Patent · US6566573B1 · B1 · US

Autothermal process for the production of olefins

(11) Publication number

US6566573B1

(21) Application number

09/388,219

(22) Filing date

1999-09-01

(30) Priority date

1998-09-03

(43) Publication date

2003-05-20

(45) Date of grant

2003-05-20

(51) IPC

B01J 23/40; B01J 23/54; B01J 23/56; B01J 23/62; B01J 23/644; B01J 23/70; B01J 23/755; B01J 23/76; B01J 23/89; B01J 23/96; B01J 37/02; B01J 37/16; C07B 61/00; C07C 11/04; C07C 11/06; C07C 11/09; C07C 11/167; C07C 4/06; C07C 5/48; C10G 11/02; C10G 11/22; C10G 27/04

(52) CPC

C07C Acyclic or carbocyclic compounds: 5/48, 2521/02, 2521/04, 2521/06, 2521/08, 2521/10, 2521/12, 2521/14, 2523/04, 2523/08, 2523/14, 2523/18, 2523/42, 2523/44, 2523/50, 2523/72, 2527/224, 5/00
B01J Chemical or physical processes, e.g. catalysis or colloid chemistry; their relevant apparatus: 21/04, 21/10, 23/40, 23/54, 23/56, 23/626, 23/6445, 23/70, 23/76, 23/8926, 23/8966, 23/96, 35/56, 35/58, 37/0201, 37/0207, 37/0238, 37/18
C10G Cracking hydrocarbon oils; production of liquid hydrocarbon mixtures, e.g. by destructive hydrogenation, oligomerisation, polymerisation; recovery of hydrocarbon oils from oil-shale, oil-sand, or gases; refining mixtures mainly consisting of hydrocarbons; reforming of naphtha; mineral waxes: 2400/20
Y02P Climate change mitigation technologies in the production or processing of goods: 20/52, 20/584
Y10S Technical subjects covered by former uspc cross-reference art collections [xracs] and digests: 502/514

(73) Assignee

Dow Global Technologies LLC

(72) Inventors

Sameer S. Bharadwaj; Joseph J. Maj; Jonathan H. Siddall; Mark D. Bearden; Craig B. Murchison; Gerald E. Lazaruk

(54) Title

Autothermal process for the production of olefins

(57) Abstract

A process and catalyst for the partial oxidation of paraffinic hydrocarbons, such as ethane, propane, naphtha, and natural gas condensates, to olefins, such as ethylene and propylene. The process involves contacting a paraffinic hydrocarbon with oxygen in the presence of hydrogen and a catalyst under autothermal process conditions. Preheating the feed decreases oxygen consumption and increases the net hydrogen balance. The catalyst comprises a Group 8B metal, preferably, a platinum group metal, and at least one promoter selected from Groups 1B, 6B, 3A, 4A, and 5A, optionally supported on a catalytic support, such as magnesia or alumina. In preferred embodiments, the support is pretreated with a support modifier selected from Groups 1A, 2A, 3B, 4B, 5B, 6B, 1B, 3A, 4A, 5A, the rare earth lanthanides, and the actinides. A modified fluidized bed reactor is disclosed for the process.

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Claims (43)

A process of preparing an olefin comprising contacting a paraffinic hydrocarbon or a mixture of paraffinic hydrocarbons, said paraffinic hydrocarbon having from 2 to about 25 carbon atoms, with oxygen in the presence of hydrogen and a catalyst, the contacting being conducted in a reactor under autothermal process conditions sufficient to prepare a product stream containing the olefin, the catalyst comprising a platinum group metal and a least one promoter wherein the process is conducted at a temperature greater than 750° C. and less than 1,150° C.
The process of claim 1 wherein the paraffinic hydrocarbon comprises ethane, propane, or mixtures thereof.
The process of claim 1 wherein the paraffinic hydrocarbon is selected from the group consisting of naphtha, natural gas condensate, gas oils, vacuum gas oils, and mixtures thereof.
The process of claim 1 wherein the molar ratio of paraffinic hydrocarbon to oxygen is greater than the molar ratio of the fuel-rich, upper flammability limit.
The process of claim 1 wherein the molar ratio of paraffinic hydrocarbon to oxygen ranges from about 3 to about 77 times the stoichiometric ratio of hydrocarbon to oxygen for complete combustion to carbon dioxide and water.
The process of claim 1 wherein the molar ratio of paraffinic hydrocarbon to oxygen is greater than 0.1:1 and less than 4.0:1.
The process of claim 1 wherein the contacting is further carried out in the presence of a diluent.
The process of claim 7 wherein the diluent is selected from the group consisting of nitrogen, argon, helium, carbon dioxide, carbon monoxide, methane, and steam.
The process of claim 7 wherein the diluent is used in an amount greater than 0.1 mole percent and less than 70 mole percent, based on the total reactant feed including paraffin, oxygen, hydrogen, and diluent.
The process of claim 1 wherein the molar ratio of hydrogen to oxygen ranges from greater than 0.1:1 to less than 4.0:1.
The process of claim 1 wherein the platinum group metal is platinum.
The process of claim 1 wherein the catalyst further comprises a ceramic support.
The process of claim 12 wherein the ceramic support is selected from the group consisting of silica, alumina, silica-aluminas, aluminosilicates, magnesia, magnesium aluminates, magnesium silicates, zirconia, titania, boria, zirconia toughened alumina, lithium aluminum silicates, silicon carbide, and oxide-bonded silicon carbide.
The process of claim 13 wherein the ceramic support comprises from 65 to 100 weight percent alpha alumina or gamma alumina.
The process of claim 13 wherein the ceramic support is a monolith.
The process of claim 15 wherein the monolith is a foam having from 5 to 100 pores per linear inch (2 to 40 pores per linear cm) and a surface area greater than 0.001 m 2 /g and less than 10 m 2 /g.
The process of claim 15 wherein the monolith is a fiber having a diameter greater than 1 micron and less than 20 microns, and a surface area greater than 0.001 m 2 /g and less than 1 m 2 /g.
The process of claim 17 wherein the fiber monolith is a fiber mat.
The process of claim 1 wherein the catalyst is in a form of particles having a size between 30 and 1,000 microns.
The process of claim 1 wherein the promoter is selected from the group consisting of the elements of Groups 1B, 6B, 3A, 4A, and 5A of the Periodic Table and mixtures of the aforementioned elements.
The process of claim 1 wherein the promoter is selected from the group consisting of tin, antimony, copper, silver, indium, and mixtures thereof.
The process of claim 1 wherein the atomic ratio of platinum group metal to promoter ranges from greater than 1:10 to less than 1:0.5.
The process of claim 1 wherein the catalyst is a metallic gauze.
The process of claim 1 wherein the paraffinic hydrocarbon and oxygen are preheated at a temperature greater than 40° C. and less than the temperature wherein reaction of the paraffinic hydrocarbon and oxygen occurs.
The process of claim 24 wherein the paraffinic hydrocarbon and oxygen are preheated at a temperature greater than 200° C. and less than 900° C.
The process of claim 25 wherein the paraffinic hydrocarbon to oxygen molar ratio is greater than 1.5:1 and less than 4.0:1.
The process of claim 25 wherein the hydrogen to oxygen molar ratio is greater than 1.5:1 and less than 4.0:1.
The process of claim 1 wherein the process is conducted at a pressure equal to or greater than 1 atm abs (100 kPa abs) and less than 20 atm abs (2,000 kPa abs).
The process of claim 1 wherein the process is conducted at a gas hourly space velocity greater than 50,000 h −1 and less than 6,000,000 h −1.
The process of claim 1 wherein the process is conducted in fixed bed or fluidized bed reactor.
The process of claim 30 wherein the fluidized bed reactor possesses an aspect ratio less than 1:1 during operation.
The process of claim 31 wherein the fluidized bed reactor possesses an aspect ratio less than 1:1 in static mode.
The process of claim 1 wherein the olefin is converted from said paraffinic hydrocarbon or mixture of paraffinic hydrocarbons at greater than 50 mole percent.
The process of claim 1 wherein the percentage of carbon atoms in the paraffinic hydrocarbon or mixture of paraffinic hydrocarbons which react to form an olefin is greater than 70 carbon atom percent.
The process of claim 1 wherein hydrogen in said product stream is recycled to the reactor.
The process of claim 1 wherein methane, carbon monoxide, and/or carbon dioxide in said product stream are recycled at least in part to the reactor.
The process of claim 1 wherein the paraffinic hydrocarbon is ethane and the contacting is conducted under autothermal conditions at an ethane to oxygen molar ratio greater than 1.5:1 and less than 4.0:1, a hydrogen to oxygen molar ratio greater than 1.5:1 and less than 4.0:1, a gas hourly space velocity greater than 80,000 h −1 and less than 6,000,000 h −1, wherein optionally a diluent is used in an amount greater than 1 mole percent and less than about 70 mole percent based on the total reactant feed, wherein the platinum group metal is platinum, and the platinum group metal and promoter are supported on a magnesia or alumina ceramic support.
The process of claim 37 wherein the ethane and oxygen feed are preheated at a temperature in the range from 400° C. to 600° C.
The process of claim 37 wherein the process is conducted in a fluidized bed reactor having an aspect ratio less than 1:1 during operation.
The process of claim 39 wherein the catalyst has a particle size ranging between 500 and 850 microns.
The process of claim 37 wherein the platinum group metal and the promoter are supported on a catalyst support which is a fiber, a foam monolith, or a pellet.
A process for preparing an olefin comprising contacting a paraffinic hydrocarbon or a mixture of paraffinic hydrocarbons, said paraffinic hydrocarbon having from 2 to about 25 carbon atoms, with oxygen in the presence of hydrogen and a catalyst, the contacting being conducted in a reactor under autothermal process conditions sufficient to prepare a product stream containing the olefin, the catalyst comprising a platinum group metal and at least one promoter, wherein the catalyst is prepared by a process comprising pretreating a catalyst support with a support modifier, depositing the platinum group metal and at least one promoter onto the pretreated support, optionally calcining the support, and thereafter reducing the metal-loaded support.
The process of claim 42 wherein the catalytic support is pretreated with a support modifier selected from the group consisting of Groups 1A, 2A, 3B, 4B, 5B, 6B, 1B, 3A, 4A, 5A, the rare earth lanthanide, and the elements of the Periodic Table.

Description

The present invention relates to the field of catalytic oxidation of hydrocarbons. More particularly, the present invention relates to the catalytic partial oxidation of paraffinic hydrocarbons, such as ethane, propane, and naphtha, to produce olefins, such as ethylene and propylene.

Olefins find widespread utility in industrial organic chemistry. Ethylene is needed for the preparation of important polymers, such as polyethylene, vinyl plastics, and ethylene-propylene rubbers, and important basic chemicals, such as ethylene oxide, styrene, acetaldehyde, ethyl acetate, and dichloroethane. Propylene is needed for the preparation of polypropylene plastics, ethylene-propylene rubbers, and important basic chemicals, such as propylene oxide, cumene, and acrolein. Isobutylene is needed for the preparation of methyl tertiary butyl ether. Long chain mono-olefins find utility in the manufacture of linear alkylated benzene sulfonates, which are used in the detergent industry.

Low molecular weight olefins, such as ethylene, propylene, and butylene, are produced almost exclusively by thermal cracking (pyrolysis/steam cracking) of alkanes at elevated temperatures. An ethylene plant, for example, typically achieves an ethylene selectivity of about 85 percent calculated on a carbon atom basis at an ethane conversion of about 60 mole percent. Undesired coproducts are recycled on the shell side of the cracking furnace to be burned, so as to produce the heat necessary for the process. Disadvantageously, thermal cracking processes for olefin production are highly endothermic.

Citations (39)

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EP0178853A2
US4652687A
US4897253A
US4886932A
US4788371A
EP0332289A2
US5105052A
US4940826A
US4886926A
US4886928A
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US4902849A
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Record as JSON

{
  "publication_number": "US6566573B1",
  "country": "US",
  "kind": "B1",
  "title": "Autothermal process for the production of olefins",
  "abstract": "A process and catalyst for the partial oxidation of paraffinic hydrocarbons, such as ethane, propane, naphtha, and natural gas condensates, to olefins, such as ethylene and propylene. The process involves contacting a paraffinic hydrocarbon with oxygen in the presence of hydrogen and a catalyst under autothermal process conditions. Preheating the feed decreases oxygen consumption and increases the net hydrogen balance. The catalyst comprises a Group 8B metal, preferably, a platinum group metal, and at least one promoter selected from Groups 1B, 6B, 3A, 4A, and 5A, optionally supported on a catalytic support, such as magnesia or alumina. In preferred embodiments, the support is pretreated with a support modifier selected from Groups 1A, 2A, 3B, 4B, 5B, 6B, 1B, 3A, 4A, 5A, the rare earth lanthanides, and the actinides. A modified fluidized bed reactor is disclosed for the process.",
  "claims": [
    "1. A process of preparing an olefin comprising contacting a paraffinic hydrocarbon or a mixture of paraffinic hydrocarbons, said paraffinic hydrocarbon having from 2 to about 25 carbon atoms, with oxygen in the presence of hydrogen and a catalyst, the contacting being conducted in a reactor under autothermal process conditions sufficient to prepare a product stream containing the olefin, the catalyst comprising a platinum group metal and a least one promoter wherein the process is conducted at a temperature greater than 750° C. and less than 1,150° C.",
    "2. The process of claim 1 wherein the paraffinic hydrocarbon comprises ethane, propane, or mixtures thereof.",
    "3. The process of claim 1 wherein the paraffinic hydrocarbon is selected from the group consisting of naphtha, natural gas condensate, gas oils, vacuum gas oils, and mixtures thereof.",
    "4. The process of claim 1 wherein the molar ratio of paraffinic hydrocarbon to oxygen is greater than the molar ratio of the fuel-rich, upper flammability limit.",
    "5. The process of claim 1 wherein the molar ratio of paraffinic hydrocarbon to oxygen ranges from about 3 to about 77 times the stoichiometric ratio of hydrocarbon to oxygen for complete combustion to carbon dioxide and water.",
    "6. The process of claim 1 wherein the molar ratio of paraffinic hydrocarbon to oxygen is greater than 0.1:1 and less than 4.0:1.",
    "7. The process of claim 1 wherein the contacting is further carried out in the presence of a diluent.",
    "8. The process of claim 7 wherein the diluent is selected from the group consisting of nitrogen, argon, helium, carbon dioxide, carbon monoxide, methane, and steam.",
    "9. The process of claim 7 wherein the diluent is used in an amount greater than 0.1 mole percent and less than 70 mole percent, based on the total reactant feed including paraffin, oxygen, hydrogen, and diluent.",
    "10. The process of claim 1 wherein the molar ratio of hydrogen to oxygen ranges from greater than 0.1:1 to less than 4.0:1.",
    "11. The process of claim 1 wherein the platinum group metal is platinum.",
    "12. The process of claim 1 wherein the catalyst further comprises a ceramic support.",
    "13. The process of claim 12 wherein the ceramic support is selected from the group consisting of silica, alumina, silica-aluminas, aluminosilicates, magnesia, magnesium aluminates, magnesium silicates, zirconia, titania, boria, zirconia toughened alumina, lithium aluminum silicates, silicon carbide, and oxide-bonded silicon carbide.",
    "14. The process of claim 13 wherein the ceramic support comprises from 65 to 100 weight percent alpha alumina or gamma alumina.",
    "15. The process of claim 13 wherein the ceramic support is a monolith.",
    "16. The process of claim 15 wherein the monolith is a foam having from 5 to 100 pores per linear inch (2 to 40 pores per linear cm) and a surface area greater than 0.001 m 2 /g and less than 10 m 2 /g.",
    "17. The process of claim 15 wherein the monolith is a fiber having a diameter greater than 1 micron and less than 20 microns, and a surface area greater than 0.001 m 2 /g and less than 1 m 2 /g.",
    "18. The process of claim 17 wherein the fiber monolith is a fiber mat.",
    "19. The process of claim 1 wherein the catalyst is in a form of particles having a size between 30 and 1,000 microns.",
    "20. The process of claim 1 wherein the promoter is selected from the group consisting of the elements of Groups 1B, 6B, 3A, 4A, and 5A of the Periodic Table and mixtures of the aforementioned elements.",
    "21. The process of claim 1 wherein the promoter is selected from the group consisting of tin, antimony, copper, silver, indium, and mixtures thereof.",
    "22. The process of claim 1 wherein the atomic ratio of platinum group metal to promoter ranges from greater than 1:10 to less than 1:0.5.",
    "23. The process of claim 1 wherein the catalyst is a metallic gauze.",
    "24. The process of claim 1 wherein the paraffinic hydrocarbon and oxygen are preheated at a temperature greater than 40° C. and less than the temperature wherein reaction of the paraffinic hydrocarbon and oxygen occurs.",
    "25. The process of claim 24 wherein the paraffinic hydrocarbon and oxygen are preheated at a temperature greater than 200° C. and less than 900° C.",
    "26. The process of claim 25 wherein the paraffinic hydrocarbon to oxygen molar ratio is greater than 1.5:1 and less than 4.0:1.",
    "27. The process of claim 25 wherein the hydrogen to oxygen molar ratio is greater than 1.5:1 and less than 4.0:1.",
    "28. The process of claim 1 wherein the process is conducted at a pressure equal to or greater than 1 atm abs (100 kPa abs) and less than 20 atm abs (2,000 kPa abs).",
    "29. The process of claim 1 wherein the process is conducted at a gas hourly space velocity greater than 50,000 h −1 and less than 6,000,000 h −1.",
    "30. The process of claim 1 wherein the process is conducted in fixed bed or fluidized bed reactor.",
    "31. The process of claim 30 wherein the fluidized bed reactor possesses an aspect ratio less than 1:1 during operation.",
    "32. The process of claim 31 wherein the fluidized bed reactor possesses an aspect ratio less than 1:1 in static mode.",
    "33. The process of claim 1 wherein the olefin is converted from said paraffinic hydrocarbon or mixture of paraffinic hydrocarbons at greater than 50 mole percent.",
    "34. The process of claim 1 wherein the percentage of carbon atoms in the paraffinic hydrocarbon or mixture of paraffinic hydrocarbons which react to form an olefin is greater than 70 carbon atom percent.",
    "35. The process of claim 1 wherein hydrogen in said product stream is recycled to the reactor.",
    "36. The process of claim 1 wherein methane, carbon monoxide, and/or carbon dioxide in said product stream are recycled at least in part to the reactor.",
    "37. The process of claim 1 wherein the paraffinic hydrocarbon is ethane and the contacting is conducted under autothermal conditions at an ethane to oxygen molar ratio greater than 1.5:1 and less than 4.0:1, a hydrogen to oxygen molar ratio greater than 1.5:1 and less than 4.0:1, a gas hourly space velocity greater than 80,000 h −1 and less than 6,000,000 h −1, wherein optionally a diluent is used in an amount greater than 1 mole percent and less than about 70 mole percent based on the total reactant feed, wherein the platinum group metal is platinum, and the platinum group metal and promoter are supported on a magnesia or alumina ceramic support.",
    "38. The process of claim 37 wherein the ethane and oxygen feed are preheated at a temperature in the range from 400° C. to 600° C.",
    "39. The process of claim 37 wherein the process is conducted in a fluidized bed reactor having an aspect ratio less than 1:1 during operation.",
    "40. The process of claim 39 wherein the catalyst has a particle size ranging between 500 and 850 microns.",
    "41. The process of claim 37 wherein the platinum group metal and the promoter are supported on a catalyst support which is a fiber, a foam monolith, or a pellet.",
    "42. A process for preparing an olefin comprising contacting a paraffinic hydrocarbon or a mixture of paraffinic hydrocarbons, said paraffinic hydrocarbon having from 2 to about 25 carbon atoms, with oxygen in the presence of hydrogen and a catalyst, the contacting being conducted in a reactor under autothermal process conditions sufficient to prepare a product stream containing the olefin, the catalyst comprising a platinum group metal and at least one promoter, wherein the catalyst is prepared by a process comprising pretreating a catalyst support with a support modifier, depositing the platinum group metal and at least one promoter onto the pretreated support, optionally calcining the support, and thereafter reducing the metal-loaded support.",
    "43. The process of claim 42 wherein the catalytic support is pretreated with a support modifier selected from the group consisting of Groups 1A, 2A, 3B, 4B, 5B, 6B, 1B, 3A, 4A, 5A, the rare earth lanthanide, and the elements of the Periodic Table."
  ],
  "description_excerpt": "The present invention relates to the field of catalytic oxidation of hydrocarbons. More particularly, the present invention relates to the catalytic partial oxidation of paraffinic hydrocarbons, such as ethane, propane, and naphtha, to produce olefins, such as ethylene and propylene.\n\nOlefins find widespread utility in industrial organic chemistry. Ethylene is needed for the preparation of important polymers, such as polyethylene, vinyl plastics, and ethylene-propylene rubbers, and important basic chemicals, such as ethylene oxide, styrene, acetaldehyde, ethyl acetate, and dichloroethane. Propylene is needed for the preparation of polypropylene plastics, ethylene-propylene rubbers, and important basic chemicals, such as propylene oxide, cumene, and acrolein. Isobutylene is needed for the preparation of methyl tertiary butyl ether. Long chain mono-olefins find utility in the manufacture of linear alkylated benzene sulfonates, which are used in the detergent industry.\n\nLow molecular weight olefins, such as ethylene, propylene, and butylene, are produced almost exclusively by thermal cracking (pyrolysis/steam cracking) of alkanes at elevated temperatures. An ethylene plant, for example, typically achieves an ethylene selectivity of about 85 percent calculated on a carbon atom basis at an ethane conversion of about 60 mole percent. Undesired coproducts are recycled on the shell side of the cracking furnace to be burned, so as to produce the heat necessary for the process. Disadvantageously, thermal cracking processes for olefin production are highly endothermic.",
  "cpc": [
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  "assignees": [
    "Dow Global Technologies LLC"
  ],
  "inventors": [
    "Sameer S. Bharadwaj",
    "Joseph J. Maj",
    "Jonathan H. Siddall",
    "Mark D. Bearden",
    "Craig B. Murchison",
    "Gerald E. Lazaruk"
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  "filing_date": "1999-09-01",
  "publication_date": "2003-05-20",
  "grant_date": "2003-05-20",
  "priority_date": "1998-09-03",
  "application_number": "US-38821999-A",
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}

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