CN109550352A - 一种***尾气制造氨合成气脱硫工艺 - Google Patents

一种***尾气制造氨合成气脱硫工艺 Download PDF

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CN109550352A
CN109550352A CN201811332264.1A CN201811332264A CN109550352A CN 109550352 A CN109550352 A CN 109550352A CN 201811332264 A CN201811332264 A CN 201811332264A CN 109550352 A CN109550352 A CN 109550352A
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杨鹏
曲思霖
杨皓
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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 by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8603Removing sulfur compounds
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025Preparation or purification of gas mixtures for ammonia synthesis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/304Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/306Organic sulfur compounds, e.g. mercaptans
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/308Carbonoxysulfide COS
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

本发明涉及一种***尾气精脱硫工艺,将***尾气预净化脱氨脱酸后,常温转化脱除无机硫到0.01ppm以下,再加热到50~90℃送第一级有机硫吸附塔,物理吸附脱除有机硫,称为粗脱气,粗脱气有机硫含量达到~0.1ppm,继续加热粗脱气到200℃~210℃,采用甲醇合成催化剂转化有机硫到<0.01ppm,同时生成的无机硫被甲醇催化剂吸收,出口气体总硫含量≤0.01ppm;物理吸附的有机硫升温脱附,脱附气冷却到50~90℃,送入第二级有机硫吸附塔,物理吸附脱除有机硫,称为第二粗脱气,第二粗脱气加压送回第一级有机硫吸附塔,物理吸附的有机硫通过升温到140℃~150℃脱附,脱附气送入有机硫350℃转化设备,转化吸收有机硫到总硫浓度达标,排放。

Description

一种***尾气制造氨合成气脱硫工艺
技术领域
本发明涉及化工、节能、环保领域,是一种有效减少使用贵金属脱氧催化剂消耗,由此节约氨合成成本的方法。
背景技术
对于以***尾气为原料生产合成氨的过程,对于氨合成气体的脱硫脱氧方法一般采用两种方法。
一种方法是将***尾气除酸除氨后,为了保护贵金属一氧化碳转化催化剂,先送高温有机硫转化再吸收无机硫,在有机硫转化到0.01ppm过程,氧气与氢气会同时优先反应,转化有机硫同时,脱除了后段脱一氧化碳所需氧气,脱一氧化碳时,需要再新增加氧气或空气送到脱一氧化碳装置,脱硫气体送一氧化碳转化,再送脱氧装置,脱氧装置采用氢气还原氧气生成水,冷却后送变压吸附制氢装置生产高纯氢气,氢气中一氧化碳二氧化碳浓度达到10ppm以下,按比例混入高纯氮气制氨合成气。全部气体送高温转化脱硫能耗很高。
一种方法是将***尾气除酸除氨后,先送低温有机硫转化再吸收无机硫,在有机硫转化到0. 1ppm过程,氧气与氢气不会同时反应,转化有机硫同时,但脱硫精度不到0.01ppm,若强行转化有机硫到0.01ppm,需要的脱硫投资极大,而且转化催化剂更换量极大。
有机硫转化到0. 1ppm时,贵金属一氧化碳转化催化剂使用寿命只有高精度0.01ppm脱硫状况下的1/5。
甲醇催化剂具有很好的有机硫与无机硫脱除能力,其价格远低于一氧化碳氧气转化贵金属催化剂。
发明内容
本发明是一种***尾气精脱硫工艺,其特征在于:将***尾气预净化脱氨脱酸后,硫组分为硫化氢≤2ppm、COS≤2ppm、CS2≤2ppm、硫醇≤2ppm,先常温转化脱除无机硫到0.01ppm以下,再加热到50~90℃送第一级有机硫吸附塔,物理吸附脱除有机硫,称为粗脱气,粗脱气有机硫含量达到~0.1ppm,继续加热粗脱气到200℃~210℃,采用甲醇合成催化剂转化有机硫到<0.01ppm,同时生成的无机硫被甲醇催化剂吸收,出口气体总硫含量≤0.01ppm;物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的30倍以上,称为一级脱附气体,将一级脱附气体冷却到50~90℃,送入第二级有机硫吸附塔,物理吸附脱除有机硫,称为第二粗脱气,第二粗脱气COS≤2ppm、CS2≤2ppm、硫醇≤2ppm,加压送回第一级有机硫吸附塔,物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的900倍以上,称为二级脱附气体,将二级脱附气体送入有机硫350℃转化设备,转化吸收有机硫到总硫浓度达标,排放。
具体实施例
实施例1:某***装置尾气气体总量为36000NM3/H,0.04MPa,酸洗碱洗后,称为原料气,气体成分为硫化氢0.2ppm、COS0.2ppm、CS20.2ppm、硫醇0.2ppm。
送原料气进入常温转化脱除无机硫到0.01ppm以下,再加热到50~90℃送第一级有机硫吸附塔,物理吸附脱除有机硫,称为粗脱气,粗脱气有机硫含量达到~0.1ppm,继续加热粗脱气到200℃~210℃,采用甲醇合成催化剂转化有机硫到<0.01ppm,同时生成的无机硫被甲醇催化剂吸收,出口气体总硫含量≤0.01ppm;物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的30倍以上,称为一级脱附气体,将一级脱附气体冷却到50~90℃,送入第二级有机硫吸附塔,物理吸附脱除有机硫,称为第二粗脱气,第二粗脱气COS0.2ppm、CS20.2ppm、硫醇0.2ppm,加压送回第一级有机硫吸附塔,物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的900倍以上,称为二级脱附气体,将二级脱附气体送入有机硫350℃转化设备,转化吸收有机硫到总硫浓度达标,排放。
实施例2:某***装置尾气气体总量为36000NM3/H,1.8MPa,酸洗碱洗后,称为原料气,气体成分为硫化氢1.2ppm、COS0.2ppm、CS21.2ppm、硫醇0.07ppm。
送原料气进入常温转化脱除无机硫到0.01ppm以下,再加热到50~90℃送第一级有机硫吸附塔,物理吸附脱除有机硫,称为粗脱气,粗脱气有机硫含量达到~0.1ppm,继续加热粗脱气到200℃~210℃,采用甲醇合成催化剂转化有机硫到<0.01ppm,同时生成的无机硫被甲醇催化剂吸收,出口气体总硫含量≤0.01ppm;物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的30倍以上,称为一级脱附气体,将一级脱附气体冷却到50~90℃,送入第二级有机硫吸附塔,物理吸附脱除有机硫,称为第二粗脱气,第二粗脱气COS0.2ppm、CS21.2ppm、硫醇0.07ppm,加压送回第一级有机硫吸附塔,物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的900倍以上,称为二级脱附气体,将二级脱附气体送入有机硫350℃转化设备,转化吸收有机硫到总硫浓度达标,排放。
实施例3:某***装置尾气气体总量为20000NM3/H,1.8MPa,酸洗碱洗后,称为原料气,气体成分为硫化氢0.07ppm、COS2ppm、CS22ppm、硫醇2ppm。
送原料气进入常温转化脱除无机硫到0.01ppm以下,再加热到50~90℃送第一级有机硫吸附塔,物理吸附脱除有机硫,称为粗脱气,粗脱气有机硫含量达到~0.1ppm,继续加热粗脱气到200℃~210℃,采用甲醇合成催化剂转化有机硫到<0.01ppm,同时生成的无机硫被甲醇催化剂吸收,出口气体总硫含量≤0.01ppm;物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的30倍以上,称为一级脱附气体,将一级脱附气体冷却到50~90℃,送入第二级有机硫吸附塔,物理吸附脱除有机硫,称为第二粗脱气,第二粗脱气COS2ppm、CS22ppm、硫醇2ppm,加压送回第一级有机硫吸附塔,物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的900倍以上,称为二级脱附气体,将二级脱附气体送入有机硫350℃转化设备,转化吸收有机硫到总硫浓度达标,排放。

Claims (1)

1.一种***尾气精脱硫工艺,其特征在于:将***尾气预净化脱氨脱酸后,硫组分为硫化氢≤2ppm、COS≤2ppm、CS2≤2ppm、硫醇≤2ppm,先常温转化脱除无机硫到0.01ppm以下,再加热到50~90℃送第一级有机硫吸附塔,物理吸附脱除有机硫,称为粗脱气,粗脱气有机硫含量达到~0.1ppm,继续加热粗脱气到200℃~210℃,采用甲醇合成催化剂转化有机硫到<0.01ppm,同时生成的无机硫被甲醇催化剂吸收,出口气体总硫含量≤0.01ppm;物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的30倍以上,称为一级脱附气体,将一级脱附气体冷却到50~90℃,送入第二级有机硫吸附塔,物理吸附脱除有机硫,称为第二粗脱气,第二粗脱气COS≤2ppm、CS2≤2ppm、硫醇≤2ppm,加压送回第一级有机硫吸附塔,物理吸附的有机硫通过升温到140℃~150℃脱附,脱附出来的气体有机硫含量为***尾气的900倍以上,称为二级脱附气体,将二级脱附气体送入有机硫350℃转化设备,转化吸收有机硫到总硫浓度达标,排放。
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