CN102679688B - 一种从合成氨尾气中回收氨的工艺 - Google Patents
一种从合成氨尾气中回收氨的工艺 Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 50
- 238000005516 engineering process Methods 0.000 title abstract description 7
- 230000015572 biosynthetic process Effects 0.000 title abstract description 3
- 238000004064 recycling Methods 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 27
- 238000007710 freezing Methods 0.000 claims abstract description 20
- 230000008014 freezing Effects 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
- F25J3/062—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/0635—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/20—Processes or apparatus using other separation and/or other processing means using solidification of components
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/24—Processes or apparatus using other separation and/or other processing means using regenerators, cold accumulators or reversible heat exchangers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/20—H2/N2 mixture, i.e. synthesis gas for or purge gas from ammonia synthesis
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/02—Separating impurities in general from the feed stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/14—External refrigeration with work-producing gas expansion loop
- F25J2270/16—External refrigeration with work-producing gas expansion loop with mutliple gas expansion loops of the same refrigerant
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/42—Quasi-closed internal or closed external nitrogen refrigeration cycle
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Abstract
本发明提供了一种从合成氨尾气中回收氨的工艺，它的主要步骤包括：(1)冷却尾气；(2)低温分离液氨；(3)冻结NH3；(4)去除氢气；(5)增压冷却氮气；(6)膨胀氮气；(7)循环压缩氮气。本发明具有工艺流程短、能耗低、三废少、产品质量高、环境零污染等特点，彻底杜绝了环境污染源稀氨水的产生，同时具有良好的经济效益。
Description
技术领域
本发明涉及一种从合成氨尾气中回收氨的工艺，属于氨回收技术领域。
背景技术
开磷合成氨一期30万吨合成氨已顺利运行一年。一期合成氨尾气主要由合成氨放空气和弛放气组成，放空气量在2000立方米/小时，氨含量在7-8％，弛放气量为1500立方米/小时，氨含量在35-36％，合总氨在12吨/天。通过无动力氨回收了弛放气中的7吨氨左右。放空气中的氨通过水洗后形成稀氨水，剩余的氨输送到公交尾气回收处理厂进行洗涤，最后也形成稀氨水。稀氨水的总量在130吨/天左右。
目前稀氨水的处理途径主要是送合资公司磷铵车间作为洗涤用，合资公司消耗不完的送到造气车间。遇合资公司生产不正常或暴雨后，稀氨水用量减少，导致合成氨减产、尾气回收厂停产。
合成氨公司远期规划将稀氨水用于吹风气锅炉脱硫，但实施起来的投资以及形成的低浓度硫酸铵的处理也是不小的费用；如果二期30万吨的合成氨投产后，还是采用这样的工艺，则锅炉脱硫也不能将稀氨水完全处理掉，为此，不管是从经济的角度(每年损失近2000吨氨)，还是环保的角度，都必须进行氨回收。
发明内容
为解决上述技术问题，本发明提供了一种从合成氨尾气中回收氨的工艺。它的主要步骤包括：(1)冷却尾气；(2)低温分离液氨；(3)冻结NH3；(4)去除氢气；(5)增压冷却氮气；(6)膨胀氮气；(7)循环压缩氮气。
所述冷却尾气是将3500Nm3/h(2330KG/H)尾气在1.6Mpa.G送入主换热器冷却到-75℃。
所述低温分离液氨是指将冷却后的尾气送入氨分离罐进行分离，得到大部分液氨产品。
所述冻结NH3是将低温分离液氨后所得的气相送入切换冷冻换热器继续冷却到-135℃，将微量NH3全部冻结在换热器内。
所述去除氢气是将冻结NH3后得到的其余组份从切换式换热器出来后送入氢冷器冷却到-170℃后进入提氢塔进行氢回收，得到大部份氢气，剩余组分经节流降温复热到30±5℃出冷箱，此时压力为0.2-0.4Mpa.G，氨的含量小于5ppm。
所述增压冷却氮气是将压力为0.96Mpa.G的4500Nm3/h的循环氮气经两级增压冷却到2.2Mpa.G后，除170Nm3/h作为冷冻换热器的复热热源外，其余送入主换热器。
所述膨胀氮气是将送入主换热器的氮气冷却到-25℃然后和去解冻冷冻换热器的氮气混合后送入膨胀机经两级膨胀到0.035Mpa.G，温度为-146℃，经切换冷冻换热器作冷源，
所述循环压缩氮气是经切换板翘换热器的部分氮气复热后再送入主换热器进一步复热到30℃送到循环压缩机进口。
本发明的有益效果：本发明具有工艺流程短、能耗低、三废少、产品质量高、环境零污染等特点，彻底杜绝了环境污染源稀氨水的产生，同时该项目具有良好的经济效益。本发明对解决合成氨尾气环境污染问题、节能降耗都有重要意义。为企业实现了经济效益和环境效益的双赢提供了有效途径。
附图说明
图1是本发明的工艺步骤图；
图2是本发明的流程图；
图中：1-合成氨尾气；2-原料气混合罐；3-主换热器；4-低温分离罐；5-液氨出口；6-切换冷冻式换热器；7-氢冷器；8-提氢塔；9-合成氨车间；10-天然气生产车间；11-中压膨胀机；12-低压膨胀机；13-进气缓冲罐；14-氮气压缩离心机组；15-排气缓冲罐；16-低压压缩机；17-增压后冷却器；18-中压压缩机。
具体实施方式
为了加深对本发明的理解，下面结合实施例对本发明作进一步详细的描述，该实施例仅用于解释本发明，并不构成对本发明保护范围的限定。
如图1所示，本发明的具体工艺流程如下：
1、冷却尾气
将3500Nm3/h(2330KG/H)合成氨尾气1(mol组份：CH4 0.236242，N20.157538 H2 0.353392 Ar0.073078 NH3 0.17915)在1.6Mpa.G通过原料气体混合罐2，送入主换热器3。
2、低温分离液氨
当送入主换热器中的原料气体冷却到-75℃后，再将其送入低温分离罐4进行分离，得到大部分液氨产品，经液氨出口5流出并收集；气相送入切换冷冻换热器6。
3、冻结NH3
当送入切换冷冻换热器6的气相继续冷却到-135℃后，将微量NH3全部冻结在切换冷冻换热器6内，其余组份从切换冷冻换热器出来后送入氢冷器7。
4、去除氢气
送入氢冷器的剩余气体冷却到-170℃后，进入提氢塔8进行氢回收，将得到的大部份氢气运输到回收H2回合成氨车间9，将部分天然气则输送到天然气生产车间10。剩余组分经节流降温复热到30±5℃出冷箱，此时压力约为0.2-0.4Mpa.G，氨的含量约为小于5ppm。
5、增压冷却氮气
将压力为0.96Mpa.G的4500Nm3/h的循环氮气经两级增压冷却到2.2Mpa.G后，除约170Nm3/h作为切换冷冻换热器6的复热热源外，其余送入主换热器3。
6、膨胀氮气
将送入主换热器3的氮气冷却到-25℃，将切换冷冻换热器6中的氮气去解冻，然后将两者混合并送入膨胀机，进入中压膨胀机11和低压膨胀机12，进行两级膨胀，到0.035Mpa.G，温度约为-146℃，经切换冷冻换热器6作冷源，部分复热后再送入主换热器3进一步复热到30℃，并送到气缓冲罐13。
7、循环压缩氮气
由主换热器3输出并经进气缓冲罐13送入的氮气，通过氮气压缩离心机组14，再经排气缓冲罐15，到压缩机中经两次压缩后，又输回到主换热器3。氮气在压缩机中依次经过低压压缩机16、增压后冷却器17、中压压缩机18、增压后冷却器17。
Claims (1)
1.一种从合成氨尾气中回收氨的工艺，其特征在于它的主要步骤包括：(1)冷却尾气；(2)低温分离液氨；(3)冻结NH3；(4)去除氢气；(5)增压冷却氮气；(6)膨胀氮气；(7)循环压缩氮气；
所述冷却尾气是将3500Nm3/h(2330KG/H)尾气在1.6Mpa.G送入主换热器冷却到-75℃；
所述低温分离液氨是指将冷却后的尾气送入氨分离罐进行分离，得到大部分液氨产品；
所述冻结NH3是将低温分离液氨后所得的气相送入切换冷冻式换热器继续冷却到-135℃，将微量NH3全部冻结在切换冷冻式换热器内；
所述去除氢气是将冻结NH3后得到的其余组份从切换冷冻式换热器出来后送入氢冷器冷却到－170℃后进入提氢塔进行氢回收，得到大部份氢气，剩余组分经节流降温复热到30±5℃出冷箱，此时压力为0.2－0.4Mpa.G，氨的含量小于5ppm；
所述增压冷却氮气是将压力为0.96Mpa.G的4500Nm3/h的循环氮气经循环压缩机两级增压冷却到2.2Mpa.G后，除170Nm3/h作为切换冷冻式换热器的复热热源外，其余送入主换热器；
所述膨胀氮气是将送入主换热器的氮气冷却到-25℃然后和去解冻切换冷冻式换热器的氮气混合后送入膨胀机经两级膨胀到0.035Mpa.G，温度为-146℃，经切换冷冻式换热器作冷源；
所述循环压缩氮气是经切换冷冻式换热器的部分氮气复热后再送入主换热器进一步复热到30℃送到循环压缩机进口。
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| CN104964515B (zh) * | 2015-07-21 | 2018-08-21 | 苏州市兴鲁空分设备科技发展有限公司 | 合成氨尾气综合利用工艺及装置 |
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| US6082133A (en) * | 1999-02-05 | 2000-07-04 | Cryo Fuel Systems, Inc | Apparatus and method for purifying natural gas via cryogenic separation |
| CN1837049A (zh) * | 2006-04-05 | 2006-09-27 | 北京科瑞赛斯气体液化技术有限公司 | 无动力氨回收工艺及装置 |
| CN1891628A (zh) * | 2005-07-06 | 2007-01-10 | 窦和轩 | 一种驰放气中氨回收的方法 |
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| CN201052970Y (zh) * | 2007-06-07 | 2008-04-30 | 北京科瑞赛斯气体液化技术有限公司 | 一种混合工质制冷回收合成氨驰放气装置 |
| CN102425916A (zh) * | 2011-08-30 | 2012-04-25 | 重庆创本深冷天然气有限公司 | 一种利用合成氨尾气生产液化氩的方法及装置 |
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| GB2081864A (en) * | 1980-08-13 | 1982-02-24 | Boc Ltd | Method and apparatus for purifying a gas mixture |
| US6082133A (en) * | 1999-02-05 | 2000-07-04 | Cryo Fuel Systems, Inc | Apparatus and method for purifying natural gas via cryogenic separation |
| CN1891628A (zh) * | 2005-07-06 | 2007-01-10 | 窦和轩 | 一种驰放气中氨回收的方法 |
| CN1837049A (zh) * | 2006-04-05 | 2006-09-27 | 北京科瑞赛斯气体液化技术有限公司 | 无动力氨回收工艺及装置 |
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