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  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
  • C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
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  • C07C2527/14—Phosphorus; Compounds thereof
  • C07C2527/16—Phosphorus; Compounds thereof containing oxygen
  • C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
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  • C07C2531/025—Sulfonic acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y10S149/00—Explosive and thermic compositions or charges
  • Y10S149/12—High energy fuel compounds

Definitions

• Hydrocarbon mixtures of my compounds can have from 11 to 42 carbon atoms, such compounds having from 11 to 30 carbon atoms beingusefully liquid over wide temperature ranges. They have relatively high boiling points and relatively low depressed freezing points. More particularly, hydrocarbon mixtures hereof have a high energy content, that is, a high B.t.u. value per gallon and relatively high energy density or specific gravity. This combination of characteristics makes the present hydrocarbon mixture including position isomers outstanding for use as jet fuels.
• dicyclic jet fuels prepared by catalytic alkylation of arcmatic monocyclic hydrocarbons with vinylaromatic compounds followed by hydrogenation, wherein the fluidity, gravity and B.t.u. values of the" product is. enhanced by the presence of hydrogenated dimers of the vinyl-aromatic hydrocarbons, the dimers forming concurrently with the alkylation reaction; the amount of dimers therein can be controlled by the methods and conditions of alkylation, and the boiling range of the C to C hydrogenated fraction can be narrower than the mixture of isomers of S. N. 833,996.
• the preferred alkylating components for the present invention are readily and economically available directly from cracked petroleum fractions, elg., cyclopentene and cyclopentadiene, and indene or by thermal dimerization of readily available conjugated dienes.
• dimers are formed as by-products of other reactions of said dienes, and always accompany storage of such dienes, e.g., butadiene, piperylene, isoprene, dime thylbutadiene, and cyclopentadiene readily form cyclic dimers in amounts directly relatable to storage time and temperatures, and the dimers contain at least one ringolefinic bond; dicyclopentadiene has two ring olefinic bonds.
• cyclic dimers other than dicyclopnt-adiene” have alkenyl groups which were also found to alkylate aromatic hydrocarbons as disclosed in my aforesaid S. N. 862,017, filed December 28, 1959.
• compositions in the several use's mentioned above thus are mixtures of hydrocarbon compounds comprising diand tri-cyclic compounds including di and tricyclohexyl, monoand di-(lower alkylcyclohexyl) cyclohexanes and other monoand di-(lower alkyl-cyclohexyl) cycloalkanes, such as (lower alkyl-cyclohexyl)-cyclohexyl cyclopentanes, di-(cyclohexylalkyl)-cyclopentanes,- cyclohexyl perhydropolycyclopentadiene, said" hydrocarbon compounds having 14 to 30 carbon atoms when they are liquid, and being formed by (a) alkylation of an aromatic hydrocarbon with a polyolefin at least one'of the olefinic bonds thereof being of the cycloalkylene' type such' as'in alkenyl cyclohexene or alkyl substituted alkenylcyclohe
• R, R, R" may be the same or different members of the group consisting of hydrogen, straight or branched chain alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl or aralkyl and the total number of carbon atoms of R plus R together with the ethyl group is from 2 to 12 and of R" is 1 to 12, Cyc is a member of the group consisting of C to C monocycloalkene, cycloalkadiene and dimers, trimers and tetramers thereof, andC to C bicyclic and tricyclic alkenes and alkadienes and dimers thereof; m is an integer of 1 to 4 and n is either 1 or 2 and the total number of carbon atoms of aFbrmula I compound is in the range of 7 to 24.
• alkyl examples are the lower straight or branched chain :alkyls having from 1 to 12 carbon atoms, 1 to 6 being preferred, i.e., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-buty1, amyl, s-amyl,'-isoamyl, t-amyl, any of the hexyls and the like up to decyl (for R or R) and up to dodecyl (for R").
• R, R or R" in Formula I are cycloalkyll mean cyclopentyl, and cyclohexyl; and by alkylcycloalkyl I mean C to C alkyl cyclophenyl, C
• Cyc group as defined for Formula I components include both mono-olefinic and di-olefinic C to C cyclic compounds and C to C mono-olefinic and diolefinic polycyclic compounds, e.g., the following groups: cyclopentene, cyclopentadiene and methylcyclopentadiene, the dimers, trimers and tetramers of cyclopentadiene and methylcyclopentadiene (as shown later the dicyclopentadiene is a tricyclic diolefin, the tricyclopentadiene is a pentacyclodiolefin and the tetramer is a heptacyclodiolefin); cyclohexene and bi-cyclohexene, bi
• isopropylcyclohexene group has five isomers depending on the points of attachment of isopropyl (i.e. the R" radical) in relation to the olefinic group. Variation in the aromatic reactant hence can be multiplied by five to calculate the number of positional isomers available from the process of the present invention.
• reactants according to Formula I are cyclopentene, cyclopentadiene, cyclohexene, bicycloheptadiene, indene, the cyclic dimers of butadiene, iso prene, piperylene, dimethylbutadiene, and cyclopentadiene, the dicyclic trirners of butadiene, isoprene, piperylene, dimethylbutadiene and cyclopentadiene and the dicyclic tetramers of butadiene, isoprene, piperlyene, dimethylbutadiene and cyclopentadiene, said tetramers also being dimers of the aforesaid dimers.
• bicycloheptadiene is meant the reaction product of acetylene and cyclopentadiene.
• cyclopentadiene gives endomethylenic type polymers.
• polymers of cyclopentadiene are as follows:
• the compounds of Formula I of this invention thus have in common at least one cycloalkene group containing one or two ring olefinic bonds each of which can react with alkylatable aromatic hydrocarbons of Formula II and they may or may not contain one or more side chain olefinic bonds of the alkene type (dependent on whether 11 is 1 or 2) which react with aromatic hydrocarbons of Formula II in accordance with my copending S.N. 862,017, filed December 28, 1959.
• R is hydrogen, or straight or branched chain alkyl
• p is an integer from 1 to 5 and the total carbon atoms are in the range of 6 to 18.
• Formula II reactants are benzene, toluene, ethylbenzene, cumene, n-propylbenzene, the butylbenzenes, the amylbenzenes, the hexylbenzenes, the heptylbenzenes, octylbenzenes, nonylbenzencs, decylbenzenes, undecylbenzenes, dodecylbenzenes, o-, m-, and p-xylenes, 0-, mand p-ethyltoluenes, o-, m-, and p-isopropyl and propyltoluenes, o-, mand p,n-propyltoluenes, the butyltoluenes, the amyltoluenes, hexyltoluenes, and the like up through undecyl
• alkylated products having at least two cyclic groups represented by Formula III are formed:
• Formula III wherein R, R, R", R, Cyc, m, n, and p have the same significance as in Formulae I and II and 1 to 3. Thus, when n is 1, q is at least 2; and when q is 1, n is 2.
• the alkylation of Formula I compounds by Formula II aromatic compounds produces a mixture of precursor products wherein in addition to alkylation of Formula 11 compounds by the ethylenic side chain, the Formula II aromatic compounds are also alkylated by the olefin group in the -Cyc-nucleus, and each alkylation group entering the alkylation results in an increased numbers of isomers resulting from the R substituent groups Also this precursor mixture contains dimers of the Formula I compounds which enhance further the number of components in the precursor product, and also in the final hydrogenated product.
• the process of producing the high-gravity high energy fuels of my invention in its simplest definition is the alkylation of the aryl ring of an arylhydrocarbon of Formula II by reaction therewith of a cycloolefin, including cyclodiolefin, or cyclopolyolefin of Formula I having at least one ring unsaturated olefinic bond (as in cyclopentene or cyclohexene ring), in the presence of a catalyst selected from the class of Friedel-Crafts catalysts and Lewis acids, followed by hydrogenation, to produce C to C liquid fuels.
• a catalyst selected from the class of Friedel-Crafts catalysts and Lewis acids
• the specific gravity of such liquid mixtures will generally exceed about 0.85 and by the term high gravity as used herein, I mean a liquid having this minimum or higher gravity.
• the B.t.u. value will usually exceed about 135,000 B.t.u. per gallon and by the term high energy as used herein I means a combustible mixture having the minimum or higher B.t.u. value.
• the gravity of the jet fuels hereof usually lie in the range of about 0.85 up to about 0.91, and the B.t.u. value preferably ranges from about 135,000 up to about 145,000 B.t.u. per gallon.
• the Cyc-group may be mono and polycycloalkene, e.g., alkylcyclohexene ring, or mono and polycycloalkenealkyl radicals, and mono and polycycloakladienealkyl and like radicals derived from the cyclo-olefin components Formula I.
• the hydrogenation of Formula III compounds to form the products of the present invention saturates first any unreacted olefinic unsaturation under relatively mild conditions e.g. at less than 100 C. under 100 to 250 psi. hytions (higher temperatures and higher hydrogen pressures drogen pressure, then finally the aromatic rings are hydrogenated under more stringent hydrogenation conditions (higher temperatures and higher hydrogen pressures).
• my invention discloses a new composition of matter comprising a mixture of fully saturated polycyclic alkane position and geometric isomers having Formula Formula IV yc L wherein R, R and R are members of a group consisting of hydrogen, straight and branched chain alkyl, alkylcycloalkyl, cycloalkyl, cycloalkylalkyl; R is a member selected from the group consisting of hydrogen, straight and branched chain alkyl; R plus R together with the ethyl radical has from 2 to 12 carbon atoms and R has from 1 to 12 carbon atoms; R is a member selected from the group consisting of hydrogen, straight and branched chain alkyl and said radical having 1 to 12 carbon atoms; Hyd.
• Cyc is a hydrogen saturated radical of C to C monocyclic cycloalkene, cycloalkadiene and dimers, trimers and tetramers thereof and a hydrogen saturated radical of C to C bicyclic and tricyclic alkenes and dimers thereof, as defined above; for example, cyclopentane, cyclohexane, bicyclohexane, endo-methylene cyclohexane, condensed polycyclopentane-endo-methylene-cyclohexane rings (derived from di-, tri-, and tetracyclopentadiene), perhydroindan, and cyclopentadienealkyl groups; said isomers being formed predominantly by alkylating a compound of the Formula II:
• R, R and R are selected from the group consisting of hydrogen, straight and branched chain alkyl, cycloalkyl, alkylcycloalkyl, aralkyl and cycloalkylalkyl; R plus R together with the ethylene radical has from 2 to 12 carbon atoms and R has from 1 to 12 carbon atoms; R is a member selected from the group consisting of hydrogen, straight and branched alkyls and said radicals having 1 to 12 carbon atoms, Cyc is a radical of C- to C monocyclic cycloalkene, cycloalkadiene and dimers, trimers and tetramers thereof and 7 to 12 carbon atoms bicyclic and tricyclic alkenes and dimers thereof; m is an integer from 1 to 4, n is an integer from 1 to 2, p is an integer from 1 to 5, q
• Lewis acids are meant substances having ability to accept electrons (more conventional definition of acids is substances having a tendency to lose a proton).
• Lewis acids also include HF, H2804, P2O5H2SO4, H3PO4, H4P2O7, and the like which may be used in both aqueous and anhydrous catalyst systems of this invention.
• the catalyst and Formula II components are placed in a reaction vessel.
• the component of Formula I are diluted with the components of Formula II in a ratio of one mole of Formula I component to about 2 moles of Formula II component and this mixture is then added gradually to the reaction vessel while stirring and cooling to maintain the desired temperature usually selected from the range of '70 to +50 C.
• the amount of component I added is regulated so that in the final reaction mixture the ratio of Formula II to Formula I components is from 5/I1 to 10/ 1. This provision for dilution of Formula I component promotes the alkylation reaction and minimizes the polymerization of Formula I component.
• the wet hydrocarbon layer may be dried with silica gel, alumina, calcium sulfate or other drying agent, or it may be distilled directly, the water being removed from the products along with the first hydrocarbon distillate therefrom, the first distillate being unreacted reactants of Formula I and II. Continued distillation after removal of the unreacted reactants yields the liquid products of the alkylation as distillate, the solid high boiling products remaining as bottoms which do not distill without decomposition above 200 C. at 2 mm. pressure.
• the total liquid distillable product is fully hydrogenated over Raney nickel or Raney cobalt catalyst at 100 to 200 C. or even higher temperatures in a suitable solvent such as n-pentane, n-heXane, n-heptane, cyclohexane, methyl cyclohexane or the like, under non-critical hydrogen pressures of 100 to 5000 p.s.i. hydrogen pressure. If only partial hydrogenation is desired the temperatures, pressures, and catalyst concentration become somewhat critical; temperatures up to 100 C. and pressures up to 1000 p.s.i. are sufficient to saturate olefinic unsaturation both acyclic and alicyclic, higher temperatures and pressures being required to completely hydrogenate the aromatic rings.
• a suitable solvent such as n-pentane, n-heXane, n-heptane, cyclohexane, methyl cyclohexane or the like.
• one mole of Eastman Kodaks vinylcyclohexene-3 (1108 g.) was added dropwise at a rate sufficient to maintain a reaction temperature of 612 C.
• the addition time of the vinyl cyclohexene was 1.2 hours; stirring was continued for an hour while maintaining 5 C. temperature.
• the acid layer was separated and the upper layer (A) was washed with two portions each of 100 ml. (96.9%) sulfuric acid to remove any hydrocarbon sulfate present from the side reaction of the vinylcyclohexene-B with sulfuric acid, and then with 200 ml. of 20% sodium carbonate solution. All three acid layers were combined, diluted with 1500 g. of a mixture of ice and water, and extracted with 450 ml.
• toluene The toluene plus extract (B) was washed with 530 ml. of sodium carbonate solution, filtered through a bed of sodium chloride, and a few ml. of emulsion breaker (a combination of Aerosol OT and Aerosol 22, both of American Cyanamid Corp.) were added.
• the upper layer B was combined with layer A above and distilled.
• the first toluene distillate carried out the traces of water by azeotropic distillation. After removal of Hydrogenation of fraction 1 was conducted over Raney nickel catalyst (10 .g.) in pentane at 1500 p.s.i. hydrogen while increasing the temperature from 100 to 200 C.
• Example 2 Alkylation of toluene with butadiene dimer
• the procedure of Example 1 was used to react 7.5 moles of toluene (690 g.) with one mole of butadiene dimer (vinylcyclohexene-3) prepared by thermal dimerization of butadiene at 250 C. in toluene solution, and separation therefrom, BJP. 126*128 C./745 mm., 11 1.4250.
• catalyst 25 g. of boron fluoride-phenolate (26% boron fluoride) was used (from Allied Chemical Co.) but without sulfuric acid.
• the toluene-catalyst mixture was cooled to 5 C.
• Example 1 The procedure of Example 1 was employed 736 g. of toluene (8 moles) and 205 g. (2 moles) of 95.5% H 80 catalyst being charged to the reaction vessel at the start. After cooling this mixture of toluene and acid one mole (136 g.) of the piperylene dimer diluted with two moles (184 g.) toluene was added dropwise at a rate sufiicient to maintain a reaction temperature of 3i1 C. The time of addition was 2.75 hours. Stirring at 2:1 C. was continued for 1.8 hours. The acid layer was separated and diluted with an equal volume of water; the new upper layer from this diluted acid was combined with the first hydrocarbon layer, and the combined hydrocarbon layer was washed with 300 ml. of 3% salt water, and twice with 500 ml. of 5% sodium carbonate solution. Partial emulsion was broken with 5 ml. carbon tetrachloride, and filtration of the upper layer through sodium chloride.
• the total yield was based on the cycloolefin (piperylene dimer) feed.
• Hydrogenation of (1) above was carried out at 1400 p.s.i. hydrogen in pentane with 25 g. Raney nickel catalyst at 180 to 225 C.
• a substantially quantitative yield of hydrogenated product resulted having n 1.4935, d 0.908, a gross heat of combustion of 19,495 B.t.u./lb. (18,245 B.t.u./lb. net, and 138,020 net B.t.u./gallon).
• the acid layer was separated from the hydrocarbon layer (A) diluted with 100 ml. water, and the resultant upper layer (B) was added to the first layer (A).
• the total hydrocarbon layer was washed with 500 ml. water.
• the upper layer was separated and washed with 250 ml. sodium carbonate (5%) solution and then with 500 ml. water. It was then distilled to remove toluene, C dimer, and moisture therefrom. The remainder (235 g.) represented 115% yield. It was distilled to give 85% distilling at 125 to 197 C./2 mm. Hg (n 1.5220) and 15% brown residual resin.
• EXAMPLE 5 Reaction of xylenes with dipentene Dipentene (Hercules Co., #122) and Sinclairs 5 xylene (containing 21% ethyl benzene, 2% toluene, 19% o-xylene, p-xylene and 48% m-xylene) were used in this example with sulfuric acid catalyst, using the procedure of Example 1.
• the xylene (1700 g.) was stirred with 203 g. of 96.6% sulfuric acid and cooled to 5 C.
• Dipentene (545 g.) was added dropwise over a period of 3.25 hours while stirring and maintaining a temperature of 5:1 C.
• Example 7 Hydrogenation as in Example 7 resulted in a fuel having a heating value over 142,000 B.t.u./ gallon.
• Example 9 Reaction of toluene and vinylcyclohexene-3
• Example 1 was repeated employing a 2/1 ratio of toluene to vinylcyclohexene-3.
• the product was recovered similarly and the distillate (70% yield on vinylcyclohexene) was hydrogenated as in Example 1.
• the product recovered practically quantitatively, distilled at 275 to 330 C./745 mm. and had a net B.t.u. value over 135,000 B.t.u./gal.
• the alkylation product contained in preponderance dimer of vinylcyclohexene which contributed to the fluidity and energy value of the hydrogenated fuel.
• the hydrogenated dimers are liquids when they contain C to C carbon atoms and contribute both to the fluidity and high B.t.u./gallon of my fuels. It has been found that the greater the number of individual components, the greater is the fluidity of my fuel and the lower the freezing point thereof.
• One of the advantages of my present invention is that it utilizes aromatic feed stocks e.g. a petroleum C to C aromatic fraction or reformate, which are readily available from the petroleum industry (Formula II components) together with cycloalkene derivatives (Formula I components) that are readily obtained as by-product polymers of conjugated dienes, these by-products having found very little use prior to my present invention, i.e., dimers, cod-imers, trimers and cotrimers and tetramers and cotetramers of butadiene, piperylene, isoprene, cyclopentadiene and the like.
• aromatic feed stocks e.g. a petroleum C to C aromatic fraction or reformate
• cycloalkene derivatives (Formula I components) that are readily obtained as by-product polymers of conjugated dienes, these by-products having found very little use prior to my present invention, i.e., dimers, cod-imers, trimers and cotrimers and tetramers and
• the alkylation reaction products of toluene (Formula II reactant) and vinylcyclohexane-3 (Formula I reactant) with a Friedel-Crafts catalyst involves the addition of toluene, in the mand p-positions to the methyl group, to one side of an ethylenic bond, the hydrogen from the substituting position of the toluene going to the other side of the double bond, and also will contain dimers of the Formula I reactant.
• the d-icyclic reaction products (Formula III) from toluene and vinylcyclohexene-3 will contain the following components.
• the fuels comprise only minor amounts of most of the position and geometric isomers, the amount depending on the relative activities of the o-, mand p-hydrogens of toluene, and also on the relative activities of the vinyl and ring unsaturation of vinylcyclohexene-3 and its dimers.
• Friedel-Crafts and Lewis acid catalysts with or without promoters are useful for the alkylation reactions described herein.
• Friedel-Crafts catalysts are often used With promoters, e.g., aluminum chloride is often used in admixture with promoters such as nitromethane, nitrobenzene, carbon tetrachloride, alkyl halide, alcohols, water, hydrogen chloride and the like.
• the reaction may be run in three different ways to obtain distinctly modified products in each. It will be apparent that in the process wherein a Lewis acid catalyst of the type described herein is employed, direct addition of such catalyst to the Formula I component would result in immediate polymerization thereof. This may be controlled by my procedures so that either low amounts or large amounts of dimer may be obtained as desired. Some of the dimerized products are present in even the preferred most efficient alkylation method A. The quantity of dimer formed is readily controlled by these methods.
• the non-polymerizable Formula II component which may be a common diluent or solvent like toluene, is first charged to the reaction vessel to serve as a diluent reactant.
• the catalyst may then be suspended therein. Since the immediate reaction comprising either alkylation or dimerization Will take place with a polymerizable reactant, the Formula I component is added only dropwise, so that it is immediately diluted by the Formula II diluent and reacts therewith catalytically.
• the polymerizable component is maintained at a very low concentration in Formula II reactant diluent and the reaction is largely alkylation of the diluent. Small amounts of dimer may also be formed and such may ultimately reenter the alkylation reaction.
• any of methods A, B and C may be modified by further addition of diluent Formula II added at intermediate stages as the reaction proceeds, to maintain the degree of alkylation if desired.
• the alkyl benzene is usually used in substantial excess, e.g., a 2 to 3 times molar excess in relation to the equivalent quantity of alkylating group material (vinyl equivalent of Formula I) employed and where higher polycyclic side reaction compounds (such as included in Formulae III and IV), a lower ratio down to about to 3 moles of Formula II compound per equivalent of alkylating compound (Formula I) is used.
• a 2 to 3 times molar excess in relation to the equivalent quantity of alkylating group material (vinyl equivalent of Formula I) employed and where higher polycyclic side reaction compounds (such as included in Formulae III and IV), a lower ratio down to about to 3 moles of Formula II compound per equivalent of alkylating compound (Formula I) is used.
• the catalyst may be added thereto at below room temperature, and if the alkylating compound is difficult to react, the temperature may be raised; if the alkylating compound is highly reactive, the temperature may be lowered, applying cooling or refrigeration as needed, and the alkylating group material is usually added slowly, such as dropwise over a several hour period usually 2 to 12 hours, with continued agitation in order to avoid excess side reaction thereof, the conditions being modified depending on the activity of the reagents, and on the desired product.
• the alkylation reaction does not terminate by joining of only two ring groups, it is preferred for high yield of fuels, to allow the reaction to convert only a portion, such as about /3 of the available alkyl benzene, to the Formula III compound before terminating the reaction.
• the reaction products (Formula III compounds containing minor amounts of dimer or dimer derived compounds) are then recovered from the reaction mixture and the excess unreacted compounds such as alkyl benzene are recycled to the reactor.
• Formula I compounds containing two functional groups such as vinylcyclohexene or methyl isopropenylcyclohexene can result in both monoand di-alk lation, i.e., alkylation of two aromatic nuclei, in the sa he reaction in the presence of the selected acid or I iedel- Crafts catalyst.
• the alkyl benzene compound (Formula II), and the alkenyl-cyclohexene reactant (Formula I) are first mixed, and the mixture usually is cooled to from 70 to 0 C., and then the aluminum chloride can be added in any suitable manner, even rapidly, with or without a promoter.
• the reaction mixture is maintained at below 5 C. for 1 to 5 hours and is then permitted to warm up gradually to 25 C. over a period of l to 2 hours to complete the reaction.
• codimers and dimers are prepared, they are freed of catalyst residues by decantation, filtration and/ or Water washing with or without the aid of acid for Friedel-Crafts catalysts removal, followed by an alkaline aqueous Wash; or in the case of the acid catalyst, catalyst removal is accomplished by washing with only water and/ or alkaline aqueous wash.
• catalyst removal is accomplished by washing with only water and/ or alkaline aqueous wash.
• the unreacted starting materials are removed by distillation, the distillate having traces of Water present from the washing; the distillate after drying, e.g., with silica gel, calcium sulfate, and the like is recycled back to feed tanks for the alkylation process.
• the product compounds remaining from said distillation are then hydrogenated.
• the Formula III product may be further distilled for greater purity to separate the tricyclic and polycyclic compounds therefrom; or the tricyclic and polycyclic compounds may be hydrogenated therewith and separated, if desired, from the hydrogenated product (Formula IV).
• the hydrogenation is usually carried out in a diluent, e.g., a paraffin solvent such as pentane or hexane, or a cycloalkane solvent such as cyclohexane or methylcyclohexane in the presence of a hydrogenation catalyst for aromatic compounds, etc.
• a diluent e.g., a paraffin solvent such as pentane or hexane, or a cycloalkane solvent such as cyclohexane or methylcyclohexane
• an active Raney nickel or Raney cobalt catalyst was preferred using from 10 to 15 g. per mole of Formula III compound.
• each aryl ring In order that hydrogenation of the aromatic rings of Formula III compounds proceed at a reasonable rate, hydrogen is employed at non-critical elevated pressures, usually from about 500 p.s.i. to 5,000 psi. To hydrogenate these aryl compounds, the temperature is raised non-critically above a minimum temperature, usually 100- 200 C., but sometimes higher, until hydrogenation commences.
• a minimum temperature usually 100- 200 C., but sometimes higher, until hydrogenation commences.
• the Formula III compounds contain unsaturation other than aromatic unsaturation such can first be removed by hydrogenation under mild conditions (below 100 C.) to yield intermediates which can have use as plasticizers, extenders, hydraulic fluids etc. and these materials can, of course, be exhaustively hydrogenated to form the polycyclic alkanes hereof.
• each aryl ring usually has a minimum or threshold hydrogenation temperature which must be exceeded and this depending on the activity of the catalyst employed and on the position of the alkyl substituents in the individual aryl rings.
• I can obtain selective hydrogenation, i.e., I can hydrogenate only a single aromatic ring of these bi-aromatic ring compounds, e.g., of Formula III, thus, producing compounds in which each alkenyl group of R, R, R" and R" of Formula III have been converted to alkyl and some, but not all, of the aromatic groups of Ar, or included in the Formula II radical of Formula III, have been hydrogenated to a cycloalkane group.
• the Formula III product can have all side chains and one of the benzene groups of Formula III bydrogenated to a cycloalkane group, but not all, if so desired.
• each catalyst system produces an ultimate product differing in amounts of the various isomers of hydrogenated alkylate and hydrodimers present. Also, the composition varies with conditions of alkylation. It has been further found that for each catalyst system there are preferred conditions of operation to attain optimum yields of precursors for hydrogenation to high energy fuels. When maximum alkylation and a minimum of dimer formation (including self-alkylation) is desired the preferred conditions for producing highest yields are shown in Table I, for a number of Lewis acids and Friedel-Crafts type catalysts. The ratio of mono unsaturated (Formula I) hydrocarbon to saturated aromatic compounds (Formula II) is always below 0.5 when alkylate is the desired major product, and the ratio is below 0.25 for diunsaturated compound to saturated aromatic compound.
• ⁇ Procedure A Ethenoid hydrocarbon added gradually to aromatic hydrocarbon catalyst mixture while agitating VlgOIOllSly and cooling the reaction flask in a cold bath (ice and salt water for 0 C. and above and Dry Ice-alcohol bath for 0 to 70 C.)
• boron fluoride-phenolate containing one or two moles phenol per mole of boron fluoride can be used in place of the boron fiuoride-etherate, or boron fluoride-methyl amine complexes, boron fluoride-pyridine complexes and the like can be used as an alkylating catalyst under the conditions outlined in Table I examples, in the process of the present invention.
• aluminum chloride promoted with water, alcohol, organic acid, a phenol, ether, ester, alkyl halide, a polyhalogenated methane, an amine, ethane, or propane (the promoter being used in a molar amount of'l to 0.1 mole per mole of catalyst under the conditions exemplified in Table I) can be used.
• novel liquiddicyclic high energy hydrocarbon fuels the mixtures of cycloalkyl alkylcycloalkane derivatives including hydrogenated dimers of cycloolefinic and polycyclolefinic hydrocarbons are provided wherein the total number of carbon atoms is in the range of 14 to 30.
• solid dicyclic and tricyclic hydrogenated fuels containing from 30 to 42 carbon atoms which in minor amounts may be retained in the liquid fuels, or may be separated for use as solid fuels. All such saturated products have other advantageous usages such as lubricants, plasticizers, dielectric oils, hydraulic fluids, power transmission fiuids and the like.
• R, R and R are members of the group consisting of hydrogen and straight and branched chain alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl and aralkyl radicals, R and R together with the two adjacent carbon atoms having 2 to 12 carbon atoms and R" having to 12 carbon atoms;
• R is a member of the group consisting of hydrogen and straight and branched chain alkyl radicals having 1 to 12 carbon atoms;
• Cyc is a member of the group consisting of cycloalkene and cycloalkadiene radicals having 5 to carbon atoms and dimers, trimers and tetramers thereof, and dicyclic and tricyclic alkene and alkadiene radicals having 7 to 12 carbon atoms and dimers thereof;
• Cyc is a saturated radical obtained by hydrogenating a Cyc radical
• n, p and q are integers from 1 to 4, 1 to 2, 1 to 5, and 1 to 3, respectively, the sum of n and q being an integer greater than 2.
• composition of matter comprising a mixture of position and geometric isomers of at least one of Formulas IV, V, VI and VII,
• R, R' and R are members of the group consisting of hydrogen and straight and branched chain alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl and aralkyl radicals, R and R together with the two adjacent carbon atoms having 2 to 12 carbon atoms and R having 0 to 12 carbon atoms;
• R is a member of the group consisting of hydrogen and straight and branched chain alkyl radicals having 1 to 12 carbon atoms;
• Cyc is a saturated radical obtained by saturating a member of the group consisting of cycloalkene and cycloalkadiene radicals having 5 to 10 carbon atoms and dimers, trimers and tetramers thereof;
• n 2
• m, p and q are integers from 1 to 4, l to S,
• composition of matter comprising essentially a mixture of position and geometric isomers of Formula IV of the formulas defined in claim 1.
• composition of matter comprising essentially a mixture of position and geometric isomers of Formula V of the formulas. defined in claim 1.
• composition of matter comprising essentially a mixture of position and geometric isomers of Formula VI of the formulas, defined in claim 1.
• composition of matter comprising essentially a mixture of position and geometric isomers of Formula VII of the formulas. defined in claim 1.

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  • 1959-12-28 US US862018A patent/US3221071A/en not_active Expired - Lifetime
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