CN110770162B - 制备氨合成气的方法 - Google Patents

制备氨合成气的方法 Download PDF

Info

Publication number
CN110770162B
CN110770162B CN201880041393.7A CN201880041393A CN110770162B CN 110770162 B CN110770162 B CN 110770162B CN 201880041393 A CN201880041393 A CN 201880041393A CN 110770162 B CN110770162 B CN 110770162B
Authority
CN
China
Prior art keywords
stream
ammonia synthesis
gas stream
oxygen
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201880041393.7A
Other languages
English (en)
Other versions
CN110770162A (zh
Inventor
P·A·汉
A·E·克勒尔延森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of CN110770162A publication Critical patent/CN110770162A/zh
Application granted granted Critical
Publication of CN110770162B publication Critical patent/CN110770162B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • 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
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
    • 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
    • C01B2203/046—Purification by cryogenic separation
    • 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
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

本发明涉及一种基于自热重整和水的电解的组合来制备氨合成气的方法。

Description

制备氨合成气的方法
发明领域
本发明涉及氨合成气的制备。更特别地，本发明在含氢和氮的氨合成气的制备中组合使用了水的电解和气态烃原料的自热重整。
发明背景
氨合成气通常通过使天然气或高级烃的烃进料在燃烧管式蒸汽重整器中通过与蒸汽重整催化剂接触而进行吸热蒸汽重整反应来制备。然后将初级重整气体送入次级绝热重整器，其中在次级重整催化剂存在下，用空气或富氧空气来部分氧化气体中的一部分氢气和残余量的烃。在次级重整器中，在上述蒸汽重整反应的原料反应过程中形成包含氢气、氮气、一氧化碳和二氧化碳的粗合成气，且在次级重整步骤中通过加入空气而向气体中引入氮气。
初级和次级重整工艺的缺点是用于加热燃烧的初级蒸汽重整器的燃料消耗相对高和因此大的CO2排放。从该工艺中捕获的CO2产物可用于下游工艺，例如尿素生产或三次采油。
在大规模氨合成设备中，初级和次级蒸汽重整可以被自热重整(ATR)代替。
ATR包括在反应中使用氧气使天然气部分氧化为CO、CO2、H2、H2O和烃，随后使烃进行蒸汽重整以形成粗合成气。采用ATR技术，特别是可以稍微降低烃的消耗以及CO2排放。
在常规的ATR工艺中，空气分离单元(ASU)为ATR提供氧气，也为氨合成提供氮气。
在ASU中处理的不到一半的氮将用于氨合成，因为ATR需要比大气空气中的氧和氮之间的比率相对更多的氧/氮。过量的氮可被认为是ASU的能量损失。
最近，至少在专利文献中，已经设想了用生产氢气的水电解与生产氮气的空气分离的组合来制备氨合成气。由此产生的氢气和氮气以化学计量比组合以形成用于氨生产的合成气。然而，电解和空气分离的组合的问题在于，在电解和空气分离两者中都产生了作为副产物的氧气，其在氨合成中没有用处，并且可被认为是能量损失。
发明内容
本发明基于这样的ATR工艺的组合：其在ATR工艺中在烃原料的部分氧化中使用来自水的电解的氧。来自电解的氢气可用于将氨合成气中的氢气/氮气摩尔比调节至大约为制备氨以及制备另外的合成气所需的化学计量比。
与使用水电解制备氢和空气分离制备氮的现有技术的方法相比，在根据本发明的方法中，来自水电解的氧产物有利地用于自热重整器中的部分氧化，使得避免了昂贵且能量密集的ASU。
因此，本发明涉及一种制备氨合成气的方法，其包括以下步骤：
(a)提供烃原料；
(b)通过水的电解制备单独的氢气流和单独的氧气流；
(c)通过用来自步骤(b)的氧气流使大气空气富集，以提供用于自热重整的工艺空气；
(d)用富氧的工艺空气将至少一部分烃原料自热重整为包含氢气、氮气、一氧化碳和二氧化碳的工艺气体流；
(e)在一个或多个水煤气变换反应中处理从自热重整步骤(d)中取出的工艺气体流；
(f)从经水煤气变换处理的工艺气体流中除去二氧化碳；以及
(g)纯化来自步骤(f)的工艺气体流；以及
(h)获得氨合成气。
工艺气体流在950-1100℃的高温下离开自热重整步骤。工艺气体的高温可以有利地用于热交换重整器中一部分烃原料的蒸汽重整。在这种方法的一种类型中，烃原料被分成两个子流，其中一个子流被引入自热重整步骤，另一个子流被引入热交换重整器，并通过与离开自热重整步骤的热工艺流进行间接传热而被蒸汽重整。在水煤气变换反应中处理混合的工艺气体流之前，将来自热交换重整的经蒸汽重整的工艺气体与来自自热重整的工艺气体流混合。
因此，在本发明的一个实施方案中，该方法包括以下另外的步骤：以与离开自热重整步骤(d)的工艺流为间接传热关系的方式对一部分烃原料进行蒸汽重整，且在步骤(e)上游将经热交换蒸汽重整的工艺气体流与经自热重整的工艺气体流混合。
在这种方法的另一类型中，热交换蒸汽重整与自热重整步骤串联进行。在串联的热交换蒸汽重整工艺中，所有烃原料通过热交换重整器，其在那里被加热和部分转化。然后将部分转化的原料进料至自热重整器，其在那里发生最终转化。来自自热重整器的热工艺流以与烃原料为间接热交换关系的方式通过热交换重整器，并为吸热的蒸汽重整反应提供必要的热量。
因此，在本发明的另一个实施方案中，该方法包括以下另外的步骤：以与离开自热重整步骤(d)的工艺流为间接传热关系的方式对烃原料进行热交换蒸汽重整，并将经热交换蒸汽重整的烃原料送到步骤(d)。
氨合成气中的氮气来自于引入至ATR工艺的大气。因为ATR需要比大气中的氧/氮的摩尔比相对更多的氧/氮，所以在根据本发明的方法中使用的大气富含来自水电解的氧，以提供氧含量在22和45摩尔％之间、优选37摩尔％的工艺空气，其中可获得低的来自ATR的甲烷逸出。
氨合成气中氢气与氮气的摩尔比要求在2.7-3.3之间。所需的摩尔比通常通过调节引入至自热重整工艺的工艺空气的量来获得。
调节氨合成气中氢气与氮气的摩尔比的另一种方法或补充方法是将水电解中得到的氢气流引入纯化的工艺气体中。
然后优选在用于氨回路的合成气压缩机的吸入口附近将氢气流引入到纯化的工艺气体中。
因此，在本发明的一个实施方案中，在步骤(g)之后，将至少一部分在步骤(b)中获得的氢气流加入到工艺气体流中，其量使得氨合成气中的氢气与氮气的摩尔比为2.7-3.3。
当使用来自水电解的氢气流调节氨合成气时，水的电解优选在对应于工艺气体压力而言升高的压力下进行，这节省了压缩能量。
优选通过使工艺气体经历一个或多个CO到CO2的水煤气变换反应以实现更多的氢气产生和CO2的去除，同时通过本领域已知的CO2的化学和/或物理吸收，来进行自热重整步骤和任选地在热交换蒸汽重整步骤中获得的工艺气体的纯化。
当在氨合成气制备中不包括ASU时，液氮不可用于通过液氮洗涤从工艺气体中除去杂质，并且在纯化步骤中使用液氮是较不可行的。
在根据本发明的方法中，纯化步骤中的氮洗涤可以优选地被甲烷化代替，以除去工艺气体中的痕量碳氧化物。
纯化步骤也可基于低温方法，如所谓的冷箱法，其也可用于通过除去过量的N2来调节N2/H2摩尔比。
本发明的方法很大程度上基于水的电解，因为在该方法中使用了两种电解产物。
本发明的优点在于，用于操作水的电解的能量可以是由风车、太阳能电池、液压能或其它可再生能源产生的可再生能源。
因此，在本发明的优选实施方案中，水的电解由可再生能源提供动力。
本发明的方法还可以有利地用于改造和/或提高现有的基于ATR的氨合成气设备的产能。
本发明的方法的主要优点之一在于，与仅使用电解和空气分离而不使用ATR或次级重整的现有技术方法的效率相比，电解装置的效率显著提高了近30％。
已报道的商业化的水电解技术的效率在40％至60％之间。水电解的效率定义为产生的氢气的低热值(LHV)除以消耗的电功率。由于没有热力学热值，因此不能给出所产生的氧气的能量值。
将水电解与ATR或次级重整技术组合用于氨合成气生产的协同作用导致用于部分氧化工艺的烃原料和燃料以及对于ASU的功率需求的总体节省，因为在本发明的方法中不存在ASU。
在下表1中，给出了2200MTPD氨装置的关键参数，以比较具有ASU的ATR和与水电解结合且不具有ASU的ATR的合成气技术。
表1
与使用ATR和ASU的方法相比，当将205.7MW的功率用于效率为60％的水电解时，根据本发明的方法节省的天然气为129MW(LHV＝39771KJ/Nm3)并且ASU为30.3MW功率。然后，水电解的总效率从60％增加到77.4％。这增加了几乎30％。此外，节省了ASU的资本支出。因为天然气消耗降低22％，CO2排放相应减少。
本发明的具体实施方案将参照附图更详细地公开，其中
图1是根据本发明的方法制备氨合成气的简化流程图，其中利用了水电解并结合了ATR和并联的热交换蒸汽重整。
在图1所示的简化框图中，该方法通过在自热重整器(ATR)6和热交换重整器(HTER)8中使与蒸汽流4混合的烃原料例如天然气(NG)的流2进行自热重整来进行。HTER 8与ATR 6并联操作，并且流2的一部分以流3b的形式绕过ATR 6并引入HTER 8中。
ATR 6用富氧空气操作。用于富集空气的氧气通过水电解槽(WE)10中的水电解产生，并且将WE10中产生的氧气流7以一定量混合到空气5中以产生具有37摩尔％的氧含量的工艺空气9。在ATR 6中，将一部分天然气4引入流3a中，并通过已知的自热重整工艺进行自热重整。取自ATR 6的温度约为1000℃的热的经自热重整的流出物11以与管线3b中供给HTER 8的天然气进行间接热交换的方式通过HTER 8，并为HTER 8中的蒸汽重整反应提供热量。含有氢气、氮气、一氧化碳和二氧化碳的经蒸汽重整和自热重整的工艺气体流13全部被送到水煤气变换(WGS)装置12，流13中的大部分碳氧化物通过已知的WGS反应转化为二氧化碳。
如本领域已知的，通过在N-甲基二乙醇胺(MDEA)中的吸收，在气液接触器14中从经水煤气变换处理的工艺气体流15中除去由WGS反应和蒸汽重整反应形成的二氧化碳。
从气-液接触器14中取出的工艺气体流17的最终纯化是在甲烷转化器16中通过使残余量的一氧化碳发生甲烷化(一氧化碳到甲烷的反应)来进行的。
通过将WE 10中形成的适量氢气通过流21引入流19中，将来自甲烷转化器16的经纯化的工艺气体流19中的氮气/氢气摩尔比调节至约3。
将这样制备的氨合成气通过管线23引入补充气体压缩机(未示出)并被送入氨合成回路(未示出)。

Claims (10)

1.一种制备氨合成气的方法，其中所述方法包括以下步骤：
(a)提供烃原料；
(b)通过水的电解来制备单独的氢气流和单独的氧气流；
(c)通过用来自步骤(b)的氧气流使大气空气富集，提供用于自热重整的工艺空气；
(d)用富氧的工艺空气将至少一部分烃原料自热重整为包含氢气、氮气、一氧化碳和二氧化碳的工艺气体流；
(e)在一个或多个水煤气变换反应中处理自热重整步骤(d)中获得的工艺气体流；
(f)从经水煤气变换处理的工艺气体流中除去二氧化碳；以及
(g)纯化来自步骤(f)的工艺气体流；以及
(h)获得氨合成气；
其中在步骤(g)之后将步骤(b)中获得的至少一部分氢气流以这样的量加入工艺气体流中，该量使得所述氨合成气中氢气/氮气的摩尔比为2.7-3.3。
2.如权利要求1所述的方法，其包括以下另外的步骤：以与离开自热重整步骤(d)的工艺流为间接传热关系的方式使一部分烃原料进行蒸汽重整，并在步骤(e)上游将经热交换蒸汽重整的工艺气体流与经自热重整的工艺气体流混合。
3.如权利要求1所述的方法，其包括以下另外的步骤：以与离开自热重整步骤(d)的工艺流为间接传热关系的方式使烃原料进行热交换蒸汽重整，并将经热交换蒸汽重整的烃原料送到步骤(d)。
4.如权利要求1至3中任一项所述的方法，其中所述工艺空气含有22摩尔％至45摩尔％的氧气。
5.如权利要求1至3中任一项所述的方法，其中步骤(b)在压力下进行。
6.如权利要求1至3中任一项所述的方法，其中步骤(f)中的所述工艺气体流的纯化通过甲烷化来进行。
7.如权利要求1至3中任一项所述的方法，其中步骤(f)中的所述工艺气体流的纯化在低温下进行。
8.如权利要求1至3中任一项所述的方法，其中所述水的电解由可再生能源提供动力。
9.如权利要求4所述的方法，其中所述工艺空气含有37摩尔％的氧气。
10.如权利要求1至9中任一项所述的方法在改造和/或提高现有氨合成气装置的产能中的用途。
CN201880041393.7A 2017-07-25 2018-07-11 制备氨合成气的方法 Active CN110770162B (zh)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DKPA201700425 2017-07-25
DKPA201700425 2017-07-25
DKPA201700522 2017-09-25
DKPA201700522 2017-09-25
DKPA201800237 2018-05-28
DKPA201800237 2018-05-28
PCT/EP2018/068808 WO2019020378A1 (en) 2017-07-25 2018-07-11 PROCESS FOR THE PREPARATION OF AMMONIA SYNTHESIS GAS

Publications (2)

Publication Number Publication Date
CN110770162A CN110770162A (zh) 2020-02-07
CN110770162B true CN110770162B (zh) 2024-03-08

Family

ID=62874919

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880041393.7A Active CN110770162B (zh) 2017-07-25 2018-07-11 制备氨合成气的方法

Country Status (14)

Country Link
US (1) US11840448B2 (zh)
EP (1) EP3658491B1 (zh)
KR (1) KR102599461B1 (zh)
CN (1) CN110770162B (zh)
AU (1) AU2018308587B2 (zh)
BR (1) BR112020001494A2 (zh)
CA (1) CA3069817A1 (zh)
CL (1) CL2020000156A1 (zh)
IL (1) IL271940B2 (zh)
PE (1) PE20200524A1 (zh)
PL (1) PL3658491T3 (zh)
UA (1) UA127164C2 (zh)
WO (1) WO2019020378A1 (zh)
ZA (1) ZA201908174B (zh)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2018305876B2 (en) 2017-07-25 2023-12-14 Haldor Topsøe A/S Method for the preparation of synthesis gas
AU2020272084A1 (en) 2019-04-08 2021-07-29 Haldor Topsøe A/S Chemical synthesis plant
BR112023014011A2 (pt) 2021-01-21 2023-11-07 Casale Sa Método para preparação de um gás de síntese
US20240158247A1 (en) * 2021-03-30 2024-05-16 Casale Sa Process for ammonia synthesis using green hydrogen
US11820657B2 (en) 2021-10-06 2023-11-21 Saudi Arabian Oil Company Combined hydrogen and electricity production from aqueous ammonia feed
US11649549B1 (en) 2021-11-11 2023-05-16 Pyrochem Catalyst Company Oxidative reforming and electrolysis system and process for hydrogen generation
US20230183083A1 (en) * 2021-12-14 2023-06-15 Saudi Arabian Oil Company Ammonia production from carbon- and water-derived hydrogen
US11617981B1 (en) 2022-01-03 2023-04-04 Saudi Arabian Oil Company Method for capturing CO2 with assisted vapor compression
WO2023139175A1 (de) * 2022-01-19 2023-07-27 Thyssenkrupp Industrial Solutions Ag AMMONIAKSYNTHESE UND HARNSTOFFSYNTHESE MIT REDUZIERTEM CO2-FUßABDRUCK
BE1030201B1 (de) * 2022-01-19 2023-08-21 Thyssenkrupp Ind Solutions Ag Ammoniaksynthese und Harnstoffsynthese mit reduziertem CO2-Fußabdruck
WO2023139179A1 (de) * 2022-01-19 2023-07-27 Thyssenkrupp Industrial Solutions Ag AMMONIAKSYNTHESE UND HARNSTOFFSYNTHESE MIT REDUZIERTEM CO2-FUßABDRUCK
BE1030199B1 (de) * 2022-01-19 2023-08-21 Thyssenkrupp Ag Ammoniaksynthese und Harnstoffsynthese mit reduziertem CO2-Fußabdruck
BE1030241B1 (de) * 2022-02-03 2023-09-04 Thyssenkrupp Ind Solutions Ag Anlage zur Erzeugung von Ammoniak
GB2619949A (en) * 2022-06-22 2023-12-27 Equinor Energy As Process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103108994A (zh) * 2010-07-21 2013-05-15 日立造船株式会社 氨的合成方法
CN103999277A (zh) * 2011-11-21 2014-08-20 沙特***石油公司 利用石油燃料联合生产氢气和电的方法和***
CN105705462A (zh) * 2013-11-08 2016-06-22 卡萨尔公司 用于生产氨合成气的方法以及用于改造氨设备前端的方法

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4479925A (en) 1982-09-13 1984-10-30 The M. W. Kellogg Company Preparation of ammonia synthesis gas
US4792441A (en) 1988-01-19 1988-12-20 Air Products And Chemicals, Inc. Ammonia synthesis
US6011073A (en) * 1997-10-10 2000-01-04 Syntroleum Corporation System and method for converting light hydrocarbons to heavier hydrocarbons with separation of water into oxygen and hydrogen
EP0999178B1 (en) 1998-11-03 2006-07-26 Ammonia Casale S.A. Process for the production of synthesis gas
US6642398B2 (en) * 1999-06-10 2003-11-04 Warner-Lambert Company Mono-and disubstituted 3-propyl gamma-aminobutyric acids
DE10055818A1 (de) * 2000-11-10 2002-05-23 Ammonia Casale Sa Verfahren zum Herstellen von Ammoniak aus einem Stickstoff-Wasserstoff-Gemisch aus Erdgas
CA2357527C (en) 2001-10-01 2009-12-01 Technology Convergence Inc. Methanol recycle stream
EP1403216B1 (en) * 2002-09-26 2011-03-23 Haldor Topsoe A/S Process for the preparation of synthesis gas
US8273139B2 (en) 2003-03-16 2012-09-25 Kellogg Brown & Root Llc Catalytic partial oxidation reforming
BRPI0408349A (pt) 2003-03-18 2006-03-21 Kellogg Brown & Root Inc processos para produzir hidrogênio, para gerar uma corrente elétrica e de hidrotratamento, e, aparelho para preparar singás
KR100514178B1 (ko) 2004-01-17 2005-09-13 한국과학기술연구원 고온 메탄 개질형 하이브리드 수전해 시스템
DE102004014292A1 (de) 2004-03-22 2005-10-20 Lurgi Ag Koproduktion von Methanol und Ammoniak aus Erdgas
US7479468B2 (en) 2004-04-15 2009-01-20 Exxonmobil Chemical Patents Inc. Integrating an air separation unit into an oxygenate-to-olefins reaction system
EP1657409A1 (en) * 2004-11-15 2006-05-17 Elsam A/S A method of and an apparatus for producing electrical power
GB0521534D0 (en) 2005-10-24 2005-11-30 Johnson Matthey Catalysts Metal passivation
US20070256360A1 (en) 2006-05-08 2007-11-08 Alchemix Corporation Method for the gasification of moisture-containing hydrocarbon feedstocks
EP2135841A1 (en) * 2008-06-20 2009-12-23 Ammonia Casale S.A. Process for the production of syngas for ammonia synthesis
EP2166064A1 (en) 2008-09-19 2010-03-24 Siemens Aktiengesellschaft A chemical product providing system and method for providing a chemical product
EP2192082B1 (en) 2008-11-28 2013-07-03 Haldor Topsoe A/S Co-production of methanol and ammonia
DE102009018126B4 (de) 2009-04-09 2022-02-17 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Energieversorgungssystem und Betriebsverfahren
CN101880046A (zh) 2009-05-05 2010-11-10 中村德彦 复合设备
CN101892492A (zh) * 2009-05-19 2010-11-24 无锡尚弗能源科技有限公司 中高压纯水水电解制氢***
BR112012017633B1 (pt) 2010-01-19 2021-10-13 Haldor Topsoe A/S Processo para a produção de gás de síntese a partir de uma carga de alimentação de hidrocarbonetos
FI20105503A (fi) 2010-05-10 2011-11-11 Neste Oil Oyj Menetelmä hiilivetykoostumuksen tuottamiseksi
EP2450449A1 (en) 2010-11-09 2012-05-09 Ineos Commercial Services UK Limited Process and apparatus for the production of alcohols
WO2012084135A1 (en) 2010-12-22 2012-06-28 Haldor Topsøe A/S Process for reforming hydrocarbon
FR2971789B1 (fr) 2011-02-22 2013-02-22 Areva Methode de production de methanol ou d'hydrocarbures a partir d'une matiere carbonee, avec une etape de reformage dont les conditions de fontionnement sont ajustees selectivement
BR112013033570A2 (pt) 2011-06-29 2017-12-19 Haldor Topsoe As processo para a reforma de hidrocarbonetos
EP2589574B1 (en) 2011-11-02 2015-10-21 Casale Sa Method for load regulation of an ammonia plant
CA2860386C (en) 2012-01-04 2020-04-28 Haldor Topsoe A/S Co-production of methanol and urea
EP2631213A1 (en) * 2012-02-24 2013-08-28 Ammonia Casale S.A. Process for producing ammonia synthesis gas and a related front-end of an ammonia plant
EP2676924A1 (en) 2012-06-21 2013-12-25 Haldor Topsoe A/S Process for Reforming Hydrocarbons
US9296671B2 (en) 2013-04-26 2016-03-29 Praxair Technology, Inc. Method and system for producing methanol using an integrated oxygen transport membrane based reforming system
EP2805914B1 (en) 2013-05-23 2017-09-13 Haldor Topsøe A/S A process for co-production of ammonia, urea and methanol
KR102349885B1 (ko) * 2013-12-12 2022-01-11 할도르 토프쉐 에이/에스 합성가스의 제조방법
US20150203359A1 (en) * 2014-01-17 2015-07-23 Air Products And Chemicals, Inc. System and Process for Producing Ammonia Using an Ion Transport Membrane, Gasifier, and Ammonia Synthesis Unit
EA034392B1 (ru) 2014-02-28 2020-02-03 Хальдор Топсёэ А/С Способ получения синтез-газа
WO2016008820A1 (en) 2014-07-18 2016-01-21 Haldor Topsøe A/S A pseudo-isothermal reactor
US20160115405A1 (en) 2014-10-24 2016-04-28 Pioneer Astronautics Organic Fuel and Waste Reformer
PL3271061T3 (pl) * 2015-03-17 2021-04-06 Lummus Technology Llc Sposoby i układy utleniającego sprzęgania metanu
GB2545474A (en) 2015-12-17 2017-06-21 Avocet Infinite Plc Integrated system and method for producing methanol product
AU2018305876B2 (en) 2017-07-25 2023-12-14 Haldor Topsøe A/S Method for the preparation of synthesis gas
KR102596324B1 (ko) 2017-07-25 2023-10-31 토프쉐 에이/에스 합성 가스의 제조 방법
PE20200652A1 (es) 2017-07-25 2020-06-11 Haldor Topsoe As Proceso para la co-produccion de metanol y amoniaco
AU2018308860B2 (en) 2017-07-25 2023-04-27 Haldor Topsøe A/S Method for the preparation of synthesis gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103108994A (zh) * 2010-07-21 2013-05-15 日立造船株式会社 氨的合成方法
CN103999277A (zh) * 2011-11-21 2014-08-20 沙特***石油公司 利用石油燃料联合生产氢气和电的方法和***
CN105705462A (zh) * 2013-11-08 2016-06-22 卡萨尔公司 用于生产氨合成气的方法以及用于改造氨设备前端的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
天然气转化生产合成氨尿素的节能减排CO_2新工艺;李琼玖等;《中外能源》;20091215(第12期);39-47 *
煤气化发电储电联产氢、氨、甲醇以及CO_2制干冰作肥料的碳循环工业发展前景;李琼玖等;《化肥设计》;20111225(第06期);4-13 *
王红林 等.化工设计.《化工设计》.2001, *

Also Published As

Publication number Publication date
PE20200524A1 (es) 2020-03-09
KR20200035268A (ko) 2020-04-02
CA3069817A1 (en) 2019-01-31
CN110770162A (zh) 2020-02-07
AU2018308587B2 (en) 2023-12-07
US20200172394A1 (en) 2020-06-04
AU2018308587A1 (en) 2020-01-23
BR112020001494A2 (pt) 2020-07-21
CL2020000156A1 (es) 2020-07-31
WO2019020378A1 (en) 2019-01-31
EP3658491A1 (en) 2020-06-03
IL271940A (en) 2020-02-27
EP3658491B1 (en) 2023-08-30
PL3658491T3 (pl) 2024-02-05
UA127164C2 (uk) 2023-05-24
ZA201908174B (en) 2024-05-30
KR102599461B1 (ko) 2023-11-08
IL271940B2 (en) 2024-04-01
IL271940B1 (en) 2023-12-01
US11840448B2 (en) 2023-12-12

Similar Documents

Publication Publication Date Title
CN110770162B (zh) 制备氨合成气的方法
US11370658B2 (en) Method for the preparation of ammonia synthesis gas
KR102599470B1 (ko) 메탄올과 암모니아의 동시 제조를 위한 과정
RU2343109C2 (ru) Способ получения потока, обогащенного водородом, способ генерирования электрического тока, способ гидроочистки, устройство для получения потока, обогащенного водородом
CN105209373B (zh) 联产氨、尿素和甲醇的方法
US20210253506A1 (en) Process for methanol production
CN110958988A (zh) 用于改善氨合成气装置的效率的方法
US20230339747A1 (en) Syngas stage for chemical synthesis plant
KR20210151776A (ko) 화학 합성 플랜트
CN116761774A (zh) 用于制备合成气的方法
EA040478B1 (ru) Способ получения синтез-газа для производства аммиака
BR112020001487B1 (pt) Método para a preparação de gás de síntese de amônia e uso do método para renovar e/ou aumentar a capacidade de produção de usina de gás de síntese de amônia

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant