CN1344711A - 氨和脲的联合制备方法 - Google Patents
氨和脲的联合制备方法 Download PDFInfo
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- CN1344711A CN1344711A CN01133108A CN01133108A CN1344711A CN 1344711 A CN1344711 A CN 1344711A CN 01133108 A CN01133108 A CN 01133108A CN 01133108 A CN01133108 A CN 01133108A CN 1344711 A CN1344711 A CN 1344711A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 57
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000004202 carbamide Substances 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- 239000000376 reactant Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000005201 scrubbing Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/10—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds combined with the synthesis of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
-
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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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 Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
用于脲和氨反应物的联合制备的方法,该方法包含以下步骤:提供含二氧化碳的氨合成气以及将合成气转化成氨反应物,使氨反应物与合成气中的二氧化碳发生反应生成氨基甲酸铵和生成脲产品,该方法还包含以下步骤:在合成气转化成氨反应物之前,(i)以氨反应物的水溶液洗涤合成气并形成富含氨基甲酸铵的溶液;(ii)通过用水洗涤从洗涤过的合成气中除去过量的氨反应物并排出氨反应物的水溶液;(iii)通过除去残留的水和氨而净化水洗涤过的合成气;并且(iv)使净化过的合成气输送到气体转化至氨反应物的反应中。
Description
发明领域
本发明涉及通过在合成脲工艺中结合入氨反应物的制备而生产脲的方法。
发明背景
脲目前是经以下反应从氨基甲酸铵制得的：
大多数脲的生产与合成氨工厂有关，因为所需的二氧化碳可从氨工厂前段的合成气净化系统获得。
世界氨产量的很大一部分都用于脲的生产。因此，脲生产的联合工艺可能会有其技术和经济优势。但是按现有技术，脲和氨的生产是在相互无甚关联的工厂中进行的。
发明内容
本发明的一般目的是提供一种经由二氧化碳与氨生成氨基甲酸铵以及氨基甲酸盐分解成脲产品的上述反应制备脲的改进方法，其中通过向合成氨的合成气净化中结合入二氧化碳和氨反应物的制备而将氨的生产和脲的生产结合在一个单一的流程中。
根据该一般目的，本发明提供用于脲和氨反应物的联合制备的方法，该方法包含以下步骤：提供含二氧化碳的氨合成气以及将合成气转化成氨反应物，使氨反应物与合成气中的二氧化碳发生反应生成氨基甲酸铵以至脲产品，该方法还包含以下步骤：
在合成气转化成氨反应物之前，
(i)以氨反应物的水溶液洗涤合成气并形成富含氨基甲酸铵的溶液；
(ii)通过用水洗涤从洗涤过的合成气中除去过量的氨反应物并排出氨反应物的水溶液；
(iii)通过吸附残留的水和氨而净化水洗涤过的合成气；并且
(iv)使净化过的合成气输送到气体转化至氨反应物的反应中。
附图说明
附图是描述一种根据本发明一个特定的实施方案从二氧化碳和氨反应物制备脲的联合方法的方框图。
具体实施方案
在由常规HDS、转化和变换区(Reforming and Shift Section)构成的气体制备单元后是一个使CO2含量高的气体的压力提高到适于合成氨的压力的单元。然后以氨水溶液洗涤该气体以除去绝大部分的CO2。形成的氨基甲酸盐溶液输送到脲反应器中去。在溶液中溶解的气体可从此处循环至压缩机的吸入端。
大部分已洗涤过的气体此时用作氨合成的补充气体。首先CO选择性methanisation除去残留的CO。从methanisation步骤出料的气体被NH3饱和并与从氨合成塔出料的气体混合。将混合料流导入洗涤单元中，在此处经水洗除氨。因为该工艺是放热性的，所以优选两阶段工艺：在第一阶段中，气体与相对较浓的氨溶液接触，吸收掉约一半量的氨。在第二阶段中，用出自脲单元的水进行最终的吸收。
离开吸收单元的气体含有一些氨，但也含一些水，在进入氨合成塔之前必需除去。该过程可借助分子筛或氧化铝在质量吸收器中进行。质量吸收器可经清洗气再生。在质量吸收器的下游，气体流过循环压缩机，然后输入由高温热交换器、合成塔和蒸汽发生器构成的常规合成单元。冷却至室温后，气体如上所述输送至水吸收单元中。
因为氨基甲酸盐反应在高温进行而且因为在工艺过程中产生大量的水，所以无需为此制造低温的无水氨。很明显，所生产的氨中含水量太高会对脲工艺有不利影响，因为水会降低脲的产率并因此而加剧循环量。因此，需要一定程度提高氨的浓度。在常规氨工艺中，在操作于中压，典型地15-17kg/cm2g的氨浓缩单元中所用的低温热量一般总有过剩。在该压力下，通过在低于120℃的低温下蒸馏的方法可使氨的浓度显著升至高达85％。
该工艺省去了两个压缩机(冷冻和CO2)、一个冷冻回路和氨工厂中的一个除CO2单元。因为合成塔入口处NH3的浓度可接近零，所以可达到减小合成塔尺寸或降低循环率的目的。脲工厂中的设备有很大一部分是用以回收CO2和NH3的。通过用氨洗涤除去CO2；经水洗涤以及蒸馏，随后除去氨。主要为氢和氮的“惰性”成分最终排放到大气中。
通过使惰性气体循环至合成气压缩机的吸入端，可简化工艺并减少脲工厂中单元数目。而且，脲工厂采用了一种工艺凝液汽提系统以净化工艺水，从而使其适用于锅炉给水。氨工厂中采用了一种类似的系统，并且两个系统的联用可以具有某些潜在的益处。
Claims (1)
1.一种用于脲和氨反应物的联合制备的方法，该方法包含以下步骤：提供含二氧化碳的氨合成气以及将合成气转化成氨反应物，使氨反应物与合成气中的二氧化碳发生反应生成氨基甲酸铵和生成脲产品，该方法还包含以下步骤：
在合成气转化成氨反应物之前，
(i)以氨反应物的水溶液洗涤合成气并形成富含氨基甲酸铵的溶液；
(ii)通过用水洗涤从洗涤过的合成气中除去过量的氨反应物并排出氨反应物的水溶液；
(iii)通过除去残留的水和氨而净化水洗涤过的合成气；并且
(iv)使净化过的合成气输送到气体转化至氨反应物的反应中。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA200001371 | 2000-09-15 | ||
| DKPA200001371 | 2000-09-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1344711A true CN1344711A (zh) | 2002-04-17 |
| CN1190414C CN1190414C (zh) | 2005-02-23 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011331089A Expired - Fee Related CN1190414C (zh) | 2000-09-15 | 2001-09-14 | 氨和脲的联合制备方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6723876B2 (zh) |
| EP (1) | EP1188710A3 (zh) |
| JP (1) | JP2002114752A (zh) |
| CN (1) | CN1190414C (zh) |
| CA (1) | CA2357256C (zh) |
| RU (1) | RU2283832C2 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509768C (zh) * | 2004-08-10 | 2009-07-08 | 乌里阿·卡萨勒有限公司 | 由氨和二氧化碳制备尿素的方法 |
| CN104039758A (zh) * | 2012-01-17 | 2014-09-10 | 阿尔斯通技术有限公司 | 通过在脲生产过程中集成氨生产过程而形成脲的方法及其系统 |
| US9428449B2 (en) | 2013-01-16 | 2016-08-30 | Alstom Technology Ltd | Method of forming urea by integration of an ammonia production process in a urea production process and a system therefor |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7642377B1 (en) | 2008-07-21 | 2010-01-05 | Kellogg Brown & Root Llc | Systems and methods for integrated ammonia-urea process |
| WO2010019662A1 (en) * | 2008-08-12 | 2010-02-18 | 4A Technologies, Llc | Modularized system and method for urea production using a bio-mass feedstock |
| EP2402308A1 (en) | 2010-06-24 | 2012-01-04 | DSM IP Assets B.V. | Urea plant |
| AU2011383480B2 (en) * | 2011-12-15 | 2015-02-05 | Mitsubishi Heavy Industries Engineering, Ltd. | Operating method for urea manufacturing plant formed from multiple systems |
| DE102013113980A1 (de) * | 2013-12-12 | 2015-06-18 | Thyssenkrupp Ag | Verfahren zur Herstellung von Ammoniakgas und CO2 für eine Harnstoffsynthese |
| EP2957544A1 (en) * | 2014-06-18 | 2015-12-23 | Casale SA | Process for production of ammonia and derivatives, in particular urea |
| EP2993158A1 (en) * | 2014-09-05 | 2016-03-09 | Casale SA | Process for production of ammonia and derivatives, in particular urea |
| DE102016203277A1 (de) | 2016-02-29 | 2017-08-31 | Thyssenkrupp Ag | Integrierte Synthese von Ammoniak und Harnstoff |
| DE102016122374A1 (de) * | 2016-11-21 | 2018-05-24 | Thyssenkrupp Ag | Vollintegrierter Ammoniak-Harnstoff-Komplex |
| IT201700121364A1 (it) * | 2017-10-25 | 2019-04-25 | Saipem Spa | Apparato e metodo per il trattamento di vapori di processo provenienti da una sezione di concentrazione sottovuoto di un impianto urea |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3303215A (en) * | 1962-03-09 | 1967-02-07 | Toyo Koatsu Ind Inc | Synthesis of urea |
| US3349126A (en) * | 1962-09-10 | 1967-10-24 | Pullman Inc | Integrated ammonia and urea process |
| JPS4830258B1 (zh) | 1969-02-08 | 1973-09-18 | ||
| IT1014987B (it) * | 1974-06-12 | 1977-04-30 | Snam Progetti | Procedimento integrato urea am moniaca |
| IT1034674B (it) * | 1975-03-28 | 1979-10-10 | Snam Progetti | Processo flessibile intergrato per la produzione di ammoniaca edurea |
| US4291006A (en) * | 1977-03-03 | 1981-09-22 | Snamprogetti S.P.A | Combined process for the production of urea and ammonia |
| US4235816A (en) | 1979-03-08 | 1980-11-25 | Snamprogetti S.P.A. | Integrated ammonia-urea process |
| US4988491A (en) * | 1989-04-11 | 1991-01-29 | Christiaan Van Dijk | Flexible integration of the production of ammonia and urea |
| US5523483A (en) * | 1995-06-16 | 1996-06-04 | The M. W. Kellogg Company | Integrated urea/ammonia process |
| EP0905127B1 (en) * | 1997-09-20 | 2001-11-28 | Urea Casale S.A. | Process for combined production of ammonia and urea |
| JP2000159519A (ja) * | 1998-11-25 | 2000-06-13 | Chiyoda Corp | アンモニア・尿素製造プラントおよび製造方法 |
-
2001
- 2001-08-31 EP EP01120959A patent/EP1188710A3/en not_active Withdrawn
- 2001-09-14 US US09/952,678 patent/US6723876B2/en not_active Expired - Lifetime
- 2001-09-14 CA CA002357256A patent/CA2357256C/en not_active Expired - Fee Related
- 2001-09-14 RU RU2001125149/04A patent/RU2283832C2/ru not_active IP Right Cessation
- 2001-09-14 CN CNB011331089A patent/CN1190414C/zh not_active Expired - Fee Related
- 2001-09-14 JP JP2001279482A patent/JP2002114752A/ja active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509768C (zh) * | 2004-08-10 | 2009-07-08 | 乌里阿·卡萨勒有限公司 | 由氨和二氧化碳制备尿素的方法 |
| CN104039758A (zh) * | 2012-01-17 | 2014-09-10 | 阿尔斯通技术有限公司 | 通过在脲生产过程中集成氨生产过程而形成脲的方法及其系统 |
| CN104039758B (zh) * | 2012-01-17 | 2016-07-13 | 阿尔斯通技术有限公司 | 通过在脲生产过程中集成氨生产过程而形成脲的方法及其系统 |
| US9428449B2 (en) | 2013-01-16 | 2016-08-30 | Alstom Technology Ltd | Method of forming urea by integration of an ammonia production process in a urea production process and a system therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1188710A2 (en) | 2002-03-20 |
| CA2357256C (en) | 2007-06-19 |
| CA2357256A1 (en) | 2002-03-15 |
| EP1188710A9 (en) | 2004-08-18 |
| JP2002114752A (ja) | 2002-04-16 |
| RU2283832C2 (ru) | 2006-09-20 |
| EP1188710A3 (en) | 2003-10-29 |
| US20020035293A1 (en) | 2002-03-21 |
| CN1190414C (zh) | 2005-02-23 |
| US6723876B2 (en) | 2004-04-20 |
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