental protection and the gradual improvement of pollutant discharge standards, the task of controlling coal-fired boiler emissions will become more and more difficult, and the cost of pollutant control will become higher and higher.
燃烧后烟气脱硫、脱硝是控制燃煤锅炉SO2、NOx排放的主要途径，目前通常分别设置独立的脱硫、脱硝装置进行控制，不仅投资运行费用巨大，而且消耗了大量石灰石、NH3等资源。而对于燃煤生成的Hg，一般采用活性炭吸附的方法控制其排放。如专利CN101422691A公开了一种燃煤烟气多污染物脱除工艺及其设备。该工艺先用SCR脱硝法脱除烟气中的NOX,其次用除尘器脱除烟气中的粉尘灰粒,然后用湿式钙基脱硫法消除烟气中的SO2,再用MEA脱碳法吸收烟气中的CO2,同时将所生成的醇胺溶液富液加热解析再生,所得醇胺溶液贫液继续循环使用,解析出的高浓度CO2气体则经过冷却、气液分离、干燥、压缩和冷凝处理,制成高纯度工业级液体二氧化碳。就是分别设置独立的脱硫、脱硝装置进行控制，投资运行费用巨大。Flue gas desulfurization and denitrification after combustion are the main ways to control SO 2 and NO x emissions from coal-fired boilers. At present, independent desulfurization and denitrification devices are usually set up for control, which not only costs a lot of investment and operation, but also consumes a lot of limestone, NH 3 , etc. resource. As for the Hg produced by coal combustion, activated carbon adsorption is generally used to control its emission. For example, patent CN101422691A discloses a coal-fired flue gas multi-pollutant removal process and its equipment. The process uses SCR denitrification method to remove NOx in the flue gas first, then removes dust and ash particles in the flue gas with a dust collector, then uses a wet calcium-based desulfurization method to eliminate SO 2 in the flue gas, and then uses MEA to decarbonize The method absorbs CO 2 in the flue gas, and at the same time heats and regenerates the rich solution of alcohol amine solution, and the poor solution of alcohol amine solution obtained continues to be recycled, and the high-concentration CO 2 gas desorbed is cooled, gas-liquid separated and dried , compression and condensation treatment to produce high-purity industrial-grade liquid carbon dioxide. That is to set up independent desulfurization and denitrification devices for control, and the investment and operation costs are huge.
环境保护部2011年发布的《火电厂大气污染物排放标准》(GB13223-2011)中规定，自2014年7月1日起，所有65t/h以上燃煤发电锅炉执行100mg/m3(新建)/200mg/m3(已有)的SO2排放标准、100mg/m3的NOx排放标准，自2015年1月1日起，执行0.03mg/m3的Hg排放标准。排放标准的提高对现有火力发电厂脱硫、脱硝装置的性能提出了更严格的要求，同时需要采取措施控制烟气中Hg的排放。According to the "Emission Standards of Air Pollutants for Thermal Power Plants" (GB13223-2011) issued by the Ministry of Environmental Protection in 2011, starting from July 1, 2014, all coal-fired power boilers above 65t/h shall implement 100mg/m 3 (newly built) /200mg/m 3 (existing) SO 2 emission standard, 100mg/m 3 NO x emission standard, since January 1, 2015, the implementation of 0.03mg/m 3 Hg emission standard. The improvement of emission standards puts forward stricter requirements on the performance of desulfurization and denitrification devices in existing thermal power plants, and measures need to be taken to control the emission of Hg in flue gas.
发明内容Contents of the invention
本发明针对上述不足，提出了一种低排放的煤燃烧方法及装置，不消耗外在资源，仅通过煤燃烧过程的调整与组织，实现低SO2、NOx、Hg排放的煤燃烧方法，从燃烧过程的源头上降低SO2、NOx、Hg排放浓度，进而降低尾部烟气污染物脱除的运行成本。Aiming at the above-mentioned deficiencies, the present invention proposes a low-emission coal combustion method and device, which does not consume external resources, and only through the adjustment and organization of the coal combustion process, realizes a coal combustion method with low SO 2 , NO x , and Hg emissions. Reduce the emission concentration of SO 2 , NO x , and Hg from the source of the combustion process, thereby reducing the operating cost of tail flue gas pollutant removal.
本发明采取的技术方案为：The technical scheme that the present invention takes is:
一种低排放的煤燃烧方法，先将部分煤或全部煤进行高温热解，热解温度区间为300℃—700℃，热解过程中煤中的部分硫以H2S析出，热解后的煤以及煤焦油送入燃烧装置中燃烧，煤中剩余的硫元素在燃烧过程中生成SO2，或者将剩余部分煤与热解后的煤以及煤焦油送入燃烧装置中一块燃烧生成SO2，生产的SO2与析出的H2S被送入催化或非催化反应器中反应生产单质硫实现自脱硫，生成的部分硫单质与烟气中的Hg反应生成HgS，实现煤燃烧自脱汞过程，剩余的硫单质通过硫冷凝器生成液态硫，净化后的气体再次通入燃烧装置合适位置进行燃烧，实现热解气的再燃脱硝。A low-emission coal combustion method. First, part or all of the coal is subjected to high-temperature pyrolysis. The pyrolysis temperature range is 300°C-700°C. During the pyrolysis process, part of the sulfur in the coal is precipitated as H 2 S, and after pyrolysis The coal and coal tar are sent to the combustion device for combustion, and the remaining sulfur element in the coal generates SO 2 during the combustion process, or the remaining part of coal, pyrolyzed coal and coal tar are sent to the combustion device to be burned together to generate SO 2 , the produced SO 2 and the precipitated H 2 S are sent to catalytic or non-catalytic reactors to react to produce elemental sulfur to realize self-desulfurization, and part of the generated elemental sulfur reacts with Hg in the flue gas to form HgS, which realizes self-demercuration of coal combustion During the process, the remaining sulfur element passes through the sulfur condenser to generate liquid sulfur, and the purified gas is passed into the combustion device for combustion at a suitable position again to realize the reburning and denitrification of the pyrolysis gas.
所述的催化反应器中的反应温度区间为170℃-350℃，所述的非催化反应器中温度范围为0℃-300℃。The reaction temperature range in the catalytic reactor is 170°C-350°C, and the temperature range in the non-catalytic reactor is 0°C-300°C.
反应器中通过反应2H2S+SO2＝3S+2H2O生成单质S，因此应严格控制烟气流量使H2S与SO2的摩尔比为2:1。Elemental S is generated by reacting 2H 2 S+SO 2 =3S+2H 2 O in the reactor, so the flue gas flow rate should be strictly controlled so that the molar ratio of H 2 S to SO 2 is 2:1.
一种低排放的煤燃烧装置，包括热解装置，热解装置的底部通过输送管与燃烧装置相连，热解装置的上部与反应器的一个进气口相连，反应器的另一进气口与燃烧装置的出气口相通，反应器的出气口与燃烧装置进气口相通，反应器的固体出口与硫冷凝器相连。A low-emission coal combustion device, including a pyrolysis device, the bottom of the pyrolysis device is connected to the combustion device through a delivery pipe, the upper part of the pyrolysis device is connected to one air inlet of the reactor, and the other air inlet of the reactor It is connected with the gas outlet of the combustion device, the gas outlet of the reactor is connected with the gas inlet of the combustion device, and the solid outlet of the reactor is connected with the sulfur condenser.
本发明的有益效果是：在不损失煤中可燃成分的条件下，通过煤燃烧过程中SO2、NOx、Hg有效控制，实现煤燃烧低SO2、低NOx和低Hg排放。本发明可通过对现有燃煤装置加以改进实现煤燃烧的低SO2、NOx、Hg排放，无需额外吸收剂或添加剂，具有成本低、经济、环保等优点，与传统脱硫脱硝脱汞方式相比，具有很高的经济性。本发明适用于燃煤锅炉、炉窑等燃煤装置。The beneficial effects of the invention are: under the condition of not losing combustible components in coal, through effective control of SO 2 , NOx and Hg in the process of coal combustion, low SO 2 , low NOx and low Hg emission of coal combustion can be realized. The present invention can achieve low SO 2 , NOx, and Hg emissions from coal combustion by improving existing coal-fired devices, without additional absorbents or additives, and has the advantages of low cost, economy, and environmental protection. ratio, with high economy. The invention is applicable to coal-burning devices such as coal-fired boilers and kilns.
附图说明Description of drawings
图1为本发明部分煤热解时低排放的煤燃烧装置；Fig. 1 is the low-emission coal combustion device during partial coal pyrolysis of the present invention;
图2为本发明全部煤热解时低排放的煤燃烧装置。Fig. 2 is a low-emission coal combustion device when all coal is pyrolyzed in the present invention.
其中，1.热解装置，2.燃烧装置，3.反应器，4.硫冷凝器，5.煤。Among them, 1. Pyrolysis device, 2. Combustion device, 3. Reactor, 4. Sulfur condenser, 5. Coal.
具体实施方式detailed description
下面结合附图和实施例对本发明做进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
一种低排放的煤燃烧装置，包括热解装置1，热解装置1的底部通过输送管与燃烧装置2相连，热解装置1的上部与反应器3的一个进气口相连，反应器3的另一进气口与燃烧装置2的出气口相通，反应器3的出气口与燃烧装置2进气口相通，反应器3的固体出口与硫冷凝器4相连。A low-emission coal combustion device, comprising a pyrolysis device 1, the bottom of the pyrolysis device 1 is connected to the combustion device 2 through a delivery pipe, the upper part of the pyrolysis device 1 is connected to an air inlet of a reactor 3, and the reactor 3 The other air inlet of the reactor communicates with the gas outlet of the combustion device 2, the gas outlet of the reactor 3 communicates with the gas inlet of the combustion device 2, and the solid outlet of the reactor 3 links to each other with the sulfur condenser 4.
实施例1Example 1
一种低排放的煤燃烧方法(燃煤部分热解)：装置如图1所示，燃煤在通入燃烧装置之前，有一部分煤先通入热解反应器进行高温热解，温度区间为300℃—700℃，具体温度由煤种以及含硫量决定。在热解反应器内发生煤的热解，热解后的煤渣和煤焦油直接通入燃烧装置，热解气通入催化反应器。同时，燃烧装置内煤燃烧后的烟气也有一部分通入催化反应器，催化反应器内发生反应2H2S+SO2＝3S+2H2O，生成单质S，控制H2S及SO2的摩尔比为2:1，同时生成的S与烟气中的Hg发生反应Hg+S＝HgS，生成HgS，剩余的S通过硫冷凝器生成液态硫。净化后的气体再次通入炉膛合适位置进行燃烧，实现热解气的再燃脱硝，再燃脱硝后烟气进入下游烟道。A low-emission coal combustion method (partial pyrolysis of coal): the device is shown in Figure 1. Before the coal is passed into the combustion device, a part of the coal is first passed into the pyrolysis reactor for high-temperature pyrolysis, and the temperature range is 300°C-700°C, the specific temperature is determined by the type of coal and the sulfur content. Coal pyrolysis occurs in the pyrolysis reactor, and the pyrolyzed coal slag and coal tar are directly passed into the combustion device, and the pyrolysis gas is passed into the catalytic reactor. At the same time, part of the flue gas after coal combustion in the combustion device is also passed into the catalytic reactor, and the reaction 2H 2 S + SO 2 = 3S + 2H 2 O occurs in the catalytic reactor to generate elemental S, and the concentration of H 2 S and SO 2 is controlled. The molar ratio is 2:1, and the generated S reacts with Hg in the flue gas at the same time Hg+S=HgS to generate HgS, and the remaining S passes through the sulfur condenser to generate liquid sulfur. The purified gas is passed into the proper position of the furnace again for combustion to realize the reburning and denitrification of the pyrolysis gas, and the flue gas enters the downstream flue after reburning and denitrification.
实施例2Example 2
一种低排放的煤燃烧方法(燃煤全部热解)：装置如图2所示，燃煤全部通入热解反应器进行高温热解，温度区间为300℃—700℃，具体温度由煤种以及含硫量决定。在热解反应器内发生煤的热解，热解后的煤渣和煤焦油直接通入燃烧装置，热解气通入反应器。同时，燃烧装置内煤燃烧后的烟气也有一部分通入反应器，反应器内发生反应2H2S+SO2＝3S+2H2O，生成单质S，控制H2S及SO2的摩尔比为2:1，同时生成的S与烟气中少量的Hg发生反应Hg+S＝HgS，生成HgS，剩余的S通过硫冷凝器生成液态硫。反应器后的尾气再次通入燃烧装置合适位置进行分级燃烧，实现热解气的分级再燃脱硝，燃烧后的烟气最后通入其它烟气净化装置。A low-emission coal combustion method (full coal pyrolysis): the device is shown in Figure 2, all the coal is passed into the pyrolysis reactor for high-temperature pyrolysis, the temperature range is 300°C-700°C, the specific temperature is determined by the coal species and sulfur content. Coal pyrolysis occurs in the pyrolysis reactor, and the pyrolyzed cinder and coal tar are directly passed into the combustion device, and the pyrolysis gas is passed into the reactor. At the same time, part of the flue gas after coal combustion in the combustion device is also passed into the reactor, and the reaction 2H 2 S + SO 2 = 3S + 2H 2 O occurs in the reactor to generate simple substance S, and the molar ratio of H 2 S and SO 2 is controlled At the same time, the generated S reacts with a small amount of Hg in the flue gas Hg+S=HgS to generate HgS, and the remaining S passes through the sulfur condenser to generate liquid sulfur. The tail gas after the reactor is passed into the appropriate position of the combustion device again for staged combustion to realize the staged reburning and denitrification of the pyrolysis gas, and the flue gas after combustion is finally passed into other flue gas purification devices.
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| CN106390716A (en) * | 2016-11-10 | 2017-02-15 | 山东大学 | Flue gas demercuration system and method |
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| CN115820276A (en) * | 2021-09-17 | 2023-03-21 | 中国科学院工程热物理研究所 | Coal processing system and processing method |
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| CN104197319A (en) | 2014-12-10 |
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