WO2001030726A1 - Production de composes oxygenes et de dimeres oxygenes - Google Patents

Production de composes oxygenes et de dimeres oxygenes Download PDF

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Publication number
WO2001030726A1
WO2001030726A1 PCT/ZA2000/000198 ZA0000198W WO0130726A1 WO 2001030726 A1 WO2001030726 A1 WO 2001030726A1 ZA 0000198 W ZA0000198 W ZA 0000198W WO 0130726 A1 WO0130726 A1 WO 0130726A1
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WO
WIPO (PCT)
Prior art keywords
branched
composition
oxygenated
alcohols
aldehydes
Prior art date
Application number
PCT/ZA2000/000198
Other languages
English (en)
Inventor
Hester De Wet
David Hedley Morgan
Alta Ranwell
Original Assignee
Sasol Technology (Pty) Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sasol Technology (Pty) Ltd filed Critical Sasol Technology (Pty) Ltd
Priority to AU18218/01A priority Critical patent/AU1821801A/en
Publication of WO2001030726A1 publication Critical patent/WO2001030726A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction

Definitions

  • oxygenated products of a dimerisation process for the production of dimers from an olefinic feedstock containing ⁇ -olefins comprising contacting the feedstock with a metallocene/aluminoxane catalyst, thereby selectively to dimerise ⁇ -olefins in the feedstock by means of a metallocene- catalysed dimerisation reaction, the feedstock being in the form of a Fischer-Tropsch-derived olefinic feedstock comprising a mixture of Fischer-Tropsch-derived hydrocarbons made up of at most 90% by mass of linear and branched ⁇ -olefins e.g.
  • olefins between 10% and 60% branched, at least 5% by mass of olefins, other than ⁇ -olefins, selected from internal olefins, cyclic olefins, dienes, trienes and mixture thereof, and at least 5% by mass of constituents, other than olefins, selected from paraffins, oxygenated hydrocarbons, aromatic hydrocarbons and mixtures thereof, the metallocene-catalysed dimerisation reaction taking place while the olefins which are dimerised form part of the mixture constituted by the feedstock.
  • a Fischer-Tropsch-derived olefinic feedstock is meant an olefinic feedstock which is a product obtained by subjecting a synthesis gas comprising carbon monoxide and hydrogen to Fischer-Tropsch reaction conditions in the presence of a suitable Fischer-Tropsch catalyst, which catalyst may be iron-based, cobalt-based or iron/cobalt-based.
  • the Fischer- Tropsch derived olefinic feedstock may be one which, after production thereof from the synthesis gas, has been subjected to no substantial further treatment, purification or processing thereof to remove unwanted constituents such as non- ⁇ -olefins therefrom, other than cutting so that a suitable cut of the Fischer-Tropsch-derived product will typically be selected for use as the feedstock to the dimerisation process
  • the feedstock may comprise 50 - 90% by mass of said linear and branched ⁇ -olefins, for example 60 - 80% by mass thereof, it may comprise 5 - 20% by mass of said olefins other than ⁇ -olefins, for example 9 - 16% by mass thereof, and it may comprise 6 - 30% by mass of said constituents other than olefins, for example 13 - 22% by mass thereof
  • the feedstock may comprise 50% by mass of linear and branched ⁇ - olefins, 20% by mass olefins other than ⁇ -olefins, and 30% by mass of constituents other than olefins
  • the metallocene/aluminoxane catalyst may have an aluminoxane component which is methylaluminoxane, and a metallocene component which is a compound of the general formula (Cp) 2 MY 2 in which Cp represents a cyclopentadienyl group, M is a metal selected from zirconium, hafnium and titanium, and Y is selected from hydrogen radicals, halogen radicals (preferably chlorine radicals), alkyl groups (preferably methyl groups) and mixtures thereof
  • the metallocene component preferably comprises a single compound of said formula (Cp) 2 MY2, but it may instead comprise a mixture of several said compounds of formula (Cp) 2 MY 2 .
  • the feedstock may comprise olefins other than linear and branched ⁇ -olefins which include internal olefins, cyclic olefins, dienes and trienes, and constituents of the feedstock other than olefins may include paraffins, aromatics and small amounts of oxygenates
  • Al M atomic ratio increases, the degree of conversion and reaction rate increase, while the selectivity with regard to dimer production decreases, while a reducing Al M atomic ratio reduces the degree of conversion and the reaction rate, and increases the selectivity for dimer production
  • An optimum or acceptable Al M atomic ratio may accordingly be selected by routine experimentation, bearing practical and economic considerations in mind It is preferred to have the feedstock in a liquid state during the feed
  • the feedstock may be in a liquid state during the contacting of the feedstock with the metallocene/aluminoxane catalyst, the contacting taking place at a reaction temperature of -60°C to 280°C and at an absolute reaction pressure of 1 - 500 atmospheres, usually at or slightly above 1 atmosphere, and in the case the reaction temperature is preferably 20 - 120°C, the process being carried out under an inert atmosphere
  • routine experimentation may be used to establish optimum or acceptable reaction conditions with regard to temperature, pressure and reaction time
  • the aluminoxane component of the catalyst dissolved in an organic solvent (conveniently the organic solvent used in the preparation of the aluminoxane component) may be admixed with a well-stirred suspension of the metallocene component of the catalyst in an organic liquid which may be inert with regard to the metallocene/aluminoxane catalyst, or conveniently may be in the form of the feedstock used for the dimerisation reaction When the feedstock is used to suspend the metallocene component, the dimerisation reaction proceeds in earnest as soon as the admixture thereof with the aluminoxane solution becomes substantially homogeneous
  • the dimerisation is conveniently carried out under an inert atmosphere, e g an argon atmosphere, at atmospheric pressure
  • the dimer reaction products of the described dimerisation process are further reacted, for example in a hydroformylation reaction zone, to produce oxygenated products such as aldehydes and alcohols
  • An isomerising cobalt catalyst may be used for the hydroformylation of these dimmer reaction products in order to obtain primary alcohols
  • the hydroformylation products may be branched
  • the hydroformylation products include mono- and/or di- and/or t ⁇ -methyl branched oxygenated products
  • the feedstock to the dimerisation process is primarily linear ⁇ -olefinic
  • the oxygenated products are predominantly monomethyl branched, for example, monomethyl branched alcohols and aldehydes
  • the feedstock to the dimerisation process includes predominantly linear ⁇ -olefins and a minor fraction e g 10% to 25%, typically 15% to 20%, of monomethyl branched ⁇ - olefins
  • the oxygenated products are predominantly monomethyl branched with a minor fraction being dimethyl branched, for example, mono- and di-methyl branched alcohols and aldehydes
  • the monomethyl branched oxygenated products will predominate
  • the oxygenated products include monomethyl branched, dimethyl branched and trimethyl branched oxygenated compounds, for example, mono-, di, and tri- methyl branched alcohols and aldehydes
  • the monomethyl branched fraction of the oxygenated products will exceed the dimethyl branched fraction of the oxygenated products which in turn will exceed the trimethyl branched fraction of the oxygenated products
  • the invention thus provides an oxygenated compound composition obtained by oxygenating the dimerisation reaction products of the abovementioned dimerisation process, which oxygenated compound composition has on average between 0 9 and 3 branches per molecule
  • the oxygenated compound composition includes at least some branched alcohol and/or aldehyde selected from the group including monomethyl branched alcohol, dimethyl branched alcohol, trimethyl branched alcohol, monomethyl branched aldehyde, dimethyl branched aldehyde, and trimethyl branched aldehyde
  • composition typically includes primary alcohols and/or primary aldehydes
  • the alcohols and/or aldehydes of the invention may be between C 4 and C 4 n, typically between C i ⁇ and C 2 o
  • the oxygenate for example alcohol or aldehyde, broadly in accordance with the invention, has one more methyl branch than the dimerisation reaction product, e.g. vinylidene , which is the intermediate feedstock for the oxygenate, which intermediate in turn has one more methyl branch than the ⁇ -olefin feedstock to the dimerisation process from which the intermediate feedstock is derived
  • one unbranched and one monomethyl branched ⁇ -olefin is dimerised to produce a monomethyl branched vinylidene from which a dim ethylated oxygenate may derived.
  • two monomethyl branched ⁇ -olefins are dimerised to produce a dimethyl branched vinylidene from which a trimethylated oxygenate may derived.
  • the oxygenated products may be represented by R'R"C-CHO and/or R'R"C-CHOH in which R' and R" are alkyl groups and may be the same of different
  • the oxygenated products derived from the dimer being formed from the ⁇ x-olefins R' - CH 2 and R" each typically have C 2 -C 3 n carbon atoms, preferably C5 - C10 carbon atoms.
  • oxygenated products of dimer reaction products of the dimerisation process, of the present invention are useful as starting materials for the production of detergents, surfactants, plasticizers or the like
  • the invention is suitable for use with any dimer derived from Fischer-Tropsch- derived olefinic feedstock, it is particularly suitable for such feedstock when derived from a high temperature Fischer-Tropsch process carried out at a temperature above 280°C, preferably above 300°C, for example at 330°C, as contrasted with feedstocks derived from low temperature Fischer-Tropsch processes, typically carried out at about 220°C
  • a metallocene/aluminoxane catalyst was prepared by admixing 3.07g of a 30% by mass methyl aluminoxane solution in toluene with 0.24g of (CP) 2 ZrCl 2 (zirconocene dichloride) with stirring at room temperature for about 15 minutes under argon, that catalyst having an Al:Zr atomic ratio of 66: 1.
  • Example 1 was repeated using 3.552g of the methylaluminoxane and 0.22g of the (Cp) 2 ZrCl 2 with 79.19 of a Fischer-Tropsch-derived C 8 out (containing about 40% by mass of 1-octene).
  • the gas-chromatographic analysis showed that the degree or conversion to a Cie product was >
  • the catalyst system consists of cobalt neodecanoate (0 833g of 13wt% cobalt) and 2.009g eicosyl phoban
  • the dimerisation product of example 1 was separated from the unreacted material lOOg of the fractionated dimerised product in example 1, the described catalyst system and 0 059 g potassium hydroxide were mixed in a 450ml Parr pressure reactor A syngas composition of 2 1 (H 2 CO) was used and the reactor was pressurised to 75 barg
  • the reaction temperature was 170°C and the total reaction time was 66 hours
  • Mainly monomethyl branched alcohols with a small percentage dimethyl and trimethyl alcohols were obtained The monomethyl branched alcohols made up between 80% and 85% of the mixture, the dimethyl branched alcohols made up 13% to 18% of the mixture and the trimethyl branched alcohols made up about 2% of the mixture
  • An advantage of the invention is that the Applicant has discovered that, surprisingly, a high degree of oc-olefinic feedstock purity is not required for an-effective dimerisation and thus for producing monomethyl branched, dimethyl branched, and trimethyl branched oxygenated products of the dimerisation reaction products
  • a Fischer-Tropsch-derived olefinic feedstock containing substantial proportions of non- ⁇ -olefinic constituents may be employed without any substantial treatment, purification or processing thereof, other than the selection of a suitable cut or cuts thereof containing oc-olefins predominantly of the desired number or numbers of carbon atoms, to produce oxygenated products of the desired number or numbers of carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une composition de composés oxygénés obtenue en oxygénant les produits de réaction de dimérisation d'un processus de dimérisation Fischer-Tropsch, cette composition de composés oxygénés présentant en moyenne entre 0,9 et 3 ramifications par molécule. Le procédé de dimérisation s'effectue en présence d'un catalyseur de métallocène/aluminoxane. Généralement, la composition de composés oxygénés comprend au moins quelques alcools et/ou aldéhydes ramifiés choisis dans le groupe constitué par alcool ramifié monométhylé, alcool ramifié diméthylé, alcool ramifié triméthylé, aldéhyde ramifié monométhylé, aldéhyde ramifié diméthylé, et aldéhyde ramifié triméthylé.
PCT/ZA2000/000198 1999-10-27 2000-10-24 Production de composes oxygenes et de dimeres oxygenes WO2001030726A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18218/01A AU1821801A (en) 1999-10-27 2000-10-24 Production of oxygenates and oxygenated dimers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16173799P 1999-10-27 1999-10-27
US60/161,737 1999-10-27

Publications (1)

Publication Number Publication Date
WO2001030726A1 true WO2001030726A1 (fr) 2001-05-03

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PCT/ZA2000/000198 WO2001030726A1 (fr) 1999-10-27 2000-10-24 Production de composes oxygenes et de dimeres oxygenes

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AU (1) AU1821801A (fr)
WO (1) WO2001030726A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020257100A1 (fr) * 2019-06-20 2020-12-24 Exxonmobil Chemical Patents Inc. Alcools ramifiés formés à partir d'oléfines de vinylidène par hydroformylation et leurs procédés de production

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4658078A (en) * 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
US5087788A (en) * 1991-03-04 1992-02-11 Ethyl Corporation Preparation of high purity vinylindene olefin
US5446213A (en) * 1992-06-10 1995-08-29 Mitsubishi Kasei Corporation Dimerization method of lower olefins and alcohol production with dimerized products
WO1997001521A1 (fr) * 1995-06-29 1997-01-16 Sasol Technology (Propietary) Limited Procede de production de produits oxygenes
WO1998052888A1 (fr) * 1997-05-23 1998-11-26 Sasol Technology (Proprietary) Limited Production d'oligomeres

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4658078A (en) * 1986-08-15 1987-04-14 Shell Oil Company Vinylidene olefin process
US5087788A (en) * 1991-03-04 1992-02-11 Ethyl Corporation Preparation of high purity vinylindene olefin
US5446213A (en) * 1992-06-10 1995-08-29 Mitsubishi Kasei Corporation Dimerization method of lower olefins and alcohol production with dimerized products
WO1997001521A1 (fr) * 1995-06-29 1997-01-16 Sasol Technology (Propietary) Limited Procede de production de produits oxygenes
WO1998052888A1 (fr) * 1997-05-23 1998-11-26 Sasol Technology (Proprietary) Limited Production d'oligomeres

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020257100A1 (fr) * 2019-06-20 2020-12-24 Exxonmobil Chemical Patents Inc. Alcools ramifiés formés à partir d'oléfines de vinylidène par hydroformylation et leurs procédés de production
CN114258389A (zh) * 2019-06-20 2022-03-29 埃克森美孚化学专利公司 由乙烯叉基烯烃通过加氢甲酰基化形成的支化醇及其制备方法

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Publication number Publication date
AU1821801A (en) 2001-05-08

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