EP1280745A1 - Process for the production of gasoline stocks - Google Patents
Process for the production of gasoline stocksInfo
- Publication number
- EP1280745A1 EP1280745A1 EP01927448A EP01927448A EP1280745A1 EP 1280745 A1 EP1280745 A1 EP 1280745A1 EP 01927448 A EP01927448 A EP 01927448A EP 01927448 A EP01927448 A EP 01927448A EP 1280745 A1 EP1280745 A1 EP 1280745A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- hydrogen
- distillation
- olefins
- distillation column
- 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.)
- Withdrawn
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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
Definitions
- the dimers produced in the oligomerization reaction are then hydrogenated preferably in a reactive distillation.
- the dimers may be fed along with a hydrogen stream to a reaction distillation column at an effectuating hydrogen partial pressure of at least about 0.1 psia to less than 70 psia, such as less than 50 psia.
- the reaction distillation column reactor contains a hydrogenation catalyst which is a component of a distillation structure and selectively hydrogenating a portion of the dimers. Within the hydrogen partial pressures as defined no more hydrogen than necessary to maintain the catalyst and hydrogenate the olefinic compounds is employed, since the excess hydrogen is usually vented.
- Typical hydrogenation catalysts are Group VIII metals supported on an alumina base and include, among others, platinum, nickel, and cobalt.
- the catalyst beds as used in the present invention may be described as fixed, meaning positioned in a fixed area of the column and include expanded beds and ebulating beds of catalysts.
- the catalysts in the beds may all be the same or different so long as they carry out the function of hydrogenation as described.
- Catalysts prepared as distillation structures are particularly useful in the present invention.
- FIGURE is a flow diagram in schematic form of a one embodiment of the invention. DETAILED DESCRIPTION OF THE INVENTION
- the olefins which may be oligomerized in the present invention include propylene, butenes and pentenes. Particularly the isobutenes and isopentenes (isoamylenes) and the linear olefins are useful. Typically the internal linear C 4 and C 5 olefins are less reactive than the ⁇ - or iso- olefins of the same carbon number.
- the oligomerization reactions of interest include:
- the tertiary olefins are more reactive and tend to form dimers, some codimers and higher oligomers
- the oligomerization reaction is preferably carried out in a boiling point reactor in the presence of an acidic particulate catalyst such as an acidic cation exchange resin or zeolite at a pressure sufficient to maintain the reaction mixture at its boiling point within the range of 120° F to 300° F whereby at least a portion but less than all of the reaction mixture is in the vapor phase.
- an acidic particulate catalyst such as an acidic cation exchange resin or zeolite
- the present invention can be used on streams containing any of the various olefins or mixtures thereof.
- the temperature must be carefully controlled to prevent formation of trimers and heavier products.
- the boiling point reactor lends itself very well to such control.
- the catalyst bed in the boiling point reactor may be described as a fixed continuous bed, that is, the catalyst is loaded into the reactor in its particulate form to fill the reactor or reaction zone, although there may be one or more of such continuous beds in a reactor, separated by spaces devoid of catalyst.
- the resin or zeolite catalyst is loaded into a partial liquid phase boiling point reactor as a fixed bed of the granules.
- the feed to the reaction is fed to the bed in liquid phase.
- the bed may be horizontal, vertical or angled.
- Preferably the bed is vertical with the feed passing downward through the bed and exiting, after reaction, through the lower end of the reactor.
- the reactor is operated at a high liquid hourly space velocity (5-20 LHSV, preferably 10-20) to avoid the reverse reaction and polymerization of the olefins. These conditions result in about 80-90% conversion of the olefins and it may be desirable to have two and possibly more of the reactors in series to obtain the desired overall conversion of the olefin.
- the oligomers may be separated from the reactants by conventional distillation with the oligomer products being removed as bottoms and unreacted feed recovered as overheads.
- the effluent from the boiling point reactor may be fed to a distillation column reactor containing the same or similar catalyst to obtain the desired conversion and concurrently separate the products from the unreacted feed.
- the extrudates or spheres are placed in porous containers and suitably supported in the distillation column reactor to allow vapor flow through the bed while providing a sufficient surface area for catalytic contact.
- metals known to catalyze the hydrogenation reaction are platinum, rhenium, cobalt, molybdenum, nickel, tungsten and palladium.
- commercial forms of catalyst use supported oxides of these metals. The oxide is reduced to the active form either prior to use with a reducing agent or during use by the hydrogen in the feed. These metals also catalyze other reactions, most notably dehydrogenation at elevated temperatures.
- the reaction system can be described as heterogenous since the catalyst remains a distinct entity.
- Any suitable hydrogenation catalyst may be used, for example Group VIII metals of the Periodic Table of Elements as the principal catalytic component, alone or with promoters and modifiers such as palladium/gold, palladium/silver, cobalt/zirconium, nickel preferably deposited on a support such as alumina, fire brick, pumice, carbon, silica, resin or the like.
- One suitable catalyst structure for the hydrogenation of the oligomers comprises at least one plurality of flexible, semi-rigid open mesh tubular elements filed with a particulate catalytic material (catalyst component) and sealed at both ends, intimately associated with and supported by a wire mesh screen coiled into a spiral having a longitudinal axis, said tubular element being arrayed at an angle to the longitudinal axis thereby forming a bale and is described in detail in U.S. Pat.
- the catalyst component may take several forms.
- particulate catalytic material generally from 60 mm to about 1 mm down through powders, is enclosed in a porous container such as screen wire or polymeric mesh.
- the material used to make the container must be inert to the reactants and conditions in the reaction system.
- the screen wire may be aluminum, steel, stainless steel, and the like.
- the polymer mesh may be nylon, teflon, or the like.
- the mesh or threads per inch of the material used to make the container is such that the catalyst is retained therein and will not pass through the openings in the material.
- the catalyst particles of about 0.15 mm size or powders may be used and particles up to about 1/4 inch diameter may be employed in the containers.
- the reaction conditions in the distillation column reactor must be sufficient to hydrogenate the olefin to the alkane.
- the conditions of pressure and temperature to hydrogenate only the dienes e.g., 150°F to a maximum temperature of 170-200 °F at 10 to 75 psig.
- To hydrogenate the mono olefins more severe conditions are required 200 -350°F, at 30 to 150 psig.
- the feed containing the olefin or olefins to be oligomerized are fed via flow line 102 to boiling point reactor 10 containing a bed of catalyst 12, either an acidic ion exchange resin or a zeolite.
- the olefins react with themselves or one another to produce a longer chain oligomer (principally dimer) which is removed from the reactor via flow line 105 to distillation column reactor 20.
- Distillation column reactor 20 contains a bed 22 of hydrogenation catalyst suitable to act as a distillation structure.
- the oligomers e.g. dimers, or at least a part, are hydrogenated to the corresponding alkane, which having a higher boiling point is removed as bottoms via flow line 108.
- the dimers can be completely hydrogenated.
- Unreacted olefin monomers, alkanes in the feed and hydrogen are removed as overheads via flow line 106.
- the overheads are condensed in condenser 1 14 and collected in separator 116. Hydrogen is removed via line 110 and may be recycled to flow line 104.
- a portion of the condensed hydrocarbons are returned as reflux via line 108 and a portion removed via line 1 12 which may be recycled to line 102.
- a rectification section 24 containing standard distillation structure such as trays or packing is provided above the catalyst bed 22. Likewise a stripping section 26 is provided below the catalyst bed 22.
- Other embodiments not shown but which are considered to be encompassed by the invention include multiple boiling point reactors to achieve the desired olefin conversion or a distillation column reactor following the boiling point reactor.
- Example A C 4 feed containing 14.2 wt.% isobutene, 72.7 wt.% other C 4 's with the balance principally C 3 's and C 5 's is passed downflow through a fixed bed of Amberlyst 15 beads bed at LHSV of 10 at 90°F to produce a conversion of isobutene of over 85%.
- the total effluent from the reaction is fed at the top of a catalyst zone located in a one inch diameter column which is loaded with 10 feet of 0.5 wt% Pd on 1/8" Al 2 O 3 (alumina) extrudates, hydrogenation catalyst, (Calsicat E144SDU) prepared as distillation structure.
- a stripping section of 2 feet containing Pall rings is below the catalyst bed.
- the total pressure is 75 psig at 175 °F at LHSV 10.
- the heavier oligomer drops into the catalyst zone where it contacts hydrogen fed below the catalyst zone at a hydrogen partial pressure of 10 psig converting substantially all of the oligomer (principally dimer) to alkane which is recovered as bottoms.
- Overheads are the C 3 's and C 4 's and C 5 's and unreacted hydrogen.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US55752300A | 2000-04-24 | 2000-04-24 | |
US557523 | 2000-04-24 | ||
PCT/US2001/040522 WO2001081278A1 (en) | 2000-04-24 | 2001-04-03 | Process for the production of gasoline stocks |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1280745A1 true EP1280745A1 (en) | 2003-02-05 |
EP1280745A4 EP1280745A4 (en) | 2004-08-18 |
Family
ID=24225759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01927448A Withdrawn EP1280745A4 (en) | 2000-04-24 | 2001-04-03 | Process for the production of gasoline stocks |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1280745A4 (en) |
JP (1) | JP2003531254A (en) |
KR (1) | KR100765669B1 (en) |
CN (1) | CN100445242C (en) |
AU (1) | AU2001253895A1 (en) |
CA (1) | CA2407035A1 (en) |
MX (1) | MX258626B (en) |
PL (1) | PL357048A1 (en) |
WO (1) | WO2001081278A1 (en) |
ZA (1) | ZA200208087B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1388528B1 (en) | 2002-08-06 | 2015-04-08 | Evonik Degussa GmbH | Process for the oligomerisation of isobutene contained in hydrocarbon streams containing n-butene |
US7145049B2 (en) * | 2003-07-25 | 2006-12-05 | Catalytic Distillation Technologies | Oligomerization process |
JP4608341B2 (en) * | 2005-03-04 | 2011-01-12 | 出光興産株式会社 | Method for producing gasoline base material |
FR2885137B1 (en) * | 2005-04-28 | 2007-07-13 | Inst Francais Du Petrole | PROCESS FOR THE DESULFURATION OF OLEFINIC ESSENCES |
CN105777472B (en) * | 2016-04-15 | 2018-01-23 | 河北工业大学 | It is a kind of to separate pentane, hexane, heptane and the method for octane mixture system |
CN108218654A (en) * | 2018-02-12 | 2018-06-29 | 安徽海德化工科技有限公司 | A kind of method that isooctane is prepared using isobutanol |
CN114395077B (en) * | 2021-12-28 | 2024-02-09 | 恒河材料科技股份有限公司 | Preparation method of cycloalkyl filling oil |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5792428A (en) * | 1994-07-18 | 1998-08-11 | Chemical Research & Licensing Company | Apparatus for conducting exothermic reactions |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4334113A (en) * | 1980-06-11 | 1982-06-08 | Gulf Research & Development Company | Synthetic hydrocarbon oligomers |
US4720600A (en) * | 1983-06-29 | 1988-01-19 | Mobil Oil Corporation | Production of middle distillate range hydrocarbons by light olefin upgrading |
GB8502034D0 (en) * | 1985-01-28 | 1985-02-27 | Emi Plc Thorn | Discharge lamps |
US5608133A (en) * | 1995-10-23 | 1997-03-04 | Mobil Oil Corporation | Catalytic oligomerization |
FR2743079B1 (en) * | 1995-12-27 | 1998-02-06 | Inst Francais Du Petrole | PROCESS AND DEVICE FOR SELECTIVE HYDROGENATION BY CATALYTIC DISTILLATION INCLUDING A LIQUID-GAS UPWARD CO-CURRENT REACTION ZONE |
US5877372A (en) * | 1997-11-21 | 1999-03-02 | Arco Chemical Technology, L.P. | Isobutylene oligomerization using isooctane diluent |
KR100558972B1 (en) * | 2002-12-30 | 2006-03-10 | 주식회사 효성 | Preparation method of 1,5-dimethyltetralin |
-
2001
- 2001-04-03 MX MXPA02010489 patent/MX258626B/en active IP Right Grant
- 2001-04-03 WO PCT/US2001/040522 patent/WO2001081278A1/en active Application Filing
- 2001-04-03 CN CNB018081630A patent/CN100445242C/en not_active Expired - Fee Related
- 2001-04-03 CA CA002407035A patent/CA2407035A1/en not_active Abandoned
- 2001-04-03 AU AU2001253895A patent/AU2001253895A1/en not_active Abandoned
- 2001-04-03 JP JP2001578376A patent/JP2003531254A/en active Pending
- 2001-04-03 EP EP01927448A patent/EP1280745A4/en not_active Withdrawn
- 2001-04-03 KR KR1020027013927A patent/KR100765669B1/en not_active IP Right Cessation
- 2001-04-03 PL PL01357048A patent/PL357048A1/en not_active Application Discontinuation
-
2002
- 2002-10-08 ZA ZA200208087A patent/ZA200208087B/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5792428A (en) * | 1994-07-18 | 1998-08-11 | Chemical Research & Licensing Company | Apparatus for conducting exothermic reactions |
Non-Patent Citations (1)
Title |
---|
See also references of WO0181278A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1280745A4 (en) | 2004-08-18 |
PL357048A1 (en) | 2004-07-12 |
MXPA02010489A (en) | 2003-03-10 |
CN100445242C (en) | 2008-12-24 |
CN1423625A (en) | 2003-06-11 |
AU2001253895A1 (en) | 2001-11-07 |
KR20020087494A (en) | 2002-11-22 |
MX258626B (en) | 2008-07-09 |
WO2001081278A1 (en) | 2001-11-01 |
JP2003531254A (en) | 2003-10-21 |
CA2407035A1 (en) | 2001-11-01 |
ZA200208087B (en) | 2003-07-23 |
KR100765669B1 (en) | 2007-10-10 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20021118 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20040701 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: 7C 10G 69/12 B Ipc: 7C 07C 5/02 B Ipc: 7B 01D 3/00 B Ipc: 7C 07C 2/00 A |
|
17Q | First examination report despatched |
Effective date: 20040728 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20081031 |