CA2376603A1 - Use of metathesis products of fischer-tropsch process products - Google Patents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/34—Organic liquids
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
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- 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
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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Abstract
The invention provides oxo-alcohols, alkyl benzenes, and drilling fluid compositions derived from hydrocarbons derived by metathesis of Fischer-Tropsch hydrocarbons.
Description
USE OF METATHESIS PRODUCTS OF FISCHER-TROPSCH PROCESS
PRODUCTS
Field of the Invention The invention relates to alkyl benzene (AB), drilling fluid and oxo-alcohols.
Background to the Invention 1o Conversion of lower olefins to higher olefins can be achieved by an isomerizing metathesis process, or metathetic oligomerisation. Conventional metathesis processes require an olefinic feedstock high in purity and linearity and produce highly linear products.
Various heterogeneous contact catalysts such as WO~/Si02, Re20,/AlzOa and Re20~/AIz03.Si0z, and also combinations of these catalysts with co-catalysts can be used for metathesis of unfunctionalized olefins. However, other catalyst and co-catalyst combinations, for example for homogeneous metathesis using WCI6 and/or ReCls and a co-catalyst, have been used successfully and the invention is not limited 2o to any specific catalyst system, nor to homogeneous or hetergeneous metathesis.
Surprisingly, and contrary to conventional thinking, it has now been found that by using metathesis on Fischer-Tropsch process products i.e. using Fischer-Tropsch feedstock to the metathesis process, which feedstock includes both branched and unbranched olefins, as well as non-olefinic components, specific hydrocarbons having from 8 to 18 carbons can be obtained, which hydrocarbons may be used to derive AB, oxo-alcohols and drilling fluid.
By a Fischer-Tropsch process product or feedstock is meant a product obtained by subjecting a synthesis gas including carbon monoxide and hydrogen, to Fischer-Tropsch reaction conditions in the presence of typically an iron based catalyst, a cobalt based catalyst, and iron/cobalt based catalyst, or any other Fischer-Tropsch catalyst, under Fischer-Tropsch reaction conditions.
Summary of the Invention This invention provides products in the 8 to 18 carbon range derived from 5 to 10 carbon Fischer-Tropsch process products, the products in the 8 to 18 carbon range having a desirable degree of branching or non-linearity.
Thus, according to a first aspect of the invention, there is provided an oxo-alcohol composition including oxo-alcohols having from 8 to 18 carbon atoms, the to oxo-alcohols being derived from olefins obtained by metathesis of one or more of 5, 6, 7, 8, 9 and/or 10 carbon containing Fischer-Tropsch derived feedstock.
Between 10% and 99% of the oxo-alcohols of the composition may be branched oxo-alcohols, typically between 10% and 90%.
The oxo-alcohols of the composition may be predominantly linear, with between 10% and 49% branched oxo-alcohols in the composition.
The composition includes between 15% and 35% branched oxo-alcohols.
The composition includes 24% branched oxo-alcohols.
The branching on the branched oxo-alcohols is predominantly mono-methyl branching, however, some di-methyl branching may also be present.
Typically, the mono-methyl branching will be in excess of 90% of the branching, or even in excess of 95%.
The branching may be predominantly on the C4+ carbon, with some 3o branching present on the C2 carbon.
The branching is typically over 70% on the C4+ carbons.
The branching may exceed 90% on the C4+ carbons.
Typically, the oxo-alcohols of the composition in the 8 to 10 carbon range are usable as plasticizes alcohols.
z Typically, the oxo-alcohols of the composition in the 10 to 16 carbon range are usable as detergent alcohols.
A typical product make up from the metathesis of a 7 carbon Fischer-Tropsch derived feedstock and suitable for deriving oxo-alcohols therefrom is set out in Table 1 at the end of the specification.
This product of Table 1 may typically be hydroformylated using a Co-EP
1o catalyst, or any other suitable catalyst, to form predominantly linear alcohols, the ratio of linear to branched alcohols being related to the ratio of linear to branched product of the metathesis of the 7 carbon Fischer-Tropsch derived feedstock.
Thus, according to a second aspect of the invention, there is provided an alkyl benzene (AB) composition including AB having from 10 to 14 carbon atoms on the alkyl chain, the AB being derived from olefins obtained by metathesis of one or more of a 6,7 and/or 8 carbon containing Fischer-Tropsch derived feedstock.
The AB composition may contain between 10% and 90% of branched alkyl 2o chain AB.
The AB composition may contain predominantly linear alkyl chain AB, with between 10% and 49% branched alkyl chain AB in the composition.
The composition includes between 15% and 35% branched alkyl chain AB.
The composition includes about 24% branched alkyl chain AB.
The branching on the branched alkyl chain of the AB is predominantly mono-3o methyl branching, however; some di-methyl and/or ethy branching may also be present.
Typically, the mono-methyl branching will be in excess of 90% of the branching, or even in excess of 95%.
The branching may be predominantly on the C4+ carbon, with some branching present on the C2 carbon.
The branching is typically over 70% on the C4+ carbons.
The branching may exceed 90% on the C4+ carbons.
A typical AB product make up produced from the products of metathesis of a 9 carbon Fischer-Tropsch derived feedstock is set out in Table 3 at the end of the specification.
1o The AB may be sulfonated to give an alkyl benzene sulfonate which may be used as a detergent. However, the AB composition itself may have uses such as for drilling fluids.
The product of Tables 3 and 4 was fractionated and a 10 to 14 carbon alkyl chain AB fraction was obtained having the following composition (represented as the linear internal olefin only):
Decenes : 16.53%
Undecenes : 27.96%
2o Dodecenes 26.19%
:
Tridecenes : 4.71 Tetradecenes 0.91 :
Methyl branched internal olefins in the 10 to 14 carbon range make up most of the remainder.
Thus, according to a third aspect of the invention, there is provided a drilling fluid composition including hydrocarbons having from 14 to 18 carbon atoms, the hydrocarbons being derived from olefins obtained by metathesis of one or more of a 8, 9 and/or 10 carbon containing Fischer-Tropsch derived feedstock.
The hydrocarbons derived from olefins obtained by metathesis of one or more of a 8, 9 and/or 10 carbon containing Fischer-Tropsch derived feedstock may be internal olefins.
The drilling fluid composition may include between 10% and 90% branched hydrocarbons.
The hydrocarbons of the drilling fluid composition may be predominantly linear, with between 10% and 49% branched hydrocarbons in the composition.
The composition includes between 15% and 35% branched hydrocarbons.
The composition includes about 24% branched hydrocarbons.
The branching on the branched hydrocarbons is predominantly mono-methyl 1o branching, however, some di-methyl and/or ethyl branching may also be present.
The branching may be predominantly on the C4+ carbon, with some branching present on the C2 carbon.
The branching is typically over 70% on the C4+ carbons.
The branching may exceed 90% on the C4+ carbons.
Typically, the mono-methyl branching will be in excess of 90% of the 2o branching, or even in excess of 95%.
A typical product make up from the metathesis of a 9 carbon Fischer-Tropsch derived feedstock and suitable for deriving the drilling fluid composition is set out in Table 2 at the end of the specification.
The product of Table 2 was fractionated and a 14 to 17 carbon fraction was obtained having the following approximate composition (represented as both methyl branched and linear internal olefins):
3o Tetradecenes : 23.03%
Pentadecenes: 38.40%
Hexadecenes : 36.22%
Heptadecene : 2.35%
Detailed Description of the Invention Example 1 - Alkyl Benzene Example An olefinic C"/C,z and and a C,~/C,4 olefininc metathesis product derived from metathesis of Fischer-Tropsch olefins, was used to alkylate benzene to produce alkyl benzenes (AB's) .
1o For the alkylation of benzene with the metathesis product, 1 mole of the metathesis olefins, 10 mole of benzene and 20 wt% based on the olefin mixture of a shape selective Beta - zeolite catalyst were added to a stainless steel autoclave.
The autoclave was purged with NZ and then charged to 1000 psig N2. The mixture was stirred and heated to 170 - 190°C for 14 - 15 hours. It was then cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst and the unreacted benzene was removed in vacuo using a rotary evaporator.
The product was sulfonated with an equivalent of chlorosulfonic acid using methylene chloride as solvent. The methylene chloride was distilled away. The 2o sulfonated product was neutralized with sodium methoxide in methanol and the methanol was evaporated to give alkyl benzene sulfonate, sodium salt mixture.
The product mixture contained methyl and di-methyl branching on the alkyl chain portion of the AB. The phenyl group of the AB's was predominantly on the carbon of the alkyl chain.
As shown in the accompanying Figures numbered I to XVI, the AB's obtained included:
3o I 1- methyldecyl benzene II 1-pentylhexylbenzene III 1-propyloctylbenzene IV 1-butylheptyl benzene V 1-ethylnonylbenzene VI 1,1-dimethylnonylbenzene VII 1,3- dimethylnonylbenzene VIII 1,6,7-trimethyloctylbenzene IX 1,4- dimethylnonylbenzene X 1,5- dimethylnonylbenzene XI 1,6- dimethylnonylbenzene XII 1,7- dimethylnonylbenzene XIII 1,8- dimethylnonylbenzene XIV 1,1,3-trimethyloctylbenzene XV 1,3,7-trimethyloctylbenzene XVI 1,1,4-trimethyloctylbenzene to Example 2 - Hydroformylation Example Three different carbon number cuts of a Fischer-Tropsch olefinic feed produced by metathesis i.e Cs/C,o, C"/C,Z and a C,~/C~4 cuts, were batch hydroformylated to evaluate their suitability as detergent alcohol (DA) feed, on the basis of reaction rate and total olefin content. Compared to conventional Fischer-Tropsch olefinic feed, the metathesis feed generally exhibited a 25% greater hydroformylation rate and this together with the higher olefinic content (>90%) should lead to significant reductions in reactor size and distillation requirements.
The linearity and n:iso ratio of the metathesis product is practically identical to that of the 2o conventional olefinic feed derived product. Metathesis feedstock thus appears to be preferable to conventional olefininc feedstock for DA process.
Batch hydroformylation 100m1 of, respectively, a C~/C,o, a C"/C,2 and a C,~/C,4 carbon number cut of metathesis product were exhaustively hydroformylated using a liganded cobalt catalyst. The reaction temperature was 170°C, the initial pressure 85 bar and the syngas CO:HZ ratio was 2:1. In each case the pressure drop with time in the autoclave was measured (i) to calculate the initial hydroformylation rate and (ii) to 3o calculate the gas consumption for complete olefin conversion (i.e.
exhaustive hydroformylation). The cobalt-EP catalyst was used to catalyse the reaction as it results in rapid double-bond isomerisation enabling full utilisation of the internal double bonds in the metathesis feed.
The results of the batch experiments are summarised in Table 5 below.
Olefin content: The olefin content of the metathesis feed was derived from the total gas consumption during the exhaustive hydroformylation studies. The total olefinic content of the metathesis feed was greater than 90%. This is significantly higher than that of conventional olefinic feed which is about 50%.
Hydroformylation rate: The hydroformylation rate was calculated from the initial pressure drop with time. While the intrinsic rate (i.e. the rate constant) of metathesis feed hydroformylation is slower than that of conventional olefinic feed hydroformylation, this is more than compensated for by the significantly higher olefin 1o content of the metathesis feed. For both the C~/C~o and the C"/C~Z
fractions the metathesis feed exhibited a 25% faster apparent hydroformylation rate than the conventional olefininc feed while the hydroformylation rate of the metathesis feed C,~/C,4 was a little slower than that of a similar conventional olefinic feed.
The slower intrinsic hydroformylation rate of the metathesis feed is most probably due to the greater number of internal olefins. Significant double bond isomerisation thus has to take place before hydroformylation can take place at the terminal position.
Linearity and n:iso ratio: The linearity and the n:iso ratio of the metathesis product was comparable to that of the conventional olefinic feed product. The 2o supposed greater number of internal double bonds in the metathesis feed did not negatively affect the linearity of the alcohol product as hydroformylation at the terminal double-bond is favoured above internal double bond hydroformylation.
g Table 5. Results of batch hydroformylation experiments Feed source ConventionalMetathesisMetathesisMetatesis Carbon number cut C,~/C,z C~IC,o C11~C12 C1~C14 Olefin content* [mass%
of 50% 90% 97% 93%
feed]
Apparent hydroformylation rate [mmolanono~hou~']
Hydroformylation rate constant, apparent klumbed = [olefin]
Linearity [mass%] 51 % 68% 63% 58%
n:iso Ratio [mol:mol]5.1 5.8 5.4 6.2 * calculated assuming 10% hydroformylation as for conventional oefininc feed Example 3 - Drilling Fluids C,6 Fischer-Tropsch internal olefins were obtained by metathesis and were 1o useable as a drilling fluid composition.
The drilling fluid composition included about 75% internal linear olefins and about 25% internal branched olefins, which internal branched olefins were predominantly mono-methyl, di-methyl and ethyl branched.
The drilling fluid compositions in accordance with the invention had the following physical properties:
The properties are for a typical C~2-C~6 internal linear and branched 2o combination of olefinic product made in accordance with the present invention:
Viscocity: 1-2 cSt @ 100'C
Flash point: >90'C
Linear:branch ratio 1:1 to 5:1 Pour Point: < 0'C
Examples of the internal olefins useful as drilling fluids include:
1) A drilling fluid including:
1o A linear component making up about 75.1 % of the composition; and A mono-methyl branched component making up about 24.9% of the drilling fluid composition.
PRODUCTS
Field of the Invention The invention relates to alkyl benzene (AB), drilling fluid and oxo-alcohols.
Background to the Invention 1o Conversion of lower olefins to higher olefins can be achieved by an isomerizing metathesis process, or metathetic oligomerisation. Conventional metathesis processes require an olefinic feedstock high in purity and linearity and produce highly linear products.
Various heterogeneous contact catalysts such as WO~/Si02, Re20,/AlzOa and Re20~/AIz03.Si0z, and also combinations of these catalysts with co-catalysts can be used for metathesis of unfunctionalized olefins. However, other catalyst and co-catalyst combinations, for example for homogeneous metathesis using WCI6 and/or ReCls and a co-catalyst, have been used successfully and the invention is not limited 2o to any specific catalyst system, nor to homogeneous or hetergeneous metathesis.
Surprisingly, and contrary to conventional thinking, it has now been found that by using metathesis on Fischer-Tropsch process products i.e. using Fischer-Tropsch feedstock to the metathesis process, which feedstock includes both branched and unbranched olefins, as well as non-olefinic components, specific hydrocarbons having from 8 to 18 carbons can be obtained, which hydrocarbons may be used to derive AB, oxo-alcohols and drilling fluid.
By a Fischer-Tropsch process product or feedstock is meant a product obtained by subjecting a synthesis gas including carbon monoxide and hydrogen, to Fischer-Tropsch reaction conditions in the presence of typically an iron based catalyst, a cobalt based catalyst, and iron/cobalt based catalyst, or any other Fischer-Tropsch catalyst, under Fischer-Tropsch reaction conditions.
Summary of the Invention This invention provides products in the 8 to 18 carbon range derived from 5 to 10 carbon Fischer-Tropsch process products, the products in the 8 to 18 carbon range having a desirable degree of branching or non-linearity.
Thus, according to a first aspect of the invention, there is provided an oxo-alcohol composition including oxo-alcohols having from 8 to 18 carbon atoms, the to oxo-alcohols being derived from olefins obtained by metathesis of one or more of 5, 6, 7, 8, 9 and/or 10 carbon containing Fischer-Tropsch derived feedstock.
Between 10% and 99% of the oxo-alcohols of the composition may be branched oxo-alcohols, typically between 10% and 90%.
The oxo-alcohols of the composition may be predominantly linear, with between 10% and 49% branched oxo-alcohols in the composition.
The composition includes between 15% and 35% branched oxo-alcohols.
The composition includes 24% branched oxo-alcohols.
The branching on the branched oxo-alcohols is predominantly mono-methyl branching, however, some di-methyl branching may also be present.
Typically, the mono-methyl branching will be in excess of 90% of the branching, or even in excess of 95%.
The branching may be predominantly on the C4+ carbon, with some 3o branching present on the C2 carbon.
The branching is typically over 70% on the C4+ carbons.
The branching may exceed 90% on the C4+ carbons.
Typically, the oxo-alcohols of the composition in the 8 to 10 carbon range are usable as plasticizes alcohols.
z Typically, the oxo-alcohols of the composition in the 10 to 16 carbon range are usable as detergent alcohols.
A typical product make up from the metathesis of a 7 carbon Fischer-Tropsch derived feedstock and suitable for deriving oxo-alcohols therefrom is set out in Table 1 at the end of the specification.
This product of Table 1 may typically be hydroformylated using a Co-EP
1o catalyst, or any other suitable catalyst, to form predominantly linear alcohols, the ratio of linear to branched alcohols being related to the ratio of linear to branched product of the metathesis of the 7 carbon Fischer-Tropsch derived feedstock.
Thus, according to a second aspect of the invention, there is provided an alkyl benzene (AB) composition including AB having from 10 to 14 carbon atoms on the alkyl chain, the AB being derived from olefins obtained by metathesis of one or more of a 6,7 and/or 8 carbon containing Fischer-Tropsch derived feedstock.
The AB composition may contain between 10% and 90% of branched alkyl 2o chain AB.
The AB composition may contain predominantly linear alkyl chain AB, with between 10% and 49% branched alkyl chain AB in the composition.
The composition includes between 15% and 35% branched alkyl chain AB.
The composition includes about 24% branched alkyl chain AB.
The branching on the branched alkyl chain of the AB is predominantly mono-3o methyl branching, however; some di-methyl and/or ethy branching may also be present.
Typically, the mono-methyl branching will be in excess of 90% of the branching, or even in excess of 95%.
The branching may be predominantly on the C4+ carbon, with some branching present on the C2 carbon.
The branching is typically over 70% on the C4+ carbons.
The branching may exceed 90% on the C4+ carbons.
A typical AB product make up produced from the products of metathesis of a 9 carbon Fischer-Tropsch derived feedstock is set out in Table 3 at the end of the specification.
1o The AB may be sulfonated to give an alkyl benzene sulfonate which may be used as a detergent. However, the AB composition itself may have uses such as for drilling fluids.
The product of Tables 3 and 4 was fractionated and a 10 to 14 carbon alkyl chain AB fraction was obtained having the following composition (represented as the linear internal olefin only):
Decenes : 16.53%
Undecenes : 27.96%
2o Dodecenes 26.19%
:
Tridecenes : 4.71 Tetradecenes 0.91 :
Methyl branched internal olefins in the 10 to 14 carbon range make up most of the remainder.
Thus, according to a third aspect of the invention, there is provided a drilling fluid composition including hydrocarbons having from 14 to 18 carbon atoms, the hydrocarbons being derived from olefins obtained by metathesis of one or more of a 8, 9 and/or 10 carbon containing Fischer-Tropsch derived feedstock.
The hydrocarbons derived from olefins obtained by metathesis of one or more of a 8, 9 and/or 10 carbon containing Fischer-Tropsch derived feedstock may be internal olefins.
The drilling fluid composition may include between 10% and 90% branched hydrocarbons.
The hydrocarbons of the drilling fluid composition may be predominantly linear, with between 10% and 49% branched hydrocarbons in the composition.
The composition includes between 15% and 35% branched hydrocarbons.
The composition includes about 24% branched hydrocarbons.
The branching on the branched hydrocarbons is predominantly mono-methyl 1o branching, however, some di-methyl and/or ethyl branching may also be present.
The branching may be predominantly on the C4+ carbon, with some branching present on the C2 carbon.
The branching is typically over 70% on the C4+ carbons.
The branching may exceed 90% on the C4+ carbons.
Typically, the mono-methyl branching will be in excess of 90% of the 2o branching, or even in excess of 95%.
A typical product make up from the metathesis of a 9 carbon Fischer-Tropsch derived feedstock and suitable for deriving the drilling fluid composition is set out in Table 2 at the end of the specification.
The product of Table 2 was fractionated and a 14 to 17 carbon fraction was obtained having the following approximate composition (represented as both methyl branched and linear internal olefins):
3o Tetradecenes : 23.03%
Pentadecenes: 38.40%
Hexadecenes : 36.22%
Heptadecene : 2.35%
Detailed Description of the Invention Example 1 - Alkyl Benzene Example An olefinic C"/C,z and and a C,~/C,4 olefininc metathesis product derived from metathesis of Fischer-Tropsch olefins, was used to alkylate benzene to produce alkyl benzenes (AB's) .
1o For the alkylation of benzene with the metathesis product, 1 mole of the metathesis olefins, 10 mole of benzene and 20 wt% based on the olefin mixture of a shape selective Beta - zeolite catalyst were added to a stainless steel autoclave.
The autoclave was purged with NZ and then charged to 1000 psig N2. The mixture was stirred and heated to 170 - 190°C for 14 - 15 hours. It was then cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst and the unreacted benzene was removed in vacuo using a rotary evaporator.
The product was sulfonated with an equivalent of chlorosulfonic acid using methylene chloride as solvent. The methylene chloride was distilled away. The 2o sulfonated product was neutralized with sodium methoxide in methanol and the methanol was evaporated to give alkyl benzene sulfonate, sodium salt mixture.
The product mixture contained methyl and di-methyl branching on the alkyl chain portion of the AB. The phenyl group of the AB's was predominantly on the carbon of the alkyl chain.
As shown in the accompanying Figures numbered I to XVI, the AB's obtained included:
3o I 1- methyldecyl benzene II 1-pentylhexylbenzene III 1-propyloctylbenzene IV 1-butylheptyl benzene V 1-ethylnonylbenzene VI 1,1-dimethylnonylbenzene VII 1,3- dimethylnonylbenzene VIII 1,6,7-trimethyloctylbenzene IX 1,4- dimethylnonylbenzene X 1,5- dimethylnonylbenzene XI 1,6- dimethylnonylbenzene XII 1,7- dimethylnonylbenzene XIII 1,8- dimethylnonylbenzene XIV 1,1,3-trimethyloctylbenzene XV 1,3,7-trimethyloctylbenzene XVI 1,1,4-trimethyloctylbenzene to Example 2 - Hydroformylation Example Three different carbon number cuts of a Fischer-Tropsch olefinic feed produced by metathesis i.e Cs/C,o, C"/C,Z and a C,~/C~4 cuts, were batch hydroformylated to evaluate their suitability as detergent alcohol (DA) feed, on the basis of reaction rate and total olefin content. Compared to conventional Fischer-Tropsch olefinic feed, the metathesis feed generally exhibited a 25% greater hydroformylation rate and this together with the higher olefinic content (>90%) should lead to significant reductions in reactor size and distillation requirements.
The linearity and n:iso ratio of the metathesis product is practically identical to that of the 2o conventional olefinic feed derived product. Metathesis feedstock thus appears to be preferable to conventional olefininc feedstock for DA process.
Batch hydroformylation 100m1 of, respectively, a C~/C,o, a C"/C,2 and a C,~/C,4 carbon number cut of metathesis product were exhaustively hydroformylated using a liganded cobalt catalyst. The reaction temperature was 170°C, the initial pressure 85 bar and the syngas CO:HZ ratio was 2:1. In each case the pressure drop with time in the autoclave was measured (i) to calculate the initial hydroformylation rate and (ii) to 3o calculate the gas consumption for complete olefin conversion (i.e.
exhaustive hydroformylation). The cobalt-EP catalyst was used to catalyse the reaction as it results in rapid double-bond isomerisation enabling full utilisation of the internal double bonds in the metathesis feed.
The results of the batch experiments are summarised in Table 5 below.
Olefin content: The olefin content of the metathesis feed was derived from the total gas consumption during the exhaustive hydroformylation studies. The total olefinic content of the metathesis feed was greater than 90%. This is significantly higher than that of conventional olefinic feed which is about 50%.
Hydroformylation rate: The hydroformylation rate was calculated from the initial pressure drop with time. While the intrinsic rate (i.e. the rate constant) of metathesis feed hydroformylation is slower than that of conventional olefinic feed hydroformylation, this is more than compensated for by the significantly higher olefin 1o content of the metathesis feed. For both the C~/C~o and the C"/C~Z
fractions the metathesis feed exhibited a 25% faster apparent hydroformylation rate than the conventional olefininc feed while the hydroformylation rate of the metathesis feed C,~/C,4 was a little slower than that of a similar conventional olefinic feed.
The slower intrinsic hydroformylation rate of the metathesis feed is most probably due to the greater number of internal olefins. Significant double bond isomerisation thus has to take place before hydroformylation can take place at the terminal position.
Linearity and n:iso ratio: The linearity and the n:iso ratio of the metathesis product was comparable to that of the conventional olefinic feed product. The 2o supposed greater number of internal double bonds in the metathesis feed did not negatively affect the linearity of the alcohol product as hydroformylation at the terminal double-bond is favoured above internal double bond hydroformylation.
g Table 5. Results of batch hydroformylation experiments Feed source ConventionalMetathesisMetathesisMetatesis Carbon number cut C,~/C,z C~IC,o C11~C12 C1~C14 Olefin content* [mass%
of 50% 90% 97% 93%
feed]
Apparent hydroformylation rate [mmolanono~hou~']
Hydroformylation rate constant, apparent klumbed = [olefin]
Linearity [mass%] 51 % 68% 63% 58%
n:iso Ratio [mol:mol]5.1 5.8 5.4 6.2 * calculated assuming 10% hydroformylation as for conventional oefininc feed Example 3 - Drilling Fluids C,6 Fischer-Tropsch internal olefins were obtained by metathesis and were 1o useable as a drilling fluid composition.
The drilling fluid composition included about 75% internal linear olefins and about 25% internal branched olefins, which internal branched olefins were predominantly mono-methyl, di-methyl and ethyl branched.
The drilling fluid compositions in accordance with the invention had the following physical properties:
The properties are for a typical C~2-C~6 internal linear and branched 2o combination of olefinic product made in accordance with the present invention:
Viscocity: 1-2 cSt @ 100'C
Flash point: >90'C
Linear:branch ratio 1:1 to 5:1 Pour Point: < 0'C
Examples of the internal olefins useful as drilling fluids include:
1) A drilling fluid including:
1o A linear component making up about 75.1 % of the composition; and A mono-methyl branched component making up about 24.9% of the drilling fluid composition.
2) A drilling fluid composition including:
A linear component of mainly hexadec-3-ene in amounts of between 2 and 40%, depending on process conditions; and A mono-methyl branched component of between 60% and 98% of the drilling fluid composition.
to Table 1: Mass and component balance of a batch reaction of water washed C7 cut COMPONENT FEED PRODUCT
mass % mass 3-Me-1-hexene 1.0693 0.0000 5-Me-1-hexene 2.365 5 0.0000 4-Me-1-hexene 3 . 8129 0. 0000 2-Me-1-hexene 6.0078 0.2428 2-Meth lhexane 1.6928 2.0457 3-Methylhexane 3.0273 3.3236 1-heptene 75.6871 0.9740 n-he tane 2.5700 2.3867 heptene (Z, E) 0.0000 0.0000 3-He tene 0.9803 3.1209 dime or cyclic olefin1.0121 0.0791 2-Heptene 0.0000 3.2820 Dimes or c clic olefins0.5094 0.0000 Ethylene 1.9997 Pro h lene 3.4060 Butenes 3.6816 Pentenes 4.1432 Hexenes 7.2954 Methyl branced heptenes 1.3442 n-octenes 9.7463 n-Nonenes 7.4719 Meth 1 branced nonenes 1.4163 n-Decenes 9.2216 Meth 1 branced decenes 2.713 8 n-undecenes 12.5128 Methyl branced undecenes 2.3198 n-dodecenes 12.0218 Methyl branced dodecenes 0.4282 tridecenes 2.9284 tetradecene 0.7476 pentadecene 0.1664 unknowns 1.2655 0.1664 Heavies 0.9803 Reaction Conditions in the above table:
MASS CATALYST (g) 51.81 MASS C7 FEED (g) 316.38 MASS PRODUCT (g) 280.55 mol me-hexenes + n-heptenes in 2.90 mol me-hexenes + n-heptenes out 0.26 to heptene conversion 91.06 mol C10 - 14 formed 0.94 mol % yield 65.18 selectivity (%) 71.58 II
TABLE 2: Mass and component balance of the batch reaction acetonitrile washed .
COMPONENT FEED PRODUCT
mass % Mass 3-Me-I-octene 0.1407 0.0000 7+4-Me-1-octene 0.9809 0.0000 6-me- I -octene 0. 963 7 0.0000 2-Me- I -octene 0. 8992 0.0000 4+2-Methyloctane 1.1467 1.4687 3-Meth loctane 1.5091 1.8279 n-nonenes 75.5614 15.3960 n-nonane 11.3149 13 .3231 dienes/cyclic olefins1.7378 1.1135 Eth lene 1.6064 Propylene 2.5809 Butenes 2.13 97 Pentenes 1.3528 Hexenes 0.7844 He tenes 1.403 5 n-octenes 4.4380 n-Decenes 10.1435 n-undecenes 1.7770 n-dodecenes 1.5719 Tridecenes 3.5240 methyl branched C 0.0000 Tetradecene 7.5024 methyl branched C 0.6842 Pentadecene 12.9260 meth I branched C 0.7234 Hexadecene 12.8760 He tadecene 0.8366 Unknowns 5.7457 0.8366 Reaction Conditions in the above table:
C9 : Re207 1000 :
MASS CATALYST (g) 0.75 MASS C9 FEED (g) 10.71 MASS PRODUCT (g) 9.99 mol me-octenes + n-nonenes 0.07 in mol me-octenes + n-nonenes 0.01 out nonene conversion 80.56 mol C14 - 18 formed 0.02 mol % yield 52.28 selectivity (%) 64.90 Table 3: Mass % of Components in Alkyl Benzene Product Component Mass%
Branched C,o benzene0.51 Branched C,o benzene0.12 Branched C,o benzene0.14 Branched C,o benzene0.20 Branched C,o benzene0.29 Branched C,o benzene0.39 5-Decylbenzene 2.91 4-Decylbenzene 2.7g Branched C,o benzene0.17 Branched C,o benzene0.76 3-Decylbenzene 4.34 Branched C,o benzene0.25 Branched C,o benzene0:82 Branched C" benzene 1.23 2-Decylbenzene 6.g7 Branched C" benzene 0.70 Branched C" benzene 0.57 Branched C" benzene 0_gg 5+6-Decylbenzene 7,g5 Branched C" benzene 0.52 4-Undecylbenzene 4.59 Branched C" benzene 1,7g 3-Undecylbenzene g.4g Branched C" benzene 1.10 Branched C,2 benzene0.41 Branched C,z benzene0.93 2-Undecylbenzene 10.22 Branched C,2 benzene0.59 Branched C,z benzene0.94 6-Dodecylbenzene 4.57 5-Dodecylbenzene 3.83 Branched C,z benzene0.71 4-Dodecyibenzene 3.85 Branched C,2 benzene0.49 Branched C,Z benzene0.54 Branched C,Z benzene0.82 3-Dodecylbenzene 5.96 Branched C,2 benzene0.66 Branched C,3 benzene0.74 2-Dodecylbenzene 7.92 5+6-Tridecylbenzene 1.04 4-Tridecylbenzene 0.73 3-Tridecylbenzene 1.42 2-Tridecylbenzene 1.38 Branched C,4 Benzenes0.46 Branched C,4 Benzenes1.45 5+6-Tetradecylbenzene0.50 4-Tetradecylbenzene 0.21 3-Tetradecylbenzene 0.51 2-Tetradecylbenzene 0.77 Table 4: Linear and Branched Analysis of Alkyl Benzene Product Component 2-Decylbenzene 6.87 3-Decylbenzene 4.34 4-Decylbenzene 2.79 5-Decylbenzene 2.91 Total linear 16.90 Total branched 3.65 2-Undecylbenzene 10.22 3-Undecylbenzene 8.49 4-Undecylbenzene 4.59 5+6-Undecylbenzene7.95 Total linear 31.26 Total branched 6.78 2-Dodecylbenzene 7.92 3-Dodecylbenzene 5.96 4-Dodecylbenzene 3.85 5-Dodecylbenzene 3.83 6-Dodecylbenzene 4.57 Total linear 26.13 Total branched 6.08 2-Tridecylbenzene1.38 3-Tridecylbenzene1.42 4-Tridecylbenzene0.73 5+6-Tridecylbenzene1.04 Total linear 4.56 Total branched 0.74 2-Tetradecylbenzene0.77 3-Tetradecylbenzene0.51 4-Tetradecylbenzene0.21 5+6-Tetradecylbenzene0.50 Total linear 1.98 Total branched 1.91
A linear component of mainly hexadec-3-ene in amounts of between 2 and 40%, depending on process conditions; and A mono-methyl branched component of between 60% and 98% of the drilling fluid composition.
to Table 1: Mass and component balance of a batch reaction of water washed C7 cut COMPONENT FEED PRODUCT
mass % mass 3-Me-1-hexene 1.0693 0.0000 5-Me-1-hexene 2.365 5 0.0000 4-Me-1-hexene 3 . 8129 0. 0000 2-Me-1-hexene 6.0078 0.2428 2-Meth lhexane 1.6928 2.0457 3-Methylhexane 3.0273 3.3236 1-heptene 75.6871 0.9740 n-he tane 2.5700 2.3867 heptene (Z, E) 0.0000 0.0000 3-He tene 0.9803 3.1209 dime or cyclic olefin1.0121 0.0791 2-Heptene 0.0000 3.2820 Dimes or c clic olefins0.5094 0.0000 Ethylene 1.9997 Pro h lene 3.4060 Butenes 3.6816 Pentenes 4.1432 Hexenes 7.2954 Methyl branced heptenes 1.3442 n-octenes 9.7463 n-Nonenes 7.4719 Meth 1 branced nonenes 1.4163 n-Decenes 9.2216 Meth 1 branced decenes 2.713 8 n-undecenes 12.5128 Methyl branced undecenes 2.3198 n-dodecenes 12.0218 Methyl branced dodecenes 0.4282 tridecenes 2.9284 tetradecene 0.7476 pentadecene 0.1664 unknowns 1.2655 0.1664 Heavies 0.9803 Reaction Conditions in the above table:
MASS CATALYST (g) 51.81 MASS C7 FEED (g) 316.38 MASS PRODUCT (g) 280.55 mol me-hexenes + n-heptenes in 2.90 mol me-hexenes + n-heptenes out 0.26 to heptene conversion 91.06 mol C10 - 14 formed 0.94 mol % yield 65.18 selectivity (%) 71.58 II
TABLE 2: Mass and component balance of the batch reaction acetonitrile washed .
COMPONENT FEED PRODUCT
mass % Mass 3-Me-I-octene 0.1407 0.0000 7+4-Me-1-octene 0.9809 0.0000 6-me- I -octene 0. 963 7 0.0000 2-Me- I -octene 0. 8992 0.0000 4+2-Methyloctane 1.1467 1.4687 3-Meth loctane 1.5091 1.8279 n-nonenes 75.5614 15.3960 n-nonane 11.3149 13 .3231 dienes/cyclic olefins1.7378 1.1135 Eth lene 1.6064 Propylene 2.5809 Butenes 2.13 97 Pentenes 1.3528 Hexenes 0.7844 He tenes 1.403 5 n-octenes 4.4380 n-Decenes 10.1435 n-undecenes 1.7770 n-dodecenes 1.5719 Tridecenes 3.5240 methyl branched C 0.0000 Tetradecene 7.5024 methyl branched C 0.6842 Pentadecene 12.9260 meth I branched C 0.7234 Hexadecene 12.8760 He tadecene 0.8366 Unknowns 5.7457 0.8366 Reaction Conditions in the above table:
C9 : Re207 1000 :
MASS CATALYST (g) 0.75 MASS C9 FEED (g) 10.71 MASS PRODUCT (g) 9.99 mol me-octenes + n-nonenes 0.07 in mol me-octenes + n-nonenes 0.01 out nonene conversion 80.56 mol C14 - 18 formed 0.02 mol % yield 52.28 selectivity (%) 64.90 Table 3: Mass % of Components in Alkyl Benzene Product Component Mass%
Branched C,o benzene0.51 Branched C,o benzene0.12 Branched C,o benzene0.14 Branched C,o benzene0.20 Branched C,o benzene0.29 Branched C,o benzene0.39 5-Decylbenzene 2.91 4-Decylbenzene 2.7g Branched C,o benzene0.17 Branched C,o benzene0.76 3-Decylbenzene 4.34 Branched C,o benzene0.25 Branched C,o benzene0:82 Branched C" benzene 1.23 2-Decylbenzene 6.g7 Branched C" benzene 0.70 Branched C" benzene 0.57 Branched C" benzene 0_gg 5+6-Decylbenzene 7,g5 Branched C" benzene 0.52 4-Undecylbenzene 4.59 Branched C" benzene 1,7g 3-Undecylbenzene g.4g Branched C" benzene 1.10 Branched C,2 benzene0.41 Branched C,z benzene0.93 2-Undecylbenzene 10.22 Branched C,2 benzene0.59 Branched C,z benzene0.94 6-Dodecylbenzene 4.57 5-Dodecylbenzene 3.83 Branched C,z benzene0.71 4-Dodecyibenzene 3.85 Branched C,2 benzene0.49 Branched C,Z benzene0.54 Branched C,Z benzene0.82 3-Dodecylbenzene 5.96 Branched C,2 benzene0.66 Branched C,3 benzene0.74 2-Dodecylbenzene 7.92 5+6-Tridecylbenzene 1.04 4-Tridecylbenzene 0.73 3-Tridecylbenzene 1.42 2-Tridecylbenzene 1.38 Branched C,4 Benzenes0.46 Branched C,4 Benzenes1.45 5+6-Tetradecylbenzene0.50 4-Tetradecylbenzene 0.21 3-Tetradecylbenzene 0.51 2-Tetradecylbenzene 0.77 Table 4: Linear and Branched Analysis of Alkyl Benzene Product Component 2-Decylbenzene 6.87 3-Decylbenzene 4.34 4-Decylbenzene 2.79 5-Decylbenzene 2.91 Total linear 16.90 Total branched 3.65 2-Undecylbenzene 10.22 3-Undecylbenzene 8.49 4-Undecylbenzene 4.59 5+6-Undecylbenzene7.95 Total linear 31.26 Total branched 6.78 2-Dodecylbenzene 7.92 3-Dodecylbenzene 5.96 4-Dodecylbenzene 3.85 5-Dodecylbenzene 3.83 6-Dodecylbenzene 4.57 Total linear 26.13 Total branched 6.08 2-Tridecylbenzene1.38 3-Tridecylbenzene1.42 4-Tridecylbenzene0.73 5+6-Tridecylbenzene1.04 Total linear 4.56 Total branched 0.74 2-Tetradecylbenzene0.77 3-Tetradecylbenzene0.51 4-Tetradecylbenzene0.21 5+6-Tetradecylbenzene0.50 Total linear 1.98 Total branched 1.91
Claims (49)
1. An oxo-alcohol composition including oxo-alcohols having from 8 to 18 carbon atoms, the oxo-alcohols being derived from olefins obtained by metathesis of one or more Fischer-Tropsch derived hydrocarbons selected from hydrocarbons having 5, 6, 7, 8, 9 and/or 10 carbon atoms.
2. An oxo-alcohol composition as claimed in claim 1, wherein between 10% and 99% of the oxo-alcohols of the composition are branched oxo-alcohols.
3. An oxo-alcohol composition as claimed in claim 1 or claim 2, wherein the oxo-alcohols of the composition are predominantly linear, with between 10% and 49% branched oxo-alcohols in the composition.
4. An oxo-alcohol composition as claimed in claim 3, wherein between 15% and 35% of the oxo-alcohols in the composition are branched oxo-alcohols.
5. An oxo-alcohol composition as claimed in claim 3, wherein 24% of the oxo-alcohols in the composition are branched oxo-alcohols.
6. An oxo-alcohol composition as claimed in any one of claims 2 to 5, wherein the branching on the branched oxo-alcohols is predominantly mono-methyl branching.
7. An oxo-alcohol composition as claimed in any one of claims 2 to 6, wherein the branching on the branched oxo-alcohols iincludes some di-methyl branching.
8. An oxo-alcohol composition as claimed in any one of claims 2 to 7, wherein the mono-methyl branching is in excess of 90% of the branching.
9. An oxo-alcohol composition as claimed in any one of claims 2 to 8, wherein the mono-methyl branching is in excess of 95% of the branching.
10. An oxo-alcohol composition as claimed in any one of claims 2 to 9, wherein the branching is predominantly on the C4+ carbons.
11. An oxo-alcohol composition as claimed in any one of claims 2 to 10, wherein some branching is present on the C2 carbon.
12. An oxo-alcohol composition as claimed in any one of claims 10 or 11, wherein the branching is over 70% on the C4+ carbons.
13. An oxo-alcohol composition as claimed in any one of claims 10 to 12, wherein the branching is over 90% on the C4+ carbons.
14. A plasticizer alcohol derived from at least a fraction of the oxo-alcohol composition as claimed in any one of the preceding claims, wherein the fraction includes hydrocarbons in the 8 to 10 carbon range.
15. A detergent alcohol derived from at least a fraction of the oxo-alcohol composition as claimed in any one of the preceding claims, wherein the fraction includes hydrocarbons in the 10 to 16 carbon range.
16. An alkyl benzene (AB) composition including AB having from 10 to 14 carbon atoms on the alkyl chain, the AB being derived from olefins obtained by metathesis of one or more Fischer-Tropsch derived hydrocarbons selected from hydrocarbons having 6, 7 and/or 8 carbon atoms.
17. An alkyl benzene (AB) composition as claimed in claim 16, which AB
composition includes between 10% and 90% of branched alkyl chain AB.
composition includes between 10% and 90% of branched alkyl chain AB.
18. An alkyl benzene (AB) composition as claimed in claim 16 or claim 17, wherein the AB composition includes predominantly linear alkyl chain AB, with between 10% and 49% branched alkyl chain AB in the composition.
19. An alkyl benzene (AB) composition as claimed in claim 18, wherein the composition includes between 15% and 35% branched alkyl chain AB.
20. An alkyl benzene (AB) composition as claimed in claim 18 or 19, wherein the composition includes 24% branched alkyl chain AB.
21. An alkyl benzene (AB) composition as claimed in any one of claims 17 to 20, wherein the branching on the branched alkyl chain of the AB is predominantly mono-methyl branching.
22. An alkyl benzene (AB) composition as claimed in any one of claims 17 to 20, wherein the branching on the branched alkyl chain of the AB includes di-methyl and/or ethyl branching.
23. An alkyl benzene (AB) composition as claimed in claim 21 or claim 22, wherein the mono-methyl branching is in excess of 90% of the branching.
24. An alkyl benzene (AB) composition as claimed in claim 21 or claim 22, wherein the mono-methyl branching is in excess of 95% of the branching.
25. An alkyl benzene (AB) composition as claimed in any one of claims 17 to 24, wherein the branching is predominantly on the C4+ carbons of the alkyl chain of the AB.
26. An alkyl benzene (AB) composition as claimed in any one of claims 17 to 25, wherein some of the branching is on the C2 carbon of the alkyl chain of the AB.
27. An alkyl benzene (AB) composition as claimed in any one of claims 17 to 26, wherein the branching is in excess of 70% on the C4+ carbons of the alkyl chain of the AB.
28. An alkyl benzene (AB) composition as claimed in any one of claims 17 to 26, wherein the branching is in excess of 90% on the C4+ carbons of the alkyl chain of the AB.
29. A detergent composition including a sulfonated alkyl benzene as claimed in any one of claims 16 to 28.
30. A drilling fluid composition including an AB composition as claimed in any one of claims 16 to 28.
31. A drilling fluid composition including hydrocarbons having from 14 to 18 carbon atoms, the hydrocarbons being derived from olefins obtained by metathesis of one or more Fischer-Tropsch derived hydrocarbons selected from hydrocarbons having 8, 9 and/or 10 carbon atoms.
32. A drilling fluid composition as claimed in claim 31, wherein the hydrocarbons are internal olefins.
33. A drilling fluid composition as claimed in claim 31 or 32, which includes between 10% and 90% branched hydrocarbons.
34. A drilling fluid composition as claimed in any one of claims 31 to 33, wherein the hydrocarbons are predominantly linear.
35. A drilling fluid composition as claimed in claim 33 or 34, which composition includes between 10% and 49% branched hydrocarbons.
36. A drilling fluid composition as claimed in claim 33 or 34, which composition includes between 15% and 35% branched hydrocarbons.
37. A drilling fluid composition as claimed in claim 33 or 34, which composition includes 24% branched hydrocarbons.
38. A drilling fluid composition as claimed in any one of claims 33 to 37, wherein the branching on the branched hydrocarbons is predominantly mono-methyl branching.
39. A drilling fluid composition as claimed in any one of claims 33 to 38, which includes some di-methyl and/or ethyl branching.
40. A drilling fluid composition as claimed in any one of claims 33 to 39, wherein the branching is predominantly on the C4+ carbons of the alkyl chain of the AB.
41. A drilling fluid composition as claimed in any one of claims 33 to 40, which includes branching on the C2 carbon of the alkyl chain of the AB.
42. A drilling fluid composition as claimed in any one of claims 33 to 41, wherein the branching is in excess of 70% on the C4+ carbons of the alkyl chain of the AB.
43. A drilling fluid composition as claimed in any one of claims 33 to 42, wherein the branching is in excess of 90% on the C4+ carbons of the alkyl chain of the AB.
44. A drilling fluid composition as claimed in any one of claims 38 to 43, wherein the mono-methyl branching is in excess of 90% of the branching.
45. A drilling fluid composition as claimed in any one of claims 38 to 44, wherein the mono-methyl branching is in excess of 95% of the branching.
46. An oxo-alcohol composition, substantially as herein described and illustrated.
47. An alkyl benzene composition, substantially as herein described and illustrated.
48. A drilling fluid composition, substantially as herein described and illustrated.
49. A new oxo-alcohol composition, a new alkyl benzene composition, or a new drilling fluid composition substantially as herein described.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14238199P | 1999-07-06 | 1999-07-06 | |
| ZA994377 | 1999-07-06 | ||
| ZA99/04377 | 1999-07-06 | ||
| US60/142,381 | 1999-07-06 | ||
| PCT/ZA2000/000123 WO2001002328A1 (en) | 1999-07-06 | 2000-07-06 | Use of metathesis products of fischer-tropsch process products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2376603A1 true CA2376603A1 (en) | 2001-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002376603A Abandoned CA2376603A1 (en) | 1999-07-06 | 2000-07-06 | Use of metathesis products of fischer-tropsch process products |
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| Country | Link |
|---|---|
| EP (1) | EP1198442A1 (en) |
| JP (1) | JP2003527315A (en) |
| CN (1) | CN1402698A (en) |
| AU (1) | AU6541500A (en) |
| BR (1) | BR0012225A (en) |
| CA (1) | CA2376603A1 (en) |
| WO (1) | WO2001002328A1 (en) |
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|---|---|---|---|---|
| DE10305562A1 (en) * | 2003-02-10 | 2004-08-26 | Sasol Germany Gmbh | Ester mixtures based on branched alcohols and / or branched acids and their use as a polymer additive |
| US8524965B2 (en) | 2005-12-21 | 2013-09-03 | Chevron Oronite Company Llc | Method of making an alkylated aromatic using acidic ionic liquid catalyst |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5116618A (en) * | 1974-07-31 | 1976-02-10 | Nissan Chemical Ind Ltd | Arukirubenzenno seizohoho |
| US4544792A (en) * | 1984-12-13 | 1985-10-01 | Mobil Oil Corporation | Upgrading Fischer-Tropsch olefins |
| EP0276096A1 (en) * | 1987-01-21 | 1988-07-27 | Mobil Oil Corporation | An olefin metathesis process |
| GB2258258B (en) * | 1991-07-27 | 1995-04-19 | David Brankling | Drilling fluid |
| WO1994012589A1 (en) * | 1991-07-27 | 1994-06-09 | Oilfield Chemical Technology Limited | Drilling fluid |
| GB9216014D0 (en) * | 1992-07-28 | 1992-09-09 | British Petroleum Co Plc | Lubricating oils |
| EG22088A (en) * | 1996-04-16 | 2002-07-31 | Procter & Gamble | Alkoxylated sulfates |
| MA24136A1 (en) * | 1996-04-16 | 1997-12-31 | Procter & Gamble | MANUFACTURE OF SURFACE AGENTS. |
| FR2789072B1 (en) * | 1999-01-29 | 2001-04-13 | Inst Francais Du Petrole | PROCESS FOR THE METATHESIS OF OLEFINS IN THE PRESENCE OF A CATALYST STABILIZING AGENT |
-
2000
- 2000-07-06 JP JP2001507773A patent/JP2003527315A/en active Pending
- 2000-07-06 CA CA002376603A patent/CA2376603A1/en not_active Abandoned
- 2000-07-06 CN CN00812371A patent/CN1402698A/en active Pending
- 2000-07-06 AU AU65415/00A patent/AU6541500A/en not_active Abandoned
- 2000-07-06 WO PCT/ZA2000/000123 patent/WO2001002328A1/en active Application Filing
- 2000-07-06 BR BR0012225-4A patent/BR0012225A/en not_active IP Right Cessation
- 2000-07-06 EP EP00952774A patent/EP1198442A1/en not_active Withdrawn
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| AU6541500A (en) | 2001-01-22 |
| WO2001002328A1 (en) | 2001-01-11 |
| CN1402698A (en) | 2003-03-12 |
| BR0012225A (en) | 2002-03-26 |
| EP1198442A1 (en) | 2002-04-24 |
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