CN1019403B - 降低锅炉烟气中二氧化硫含量工艺 - Google Patents

降低锅炉烟气中二氧化硫含量工艺

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Publication number
CN1019403B
CN1019403B CN88108858.7A CN88108858A CN1019403B CN 1019403 B CN1019403 B CN 1019403B CN 88108858 A CN88108858 A CN 88108858A CN 1019403 B CN1019403 B CN 1019403B
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sulphur
coal
fixing agent
boiler
content
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CN88108858.7A
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CN1043734A (zh
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黄钟成
王佩兰
雷晓旭
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Briquetting Research And Design Institute Beijing Graduate School Of China University Of Mining And Technology
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Briquetting Research And Design Institute Beijing Graduate School Of China University Of Mining And Technology
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Priority to CN88108858.7A priority Critical patent/CN1019403B/zh
Priority to US07/456,303 priority patent/US5049163A/en
Publication of CN1043734A publication Critical patent/CN1043734A/zh
Publication of CN1019403B publication Critical patent/CN1019403B/zh
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00Solid fuels
    • C10L5/02Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34Other details of the shaped fuels, e.g. briquettes
    • C10L5/36Shape
    • C10L5/38Briquettes consisting of different layers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/10Treating solid fuels to improve their combustion by using additives

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Treating Waste Gases (AREA)

Abstract

本发明提供减轻锅炉燃煤过程SO2对大气污染的工艺和设备。将以Ca系列化合物为主的多孔固硫剂,覆于锅炉型煤或锅炉燃煤层的表面进行燃烧,可使燃煤烟气中的SO2排放量降低,总固硫率可达到60~70%。

Description

本发明涉及减轻锅炉燃烧过程SO2对大气污染的工艺和设备。
我国大气中的SO2污染源主要是燃煤时排放的煤烟。
煤炭是我国的主要能源,直接燃烧原煤的工业锅炉近50万台,加上工业炉窑和民用茶炉等,年耗煤量几达5亿吨。据统计,全国一年排入大气中的1850万吨SO2中,89%是燃烧原煤时排放的:排入大气中的2195万吨烟尘中,79%是燃煤时排放的。加之我国锅炉的燃烧热效率低,因此,实现锅炉的无烟、低硫燃烧并提高燃烧热效率,是控制煤烟型污染的关键。由于无烟燃烧和提高燃烧效率的型煤生产已付诸工业实施,这样,减轻锅炉燃煤过程SO2对大气污染,已成为目前的当务之急了。
当前,国外都采用向原煤中掺加固硫剂的办法来降低燃煤排烟中的SO2含量。经检索,USP4226601号、JP昭57-70193号USP4322218号专利等都是这项专利技术。但这些已有技术的共同点,是只靠将固硫剂简单地掺加到原煤中而未采取相应的技术措施。以致在炉膛温度高达800~1300℃的锅炉中实际使用时,与实验室试验结果相比,固硫率显著下降,减轻大气中SO2污染的效果不佳。
本发明的目的,是提供降低燃煤过程SO2排放量的富集固硫剂的型煤和多孔粒状固硫剂及其使用方法。
本发明所用的固硫剂是公知的,主要是廉价的Ca系列化合物〔CaO、Ca(OH)2、CaCO3〕。如果以Ca系列固硫剂为主,添加少量固硫反应活性强的K、Na、Ba、Sn、Mn或Fe化合物,还可提高固硫率。
本发明的型煤加工工艺,由原料筛分、配料、粉碎,加入公知的粘结剂、混捏、成型和固结等7个现有技术工序组成,成型靠经过改装的对辊,式成型机实现,成型压力一般为250~550千克厘米。
研究结果表明,成型粉煤中的硫分与固硫剂Ca的反应分两步进行:
第一步是生成中间产物CaS
第二步是CaS氧化生成CaSO4,即固硫
由于CaS的氧化能力低于C的氧化能力,因此,需要在强氧化气氛中才能使CaS氧化。加之在高温下CaS容易分解、氧化生成SO2。这两种情况就会大大降低固硫剂的固硫效果。因此必须采取相应的措施来提高固硫剂的固硫率,降低SO2对大气的污染。
首先,固硫剂的用量,是按固硫剂的Ca当量与原煤的硫当量之比(即Ca/S)计算的。本发明采用的钙硫比(Ca/S)小于2,如以原煤的硫分计算,则S=1%,固硫剂(以CaO为例)用量小于3.5%。如采用K的化合物作固硫剂,则以K当量折算成Ca当量计算,余类推。
其次,将固硫剂富集在型煤表面或给料原煤层表面,型煤或原煤燃烧时,在煤与碳等还原物质相当少的条件下,固硫剂与SO2接触,使固硫反应能在强氧化气氛下进行。
为此,本发明采用两种改进设备的方法来实现上述要求,一是在对辊式成型机给料斗两侧各装一 个固硫剂给料斗(附图1∶2):因两个新增给料斗在成型机给料斗的前方,即先向球窝中给入固硫剂然后再给入成型粉煤,压出的型煤表面会包覆一层固硫剂。二是在原煤层燃炉给料斗后方增设一个固硫剂给料斗(附图3),因原煤先给到给料输送机上,这样,就在原煤层上面覆盖了一层固硫剂。这两种新增的给料斗都能使固硫反应在强氧化的气氛下进行。
第三,利用部分煤炭使固硫剂形成多孔状,大大增加固硫剂的比表面,以提高其固硫率。这种固硫剂可包覆在型煤表面,也可用公知的方法将其加工成粒状固硫剂覆盖在锅炉的原煤层上。
此外,以Ca/S小于2的用量,将固硫剂掺加到沸腾燃烧锅炉的原煤中,也可以降低SO2对大气的污染。
在燃烧型煤或在直接燃烧原煤的锅炉中使用本发明提出的固硫型煤或固硫剂,在炉温1000~1300℃的条件下,降低烟气中的SO2含量效果显著:在实验室条件下,总固硫率超过90%,在锅炉中也能达到60~70%;固硫剂用量(Ca/S)由通常的2~3以上降低到2%以下。
附图1和2是在对辊式成型机给料斗两侧安装固硫剂给料斗示意图,给料斗的宽度与成型辊的宽度相等。附图3是在层燃炉给料斗后方安装固硫剂给料斗示意图。
在附图中:
1-增设的固硫剂给料斗;
2-对辊式成型机型煤原料给料斗;
3-压辊;
4-球窝;
5-包覆固硫剂的型煤;
6-锅炉给煤斗;
7-原煤层;
8-覆盖的固硫剂层;
9-锅炉。
现举一项本发明的实施例如下:
用北京销售的混烟煤1号与兴隆高硫煤配成全硫分为3.69%的试验用煤。将以CaO为主、掺加少量Na和Ba化合物的多孔固硫剂,按钙硫比1.89的用量,加入试验用煤中加工成型煤。投入KZL-4-18型快装链条锅炉中燃烧。在炉膛温度为1150°~1250℃的工况下,总固硫率为63.5%,烟尘减少74%,烟气黑度小于12林格曼级。

Claims (5)

1、一种降低锅炉烟气中SO2含量的工艺,其特征是将以Ca系列化合物为主的固硫剂(其中也可掺加少量煤炭)包覆在锅炉型煤表面或铺在层燃锅炉燃烧煤层表面上或掺到沸腾锅炉的给煤中,以降低锅炉排烟中的SO2含量,在燃烧时掺加的少量煤炭燃尽而形成多孔状,增加固硫剂的比表面,以提高其固硫率。
2、一种如权利要求1所述的降低锅炉烟气中SO2含量的工艺,其特征是所用固硫剂以Ca的氧化物、氢氧化物或碳酸盐(即Ca系列化合物)为主,配加少量K、Na、Ba、Sn、Mn或Fe化合物,用量为钙硫比(Ca/s)小于2。
3、一种如权利要求1所述的降低锅炉烟气中SO2含量的工艺,其特征是在对辊式成型机的型煤原料给料斗两侧,各加装一个固硫剂给料斗,在给料斗下面也可增设给料装置,因固硫剂先加到球模中,使压成的型煤表面包覆一层固硫剂或掺加少量煤炭的固硫剂。
4、一种如权利要求1所述的降低锅炉烟气中SO2含量的工艺,其特征是在层燃锅炉给煤斗后方加装一个固硫剂给料斗,使给人锅炉的煤层上面覆盖一层固硫型煤或固硫剂。
5、一种如权利要求2所述的降低锅炉烟气中SO2含量的工艺,其特征是固硫剂按Ca/S小于2的用量加到沸腾锅炉的给煤中起固硫作用。
CN88108858.7A 1988-12-28 1988-12-28 降低锅炉烟气中二氧化硫含量工艺 Expired CN1019403B (zh)

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US07/456,303 US5049163A (en) 1988-12-28 1989-12-26 Process for reducing sulphur dioxide emission from burning coal containing sulphur

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