CN113150837B - 一种焦炉煤气脱硫工艺 - Google Patents
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Abstract
本发明公开了一种焦炉煤气脱硫工艺，采用了浓氨水脱硫工艺，将煤气脱硫和脱氨工艺分离，利用煤气自身氨资源作为碱源进行脱硫，利用蒸氨塔顶的高温浓氨气通入负压脱酸塔作为热源进行脱酸，能耗低，脱硫效果好。本工艺的废气经过冷却后，送到煤气负压系统，不会造成二次污染。净化后的酸性气体利用克劳斯炉生产硫磺，产品质量高，环境清洁。整体系统没有难处理的废水。
Description
技术领域
本发明涉及一种焦炉煤气脱硫工艺，属于煤炭清洁技术领域。
背景技术
在我国已探明的煤炭储量中一半以上为低阶煤，其中蕴藏的挥发分相当于1000亿吨的油气资源。低阶煤主要具有高水分、高挥发性的物质特性，在燃烧时火焰较长且有烟，煤化程度较低，典型煤种为褐煤和长焰煤。煤的主要利用方式就是直接燃烧或气化，在燃烧过程中通常会产生大量的二氧化硫，如果不对烟气中的二氧化硫进行处理，直接排放在大气中，容易形成酸雨，影响大气环境。
我国环保要求烟囱SO2排放量小于400mg/m3，焦炉煤气作为冶炼的热源，煤气含硫化氢含量也要求在200mg/m3以下，而随着环境的持续的恶化，部分环保部门提高了排放要求，例如要求煤气含氢化硫的量在50mg/m3，而提高排放要求必然是我国在以后的大气保护方面的趋势。
烟气脱硫技术是控制大气中二氧化硫污染的重要手段，并已经在世界范围内进行商业化地应用。现有的焦炉气脱硫工艺包括AS洗氨脱硫一体化流程、HPF脱硫工艺、真空碳酸钾脱硫工艺，AS洗氨脱硫一体化流程，由于洗氨和脱硫工艺相互影响，保证不了脱硫和脱氨均取得较好的效果，洗氨富液含氨高时，影响煤气脱氨效果，但对脱硫有利；如果富氨水含氨低时，对脱氨有利，但对脱硫不利。HPF脱硫工艺，也是利用氨水脱硫，但使用的是湿式催化氧化法，有大量的废气和副盐产生，硫膏的质量也差，环境质量差。真空碳酸钾脱硫工艺，消耗大量碱液，并有部分废液产生。
发明内容
本发明克服了上述现有技术的不足，提供一种焦炉煤气脱硫工艺，利用煤气自身氨资源作为碱源进行脱硫，利用蒸氨塔顶的高温浓氨气通入负压脱酸塔作为热源进行脱酸，能耗低，脱硫效果好，环境质量高。
一种焦炉煤气脱硫工艺，包括如下步骤：
(1)来自电捕焦油器的焦炉煤气进入真空脱硫塔底部，与自下而上分别与脱硫贫液逆流接触和冷却的剩余氨水逆流接触，煤气中的酸性气体被氨水收获得脱硫富液，将除去夹带液滴后的煤气送往煤气管网。
(2)蒸氨塔的高温浓氨气通入真空脱酸塔中，将步骤(1)获得的脱硫富液分成二部分，其中1/3送到真空脱酸塔的上部进行喷洒；其余2/3的富液与真空脱酸塔中的脱硫贫液换热后送到真空脱酸塔的中部喷洒，脱硫富液与底部上升的水蒸气逆流接触，使酸性气体从富液中解析出来，获得酸性气体A；
(3)步骤(2)中获得酸性气体A使用稀硫酸或硫氨母液对酸性气体进行洗涤，获得净化的酸性气体；
(4)将1/3体积的步骤(3)中获得净化的酸性气体送入劳斯炉的顶部燃烧，生产SO2和水；2/3体积的步骤(3)中获得净化的酸性气体由燃烧器旁通管道进入克劳斯炉内，生产硫磺。
进一步的，步骤(1)中所述的脱硫塔的入口的煤气温度为27-30℃，所述的脱硫塔的入口的贫液温度为28-30℃，所述冷却的剩余氨水的温度为20-22℃。
进一步的，步骤(2)中所述的酸性气体A的组成如下所示，按百分比计：
H2S 31-32％、HCN 1-2％、CO2 46-47％、NH3 3-4％、BTX 1-2％。
进一步的，步骤(2)中所述的脱酸塔的上部的温度为55-60℃。
进一步的，步骤(2)中所述的高温浓氨气温度为102-103℃的浓氨气。
进一步的，步骤(3)中所述的稀硫酸或硫氨母液为5％稀硫酸或硫氨母液，酸度为2％-6％。
进一步的，上述真空脱硫塔中压强为18-19KPa。
进一步的，真空脱硫塔中的脱硫贫液抽出相当于送入该系统中的剩余氨水的体积的量送入蒸氨系统进行蒸氨。
有益效果：
(1)本申请采用了浓氨水脱硫工艺，将煤气脱硫和脱氨工艺分离，改变了AS脱硫工艺的弱点，吸收了相关工艺的优点，不用催化剂湿式空气氧化脱硫和不用碳酸钾做脱硫剂。同时，采用蒸氨塔顶的高温浓氨气作为脱酸塔的热源，可以节约能源。
(2)与真空碳酸钾工艺相比，利用氨做脱硫剂，不需外购碳酸钾脱硫剂，降低脱硫剂成本。
(3)与HPF工艺相比，避免了湿法脱硫用空气供氧，造成大量空气被严重污染及副盐产生，副盐和废气难以处理的问题。与HPF工艺比较，没有副盐产生。与AS工艺相比，脱硫液含氨量高，脱硫效率提高，不受煤气脱氨要求氨水含氨低的影响。
(4)本工艺的废气经过冷却后，送到煤气负压系统，不会造成二次污染。净化后的酸性气体利用克劳斯炉生产硫磺，产品质量高，环境清洁。整体系统没有难处理的废水。
附图说明
图1焦炉煤气真空脱硫工艺图。
具体实施方式
为了使本技术领域人员更好地理解本申请中的技术方案，下面结合实施例对本发明作进一步说明，所描述的实施例仅是本申请一部分实施例，而不是全部，本发明不受下述实施例的限制。
实施例1焦炉煤气脱硫工艺
(1)来自电捕焦油器的焦炉煤气进入脱硫塔底部，与自下而上分别与脱硫贫液逆流接触和被冷却到22℃剩余氨水逆流接触，之后煤气在经过碱段，煤气中的酸性气体被吸收液吸收，煤气中H2S、HCN含量降到200mg/L，自脱硫塔出来，经除去夹带液滴后的煤气送往下道工序。
(2)脱硫塔底部吸收焦炉煤气中酸性气体的脱硫富液分成二部分，其中1/3送到负压脱酸塔的上部进行喷洒，控制塔顶温度在55-60℃；其余2/3的富液与脱酸塔底部的贫液换热后送到脱酸塔的中部喷洒，富液与底部上升的水蒸气逆流接触，使酸性气体从富液中解析出来，脱酸塔所需的热源取自蒸氨塔顶的浓氨气。
表1 脱酸贫液的组成
| 项目 | 游离氨 | H<sub>2</sub>S | 固定氨盐 |
| 组成 | 25g/L | 3.0g/L | 2.0mg/L |
(3)步骤(2)中脱酸塔顶部排出的酸性气体造组成
表2 酸性气重量百分组成％
| 项目 | H<sub>2</sub>S | HCN | CO<sub>2</sub> | NH<sub>3</sub> | BTX |
| 组成 | 32.26 | 1.89 | 46.7 | 3.95 | 1.89 |
酸性气含H2S为31％-33％，含氨约3-4％。
为了防止氨和二氧化碳生成(NH4)2CO3，堵塞管道，在此用稀硫酸或硫氨母液对酸性气体进行洗涤净化，获得净化的酸性气体。
(4)为了防止硫代硫酸铵和硫氰酸氨的积累，从脱酸贫液中抽出部分溶液送到蒸氨系统进行蒸氨。
(5)由脱酸塔来的经过脱氨的约55-60℃酸性气体，约1/3进入克劳斯炉的顶部燃烧，生产SO2和水，其反应式为
H2S+1/2O2→S+H2O
H2S+3/2O2→SO2+H2O △H＝-518kj/kg
2/3的酸性气体由燃烧器旁通管道进入克劳斯炉内，H2S与SO2的最佳配比为2:1，炉内过程气对温度保持在1100℃-1200℃，需要加入少量的煤气和空气来调节炉温，过程中H2S和SO2在炉内发生如下化学反应
2H2S+SO2→2H2O+3S2、
表3本工艺的主要操作制度
| 脱硫塔入口煤气温度 | 27-30℃ |
| 脱硫塔入口贫液温度 | 28-30℃ |
| 真空脱酸塔顶酸性气温度 | 55℃ |
| 脱酸塔底温度 | 65-70℃ |
| 脱酸塔顶压力(绝压) | 18KPa |
| 真空泵出口压力(绝压) | 30KPa |
| 克劳斯炉催化层温度 | 900～1050℃ |
| 克劳斯炉废热锅炉出口过程气温度 | 280～350℃ |
| 克劳斯反应器一段过程气出口温度 | 270～300℃ |
| 克劳斯反应器二段过程气出口温度 | 170～200℃ |
| 硫冷凝器二段过程气出口温度 | 130～150℃ |
图1中的1为脱硫塔，2为真空脱酸塔，3为贫富油换热器，4为贫油冷却器，5为塔底加热器，6为脱氨塔，7为真空泵，8为克劳斯炉，9为废热锅炉，10为一段反应器，11为二段反应器，12为过程其换热器，13为硫冷凝器，14为和15为硫分离器，16、17、18为硫封槽，19为硫池，20为硫泵，21为转鼓结电机，22为蒸氨氨气。
Claims (3)
1.一种焦炉煤气脱硫工艺，其特征在于，包括如下步骤：
（1）来自电捕焦油器的焦炉煤气进入真空脱硫塔底部，与自下而上分别与脱硫贫液逆流接触和冷却的剩余氨水逆流接触，煤气中的酸性气体被氨水收获得脱硫富液，将除去夹带液滴后的煤气送往煤气管网；脱酸贫液中游离氨含量25g/L；所述真空脱硫塔中压强为18-19KPa；所述的真空脱硫塔中的脱硫贫液抽出相当于送入系统中的剩余氨水的体积的量送入蒸氨系统进行蒸氨；所述的脱硫塔的入口的煤气温度为27-30℃，所述的脱硫塔的入口的贫液温度为28-30℃，所述冷却的剩余氨水的温度为20-22℃；
（2）蒸氨塔的温度102-103℃的高温浓氨气通入真空脱酸塔中，将步骤（1）获得的脱硫富液分成二部分，一部分送到真空脱酸塔的上部进行喷洒；其余的富液与真空脱酸塔中的脱硫贫液换热后送到真空脱酸塔的中部喷洒，脱硫富液与底部上升的水蒸气逆流接触，使酸性气体从富液中解析出来，获得酸性气体A；
（3）步骤（2）中获得酸性气体A使用稀硫酸或硫氨母液对酸性气体进行洗涤，获得净化的酸性气体；
（4）将一部分的步骤（3）中获得净化的酸性气体送入劳斯炉的顶部燃烧，生产SO2和水；剩余的步骤（3）中获得净化的酸性气体由燃烧器旁通管道进入克劳斯炉内，生产硫磺。
2.如权利要求1所述的焦炉煤气脱硫工艺，其特征在于，步骤（2）中所述的脱酸塔的上部的温度为55-60℃。
3.如权利要求1所述的焦炉煤气脱硫工艺，其特征在于，步骤（3）中所述的稀硫酸为5%稀硫酸。
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