CN107001200A - 联产氨和甲醇的方法 - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 16
- 230000023556 desulfurization Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 238000013519 translation Methods 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000002349 favourable effect Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 6
- 238000010561 standard procedure Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
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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
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
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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
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
本发明涉及一种联产氨和甲醇的方法，其中将来自重整器的出口料流分成两部分，其中一部分进行变换、二氧化碳去除、甲烷化、压缩和氨合成，而另一部分被压缩并进料至单程甲醇合成工段。从甲醇合成工段抽出甲醇，并将来自所述工段的剩余流出物分成两个包含氢的料流，将其中一个进料至变换工段，而将另外一个再循环至脱硫单元。以这种方式获得了有利的联产方法，因为提供了用于脱硫的再循环氢，并且还避免了压缩步骤。
Description
本发明涉及一种用于联产氨和甲醇的新方法。
已知可以通过如图1所示的标准方法来联产氨和甲醇，所述标准方法包括以下步骤：
-在压缩的再循环氢的存在下进行烃进料气体的脱硫，
-向脱硫的天然气添加蒸汽，然后进行工艺料流的重整、变换、CO2去除和甲烷化，
-将一部分甲烷化的料流再循环至脱硫步骤，从而向该步骤提供压缩的再循环氢，以及
-将甲烷化料流的剩余部分压缩，然后进行氨的合成。
烃进料是蒸汽和任选的预重整的烃的混合物。这些烃可以源自任何可用于重整器进料的烃来源，例如天然气。
根据本发明的新方法，如图2所示，涵盖上述标准方法的如下修改：
-不将甲烷化料流的一部分再循环至脱硫步骤，
-将重整的料流分成两部分：(a)第一重整的料流，根据标准方法对其进行变换、CO2去除和甲烷化，和(b)第二重整的料流，将其压缩并在包括1至3个串联反应器的单程甲醇合成工段中用于甲醇合成，
-从甲醇合成工段除去气态组分的料流并将该料流分成两个包含氢的料流，
-将包含氢的第一料流转移至变换工段，通常转移至高温变换和低温变换之间的点，
-将包含氢的第二料流转移至脱硫步骤，从而提供用于脱硫的再循环氢，并因此替换先前在标准方法中由甲烷化的料流所提供的再循环氢。
与标准方法相比，本发明的关键是利用来自甲醇合成的部分合成气作为再循环氢。这样，可以节省专用的再循环压缩机。类似地，对于现有的需要少量甲醇的氨工厂，用于向脱硫步骤提供压缩的再循环氢的压缩机也可以用作用于甲醇合成的压缩机。
用于联产氨和甲醇的一体化方法是本领域已知的。因此，WO 2011/020618涉及一种联产甲醇和氨的方法，其中首先使基本上由CO、CO2和H2组成的合成气混合物部分地在甲醇单程反应器中反应，将未反应的合成气分成第一和第二料流，将第一料流纯化并进料至氨合成工段，并将第二料流进料至甲醇合成和纯化。该方法能够在采用不超过当前实际产能限制的单元操作下在一体化的单一方法中实现甲醇和氨的高产能生产。
US 6,333,014中也公开了一种用于联产甲醇和氨的一体化方法，该方法包括以下步骤：在初级和次级重整器中用蒸汽和空气对脱硫的烃进行重整以制备合成气混合物，将合成气混合物分成第一和第二合成气料流，将第一合成气料流冷却以除去水料流，并将剩余的合成气进料至甲醇单程反应器以制备含甲醇的混合物，将含甲醇的混合物分离成粗甲醇和不含甲醇的气体，将第二合成气料流进料至高温CO转换器，将来自高温CO转换器的流出物、不含甲醇的气体和水料流进料至低温CO转换器，以及将来自低温CO转换器的流出物进料至氨合成工段以制备氨。
US 5,180,570公开了一种与本发明类似的用于制备甲醇和氨的一体化方法。它包括两个再循环：将第一部分未反应的甲醇合成气再循环至甲醇合成反应器，并将第二部分的未反应的甲醇合成气作为含有例如H2(70-90摩尔％)、CO(1-7摩尔％)和CO2(1-7摩尔％)的吹扫气流而提取出来。当未反应的甲醇合成气吹扫料流中的CO组分与在变换工段中的蒸汽发生催化反应时，可以促进氨的生产。随后进行CO2去除，从而进一步提高氢含量。进一步的加工包括洗涤、压缩和合成氨；没有提及甲烷化。在公开的方法中，消除了对蒸汽变换和甲烷化的需要，除非需要促进氨的生产。
US 3,598,527公开了一种氨和甲醇的生产方法，其显示出与本发明的一些相似性。将一部分的甲醇合成气料流送至低压水煤气变换区，以将CO转化成CO2。此外，将来自甲醇合成回路的吹扫气体进料至高温变换。该美国专利中公开的方法使用单一的工艺链，从而获得了二氧化碳压缩的操作成本方面的极大节省，并且通过使用单一的工艺链代替独立的甲醇和氨设备而获得了额外的节省。
上述现有技术没有公开这样一种方法，其中在甲醇合成中只压缩和使用第二重整的料流。此外，现有技术没有公开将含氢的第二料流转移到脱硫步骤，从而为脱硫提供再循环氢并且还避免了压缩步骤。
因此，参照图2，本发明涉及一种用于联产氨和甲醇的新方法，其包括在氢的存在下进行烃进料(例如天然气(NG))的脱硫(Des.)，向脱硫的天然气添加蒸汽，然后进行重整(Ref.)、变换、二氧化碳去除(CO2rem.)和甲烷化(Meth.)，其中
-将来自重整器的出口料流分成两部分，其中一部分进行变换、二氧化碳去除、甲烷化、压缩(comp.)和氨合成(NH3synth)，而另一部分被压缩并进料至单程甲醇合成工段(CH3OH synth)，
-从甲醇合成工段抽出甲醇(CH3OH)，并将来自所述工段的剩余流出流分成两个包含氢的料流，
-将两个包含氢的料流中的一个进料至变换工段，以及
-将另一个包含氢的料流再循环至脱硫单元。
烃进料优选为天然气，但它可以是蒸汽与任选的预重整的烃的任何混合物，其中这些烃可以源自可用作重整器进料的任何烃来源。被压缩并进料至甲醇合成工段的一部分重整器出口料流优选被压缩到40-100巴，最优选约80巴。
甲醇合成工段包括一个甲醇合成反应器或者两个或三个这样的串联连接的反应器。
通过下面的实施例进一步说明本发明的方法。
实施例
通过在氢的存在下对烃进料气体进行脱硫而获得的重整器出口气体具有以下由百分比表示的组成(干气体)：
该干气体的流速为22996Nm3/h。
将气体分成两个料流，使这些中的一个(43.5％)通过甲醇工段，在此将其压缩至高于80巴的压力，并转化成18950kg/h的甲醇和56763Nm3/h的具有以下由百分比表示的组成(干气体)的富氢气体：
对于在氢的存在下进行的烃进料的脱硫，必须将3275Nm3/h的压力高于45barg的干燥的富氢气体再循环至脱硫工段。
来自组合的重整器和甲醇工段流出物的氨产量为60854kg/h。
Claims (5)
1.一种联产氨和甲醇的方法，包括在氢的存在下进行烃进料气体的脱硫，向脱硫的天然气添加蒸汽，然后进行重整、变换、二氧化碳去除和甲烷化，其中
-将来自重整器的出口料流分成两部分，其中一部分进行变换、二氧化碳去除、甲烷化、压缩和氨合成，而另一部分被压缩并进料至单程甲醇合成工段，
-从甲醇合成工段抽出甲醇，并将来自所述工段的剩余流出物分成两个包含氢的料流，
-将两个包含氢的料流中的一个进料至变换工段，并且
-将另一个包含氢的料流再循环至脱硫单元。
2.根据权利要求1所述的方法，其中所述甲醇合成工段包括一个甲醇合成反应器或者两个或三个这样的串联连接的反应器。
3.根据权利要求1所述的方法，其中被压缩并进料至甲醇合成工段的部分重整器出口料流被压缩到40-100巴。
4.根据权利要求3所述的方法，其中被压缩并进料至甲醇合成工段的部分重整器出口料流被压缩到约80巴。
5.根据权利要求1所述的方法，其中被转移至变换工段的所述包含氢的料流被引导至高温变换和低温变换之间的点。
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| CN202410104529.1A CN117865068A (zh) | 2014-12-15 | 2015-12-02 | 联产氨和甲醇的方法 |
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| Application Number | Priority Date | Filing Date | Title |
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| EP14197991.4A EP3034488B1 (en) | 2014-12-15 | 2014-12-15 | A process for co-production of ammonia and methanol |
| EP14197991.4 | 2014-12-15 | ||
| PCT/EP2015/078272 WO2016096410A1 (en) | 2014-12-15 | 2015-12-02 | A process for co-production of ammonia and methanol |
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| US (1) | US10259718B2 (zh) |
| EP (1) | EP3034488B1 (zh) |
| CN (2) | CN107001200A (zh) |
| EA (1) | EA032809B1 (zh) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3598527A (en) * | 1968-10-11 | 1971-08-10 | Pullman Inc | Ammonia and methanol production |
| CN1196041A (zh) * | 1995-09-11 | 1998-10-14 | 卡萨尔甲醇公司 | 氨和甲醇联合生产方法 |
| CN102050699A (zh) * | 2010-11-04 | 2011-05-11 | 茌平信祥化工有限公司 | 利用电石尾气联合生产甲醇和氨的工艺 |
| CN103896306A (zh) * | 2012-12-26 | 2014-07-02 | 昭和电工株式会社 | 高纯度氨及其制造方法以及高纯度氨制造装置 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5180570A (en) | 1992-01-23 | 1993-01-19 | Lee Jing M | Integrated process for making methanol and ammonia |
| JP5355062B2 (ja) * | 2008-12-15 | 2013-11-27 | 東洋エンジニアリング株式会社 | メタノール及びアンモニアの併産方法 |
| EP2467354B1 (en) * | 2009-08-20 | 2013-12-04 | Saudi Basic Industries Corporation | Process for methanol and ammonia co-production |
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- 2015-12-02 CN CN202410104529.1A patent/CN117865068A/zh active Pending
- 2015-12-02 WO PCT/EP2015/078272 patent/WO2016096410A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| US20170327383A1 (en) | 2017-11-16 |
| CN117865068A (zh) | 2024-04-12 |
| WO2016096410A1 (en) | 2016-06-23 |
| EP3034488A1 (en) | 2016-06-22 |
| EP3034488B1 (en) | 2017-10-18 |
| PL3034488T3 (pl) | 2018-03-30 |
| EA032809B1 (ru) | 2019-07-31 |
| EA201791320A1 (ru) | 2017-11-30 |
| US10259718B2 (en) | 2019-04-16 |
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