WO2018002838A1 - An improved process for producing olefins from syngas - Google Patents
An improved process for producing olefins from syngas Download PDFInfo
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- WO2018002838A1 WO2018002838A1 PCT/IB2017/053865 IB2017053865W WO2018002838A1 WO 2018002838 A1 WO2018002838 A1 WO 2018002838A1 IB 2017053865 W IB2017053865 W IB 2017053865W WO 2018002838 A1 WO2018002838 A1 WO 2018002838A1
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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- C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
- C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
- C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
- C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
- C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
- C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
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- C07C43/04—Saturated ethers
- C07C43/043—Dimethyl ether
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- 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
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
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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
- 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
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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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- Y02P30/40—Ethylene production
Definitions
- the present disclosure relates to an improved process for producing olefins from syngas.
- Syngas is generally a mixture of hydrogen (H 2 ), carbon monoxide (CO). However, due to process inefficiency, carbon dioxide (C(3 ⁇ 4) is also produced along with syngas. Syngas can be used in a variety of applications such as production of methanol, production of dimethyl ether (DME), production of olefins, production of ammonia, production of urea, heating, generation of steam and generation of power. Syngas can be produced by utilizing methane or natural gas, liquid fuels or solid fuels such as coal, petcoke, biomass, solid wastes, and the like.
- the ratio of H 2 and CO in syngas varies depending upon the raw materials used and the process or reaction conditions used for producing syngas.
- FIG. 1 depicts a flow-path, illustrating a conventional process for producing olefins from syngas.
- Syngas (1) is first converted into methanol (3), and then methanol is converted into olefins.
- syngas (1) comprising 2: 1 ratio of H 2 and CO is used.
- Syngas (1) is introduced into a water-gas shift reactor/section (50), wherein the proportion of 3 ⁇ 4 can be increased. Since the amount of CO 2 (2) produced during the production of syngas (1) is significant, in order to meet the requirement of 2: 1 ratio of 3 ⁇ 4 and CO, there is a need to separate CO 2 (2) from the syngas (1). Therefore, the syngas (1) from the water-gas shift reactor/section (50) is introduced into a separator (100). After the separation of CO 2 (2), the syngas (1), which is deficient of CO 2 , is introduced into a reactor (200) for producing methanol (3).
- the reaction for producing methanol (3) is depicted herein below:
- Methanol (3) is then introduced into a reactor (300), wherein methanol (3) is dehydrogenated to produce a stream (4) comprising olefins (5), unconverted DME (6) and 3 ⁇ 40 (7) in the reactor (300).
- the stream (4) is further introduced into a separator (400) for separating unconverted DME (6) and H 2 0 (7) from stream (4) to obtain olefins (5).
- the separated H 2 0 (7) and the unconverted DME (6) can be further utilized for producing syngas (1) and olefins (5) respectively.
- syngas with low 3 ⁇ 4 and high CO needs to be converted to syngas comprising 2: 1 ratio of 3 ⁇ 4 and CO. This can be done by water-gas shift, wherein CO is reacted with water to generate H 2 , and CO 2 as a by-product.
- a separate process equipment is required for separating carbon dioxide from syngas. Also, the amount of energy required to separate carbon dioxide from syngas is more due to the presence of a significant amount CO 2 in syngas. This increases the capital expenditure (CAPEX) and operational expenditure (OPEX) of the conventional process for producing olefins.
- syngas comprising 2:1 ratio of 3 ⁇ 4 and CO results in the conversion of syngas to methanol at a particular temperature (in the range of 300°C to 400°C) and pressure (in the range of 60 bar to 90 bar) conditions, thereby requiring a reactor for producing methanol.
- different process equipment like heaters and compressors are required for achieving the specific temperature and pressure conditions in the reactor.
- An object of the present disclosure is to provide a process with reduced generation of C(3 ⁇ 4.
- Yet another object of the present disclosure is to provide a process which can inherently consume less energy along with elimination of equipment/process conditions for the intermediate process.
- Yet another object of the present disclosure is to separate C(3 ⁇ 4 post the DME production to minimize the energy need for separation.
- Still another object of the present disclosure is to efficiently utilize separated streams like CO2, methane, ethane, and propane to produce syngas.
- Another object of the present disclosure is to provide a process for producing olefins with reduced CAPEX and OPEX of the process.
- the present disclosure envisages a process for producing olefins from syngas comprising 3 ⁇ 4, CO and CO2.
- the ratio of 3 ⁇ 4 and CO of the syngas (first stream) is 1: 1.
- the syngas is contacted with at least one first catalyst, at a pre-determined temperature and at a predetermined pressure, to produce an intermediate stream comprising dimethyl ether (DME) and unconverted CO2, H 2 and CO.
- DME dimethyl ether
- the unconverted 3 ⁇ 4 and CO is recycled to a first catalyst section, and a portion of the separated CO2 is recycled for producing the syngas.
- the remaining intermediate stream is further contacted with a second catalyst, at a pre-determined temperature and at a pre-determined pressure, to produce a second stream comprising olefins, H2O, methane, ethane, and propane.
- a second catalyst at a pre-determined temperature and at a pre-determined pressure, to produce a second stream comprising olefins, H2O, methane, ethane, and propane.
- 3 ⁇ 40, methane, ethane, and propane are separated from the second stream to obtain olefins.
- the separated C(3 ⁇ 4, H2O, methane, ethane, and propane are further recycled for producing the syngas.
- the olefins can be at least one of ethylene and propylene.
- the process of the present disclosure reduces the generation of C(3 ⁇ 4.
- the process of the present disclosure also reduces the CAPEX and the OPEX of the entire process.
- Figure 1 depicts a flow-path, illustrating a conventional process for producing olefins
- Figure 2 depicts a flow-path for producing olefins in accordance with the present disclosure.
- Table 1 provides a list the elements of the process of the present disclosure and their respective reference letters:
- Raw material (a) is treated in a gasifier/reformer (R), typically at a temperature in the range of 300°C to 1000°C and at a pressure in the range of 1 kg/cm 2 to 80 kg/cm 2 , to produce a first stream (b), i.e., syngas comprising 3 ⁇ 4, CO and C(3 ⁇ 4 , wherein the ratio of 3 ⁇ 4 and CO in the syngas is 1 :1.
- R gasifier/reformer
- the raw material (a) can be at least one of coal, petcoke, biomass, natural gas or liquid fuels.
- the amount of CO2 produced during the production of syngas is significantly less. Additionally, the one-step dimethyl ether (DME) process of the present disclosure can handle a significant amount of CO2 in the feed, as compared to the conventional methanol process. Therefore, separation of CO2 from syngas (b) in a separate process equipment is obviated at this stage.
- DME dimethyl ether
- the first stream i.e., syngas
- (b) is directly introduced into a DME reactor (D), wherein syngas (b) is contacted with a first catalyst in the DME reactor (D), typically at a temperature in the range of 100°C to 400°C and at a pressure in the range of 1 kg/cm 2 to 60 kg/cm 2 , to produce an intermediate stream (c) comprising dimethyl ether (DME) and unconverted CO2, 3 ⁇ 4 and CO.
- DME dimethyl ether
- CO2 and the unconverted 3 ⁇ 4 and CO can be separated from the intermediate stream (c) with less energy requirement as CO2 concentration is relatively higher. Due to the reduced criticality of the process equipment used for separating CO2 , a simpler separation process equipment can be used.
- the separated portion (g) is introduced into a separator (s) for separating CO2 (h), 3 ⁇ 4 and CO (i).
- the separated CO2 (h) can be recycled for producing syngas, and the separated 3 ⁇ 4 and CO (i) can be recycled to the DME reactor (D).
- the first catalyst includes, but is not limited to, copper oxide, chromium oxide, zinc oxide and aluminium oxide.
- One-step DME process requires 3 ⁇ 4: CO ratio of 1 : 1, which leads to smaller water-gas shift reaction and lower water consumption and CO2 generation. As the portion of CO2 in the syngas is lower, the one-step DME process can handle syngas without removing CO2.
- the intermediate stream (c) is introduced into a reactor (O) and contacted with a second catalyst in the reactor (O), typically at a temperature in the range of 200°C to 600°C and at a pressure in the range of 0.5 kg/cm 2 to 10 kg/cm 2 , to produce a second stream (d) comprising olefins, 3 ⁇ 40, unreacted DME, methane, ethane, and propane.
- the second catalyst includes, but is not limited to, molecular sieve catalysts.
- the second catalyst is at least one selected from the group consisting of salts, aluminophosphate (ALPO) molecular sieves, and silicoaluminophosphate (SAPO) molecular sieves, as well as substituted forms thereof.
- the second catalyst is ZSM-5.
- the second stream (d) is introduced into a fractionation column or a divided wall column (Dw) for separating H2O, unreacted DME, methane, ethane, and propane from the second stream (d) to obtain olefins (e) and a separated stream (f).
- the separated C(3 ⁇ 4, H2O, methane, ethane, and propane can be recycled into the reformer for producing syngas by at least one of dry reforming, bi-reforming, or tri-reforming, wherein syngas with higher 3 ⁇ 4 and CO is produced as compared to gasification.
- Dry reforming of natural gas is depicted herein below:
- the amount of raw materials required for producing syngas (b) is reduced, since the separated methane, ethane and propane are utilized for producing syngas, which is significantly rich in 3 ⁇ 4. Also, the separated unreacted DME can be recycled into the DME reactor (D) for producing the intermediate stream (c).
- a portion of the separated CO2 is recycled into the reformer and a remaining portion of the separated C(3 ⁇ 4 is vented out to the atmosphere.
- the amount of H2O generated in the reactor (O) can be approximately 50% less as compared to that generated conventionally during the production of olefins from syngas comprising 2: 1 ratio of 3 ⁇ 4 and CO.
- the second stream (d) can be introduced into a de-methanation column (not shown in Figure 2) for separating methane contained therein.
- syngas (b) comprising 1: 1 ratio of 3 ⁇ 4 and CO is utilized for producing olefins (e). Due to 1 : 1 ratio of 3 ⁇ 4 and CO: • the amount of raw materials required for producing syngas (b) is reduced, because the separated C(3 ⁇ 4, methane, ethane and propane are utilized for producing syngas which is significantly rich in 3 ⁇ 4;
- the CAPEX is significantly reduced and the OPEX is reduced upto 30%, as compared to that of the conventional process.
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Abstract
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Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018566831A JP2019521119A (en) | 2016-06-29 | 2017-06-28 | Process to improve olefin production from syngas |
| DE112017003296.2T DE112017003296T5 (en) | 2016-06-29 | 2017-06-28 | Improved process for the production of olefins from synthesis gas |
| CA3027836A CA3027836A1 (en) | 2016-06-29 | 2017-06-28 | An improved process for producing olefins from syngas |
| CN201780041410.2A CN109563007A (en) | 2016-06-29 | 2017-06-28 | A kind of improved process with synthesis gas production alkene |
| KR1020197000211A KR20190033055A (en) | 2016-06-29 | 2017-06-28 | Improved process for producing olefins from syngas |
| US16/314,177 US10800716B2 (en) | 2016-06-29 | 2017-06-28 | Process for producing olefins from syngas |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN201621022322 | 2016-06-29 | ||
| IN201621022322 | 2016-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018002838A1 true WO2018002838A1 (en) | 2018-01-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2017/053865 Ceased WO2018002838A1 (en) | 2016-06-29 | 2017-06-28 | An improved process for producing olefins from syngas |
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| Country | Link |
|---|---|
| US (1) | US10800716B2 (en) |
| JP (1) | JP2019521119A (en) |
| KR (1) | KR20190033055A (en) |
| CN (1) | CN109563007A (en) |
| CA (1) | CA3027836A1 (en) |
| DE (1) | DE112017003296T5 (en) |
| WO (1) | WO2018002838A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022259020A1 (en) * | 2021-06-08 | 2022-12-15 | Stryker European Operations Limited | Surgical guiding system for computer-assisted-surgery cas |
| US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
| US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
| US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
| US12258272B2 (en) | 2021-08-12 | 2025-03-25 | Saudi Arabian Oil Company | Dry reforming of methane using a nickel-based bi-metallic catalyst |
| US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008101403A1 (en) * | 2007-02-07 | 2008-08-28 | China Petroleum & Chemical Corporation | A method for increasing yields of ethylene and propene in mto process |
| WO2009130292A2 (en) * | 2008-04-24 | 2009-10-29 | Shell Internationale Research Maatschappij B.V. | Process to prepare an olefin-containing product or a gasoline product |
| US20130197288A1 (en) * | 2012-01-31 | 2013-08-01 | Linde Ag | Process for the conversion of synthesis gas to olefins |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3447494B2 (en) * | 1996-12-26 | 2003-09-16 | ジェイエフイーホールディングス株式会社 | Method for producing dimethyl ether |
| US7592496B2 (en) * | 2005-12-30 | 2009-09-22 | Uop Llc | Light olefin production via dimethyl ether |
| AU2009331847B2 (en) * | 2008-12-22 | 2012-06-07 | Air Products And Chemicals, Inc. | Process to prepare methanol and/or dimethylether |
| CN103402632A (en) * | 2010-11-02 | 2013-11-20 | 沙特基础工业公司 | Method for producing light olefins by using ZSM-5-based catalyst |
| CA2863285A1 (en) * | 2012-01-31 | 2013-08-08 | Basf Se | Process for the conversion of synthesis gas to olefins |
| CN106132511A (en) * | 2014-02-04 | 2016-11-16 | 林德股份公司 | Process for the preparation of higher molecular weight compounds from synthesis gas using indirectly heated CO2‑TSA |
-
2017
- 2017-06-28 CN CN201780041410.2A patent/CN109563007A/en active Pending
- 2017-06-28 US US16/314,177 patent/US10800716B2/en active Active
- 2017-06-28 DE DE112017003296.2T patent/DE112017003296T5/en not_active Withdrawn
- 2017-06-28 JP JP2018566831A patent/JP2019521119A/en active Pending
- 2017-06-28 CA CA3027836A patent/CA3027836A1/en not_active Abandoned
- 2017-06-28 WO PCT/IB2017/053865 patent/WO2018002838A1/en not_active Ceased
- 2017-06-28 KR KR1020197000211A patent/KR20190033055A/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008101403A1 (en) * | 2007-02-07 | 2008-08-28 | China Petroleum & Chemical Corporation | A method for increasing yields of ethylene and propene in mto process |
| WO2009130292A2 (en) * | 2008-04-24 | 2009-10-29 | Shell Internationale Research Maatschappij B.V. | Process to prepare an olefin-containing product or a gasoline product |
| US20130197288A1 (en) * | 2012-01-31 | 2013-08-01 | Linde Ag | Process for the conversion of synthesis gas to olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190284108A1 (en) | 2019-09-19 |
| DE112017003296T5 (en) | 2019-03-14 |
| JP2019521119A (en) | 2019-07-25 |
| US10800716B2 (en) | 2020-10-13 |
| CA3027836A1 (en) | 2018-01-04 |
| CN109563007A (en) | 2019-04-02 |
| KR20190033055A (en) | 2019-03-28 |
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