Патент USA US2408330код для вставки
2,408,329 Patented Sept. 24, 1946 UNITED ‘STATES PATENT oFFicE ALKYATION PROCESS Jacob R. Meadow, Lexington, Ky., assignor to Socony-Va'cuum Oil Company, Incorporated, a corporation of New York ,‘No Drawing. Original application October 9, 1943, Serial No.__505,661. Divided and this ap plication May 23, 1945, Serial No. 595,492 ' 5 Claims. (o1. zoo-683.45 2 This invention relates to the alkylation of par a?inic hydrocarbons with ole?nic hydrocarbons, and is more particularly concerned with the cat alytic alkylation of isopara?inic hydrocarbons with ole?nic hydrocarbons in the presence of hy-v dro?uoric acid. ' trifluoride and the like, of sulfuric acid, of phos phoric acid, of metal phosphates, of activated clays,’ and the like. In these processes, the alkyla tion catalysts are used in amounts varying be tween about 10% and 200% by weight, on the charge, depending upon the alkylation catalyst ' It is well known in the art to eifect the union and conditions used. of parai?nic hydrocarbons and ole?nic hydrocar bons by processes broadly called alkylation proc esses. In alkylation processes, a charge including that these and similar alkylation catalysts have a mixture of a parai?nic hydrocarbon called the However, it would seem one or more de?nite disadvantages, among which the most important are promotion of the afore mentioned secondary reactions and loss oi?v alkyla tion catalytic activity on the part of the catalyst, para?inic reactant, and an ole?nic hydrocarbon relatively rapidly. Notably, the metal halides called the ole?nic reactant, is introduced into a form additional compounds with olefinic reac reaction zone under suitable reaction ‘conditions of temperature and pressure, referred to as alkyl 15 tants, that ultimately degenerate into tarry masses that represent loss of catalytic activity of ating conditions, to yield a product called the hy-. the alkylation catalysts and loss of potential ole drocarbon alkylate, which comprises constituents ?nic reactant. Similarly, sulfuric acid causes the of a saturated character. Since the alkylating formation of various organic compounds that conditions cause also polymerization of the ole?n ic reactant, it is necessary to maintain a relatively 20 ultimately reduce the catalytic activity of the acid necessitating periodic removal of the sulfuric low concentration of the ole?nic reactant in the acid contaminated with thesecompounds, and charge. Generally speaking, the more severe the replacement with fresh acid. It must be noted alkylating conditions, i. e. the higher the tem further, that sulfuricacid'is a powerful oxidizing peratures and pressures, the higher the Yield of hydrocarbon alkylate.v The only limit'to the pres 25 agent and its use, at temperatures above about‘ ‘ 125° E, entails extensive undesirable secondary sure used appears to be the feasibility of main reactions that consume the acid and the valuable taining high pressures.’ "On the other hand, the hydrocarbon reactants. I ‘_ 'i V temperature used is limited by the degradation of Concentrated hydro?uoric acid, when used as the hyqdrocarbo-n reactants in the charge to low molecular weight hydrocarbons, and the occur 30 an alkylation catalyst, apparently does not have these disadvantages. It is a non-oxidizing‘and rence of secondary reactions, including polymeri non-reducing substance and hence, it may be zation of the ole?nic reactant, under high tem used at elevated temperatures without any of perature conditions, that substantially reduce the the undesirable results referred to hereinbefore. purity of the product obtained, Alkylation may be conducted at vhigh tempera tures and pressures, on the order of over 900° F. and over 4000. pounds per square inch, respec tively; ormay be carried out at lower tempera 35 Several processes are known in the art for cat alytically alkyiating para?inic hydrocarbons with ole?nic hydrocarbons in the presence of hydro ?uoric acid. ‘Generally speaking, the process is carried out with the hydrocarbon reactants sub tures and pressures, in the presence of substances _ that facilitate the union‘ of para?inic hydrocar 40 stantially in liquid phase and in the presence of . suf?cient amounts of hydrofluoric acid to effect ‘bons and ole?nic ‘hydrocarbons, hence called al substantial saturation of the‘hydrocarbon liquid kylation catalysts, thereby assuring a high yield with hydrogen ?uoride. I of desired hydrocarbon alkylate by avoiding ex In some instances, the alkylation catalyst con tensive degradation of the reactants, the occur rence of secondary reactions, and appreciable 45 sists of two 'or ‘more of‘ the alkylation catalysts referred to. Thus, it is known to effect the alkyla- _ polymerization of the ole?nic reactants. The two tion of paraf?nic hydrocarbons with ole?nic hy methods are known as thermal alkylation "and drocarbons in the presence of alkylation catalysts ' as Several catalyticmethods alkylation, arerespectively. known for the catalytic consisting of mixtures of sulfuric acid/and hydro alkylation of para?inic hydrocarbons with ole?nic 50 ?uoric acid, or of mixtures of sulfuric acid and hydrochloric or hydrobromic acids, or of mix hydrocarbons. Thus, it is known to carry out the tures of a metal halide‘ and the corresponding I alkylation of parai?nic hydrocarbons with ole-' hydrogen halide. ‘ . v ' ?nic hydrocarbons in the presence of alkylation It is also known that certain substances called catalysts consisting essentially of metal and non promoters, promote .the catalytic action of al metal halides, such as aluminum chloride, boron 3 4 kylation catalysts, particularly those consisting 60% of the total charge, on a liquid volume basis‘. Aqueous solutions of hydro?uoric acid in Which essentially of metal halides. Accordingly, sev eral processes have been proposed wherein small amounts of these promoters, on the order of about 0.5 to 3% by weight, on the charge, are added to the alkylation catalysts to promote their alkyla tion catalytic activity. hydrogen ?uoride is present in concentrations greater than 80% may be used, but the use of 95% to 100% hydro?uoric acid is to be preferred, and substantially anhydrous hydro?uoric acid or hydrogen ?uoride is very effective aS‘an alkyla ' tion catalyst in the process of my invention. I have now found that the alkylation catalytic The reaction temperature may be varied over activity of anhydrous hydrogen ?uoride may be appreciably enhanced through the addition of or ,10 a wide range depending upon the paraf?nic re actant used in the reaction. Generally speaking ganic or inorganic halogen compounds, excluding the temperature of reaction varies between about ?uorides, or of elemental halogens, excluding, 0° F. and about 400° F., lower temperatures being ?uorine. used when the more reactive para?imc or ole It is an object of the present invention to pro vide an efficient process for catalytically alkylat 15 ?nic reactants are employed and higher tem ing para?’lnic hydrocarbons with ole?nic hydro carbons. Another object of the‘ present inven peratures becoming necessary when the less re active paraf?nic or ole?nic reactants are em tion is to provide an efficient process for cata ployed. For instance, when the paraf?nic react ant is isobutane or isopentane, and when the ole?nic reactant is propylene or butylene, alkyla ole?nio hydrocarbons in the presence of hydro tion may be readily effected at temperatures ?uoric acid. A more speci?c object is to provide varying between about 35° F. and about 100° F. a process for catalytically alkylating para?inic Ordinarily, alkylation in the presence of hydro hydrocarbons with ole?nic hydrocarbons to pro ?uoric acid as ‘the alklation catalyst, is carried duce high yields of high-octane ‘blendingr agents for the manufacture of improved motor fuels. A 25 out under super atmospheric pressure, and pres sures varying between about 20 pounds per square very important object of the present invention is inch and 500 pounds per square inch have been to afford a process capable of carrying out the found ample in most instances. As a general . above objects by carrying out the reaction in the rule, the most suitable pressure is more or less presence of halogens, other than ?uorine, or of halogen compounds, other than ?uorides. Other .30 dependent upon the particular temperature in volved and when high temperatures are em objects and advantages of the present invention ployed, pressures as high as 2000 pounds per will become apparent to those skilled in the art square inch may ‘be employed, if desired. from the following description. In carrying out alkylation of para?inic hydro Broadly stated, the present invention provides a ‘process for alkylating para?im'c hydrocarbons .35 bons with ole?nic hydrocarbons, it is well known, as stated hereinbefore, to maintain a relatively with ole?m'c hydrocarbons, which comprises con low concentration of the ole?nic reactant in the tacting a paraf?nic hydrocarbon and an ole?nic reaction zone, in order to preclude extensive hydrocarbon in a reaction zone under alkylating polymerization of the ole?nic hydrocarbon. Ac conditions, with an alkylation catalyst consist ing essentially of anhydrous hydrogen ?uoride, in 40 cordingly, it is advisable to maintain the ole?nic hydrocarbon concentration in the reaction zone the presence of organic or inorganic halogen below about 25% by volume, and preferably, be compounds, excluding ?uorides, or of elemental lytically alkylating para?inic hydrocarbons with halogens, excluding ?uorine. While it is well known that hydro?uoric acid .tween about 7% and about 12% by volume. In continuous operation, this is effected by introduc is a good alkylation catalyst, see U. S. Patent No. ing the ole?nic reactant over a period of time corresponding to the reaction period. The “reaction period duringwhi-ch the ole?nic 2,267,730, my invention indicates very de?nitely that halogen compounds, other than ?uorides and elemental halogens, other than ?uorine, improve the quality and quantity of the hydrocarbon a1 reactant is introduced into the reaction zone to react with the paraf?nic reactant to produce kylate, when these compounds or elemental halo- , , the hydrocarbon alkylate, depends upon the gens are added to the hydrogen ?uoride, before the alkylation operation is carried out. temperature, and to a certain extent, upon the pressure. Ordinarily, a reaction period varying between 15 minutes and 2 hours is satisfactory. When a mixture of a paraf?nic hydrocarbon, At higher temperatures, the time of reaction may bon such as isobutane, anhydrous or concentrated 55 be as low as 5 minutes and even lower, while at lower temperatures, the time of reaction may be hydro?uoric acid, and an olen?nic hydrocarbon ‘as high as 5'hours. such as isobutylene, is maintained at a reduc It must be understood, that the reaction vari tion temperature, a union takes place between the ables are‘ more or less interdependent, hence para?inic hydrocarbon and the ole?nic hydro ‘when one is arbitrarily ?xed, the limits within carbon to produce a higher boiling para?inic hy which the others may bejvaried, are somewhat drocarbon which generally represents structural particularly a low-boiling isopara?‘inic hydrocar restricted. In any particular instance, the most desirable conditions can be'readily ascertained ly, the addition of the ‘original hydrocarbon re actants. Valuable high-octane blending agents by one skilled in the art, the preferred ranges of for the manufacturing of improved motor fuels may be thus produced. For example, 765 these variables having been indicated hereinbe 0H3 , l H l CH3 2: ' HF CH3 H CH3 l CH3—(IJ—H + (‘3: —CH3 -—> CHa—C—-— — -—CH3 CH3 Isobutane H Isobutylene CH3 H Isooctane In carrying out the alkylation of para?inic hy drocarbons with olefinic hydrocarbons in the presence of hydro?uoric acid as alkylation cata lyst, the hydro?uoric acid should be used in 70 fore. , The paraf?nic and. ole?nic hydrocarbons to be used in my process may be derived from any suit ,able source, as is well known in the art, and may be usedeither in the pure state or, in admixture with other constituents not undesirable. The ,paraf?nic and ole?nic hydrocarbons usually em ployed in the preferred operation of manufac turing motor fuels will be the normally gaseous amounts of at least about 10% and up to about 175 para?inic hydrocarbons, except methane and 72,408,329 5 6 ethane, and the normally gaseous ole?nlc hy 5% and ab.out'50% with respect to the amount of hydrogen _ ?uoride employed. Larger' amounts ~ drocarbons, propylene, butylene‘ and pentene, as appear to be unnecessary; however, it must be is well understood in the art. A conventional and noted thatthey may be employed if desired, al preferred source of para?inic and ole?nic hydro carbons is the ?xed gases obtained around petro- 5 though no additional advantages result there from. The amounts of hydrogen vfluoride addi leum re?neries. .These ?xed gases may furnish tives used may be smaller, on the order of 1% to substantially all the desired para?inic and ole about 5%, when larger amounts of hydrogen ?uo~ ?nic hydrocarbons, or it may be necessary or ride catalyst are employed. _ ' desirable to obtain additional supplies, as is well understood. ; Additional ole?nic hydrocarbons, if 10 Numerous experimental data could be-adduced to'indicate the results obtainable by employing required, may be formed from a portion of the para?inic hydrocarbons. the hydrogen fluoride additives of the present in vention in the catalytic alkylation of para?inic hydrocarbons with cle?nic hydrocarbons in the On the other hand, ' additional amounts of para?inic hydrocarbons may be admixed in order to increase the concen ~ tration of para?inic hydrocarbons to 2. _desired 15 presence of hydrogen fluoride, but the following magnitude. - examples are su?iciently characteristic: . Runl B11112 Run3 275. 87. Isobutane, weight in grams ____________________ ._ Isobutylene, weight in grams ____________ __ __ _. Hydrogen ?uoride, weight in grams _____ ._ Hydrogen ?uoride additive, weight in gram ‘Rum 35. _ T_butyl-bromide 18. ___ 25-30. Temperature, ° 0 Pressure in pounds per square inch ____________ __ Hydrocarbon alkylate, weight in grams ________ __ . Total octanes 90° C.—l25° 0., weight in grams“. Isooctane 98° O.—101° 0., weight in grams _____ ._ 39 The‘ octane fraction of the hydrocarbon alkyl ate produced by my process contains 2,2,4-tri; methylpentane in predominant amounts, and the The organic and inorganic halides, other than ?uorides, and the elemental halogens, other than ?uorine, that are used in accordance with the process of my invention, may be solids, liquids or gases under normal conditions. It is suspected that the improved results obtained with those substances, is probably due more to an ultimate activation of the ole?nic reactant during the alkylation operation, than to promoter action on the hydrogen ?uoride catalyst, although the lat ter should not be excluded'altogether.‘ What ever the function of these substances is, the qual ity and quantity of the hydrocarbon alkylate are substantially improved through their use. In view of the relative uncertainty ofthe' n'ii‘nner in which these substances'function during the al results of infra-red analysis indicate the presence also of 2,3,3-trimethylpentane. This octane is not present in the hydrocarbon alkylates ob _ tained when the alkylation is conducted in the 3" absence of vmy hydrogen ?uoride additives and under the conditions outlined hereinbefere. In fra-red analyses also indicate that the hydrocar bon alkylates obtained when alkylation is carried out in the absence of the hydrogen ?uoride addi 40 tives of my invention and under conditions out lined in the preceding table, contain appreciable concentrations of unsaturates whichare not pres ent in the hydrocarbon alkylates obtained in the process of my invention. kylation operation, these substances may be re The present application is a division of copend ferred to more correctly, as hydrogen ?uoride 45 ing application Serial Number 505,661, ?led Oc additives, rather than as promoters or as activa tors. tober 9, 1943. . I The present invention may be embodied in The hydrogen ?uoride additives of my inven other speci?c forms without departing from the tion include various metallic chlorides, bromides and iodides, for example, anhydrous calcium '50 spirit or essential attributes thereof, and it is therefore desired that the present embodiments chloride; organic halogen compounds, excepting be considered in all respects as illustrative and ?uorides, such as alkyl chlorides, bromides and not restrictive, reference being had to the ap iodides, especially secondary and tertiary halides; pended claims rather than to the foregoing de aralkyl halogen compounds, excepting ?uorides; aliphatic and aromaticiacid chlorides, bromides 55 scription to indicate the. scope of the invention. and iodides; non-metallic halides, excepting ?u- ' orides, such as phosphorus and sulfur chlorides, bromides and iodides; hydrogen halides, except ing of course hydro?uoric acid; and ?nally, the. halogens themselves, excepting ?uorine. I claim: _ 1. In a process for alkylating a paraf?nic hy drocarbon having at least three carbon atoms with an ole?nic hydrocarbon having at least three 60 carbon atoms, which includes contacting said I especially prefer to use, as hydrogen fluoride paraf?nic hydrocarbon with‘ said ole?nic hydro additives, alkyl chlorides and bromides, particu larly tertiary alkyl chlorides and bromides and secondary alkyl chlorides and bromides, hydro carbon in a reaction zone under alkylating con ditions, in the presence of a hydrogen ?uoride alkylation catalyst, and maintaining said paraf gen halides other than hydro?uoric acid,‘ and hal- 65 ?nic hydrocarbon in excess over said ole?nic hy ogens other than ?uorine. Speci?c and preferred hydrogen ?uoride additives. that may be men tioned by way of non-limiting examples are: drocarbon in said reaction zone so that alkyla tion is the principal reaction; the improvement which comprises contacting said para?inic hy drocarbon and said ole?nic hydrocarbon with a tertiary butyl chloride, tertiary butyl bromide, tertiary amyl chloride, tertiary amyl bromide, iso- 70 hydrogen ?uoride alkylation catalyst in said re action zone, in the presence of a material selected propyl chloride, isopropyl bromide, propylene ‘from the group consisting of chlorine, bromine, chloride, propylene bromide, hydrogen chloride, and iodine. I hydrogen bromide, chlorine and bromine. The amounts of hydrogen ?uoride additives or dinarily used in my process, vary between about 75 2; The process of manufacturing high-octane gasoline, which'comprises contacting a normally "£408,329 8 gaseous isopara?inic hydrocarbon and a nor gaseous ole?nic hydrocarbon in said reaction mally gaseous ole?nic hydrocarbon having at zone so that alkylation is the principal reaction. 4. The process of manufacturing high-octane least ‘three carbon atoms in a reaction zone un der alkylating conditions, with a hydrogen ?uo ride alkylation catalyst, in the presence of ch10 rine, and maintaining said normally gaseous iso para?inic hydrocarbon in excess over said nor mally gaseous ole?nic hydrocarbon in said reac-_ tion zone so that alkylation is the principal reaction. 3. The process of manufacturing high-octane gasoline, which comprises contacting a normally gaseous isoparamnic hydrocarbon and a normally gaseous ole?nic hydrocarbon having at least three carbon atoms in a reaction zone under alkylating conditions, with a hydrogen ?uoride alkylation catalyst, in the presence of bromine, and maintaining said normally gaseous isoparaf ?nic hydrocarbon in excess over said normally gasoline, which comprises contacting isobutane and isobutylene, in a reaction zone under alkyl ating conditions, with a hydrogen ?uoride alkyla tioncatalyst, in the presence of chlorine, and maintaining said isobutane in excess over said isobutylene in said reaction zone, so that alkyla tion is the principal reaction. 5. The process of manufacturing high-octane gasoline, which comprises contacting isobutane and isobutylene, in a reaction zone under alkyl ating conditions, with a hydrogen ?uoride alkyl ation catalyst, in'the presence of bromine, and maintaining said isobutane in excess over said isobutylene in said reaction zone, so that alkyla tion is the principal reaction. JACOB R. MEADOW.