CA2194616A1 - Increased degree of olefin oligomerization yield through process modifications - Google Patents
Increased degree of olefin oligomerization yield through process modificationsInfo
- Publication number
- CA2194616A1 CA2194616A1 CA 2194616 CA2194616A CA2194616A1 CA 2194616 A1 CA2194616 A1 CA 2194616A1 CA 2194616 CA2194616 CA 2194616 CA 2194616 A CA2194616 A CA 2194616A CA 2194616 A1 CA2194616 A1 CA 2194616A1
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- Prior art keywords
- alcohol
- hexanol
- butanol
- mole
- pro
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- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process is described for producing a synthetic hydrocarbon especially useful as a base for high performance motor oils. The material is an .alpha.-olefin monomer having a uniquely selective product distribution emphasizing tetramers and pentamers. This distribution is achieved by using a catalyst comprising boron trifluoride and a long, straight-chain alcohol promoter, such as 1-hexanol.
Description
INCI~F'\S'n DEGREE OF OLEFIN OLIGOMERIZATION YIELD
THROUGH PROCESS MODIFICATIONS
The present invention relates to a pr~cess of producing a higher degree 5 of olefin oligo,neri~dlion.
BACKGROUND OF THE INVENTION
Synthetic lubricants prodl)ced by the oligo",eri~alion of alpha-olefins are 10 well-known. The nature of the alpha-olefin from which these oligomers are produced prescribes the properties of the resultant lubricant.
While it has been repo, led that even fairly large amounts of intemal or branched-chain olefins may be present without extremely adverse effect on the 15 alpha~lefin oligomerization the resultant lubricants have restricted utility and do not justify their usage as a replace" ,e, It for naturally occurring petroleum fluids.
In general linear olefins of from eight to twelve csrbo"s have proven most effective. Normal alpha-olefins are generally ,ureferred.
OligG",eri~alion may be achieved with a wide variety of catalysts.
Represenlati~/e catalyst include such Friedel-Crafts agents as AlCb AlBr3 BF3 BCI3 GaCI4 and the like. Although each such agent fadlitates 01igo",6ri~lion the activity of the catalyst will dmer widely. The very active catalyst such as 25 AlCb will produoe e~lr~ ely high moleu ~ weight polymers in conjunction with use of appropriate pro",oter:~. Other Friedel~raft catalysts such as SnC14 or GaCb may present ~1;SPOSAI proble.ns after use. Moreover solid catalysts present difficulties with r~spect to control of the exoU ,el " lic oligo" ,eri~ation reaction due to the I ,eterogeneous nature of the reaction system.
A pref~r,ed catalyst has been boron trifluoride (BF3), which forms a liquid complex with the necess~- y pr~,l,oter:~, and thus lends itself to conven~ional reaction systems.
Boron trifluoride and the other catalysts must be used in comb-.nation with a pr~l"o~er. The pro",o~er complexes with the BF3 and in so doing provides an ~1 946 1 6 activated system needed for ir,ilialion of the oliyo",eri~lion reaction. Among the most widely used promoter~ are the alkanoic and/or inorganic acids which are suitable for selective foi",alion of oligom~f~ ranging from two to four monomeric units.
Conventional practice for conducting the oligo",e, i~alion reaction has been to admix the pro",oter with the monomeric olefin in the prese,)ce of an imposed al",ospl,ere of BF3 which is normally ~seo~s The presence of excess BF~ necess~ry for the reaction is delineated by the observed pressure of 10 BF3 in the reaction vessel.
The rate of oligo"~eri,alion is related to some degree to the BF3 pressure since the p~bability of excess BF3 in the liquid reactants is directly related to its pressure.
The use of a variety of alcohols as pro,nol~rs is disclosed by Shubkin in - U.S. Patent No. 3 780128 entitled ~Syntl,etic Lubric~,)ls by Oligo",eri~alion and H~,drogenalion.~ There is no ~isa Issi^n on the pros and cons of the various alcohols but the prerer,ed alcohol is propanol.
The use of variety of alcohols as pro",ot~r~ is also disclosed by Cupples et al. in U.S. Patent No. 4,045,508 entitled ~Method of Mal;ing Alpha-Olefin Oli~o",ers,~ but that ,ererence does not disalss the relative ad\,an~ages and disadvantages of each pr~moter.
A two-step process using a mixture propanol and hexanol is disclosed by Pratt in U.S. Patent No. 4,587 368 entitled "rrocess for Producing Lubricant 1\1aterial,~ where an aliquot of ",o"on,er is added to an inle""ediale oligo",er.
Example 2 shows that a 75:25 mixture of hexanol and p~,a, lol leads to a 30 heavier product than a 50:50 mixture of I ,exanol and propa, lol U.S. Patent Nos. 3,780,128; 4,045,508; and 4,587,368 are hereby inCGI ~.oraled by r e~r~"ce for all p~" poses.
The s~hseguent reri,)i"~ processes can be ",~lrried to yield particular product co",posilions. Where for example a lubricant c~"sisli"g chiefly of ~ 21 9461 6 ,, higher oligomers is desired, one may remove u"reacted " ,GnGmer and low boiling dimer by distillation at at"lospl ,eric pressure. Trimer has also been removed in this "~an,)er, but through conditions of high vacuum distillation.
After hyd,oge"alion, the suL~lantially saturated lubricant material is then ready for co""~ounding. Depending upon its co"~posilion and properties, it may be used directly in a wide variety of known applications. Allel ndli~ely, known lubricant additives may be incorporated. The material may be mixed with other available lubricants, to achieve the characteristics necessary for given conventional utilities.
Products of many of these known oligomerization reactions have been primarily designed for specialized applications. Aircraft hydraulic or turbine oils, for example, possess low viscosity requirements requiring oligomerization limited to dimers, trimers and tetramers (with emphasis on the trimer). Polymers resulting from such a procedure, however, have limited application as conventional lubricants. Lubricants for higher temperature, e.g., motor oils andindustrial lubricants use, require considerably higher viscosilies.
In general, higher viscosity fluids can only be made with a severe production rate penalty, since longer resi"e"ce times are required to achieve the target viscosity with current technology.
SUMMARY OF THE INVENTION
The present invention provides a process for producing a high degree of olefin oligoi"eri~alion. We have found that the oligomer distribution can be affected by the size of the primary alcohol that is used as pro,noter. A higher degree of oligomerization can be achieved by in~easin~ the carbon to hydroxyl ratio for alcohol pro",oters. Moreover, we have also found that by using longer straight chain alcohols, we can produce a heavier product viscosily with greaterBF3 efficiency.
In our process, a synthetic lubricant material is pro~4lced by oligo"~eri~i"g a C~.,6 a-olefin monomer in the presence of a boron trifluoride catalyst and a straight-chain alcohol promoter, wherein subslar,lially all of the alcohol proi"oter has a carbon number of at least four, and at least 80 wt.% of the alcohol pr~rnoter has a ca, ~on number of at least five.
r~ eferably the olefinic " ,onG"~er contains pr~dG" linately 10 to 12 carbon 5 atoms.
Pfeferably s~ s~ tially all of the alcol ,ol pro",oter has a carbon number of at least five and least 80 wt.% of the alcohol promoter has a carbon number of at least six. Most preferably the alcohol pro",oter is 1 ~exanol.
BRIEF DESCRIPTION OF THE DRAWINGS
In order to assist the understanding of this invention reference will now be made to the appended drawings. The drawings are exemplary only and 15 should not be construed as limiting the invention.
The Figure shows the effect of longer chain alcohols on the oligomer distribution of the product. It shows the data from Exan,ples 6 through 8 and Compardli~e Example B.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect the presenl invention involves the oligomeri~alion of an olefinic ",Gno",er by contacting that ",onoi"er with boron trifluoride and a 25 straight-chain alcohol ,l~r~",oler. Sul~sl&nt.ally all of the ~Icol lol pr~i"oler has a carbon number of at least four at least 80 wt.% of the alcohol pr~""oler has a carbon number of at least five.
OLEFINIC MONOMER
The olefins used in ".ahing the oligomer are predominately (at least 50 mole %) C~C,6 sl,a4ht-chain, mono-olefinically unsaturated hyd~ca,bo,)s in which the olefinic unsaturation occurs at the 1- or a-position of the straight carbon chain. Straight~hain a-olefins are used beoPuse they are more reactive 35 and co",n,er~ally available. Such a-olefins can be made by the thermal craching of parafrinic hyd(oca, bons or by the well hnown Ziegler ethylene chain growth and lispl~cement on triethyl aluminum. Individual olefins may be used as well as mixtures of such olefins. Examples of such olefins are 1-octene 1-decene 1-dodecene 1-hexsde~eneand1-tetradecene. Thepreferlednormal a-olefin mono",er-~ are those co"lab~ing about 10 to 12 carbon atoms. The olefinI~Gnomers can also cGntai,l minor amounts of up to about 50 mole % and usually less than 25 mole % of i"le",al olefins and vinylidene olefins.
OLIGOMERIZATION REACTION
The alcohol promoter can be either a single straight~hain alcohol or a mixture of straight-chain alcohols. Examples of preferable single alcohols are 1-pentanol 1-hexanol 1-octanol 1~ecanol 1~odecanol and 1-tetradecanol.
Most preferably the alcohol promoter is 1-hexanol.
Substantially all of the alcohol promoter has a carbon number of at least four and at least 80 wt.% of the alcohol pro"~oter should have a carbon number of at least five. In other words the pro,l,oter should have no ethanol or propar,ol and should have no more than 20% butanol.
rleferably sub~lanlially all of the alcohol p,-o",oter has a carbon number of at five and at least 80 wt.% of the alcohol pror"oter should have a carbon number of at least six. In other words the promoter preferably should have no ethanol propanol or butanol and should have no more than 20% pe"tanol.
The alcohol promoter is used in minor but effective amounts. For example the total amount of alcohol pror"oter used can be from about 0.001 to 0.04 moles per mole of ",o"on,er (0.1 to 4.0 mole percent). In general the boron trifluoride is used in molar ~ ess to the amount of pr~" ,oter. This can be accon ,plished by using a closed reactor and maintaWng a positive boron trifluoride pressure over the reaction mixture.
The alcohol can be mixed with the olefin feed and the reaction can be carried out in a batch or continuous process at temperatures of about 0 to 200 C and pressures ranging from atmos~JI ,eric up to, for example 1,000 psig.
The reaction temperature will ~;ha. ,ge the oligon)er distribution with increasing 2~ 9 461 6 temperatures favoring the production of dimers. Preferred reaction temperatures and pressures are about 20 to 90 C and 5 to 100 psig.
When a desired oligomer distribution is reached, the reaction is 5 ten"ina(ed by venting off excess boron trifluoride gas and purging with nitrogen gas to replace all boron trifluoride gaseous residue. The reaction product, unreac~ed monomer, and boron trifluoride-prol),oter complex residue are removed from the reactor for further processing. The reactor product is then washed with an aqueous caustic solution and followed by several water washes 10 to ensure neutralization.
The oligomer mixture from the reaction contains monomer, which can be removed by distillation. The monomer has been found to contain appreciable amounts of less reactive, isomerized material. However, this monomer can be 15 recycled because it will react to form oligomers in the presence of fresh a-olefin monomer. For example, portions of up to about 25 wt. %, and preferably 5 to 15 wt. % recycled ",ono",er, based on total monomer, can be mixed with fresh monomer. The product mixture can be further separated by distillation to provide one or more product fractions having the desired viscosities for use in 20 various lu6ricanl applications such as drilling, hydraulic or metal working fluids, gear oils and crankcase lubricants.
The oligomer product can be hydrogenated by conventional methods to increase the oxidation stability of the product. Supported nickel catalysts are 25 useful. For exal"ple, nickel on a Kieselguhr support gives good results. Batch or continuous processes can be used. For example, the catalyst can be added to the liquid and stirred under hydr~,gen pressure or the liquid may be trickledthrough a fixed bed of the supported catalyst under hydrogen pressure.
Hydrogen pressures of about 100 to 1,000 psig at te,nperatures of about 150 to 30 300 C are especially useful.
EXAMPLES
The invention will be further illusl~te{l by following examples, which set 35 forth particularly advantageous method e,nbodi",enls. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
21946t6 COMPARATIVE EXAMPLE A
BF3:1-BUTANOL BATCH PROCESS
The oligo",eri~d~ion reaction was carried out in an ~utocl~ve reactor 5 equipped with a packless stirrer; and all wetted surfaoes were made of 316 stainless steel. The reactor had an exte" ,al electrical heater and an inte,nal cooling coil for temperature control. The reactor was equipped with a dip tube, gas inlet and vent valves, and a pressure relief rupture disc. Prior to the monomer charge, the reactor was cleaned, purged with nitrogen and tested for 1 0 leaks.
One thousand grams of 1 ~ecene was charged into the reactor. The promoter, 1-butanol, was added to a concenl,ation of 3.2 mole % based on feed.
The entire reactor content was under vacuum. Boron trifluoride gas was then 15 sparged slowly with agitation and controlled at 30 C via a cooling coil to avoid reactor temperature overrun. Additional boron trifluoride was added as neoess~ry to maintain a reactor pressure of 60 psig. The reaction was terminated after two hours by venting off excess boron trifluoride gas and purging with nitrogen. The reaction product was then washed with a 4 wt. %
20 A9 ueo~ Is sodium hydroxide solution followed by several water washes to ensure neutr~li7~tion. The product was saved for further l(eal",ents such as hydrogenation and fractionation.
In these examples the following alcohols are substituted one at a time for the n-butanol pro",oter employed in Comparative Example A and the rest of the procedure of Colnparative Example A was carried through in the same manner.
(1 ) n-hexanol (2) n~tanol (3) n-decanol (4) n-dodecanol (5) n-tetradecanol Table 1. Effects of Longer Chain Alcohols on 100C Kil ~ema~ic Viscosity (1 Hour Batch Re~clions) - Type of rercent PercentTrimer~ Cala ~ ed Example Plo",oter1~1Onoi"er Dimer Viscosity A n-butanol 2.67 6.74 5.66 n-hexanol 3.30 12.36 5.83 2 n-octanol 1.58 14.12 6.21 3 n-decanol 2.85 13.82 6.40 4 n-dodecanol 3.41 13.51 6.30 n-tetradecanol 2.91 12.06 6.46 COMPARATIVE EXAMPLE B
BF3:1-BUTANOL IN CONTINUOUS PRODUCTION MODE
The continuous ",onG,ner feed reactor was equipped with monomer pro"~oler and gas inlet ports vent valves, and a pressure relief rupture disc. At the onset of oligol"eri~alion ,eaction the reactor was cleaned purged with nitrogen and tested for leaks. A 1~Jodecene ",onG",er flow rate of 2000 grams 20 per hour, a reactor te"~peral,Jre of 30C and a, eaclor pressure of 60 psig were controlled throughout the reaction period. The reactor had a gas cap and its liquid volume was controlled through a level control device and approxi"~alely one half of the reactor volume. A prefo""ed BF3:n-butanol complex was added at a concenlrdlion of 0.3 mole % based on feed. The r~actio" product was 25 d;scl ,argeJ to a low pressure flash tank to remove the g~seo~ ~s r eacta,)t. The liquid product stream was then subjected to neutralization and washing steps.
The product was saved for further treatments such as hydrogenation and r, a~tionalio~ ).
EFFECT OF LONGER CHAIN ALCOHOLS IN CONTINUOUS MODE
In these e~a",ples the following alcohols are substituted one at a time for the n-butanol p,-on,oler employed in Co""~ar~live Example B and the rest of the 35 procedure of Co,nparalive Example B was carried through in the same manner.
-- 21 946~6 g (6) n-hexanol (7) n~ctanol (8) n~ecanol Table 2. Effects of Longer Chain A!cohols on 100C Kinei"alic Viscosity for Continuous Production Example % Monomer % DimerTrimer+ Calcul~ted Viscosity B 0.3 1.0 6.88 6 1.3 2.1 7.76 7 4.0 5.0 8.12 8 6.6 6.9 8.19 EFFECT OF MIXED ALCOHOLS
In these exal"ples the follo~.ing alcohols are substituted one at a time for the n-butanol promoter employed in CG",parali~/e E~xa",ple A and the rest of the20 proced~re of Con)parali-~e Example A carried through in the same ",anner.
(C) n-propanol (D) 2.30 mole % n~ropanol and 0.77 mole % n~)exa"ol (E) 0.77 mole % n-pnjpaool and 2.30 mole % n~)exanol (F) 2.30 mole % nbutanol and 0.77 mole % n~exa"ol (G) 0.77 mole % n-butanol and 2.30 mole % n~,e~anol Table 3 Mixed Alcohols with n l lexanol (1 Hour Batch Reactions) Ratio Trimer+
TypeofLighter LighterAlcoholto Per~nl Per~enl Calculated S Example Alcohol Hexanol 1~1OnG",er DimerViscosity C n-propanol ' - 1.84 9.71 5.37 D n-pro,,~anol 75:25 2.83 11.985.26 E n-pr panol 25:75 3.81 12.915.39 A n-butanol' - 2.67 6.74 5.66 F n-butanol 75:25 2.58 12.825.20 G n-butanol 25:75 2.56 12.755.44 n-hexanol - 3.30 12.365.83 15 'no hexanol used Table 3 shows the results of mixtures of alcohols as promotors on the calu ll~ted 100 C kinemalic viscosily of the trimer and higher oligomers. As this invention teaches n-hexanol gives a heavier product than n-butanol which in 20 tum prod! ues a heavier product than n-propa, lol. One would expect that mixtures would produce products with viscosities bounded by that which is produced from the pure alcohols (i.e. pr~panol and hexanol). However this data shows that mixtures produce lower viscosities than that produced by the lighter of the two alcohols. For example, a 25:75 mixture of propanol:l ,exa"ol 25 gives a product viscosit~ of less than that produced by propa, lol alone. Butanol and hexanol mixtures behave in a similar manner.
In Co,nparali~/e Example H n-butanol was substituted as the pro",oter for the pro",oter complex employed in Co",parati~/e Example B. Furthermore the feed was 1-decene inslead of 1~odecene the BF3 pressure was 80 psig and the mole % pro",oler was 2.21. The rest of the procedure was carried through in 35 the same manner as Co,nparalive Example B.
~94616 In Examples 9 and 10, n~ ,exa"ol was substituted for the n-butanol ~ro,noter used in Co",~ afative Example H. In Example 9 1.63 mole % of n~)exanol was used and in Exa",pla 10, 2.24 mole % of n-hexanol was used.
The rest of the procedure was ca" ied through in the same ma"ner as 5 Co""~arative Example H.
Table 4 BF3 Consumption Type ofMole % rro",oter Trimer+ Calculated BF3 10 Example Promoterof Feed Viscosity cSt wt% of Feed H n-butanol2.21 8.5 1.16 9 n-hexanol1.63 8.3 0.92 n-hexanol2.24 9.6 1.17 Table 4 shows the effect of n-hexanol as compared to n-butanol in producing near equivalent product viscosity with a savings of the amount of BF3 consumed. CGi"paralive Example H and Example 9 show that if n-hexanol is used inslead of n~utanol a 8.3 cSt product can be produced with about 20%
savings in BF3. Conversely a 9.5 cSt can be produced with near equivalent use 20 of BF3 by using n-hexanol instead of n-butanol at equivalent mole % of the promoter.
While the present invention has been described with reference to specific e",bodi"~ents this application is intended to cover those various changes and 25 substitutions that may be made by those skilled in the art without depal ~ing from the spirit and scope of the appended claims.
THROUGH PROCESS MODIFICATIONS
The present invention relates to a pr~cess of producing a higher degree 5 of olefin oligo,neri~dlion.
BACKGROUND OF THE INVENTION
Synthetic lubricants prodl)ced by the oligo",eri~alion of alpha-olefins are 10 well-known. The nature of the alpha-olefin from which these oligomers are produced prescribes the properties of the resultant lubricant.
While it has been repo, led that even fairly large amounts of intemal or branched-chain olefins may be present without extremely adverse effect on the 15 alpha~lefin oligomerization the resultant lubricants have restricted utility and do not justify their usage as a replace" ,e, It for naturally occurring petroleum fluids.
In general linear olefins of from eight to twelve csrbo"s have proven most effective. Normal alpha-olefins are generally ,ureferred.
OligG",eri~alion may be achieved with a wide variety of catalysts.
Represenlati~/e catalyst include such Friedel-Crafts agents as AlCb AlBr3 BF3 BCI3 GaCI4 and the like. Although each such agent fadlitates 01igo",6ri~lion the activity of the catalyst will dmer widely. The very active catalyst such as 25 AlCb will produoe e~lr~ ely high moleu ~ weight polymers in conjunction with use of appropriate pro",oter:~. Other Friedel~raft catalysts such as SnC14 or GaCb may present ~1;SPOSAI proble.ns after use. Moreover solid catalysts present difficulties with r~spect to control of the exoU ,el " lic oligo" ,eri~ation reaction due to the I ,eterogeneous nature of the reaction system.
A pref~r,ed catalyst has been boron trifluoride (BF3), which forms a liquid complex with the necess~- y pr~,l,oter:~, and thus lends itself to conven~ional reaction systems.
Boron trifluoride and the other catalysts must be used in comb-.nation with a pr~l"o~er. The pro",o~er complexes with the BF3 and in so doing provides an ~1 946 1 6 activated system needed for ir,ilialion of the oliyo",eri~lion reaction. Among the most widely used promoter~ are the alkanoic and/or inorganic acids which are suitable for selective foi",alion of oligom~f~ ranging from two to four monomeric units.
Conventional practice for conducting the oligo",e, i~alion reaction has been to admix the pro",oter with the monomeric olefin in the prese,)ce of an imposed al",ospl,ere of BF3 which is normally ~seo~s The presence of excess BF~ necess~ry for the reaction is delineated by the observed pressure of 10 BF3 in the reaction vessel.
The rate of oligo"~eri,alion is related to some degree to the BF3 pressure since the p~bability of excess BF3 in the liquid reactants is directly related to its pressure.
The use of a variety of alcohols as pro,nol~rs is disclosed by Shubkin in - U.S. Patent No. 3 780128 entitled ~Syntl,etic Lubric~,)ls by Oligo",eri~alion and H~,drogenalion.~ There is no ~isa Issi^n on the pros and cons of the various alcohols but the prerer,ed alcohol is propanol.
The use of variety of alcohols as pro",ot~r~ is also disclosed by Cupples et al. in U.S. Patent No. 4,045,508 entitled ~Method of Mal;ing Alpha-Olefin Oli~o",ers,~ but that ,ererence does not disalss the relative ad\,an~ages and disadvantages of each pr~moter.
A two-step process using a mixture propanol and hexanol is disclosed by Pratt in U.S. Patent No. 4,587 368 entitled "rrocess for Producing Lubricant 1\1aterial,~ where an aliquot of ",o"on,er is added to an inle""ediale oligo",er.
Example 2 shows that a 75:25 mixture of hexanol and p~,a, lol leads to a 30 heavier product than a 50:50 mixture of I ,exanol and propa, lol U.S. Patent Nos. 3,780,128; 4,045,508; and 4,587,368 are hereby inCGI ~.oraled by r e~r~"ce for all p~" poses.
The s~hseguent reri,)i"~ processes can be ",~lrried to yield particular product co",posilions. Where for example a lubricant c~"sisli"g chiefly of ~ 21 9461 6 ,, higher oligomers is desired, one may remove u"reacted " ,GnGmer and low boiling dimer by distillation at at"lospl ,eric pressure. Trimer has also been removed in this "~an,)er, but through conditions of high vacuum distillation.
After hyd,oge"alion, the suL~lantially saturated lubricant material is then ready for co""~ounding. Depending upon its co"~posilion and properties, it may be used directly in a wide variety of known applications. Allel ndli~ely, known lubricant additives may be incorporated. The material may be mixed with other available lubricants, to achieve the characteristics necessary for given conventional utilities.
Products of many of these known oligomerization reactions have been primarily designed for specialized applications. Aircraft hydraulic or turbine oils, for example, possess low viscosity requirements requiring oligomerization limited to dimers, trimers and tetramers (with emphasis on the trimer). Polymers resulting from such a procedure, however, have limited application as conventional lubricants. Lubricants for higher temperature, e.g., motor oils andindustrial lubricants use, require considerably higher viscosilies.
In general, higher viscosity fluids can only be made with a severe production rate penalty, since longer resi"e"ce times are required to achieve the target viscosity with current technology.
SUMMARY OF THE INVENTION
The present invention provides a process for producing a high degree of olefin oligoi"eri~alion. We have found that the oligomer distribution can be affected by the size of the primary alcohol that is used as pro,noter. A higher degree of oligomerization can be achieved by in~easin~ the carbon to hydroxyl ratio for alcohol pro",oters. Moreover, we have also found that by using longer straight chain alcohols, we can produce a heavier product viscosily with greaterBF3 efficiency.
In our process, a synthetic lubricant material is pro~4lced by oligo"~eri~i"g a C~.,6 a-olefin monomer in the presence of a boron trifluoride catalyst and a straight-chain alcohol promoter, wherein subslar,lially all of the alcohol proi"oter has a carbon number of at least four, and at least 80 wt.% of the alcohol pr~rnoter has a ca, ~on number of at least five.
r~ eferably the olefinic " ,onG"~er contains pr~dG" linately 10 to 12 carbon 5 atoms.
Pfeferably s~ s~ tially all of the alcol ,ol pro",oter has a carbon number of at least five and least 80 wt.% of the alcohol promoter has a carbon number of at least six. Most preferably the alcohol pro",oter is 1 ~exanol.
BRIEF DESCRIPTION OF THE DRAWINGS
In order to assist the understanding of this invention reference will now be made to the appended drawings. The drawings are exemplary only and 15 should not be construed as limiting the invention.
The Figure shows the effect of longer chain alcohols on the oligomer distribution of the product. It shows the data from Exan,ples 6 through 8 and Compardli~e Example B.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect the presenl invention involves the oligomeri~alion of an olefinic ",Gno",er by contacting that ",onoi"er with boron trifluoride and a 25 straight-chain alcohol ,l~r~",oler. Sul~sl&nt.ally all of the ~Icol lol pr~i"oler has a carbon number of at least four at least 80 wt.% of the alcohol pr~""oler has a carbon number of at least five.
OLEFINIC MONOMER
The olefins used in ".ahing the oligomer are predominately (at least 50 mole %) C~C,6 sl,a4ht-chain, mono-olefinically unsaturated hyd~ca,bo,)s in which the olefinic unsaturation occurs at the 1- or a-position of the straight carbon chain. Straight~hain a-olefins are used beoPuse they are more reactive 35 and co",n,er~ally available. Such a-olefins can be made by the thermal craching of parafrinic hyd(oca, bons or by the well hnown Ziegler ethylene chain growth and lispl~cement on triethyl aluminum. Individual olefins may be used as well as mixtures of such olefins. Examples of such olefins are 1-octene 1-decene 1-dodecene 1-hexsde~eneand1-tetradecene. Thepreferlednormal a-olefin mono",er-~ are those co"lab~ing about 10 to 12 carbon atoms. The olefinI~Gnomers can also cGntai,l minor amounts of up to about 50 mole % and usually less than 25 mole % of i"le",al olefins and vinylidene olefins.
OLIGOMERIZATION REACTION
The alcohol promoter can be either a single straight~hain alcohol or a mixture of straight-chain alcohols. Examples of preferable single alcohols are 1-pentanol 1-hexanol 1-octanol 1~ecanol 1~odecanol and 1-tetradecanol.
Most preferably the alcohol promoter is 1-hexanol.
Substantially all of the alcohol promoter has a carbon number of at least four and at least 80 wt.% of the alcohol pro"~oter should have a carbon number of at least five. In other words the pro,l,oter should have no ethanol or propar,ol and should have no more than 20% butanol.
rleferably sub~lanlially all of the alcohol p,-o",oter has a carbon number of at five and at least 80 wt.% of the alcohol pror"oter should have a carbon number of at least six. In other words the promoter preferably should have no ethanol propanol or butanol and should have no more than 20% pe"tanol.
The alcohol promoter is used in minor but effective amounts. For example the total amount of alcohol pror"oter used can be from about 0.001 to 0.04 moles per mole of ",o"on,er (0.1 to 4.0 mole percent). In general the boron trifluoride is used in molar ~ ess to the amount of pr~" ,oter. This can be accon ,plished by using a closed reactor and maintaWng a positive boron trifluoride pressure over the reaction mixture.
The alcohol can be mixed with the olefin feed and the reaction can be carried out in a batch or continuous process at temperatures of about 0 to 200 C and pressures ranging from atmos~JI ,eric up to, for example 1,000 psig.
The reaction temperature will ~;ha. ,ge the oligon)er distribution with increasing 2~ 9 461 6 temperatures favoring the production of dimers. Preferred reaction temperatures and pressures are about 20 to 90 C and 5 to 100 psig.
When a desired oligomer distribution is reached, the reaction is 5 ten"ina(ed by venting off excess boron trifluoride gas and purging with nitrogen gas to replace all boron trifluoride gaseous residue. The reaction product, unreac~ed monomer, and boron trifluoride-prol),oter complex residue are removed from the reactor for further processing. The reactor product is then washed with an aqueous caustic solution and followed by several water washes 10 to ensure neutralization.
The oligomer mixture from the reaction contains monomer, which can be removed by distillation. The monomer has been found to contain appreciable amounts of less reactive, isomerized material. However, this monomer can be 15 recycled because it will react to form oligomers in the presence of fresh a-olefin monomer. For example, portions of up to about 25 wt. %, and preferably 5 to 15 wt. % recycled ",ono",er, based on total monomer, can be mixed with fresh monomer. The product mixture can be further separated by distillation to provide one or more product fractions having the desired viscosities for use in 20 various lu6ricanl applications such as drilling, hydraulic or metal working fluids, gear oils and crankcase lubricants.
The oligomer product can be hydrogenated by conventional methods to increase the oxidation stability of the product. Supported nickel catalysts are 25 useful. For exal"ple, nickel on a Kieselguhr support gives good results. Batch or continuous processes can be used. For example, the catalyst can be added to the liquid and stirred under hydr~,gen pressure or the liquid may be trickledthrough a fixed bed of the supported catalyst under hydrogen pressure.
Hydrogen pressures of about 100 to 1,000 psig at te,nperatures of about 150 to 30 300 C are especially useful.
EXAMPLES
The invention will be further illusl~te{l by following examples, which set 35 forth particularly advantageous method e,nbodi",enls. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
21946t6 COMPARATIVE EXAMPLE A
BF3:1-BUTANOL BATCH PROCESS
The oligo",eri~d~ion reaction was carried out in an ~utocl~ve reactor 5 equipped with a packless stirrer; and all wetted surfaoes were made of 316 stainless steel. The reactor had an exte" ,al electrical heater and an inte,nal cooling coil for temperature control. The reactor was equipped with a dip tube, gas inlet and vent valves, and a pressure relief rupture disc. Prior to the monomer charge, the reactor was cleaned, purged with nitrogen and tested for 1 0 leaks.
One thousand grams of 1 ~ecene was charged into the reactor. The promoter, 1-butanol, was added to a concenl,ation of 3.2 mole % based on feed.
The entire reactor content was under vacuum. Boron trifluoride gas was then 15 sparged slowly with agitation and controlled at 30 C via a cooling coil to avoid reactor temperature overrun. Additional boron trifluoride was added as neoess~ry to maintain a reactor pressure of 60 psig. The reaction was terminated after two hours by venting off excess boron trifluoride gas and purging with nitrogen. The reaction product was then washed with a 4 wt. %
20 A9 ueo~ Is sodium hydroxide solution followed by several water washes to ensure neutr~li7~tion. The product was saved for further l(eal",ents such as hydrogenation and fractionation.
In these examples the following alcohols are substituted one at a time for the n-butanol pro",oter employed in Comparative Example A and the rest of the procedure of Colnparative Example A was carried through in the same manner.
(1 ) n-hexanol (2) n~tanol (3) n-decanol (4) n-dodecanol (5) n-tetradecanol Table 1. Effects of Longer Chain Alcohols on 100C Kil ~ema~ic Viscosity (1 Hour Batch Re~clions) - Type of rercent PercentTrimer~ Cala ~ ed Example Plo",oter1~1Onoi"er Dimer Viscosity A n-butanol 2.67 6.74 5.66 n-hexanol 3.30 12.36 5.83 2 n-octanol 1.58 14.12 6.21 3 n-decanol 2.85 13.82 6.40 4 n-dodecanol 3.41 13.51 6.30 n-tetradecanol 2.91 12.06 6.46 COMPARATIVE EXAMPLE B
BF3:1-BUTANOL IN CONTINUOUS PRODUCTION MODE
The continuous ",onG,ner feed reactor was equipped with monomer pro"~oler and gas inlet ports vent valves, and a pressure relief rupture disc. At the onset of oligol"eri~alion ,eaction the reactor was cleaned purged with nitrogen and tested for leaks. A 1~Jodecene ",onG",er flow rate of 2000 grams 20 per hour, a reactor te"~peral,Jre of 30C and a, eaclor pressure of 60 psig were controlled throughout the reaction period. The reactor had a gas cap and its liquid volume was controlled through a level control device and approxi"~alely one half of the reactor volume. A prefo""ed BF3:n-butanol complex was added at a concenlrdlion of 0.3 mole % based on feed. The r~actio" product was 25 d;scl ,argeJ to a low pressure flash tank to remove the g~seo~ ~s r eacta,)t. The liquid product stream was then subjected to neutralization and washing steps.
The product was saved for further treatments such as hydrogenation and r, a~tionalio~ ).
EFFECT OF LONGER CHAIN ALCOHOLS IN CONTINUOUS MODE
In these e~a",ples the following alcohols are substituted one at a time for the n-butanol p,-on,oler employed in Co""~ar~live Example B and the rest of the 35 procedure of Co,nparalive Example B was carried through in the same manner.
-- 21 946~6 g (6) n-hexanol (7) n~ctanol (8) n~ecanol Table 2. Effects of Longer Chain A!cohols on 100C Kinei"alic Viscosity for Continuous Production Example % Monomer % DimerTrimer+ Calcul~ted Viscosity B 0.3 1.0 6.88 6 1.3 2.1 7.76 7 4.0 5.0 8.12 8 6.6 6.9 8.19 EFFECT OF MIXED ALCOHOLS
In these exal"ples the follo~.ing alcohols are substituted one at a time for the n-butanol promoter employed in CG",parali~/e E~xa",ple A and the rest of the20 proced~re of Con)parali-~e Example A carried through in the same ",anner.
(C) n-propanol (D) 2.30 mole % n~ropanol and 0.77 mole % n~)exa"ol (E) 0.77 mole % n-pnjpaool and 2.30 mole % n~)exanol (F) 2.30 mole % nbutanol and 0.77 mole % n~exa"ol (G) 0.77 mole % n-butanol and 2.30 mole % n~,e~anol Table 3 Mixed Alcohols with n l lexanol (1 Hour Batch Reactions) Ratio Trimer+
TypeofLighter LighterAlcoholto Per~nl Per~enl Calculated S Example Alcohol Hexanol 1~1OnG",er DimerViscosity C n-propanol ' - 1.84 9.71 5.37 D n-pro,,~anol 75:25 2.83 11.985.26 E n-pr panol 25:75 3.81 12.915.39 A n-butanol' - 2.67 6.74 5.66 F n-butanol 75:25 2.58 12.825.20 G n-butanol 25:75 2.56 12.755.44 n-hexanol - 3.30 12.365.83 15 'no hexanol used Table 3 shows the results of mixtures of alcohols as promotors on the calu ll~ted 100 C kinemalic viscosily of the trimer and higher oligomers. As this invention teaches n-hexanol gives a heavier product than n-butanol which in 20 tum prod! ues a heavier product than n-propa, lol. One would expect that mixtures would produce products with viscosities bounded by that which is produced from the pure alcohols (i.e. pr~panol and hexanol). However this data shows that mixtures produce lower viscosities than that produced by the lighter of the two alcohols. For example, a 25:75 mixture of propanol:l ,exa"ol 25 gives a product viscosit~ of less than that produced by propa, lol alone. Butanol and hexanol mixtures behave in a similar manner.
In Co,nparali~/e Example H n-butanol was substituted as the pro",oter for the pro",oter complex employed in Co",parati~/e Example B. Furthermore the feed was 1-decene inslead of 1~odecene the BF3 pressure was 80 psig and the mole % pro",oler was 2.21. The rest of the procedure was carried through in 35 the same manner as Co,nparalive Example B.
~94616 In Examples 9 and 10, n~ ,exa"ol was substituted for the n-butanol ~ro,noter used in Co",~ afative Example H. In Example 9 1.63 mole % of n~)exanol was used and in Exa",pla 10, 2.24 mole % of n-hexanol was used.
The rest of the procedure was ca" ied through in the same ma"ner as 5 Co""~arative Example H.
Table 4 BF3 Consumption Type ofMole % rro",oter Trimer+ Calculated BF3 10 Example Promoterof Feed Viscosity cSt wt% of Feed H n-butanol2.21 8.5 1.16 9 n-hexanol1.63 8.3 0.92 n-hexanol2.24 9.6 1.17 Table 4 shows the effect of n-hexanol as compared to n-butanol in producing near equivalent product viscosity with a savings of the amount of BF3 consumed. CGi"paralive Example H and Example 9 show that if n-hexanol is used inslead of n~utanol a 8.3 cSt product can be produced with about 20%
savings in BF3. Conversely a 9.5 cSt can be produced with near equivalent use 20 of BF3 by using n-hexanol instead of n-butanol at equivalent mole % of the promoter.
While the present invention has been described with reference to specific e",bodi"~ents this application is intended to cover those various changes and 25 substitutions that may be made by those skilled in the art without depal ~ing from the spirit and scope of the appended claims.
Claims (4)
1. A process for producing a synthetic lubricant material comprising oligomerizing a C8-16 .alpha.-olefin monomer in the presence of a boron trifluoride catalyst and a straight-chain alcohol promoter:
(a) wherein substantially all of the alcohol promoter has a carbon number of at least four, and (b) wherein at least 80 wt.% of the alcohol promoter has a carbon number of at least five.
(a) wherein substantially all of the alcohol promoter has a carbon number of at least four, and (b) wherein at least 80 wt.% of the alcohol promoter has a carbon number of at least five.
2. A process according to Claim 1 wherein substantially all of the alcohol promoter has a carbon number of at least five and wherein at least 80 wt.%
of the alcohol promoter has a carbon number of at least six.
of the alcohol promoter has a carbon number of at least six.
3. A process according to Claim 2 wherein the alcohol promoter is 1-hexanol.
4. A process according to Claim 1 wherein the olefinic monomer contains predominately 10 to 12 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58598196A | 1996-01-12 | 1996-01-12 | |
| US08/585,981 | 1996-01-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2194616A1 true CA2194616A1 (en) | 1997-07-13 |
Family
ID=24343797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2194616 Abandoned CA2194616A1 (en) | 1996-01-12 | 1997-01-08 | Increased degree of olefin oligomerization yield through process modifications |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0785245A3 (en) |
| JP (1) | JPH09194864A (en) |
| CA (1) | CA2194616A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780128A (en) | 1971-11-03 | 1973-12-18 | Ethyl Corp | Synthetic lubricants by oligomerization and hydrogenation |
| US4045507A (en) * | 1975-11-20 | 1977-08-30 | Gulf Research & Development Company | Method of oligomerizing 1-olefins |
| US4045508A (en) | 1975-11-20 | 1977-08-30 | Gulf Research & Development Company | Method of making alpha-olefin oligomers |
| US4587368A (en) | 1983-12-27 | 1986-05-06 | Burmah-Castrol, Inc. | Process for producing lubricant material |
| EP0323759A3 (en) * | 1988-01-06 | 1990-03-07 | Mobil Oil Corporation | Olefin polymerization process with product viscosity and pour point control |
| DE69509082T2 (en) * | 1995-06-12 | 1999-11-25 | Amoco Corp | Process for the preparation of oligomers of mono-olefins |
-
1997
- 1997-01-08 CA CA 2194616 patent/CA2194616A1/en not_active Abandoned
- 1997-01-10 JP JP314497A patent/JPH09194864A/en active Pending
- 1997-01-13 EP EP97300152A patent/EP0785245A3/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0785245A2 (en) | 1997-07-23 |
| EP0785245A3 (en) | 1998-05-06 |
| JPH09194864A (en) | 1997-07-29 |
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