CN112437764A - 用于在具有旁路的反应器中生产甲醇的方法 - Google Patents
用于在具有旁路的反应器中生产甲醇的方法 Download PDFInfo
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- CN112437764A CN112437764A CN201980047941.1A CN201980047941A CN112437764A CN 112437764 A CN112437764 A CN 112437764A CN 201980047941 A CN201980047941 A CN 201980047941A CN 112437764 A CN112437764 A CN 112437764A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 242
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 59
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C29/152—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 characterised by the reactor used
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
Abstract
本发明涉及一种用于生产甲醇的方法,其包括以下步骤:使甲醇合成气的进料流通过含有甲醇合成催化剂的主甲醇反应器,以形成含有甲醇的混合气体;冷却含有甲醇的混合气体;从混合气体中分离出甲醇;以及加热混合气体。使经加热的混合气体的流通过含有甲醇合成催化剂的另外的甲醇反应器,和将来自另外的甲醇反应器的流出物与甲醇合成气的进料流混合并通过主甲醇反应器。
Description
本发明涉及一种用于在具有旁路的反应器中生产甲醇的方法,该旁路为另外的甲醇反应器的形式。
在传统的甲醇回路中,先将进料气体压缩并与再循环的未反应的气体混合,然后送入甲醇反应器,在其中由合成气(syngas)通过在高温高压下进行的平衡反应生成甲醇。合成反应为:
CO+H2O<->CH3OH+热量 (1)
CO2+3H2<->CH3OH+H2O+热量 (2)
CO+H2O<->CO2+H2+热量 (3)
由于反应是放热的,因此甲醇反应器必须配备有许多冷却管来控制温度。
为了减小传统甲醇反应器的尺寸(或提高产量),在传统反应器上游的另外的反应器中安装催化剂层是有利的。该另外的反应器可以是不那么复杂的或冷却程度较低的(或者,绝热的)反应器。但是,如果新的另外的反应器是绝热反应器(或者,冷却程度较低),则温度曲线将随着容量、气体组成和催化剂活性而变化,并且存在催化剂床的出口温度过高的风险。催化剂床中的高温将导致副产物的形成增加和催化剂烧结。
US 8.536.235公开了一种用于合成甲醇的方法,该方法包括(a)使回路气体和补充气体的合成气混合物在压力下通过经由沸水冷却并含有甲醇合成催化剂的第一合成反应器,以形成含有甲醇的混合气体,(b)冷却所述混合气体,(c)使所述混合气体通过含有甲醇合成催化剂的第二合成反应器,其中合成进一步的甲醇以形成产物气体流,(d)冷却所述产物气体流以冷凝甲醇,和(e)回收甲醇并将未反应的气体作为回路气体返回到第一合成反应器。来自第一合成反应器的含有甲醇的混合气体在与回路气体或补充气体的热交换中冷却。
CN 107382665 A公开了一种用于合成甲醇的技术,该技术包括通过第一反应器从含有新鲜气体的合成气生成甲醇,将含有合成气和甲醇蒸汽的混合气体的热量与待进料至第一反应器的含有新鲜气体的合成气的热量进行交换,然后通过第二反应器生成甲醇,将反应后的较高甲醇浓度的合成气冷却,然后将其引导到甲醇分离器中并分离甲醇,将分离甲醇后的合成气与新鲜气体混合,从而获得含有新鲜气体的合成气,将含有新鲜气体的合成气再次引导到第一反应器中,利用阀A将一部分新鲜气体直接引导到第二反应器中并将第二反应器的催化剂床的热点温度控制在约250℃,使一部分含有新鲜气体的合成气保持无热交换,并通过阀B将其直接引入到第一反应器中,并将第二反应器的进气温度控制在200-240℃。这样,增加了催化剂的使用率并且改善了甲醇产物的质量。
在US 2011/0065966中,使用于生产甲醇的含有氢和碳氧化物的合成气通过第一(优选为水冷却的)反应器,在其中将一部分碳氧化物催化转化为甲醇。将所得的含有合成气和甲醇蒸汽的混合物进料至第二(优选为气体冷却的)反应器,在其中将另一部分碳氧化合物转化为甲醇。为了即使在老化的催化剂下也能达到最大的甲醇收率,引导部分合成气流绕过第一反应器并直接引入到第二反应器中。
为了增加冷却介质反应器的容量,在某些情况下,催化剂不仅将被装载到反应管中,而且还将被装载到安装有反应管的上管板的上方。对于放热反应,即使在反应物到达与冷却介质为热接触的反应管之前,这也会提高反应气体的温度。因此,存在管板温度过高的风险,从而有损坏管板或损坏反应管顶部和上管板的随后风险。申请人的WO 2017/186538解决了这个问题,其公开了用于放热反应的冷却介质反应器。该反应器包括反应管插入物,以在设置在上管板顶部上的上管板插入物的顶部上提供绝热催化剂层;以及该插入物的引导装置,该引导装置使上管板与插入物内部的放热反应绝热。
本发明的目的是添加额外的反应器并在第一(或多个)反应器周围布置进料气体旁路,以控制反应器出口处的温度。被分流的进料气温度较低,并且在反应器出口处与热的气体混合,以将温度控制在期望的水平。气体旁路取自进料气体,使再循环气体的全部流量通过第一反应器,并减少了进入绝热的(或冷却程度较低的)反应器的新鲜进料气体的量,如附图所示。
因此,本发明涉及一种用于生产甲醇的方法,其包括以下步骤:
(a)使甲醇合成气的进料流通过含有甲醇合成催化剂的主甲醇反应器,以形成含有甲醇的混合气体,
(b)冷却含有甲醇的混合气体,
(c)从混合气体中分离出甲醇,以及
(d)加热混合气体,其中
-使来自步骤(d)的经加热的混合气体的流通过含有甲醇合成催化剂的另外的甲醇反应器,和
-将来自另外的甲醇反应器的流出物与甲醇合成气的进料流混合并通过所述主甲醇反应器。
为了减小甲醇回路中的沸水反应器(BWR)的尺寸(或者,提高现有BWR的产量),可以在管板的顶部放置绝热催化剂层。对于大型装置,将绝热床放置在单独的反应器中可能是一个优势。该想法与WO 2017/186538中描述的绝热顶层(催化剂插入物)之间的主要区别在于在冷却的反应器外部进行控制的能力,这使得可以以不同的方式操作回路。如果将催化剂床放置在单独的反应器中,则可以添加额外控制以限制低负载或瞬态情况下的温度。
随着流向新反应器的新鲜气体的减少,另外的反应器的入口处的气体反应性降低,这导致催化剂床中的峰值温度降低,以及副产物形成的减少。
在附图中说明了在现有甲醇反应器上游使用另外的反应器并通过气体旁路控制出口温度(现有反应器入口温度)的想法:
甲醇合成进料气体f的流被分为两个流,其中一个流通过节流阀v被送到主甲醇反应器A,而另一个流在经过进料/流出物热交换器Hex后被送到另外的甲醇反应器B。
因此,主甲醇反应器A是用新鲜甲醇合成进料气体f和来自另外的甲醇反应器B的流出物e2的混合物进行进料。
来自主甲醇反应器A的流出物e1在回路空气冷却器lac和回路水冷却器lwc中冷却,然后进料至分离器S,其中将液态甲醇产物(MeOH)与气相分离,将后者与新鲜的进料气体混合,并送至另外的甲醇反应器B。
Claims (3)
1.一种用于生产甲醇的方法,包括以下步骤:
(a)使甲醇合成气的进料流通过含有甲醇合成催化剂的主甲醇反应器,以形成含有甲醇的混合气体,
(b)冷却含有甲醇的混合气体,
(c)从混合气体中分离出甲醇,以及
(d)加热混合气体,其中
-使来自步骤(d)的经加热的混合气体的流通过含有甲醇合成催化剂的另外的甲醇反应器,和
-将来自另外的甲醇反应器的流出物与甲醇合成气的进料流混合并通过所述主甲醇反应器。
2.根据权利要求1所述的方法,其中所述主甲醇反应器是沸水反应器(BWR)。
3.根据权利要求2所述的方法,其中在管板的顶部放置绝热的催化剂层,以减小沸水反应器的尺寸。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DKPA201800475 | 2018-08-17 | ||
DKPA201800475 | 2018-08-17 | ||
PCT/EP2019/068678 WO2020035231A1 (en) | 2018-08-17 | 2019-07-11 | A method for producing methanol in a reactor with bypass |
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CN112437764A true CN112437764A (zh) | 2021-03-02 |
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CN201980047941.1A Pending CN112437764A (zh) | 2018-08-17 | 2019-07-11 | 用于在具有旁路的反应器中生产甲醇的方法 |
Country Status (12)
Country | Link |
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US (1) | US11407702B2 (zh) |
EP (1) | EP3837232A1 (zh) |
KR (1) | KR20210045980A (zh) |
CN (1) | CN112437764A (zh) |
AR (1) | AR115958A1 (zh) |
AU (1) | AU2019320977A1 (zh) |
BR (1) | BR112021002868A2 (zh) |
CA (1) | CA3109305A1 (zh) |
EA (1) | EA202190526A1 (zh) |
MX (1) | MX2021001680A (zh) |
WO (1) | WO2020035231A1 (zh) |
ZA (1) | ZA202100602B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1989092A (zh) * | 2004-08-20 | 2007-06-27 | 戴维加工技术有限公司 | 用于气相反应的方法 |
US20110065966A1 (en) * | 2007-08-29 | 2011-03-17 | Lurgi Gmbh | Process and plant for producing methanol |
CN107427802A (zh) * | 2015-03-20 | 2017-12-01 | 托普索公司 | 沸水反应器 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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GB0710022D0 (en) | 2007-05-25 | 2007-07-04 | Johnson Matthey Plc | Methonal process |
DK201600257A1 (en) | 2016-04-28 | 2017-11-20 | Haldor Topsoe As | Cooling Medium Reactor |
GB201710951D0 (en) * | 2017-07-07 | 2017-08-23 | Johnson Matthey Plc | Methanol synthesis process |
CN107382665B (zh) | 2017-07-13 | 2023-06-30 | 南京国昌化工科技有限公司 | 一种甲醇合成的工艺和装置 |
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2019
- 2019-07-11 CA CA3109305A patent/CA3109305A1/en active Pending
- 2019-07-11 CN CN201980047941.1A patent/CN112437764A/zh active Pending
- 2019-07-11 EA EA202190526A patent/EA202190526A1/ru unknown
- 2019-07-11 EP EP19739585.8A patent/EP3837232A1/en active Pending
- 2019-07-11 MX MX2021001680A patent/MX2021001680A/es unknown
- 2019-07-11 KR KR1020217002018A patent/KR20210045980A/ko unknown
- 2019-07-11 US US17/261,235 patent/US11407702B2/en active Active
- 2019-07-11 BR BR112021002868-4A patent/BR112021002868A2/pt unknown
- 2019-07-11 WO PCT/EP2019/068678 patent/WO2020035231A1/en active Application Filing
- 2019-07-11 AU AU2019320977A patent/AU2019320977A1/en active Pending
- 2019-08-15 AR ARP190102323A patent/AR115958A1/es unknown
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2021
- 2021-01-27 ZA ZA2021/00602A patent/ZA202100602B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1989092A (zh) * | 2004-08-20 | 2007-06-27 | 戴维加工技术有限公司 | 用于气相反应的方法 |
US20110065966A1 (en) * | 2007-08-29 | 2011-03-17 | Lurgi Gmbh | Process and plant for producing methanol |
CN107427802A (zh) * | 2015-03-20 | 2017-12-01 | 托普索公司 | 沸水反应器 |
Also Published As
Publication number | Publication date |
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AR115958A1 (es) | 2021-03-17 |
ZA202100602B (en) | 2023-10-25 |
US11407702B2 (en) | 2022-08-09 |
WO2020035231A1 (en) | 2020-02-20 |
EA202190526A1 (ru) | 2021-05-26 |
AU2019320977A1 (en) | 2021-02-11 |
EP3837232A1 (en) | 2021-06-23 |
BR112021002868A2 (pt) | 2021-05-11 |
US20210269380A1 (en) | 2021-09-02 |
CA3109305A1 (en) | 2020-02-20 |
MX2021001680A (es) | 2021-04-19 |
KR20210045980A (ko) | 2021-04-27 |
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