DE2256949A1 - PROCESS FOR ALKYLATING HYDROCARBONS - Google Patents

Description

Process for alkylating hydrocarbons

The invention relates to processes for alkylating hydrocarbons open ^ and in particular processes for the production of branched-chain hydrocarbons by reacting saturated Hydrocarbons with olefins in the presence of acidic catalysts.

Hydrocarbon conversion processes by acid-catalyzed conversion of alkanes with alkenes are known. The reactants are generally reacted in liquid phase and in a broad temperature range of about -73.3 to +37.8 ⁰ G with an acid catalyst such as sulfuric acid, fluoro sulfuric acid or a halogen acid, such as hydrofluoric acid. Alkylation processes using fluorosulfuric acid as a catalyst are for example in US Pat

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U.S. Patents 231,310 and 2,344,469 and GD-PS 537,589. The use of other acids such as trifluoromethanesulfonic acid as an alkylation catalyst is for example by T. Gramstad and R.N. Haszeldine, J. Chem. Soc., 1957, ΊΟ69-79.

However, alkylation processes of this type present numerous difficulties resulting from the high activity of the in the Reactions used strongly acidic catalysts result. Su conduct, for example, the intermediate in the strongly acidic medium formed alkyl carbonium ions initiate a series of side reactions that initially lead to heavier hydrocarbons, which in turn are subject to cracking reactions with the formation of undesirable light hydrocarbons. From it there is a decrease in the formation of the desired Cg bis Cq hydrocarbons and a decrease in the octane number of the Conversion products. In addition, alkylation processes using strongly acidic catalysts have a pronounced effect Lack of selectivity with regard to the formation of Cg hydrocarbons on. Since the octane number of the alkylated reaction mixtures is caused by high concentrations of Cg hydrocarbons is significantly improved, trimethylpentane is considered a particularly valuable alkylation product.

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When using strong acids such as Fluorselwefel-acid has already been tried ₃ as low as possible and the side reactions the selectivity of Cg-hydrocarbons by the use of low reaction temperatures such as about -80 to - C as high as possible to make ^ l3; However, maintaining such low temperatures throughout the process is so difficult _s that these methods are not economically "are feasible addition, it has been attempted to improve the selectivity of Cg-hydrocarbons by the strong acids are mixed with small amounts of additives -like for example according to US-PS 2 .366 731 with BF _3, in accordance with US Patent 2,259,723 with hydrogen halides or according to US-PS 3 23I 633 with surface-active compounds such as methyl-isobutyl-oxoniumchlorid, dimethyl-isopropyl-sulfonium chloride or sulfuric ₉ wherein in In the latter case, the function of the surface-active compound is to reduce the very long induction period of the reaction (up to about 210 hours) in which predominantly C ₁₂ + -alkylation products are formed at the expense of the desired Cg hydrocarbons the fluorosulfuric acid used as a catalyst was a shortening of the Induction period found to be about 125 hours; however, this is still a time span that is hardly acceptable for economic reasons, since the specified process is carried out at a temperature of +10 ⁰ C and a pressure of 7.03 kg / cm ^t '

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is carried out. Furthermore, the addition of mercaptans, which must contain at least 8 carbon atoms per molecule, is in in US Pat. No. 2,880,255 or the addition of amines in US Pat. Nos. 2,880,255 and 3,32,1196 to fluorosulfuric acid has been attempted. However, the disadvantage of the previously proposed processes is that they generally do not have a sufficiently high selectivity for Formation of the desired Cg hydrocarbons develop or that they are not suitable for economic use for reasons of cost.

The invention is therefore based on the object of providing new alkylation to develop processes for hydrocarbons with high selectivity.

To achieve the object a process for the conversion of hydrocarbons by reaction of saturated hydrocarbons with olefins under conversion conditions in a conversion zone using an acidic catalyst is proposed, which is characterized in that the catalyst consists of a major amount of a strong acid and a minor amount of a promoter the group of (a) compounds with a hydroxyl group or with a hydroxyl group precursor, (b) the saturated aliphatic or cycloaliphatic thiqethers, (c) the saturated aliphatic or cycloaliphatic thiols with 1 to 7 carbon atoms per molecule, (d) difluorophosphoric acid . or their mixtures contain ^ g _g ^ ^ / jj

mm EC _

Surprisingly, it has been found that alkylation processes can be carried out with high conversion selectivity can, if the alkylation in the presence of a catalyst mixture with a larger proportion of a strong acid such as for example halosulfuric acids of the formula XSO-, Η, in the X denotes a halogen, trihalomethanesulfonic acids of the formula CX, SO, H, in which X denotes a halogen, or mixtures thereof, in combination with a smaller amount of one or more Catalyst promoters such as water, aliphatic and cycloaliphatic Alcohols, thiols, ethers or thioethers, aliphatic, cycloaliphatic and aromatic sulfonic and carboxylic acids or their derivatives or inorganic acids is carried out.

A particular advantage of the process according to the invention is that the spent catalyst system may optionally can be regenerated and returned to the process by using an olefin and a paraffin under alkylation conditions the alkylation catalyst according to the invention are reacted with a content of fluorosulfuric acid, with a hydrocarbon phase containing the alkylation product and containing at least a portion of the catalyst forms, and then at least a part of the hydrocarbon phase is washed out with an acid mixture with .Sulfuric acid is, wherein an acid phase with a content of fluorosulphuric acid, hydrofluoric acid and sulfuric acid and a

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Hydrocarbon phase with a content of the desired Forms alkylation product, the acid phase is then mixed with water, so that at least part of the fluorosulfuric acid splits into hydrogen fluoride and sulfuric acid, with at least part of the hydrogen fluoride from the so treated Acid phase due to the action of a paraffin with the formation of a hydrocarbon phase with a content of hydrogen fluoride is removed and finally the hydrocarbon phase thus formed with regeneration of the fluorosulfuric acid is treated with sulfur trioxide so that at least part of the regenerated fluorosulfuric acid is used again as an alkylation catalyst can be used.

The alcohols and thiols preferably contain 1 to 10 carbon atoms and 1 to 10 hydroxyl or mercapto groups per molecule. The low molecular weight saturated alcohols and thiols having 1 to 7 carbon atoms and 1 to k hydroxyl or mercapto groups per molecule can be used with particular advantage. Ethers and thioethers which can be used are preferably saturated compounds with mostly 2 to 10 and preferably 2 to 5 carbon atoms per molecule, of which in particular monoethers and monothioethers and optionally compounds with up to three or more alkoxy or thioalkoxy groups are used. The sulfonic and carboxylic acids that can be used contain 1 to 10 and preferably 1 to 7 carbon atoms per molecule and can optionally be replaced by one or more carboxy or

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SuIf © groups be substituted. Usable acid derivatives are Esters and anhydrides with 2 to 20 and preferably 2 to 1Q carbon atoms per molecule.

The aliphatic, cycloaliphatic or aromatic moiety of these promoters can optionally be replaced by various substituents such as halpgeriatoms or hydroxy, mercapto, C. to C ^ alkoxy, .CL to Cc alkylthio, G ^ to Cc perhaloalkyl Cp to Cg-carbalkoxy, carboxy, C ^, - to G ₁₀ -Hy drocarbyl- ', preferably C.τ to Gc ~ alkyl or G, - to CQ ^ cyeloalkyl groups or be substituted by more of these groups.

The inorganic acids which can be used are generally few Less acidic than the strongly acidic components of the catalyst mixture and preferably have H ^ values (i.e. -log h the Hammett acidity function o.n) (see E. Gould, Mechanism and Structure in Organic Chemistry, Hew Yprk, Holt j ftinehart and Winston, 1959 * J06) .from less than -11 to .. are preferred inorganic acids with 1 to 1 hydroxyl groups per molecule are used.

These catalyst promoters can be used with a large number of strong acids. Strong, acidic components can be mixed with strong acid and lately sat prprpmotor bsispi.elßW-Eis ^ haloge ^ sulfuric acids such as U ¹ , sulfuric acid, chlorosulfuric acid, chlorosulfuric acid, jijid irpmschwßfelsäurfi, frihalpge «"

methanesulfonic acids such as trifluoromethanesulfonic acid, trichloromethanesulfonic acid and tribromomethanesulfonic acid or mixtures thereof and similar compounds can be used. Preferred The strong acids used are fluorosulfuric acid, trifluoromethanesulfonic acid or their mixtures. Possibly can also use the phosphorus analogues of trihalomethanesulfonic acids such as, for example, trihalomethanephosphonic acids are used as an effective strong acid.

Suitable promoters are, for example, water, methanol, ethanol, n-propanol, isobutanol, 3-chloro-2-methyl-1-butanol, 6-mercapto- ^ l-methoxy-2-hexanol, 2,2-dimethyl- ¹ J- methylthio-3-perfluoromethyl-1-hexanol, 4, ^ - dimethyl-3-phenolthio-1-heptanol, S-carbethoxy-'JjJl-dimethyl-1-pentanol, 2-decanol, cyclopropanol, cyclopentanol, 2-chlorocyclohexanol, 2 -Methyl-3-methylthiocyclohexanol, cyclodecanol, 1,2-dihydroxyethane, 1,2,3-trihydroxypropane, 2,4,5-trihydroxypentane, 1,3,5-trihydroxycyclohexane, 1,2-dihydroxycyclooctane, pentaerythritol, n-butanethiol , Cyclohexanethiol, methanethiol, ethanethiol, methylsulphonic acid, 2-chloroethylsulphonic acid, propylsulphonic acid, ethy1-propanesulphonate, methyl-2-phenoxy-ethanesulphonate, benzenesulphonic acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, propionic acid, benzoic acid, benzoic acid, methylbenzoate, benzoic acid, benzoic acid , 2-chlorobutanoic acid, 2-hydroxy-5-methylhexanoic acid, phenyl acetate, trifluoroacetic acid, 3,3,3-trifluoropropionic acid, acetic anhydr id, propionic anhydride, ethanoic anhydride, butane

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acid anhydride, oxalic acid, malonic acid, phthalic acid, diethyl malonate, 1,2,3-tricarboxypropane, dimethyl ether, diethyl ether, Dipropyl ether, diphenyl ether, diethyl thioether, dioctyl ether, Ethyl methyl ether, chloromethyl ethyl ether, dicyclobutyl thioether, Dinonyl thioether, decyl nonyl ether, 1-methoxycyclopentyl ethyl ether, Ethylene oxide, ethylene sulfide, tetrahydrothiofuran, phosphoric acid, phosphorous acid, sulfuric acid, sulphurous acid, monofluorophosphoric acid, difluorophosphoric acid, Orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid.

Catalyst promoters used with preference contain either a hydroxyl group, such as, for example, alcohols, or a hydroxyl group precursor such as ether, which under the strongly acidic conditions of the process with the formation of alcohols are cleaved, a thiol group such as ethylthiol or a thiol group precursor such as diethyl thioether. Alcohols and water can be used particularly favorably as promoters. True, the promoters and the strong Acid preferably mixed prior to addition to the reactor, if appropriate however, the catalyst system can also form in situ.

In general, aromatic compounds are not particularly useful catalyst promoters because under the alkylation reaction conditions competitive sulfonation of the aroma

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table cores can occur. However, if the aromatic nuclei are sufficiently deactivated by suitable electrophilic substitution, such compounds are also effective promoters. Strongly electron-withdrawing groups such as -COOH, -SO-H, -COOR and the like deactivate aromatic nuclei sufficiently strong and allow them to be used in the process according to the invention. In general there are aromatic ring substituents with G ~~. and C ^ _ „„ „ Hammett values in the order of magnitude of or above 0.01 can be used. Detailed information on the meaning of the Hammett equation and the electrophilic aromatic substitution are given in ES Gould, Mechanism and Structure in Organic Chemistry, Holt, Rinehart & Winston, Inc., pages 220-227 and 412-463. It should also be noted that strongly basic compounds such as amines, such as, for example, triethylamine, cannot be used in the specified concentrations under the conditions of the process according to the invention, since they react with the strong acids.

Inorganic acids such as HCl, HBr and III have already been used as promoters, but their effectiveness is impaired by the tendency to form stable halides with the olefinic reaction partners. Halide formation is not a serious problem with HF alone. It should also be noted that oxidizing acids, such as HNO .. and HClO ₁ , due to

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the oxidative side reactions with the olefins not as Promoters can be used.

The concentration of the promoter in the two-component catalyst system according to the invention forms an important variable in the production of high quality alkylation products, the promoter is used with the strong acid in amounts of about 5 to ^ 5 mol #, based on the acid, usually from about 10 to 30 Molj £ and preferably in amounts from 15 to 25 mol # such as, for example 20 minor mixed. In certain cases it can be in view be appropriate for increased catalyst activity or selectivity, slightly higher or lower concentrations of the promoter ..

In this context 2 of the accompanying drawings is to FIG. ₅ taken in the relationship between concentration of KatalysatorprOTriotors and Mot or octane number (MON) is shown graphically by Cg + -ÄlkylierungsprodTikten. The diagram refers to the alkylation of isobutane with butene-! and shows the effect of the water concentration in the catalyst on the MOZ of the Cg and higher alkylation products. From the illustration that optimum results eikalt at a £ can be seen, from about 15 to 2Q ffiolSS water "referred to the acid - _s will behave. '.

When using promoters or promoters containing hydroxyl groups with hydroxyl group precursors, i.e. latent hydroxyl groups, the concentration of the promoter in the entire Catalyst system below the concentration range given above from about 5 to ^ 5 mol? fall. The promoter effectiveness the hydroxy compounds appear directly to the total number of hydroxy groups or latent hydroxy groups present to be linked in the molecule, since, for example, ethanol with a hydroxyl group in the promoter activity is about 0.5 mol Corresponds to ethylene glycol with 2 hydroxyl groups. It follows that if the number of hydroxyl groups or latent Hydroxy groups in the promoter molecule increases, the total required The concentration of the compound in the catalyst mixture decreases.

The concentration ranges given are in general regardless of the type of promoter used, the preferred and optimal ranges depend, however to some extent on the structure of the promoter, the reaction temperature, the concentration of the olefin in the feed and the flow rate of the olefin.

As already stated, has trifluoromethanesulfonic acid as a particularly effective alkylation catalyst when added of a promoter. The properties of the connection are

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in "Chemical and Engineering News", January 18, 1971 and in J. Org. Chem. 39 (D, January 15, 1971; accordingly the acid is a stable, colorless liquid with a strong pungent odor that smokes heavily in moist air. Possibly can also use the simple alkyl esters of the acid as alkylating agents be used. The acid shows no oxidizing properties and has proven to be one of the strongest known Protonic acids proved. The alkylation rates are very high, but on the other hand the polymerization reactions also run very quickly, so that the effectiveness of the acid as an alkylation catalyst is reduced. aside from that the selectivity for Cn-alkylates is only low. These Disadvantages can be caused by mixing the acid with one of the inventive Catalyst promoters are overcome because of a substantial decrease in the polymerization side reactions a corresponding increase in the selectivity for C ^ - Hydrocarbons compared to pure acid enters.

In addition to the classic alkylation reactions, the catalyst systems according to the invention can also be used in self-alkylation processes. For example, self-alkylations are generally described in US Pat. No. 3,150,20A. It is preferred to use branched Cg to C ... olefins and C ₁ to Cg isoparaffins in the liquid phase, since the isoparaffins dimerize and the olefins are saturated with the formation of high-quality alkylation products. Unwanted

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Side reactions can be suppressed by using the catalyst systems according to the invention, so that in these processes can achieve high yields of the desired products.

In general, the amount of olefin contacted with the catalyst is about 0.05 to 1,000 volumes of olefin / hour / volume j of the total amount of catalyst in the reactor (v / v / h), this is referred to as the olefin flow rate. Usually the olefin throughput is about 0.05 to 10.0 V / V / h and preferably about 0.05 to 1.0 such as 0.1 V / V / h. The vol.j6ige concentration of the total catalyst in the reaction mixture or emulsion when working in the liquid phase in the reactor can be between about * J0 to 80 vol. #, Based on the total reaction mixture and preferably from about 50 to 70 vol. lie. The concentration of isoparaffins including the alkylates in the hydrocarbon phase when working in the liquid phase can make up about 10 to 100 vol. 56, based on the total volume of the hydrocarbon phase, and preferably about 50 to 90 vol. % . These concentrations of isoparaffins can be maintained by returning unconverted isoparaffins to the reactor.

Suitable olefinic reaction partners are, for example, Cp- to C ₁ "monoolefins with terminal or central double

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bond such as ethylene, propylene, isobutylene, butene-1, butene ~ 2, trimethylethylene, isomeric pentenes and similar higher monoolefinic hydrocarbons with straight or branched chains. The Cp to Cg monoolefins are preferably used, although the more highly branched C ₇ - to Ci? - monoolefins can optionally also be processed. The reaction mixtures can optionally also contain small amounts of diolefins.

For economic reasons, these are usually the norm gaseous olefins are used as reaction partners, but the normally liquid olefins can also be added will. This also includes, for example, reactive polymers, copolymers, interpolymers and similar reaction products of above-mentioned olefins such as biisobutylene and Triisobutylene polymers, Codiraere made from normal butylenes and Isobutylenes, from butadiene and isobutylene and similar compounds. In addition, two or more of these olefins can be mixed als.Einsatzmaterial used for the method according to the invention will.

The catalyst preparations according to the invention are particularly suitable for use in refinery alkylation processes. In particular, various raffinate cuts can be used as feed material, such as C _? -, C, -, Cjl- and / or C '"Qlofinüchni'tte from thermal and / or catalytic

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Cracking units, field butanes previously subjected to partial isomerization or dehydrogenation, Bottoms from refinery stabilization columns, consumed Gases, usually liquid products, from polymerization and copolymerization processes catalyzed by sulfuric acid or phosphoric acid and normally liquid products from thermal and / or catalytic cracking units. Such Mixtures are excellent uses for carrying out the process of the invention. The stakes are preferred before feeding into the reactor to avoid excessive water absorption to a water content of about 5 to 15 ppm, based on weight, dried.

The hydrocarbon feedstocks to be reacted with the olefins preferably contain straight and / or branched chain C "- to C _1Q -paraffins such as hexane, butane and similar compounds and Cj. - to C ^ -isoparaffins such as isobutane, isopentane, isohexane and. similar connections. Although open-chain hydrocarbons are preferably processed, cycloparaffins can also be used if necessary.

The olefin is preferably first diluted with the paraffin before it is fed into the reactor, so that the olefin concentration in the paraffin feed material at about 0.5 to? 5 vol.? » based on the entire use, and preferably below 10 Vol.5? lies.

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In relation to volume ratios, it follows that high volume ratios of paraffin: olefin of about 10: 1 to 200: 1 or higher are preferred; in special cases, lower ratios such as ~ 5: 1 can also be used. Correspondingly high paraffin: olefin volume ratios should preferably also be present in the reaction zone, such as, for example, paraffin: olefin ratios of about 20: 1 to 2000: 1 or higher.

The process according to the invention can be carried out batchwise and from economic Reasons are preferably carried out continuously. It is well known that in alkylation processes the better the yields of saturated products, the better and more intimate the contact between the feedstock and the catalyst is. So if the process according to the invention is carried out in batches, should be for improvement of contact, the reaction partners and the catalyst are mechanically stirred or shaken vigorously;

In a preferred embodiment of the invention are at continuous operation, the reactants are kept in the liquid phase by means of suitable pressure and temperature conditions, so that they can then be fed continuously into the reaction zone through dispersing devices. As a dispersing device can be nozzles, porous plates or the like

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can be used. The reactants are then mixed by known mixing devices such as mechanical Agitators mixed with the catalyst system, so that after a sufficiently long time the reaction product is continuous separated from the catalyst and withdrawn from the reaction zone while the partially consumed catalyst is returned to the reactor. If necessary, a Part of the catalyst mixture is continuously regenerated or reactivated in a suitable manner and fed into the alkylation reactor be returned.

As with other alkylation processes, better control over the quality of the end product can be achieved if the reactor is equipped with a return system in which the partially converted hydrocarbons with fresh The feedstock can be mixed and recycled to the feeders of the reactor. But since the invention Process leads to a very high conversion rate, the alkylation can preferably also be carried out in a one-step process can be carried out with short response times.

In general, the process according to the invention can be used according to the reaction and / or recovery schemes and with the per se of liquid acidic catalyst systems known devices are carried out. Applicable process technologies

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and devices are disclosed, for example, in U.S. Patent 2.4.33 2,479,366, 2,701,184, 2,717,913 and, 2,775,636 and in GB-PS 543 046, 577 869, 731 806, 738 348 »803 458, 804 966 and 881 892, to which reference is hereby made.

At de? Carrying out alkylations with the catalyst system according to the invention can be carried out in a wide temperature range from about -62 to +3> 8 ° C. In most cases, however, relatively low reaction temperatures of about -62 to +21 and preferably of about -29 to +4 C are preferred. When using sulfuric acid as promoter the preferred temperature range between -29 to -1 is C, in particular about -18 ₉ since this can substantially avoid to -7 ⁰ C, the induction period as described in U.S. Patent No. 3,231,633. If the reaction is ^{carried out at temperatures above -12 0} C, must 'work simultaneously under pressure in order to keep both the reaction partners and the catalyst essentially in the liquid phase .. Alley lierungsreakt ions are usually at pressures of about 1 to 20 .atm carried out, in general, the applied sraefce will be sufficient to keep the implementation partners in the liquid phase, if necessary, the reaction can also be carried out in the vapor phase. In order to be able to work in the liquid phase, self-cooling reactors or similar devices can be used. The process can preferably be carried out without a solvent

or optionally carried out with solvents or diluents will.

In another preferred embodiment of the invention, the catalyst mixture can be applied to a suitable solid support, this solid support having to be essentially inert towards the catalyst mixture under the reaction conditions. Active carriers can be made inert by coating them with inert materials such as antimony trifluoride or aluminum trifluoride. Suitable carriers are, for example, silica gel, anhydrous AlP _1. , Aluminum phosphate, carbon, coke, firebricks and the like. When using catalyst mixtures applied to a carrier, the reaction partners are brought into contact in vapor form and / or liquid form with the catalyst particles under alkylation conditions. The catalysts can be accommodated in the reaction zone as a fixed bed, moving bed or fluidized bed.

The mentioned olefins and saturated hydrocarbons are with the catalyst mixture for one to achieve the desired Degree of alkylation brought into contact for a sufficiently long time. The contact time can be varied within wide limits and depends in part on the reaction stone temperature used Olefin and the concentration of the analyzer mixture,

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For example, contact times of about 5 minutes to 1 hour or more and possibly also significantly shorter contact times, such as about 0.1 seconds, can lead to good results. _{Portions of the catalyst mixture 3} which are carried over into the alkylated product can be recovered and regenerated according to the method described in detail below.

This method is explained in more detail below with reference to the drawings.

1 shows the method according to the invention in a flow chart.

FIG. 2 shows a graph of the relationship between the concentration of the catalyst _{promoter and the MOZ of the C 6} ⁺ -alkylates.

From Fig. 1 it can be seen that the olefin fed in through a line 2 is preferably mixed with that fed in from the lines 4 and 6 Paraffins is mixed before the combined stream is fed into a reactor 8. If necessary, the Olefin and paraffin stream also fed directly into the reactor. 8 are., The olefin concentration in the feed is about 0.5 to 25 vol. # and preferably below 10 vol.%, based on

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all the effort. In terms of volume ratios, this means that high volume ratios of paraffin: olefin of about 10: 1 to 200: 1 or higher are preferred, although in special cases somewhat lower ratios such as, for example 3: 1 can be used. Correspondingly high Paraffin: olefin volume ratios are also preferred in the reaction zone where this ratio is from about 20: 1 to 2000: 1 or higher. The catalyst mixture of fluorosulfuric acid and a promoter such as water is in the Reactor fed through line 10; additional water can be introduced into the reactor through line 12.

The process can be carried out batchwise or, for economic reasons, preferably continuously. It is known, that in alkylations, the greater the yield of saturated product, the more intimate the contact between the feed and the catalyst mixture. For this reason, the method according to the invention is used in batches The procedure is conducted in such a way that the reactants and the catalyst mixture are vigorously mechanically stirred or shaken will.

In the continuous procedure shown in the drawing the implementation partners are kept under such pressure and time constraints that they essentially

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are in the liquid state and can be fed continuously into the reaction zone through dispersion devices. The dispersion devices can be nozzles, porous plates or the like. The reactants are then mixed with the catalyst mixture in the reactor 8 by mixing devices which are known per se and are not shown, such as, for example, mechanical stirring devices or the like. The Älkylierungsreaktion, in a temperature range of about -62 to 38 ⁰ C, usually at relatively low temperatures such as from -62 to +21 C, and preferably at about -29 to + h C are performed. When working at reaction temperatures above about -12 ° C, the reaction must be carried out under excess pressure so that both the reaction partners and the catalyst mixture remain essentially in the liquid state. In general, the alkylation • reactions are carried out at pressures of about 1 to 20 atm.

The process according to the invention is preferably carried out at such a pressure that the reactants are in the liquid State, but may also be in the Steam phase can be worked. Self-cooling reactors or similar can be used to maintain operation in the liquid phase Devices may be provided. The reactions are mostly without Solvent carried out, although possibly in certain In some cases, solvents or thinners can be added .hormone,

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After a sufficiently long residence time in the reaction zone of usually about 5 minutes to an hour or more, the reaction mixture is withdrawn from the reactor through a line 14 and transferred to a settling tank. The reaction mixture separates in the settling tank 16 into a heavy acid phase composed of fluorosulfuric acid and promoter and a hydrocarbon phase containing alkylation products together with smaller amounts of water, fluorosulfuric acid and hydrogen fluoride dissolved and / or dispersed therein. The acid phase is withdrawn from the settling tank 16 through a line 18 and at least a portion of this phase can be returned to the reactor 8 through a line 10 or, if necessary, transferred to another alkylation reactor. If necessary, part of the acid phase 20 can also be withdrawn from the line 18 for cleaning in a regeneration stage. The hydrocarbon phase is drawn off from the settling tank 16 through a line 22 and transferred to a scrubber 2k , in which it is intimately mixed with sulfuric acid fed in through a line 26. The sulfuric acid is preferably in concentrated form as 99.5 to 100% HpSO ₁ . used, but more dilute acids (97 to 98 %) can be used without affecting the effectiveness of the process. The renewal of the sulfuric acid in the line 26 is carried out by feeding it through a line 25

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The hydrocarbon phase contains in the dissolved and / or dispersed state fluorosulfuric acid, water and hydrogen fluoride from the partial dissociation of the acid used as well as other acidic components such as sulfur dioxide, surprisingly it was found that the acidic components dissolved and / or dispersed in the hydrocarbon phase by washing the Hydrocarbon phase can be effectively removed with concentrated sulfuric acid. The washing can be carried out in a manner known per se, for example by feeding the sulfuric acid and the hydrocarbon mixture through mixing nozzles, countercurrent contact towers or through. Feeding into a centrifugal pump takes place, provided that there is close contact between the hydrocarbon phase and the sulfuric acid. The acid to hydrocarbon ratio is not critical and can be about 5 to 95 percent of the hydrocarbon stream. This ratio is controlled by feedback of the acid from line kO through a line ¹ into the conduit Jl 26th The temperature during the washing process is generally about -7 to 38 C; the pressures can be between atmospheric pressure and about 35> 2 kg / cm. After mixing in the washer, the resulting phases separate.

In the sulfuric acid scrubber, the largest amounts of the acidic reacting material present in the hydrocarbon phase are

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rials removed, but traces of acidic compounds, mainly HpSOj., remain in the one flowing out of the scrubber Phase back. The outflowing hydrocarbons are drawn off from the sulfuric acid scrubber through a line 28 and transferred to an alkali treatment plant 30 to remove the acids still present in traces. These Alkali treatment plant may be of a conventional type in which, for example, solid alkali oxides such as potassium oxide and sodium oxide react with sulfuric acid to form potassium sulfate, potassium fluoride, sodium sulfate, sodium fluoride and water, which can then be withdrawn from the hydrocarbon phase, for example through a line 32. The hydrocarbon phase is withdrawn from the system for alkali treatment through a line 3 * 1 and into a separation system for the separation of Isobutane 36 transferred, the one known per se for the separation of isobutane can be a suitable column in which an isobutane stream is withdrawn from the hydrocarbon phase, which then withdrawn through a line 6 and recycled to the alkylation reactor 8. The end product of the alkylation process is withdrawn through a line 38. Possibly the isobutane is not fed back into the reactor, but can be made available for further processing.

In the washing plant 2'I the sulfuric acid flow is through a Line '(O removed and, if necessary, with the one for cleaning

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- ■ 27 -

certain stream 20 combined. The combined streams flow through conduit 42 into a conversion tower 44, in the so much water is fed through a line 46 that the fluorosulphuric acid according to the following equation decomposed in free hydrogen fluoride and sulfuric acid:

H _o 0 + HS0, FH ₀ SO .. + HF 4 + heat

In a preferred embodiment of the invention \ fird bis to 1 mol of water is added in excess over the stoichiometrically required amount, usually less than 0.5 mol of excess Water added. The resulting mixture of water, hydrogen fluoride, sulfuric acid and fluorosulfuric acid is made from the Conversion tower 44 withdrawn through a line 48 and into a Stripper column 50 transferred, in which the hydrogen fluoride from the mixture is withdrawn by intimate contact with a hydrocarbon stream fed through line 52. Preferably η-butane is used for this. In a preferred embodiment According to the invention, the conversion tower and the stripping tower form a unit. In an upper part 54 of the Stripper column 50, the hydrogen fluoride is converted with sulfur trioxide according to the following equation:

HF + SO-. -> HSO-.F + heat

3 3

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tan

The sulfur dioxide is fed in through a line 56 and regenerates the fluorosulfuric acid catalyst mixture, which is then drawn off together with the hydrocarbons and some water at the top through a line 58, condensed in a condenser 60 and transferred to a separation system 62. Here the fluorosulfuric acid is separated from the hydrocarbons present in the mixture. The regenerated fluorosulfuric acid containing water is withdrawn from the separation system through a line 6 ^ 4 and at least part of this mixture is combined with the return stream 18 for recycling into the reactor 8 through line 10. The hydrocarbon phase from the separation system 62 taken through a line 66 for further processing or for temperature control by lines 55 "63, 4, 3 and ¹ 5 J returned to the tower M and stripper column 50th In addition, part of this hydrocarbon stream can be used as a stripping agent in the stripping column 50 if this part is fed in through a line 52. Additional hydrocarbon stripping agents can be added to the stripping column through line 53. The sulfuric acid used for cleaning can be withdrawn from the bottom of the regeneration tower 50 through a line 68 and passed to a sulfuric acid regeneration plant (not shown) for the removal of carbon and re-concentration, or it can be discharged as waste. The stripper column 50 is usually at temperatures of about 50 to 150 ⁰ C and preferably from about 66 to 93 C and

309824/113 7

operated at pressures of about 2.11 to 7 * 03 kg / cm; Indeed these temperatures and pressures can be varied to maintain a suitable phase relationship.

For stripping in the stripping column 50, all saturated Hydrocarbons are used; but it has proven to be particularly advantageous to use η-butane, since this with the action of hydrogen fluoride and fluorosulfuric acid in the column partially in the as feedstock for the Alkylation reactor required isobutane is isomerized. The hydrocarbon phase withdrawn from the separation system 62 contains then considerable amounts of isobutane, which are separated off after washing in the separation plant for the separation of isobutane 36 and can be mixed directly with the olefin feed in line 2 through line 6.

The following examples are intended to explain the invention in more detail. Unless otherwise stated, all percentages and parts are based on weight.

example 1

The isoparaffin-olefin alkylation reactions were in continuous Working method carried out. The following devices were used for the experiments:

309824/1 "137

A. Glass reactors for continuous operation

(1) For alkylations with low hydrocarbon throughput rates of, for example, 13 to 18 V / V / h, based on acid, a cylindrical glass reactor with a volume of 300 ecm used. The reactor was mechanical Equipped with a stirrer with a flat blade, so that the reactants and the catalyst mixture are uniform with one another came into contact. Furthermore, the reactor was provided with a dry ice-cooled reflux condenser through which the condensed hydrocarbon feed from isoparaffins diluted with olefins was fed, as well as with a to a cooled receptacle for collecting the alkylate on the side neck and with a nitrogen inlet tube, through which nitrogen was introduced to prevent the catalyst mixture and the incoming Separate feedstock.

(2) For tests with high hydrocarbon flow rates such as 9.1 V / V / h, based on acid, an elongated glass reactor with a volume of 35 ecm was used, the with a device for returning what was torn over with the product Provided catalyst and otherwise constructed similar to the reactor in (1) was.

309824/1137

These glass reactors for continuous operation were converted into a cooling mixture such as, for example, a dry ice-alcohol mixture immersed so that the reaction partners and the catalyst mixture remained in the liquid phase. First the catalyst mixture was then poured into the reactors and cooled to the desired temperature, then was the catalyst mixture is diluted with isoparaffins and then the olefin diluted with further amounts of isoparaffin was added through the reflux condenser into the reactor. The alkylated product was continuously withdrawn, collected in a collecting vessel and cooled with a dry ice-alcohol mixture. The alkylated Product was then washed with 10 # NaOH solution and analyzed. The strong acid component of the catalyst mixture was regularly distilled prior to use.

B. capillary reactor

A capillary reactor was used when working with very short contact times. The Kätalysatormischung and the hydrocarbon feed were separated by capillary tubes pressed at a pressure of about 10.0 to 17.6 kg / cm in a mixing chamber with dimensions of 0.127 x 0.127 cm, ~ long with a 2, ¹ J to 3.0 m No. 18 stainless steel cannula tube was connected. The feed tubes, mixing chamber, and capillary tubes were immersed in a dry ice-alcohol cooling bath maintained at the desired temperature. The one from dom

309824/1137

The mixture of catalyst mixture and hydrocarbons escaping from the capillary reactor was collected in a receptacle and cooled with liquid nitrogen. The hydrocarbons were then melted, from which Acid decanted, washed with 10 55% NaOH solution and analyzed.

In Tables I and II are those when used with fluorosulfuric acid in a mixture with water or sulfuric acid as promoters obtained results compared to the use pure fluorosulfuric acid as a catalyst for continuous alkylations in glass and capillary reactors.

When using a strong acid mixed with a promoter, there is a significant increase in the RON and MON of the alkylate compared to the use of the pure strong acid. Water and sulfuric acid are particularly effective catalyst promoters, in particular at concentrations of about 20 mol?, Based on the acid used. In addition, high volume ratios of isoparaffins: olefins and low olefin throughput rates of about 0.1 % promote the selective formation of large amounts of Cg alkylates.

In addition, it can be seen from these tables that the alkylations in the capillary reactor with very short contact times and

3 0 9 8 2 4/113 7

results obtained with high olefin throughputs with those obtained when using glass reactors in continuous operation to match.

Example 2

Table III shows the results when using trifluoromethanesulfonic acid CF, SO, H combined with promoters. The procedures and reaction conditions corresponded to those given in Example 1. - ·

Again, it should be noted that the use of a catalyst promoter together with CF, SO, H or FSO, H / CF, SO, H to improve RON and MON of the alkylate leads.

Example 3

In Table IV are the results of alkylation experiments using other olefins in place of butene-1 such as Refinery olefin streams listed as feed. the The reaction conditions corresponded to those already given. The composition of the refinery C |. Oil stream was as follows:

Weight %

Propane 0.96

Propylene 0.1-4

Isobutane, 35> 13

η-butane. 12.89

309824/1137

Weight%

Butene-1 11.46

Isobutylene 7.55

trans-butene-2 16.15

cis-butene-2 11.67

Isopentane 3.21

n-pentane 0.02

3-methylbutene-1 0.52

Butadiene 0.02 pentene-1. 0.11

2-methyl-butene-l 0.16

Total olefin content in% by weight 47.78

The results show the broad applicability of the invention Catalyst system for numerous olefins. Even ethylene, which cannot be effectively alkylated with sulfuric acid can, is converted into a high quality alkylate without difficulties when using the catalyst mixture according to the invention. Mixed refinery olefin streams with a major Content of C ^ olefins result in large yields of higher quality Alkylates.

It should also be noted that isobutylene (compare Experiment 4) using the catalyst mixture according to the invention can be converted into high-octane alkylates. This is particularly surprising since isobutylene is more common when used HF or H-SOj alkylation catalysts are extremely difficult is to be alkylated.

309824/1137

Example M

Several batch tests were carried out with the catalyst system according to the invention on a solid support. In these The catalyst mixture and the solid support were tested in a 1 liter three-necked flask with a stirrer, one with Introduced dry ice-cooled reflux condenser with calcium chloride tube and gas inlet tube. Isobutane became 7> 5 minutes long into the flask with a flow rate of 5.5 liters of gas per minute initiated. 5 minutes after the start of the isobutane feed was Butene-1 with a flow rate of 0.055 liters of gas per minute supplied for a total of 9 minutes. After the supply of hydrocarbons had been interrupted, was the reaction was continued under reflux for a further 6 minutes, then the reaction mixture was rapidly cooled in dry ice-alcohol and part of the hydrocarbon phase decanted, with Washed 10 # NaOH solution and analyzed. The results these experiments are summarized in Table V.

The results obtained are not as good as when working with reactors in continuous operation, but they are in the desired direction and "show that the catalyst mixture after impregnation on solid supports in alkylation reactions can be used.

309824/1137

Example 5

Further attempts were made with various catalyst promoters. The experimental conditions corresponded to those in Examples 1 to 3 described. The results are summarized in Table VI.

The results show that promoters such as trifluoroacetic acid and chlorosulfuric acid are not as selective for the production of Are alkylates with a high content of trimethylpentane. On the other hand turn out to be difluorophosphoric acid, diethyl ether, ethanol and benzenesulfonic acid as effective promoters for production of high quality alkylates.

Table VII summarizes the effects of water concentrations in the acid on the quality of the alkylate. The increasing amount of trimethylpentanes in the alkylate with increasing water concentration of up to about 20 mol%, based on the acid, is noticeable, followed by a sharp drop in the concentration of these compounds at water concentrations above about 20 hectol% . The results are shown graphically in FIG.

309824/1137

Table I.

Experiment no _.: 1

Reaction conditions (1)

Olefin

Isoparaffin

Isoparaffin / olefin,, ■ (volume ratio in use) temperature in ⁰ C. ■.

Throughput amount KW V / V / h based on the catalyst olefin throughput amount V / V / h,

based on catalyst catalyst - acid _o - promoter

CD,

oo catalyst volume m cnr fo volume Ck ⁺ alkylate yield / ■ ^ volume olefin (3)

- ^ product composition in% (2) co '5.

Total Co
Trimethylpentanes

Cg-Cg alkylate RON (3) Cg-Cg alkylate MOZ. (5) Cg ⁺ alkylate MOZ (3)

(1) Experiments in a glass reactor with continuous operation

(2) Determination by gas-liquid chromatography using a 90 m long capillary tube with 0.025 cm clear width and coating with DC-550 silicone oil and hydrogen flame ionization detector .

"(3) Computer calculation from analysis of gas-liquid chromatography (4) Based on fluorosulfuric acid

11/1
-17.8 11/1
-17.8 176.9 / 1
-17.8 176.9 / 1
-17.8. I. 104 . 91 13.7 13.7 I. 11/1
■ -17.8 8.63
FSO3H
14 mol %
H ₂ O
15.7 7.55
FSO3H
(4) 20 moles. # (4)
* 15 0.08
100 % FSO ₃ H
100 0.08
FSO3H.
20 moles SS (4).
H ₂ O
100 \ 104 1.73 ' 1.76 ' 1.74 1.72, 8.63
100 % FSCH,
15th 1.98 4.18 '■ 1.37 0.16 1.77 4.20 5.40 1.90 0.32 5> O8 86.11 82.48 93.33 98.33 6.84 77.10 70.54 73.95 94.33 78.19 7.65 7.94 ' 3.40 1.19, S ₀ 64.09 97.50 96.10 '93.70 100.50 'NJ 9.89 95.70 ' 94.50 92.10 98.10 S 94.30 95.00 94.00 91.90 98.00 <P. 92.80 92.20

Attempt no.

Reaction conditions (1)

Olefin

Isoparaffin

Isoparaffin / olefin (volume ratio in use) Temperature in ⁰ C% by volume of acid in the reactor Olefin throughput V / V / h, based on catalyst catalyst - acid

Promoter

Volume Cc ⁺ alkylate yield / volume olefin (3) acid feed, volume olefin / volume acid
Contact time in seconds

Product composition in wt.% (2)

° 6 "° 7
Overall C

Trimethylpentanes Cq +

C ^ -Co alkylate RON C ^ -Cq alkylate MOZ Cc ⁺ alkylate MOZ

(3) (3) (3)

Table II 1 2 Butene-1
Isobutane Butene-1
Isobutane 88.4
4.4
50.5 88.4
4.4
40.7 34.81
100 % FSO ₅ H 53.3
FSO 3H
20 mole percent (4) H ₂ O 1.77 1.74 0.011
1.13 0.016
1.10 3.84 1.69 4.03 2.68 86.63 92.29 69.94 86.19 5.50 3.34 94.20 99.40 93.00 96.90 92.70 96.60

(1) Experiments in a capillary reactor

(2) Determination by gas-liquid chromatography using a 90 m long Capillary tube with 0.025 cm clear width and coating with DC-550 silicone oil as well Hydrogen flame ionization detector

(3) Computer calculation from analysis of gas-liquid chromatography ( ^ü ) based on fluorosulfuric acid

I-araffin / oil

fin

CO

CL * rir. Quantity V / Y / h, each rain on catalyst catalyst: V acid., - promoter

• z

Catalyst volume in cm.

'• "o lumen S ^ ⁺ alkylate yield /

Product composition in weight % ' (4)

Trimethylpentanes

Co ⁺ '''''C.-Cg alkylate. RON. '(5); C.-C ^ alkylate MOZ 'C5)' C ^ ⁺ alkylate- MQZ, ....

T 83.4 / 1
-17.8 section III .... .., 3. . ,. ■■ , 4 ro 91 2 "BUten-l" ——--——'— CD
CO 1.02
10054 CF3SO3H
15th v 176.9 / 1
-17.8 176.9 / 1
-17.8 ν -Α »79 91 ■ 91 4.33 .-. 9I- ■ ■ '0.51
.; · '15;. ■ -, 0.51
3O3H / CF3SO3
20 mole %
H ₂ O (3)
15th -: ■■■. 6, QO 0.51
OX ¹ 'SO / v-'"2 J
20 moles
H ₂ O '(■ 1.98 1.71 86.47 1.71- 17 ^ 46 ^:. ; ·. 0.07 79.78 0.4 2 \ 1.56 0.56 3.20 0.85 79.38 ■ ■ 97.08 96.80 96/55 72.9-5. '■. - - ■ ■ · ', 93v5O 95.20 91.1-7 1.60 ^; v,; :: . 2.29 94.90 • 'S, 18 98.70 101.00 100 ·, 60 97.00 ■■■, -, 97.70 97.50 96.80,. , 97.5.0 97 ^ 30:

(1) experiments in ; Glass reactor in continuous operation . '^;'

(2) Iolyester ratio 1: 1. ;:. ■:. ■■><.: ■■■ · ₍ - .-

(3) In relation to the 'overall picture' '

(4) Determination by gas-liquid chromatography using a - $ Q m, tube 'with 0.025 cm inside diameter and coating with DC-550 silicone oil as well

long capillary hydrogen

Flame intelligence detector VjJ VO

input calculation from analysis of gas-liquid chromatography

Attempt no.
Reaction conditions (1)

Λ > -. ^ ν.
• J iSi 4th Γι

Isoparaffin
Isoparaffin / olefin (volume ratio in use) • Temperature in ⁰ C dura- tion rate KW V / V / h, based on / catalyst olefin throughput rate V / V / h, based on catalyst catalyst - acid

Promoter

^σ catalyst volume in cm- ^ volume of C- ⁺ alkylate yield / Γ *? Volume Oiefin (3)

⁴ ^ product composition in wt.% (2)

~ o total C ₀

Trimethylpentanes

C ^ -C ₀ alkylate RON (3) C ^ -Cg alkylate MOZ (3) C ₁ J ⁺ alkylate MOZ (3)

Table IV 1 . 2 I. 3 U Propylene
Isobutane Propylene
Isobutane Ethylene
Isobutane Isobutylene
Isobutane 184/1
-17.8 184/1
-17.8 180/1
-17.8 176.6 / 1
-17.8 91.0 13.1 13.7 18.0 0.50 (5)
FSO ₃ H
20 moles 55 (4)
H ₂ O
15th 0.07 (5)
FSO ₃ H
20 moles 1 (4)
H ₂ O
100 0.08 (5)
FSO ₃ H
20 moles 55 (4)
H ₂ O
100 0.10 (5)
FSO ₃ H
20 mole % W
H ₂ O
100

1.62 1.56

1.72 (5)

1.73

0.42 0.00 1.33 hü
cn -CT 2.13 17.45 28.06 1.44 cn O 34.97 79.41 66.75 92.93 I. 58.50 78.57 66.16 90.40 56.92 2.53. 5.19 ' 4.30 4.40 98.70 101.00 100.00 96.00 97.10 97.20 98.50 94.20 96.90 96.70 98.00 93.90

(1) Experiments in a glass reactor with continuous operation

(2) Determination by gas-liquid chromatography using a 90 m pipes with a clear width of 0.025 cm and coating with * DC-550 silicone oil as well as Flame ionization detector

\ Z) Computer calculation from analysis of gas-liquid chromatography

long capillary hydrogen

^ • i-r

on fluorosulfuric acid

f "

IMlr.ertingswert

Table IV (continued)

CO
O
CD
OO

Attempt no.

Reaction Conditions (1) olefin

Isoparaffin
Isoparaffin / olefin (volume ratio in use) Temperature in ⁰ C Flow rate KW V / V / h, based on the catalyst Olefin throughput V / V / h, based on the catalyst catalyst - acid

Promoter

Catalyst volume in cm volume Cc ⁺ alkylate yield / volume olefin (3)

Product composition in wt. % (2)

Overall C

Trimethylpentanes

C ₆ -Cg alkylate RON Cg-Cg alkylate MOZ Cg ⁺ alkylate MOZ

(3) (3) (3)

5 6th 7th 8th 2-methyl
butene-2
Isobutane Refinery-
Ci | -01efine
Isobutane Refinery-
Ci | -01efine
Isobutane Refinery-
C / 4 olefins
Isobutane 170/1
-17.8 113.4 / 1
-17.8 181.5 / 1
-17.8 181.5 / 1
-17.8 ■ 91.0 16., 3 91.0 13.1 0.50 (5)
■ FSO3H
20 mol% (4)
H ₂ O
15 ' 0.14 (5)
$ 100 FSO3H
100 ■ 0.50 (5)
FSO3H
20 mol % (k)
H ₂ O
'15 0.07 (5)
FSO3H
20 mol % (k)
H ₂ O
100 2.50 (5) 1.84 1.85 1.83 34.37 5.46 7.48 5.72 1.69 3.91 2.02 1.04. 61.22 86.13 86.59 91.56 59.81 66.53 '81, 6O 88.23 2.72 4.50 3.91. 1.34 ' 99.70 92.20 99.80 100.20 98.40 90.70 97.40. 98.20 98.00 90.60 97.00 98.00

(1) Experiments in a glass reactor with continuous operation

(2) Determination by gas-liquid chromatography using a 90 m tube with 0.025 cm clear width and coating with DC-550 silicone oil and flame ionization detector

(3) Computer calculation from analysis of gas-liquid chromatography

(4) Based on fluorosulfuric acid (5) Approximate value

long capillary hydrogen

Table V

σ
co
co

Attempt no.

Reaction conditions
Olefin
Isoparaffin
carrier

Weight of the wearer
in the catalyst in g
Isoparaffin / olefin
(Volume ratio in use) Temperature in ⁰ C
Olefin throughput in V / V / h, based on the catalyst
Response time in minutes
Catalyst - acid

Promoter

Volume Cc ⁺ alkylate yield /
Volume olefin (5)

Product composition in wt. % (4)

1 (1) 2 (2)

3 (1)

ρ - c

6 7
Overall C

Trimethylpentanes
C ^ -Co alkylate RON

0 0

Qr ⁺ alkylate MOZ

anhydrous AlF.

20th

110.6 / 1 -11.7

15 100 % FSO ₃ H

3.13

4.99

85.73

71.40

6.15 95.60 93.80

- butene-1

- isobutane

anhydrous AlF.

20th

110.6 / 1 -11.7

0.13 20

Mol %: H ₂ O (6) 1.78

5.82

5.80 79.38 70.68

9.00 97.40 94.60

calcined

Silica gel

25th

11.1 / 1 -11.7

60 % FSO ₃ H

6.02

4.51

84.60

73.52

4.87

96.70

94.70

ro ro οι cn co

-P- * CD

(1) Experiments in a glass reactor at pH, mixed operation

(2) Experiments in a glass reactor with continuous operation

(3) Weight of FSO ₃ K on carrier - % 5 g

Long (4) Determination by Gäe-Fiüssifskeitschromatographie using ^ 4 ¥ i "i ** 5Q π capillary tubing" with 0.025 cm clear V'eite _t and Eescnichtit ^ iHnii DC-550 silicone oil, hydrogen? Lammenionisatiodidetektor

(5) Computer calculation from analysis of the gas-liquid chromatography

(6) Based on acid

Table VI

tU \ Tk.

rg-.ction conditions (1) ,

Isoparaffin- ■ <■ · ■■■ Isoparaffin / Qlefin (volume ratio in use) temperature in ⁰ C Clefine throughput in V / V / h, prove on catalyst catalyst * · acid

- Proinotor

Volume of C ^ ⁺ alkylate yield / volume of olefin (3)

Product composition in weight% (2)

Overall C

Trimethylpentanes, C ⁺

C ^ -Cp alkylate RON C.-Cg alkylate MOZ Alkylate MOZ

r +

^G 6

(3) (3) (3)

20 mole percent (5) CF ^ COÖH

1.73

0.75-0.84

95.55

84.64

2.86

97.60

• 95.80

95.60

• - '' butene-1 ■ · - Isobutane

110.6 / 1 -17.8

■ 0.12 ■

Mole % (5)

HF ₂ PO ₂ '■'

1.74

0.49 '0.53 98.26

¹ 0, f2

100, | o 98.30 98.20

20 mole percent (5) ClSO H

'■ * ■%>

1.97

2.52

94.13

72.00

1.38

90.90 90.80

cn

CD CD 4> CD

(1) Experiments in a glass reactor with continuous operation ■ ·.

(2) Determination by gas-liquid chromatography using a 90 m long capillary tube with 0.025 cm clear width and coating with DC-550 silicone oil and hydrogen flame ionization detector ■,. . ·.

(3) Computer calculation from analysis of gas-liquid chromatography

(4) As a monohydrate - effective hydroxyl group content 20 mol, based on fluorosulfuric acid

(5) Based on fluorosciulfuric acid

OJ

OO

Attempt no.

Reaction conditions (1)

Olefin
Isoparaffin
Isoparaffin / olefin (Vclun ratio in use) "ί ',; οτ.? Ί; νγ. J _> -. Of) Cleind throughput in V / V / h, based on catalyst catalyst - acid

Promoter

Volume Zzy Alkylate Yield / Volume Olefin (3)

Product composition in wt. % (2)

C -

j es sum; ο ρ
Trimethylpentanes

C ^ -Ca alkylate RON (3) Cg-Cg alkylate MOZ (3) Cr * alkylate MOZ (3) Table VI (continued)
4th

0.12

Mole % (4)
CgH ₅ SO ₃ H

1.73

0.11

0.12
98.89
95.27

0.88

100.50

98.50

98.40

Butene-1 ■
Isobutane

110.6 / 1 ■
-17.8

0.12

■ ^ T? ^ C ^ τ τ _ ^ ^ _- ___ _mmm

Μοϊ % (5)

1.72

0.00
0.14

99.33

95.92

0.53

100.70

98.40

98.30

0.13

20 mole percent (5) ethanol

1.73

0.43

0.38

98.44

95.44

0.75

100.80

98.40

98.30

ro cn cn co

(1)

(2}

Experiments in a glass reactor with continuous operation Determination by gas-liquid chromatography using a 90 m long capillary tube with 0.025 cm clear width and coating with DC-550 silicone oil and hydrogen flame ionization detector

Computer calculation from analysis of gas-liquid chromatography As xonohydrate - effective hydroxyl group content 20 'MoIJS, based on fluorosulfuric acid Based on fluorosulfuric acid

Attempt no.

Reaction Conditions (1) olefin
Isoparaffin
Isoparaffin / olefin (volume ratio in use) Temperature in ⁰ C throughput KV / in V / V / h, based on the catalyst Olefin throughput in V / V / h, based on the catalyst, catalyst - acid - promoter

U ₃ catalyst volume in cm

oo volume of Cc ⁺ alkylate yield / ro volume of olefin · (3);

"% ^ Product composition in wt. (2)

Trimethylpentanes

₆₈ alkylate RON. (3) C ₆ -C ₃ alkylate MOZ (3) C ₆ ⁺ alkylate MOZ (3)

Table VII I. 3 4th ) ro
ro I. 1 2 .cn
co 4 =
ui
I. CD CD 110.6 / 1
-17.8 176.9 / 1
-17.8 176.9 / 1
-17.8 110.6 / 1
-17.8 14.2 13.7 13.7 14.8 0.13
FSO3H
H ₂ O
100 0.08
FSO3H
20 mol % (H.
H ₂ O
100 0.08
FSO3H
.. 100 0.13
FSO3H
5 mole percent (4) 10
HpO
96 1.73 1.72 1.74 1.74 0.40
0.73 0, 'l6
0.32 1.37
1.90 0.91
1.63 97.60 '' 98.33 93.33 95.40 91.72 94.33 73.95 85.50 1.27 1.19 3.40 2.06. 99.50. 100.50 93.70 97.80 97.60 98.10 92.10 96.00 97.50 98.00 91.90 95.80

(1) Experiments in a glass reactor with continuous operation

(2.) Determination by gas-liquid chromatography using a 90 m long capillary tube with 0.025 cm clear width and coating with DC-55O silicone oil and hydrogen flame ionization detector

(3) Computer calculation from analysis of gas-liquid chromatography. ,

(4) Besoden for acid

Table VII (continued)

to try

Reaction conditions (1)

Olefin

Isoparaffin

Isoparaffin / olefin

(Volume ratio in use)

Temperature in ⁰ C

Flow rate KW in V / V / h,

based on catalyst

Amount of oil index in V / V / h,

based on catalyst

Catalyst - acid

promoter

Catalyst volume in cm
Volume C ^ ⁺ alkylate yield /
Volume olefin (3)

-ν. Product composition in wt% (2) _ "C. -

ω ^C 6 " ^C 7

* · * Total C ₀

Trimethylpentanes

C -: - Cg alkylate RON (3)
Cg-Cg alkylate MOZ (3)
Cr ⁺ alkylate MOZ (3)

88 4/1 VJl -17 ,8th 91 , 0 1, 02 FSO 3 ^H. 25 MoI H ₂ O 1

1.72

0.49

1.90

94.54

88.02

3.07

99.20

96.80

96.50 butene-1 ■
Isobutane

88.4 / 1
-17.8

91.0

1.02
FSO ₃ H

Mole% (4)
H ₂ O

.

1.67

1.00

2.33
84.66
79.34
12.03
98.40
96.20
95.10

11.1 / 1 -17.8

91.0

7.55 FSO ₃ H moles JS (4)

H ₂ O 15.

1.50

1.98

3.05 50.82 46.63 43.85 98.10 95.20 91.60

CD CD -Ο-CD

(1) Experiments in a glass reactor with continuous operation

(2) Determination by gas-liquid chromatography using a 90 m long capillary tube with 0.025 cm clear width and coating with DC-550 silicone oil and hydrogen flame icnisation detector

(3) Computer calculation from analysis of gas-liquid chromatography

(4) Based on acid

Example 6 ^;

A sample of a commercially available alkylate containing fluorosulfuric acid was divided into two parts A and B. Part A was carefully washed with dilute sodium hydroxide solution, the aqueous phase was separated off and examined for sulfate. The amount of sulfate found corresponded to 0.121% by weight of fluorosulfuric acid, based on the amount of hydrocarbons. Part B was stirred with concentrated sulfuric acid for 30 minutes. After the mixture had settled, the hydrocarbon phase was separated off and washed with excess dilute sodium hydroxide solution. The aqueous phase was separated off after washing and examined for sulfate. The 'found .- sulfate amount corresponded to 0.0116 wt. # Fluorschwefeisäure, based on the amount of hydrocarbon. These experiments clearly show that about 91.7 % of the fluorosulfuric acid can be removed from the hydrocarbon phase by sulfuric acid. ■

Example 7

1,600 g of h-hexane containing fluorosulfuric acid were used divided into two parts A and B, part A then with excess diluted caustic soda washed that. separated aqueous phase and examined for sulfate. The sulphate content corresponded to 0.632% w / Fluorosulfuric acid, based on the amount of hydrocarbons. Part B was vigorous through 100 ecm one at 500 to 550 rpm

30982A / 1 1 3 7

stirred concentrated (97 to 98 %) sulfuric acid at room temperature with a throughput of about 8.7 V / V / h, based on the acid, in a total amount of 1,000 ecm η-hexane. The η-hexane collected after this wash was then washed with excess dilute sodium hydroxide solution, and the resulting aqueous phase was separated off and examined for sulfate. The amount of sulphate found corresponded to 0.0037 wt.% Fluorine sulfuric acid, based on the amount of hydrocarbon. The treatment with sulfuric acid removed about 99.5% of the fluorosulfuric acid contained in the hydrocarbon mixture.

Example 8

A feed of olefins and fresh isobutane with a content of nC.Hß, C ^ Hg, i-Cj, H ₁₀ and nC ^ H .. »is carried out at a flow rate of 10,000 barrels / day with a reflux isobutane stream with a content of nC, Hg, 1-C ₁ -H ₁₀ and n-Cj.H _{10 are} brought together and mixed at a flow rate of 28,560 barrels / day. The mixed stream is then passed at a total flow rate of 38 x 560 barrels / day into an alkylation reactor in which it is mixed with a catalyst mixture of 80 mol # fluorosulfuric acid and 20 mol # water, based on the acid content. The olefin throughput, based on the acid, is kept constant at about 0.27 V / V / h. The self-cooling reactor is at a temperature of about

309824/1137

-6.65 ° C and a pressure of -1.07 kg / cm. The reaction partners and the catalyst mixture are intimately mixed in the reactor by means of a turbine mixer. The percentage by volume of acid in the emulsion present in the reactor is
held constant at about 50 %.

The amount of 37,055 barrels per day is around 70
Isobutane-containing alkylation product was transferred to a settling tank in which it was in .Mengen of about
37 · 055 barrels / day present catalyst system separates into a hydrocarbon and acid phase. The hydrocarbon phase contains about 600 ppm fluorosulfuric acid and about 200 ppm hydrogen fluoride. About 37 · 45 barrels / day of the acid phase are returned to the reactor and about 10 barrels / day with it
cleaned with a content of fluorosulfuric acid and solids
and transferred to the catalyst regeneration system. The hydrocarbon phase is fed through a mixing nozzle together with 100
Barrels / day or less of fresh concentrated sulfuric acid such that the total acid flow rate of fresh and recycled acid is approximately 1,860 barrels / day, of which 1,760 barrels / day are recycled. Intensive mixing of the hydrocarbon and sulfuric acid phase converts the major part of the fluorosulfuric acid and the hydrogen fluoride into the sulfuric acid phase.

3098 2-54 / 1137

The hydrocarbon and acid phases separate by settling. The sulfuric acid phase with a content of hydrogen fluoride and fluorosulfuric acid is then combined with the acid stream coming from the settling tank and form a regeneration tower headed for fluorosulfuric acid. After washing, the hydrocarbon phase only contains small amounts Acid produced by passing the hydrocarbon phase over solid potassium oxide and sodium oxide are eliminated. The deacidified hydrocarbon phase is then transferred to a separation column transferred to the separation of isobutane. The combined acid streams, namely the acid from the settling tank and the acid phase from the scrubber are transferred to the lower part of a fluorosulfuric acid regeneration plant transferred, where they vigorously with liquid η-butane at a temperature of about 80 to 120 ° C be mixed because the liquid η-butane partially evaporates.

In the regeneration tower, the η-butane is partially isomerized to isobutane, while the fluorosulfuric acid is mixed with water Formation of hydrogen fluoride and sulfuric acid reacts. Hydrogen fluoride, isobutane and remnants of the not yet decomposed Sulfuric acid form a gas phase that flows upward through a series of columns into the top of the tower, in which Gaseous or liquid sulfur dioxide is fed in, so that the sulfur trioxide is formed with hydrogen fluoride of fluorosulfuric acid.

309824/1 137

In the case of the reactions taking place in the regeneration tower, heat is constantly developed, which must accordingly be continuously removed from the reaction space a temperature ^vori: about 37.8 C and a pressure of about 4.2-bis' 4.9 kg / dm in a Kondensieranlage is introduced g'ekühlte the mixed stream is then transferred to a separation plant ^ \ from the Fluorschwefel-. · Acid with · a low content of water on the soil can be withdrawn and returned to the alkylation reactor as input material for '. the alkylation reactor can be used. The hydrocarbon phase remaining after the isobutane has been separated off contains the alkylation products and also only about: L to. .5 ppm fluorosulfuric acid. - - ',. · ■ -, · -. · .., .. ·

30 9 8 2Ά7 1 13 7 .- ·

Claims (1)

Claims 1.! Process for converting hydrocarbons by reaction using saturated hydrocarbons with olefins under conversion conditions in a conversion zone a catalyst mixture with a larger content of a strong acid, characterized in that the Catalyst mixture a smaller amount of a promoter from (a) compounds with a content of hydroxyl groups, or hydroxyl group precursors, (b) saturated aliphatic or cycloaliphatic thioethers, (c) saturated aliphatic or cycloaliphatic thiol compounds with 1 to 7 carbon atoms per molecule, (d) difluorophosphoric acid or mixtures of (a), (b) and (c). 2. The method according to claim 1, characterized in that the compounds of group (a) V / water, saturated aliphaticc or cycloaliphatic alcohols or ethers, aliphatic, cycloaliphatic or aromatic carboxylic acids or their Derivatives or mixtures of these compounds are used will. 3. The method according to claim 1 or 2, characterized in that the catalyst mixture is about ^! j bit; '15 Hol% dec promoters', based on the strong o'iure. 3 0 9 fl; / / 1 1 3; k * Process according to claim % to 3, characterized in that the strong acid used is halogensulfuric acid triialogeK-raefehansulfonic acids or mixtures thereof. 3 ". Method according to. Claims 1 to k> characterized in that water is used as the promoter 6. The method according to claims 1 to 5, characterized in that: that water in Mangen before 1 bisj 3Ώ KöUSI; ,, be-ziogem; on/ strong acid is used. T ..,. Method according to: Claim 1: bist 6 _}> thereby · that5 as. strong acid fluorosulfuric acid used; ride;% 8> - Verfitert- nach, Aiisprucil ·; 1: to 4;,. dadurcih; g ^ ffeerirt ^ etch that. ail®; BrornQtior ethanol; etege U proceed according to- ÄTisprüi % bis ^, by the fact that "alas, Erornqtor Dd ^ t Qv method according to claim Λ to; %. through this, that the implementation at 'temperatures vp.n about. ^ Ζ9 < to: + ^ pr (i _y at; Jerks from about 1 to 20 atm, pulpy; an amount of about 0.05 to 1,000 volumes; Otefi of the total catalyst present and; at a. _: Vatlu-r 9824 / T Λ 31 ratio of saturated hydrocarbons: olefins in the input material of about 3 *! to 200: 1 carried out, one Reaction mixture of a hydrocarbon and a Catalyst phase formed and an alkylate with a high octane number is won. 11. The method according to claim 1 to 10, characterized in that a C ₂ - to C _12. -01efin and a saturated C ' ₂ ~ to C _iQ hydrocarbon »erstoff under conversion conditions with a catalyst consisting of a strong acid and about 5 to 45 minor, based on the acid, of a proiiotor is converted and that the promoter is water, a saturated aliphatic or cycloaliphatic C ₁ - to C ^ alcohol »a saturated aliphatic or cycloaliphatic ^ C ^ - to C ₇ thiol, a saturated aliphatic or cycloaliphatic C ₂ - to CjQ ether or thioether, an aliphatic, ■, ■ cycloaliphatic or aromatic C ₁ - to C ^ sulfonic or carboxylic acid or mixtures thereof. 12. The method according to claim 11, characterized in »that as Benzene sulfonic acid promoter is used. 13. The method according to claim 1 to 12, characterized in that that the catalyst mixture within the alkylation zone j is formed. \ 9824/1137 I ¹ W Process according to Claim 10, characterized in that the saturated hydrocarbons contain isoparaffins and that the isoparaffins content of the hydrocarbon phase is approximately 50 to 90% by volume, based on the total amount of hydrocarbons. 15. The method according to claim 1 to 1'4, characterized in that that the volumenpi'ozentige content of the catalyst mixture in the reaction mixture about Ί0 to 80 vol. #, based on the total mixture. 16. The method according to claim 1 to 1'5> characterized in that the olefin concentration in the feed material is saturated Hydrocarbons about 0.5 to 25 vol. #, Based on the total stake. 17. The method according to claim 1 to ΐβ, characterized in that that the saturated hydrocarbons are isoparaffins and that the volume ratio of isoparaffins: olefins in the conversion zone is about 20: 1 to 2,000: 1. 18. The method according to claim 1 to 17, characterized in that that saturated in a Kohleriwasserstoffalkyliorungsverfahren 'Hydrocarbons' and olefins with oleic acid as Catalyst · with the formation of a hydrocarbon phase 30982 4M 1 a content of alkylated reaction products and at least a part of the fluorosulfuric acid and formation of an acid phase is reacted that (a) the hydrocarbon phase then with sulfuric acid to remove at least part of the fluorosulfuric acid contained in the hydrocarbon phase is washed, a sulfuric acid phase containing fluorosulfuric acid and a hydrocarbon phase with a content of alkylation products, (b) that the acid phase from (a) is reacted with water at least some of the fluorosulfuric acid contained therein converts to hydrogen fluoride and sulfuric acid decomposes, (c) that the acid phase from (b) with a paraffin to form a hydrocarbon phase with a content is treated with hydrogen fluoride, (d) that the hydrocarbon phase from (c) with sulfur trioxide for the regeneration of Fluorosulfuric acid is treated and that (e) at least part of the regenerated fluorosulfuric acid as alkylation catalyst is used. 19. The method according to claim 18, characterized in that fl « Paraffin is used in step (c) η-butane. 20. The method according to claim 19, characterized in that the η-butane at least partially through contact with hydrogen fluoride and Fluorschwefels.'ture is isomerized to isobutane 3 0 9 8 2 /. / 1 1 3 Ί - 51 - and that this isobutane as part of the saturated hydrocarbon feed is used in the alkylation. 21. The method of claim 18 to 20, characterized in that the alkylation is effected at temperatures of about -29 is performed 4 ⁰ C to +. 22. The method according to claim 21, characterized in that the Process step (c) at temperatures of about 49 to 150 ° C is carried out. si: kö 309824/1137