RU2018133588A - Окислительное дегидрирование алканов (од) - Google Patents

Окислительное дегидрирование алканов (од) Download PDF

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RU2018133588A
RU2018133588A RU2018133588A RU2018133588A RU2018133588A RU 2018133588 A RU2018133588 A RU 2018133588A RU 2018133588 A RU2018133588 A RU 2018133588A RU 2018133588 A RU2018133588 A RU 2018133588A RU 2018133588 A RU2018133588 A RU 2018133588A
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reactor
downstream
upstream
catalyst
oxidative dehydrogenation
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RU2018133588A
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RU2018133588A3 (ru
RU2730518C2 (ru
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Алауисиус Николас Рене БОС
Гус РОССУМ ВАН
Роналд Ян СХОНЕБЕК
Михал Йоханнес Франсискус Мария ВЕРХАК
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Шелл Интернэшнл Рисерч Маатсхаппий Б.В.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • B01J2208/00221—Plates; Jackets; Cylinders comprising baffles for guiding the flow of the heat exchange medium
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    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00513—Controlling the temperature using inert heat absorbing solids in the bed
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    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
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    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Claims (46)

1. Способ окислительного дегидрирования алкана, содержащего от 2 до 6 атомов углерода, предпочтительно этана или пропана, более предпочтительно этана, до алкена, содержащего от 2 до 6 атомов углерода, предпочтительно этилена или пропилена, более предпочтительно этилена, включающий
подачу исходного газа, содержащего алкан и кислород, во входное отверстие в реакторе, причем реактор содержит корпус реактора, множество реакторных труб, расположенных внутри корпуса реактора, и перфорированную перегородку, которая разделяет внутреннюю часть реактора на расположенный выше по потоку участок и расположенный ниже по потоку участок, при этом множество реакторных труб содержат:
(i) расположенный выше по потоку слой катализатора, расположенный в участке выше по потоку, который содержит катализатор окислительного дегидрирования, содержащий теллур, и
(ii) расположенный ниже по потоку слой катализатора, расположенный в участке ниже по потоку, который содержит катализатор окислительного дегидрирования/удаления кислорода;
приведение в контакт исходного газа с катализатором окислительного дегидрирования в слое катализатора, расположенном выше по потоку, с последующим приведением в контакт с катализатором окислительного дегидрирования/удаления кислорода в слое катализатора, расположенном ниже по потоку с получением выходящего из реактора потока, содержащего алкен; и
подачу охлаждающей жидкости в верхнее пространство корпуса реактора из контура охлаждающей жидкости выше по потоку и подачу охлаждающей жидкости в нижнее пространство корпуса реактора из контура охлаждающей жидкости ниже по потоку.
2. Способ по п. 1, отличающийся тем, что слой катализатора выше по потоку имеет высоту слоя катализатора от 50 до 99% длины реакторной трубы и слой катализатора ниже по потоку имеет высоту слоя катализатора от 1% до 50% длины реакторной трубы.
3. Способ по п. 1 или 2, отличающийся тем, что охлаждающая жидкость выше по потоку подается в верхнее пространство корпуса реактора при температуре от 250°C до 400°C.
4. Способ по любому из пп. 1-3, отличающийся тем, что охлаждающая жидкость ниже по потоку подается в нижнее пространство корпуса реактора при температуре от 120°C до 500°C.
5. Способ по любому из пп. 1-4, отличающийся тем, что поток, выходящий из реактора, содержит не более чем 500 об.м.д. кислорода.
6. Способ по любому из пп. 1-5, отличающийся тем, что катализатор окислительного дегидрирования, содержащий теллур в находящемся выше по потоку слое катализатора, имеет следующую формулу
Mo1VaTebNbcOn,
где:
a, b, c и n представляют собой соотношение молярного количества рассматриваемого элемента к молярному количеству молибдена;
a равно от 0,01 до 1;
b равно от >0 до 1;
c равно от >0 до 1; и
n равно числу, которое определяется валентностью и количеством элементов, отличных от кислорода.
7. Способ по любому из пп. 1-6, отличающийся тем, что катализатор окислительного дегидрирования/удаления кислорода в находящемся ниже по потоку слое катализатора, имеет одну из следующих формул
a) Mo1VaSbbNbcAdOn;
b) Mo1VaSbbNbcOn;
c) Mo1VaSbbAdOn; или
d) Mo1VaSbbOn;
где:
A представляет собой по меньшей мере один металл, выбранный из группы, состоящей из Pt, Pd, Cu, Ag и Fe;
a, b, c, d и n представляют собой соотношение молярного количества рассматриваемого элемента к молярному количеству молибдена;
a равно от 0,01 до 1;
b равно от >0 до 1;
c равно от >0 до 1;
d равно от >0 до 0,3; и
n (для O) равно числу, которое определяется валентностью и количеством элементов, отличных от кислорода.
8. Способ по любому из пп. 1-6, отличающийся тем, что катализатор окислительного дегидрирования/удаления кислорода в находящемся ниже по потоку слое катализатора, имеет следующую формулу
Mo1VaTebNbcAdOn,
где:
A представляет собой по меньшей мере один металл, выбранный из группы, состоящей из Pt, Pd, Cu, Ag и Fe;
a, b, c, d и n представляют собой соотношение молярного количества рассматриваемого элемента к молярному количеству молибдена;
a равно от 0,01 до 1;
b равно от >0 до 1;
c равно от >0 до 1;
d равно от >0 до 0,3; и
n равно числу, которое определяется валентностью и количеством элементов, отличных от кислорода.
9. Реакционная система для окислительного дегидрирования алкана, содержащего от 2 до 6 атомов углерода, предпочтительно этана или пропана, более предпочтительно этана, до алкена, содержащего от 2 до 6 атомов углерода, предпочтительно этилена или пропилена, более предпочтительно этилена, включающая
реактор, который содержит входное отверстие для подачи газа, жидкостно соединеннoе с источником алкана и кислорода, корпус реактора, перфорированную перегородку, которая делит внутреннюю часть реактора на участок выше по потоку и участок ниже по потоку, и множество реакторных труб, расположенных внутри корпуса реактора, содержащего:
(i) находящийся выше по потоку слой катализатора, расположенный в участке выше по потоку, который содержит катализатор окислительного дегидрирования, содержащий теллур, и
(ii) слой катализатора, расположенный в участке ниже по потоку, который содержит катализатор окислительного дегидрирования/удаления кислорода; контур охлаждения выше по потоку, жидкостно соединенный с корпусом реактора выше по потоку;
а также контур охлаждения ниже по потоку, жидкостно соединенный с корпусом реактора ниже по потоку.
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