CN1684908A - 含氰化氢、氨和水的气体的除氨方法 - Google Patents
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 27
- 239000007789 gas Substances 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 10
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims description 19
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 60
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 60
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 60
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 60
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- -1 phosphate anion Chemical class 0.000 claims description 8
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 7
- 229940048102 triphosphoric acid Drugs 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 150000003891 oxalate salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- 239000000463 material Substances 0.000 description 17
- 239000006096 absorbing agent Substances 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 235000001014 amino acid Nutrition 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0295—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/10—Separation of ammonia from ammonia liquors, e.g. gas liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
一种从含氰化氢、氨和水的气体中除去氨的方法，首先使气体同磷酸铵水溶液接触除去气体中的氨，然后使产生的磷酸铵溶液通过电解池从而使草酸盐和甲酸盐转变为氢和二氧化碳。
Description
发明背景
氢氰酸(或“氰化氢”)(HCN)可以通过氨和天然气(甲烷)及含氧气体在适当催化剂的存在下、在转炉内于高温下进行反应(US1,934,838)而进行工业化生产。转炉排出的气体含有未反应的氨及少量草酸和甲酸(或草酸和甲酸的前体)。未反应的氨是通过在氨吸收器中使转炉排气与磷酸铵水溶液接触而在吸收器中与HCN分离。在磷酸铵溶液中初始铵对磷酸盐的摩尔比是1-1.5，此溶液可被称为“贫磷酸铵溶液”。草酸和甲酸在水溶液中消失，转变为草酸盐和甲酸盐。吸收后，磷酸铵溶液中最终的铵对磷酸盐的摩尔比的范围是1.5-2.0，此溶液可被称为“富磷酸铵溶液”。在蒸馏塔(氨汽提塔)中，用水蒸气汽提富磷酸铵溶液中的氨而将其转变成贫磷酸铵溶液。由此得到的贫磷酸铵溶液在氨吸收器中被重复利用。氨汽提塔中的蒸馏操作未除去草酸盐和甲酸盐。结果这些化合物聚积在磷酸铵溶液中。存在的草酸盐和甲酸盐化合物可导致侵蚀和使工艺设备出现故障。超过1％的草酸盐浓度和超过3％的甲酸盐浓度是不理想的。因此，必须将一部分磷酸铵溶液作为废料从回路清除。废物处理成本与该清除有关。此步骤也需要补充额外的磷酸铵溶液，导致成本增加。
已知磷酸铵溶液的凝固点随其浓度的增加而降低。在如上所述的方法中，氨吸收器是在约55℃的温度下工作的。贫磷酸铵溶液中存在的草酸盐和甲酸盐促进溶液凝固点的升高。但是，即使有草酸盐和甲酸盐存在，磷酸铵溶液浓度的上限值为约35％，以避免磷酸铵溶液的凝固及因溶液凝固造成的设备堵塞。但是，如果能从贫磷酸铵溶液中除去草酸盐和甲酸盐，凝固点就会降低，结果是能使用较高浓度的磷酸铵溶液而不会出现凝固的危险。这种较高的磷酸铵浓度会提高生产能力。
因此，理想的是提供一种生产HCN的方法，其中的草酸盐和甲酸盐化合物被持续地分解，从而避免其在此过程中聚积而增加基本清除步骤，并且允许使用较高浓度的贫磷酸铵，使生产能力增加。
发明概要
在本发明中，利用电化学电池使磷酸铵溶液中存在的草酸盐和甲酸盐化合物连续地分解为二氧化碳和氢。所以不需要持续地进行清除。因此，降低了废物的产生，并节省了处理废物所需的费用。还降低了补充磷酸铵溶液的需求。草酸盐和甲酸盐化合物浓度的降低导致磷酸铵溶液的凝固点降低。这种降低允许使用磷酸铵浓度较高的磷酸铵溶液，因此提高了生产能力。
因此，本发明提供一种从含氰化氢、氨和水的气体中除去氨的方法，包括：
a.使气体与第一磷酸铵水溶液接触，产生基本上不含氨的HCN气体和第二磷酸铵水溶液，其中第一磷酸铵水溶液具有铵离子对磷酸根离子的第一摩尔比，第二磷酸铵水溶液具有铵离子对磷酸根离子的第二摩尔比，该第二摩尔比高于第一摩尔比，所述第二磷酸铵水溶液含有草酸铵和甲酸铵；
b.蒸馏该第二磷酸铵溶液得到氨气和第三磷酸铵溶液，第三磷酸铵溶液具有低于第二摩尔比的铵离子对磷酸根离子的第三摩尔比，并且含有草酸铵和甲酸铵；
c.冷却所述第三磷酸铵溶液得到第四磷酸铵溶液；
d.使第四磷酸铵溶液通过至少一对电极之间，所述至少一对电极上加有DC电压、能够产生足够的电流以氧化所述草酸盐和甲酸盐，从而产生含有二氧化碳和氢的氧化产物以及基本上不含草酸盐和甲酸盐的第五磷酸铵溶液；和
e.从第五磷酸铵溶液中分离出氧化产物。
附图简述
附图包括两幅图。图1示出了一种采用本发明方法的方框图，图2示出了本发明中使用的电解池的示意图。
发明详述
现在参考图1，示出了实施本发明的设备10的方框图。
从HCN转炉(未示出)中排放的废气12通入含有磷酸铵溶液(贫磷酸铵溶液)(未示出)的氨吸收器14中，所述磷酸铵溶液具有铵离子对磷酸根离子的初始比率。氨吸收器可以是含不锈钢填充材料的填充塔。贫磷酸铵溶液从其与转炉废气密切接触处滴下，并吸收废气中的氨。该填料提供了良好的接触。
不含氨的HCN气流16离开氨吸收器14的顶部作进一步处理或使用。铵离子对磷酸根离子比率高于贫磷酸铵溶液(富磷酸铵溶液)的磷酸铵溶液的料流18离开氨吸收器并通入氨汽提塔20中。氨汽提塔可以是一个具有多个塔盘的蒸馏塔。通过蒸馏塔的再沸器部分(未示出)提供的热量产生水蒸气，从而迫使氨从富磷酸铵溶液中解吸附。富磷酸铵溶液通过这种作用转变成贫磷酸铵溶液。
氨和水蒸气的气流22离开氨汽提塔20的顶部以再利用。贫磷酸铵溶液的料流24流过泵26，并通过冷却器28被冷却以产生冷却的贫磷酸铵溶液的料流30。料流30被分成两部分：料流32和料流34。
料流34在冷却器36中被进一步冷却得到料流38。料流38被供入到过滤器40中。该过滤器除去料流38中的粒状污染物以产生基本上不含粒状物的料流42，并将其供入电解池44中。
现在参考图2，示出了本发明使用的电解池44的示意结构。在此电解池中，在约7000安培的电流下，对一对或多对电极52、54施加了3.5-4.0的直流电压。电解池的阳极52优选为一个涂有氧化铱的钛丝细筛。电能使过滤料流42中存在的甲酸盐和草酸盐的至少一部分转变为二氧化碳和氢，它们作为料流50随同水电解产生的一些氧气离开电解池。
含有二氧化碳和氢的料流50作为废气离开电解池。电解池产生了同料流32混合的基本上不含甲酸盐和草酸盐的贫磷酸铵溶液46。混合的贫磷酸铵溶液料流48被供入氨吸收器14中。料流48的温度应在50-60℃的范围内以实现氨的良好吸收。
Claims (1)
1.一种从含氰化氢、氨和水的气体中除去氨的方法，包括：
a.使气体与第一磷酸铵水溶液接触，产生基本上不含氨的HCN气体和第二磷酸铵水溶液，其中第一磷酸铵水溶液具有铵离子对磷酸根离子的第一摩尔比，第二磷酸铵水溶液具有高于第一摩尔比的铵离子对磷酸根离子的第二摩尔比，所述第二磷酸铵水溶液含有草酸铵和甲酸铵；
b.蒸馏第二磷酸铵溶液产生氨气和第三磷酸铵溶液，第三磷酸铵溶液具有低于第二摩尔比的铵离子对磷酸根离子的第三摩尔比，所述第三磷酸铵溶液含有草酸铵和甲酸铵；
c.冷却所述第三磷酸铵溶液得到第四磷酸铵溶液；
d.使第四磷酸铵溶液通过至少一对电极之间，所述至少一对电极上加有直流电压，能够产生足够的电流以氧化所述草酸盐和甲酸盐，从而产生含有二氧化碳和氢的氧化产物以及基本上不含草酸盐和甲酸盐的第五磷酸铵溶液；和
e.从第五磷酸铵溶液中分离出氧化产物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/209,258 US6872296B2 (en) | 2002-07-30 | 2002-07-30 | Method for removing ammonia from a gas comprising hydrogen cyanide, ammonia and water |
| US10/209,258 | 2002-07-30 |
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| CN1684908A true CN1684908A (zh) | 2005-10-19 |
| CN1307103C CN1307103C (zh) | 2007-03-28 |
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| US (1) | US6872296B2 (zh) |
| EP (1) | EP1551765B1 (zh) |
| JP (1) | JP2005534600A (zh) |
| KR (1) | KR20050026970A (zh) |
| CN (1) | CN1307103C (zh) |
| AT (1) | ATE350339T1 (zh) |
| AU (1) | AU2003256980A1 (zh) |
| BR (1) | BR0313348A (zh) |
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| MY (1) | MY131917A (zh) |
| RU (1) | RU2318727C2 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936033A (zh) * | 2012-12-18 | 2014-07-23 | 英威达科技公司 | 从Andrussow工艺的氨解吸塔中回收热量的方法 |
| CN104619641A (zh) * | 2012-07-19 | 2015-05-13 | 因温斯特技术公司 | 利用排出控制腐蚀的氨的回收 |
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| BRPI0513548A (pt) * | 2004-07-22 | 2008-08-26 | Ineos Usa Llc | processos de recuperação de amÈnia a partir de fluxo de vapor e de efluente de reator |
| US8968515B2 (en) | 2006-05-01 | 2015-03-03 | Board Of Trustees Of Michigan State University | Methods for pretreating biomass |
| US9206446B2 (en) | 2006-05-01 | 2015-12-08 | Board Of Trustees Of Michigan State University | Extraction of solubles from plant biomass for use as microbial growth stimulant and methods related thereto |
| US20080053913A1 (en) * | 2006-09-06 | 2008-03-06 | Fassbender Alexander G | Nutrient recovery process |
| US20080156726A1 (en) * | 2006-09-06 | 2008-07-03 | Fassbender Alexander G | Integrating recycle stream ammonia treatment with biological nutrient removal |
| GB0709109D0 (en) * | 2007-05-11 | 2007-06-20 | Enpar Technologies Inc | Wastewater ammonium extraction and electrolytic conversion to nitrogen gas |
| US8945245B2 (en) | 2009-08-24 | 2015-02-03 | The Michigan Biotechnology Institute | Methods of hydrolyzing pretreated densified biomass particulates and systems related thereto |
| US10457810B2 (en) | 2009-08-24 | 2019-10-29 | Board Of Trustees Of Michigan State University | Densified biomass products containing pretreated biomass fibers |
| WO2011028543A2 (en) | 2009-08-24 | 2011-03-10 | Board Of Trustees Of Michigan State University | Pretreated densified biomass products and methods of making and using same |
| BR112012026710B8 (pt) | 2010-04-19 | 2020-06-23 | Univ Michigan State | método para produzir um produto extraído a partir de biomassa lignocelulósica e método para produzir um produto digerido a partir de biomassa lignocelulósica |
| US8394177B2 (en) | 2010-06-01 | 2013-03-12 | Michigan Biotechnology Institute | Method of separating components from a gas stream |
| DE102010025880A1 (de) * | 2010-07-02 | 2012-01-05 | Emitec Gesellschaft Für Emissionstechnologie Mbh | Abgasbehandlungsvorrichtung |
| JP2018521946A (ja) * | 2015-07-14 | 2018-08-09 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | シアン化水素からニトリル類を除去するための方法 |
| JP6903435B2 (ja) * | 2017-01-11 | 2021-07-14 | キヤノンメディカルシステムズ株式会社 | 核医学診断装置及びキャリブレーション方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1934838A (en) * | 1930-04-14 | 1933-11-14 | Ig Farbenindustrie Ag | Production of hydrocyanic acid |
| US2899274A (en) * | 1956-12-31 | 1959-08-11 | Recovery of ammonia and hydrogen | |
| US4287162A (en) * | 1979-07-18 | 1981-09-01 | Suntech, Inc. | Separation of ammonia from ammonia containing gases |
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2002
- 2002-07-30 US US10/209,258 patent/US6872296B2/en not_active Expired - Fee Related
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- 2003-04-30 TW TW092110150A patent/TWI293621B/zh not_active IP Right Cessation
- 2003-07-29 AT AT03772048T patent/ATE350339T1/de not_active IP Right Cessation
- 2003-07-29 WO PCT/US2003/023699 patent/WO2004011374A1/en active IP Right Grant
- 2003-07-29 CN CNB038180669A patent/CN1307103C/zh not_active Expired - Lifetime
- 2003-07-29 EP EP03772048A patent/EP1551765B1/en not_active Expired - Lifetime
- 2003-07-29 MY MYPI20032839A patent/MY131917A/en unknown
- 2003-07-29 AU AU2003256980A patent/AU2003256980A1/en not_active Abandoned
- 2003-07-29 RU RU2005105583/15A patent/RU2318727C2/ru not_active IP Right Cessation
- 2003-07-29 JP JP2004525024A patent/JP2005534600A/ja not_active Ceased
- 2003-07-29 KR KR1020057001572A patent/KR20050026970A/ko not_active Application Discontinuation
- 2003-07-29 DE DE60310971T patent/DE60310971T2/de not_active Expired - Lifetime
- 2003-07-29 BR BR0313348-6A patent/BR0313348A/pt active Search and Examination
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104619641A (zh) * | 2012-07-19 | 2015-05-13 | 因温斯特技术公司 | 利用排出控制腐蚀的氨的回收 |
| CN104619641B (zh) * | 2012-07-19 | 2017-03-15 | 因温斯特技术公司 | 利用排出控制腐蚀的氨的回收 |
| CN103936033A (zh) * | 2012-12-18 | 2014-07-23 | 英威达科技公司 | 从Andrussow工艺的氨解吸塔中回收热量的方法 |
| CN103936033B (zh) * | 2012-12-18 | 2017-08-11 | 英威达科技公司 | 从Andrussow工艺的氨解吸塔中回收热量的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60310971D1 (de) | 2007-02-15 |
| AU2003256980A1 (en) | 2004-02-16 |
| TW200401748A (en) | 2004-02-01 |
| EP1551765B1 (en) | 2007-01-03 |
| JP2005534600A (ja) | 2005-11-17 |
| BR0313348A (pt) | 2005-07-12 |
| US6872296B2 (en) | 2005-03-29 |
| US20040022709A1 (en) | 2004-02-05 |
| EP1551765A1 (en) | 2005-07-13 |
| RU2005105583A (ru) | 2005-08-10 |
| WO2004011374A1 (en) | 2004-02-05 |
| TWI293621B (en) | 2008-02-21 |
| RU2318727C2 (ru) | 2008-03-10 |
| ATE350339T1 (de) | 2007-01-15 |
| MY131917A (en) | 2007-09-28 |
| KR20050026970A (ko) | 2005-03-16 |
| CN1307103C (zh) | 2007-03-28 |
| DE60310971T2 (de) | 2007-10-04 |
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