CN101759147A - 合成氨原料气低压下净化联产甲醇的方法 - Google Patents
合成氨原料气低压下净化联产甲醇的方法 Download PDFInfo
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- CN101759147A CN101759147A CN200810234482A CN200810234482A CN101759147A CN 101759147 A CN101759147 A CN 101759147A CN 200810234482 A CN200810234482 A CN 200810234482A CN 200810234482 A CN200810234482 A CN 200810234482A CN 101759147 A CN101759147 A CN 101759147A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000006835 compression Effects 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 8
- 230000023556 desulfurization Effects 0.000 claims abstract description 8
- 238000005261 decarburization Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 210000000952 spleen Anatomy 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000005262 decarbonization Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000003337 fertilizer Substances 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种合成氨原料气低压下净化联产甲醇的方法,属于肥料技术领域。本发明是原料气经压缩后送变换,再经湿法脱硫、碳化或脱碳,脱碳气经压缩后干法脱硫;然后通过低压“甲醇-甲烷化”系统,使原料气中的一氧化碳和二氧化碳残余量达到精制气的标准。该方法由于甲醇过程转化率很高,使甲烷化过程产生的惰性气体甲烷大为减少,合成氨原料气消耗也减少,吨氨成本消耗下降,提高了市场竞争力。
Description
技术领域:本发明属于化学工业技术领域,具体涉及一种合成氨原料气净化的方法。
背景技术:合成氨过程是现今所有氮肥工业的基础,所用的α-Fe为活性中心的催化剂对微量的氧和氧化物的毒性十分敏感,CO是一种既非酸性又非碱性的气体。彻底脱除的难度和费用很大。但对合成氨工业生产来讲,必须将其脱至PPm(10-6)级的浓度,否则合成氨过程将无法进行。
目前,国内脱除微量CO+CO2的方法主要有铜洗法、低压甲烷化法、甲醇甲烷化法。铜洗法存在原料气净化度低、操作费用高、工艺复杂、操作难度大等缺点,还存在环境污染和设备投资大等问题。低压甲烷化法反应须消耗氢气,导致能耗增加,同时降低生产能力;中压联醇与中压甲烷化工艺是在12.0-13.0MPa压力下将变换、脱硫后含3%-5%的CO+CO2的气体,通过中压甲醇系统,生产一部分甲醇,残余0.5%-2%的CO+CO2再去12.0-13.0MPa中压甲烷化。由于受化学平衡制约,甲醇转化率不是很高,因甲烷化过程仍然产生0.5%-0.8%的惰性气体甲烷,合成氨原料气消耗也较高。高压甲醇化和甲烷化工艺是采用24.0-31.4MPa高压甲醇化和高压甲烷化反应,使中压联醇后的原料气或经脱硫后的脱碳原料气,经无油润滑技术的压缩机七段(六段)提高压力至合成氨合成高压圈相等的压力,要求残余的CO+CO2在0.5%-2%之间,须经常温水解精脱硫装置使硫含量小于0.01PPm,总硫过高影响甲醇催化剂寿命。同时,高压操作条件下,设备要求高,特别是甲醇催化剂和甲烷化催化剂操作难度大,要求有很高的催化剂强度。
发明内容:本发明目的是:提出一种合成氨原料气消耗减少,吨氨成本消耗下降的合成氨原料气净化并联产甲醇的方法。
具体地说本发明是原料气经压缩后送变换,再经湿法脱硫、碳化或脱碳,脱碳气经压缩后干法脱硫;然后通过低压“甲醇-甲烷化”系统,使原料气中的一氧化碳和二氧化碳残余量达到精制气的标准。
低压“甲醇-甲烷化”系统是在反应压力3.0MPa~6Mpa,反应温度180℃~220℃,合成气空速为1000h-1~3000h-1条件下,将脱碳气通过脱硫后在甲醇合成塔生成甲醇,甲醇合成塔里装入铜锌铝催化剂,最好催化剂中铜重量百分含量介于40-45%之间,从而除掉CO+CO2,使甲醇合成塔出口气中CO+CO2含量<0.5%;甲醇合成塔出口气经分离粗醇后进入甲烷化塔,在反应压力3.0MPa~6Mpa,反应温度300℃~350℃,合成气空速5000h-1~15000h-1的条件下进行甲烷化反应,甲烷化塔出口气中CO+CO2含量<10PPm。
该方法由于甲醇过程转化率很高,使甲烷化过程产生的惰性气体甲烷大为减少,合成氨原料气消耗也减少,吨氨成本消耗下降,提高了市场竞争力。
具体实施方式:下面结合实例进一步说明本发明。
实施例一
以煤为原料用间歇气化法生产半水煤气。半水煤气经压缩后送变换,再经湿法脱硫、碳化或脱碳,脱除H2S和CO2。脱碳气经压缩后经干法脱硫,再经装有C501型甲醇催化剂的合成塔合成甲醇,合成条件为:反应温度200℃,反应压力4MPa,空速2000h-1,甲醇合成塔后气组成为:CO+CO2<0.2%,H2 72%~75%,N2 21%~23%CH4 0.5%~0.6%。再经甲烷化反应器,甲烷化气经压缩后送往合成氨工序。甲醇合成塔出口气中CO+CO2含量<0.2%;甲烷化塔出口气中CO+CO2含量<1PPm。
Claims (2)
1.合成氨原料气低压下净化联产甲醇的方法,其特征是原料气经压缩后送变换,再经湿法脱硫、碳化或脱碳,脱碳气经压缩后干法脱硫;然后通过低压“甲醇-甲烷化”系统,使原料气中的一氧化碳和二氧化碳残余量达到精制气的标准。
2.如权利要求1所述的方法,其特征在于低压“甲醇-甲烷化”系统是在反应压力3.0MPa-6Mpa,反应温度180℃-220℃,合成气空速为1000h-1-3000h-1条件下,将脱碳气通过脱硫后在甲醇合成塔生成甲醇,甲醇合成塔里装入铜锌铝催化剂催化剂中铜重量百分含量介于40-45%之间,从而除掉CO+CO2,使甲醇合成塔出口气中CO+CO2含量<0.5%;甲醇合成塔出口气经分离粗醇后进入甲烷化塔,在反应压力3.0MPa-6Mpa,反应温度300℃-350℃,合成气空速5000h-1-15000h-1的条件下进行甲烷化反应,甲烷化塔出口气中CO+CO2含量<10PPm。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102603453A (zh) * | 2012-02-15 | 2012-07-25 | 山东洪达化工有限公司 | 提高合成氨甲烷化炉入口脱碳气温度的装置和方法 |
CN103588222A (zh) * | 2013-11-25 | 2014-02-19 | 安徽淮化股份有限公司 | 一种低碳合成氨生产工艺 |
CN106672898A (zh) * | 2017-01-17 | 2017-05-17 | 青海盐湖工业股份有限公司 | 一种以天然气裂解制乙炔的副产尾气为原料合成氨的方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102603453A (zh) * | 2012-02-15 | 2012-07-25 | 山东洪达化工有限公司 | 提高合成氨甲烷化炉入口脱碳气温度的装置和方法 |
CN103588222A (zh) * | 2013-11-25 | 2014-02-19 | 安徽淮化股份有限公司 | 一种低碳合成氨生产工艺 |
CN106672898A (zh) * | 2017-01-17 | 2017-05-17 | 青海盐湖工业股份有限公司 | 一种以天然气裂解制乙炔的副产尾气为原料合成氨的方法 |
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