CA2553962A1 - Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps - Google Patents
Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps Download PDFInfo
- Publication number
- CA2553962A1 CA2553962A1 CA002553962A CA2553962A CA2553962A1 CA 2553962 A1 CA2553962 A1 CA 2553962A1 CA 002553962 A CA002553962 A CA 002553962A CA 2553962 A CA2553962 A CA 2553962A CA 2553962 A1 CA2553962 A1 CA 2553962A1
- Authority
- CA
- Canada
- Prior art keywords
- recited
- catalytic distillation
- distillation column
- fixed bed
- catalyst
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/002—Apparatus for fixed bed hydrotreatment processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
Abstract
Presented is an improvement to a previous invention involving the catalytic hydrogenation of the C2 to C5 and heavier acetylenes and dienes in a thermally cracked feed stream without significantly hydrogenating the C2 and C3 olefins.
The improvement involves the use of a fixed bed hydrogenation reactor system in combination with a modified version of the catalytic distillation unit used in the prior art. The modification to the catalytic distillation unit involves improvement of the liquid recycle scheme. The fixed bed reactors combined with the modified catalytic distillation allows for 100% conversion of acetylene and helps to maintain high conversion of the other dienes and acetylenes with no ethylene or propylene conversion under a variety of conditions. These condition variations include but are not limited to the feed diene and acetylene composition, the mol% carbon monoxide in the feed, and catalyst deactivation. With catalytic distillation alone, complete conversion of the acetylene as stated above can not be achieved without ethylene loss, nor would satisfactory operation and control be possible under the variety of conditions experienced during a commercial operation.
The improvement involves the use of a fixed bed hydrogenation reactor system in combination with a modified version of the catalytic distillation unit used in the prior art. The modification to the catalytic distillation unit involves improvement of the liquid recycle scheme. The fixed bed reactors combined with the modified catalytic distillation allows for 100% conversion of acetylene and helps to maintain high conversion of the other dienes and acetylenes with no ethylene or propylene conversion under a variety of conditions. These condition variations include but are not limited to the feed diene and acetylene composition, the mol% carbon monoxide in the feed, and catalyst deactivation. With catalytic distillation alone, complete conversion of the acetylene as stated above can not be achieved without ethylene loss, nor would satisfactory operation and control be possible under the variety of conditions experienced during a commercial operation.
Claims (29)
1. A method of processing a thermally cracked feed stream containing hydrogen, ethylene, propylene, acetylene, methyl acetylene, propadiene and other C4, C5, C6 and heavier unsaturated hydrocarbons to hydrogenate and convert essentially all of said acetylene in high proportion to ethylene and hydrogenate at least a portion of the methyl acetylene, propadiene and other C4, C5, C6 and heavier unsaturated hydrocarbons to olefins and to thereby consume a portion of said hydrogen without hydrogenating ethylene and propylene comprising the steps of:
a. ~introducing said feed stream into a catalytic distillation column containing at least one hydrogenation catalyst bed and concurrently:
(i) ~selectively hydrogenating a portion of said acetylene to form ethylene and hydrogenating, portions of said ~
methyl acetylene, propadiene and C4, C5, C6 and heavier unsaturated hydrocarbons and controlling the hydrogenation conditions whereby said ethylene and propylene are not hydrogenated; and (ii) ~separating by fractional distillation said feed stream into lighter hydrocarbons and heavier hydrocarbons;~
b. ~removing substantially all of the remaining portion of said hydrogen and said lighter hydrocarbons as a vapor phase overhead and substantially all of said heavier hydrocarbons as bottoms from said catalytic distillation column;
c. ~introducing at least a portion of said vapor phase overhead into a vapor phase fixed bed reactor system containing a hydrogenation catalyst and hydrogenating the remaining portion of said acetylene to form further ethylene and hydrogenating further portions of said methyl acetylene, propadiene and C4, C5, C6 and heavier unsaturated hydrocarbons and controlling the hydrogenation conditions whereby said ethylene and propylene are not hydrogenated; and d. ~removing mixed product from said fixed bed reactor system.
a. ~introducing said feed stream into a catalytic distillation column containing at least one hydrogenation catalyst bed and concurrently:
(i) ~selectively hydrogenating a portion of said acetylene to form ethylene and hydrogenating, portions of said ~
methyl acetylene, propadiene and C4, C5, C6 and heavier unsaturated hydrocarbons and controlling the hydrogenation conditions whereby said ethylene and propylene are not hydrogenated; and (ii) ~separating by fractional distillation said feed stream into lighter hydrocarbons and heavier hydrocarbons;~
b. ~removing substantially all of the remaining portion of said hydrogen and said lighter hydrocarbons as a vapor phase overhead and substantially all of said heavier hydrocarbons as bottoms from said catalytic distillation column;
c. ~introducing at least a portion of said vapor phase overhead into a vapor phase fixed bed reactor system containing a hydrogenation catalyst and hydrogenating the remaining portion of said acetylene to form further ethylene and hydrogenating further portions of said methyl acetylene, propadiene and C4, C5, C6 and heavier unsaturated hydrocarbons and controlling the hydrogenation conditions whereby said ethylene and propylene are not hydrogenated; and d. ~removing mixed product from said fixed bed reactor system.
2. A method of claim 1 where said lighter hydrocarbon consists of C4 and lighter hydrocarbons and said heavy hydrocarbon consists of C5 and heavier hydrocarbons.
3. A method of claim 1 where said lighter hydrocarbon consists of C5 and lighter hydrocarbons and said heavy hydrocarbon consists of C6 and heavier hydrocarbons.
4. A method as recited in claim 1 and further comprising the steps of condensing a portion of said vapor phase overhead and returning said condensed portion to said catalytic distillation column as reflux.
5. A method as recited in claim 1 wherein essentially all of said vapor phase overhead is introduced into said vapor phase fixed bed reactor system and further comprising the step of returning a portion of said product from said fixed b,ed reactor system to said catalytic distillation column as reflux.
6, A method as recited in claim 1 wherein said step of controlling said step of selectively hydrogenating in said catalytic distillation column and in said vapor phase fixed bed reactor includes the steps of controlling the temperature profile therein.
7. A method as recited in claim 6 wherein said step of controlling the temperature profile in said catalytic distillation column includes the step of withdrawing a portion of liquid descending in said column at a selected point as a sidestream, cooling said sidestream and injecting said cooled sidestream back into said column at or above said selected point.
8. A method as recited in claim 7 and further including the step of hydrogenating said sidestream.
9. A method as recited in claim 6 wherein said step of controlling the temperature profile in said catalytic distillation column includes the step of withdrawing a pumparound stream from a point in said column below said hydrogenation catalyst beds, cooling said pumparound stream and injecting said cooled pumparound stream back into said column above said hydrogenation catalyst beds.
10. A method as recited in claim 1 wherein said vapor phase fixed bed reactor system comprises at least one reactor and wherein said step of controlling the temperature therein comprises the step of controlling the temperature in heat exchangers prior to said reactor.
11. A method as recited in claim 1 wherein said vapor phase fixed bed reactor system comprises two or more reactors in series and wherein said step of controlling the temperature therein comprises the steps of controlling the temperature in heat exchangers prior to each of said reactors.
12. A method of claim 1 where said step of selectively hydrogenating consists of the step of operating said catalytic distillation column such that the concentration of ethylene in the liquid phase in the catalyst bed is less than 2% by weight.
13. A method of claim 1 where said step of selectively hydrogenating consists of the step of operating said catalytic distillation column such that the liquid flow down the column is greater than 800 lb/hr/ft2 of cross-sectional area in the area of the catalyst bed.
14. A method as recited in claim 1 wherein said step of introducing said feed stream into said catalytic distillation column includes the step of mixing said feed stream with a recycle liquid from said catalytic distillation column and introducing said mixed feed stream and recycle liquid into a fixed bed hydrogenation pre-reactor prior to said catalytic distillation column ;whereby a portion of the highly unsaturated hydrocarbons is hydrogenated and the vapor and liquid streams are introduced into said catalytic distillation column.
15. A method as recited in claim 1 wherein said hydrogenation catalyst bed in said catalytic distillation column contains a catalyst consisting of a group VIIIA metal on a support.
16. A method as recited in claim 12 wherein said catalyst comprises palladium on alumina.
17. A method as recited in claim 13 wherein said catalyst also includes an additive selected from the group consisting of gold, silver and alkali metals.
30~
30~
18. A method as recited in claim 14 wherein catalysts having different quantities of palladium thereon are located in selected portions of said catalytic distillation column.
19. A method as recited in claim 15, wherein different catalysts are located in different portions of said catalytic distillation column.
20. A method as recited in claim 19 wherein said different catalysts contain different metals.
21. A method as recited in claim 19 wherein said different catalysts have different metal loadings.
22. A method as recited in claim 15 wherein said catalyst comprises nickel on a support.
23. A method as recited in claim 15 wherein said catalyst comprises a combination of palladium on a support and nickel on a support in different portions of said catalytic distillation column.
24. A method as recited in claim 1 wherein said hydrogenation catalyst in said fixed bed reactor system comprises a group VIIIA
metal on a support,
metal on a support,
25. A method as recited in claim 24 wherein said hydrogenation catalyst in said fixed bed reactor system comprises palladium on alumina.
26. A method as recited in claim 24 wherein said hydrogenation catalyst in said fixed bed reactor system comprises palladium on alumina with a promoter consisting of gold, silver, an alkali metal or combinations.
27. A method as recited in claim 14 wherein said fixed bed hydrogenation pre-reactor contains a nickel catalyst and said pre-reactor causes the reaction of sulfur compounds for removal.
28. A method as recited in claim 1 and further comprising the step of removing catalyst poisons from said feed stream prior to the introduction into said catalytic distillation column.
29, A method as recited in claim 28 wherein said catalyst poisons are lead, arsenic and mercury.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2004/001379 WO2005080530A1 (en) | 2004-01-20 | 2004-01-20 | Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2553962A1 true CA2553962A1 (en) | 2005-09-01 |
| CA2553962C CA2553962C (en) | 2011-08-30 |
Family
ID=34887914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2553962A Expired - Fee Related CA2553962C (en) | 2004-01-20 | 2004-01-20 | Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1711581A1 (en) |
| JP (1) | JP4376908B2 (en) |
| CN (1) | CN1961059B (en) |
| BR (1) | BRPI0418414A (en) |
| CA (1) | CA2553962C (en) |
| WO (1) | WO2005080530A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433841B (en) * | 2007-12-13 | 2010-04-14 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN104974792B (en) * | 2014-04-01 | 2017-10-17 | 中国石化工程建设有限公司 | A kind of fluidized-bed hydrogenation system and method for hydrotreating |
| US20230024175A1 (en) * | 2021-07-16 | 2023-01-26 | Uop Llc | Process for saturating aromatics in a pyrolysis stream |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404124A (en) * | 1981-05-06 | 1983-09-13 | Phillips Petroleum Company | Selective hydrogenation catalyst |
| ZA945342B (en) * | 1993-12-08 | 1995-03-01 | Chemical Res & Licensin | Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams |
| US5679241A (en) * | 1995-05-17 | 1997-10-21 | Abb Lummus Global Inc. | Olefin plant recovery system employing catalytic distillation |
| US6576588B2 (en) * | 2000-04-07 | 2003-06-10 | Catalytic Distillation Technologies | Process for selective hydrogenation of alkynes and catalyst therefor |
| CN1163457C (en) * | 2000-10-18 | 2004-08-25 | 中国石化集团齐鲁石油化工公司 | Combined technological and comprehensive utilizing method in C5 prodn. splitting process |
| US6420619B1 (en) * | 2001-01-25 | 2002-07-16 | Robert J. Gartside | Cracked gas processing and conversion for propylene production |
-
2004
- 2004-01-20 CA CA2553962A patent/CA2553962C/en not_active Expired - Fee Related
- 2004-01-20 WO PCT/US2004/001379 patent/WO2005080530A1/en active Application Filing
- 2004-01-20 JP JP2006551012A patent/JP4376908B2/en not_active Expired - Lifetime
- 2004-01-20 CN CN200480042493XA patent/CN1961059B/en not_active Expired - Fee Related
- 2004-01-20 BR BRPI0418414-9A patent/BRPI0418414A/en not_active Application Discontinuation
- 2004-01-20 EP EP04703646A patent/EP1711581A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005080530A1 (en) | 2005-09-01 |
| EP1711581A1 (en) | 2006-10-18 |
| CN1961059B (en) | 2010-04-28 |
| JP2007518864A (en) | 2007-07-12 |
| BRPI0418414A (en) | 2007-05-15 |
| CN1961059A (en) | 2007-05-09 |
| CA2553962C (en) | 2011-08-30 |
| JP4376908B2 (en) | 2009-12-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20140121 |