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RU2002114828A - Модернизация установки по выпуску метанола для производства уксусной кислоты - Google Patents

Модернизация установки по выпуску метанола для производства уксусной кислоты

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Publication number
RU2002114828A
RU2002114828A RU2002114828/04A RU2002114828A RU2002114828A RU 2002114828 A RU2002114828 A RU 2002114828A RU 2002114828/04 A RU2002114828/04 A RU 2002114828/04A RU 2002114828 A RU2002114828 A RU 2002114828A RU 2002114828 A RU2002114828 A RU 2002114828A
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RU
Russia
Prior art keywords
stream
methanol
hydrogen
carbon dioxide
synthesis gas
Prior art date
Application number
RU2002114828/04A
Other languages
English (en)
Other versions
RU2250894C2 (ru
Inventor
Даниэль Марсель ТИБО (FR)
Даниэль Марсель ТИБО
Кеннет Эбеннес ВИДАЛИН (CA)
Кеннет Эбеннес ВИДАЛИН
Original Assignee
Асетэкс (Кипр) Лимитед (Cy)
Асетэкс (Кипр) Лимитед
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27028819&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=RU2002114828(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US09/430,888 external-priority patent/US6274096B1/en
Application filed by Асетэкс (Кипр) Лимитед (Cy), Асетэкс (Кипр) Лимитед filed Critical Асетэкс (Кипр) Лимитед (Cy)
Publication of RU2002114828A publication Critical patent/RU2002114828A/ru
Application granted granted Critical
Publication of RU2250894C2 publication Critical patent/RU2250894C2/ru

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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    • C01—INORGANIC CHEMISTRY
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
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    • 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
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    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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    • 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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    • 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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    • 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
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    • F25J3/0261—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
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    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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    • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
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    • F25J3/04563—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating
    • F25J3/04587—Integration with a nitrogen consuming unit, e.g. for purging, inerting, cooling or heating for the NH3 synthesis, e.g. for adjusting the H2/N2 ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (40)

1. Способ модернизации установки по получению метанола, включающий следующие стадии: устанавливают сепаратор диоксида углерода, монооксида углерода и водорода в соединение с исходной установкой по выпуску метанола, включающей (1) по крайней мере одну установку реформинга для превращения углеводорода в поток синтез-газа, содержащий диоксид углерода, монооксид углерода и водород, и (2) контур синтеза метанола для превращения водорода и монооксида углерода из потока синтез-газа в метанол; устанавливают линию для отвода по крайней мере части потока синтез-газа в сепаратор для разделения всего или части потока синтез-газа на соответствующие потоки с повышенным содержанием диоксида углерода, монооксида углерода и водорода; переналаживают исходную установку по выпуску метанола для подачи по крайней мере части потока с повышенным содержанием диоксида углерода в установку реформинга, в контур синтеза метанола или их сочетание; переналаживают контур синтеза мтанола для работы с уменьшенной производительностью по сравнению с исходной установкой по выпуску метанола; и устанавливают реактор для проведения реакции по крайней мере части потока с повышенным содержанием диоксида углерода из сепаратора с метанолом из контура синтеза метанола с образованием продукта, выбранного из группы, состоящей из уксусной кислоты, уксусного ангидрида, метилформиата, метилацетата и их комбинаций.
2. Способ по п.1, согласно которому контур синтеза метанола эксплуатируется с использованием сырьевого потока, включающего (1) диоксид углерода и (2) часть потока с повышенным содержанием водорода из сепаратора.
3. Способ по п.2, согласно которому сырье, поступающее в контур синтеза метанола, включает подаваемый извне диоксид углерода.
4. Способ по п.2 или 3, согласно которому сырье, поступающее в контур синтеза метанола, включает часть синтез-газа.
5. Способ по п.2 или 3, согласно которому весь поток синтез-газа поступает на стадию разделения в сепараторе.
6. Способ по любому из пп.1-5, согласно которому величина потока с повышенным содержанием водорода превышает стехиометрическую потребность в водороде для контура синтеза метанола.
7. Способ по любому из пп.1-6, согласно которому весь поток с повышенным содержанием диоксида углерода поступает в контур синтеза метанола.
8. Способ по любому из пп.1-6, согласно которому весь поток с повышенным содержанием монооксида углерода поступает в реактор.
9. Способ по любому из пп.1-4 и 6-8, согласно которому
большая часть потока синтез-газа поступает в сепаратор, и
контур синтеза метанола функционирует с использованием сырьевого потока, включающего поток с повышенным содержанием диоксида углерода из сепаратора, небольшой части потока синтез-газа и дополнительного источника диоксида углерода для образования потока метанола.
10. Способ по любому из пп.1-4 и 6-9, согласно которому
контур синтеза метанола функционирует с использованием сырьевого потока, включающего поток с повышенным содержанием диоксида углерода из сепаратора, небольшой части потока синтез-газа и диоксида углерода из дополнительного источника.
11. Способ получения продукта, согласно которому: осуществляют реформинг углеводорода водяным паром с образованием синтез-газа, содержащего водород, монооксид углерода и диоксид углерода; осуществляют рекуперацию тепла синтез-газа с образованием охлажденного потока синтез-газа; осуществляют сжатие охлажденного потока синтез-газа до давления, необходимого для разделения; осуществляют обработку синтез-газа в сепараторе для отделения потока с повышенным содержанием монооксида углерода от водорода и диоксида углерода; приводят в действие контур синтеза метанола для проведения реакции первой части водорода из сепаратора с сырьевым потоком, включающим большую часть диоксида углерода и, по выбору, небольшую часть монооксида углерода для получения потока метанола, причем диоксид углерода подается из сепаратора и из другого источника; проводят реакцию потока с повышенным содержанием монооксида углерода из сепаратора с потоком метанола из контура синтеза метанола в стехиометрическом соотношении с образованием продукта, выбранного из группы, состоящей из уксусной кислоты, уксусного ангидрида, метилформиата, метилацетата и их комбинаций.
12. Способ модернизации установки по выпуску метанола, включающий следующие стадии: устанавливают сепаратор монооксида углерода и водорода в соединение с исходной установкой по выпуску метанола, включающей (1) по крайней мере одну установку парового реформинга для превращения углеводорода в поток синтез-газа, содержащий водород и монооксид углерода, (2) секцию рекуперации тепла для охлаждения потока синтез-газа, (3) компрессорное устройство для сжатия потока синтез-газа, и (4) контур синтеза метанола для превращения по крайней мере части водорода и монооксида углерода в потоке синтез-газа в метанол при сохранении исходной производительности по метанолу; устанавливают линию для отвода части потока синтез-газа после по крайней мере одной установки реформинга в сепаратор для разделения отведенного синтез-газа на по крайней мере поток с повышенным содержанием монооксида углерода и поток с повышенным содержанием водорода, в котором количество водорода в потоке с повышенным содержанием водорода превышает общую производительность по водороду исходной установки по выпуску метанола; переналаживают контур синтеза метанола для эксплуатации с использованием сырьевого потока, включающего оставшуюся часть потока синтез-газа, для производства метанола с уменьшенной производительностью по сравнению с исходной производительностью по метанолу; устанавливают реактор для проведения реакции потока с повышенным содержанием монооксида углерода из сепаратора с метанолом из контура синтеза метанола с образованием продукта, выбранного из группы, состоящей из уксусной кислоты, уксусного ангидрида, метилформиата, метилацетата и их комбинаций, в котором количество отбираемого потока синтез-газа балансируют для обеспечения стехиометрического превращения в продукт при производстве метанола из контура синтеза метанола и потока с повышенным содержанием монооксида углерода из сепаратора.
13. Способ по п.12, согласно которому дополнительно модифицируют по крайней мере одну установку парового реформинга для обеспечения увеличения производства монооксида углерода в потоке синтез-газа.
14. Способ по любому из пп.1-6, 8 или 12-13, согласно которому поток синтез-газа включает диоксид углерода, по крайней мере одна установка парового реформинга представляет собой установку каталитического парового реформинга, сепаратор вырабатывает поток с повышенным содержанием диоксида углерода, и по крайней мере часть потока с повышенным содержанием диоксида углерода рециркулируют на по крайней мере одну установку парового реформинга для увеличения производства монооксида углерода.
15. Способ по п.14, согласно которому поток синтез-газа исходной установки характеризуется величиной молярного соотношения R=((Н2-СО2)/(СО+СО2)) менее 2,0 или более 2,9, а модернизированная установка характеризуется величиной соотношения R от 2,0 до 2.9.
16. Способ по п.14 или 15, согласно которому рециркулирование потока с повышенным содержанием диоксида углерода из сепаратора на по крайней мере одну модифицированную установку парового реформинга увеличивает образование монооксида углерода по сравнению с исходной установкой по выпуску метанола и повышает молярное соотношение монооксида углерода к водороду.
17. Способ по п.13, согласно которому модификация установки парового реформинга произведена с целью обеспечения возможности работы этой установки при повышенной температуре.
18. Изобретение по любому из пп.1-17, согласно которому сепаратор включает абсорбер на основе растворителей и десорбер для извлечения диоксида углерода, а также установку криогенной дистилляции для извлечения монооксида углерода и водорода.
19. Способ по п.12 или 13, согласно которому компрессорное устройство включает трехступенчатый компрессор, и отвод потока синтез-газа происходит между второй и третьей ступенями сжатия.
20. Способ по п.19, согласно которому дополнительно модифицируют третью ступень компрессора для обеспечения его функционирования с меньшей производительностью по сравнению с исходной установкой по выпуску метанола.
21. Способ по п.12, 13, 17, 19 или 20, согласно которому контур синтеза метанола исходной установки по выпуску метанола включает компрессор контура рециркуляции, причем этот компрессор контура рециркуляции модифицирован для обеспечения функционирования с меньшей производительностью.
22. Способ по любому из пп.1-21, согласно которому дополнительно включают стадию взаимодействия водорода в потоке с повышенным содержанием водорода с азотом для получения аммиака.
23. Способ по любому из пп.1-10 и 12-20, согласно которому в исходной установке по выпуску метанола, в которой для получения аммиака приводили во взаимодействие с азотом поток с повышенным содержанием водорода, включающий продувочный поток из контура синтеза метанола, после ее модернизации в качестве основного источника водорода для производства аммиака используют поток с повышенным содержанием водорода из сепаратора.
24. Способ по п.23, согласно которому модернизированная установка обеспечивает производство дополнительного количества аммиака по сравнению с исходной установкой по выпуску метанола.
25. Способ по п.24, согласно которому конечный продукт содержит уксусную кислоту, при этом дополнительно устанавливают устройство по получению мономера винилацетата, в котором проводят реакцию части уксусной кислоты с этиленом и кислородом для получения мономера винилацетата.
26. Способ по п.25, согласно которому с целью получения кислорода для устройства по получению мономера винилацетата дополнительно устанавливают устройство разделения воздуха, причем количество азота, вырабатываемого устройством разделения воздуха, соответствует потребности в азоте для производства добавочного количества аммиака.
27. Способ получения водорода и продукта, выбираемого из группы, состоящей из уксусной кислоты, уксусного ангидрида, метилформиата, метилацетата и их комбинаций, из углеводорода через метанол и монооксид углерода, включающий следующие стадии: осуществляют каталитический реформинг углеводорода водяным паром в присутствии относительно небольшого количества диоксид углерода с образованием синтез-газа, содержащего водород, монооксид углерода и диоксид углерода, в котором синтез-газ характеризуется величиной молярного соотношения R=((Н2-СО2)/(СО+СО2)) от 2,0 до 2,9; осуществляют рекуперацию тепла синтез-газа с образованием охлажденного потока синтез-газа; осуществляют сжатие охлажденного потока синтез-газа до давления, необходимого для разделения; осуществляют отведение большей части сжатого синтез-газа в сепаратор; осуществляют разделение синтез-газа, отведенного в сепаратор, на поток с повышенным содержанием диоксида углерода, поток с повышенным содержанием монооксида углерода и поток с повышенным содержанием водорода; осуществляют рециркуляцию потока с повышенным содержанием диоксида углерода на стадию реформинга; осуществляют дополнительное сжатие оставшейся относительно небольшой части синтез-газа до давления, необходимого для синтеза метанола, превышающего величину давления, необходимого для разделения; приводят в действие контур синтеза метанола для превращения водорода, монооксида углерода и диоксида углерода в дополнительно сжатом синтез-газе в поток метанола; проводят взаимодействие потока с повышенным содержанием монооксида углерода из сепаратора с потоком метанола из контура синтеза метанола с образованием продукта, выбранного из группы, состоящей их уксусной кислоты, уксусного ангидрида, метилформиата, метилацетата и их комбинаций, при этом стадия отвода балансируется таким образом, чтобы получить приблизительно стехиометрические количества монооксида углерода и метанола.
28. Способ по п.27, согласно которому контур синтеза метанола эксплуатируется с производительностью, меньшей полной максимальной производительности всех реакторов синтеза метанола в указанном контуре.
29. Способ по п.27 или 28, согласно которому дополнительно проводят реакцию водорода в потоке с повышенным содержанием водорода с азотом в реакторе синтеза аммиака для получения аммиака.
30. Способ по п.29, согласно которому дополнительно осуществляют стадию разделения воздуха на поток азота и поток кислорода и подачу потока азота в реактор синтеза аммиака.
31. Способ по п.30, согласно которому конечный продукт включает уксусную кислоту или продукт уксусной кислоты предшествующей стадии реакции, который превращают в уксусную кислоту, при этом дополнительно подают поток кислорода из устройства разделения воздуха в реактор синтеза винилацетата вместе с частью уксусной кислоты со стадии реакции монооксида углерода и метанола и этиленом для производства потока мономера винилацетата.
32. Способ по п.27, согласно которому молярное соотношение диоксида углерода к природному газу, содержащему углеводород, в сырьевом потоке для проведения стадии реформинга составляет от 0,1 до 0,5.
33. Способ по любому из пп.1-32, согласно которому конечный продукт включает уксусную кислоту, а стадия реакции включает проведение реакции метанола, метилформиата или их комбинации в присутствии реакционной смеси, включающей монооксид углерода, воду, растворитель и каталитическую систему, включающую по крайней мере один галогенированный промотор и по крайней мере одно соединение родия, иридия или их комбинацию.
34. Способ по п.33, согласно которому реакционная смесь имеет содержание воды до 20 массовых процентов.
35. Способ по п.34, согласно которому стадия реакции включает простое карбонилирование, а содержание воды в реакционной смеси составляет от 14 до 15 массовых процентов.
36. Способ по п.34, согласно которому стадия реакции включает карбонилирование при пониженном содержании воды, а содержание воды в реакционной смеси составляет от 2 до 8 массовых процента.
37. Способ по п.34, согласно которому стадия реакции включает изомеризацию метилформиата или сочетание указанной изомеризации и карбонилирования метанола, а реакционная смесь содержит ненулевое количество воды, не превышающее 2 массовых процентов.
38. Способ по п.34, согласно которому стадия реакции осуществляется в непрерывном режиме.
39. Способ по любому из пп.1-32, согласно которому стадия реакции включает промежуточное образование метилформиата и изомеризацию метилформиата до уксусной кислоты.
40. Способ по любому из пп.1-32, согласно которому стадия реакции включает промежуточную реакцию СО с двумя молями метилового спирта с образованием метилацетата и гидролиз метилацетата до уксусной кислоты и метанола.
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