Patent Application
20130137911
The present invention relates to the dimerization of isobutene. More particularly a subject of the present invention is a novel catalytic composition and a process for the dimerization of isobutene (pure or in a mixture with other hydrocarbons) using this novel catalytic composition.
It is known that the dimers of isobutene (2,4,4-trimethyl-1-(and -2-) pentene) are useful intermediates for the production of different products of commercial interest. By way of example, the higher alcohols, aldehydes and the acids can be mentioned.
2,2,4-Trimethylpentane can be obtained by hydrogenation of trimethylpentenes and constitutes a sought additive for the reformulation of gasolines (absence of sulphur, aromatics and olefins, and low volatility added to a high octane number: Motor octane number (MON) (sic)=Research octane number (RON)=100).
Thus, the selective dimerization of isobutene, followed by hydrogenation of the obtained products to 2,2,4-trimethylpentane having a high octane number, constitutes a useful route which allows
The dimerization (and also the oligomerization) of isobutene is an exothermic reaction catalyzed by acids. Different acids have been described in the literature such as sulphuric acid, or derivatives thereof, the chlorinated or fluorinated aluminas, zeolites, silica-aluminas etc. However, those most typically used in industry are phosphoric acid, generally supported, and ion-exchange resins (SP-Isoether process licensed by Snamprogetti or UOP's InAlk process).
The main difficulty associated with these processes is obtaining good dimer selectivity. In fact, the exothermicity of the reaction is often difficult to control and leads to the formation of oligomers (essentially C12 olefins and C16 olefins) obtained by parallel reactions starting from isobutene. These oligomers have boiling points which are too high, and are outside, or at the limit, of the specifications required for reformulated gasolines. Moreover, these oligomers contribute to deactivation of the catalysts.
Different works in the literature describe certain solutions for minimizing the formation of these oligomers.
In the case of the ion-exchange resins (Amberlyst-15 or -35 type), the use of a diluent (or solvent) is often recommended. The dimer selectivity depends on the choice of this solvent. The most efficient additives are the alcohols (U.S. Pat. No. 5,877,372; U.S. Pat. No. 4,100,220), which lead to the co-production of ethers, or ethers (in U.S. Pat. No. 4,447,668, MTBE, ETBE, etc.). Mention may be made of the works by Snamprogetti (M. Marchionna et al. Catal. Today, 65 (2001) 397-403, GB 2 325 237) studying the influence of the addition of MTBE or MeOH with the objective of reusing the existing units of MTBE. Useful trimethylpentene selectivities can thus be achieved but often with less than 85% isobutene conversion.
International patent application WO-A-01/51 435 describes a series of processes in which isobutene is produced by dehydration of tert-butyl alcohol. The isobutene is preferentially dimerized by an Amberlyst A-15® type resin in the presence of tert-butyl alcohol (selectivity promoter) and alkane (butane or isobutane) as diluent. The presence of a hindered alcohol discourages the formation of ether but also reduces the rate of reaction.
All the processes described previously have limitations such as the risks of premature deactivation of the catalyst by “clogging” with the heavier oligomers or also the need to use organic additives to control the selectivity of the reaction, organic additives which are often converted and consumed during the reaction and are therefore not recyclable.
The non-aqueous ionic liquids of composition Q+A− have been the subject of several articles (for example, H. Olivier-Bourbigou et al., Appl. Catal. A: General, 2010, 1-56). They find numerous applications as solvents for catalysis by transition metals or as extraction solvents for carrying out liquid-liquid extractions.
The patent application WO-A-00/16902 describes the use of an ionic liquid free of Lewis acidity obtained by reaction of a nitrogen-containing (for example an amine or a quaternary ammonium) or phosphorus-containing compound with a Brønsted acid in quantities such that the ratio of said nitrogen-containing or phosphorus-containing compound to the acid is less than 1. These media are used to catalyze in particular the alkylation of benzene with 1-decene.
It has also been described in the application FR2829039 that the addition of at least one Brønsted acid, designated HB, in a non-aqueous liquid medium (“molten salt” type medium) comprising at least one organic cation Q+ and an anion A− and in which, when A and B are identical, the molar ratio of the Brønsted acid to the ionic liquid is less than 1/1, leads to liquid compositions which can be used as catalysts and solvents for acid catalysis reactions.
In this patent application, it was mentioned that the catalytic composition described could be used more particularly in the alkylation of aromatic hydrocarbons, but also in the oligomerization of olefins, the dimerization of isobutene, the alkylation of isobutane by olefins, the isomerization of n-paraffins to iso-paraffins and the isomerization of n-olefins to iso-olefins.
The use of the ionic liquids as solvents and acid catalysts for the selective dimerization of isobutene has also been described in the U.S. Pat. No. 7,256,152. The advantage of these liquid catalytic systems for the dimerization reaction of isobutene to isooctenes is that they are not very miscible with the reaction products which can therefore be separated by decantation. The catalytic phase can then be recycled and reused, the consumption of catalyst is thus reduced. However, these systems also have limitations. Like heterogeneous catalysts, it is sometimes difficult to maintain good selectivity of dimerization products at a high isobutene conversion.
A subject of the present invention is to provide a novel catalytic composition making it possible to improve the selectivity of the isobutene dimerization reaction.
Furthermore, the catalytic composition can be recycled without a significant lowering of its catalytic activity and without a significant lowering of its dimer selectivity. The additive included in the catalytic composition according to the invention is therefore neither converted nor consumed during the reaction and is therefore recyclable. It is therefore not necessary to continuously inject an additive.
More particularly, the present invention relates to a catalytic composition comprising at least one Brønsted acid, designated HB, dissolved in a non-aqueous liquid medium of general formula Q1+A1−, in which Q1+ represents an organic cation and A1− represents an anion, said composition also comprising an additive Q2+A2− in which Q2+ represents an organic cation comprising at least one alcohol function and A2− represents an anion.
The ionic liquid Q1+A1−, in which the Brønsted acid HB is dissolved, is defined such that Q1+ represents a quaternary ammonium and/or a quaternary phosphonium and/or a trialkylsulphonium and A1− represents any anion known to be non-coordinating and capable of forming a liquid salt at low temperature, i.e. below 150° C. The additive Q2+A2− is defined such that Q2+ represents a quaternary ammonium and/or a quaternary phosphonium and/or a trialkylsulphonium comprising at least one alcohol function and A2− represents any anion known to be non-coordinating and capable of forming a liquid salt at low temperature, i.e. below 150° C.
The anions A1− or A2− considered in the invention are preferably chosen from the following anions: tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulphonates and arylsulphonates (for example methylsulphonate or tosylate), perfluoroalkylsulphonates (for example trifluoromethylsulphonate), fluorosulphonate, sulphates, phosphates, perfluoroacetates (for example trifluoroacetate), perfluoroalkylsulphonamides (for example bis-trifluoromethanesulphonyl amide (N(CF3SO2)2−), fluorosulphonamides, perfluoroalkylsulphomethides (for example tris-trifluoromethanesulphonyl methylide (C(CF3SO2)3−) and carboranes, A1 and A2− being identical or different. Preferably, A1 and A2− are identical.
The cations Q1+ and Q2+ considered in the invention are preferably chosen from the quaternary ammoniums and/or the quaternary phosphoniums and/or the trialkylsulphoniums. The chemical nature of Q1+ and Q2+can be identical or different, it is preferably identical. By “identical chemical nature” is meant that if, for example, the cation Q1+ is a quaternary ammonium, Q2+ is also a quaternary ammonium. By “different chemical nature” is meant that if, for example, the cation Q1+ is a quaternary ammonium, Q2+ is chosen from a quaternary phosphonium or a trialkylsulphonium. In any case, the organic cation Q2+ of the additive Q2+A2− contains at least one alcohol function, while the substituents of the organic cation Q1+ do not have an alcohol function. By “alcohol function” is meant an OH group grafted onto the cation Q2+, either directly onto a carbon of the cation Q2+, or via an aryl, aralkyl, alkyl or cycloalkyl group, preferably comprising from 1 to 12 carbon atoms.
The quaternary ammoniums and/or phosphoniums of general formula Q1+ and Q2+ preferably correspond to the formulae NR1R2R3R4+ and PR1R2R3R4+, or to general formulae R1R2N═CR3R4+ and R1R2P═CR3R4+ where
The quaternary ammoniums and/or phosphoniums of general formula Q1+ and Q2+ can also be derived from nitrogen-containing (imidazolium, pyridinium, pyrrolidinium, pyrazolium, triazolium) or phosphorus-containing heterocycles comprising 1, 2 or 3 nitrogen and/or phosphorus atoms, of general formulae:
in which the rings are constituted by 4 to 10 atoms, preferably 5 to 6 atoms, R1 and R2 for Q1+ or Q2+ being defined as previously.
The quaternary ammoniums and/or phosphoniums of general formula Q1+ and Q2+ can also consist of a cation corresponding to one of general formulae:
R1R2+N═CR3—R5—R3C═N+R1R2 and
R1R2+P=CR3—R5—R3C═P+R1R2
in which R1, R2 and R3, identical or different, are defined as previously for Q1+ or Q2+ and R5 represents an alkylene or phenylene radical.
Among the R1, R2, R3 and R4 groups the methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, phenyl or benzyl radicals will be mentioned; R5 can be a methylene, ethylene, propylene or phenylene group.
Among the R1, R2, R3 and R4 groups containing an alcohol function, the —CH2OH, —(CH2)2OH, —(CH2)3OH, —(CH2)4OH, —C(CH3)2—CH2OH, —CH2—C(CH3)2OH, —C(CH3)H—CH2OH, —C6H4—CH2OH radicals will be mentioned.
The quaternary ammonium and/or phosphonium cation Q1+ is preferably chosen form the group formed by N-butylpyridinium, N-ethylpyridinium, 1-butyl-3-methylimidazolium, diethylpyrazolium, 1-ethyl-3-methylimidazolium, pyridinium, trimethylphenylammonium, tetrabutylphosphonium, N-ethyl-N-methylpyrrolidinium and N-butyl-N-ethylpyrrolidinium.
The quaternary ammonium and/or phosphonium cation Q2+ is preferably chosen from the group formed by 1-butyl-3-(2-hydroxyethyl)imidazolium, 1-ethyl-3-(2-hydroxyethyl)imidazolium, N-butyl-N-(2-hydroxyethyl)pyrrolidinium, N-ethyl-N-(2-hydroxyethyl)pyrrolidinium, (2-hydroxyethyl)triethylammonium and triphenyl(3-hydroxypropyl)phosphonium.
The trialkylsulphoniums Q1+ or Q2+ considered in the invention have a general formula of SR1R2R3+ in which
As examples of the ionic liquids Q1+A1− which can be used, N-butylpyridinium hexafluorophosphate, N-ethylpyridinium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethylsulphonate, pyridinium fluorosulphonate, trimethylphenylammonium hexafluorophosphate, 1-butyl-3-methylimidazolium bis-trifluoromethylsulphonylamide, N-ethyl-N-methylpyrrolidinium bis-trifluoromethylsulphonylamide, triethylsulphonium bis-trifluoromethylsulphonylamide, tributylhexylammonium bis-trifluoromethylsulphonylamide, 1-butyl-3-methylimidazolium trifluoroacetate and 1-butyl-2,3-dimethylimidazolium bis-trifluoromethylsulphonylamide can be mentioned.
These ionic liquids can be used alone or in a mixture. They have a solvent function.
As examples of the additives Q2+A2− which can be used, N-(4-hydroxybutyl)pyridinium hexafluorophosphate, N-(2-hydroxyethyl)pyridinium tetrafluoroborate, 1-(4-hydroxybutyl)-3-methylimidazolium hexafluoroantimonate, 1-(4-hydroxybutyl)-3-methylimidazolium hexafluorophosphate, 1-(4-hydroxybutyl)-3-methylimidazolium trifluoromethylsulphonate, N-(2-hydroxyethyl)pyridinium fluorosulphonate, trimethyl(2-hydroxyethyl)ammonium hexafluorophosphate, 1-(4-hydroxybutyl)-3-methylimidazolium bis-trifluoromethylsulphonylamide, N-(2-hydroxyethyl)-N-methylpyrrolidinium bis-trifluoromethylsulphonylamide, diethyl(2-hydroxyethyl)sulphonium bis-trifluoromethylsulphonylamide, tri butyl (4-hydroxybutypammonium bis-trifluoromethylsulphonylamide, 1-(4-hydroxybutyl)-3-methylimidazolium trifluoroacetate, 1-(4-hydroxybutyl)-2,3-dimethylimidazolium bis-trifluoromethylsulphonylamide and 1-butyl-3-(2-hydroxyethyl)imidazolium bis-trifluoromethylsulphonylamide can be mentioned.
These additives can be used alone or in a mixture. They make it possible to improve the dimer selectivity and are recyclable.
Preferably, the anions A1− and A2− are identical in the catalytic composition used according to the invention. The molar ratio between the additive Q2+A2− and the ionic liquid Q1+A1− is preferably less than 2/1, and yet more preferably less than 1/1.
The Brønsted acids are defined as being organic acid compounds capable of donating at least one proton. These Brønsted acids have a general formula HB, in which B represents an anion.
The anions B are preferably chosen from tetrafluoroborate, tetraalkylborates, hexafluorophosphate, hexafluoroantimonate, alkylsulphonates and arylsulphonates (for example methylsulphonate or tosylate), perfluoroalkylsulphonates (for example trifluoromethylsulphonate), fluorosulphonate, sulphates, phosphates, perfluoroacetates (for example trifluoroacetate), perfluoroalkylsulphonamides (for example bis-trifluoromethanesulphonyl amide (N(CF3SO2)2−), fluorosulphonamides, perfluoroalkylsulphomethides (for example tris-trifluoromethanesulphonyl methylide (C(CF3SO2)3−) and carboranes.
The Brønsted acids can be used alone or in a mixture. Preferably, the anions B, A1− and A2− are identical in the formula of the Brønsted acids used.
In all cases, the molar ratio of the Brønsted acid to the sum of (Q1+A1−+Q2+A2−) is less than 2/1, preferably less than 1/1.
The compounds involved in the catalytic composition used in the process of the invention can be mixed in any order. The mixing can be done by simply bringing them into contact followed by stirring until a homogeneous liquid is formed. This mixing can be done outside the reactor used for the catalytic application or inside this reactor.
Also a subject of the present invention is an isobutene dimerization process using the catalytic composition. The dimerization process according to the invention applies to pure isobutene or isobutene in a mixture with other hydrocarbons.
The sources of isobutene are varied. However, the most common are the dehydrogenation of isobutane and the dehydration of tert-butyl alcohol The isobutene can also originate from a C4 cut from catalytic cracking in a fluidized bed or from steam cracking. In this latter case, the isobutene can be used in a mixture with n-butenes, isobutane and butane. The process according to the present invention then has the additional advantage of making it possible to selectively convert the isobutene without having to separate the other constituents of the cut. Another advantage of the process according to the invention is that the isobutene-butene co-dimerization can be limited.
Recent advances in the field of biotechnologies show that it is also possible to produce isobutene from 2-methyl-propanol (isobutanol), itself obtained from sugars originating from the fermentation of biomass.
The ratio by volume of the isobutene to the catalytic composition can be comprised between 0.1/1 and 1000/1, preferably between 1/1 and 100/1. It is chosen so as to obtain the best selectivities.
The reaction can be carried out in a closed system, in a semi-open system or continuously with one or more reaction stages. At the reactor outlet, the organic phase containing the reaction products is separated.
In the dimerization process of the invention, an organic solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon immiscible or partially miscible with the ionic liquid can be added to the catalytic composition which allows a better separation of the phases. As aliphatic hydrocarbon for example pentane, heptane, cyclohexane, decane, dodecane or a paraffinic feedstock can be used, alone or in a mixture. As aromatic hydrocarbon for example toluene or xylene can be used, alone or in a mixture.
The temperature at which the dimerization reaction is carried out ranges for example from −50° C. to 200° C.; it is advantageously below 100° C.
The reaction can be carried out at autogeneous pressure, this can also be increased up to 10 MPa.
The dimerization reaction can be carried out using a reactive distillation technique.
The products obtained by the present invention can be subsequently converted according to different reactions, such as hydrogenation, hydroformylation, oxidation, etherification, epoxidation or hydration.
The following examples illustrate the invention without limiting its scope.
20 g (0.16 mol) of N-butylimidazole as well as 25.9 g (0.32 mol) of 1-chloroethanol are introduced under an inert atmosphere into a 500 ml flask. Then 150 mL of acetonitrile is added. The mixture is refluxed for 5 days. After returning to ambient temperature, the acetonitrile is removed under vacuum. A viscous yellow-coloured liquid is obtained. This compound is dissolved in 100 mL of dichloromethane. Then 48.2 g (0.168 mol) of lithium bis(trifluoromethylsulphonyl)amide is added. After reaction for 2 h at ambient temperature, the mixture is filtered on “neutral celite 545/Al2O3” before the solvent is evaporated off under dynamic vacuum. The liquid residue is washed several times with water then dried at 80° C. under dynamic vacuum. 34.5 g (yield 48%) of [BuIm(CH2)2OH][N(CF3SO2)2] is obtained. 1H and 13C NMR analyses confirm the structure of the expected product.
4.97 g (11.9 mmol) of 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)amide [BMIm][N(CF3SO2)2)] is mixed at ambient temperature, under an inert atmosphere, with 0.85 g (1.9 mmol) of [BuIm(CH2)2OH][N(CF3SO2)2] described in Example 1. The mixture represents a volume of 4 mL. Then 0.014 g (0.051 mmoles) of bis-triflylamide acid HN(CF3SO2)2 is added. The mixture is stirred for a few minutes and leads to a clear solution containing 0.013 mol/L of acid.
4 mL (5.5 g, 13.1 mmol) of 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)amide [BMIm][N(CF3SO2)2) is mixed at ambient temperature, under an inert atmosphere, with 0.015 g (0.054 mmoles) of bis-triflylamide acid HN(CF3SO2)2. The mixture is stirred for a few minutes and leads to a clear solution containing 0.013 mol/L of acid.
4 mL (4.8 g, 10.7 mmol) of [BuIm(CH2)2OH][N(CF3SO2)2] described in Example 1 is mixed at ambient temperature, under an inert atmosphere, with 0.014 g (0.013 mmoles) of bis-triflylamide acid HN(CF3SO2)2. The mixture is stirred for a few minutes and leads to a clear solution containing 0.013 mol/L of acid.
All of the mixture prepared in Example 2 is introduced, under an argon atmosphere, into a 100 mL Fisher-Porter tube, provided with a magnetic stirring bar and dried and brought under vacuum before the study. Then, 20 mL (11.2 g) of a liquid feedstock containing 95% isobutene and 5% n-butane is introduced, at ambient temperature. Stirring is then started (reaction time zero). After reaction for 20 minutes at 25° C., the stirring is stopped. The supernatant organic phase is separated from the ionic liquid phase and analyzed by GC (gas chromatography, with heptane as external standard) after treatment with soda (10N) in order to remove any traces of acid and drying over MgSO4. The isobutene conversion is 73%. The dimerization product selectivity (C8) is 74%, the trimer selectivity (C12) is 23% and the tetramer selectivity (C16) is 3%.
The ionic liquid phase containing the [BuIm(CH2)2OH][N(CF3SO2)2]/[BMIm][N(CF3SO2)2]/HN(CF3SO2)2 mixture was isolated and reused over several catalysis cycles without adjustment of the catalytic composition (Examples 6 to 11). The results obtained are shown in Table 1.
The protocol is identical to that described in Example 5 except that the catalytic composition described in Example 3 is used. After reaction for 7 minutes at 25° C., the stirring is stopped. The supernatant organic phase is separated from the ionic liquid phase and analyzed by GC. The isobutene conversion is 84%. The dimerization product selectivity (C8) is 47%, the trimer selectivity (C12) is 46% and the tetramer selectivity (C16) is 6% (see Table 2).
The protocol is identical to that described in Example 5 except that the catalytic composition described in Example 4 is used. After reaction for 20 minutes at 25° C., the stirring is stopped. The supernatant organic phase is separated from the ionic liquid phase and analyzed by GC. No conversion of isobutene was observed (see Table 2).
The catalytic composition containing the additive Q2+A2− according to the invention makes it possible to obtain a better selectivity of C8 dimers compared to a catalytic composition without additive. It can also be seen that the catalytic system is recyclable.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
The entire disclosures of all applications, patents and publications, cited herein and of corresponding French application Ser. No. 11/03654, filed Nov. 30, 2011, are incorporated by reference herein.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11/03.654 | Nov 2011 | FR | national |
