Патент USA US2405997код для вставки
2,405,997 Patented Aug. 20, 1946 UNITED STATES PATENT OFFICE 2,405,997 ' AVERAGING WITH PENTANE Robert E. Burk, Novelty, Ohio, assignor to The Standard Oil Company, Cleveland, Ghio, a cor poration of Ohio No Drawing. Application August 9, 1944, - Serial No. 548,807 10 Claims. (Cl. 260—-683.4) 1 This invention relates to the treatment of a heavier molecular weight hydrocarbon fraction and a lighter hydrocarbon fraction comprising normal pentane with a catalyst comprising pri marily hydrogen ?uoride promoted by a minor proportion of boron tri?uoride to produce hy ‘drocarbons of intermediate molecular weight, a process termed “averaging.” A preferred and important embodiment of the 2 ,. carbons as well as converted to isobutane which may be fractionated and used in other processes such as alkylation. Still another object of the invention is to carry out the averaging reaction in the presence of an amount of the lighter hydrocarbon frac tion in excess of that entering into the reaction, and in which the excess of the lighter hydrocar bon fraction may be recycled to the averaging re- invention comprises the use of a normal pentane 10 action in a continuous or semi-continuous process. containing fraction as the lighter hydrocarbon, A further object of the invention is to carry and a liquid hydrocarbon boiling above the gaso out the above process, utilizing a pentane frac-. line range as the heavier hydrocarbons, to pro tion containing normal pentane in excess of that duce gasoline of desirable properties. It is one of the objects of the invention to 15 entering into the reaction, fractionating the ex cess to remove all or a portion of isobutane or utilize normal pentane as one of the raw mate isopentane which is formed during the averaging rials in making more valuable hydrocarbon reaction if desired and recycling the balance of products. the lighter fraction to the reaction zone. , A further object of the invention is to utilize Still a further object of the invention is to heavier hydrocarbon fractions, such as kerosene 20 carry out the above reactions in the liquid .phase or naphthas, in the formation of hydrocarbons in the presence of a liquid catalyst comprising of lower molecular weight, such as gasoline, primarily hydrogen fluoride and promoted by a without the production of large amounts of un minor proportion of boron tri?uoride, and if de saturated hydrocarbons or ?xed gases, and also without the destructive in?uences and losses in 25 sired, also promoted by the presence of an un saturated hydrocarbon. . cident to conventional methods of cracking. Another object is the provision of a process in An additional object of the invention is to which ?uorides containing the impurities pres utilize both a pentane containing hydrocarbon ent in commercial grades may be used. fraction and a heavier hydrocarbon fraction An additional object of the invention is to simultaneously in a single reaction to produce 30 carry out the pentane averaging process under valuable products intermediate said fractions re conditions of temperature and pressure not lower sulting from a net consumption of both of them nor higher than can be obtained conveniently at the same time. An additional object of the invention is to provide a process in which a mixture of butanes 35 and pentanes may be used as the lighter fraction in ordinary plant operations. . The invention has as a further object the pro vision of a process of the character described in which the activity of ‘the catalyst, in addition to being controlled by variations in temperature, .sumption of normal pentane to form more valu pressure and other factors ordinarily employed able hydrocarbons. , Still a further object of the invention is the 40 in catalytic operations, also can be controlled readily by means of the partial pressure of the provision of a process in which a butane and boron tri?uoride constituent of the catalyst. pentane containing lighter fraction may be used in an averaging process resulting in a net con Still a further object is the provision of a as the lighter hydrocarbon in an averaging re process of averaging as described in which the action and the proportions adjusted so as to re sult in .a net consumption of the butanes along 45 catalyst can be readily recovered and reused. with the pentanes. A further object is to provide a process in’ which the normal pentane in the lighter fraction is used in the manufacture of higher hydro— Other objects of the invention will appear from the following description. In carrying out the process of the invention, a lighter hydrocarbon fraction comprising normal 2,405,997 ' 3 4 pentane is mixed with the heavier boiling frac tion, such as a normally liquid hydrocarbon. tain normal hydrocarbons, isomers, napthanes carbon and lighter than the heavier hydrocarbon starting materials. At the conclusion of the phase and may be fractionated, and the catalyst is separated as another phase. The catalyst phase stock boiling from 70° to above 400° F., or crude oil or reduced crude as such, may be used in the averaging reaction. The presence of aromatics in the feed stocks, particularly in the heavier fraction where they may be reused as such or may be regenerated and reused. are more apt to be present, is undesirable be cause these aromatics tend to form a complex or small amounts of hydrocarbons other than These are caused to react preferably in a liquid normal or unsaturated hydrocarbons. The lat state, in the presence of a liquid catalyst and un ter may be bene?cial as mentioned heretofore. der conditions of temperature and pressure as 5 In some instances both the light and the heav will be pointed out more particularly hereinafter, ier fractions to be reacted in the process may be to produce products heavier than the light hydro in the form of a single fraction. For example, a treatment the hydrocarbons are separated as one The light hydrocarbon may be normal pentane or a mixture of normal and isopentane. It may also be a mixture of normal (or normal and iso-) pentane with normal butane or a mixture of nor mal and isobutane. Normal pentane is readily reacted in accordance with the invention and with the catalyst and decrease its activity. For this reason it is desirable that the feed stock should contain a minimum of aromatics. While it is not essential that the stock be free from aromatics if other conditions are adjusted suit ably, it will be generally preferable at least to since it is not of great value in itself as a motor reduce the aromatic content of the stock some fuel, the invention assumes particular importance what by a dearomatization process if the stock with reference to its use as the lighter reacting is high in aromatics. This may be done by any component. means conventional in the art, such as solvent The lighter hydrocarbon fraction may be ob 25 extraction, or the fluorides may be used for de tained from any re?nery operation; it is imma terial if it contains small amountsof other con stituents, and for this reason it need not be highly puri?ed. It is also immaterial, and in fact it is aromatizing in accordance with the process de scribed in my Patent No. 2,343,744, granted March 7, 1944. p > The ratio of the light to the heavier fraction an advantage as pointed out later, if it contains a 30 may vary over a relatively wide range. Gener ally it is preferred to have at least i mol of the small amount of unsaturated hydrocarbons. For this reason it is not necessary to fractionate the unsaturated hydrocarbons and other ingredients from the lighter fraction. Generally the normal pentane is found mixed with‘ some isopentane and no harm is done if the latter is present. Un lighter fraction per mol of the heavier fraction. Two to 6 mols of the light fraction per mol of the heavier fraction is the preferred range. There is no object in having present more of the lighter fraction than will re?ect an improvement, since der some conditions the reaction may be facil there is no point in recycling a larger excess of itated by the presence of isopentane. However, this fraction than can accomplish a corresponding since isopentane is more useful in itself as a improvement in the reaction. motor fuel, the ability to use normal pentane 40 The catalyst used in the process comprises hy as a raw- material in the averaging process is of drogen ?uoride promoted with a minor propor great importance. If the lighter fraction contains tion of boron tri?uoride therein, and in some butanes, as it may especially in a continuous instances with an ole?n. It is used preferably process, the presence of the latter does not in in the liquid phase. ' terfere with the net consumption of the normal 45 Hydrogen ?uoride boils at about 67° F. and is pentane. therefore a liquid at temperatures just under In ‘a continuous operation in which an excess room temperature and may be kept liquid at of the lighter fraction is used, a part of the nor higher temperatures by moderate pressures. The _mal pentane may be isomerized to isopentane and temperatures and pressures used in the process a part converted to isobutane. When the ex 50 of the invention are conveniently those that cess of the lighter fraction is recycled the amounts maintain the hydrogen ?uoride liquid. Boron of the isopentane and/orisobutane in the re tri?uoride boils at ~l50° F. and is a gas at the cycled fraction may be varied and this becomes temperatures and pressures conveniently em a controllable variable. ployed in hydrocarbon treating processes. How The heavier fraction, in general, should be a 55 ever,,boron tri?uoride dissolves in liquid hydro heptane or heavier hydrocarbon. While the heav gen fluoride to agiven extent and the amount ier fraction may be a pure hydrocarbon, gen which dissolves at any given temperature depends erally it will be a mixture, such as naphthas on the partial pressure of boron tri?uoride. At (250-400" F), kerosenes (350-550° F), light gas higher partial pressures, a larger amount of boron oils MOO-625° F), heavy gas oils (SOD-710° F), tri?uoride is dissolved. mixtures of light and heavy gas oils (LlOO-‘l'lOo The boron tri?uoride in the hydrogen ?uoride F), deasphaltized and dearomatized residues in the liquid phase possibly may react at least (above 700° F), the portion of crude boiling to to some extent, but an understanding of the 550° F., the portion of crude boiling to 700° F., chemistry involved is not necessary to practice the portion of crude oil boiling between 250-710” " my invention, and I do not intend to be bound F., mixtures of naphthas with kerosenes, and by any theory. At any event the amount of the fractions boiling higher than 825° F. In these boron tri?uoride in the hydrogen ?uoride, which stocks the presence of hydrocarbons lower than controls the activity of the catalyst, is a function heptanes is no disadvantage. Other stocks that of the partial pressure of the boron tri?uoride. may be used are Fischer-Tropsch (Hz-l-CO‘Y 70 The amount of boron tri?uoride dissolved in stock, Houdry cycle stock and thermal cycle the hydrogen ?uoride, at any given temperature, stock. Some of the above fractions may require may be expressed conveniently in terms of the partial pressure of boron tri?uoride. This may vary, in accordance with the invention, from .5 aromatic extraction because the stock should be relatively low in aromatics as explained herein after. The heavier fractions described may con to 1000 Pounds per square inch; generally about 2,405,997 5 50 to ‘300 pounds .per square inch will be ‘used. However, the partial pressure should under no circumstances be such that the amount of boron tri?uoride exceeds 50 mol per cent of the'?uo This may enable a reduction in the amount of catalyst per unit of the product formed, and may also have a bene?cial effectin causing some of the hydrocarbons to shift from the catalyst phase of the ‘reaction to the hydrocarbon phase. The amount of the catalyst employed must be rides' With the partial pressures usually used the amount does not exceed 25 mol per cent. The words “dissolved” and “solution” are used considered with reference to both of the ?uoride as generic to both a physical admixture and a ingredients comprising :it. The amount of the hydrogen ?uoride may be 5 to 1300 volume per cent One of the advantages of the process of the v10 based on the hydrocarbons to be treated when in liquid form, preferably-the amount should be invention is the ability to control the reaction about 15 to 1.00 volume per cent. Amounts as by adjusting the activity of the catalyst through low as 1 volume per cent may be used in a multi control of its composition. This may be accom reaction product. plished by varying the partial pressure of the boron tri?uoride, because a change in this partial pressure results in a change in the amount of boron tri?uoride dissolved. If the partial pres sure of the boron trifluoride is increased, by ad mitting boron tri?uoricle to the reaction zone from a high pressure source of supply, the activ ity of the catalyst is greater under conditions otherwise the same. If this partial pressure is decreased, vby bleeding boron tri?uoride, the ac. tivity of the catalyst is reduced. If an ole?n is added, or is present in the re action zone in an amount less than that which acts as a poison, the ole?n appears to act as stage treatment in which the total ‘would be at least 5%. The use ,of larger amounts increases the rate of conversion and the yield in- a‘ given time under conditions otherwise the same. The amount used may depend. to a large extent upon the economics involved and the maximum con version desired per pass .of the material. The total amount necessary ‘may also be less if it is supplied in increments'during the reaction. If desired the used catalyst may be removed before the next increment is supplied. ~No more-is used than is necessary to ve?ect the desired ‘reaction in the desired time since to use more would only add to the amount to be recovered or regener a promoter. The available evidence indicates The amount of the ‘boron ?uoride used, as ex that the ole?n acts as ;a “hydrogen acceptor” and that the hydrogen ?uoride-boron tri?uoride so 30 pressed in termso-f partial pressure, has been, indicated ‘heretofore in describing the composi lution or the reaction product may form a new tion of the catalyst. compound or chemical complex with the ole?n. ated. Since ole?ns may be formed in the process, espe cially when heavier stocks are used, the addition ' I When an ole?n is added ‘separately as an in gredient it may vary from extremely small of an ole?n as a separate addcd'ingredient to the 35 amounts to 100 or more mol per cent based on the stocks may not re?ect a separate improvement. The catalyst to be used in practicing the in vention, therefore, may be viewed as hydrogen ?uoride promoted by a minor proportion of amount of the boron tri?uoride dissolved in the hydrogen fluoride. ‘Expressed in practical terms, the amount of the ole?n may be % to 125% based on the hydrocarbons being treated. The total pressure .should be .suf?cient to keep boron tri?uoride; or it may be viewed as hy 40 the hydrogen ?uoride in the liquid phase, and drogen ?uoride promoted by ‘both boron tri preferably also to keep all the hydrocarbons in ?uoride and an ole?n; or a combination of ‘both the liquid phase. It must, of course, exceed the ?uorides promoted by the ole?n. ' The presence partial pressure of the boron tri?uoride. The of an ole?n generally gives somewhat better re sults. The hydrogen ?uoride and boron tri?uoride may be the available commercial grades. It is not necessary to have chemically :pure ?uorides. 45 total pressure may vary up to 1000 pounds per square inch, such as might be obtained ‘by the presence of an inert gas, but generally no ad vantage is gained 5(un'less hydrogen is used as .de scribed later) by ~having a total pressure greater The impurities in the commercial grades, in cluding water, which are generally present in 50 than the sum .of the partial pressure of the boron tri?uoride and the partial ‘pressures of the hy drogen ?uoride and the hydrocarbons at the tem fere materially with the operation of the catalyst. perature utilized. In view of the economic advantage of using the The time of contact ‘between the pentane and commercial grade, .it is preferred, and was used in the following examples. Reference to the 55 other hydrocarbons and the catalyst may vary with the temperature, thoroughness of contact ?uorides hereinafter is intended to include such or mixing between the hydrocarbon and the cat commercial grades and their normal impurities alyst, and other factors. Depending upon such or their equivalent in composition. other factors, the time should be selected to The conditions under which the process is car give optimum yields. ‘This may be from ‘5 min 60 ried out are selected within convenient ranges utes to 13 hours, although in the higher tempera so as to produce maximum yields. In general an amount of about 1A; to 5 per cent, do not inter ture ranges and with very thorough mixing, as ~ the temperature may ‘vary from —30° to 400° F., might be accomplished with the ‘best commercial preferably from about 20° to 212° F. Averaging mixing apparatus available, the time ‘might ‘be re with kerosene as the heavier stock shows that the process can be carried out conveniently at 65 duced to the order of a minute. ‘In a commercial operation, it is desirable, of course, to ‘keep the a temperature within a range of about 32° to reaction time as short as possible since this de 150° F. It is an advantage of the process that creases the size of the reactor necessary to pro extreme temperatures in either direction are not duce a given amount of product. Observations necessary. A single temperature may ‘be used indicate .that the reaction proceeds quite quickly, throughout the reaction, or it may be varied dur and readily reaches :a condition where more time ing the reaction. If the catalyst is reused a some does not materially alter the distribution ‘of the what higher temperature may be desirable than products to such an extent that it .is of economic is the case when the catalyst is ‘fresher. It may be desirable, for this reason, to operate with ascending temperatures in the direction of ?ow. advantage to continue the reaction longer. The .agitation may be accomplished with any 2,405,997 7 8 type of a mechanical agitator or stirrer, or it or absorbed in ‘the ?uorides. If hydrogen is to be used, thismay' be introduced from a separate high pressure source of the supply. The order of mixing the components is not critical. The pentane-containing fraction and heavier hydrocarbons may be fed separately or .mixed and introduced into the ?uorides or vice may be accomplished by induced ?ow suchas by the introduction of one vof the ingredients from an'ori?ce under high pressure. ‘ The temperature, composition of the catalyst, ‘time of contact, and other factors mentioned heretofore are more or less interdependent.‘ The ‘ranges described heretofore are not intended to versa. Alternatively the pentane-containing mean that any temperature may be used with component may be mixed with the ?uorides and any length of time or any composition of cat 10 this mixture fed gradually to the heavier hydro alyst to obtain the identical result. For example, if a lower temperature is used, a somewhat larger carbons or vice versa in one or more stages. In I either a batch or continuous process, the ?uo amount of catalyst may be present or a some rides may be introduced in increments at differ what higher partial pressure of boron tri?uoride ent intervals during the total reaction period. may be used, or the treating time may be longer, 15 When using a continuous mixer having a plural or mixing better, or any or all of them, to obtain ity of stages, the ?uorides may be introduced at about the same result that would be obtained each stage. The operation may be countercur with a higher temperature and with a lesser rent or concurrent. ' amount of catalyst, or a’ lower partial pressure In a multiple treatment process the ?rst treat of boron trifluoride, or with a, shorter treating 20 ment with the catalyst may be largely or in part ‘time. Thus, for example, any temperature within one of dearomatizing, and subsequent treatments the range may be employed and the other vari may be responsible for the major portion of the ables‘ may be adjusted within their ranges so as pentane averaging reaction. Although the cat “to obtain, averagingiwith pentane. It is a particularly important part of the proc ess that in addition to varying the time of con alyst may be reduced in activity during the av-, 25 eraging reaction so as to render it ineffective for further reacting pentane, it may still be used tact, the amount of catalyst, and the temperature, to dearomatize and the. dearomatization of the which are the variables with which the prior art heavier fraction feed stock with the used cata hasv had to work, it is possible, in accordance with lyst from the pentane averaging reaction is an thef process to vary the composition of the cat 30 important aspect of the invention. This could alyst by. varying the partial pressure of the boron be accomplished, for example, in a two-stage ?uoride. Thus, for any given temperature, time countercurrent treatment. The catalyst con of contact, etc., at which it is desirable to oper taining the aromatics may then be subjected to ate because of plant equipment or economic a regenerating action in accordance with any of reasons, the activity of the catalyst and the rate the processes indicated heretofore, and the ?uo of the pentane averaging reaction can be varied rides returned to the averaging zone. simply by adjusting the partial pressure of the The following examples are given merely as il boron trifluoride. lustrative of the results that may be accom It will be apparent that the control of the plished when the invention is practiced on a lab process is an important aspect of the invention 40 oratory scale. This may be transferred to a com and that it is not possible to interrelate the vari mercial basis with the incident improvements as ables mathematically. However, it is believed described heretofore. that one skilled in the art, in view of the disclo Example 1 sure in this application, will be able to adjust the conditions without difficulty so as to obtain An Illinois kerosene, containing 16% aromatics the desired new results. I The process may also be carried out in the presence of hydrogen, which may be introduced into the reaction in an amount to provide a par was used as the heavier stock for averaging with a pentane fraction. Five per cent of the kerosene boiled below 360° F. and 50% below 425° F.; the tial pressure of hydrogen of 100 to 1000 pounds 50 end point was 551° F. ' The process was carried out in a two stage treatment. In the ?rst stage per square inch. This tends to minimize the the kerosene was treated with 15 volume per cent amount of hydrocarbons entering the lower layer. of liquid hydrogen ?uoride (based on the volume The process is adapted either for batch oper of the kerosene) in which boron tri?uoride was ation or for continuous operation. In either type dissolved in an amount to provide a partial pres of operation the feed stocks may be dried, if de sure of 150 pounds per square inch. The reac sired, by suitable driers. In a batch operation tion was continued for 15 minutes at 90° F. by the pentane-containing fraction and the higher agitating the kerosene and the catalyst. After hydrocarbons are brought together with the ?u the kerosene and the catalyst have been mixed orides in the desired amounts in a closed con under the above conditions for the stated time, tainer or autoclave where they are preferably the agitation was discontinued and the catalyst subjected to agitation and maintained under the phase and the hydrocarbon phase, being mutu desired temperature and pressure for the re ally insoluble in each other, was separated by quired length of time. In a continuous process gravity. If desired, forces greater than gravity, the ?uorides and the hydrocarbons to be treated such as centrifuging, could be used in effecting are fed into a continuous type mixer, for exam the separation. The lighter or upper layer con ple, a three-stage mixer, and maintained at the desired temperature and under the appropriate tains the hydrocarbons and the lower layer com pressure. The ?ow through the mixer may be prises the catalyst phase. This separating op intermittent or continuous and may be adjusted eration was carried out under the pressure used so that the hydrocarbons are in contact with the 70 in effecting the reaction. catalyst for the desired length of time. 7 The upper layer and 400 volume per cent of In either the batch of continuous operation, if a pentane fraction was placed in the second an ole?n is to be added as a promoter, this may stage reaction vessel in the presence of 100 vol be contained in either of the pentane or other ume per cent of liquid hydrogen ?uoride (based 'raw materials or may be introduced separately 75 , on the volume of the kerosene) in which boron 2,405,997 9 10 trifluoride was dissolved in an amount to pro-‘ vide a partial pressure of 150 pounds per square inch under the reaction conditions. The mixture .is agitated at a temperature of 90° F. for a pe riod of 60 minutes. low 300°‘F. and about 31% boiling below 400° F.» The results are as follows: Hydrocar bons pro At the conclusion of the reaction, the upper bHydilrlocar-d (weig ducgcti, 11er in g ons c arge . layer containing the averaged hydrocarbons and Hydl ocmbon any unreacted hydrocarbons, was separated and its constituents determined. hydrocarbons charged, are as follows: Hydrocar produc Hydrocar bons ed bons charged per(weight cent of (weight per cent) Propane and lighter _____ __1___\___- ____ __ total hydro carbons charged) 0 0. l _._ 35. 9 42. 3 _ 4. 9 9. 3 Isopentane _____ .. 25.‘ 6 l5. 5 Normal pentane.. 8.0 3. 3_ l. 2 15.0 Isobutane _____ __~ ____ __ Normal butane Hexane to 300° F_ 15 Propane and lighter cent of the cent) - The composition of the hydrocarbons charged 10 to the over-all two stage process in weight per cent, and the hydrocarbons resulting from. the process, expressed in weight per cent of the total Hydrocarbon (weight per- 300° to 400° F ____ __~___ _ ___ 7.9 Above 400° F _______________________ ._ __ __ l6. 5 Hydrocarbons in catalyst phase. 2. 4‘ 8. 2 3. 9 It will be seen that there is a net production the total hydrocarbons 20 of hydrocarbons boiling in the hexane to 300° F. charged) range and a substantial net consumption of the kerosene and a net consumption of the pentane fraction, particularly of the normal pentane. While there is an increase in the amount of 25 butanes from 40.8%. to 51.6%, this increase‘ is less than the amount of the heavier fraction and the lighter fraction consumed, indicating the the accomplishment of averaging. By extrapolation of- the data from the above two examples, and by further research, it has From the above reaction it will be seen that 30 been ascertained thatupon recycling the‘ entire Hydrocarbons in catalyst phase ____ -I: there is a net production of 14.3% boiling within the range of hexane to 300° F. There is a sig ni?cant consumption of kerosene and a large consumption of the pentane fraction, particu larly anet consumption of the normal pentane to result in these valuable intermediate boiling hydrocarbons. The fraction boiling above 300° F. comprising lighter fraction the amount of butanes may be expected» to increase until they represent about 80% of the lighter fraction. At this stage there ' will be a net consumption of both the butanes and the pentanes in‘ the averaging. The above examples are given merely as illus trative of the results that may be accomplished and not as a limitation upon the scope of the 21.8% can be recycled to the reaction zone as 40 invention as described heretofore. well as the pentanes and butanes, if desired. In the above examples the upper layer com Since this stock is substantially aromatic free prising the hydrocarbons may be sent to a pri there would be less lower layer hydrocarbon in mary fractionating column and the excess of such a continuous process. lighter fraction and any ?uorides dissolved in If desired, the fraction boiling from isopentane 46 the upper phase may be separated at the top to 300° F. may be separated. This amounts to of the column and recycled to the reaction zone. 39% of the hydrocarbons charged and is a good ‘Since an excess of the lighter fraction in the re grade of gasoline in View of the small amount action zone is preferable, a part of the feed for of normal pentane. The butane fraction may for the reaction in a continuous process may be used in alkylating or may be recycled to the comprise the recycled lighter fraction and fresh reaction zone and mixed- with the fresh charge 50 pentane feed. The amount of the fresh feed of pentanes. stock need be only equal to that which is con The consumption of kerosene is not as large sumed in the averaging reaction and it- may be as in the- following examples, but the process is a all normal pentane. desirable one in making a hexane to 300° F. During the averaging process the normal pen 65 gasoline from pentanes. The incidental iso tane fed into the averaging reaction zone may butane formation is desirable since it is a valu become at least partially isomerized and also able intermediate product. converted to butanes as shown in the examples. The lighter components that are taken from the Example 2 60 top of the primary fractionating' column may be If the entire butane-pentanes fraction from ' further fractionated in one or more secondary fractionating columns to separate a portion or Example 1 is to be recycled or if the butanes are all of the isobutane for use in other processes, to be recycled with the addition of a fresh charge such as alkylation, and the remainder of the of pentane, the results that may be obtained are excess of the lighter fraction may be returned indicated in this example, in which a mixture of 65 to the averaging zonep When they alkylation is butanes and pentanes (approximating the to‘ be accomplished" with the same catalyst it is butanes-pentanes fraction from Example 1) is not necessary to separate any fluorides that may used as the light stock. This light fraction, in an distill with the isobutane. Similarly isopentane amount of 400 volume per cent (based on the 70 may be fractionated if it is not to be recycled or kerosene) is averaged with a kerosene, with the taken off in the gasoline fraction. Thus the in same catalyst and in the same amount, and for vention contemplates the ability not only to the same length of time as in Example 1. The utilize the normal pentane and convert it into a higher molecular weight hydrocarbon, but at kerosene used contains about 6% aromatics, about 5% of the total hydrocarbons boiling be 76 the same time to ‘convert normal pentane to: 2,405,997 11 12 isopentane and isobutane, -a portion-of which may be withdrawn and used in other reactions. The lighter fraction separated for recycling may be depropanized by fractional distillation, be collected and condensed and/or compressed absorption, or any other fractionation or suit able method before recycling, if the propane builds up to an undesirable level. - The wanted products may be withdrawn fro intermediate plates in the primary fractionating and returned to the mixing zone or stored or otherwise used. Alternatively, instead of distilling the ?uorides, 5 the lower layer or catalyst phase may be treated with a material which exerts a solvent action on the ?uorides and which is immiscible with the hydrocarbons in the lower layer, or which forms a chemical compound or complex with the ?uo rides, and from which the ?uorides may be re column. The heavier unconverted products may be leased later, for example, by heating. withdrawn from the bottom of the column. Fluorides can be extracted from the upper or These may or may not be recycled to the reaction lower layers, for example, with an oxy?uoboric zone, depending upon their character, or they acid, such as H3BF2O2 or H4BF'3O2. may befurther fractionated and a part returned 15 The reference .to a “hydrocarbon fraction” is to the reaction zone.’ ' If desired, a single product, such as isopen tane or neo-hexane or a mixture boiling from about 75° to 141° F. (since only a small amount intended to refer to a pure hydrocarbon as well as a mixture of hydrocarbons. It will be apparent that the invention is capa ble of many applications and variations and I of normal pentane remains after the reaction 20 intend all of them to be included as are within the following claims. process) may be withdrawn from the fractionat This application is a continuation-in-part of ing column and all of the lighter (butanes) and all of the heavier (normal hexane and heavier) applications Ser. No. 422,744, filed December 12, materials maybe recycled to the averaging re 1941; Ser. No. 451,216, ?led July 16, 1942, and action zone. This will shift the conditions in the 25 Ser. No. 529,681, ?led April 5, 1944. averaging reaction so as to form primarily the I claim: 1. A process of catalytically averaging hydro product being withdrawn. The pentane averag ing process thus may be used essentially for mak carbons which comprises reacting a normally liq uid hydrocarbon fraction comprising para?inic ing a single wanted product with the return of all other products as raw materials. , 30 hydrocarbons having at least seven carbon atoms The lower layer or catalyst phase is separated and a lighter hydrocarbon fraction comprising from the hydrocarbons at such a temperature normal pentane, in the presence of a liquid cata lyst the inorganic ingredients of which comprise and pressure that the catalyst remains as a dis tinct liquid phase, in accordance with the pre essentially liquid hydrogen ?uoride in which is ferred embodiment, the catalyst phase may be 35 dissolved not over 50 mol per cent of boron tri recycled and reused for the treatment of a fresh ?uoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liq current system for dearomatizing mentioned uid and at a temperature and for a period of heretofore. The used catalyst phase may also be time while regulating the activity of the catalyst employed in other averaging operations which 40 by adjusting the partial pressure of the boron require a less active catalyst. For example, the tri?uoride to result in a net production of hy catalyst may be used initially on a stock which is - drocarbons intermediate said liquid hydrocarbon di?icult to react and after separation from said fraction and said normal pentane. stock, it may be reused with stocks that are. 2. A process of catalytically averaging hydro easier to react. Alternatively the used catalyst 45 carbons, which comprises reacting a normally phase may be used as an alkylation catalyst where liquid petroleum fraction boiling higher than a less active catalyst is required. gasoline, and a hydrocarbon fraction compris Certain hydrocarbons, notably unsaturates and ing normal pentane, in the presence of a liquid aromatics, tend to accumulate in the catalyst catalyst the inorganic ingredients of which com phase in the form of a complex during the aver 50 prise essentially liquid hydrogen ?uoride in which aging reaction. In the above examples it will is dissolved not over 50 mol per cent of boron be noted that the catalyst phase contains a trifluoride, and continuing the reaction under a slight amount of hydrocarbons. A small amount pressure to maintain the hydrogen'?uoride liquid of a complex with an unsaturate in the catalyst and at a temperature and for a period of time phase is thought to be helpful as a promoter, and while regulating the activity of the catalyst by for this reason the presence of an ole?n has been adjusting the partial pressure of the boron tri indicated as desirable. But the accumulation of ?uoride to result in a net production of hydro too much hydrocarbon in the catalyst phase ex carbons intermediate said liquid petroleum frac erts a poisoning effect. Therefore, if the amount tion and said normal pentane. of hydrocarbon in the catalyst phase is keptat 60 3. A process of catalytically averaging hydro supply of raw materials or such as in the counter the optimum value, the reaction will proceed carbons, which comprises reacting kerosene and more rapidly and less of the catalyst will be re a hydrocarbon fraction comprising normal pen tane and isopentane, in the presence of a liquid quired. To overcome this poisoning effect, a part or catalyst the inorganic ingredients of which com all of the used or reused catalyst may be with 65 prise essentially liquid hydrogen ?uoride in which drawn and subjected to a relatively high tem is dissolved not over 50 mol per cent of boron perature, for example, 250-600° F. This may be tri?uoride, and continuing the reaction under by way of a pot still, or by means of ?ash distil a pressure to maintain the hydrogen ?uoride liq lation. Preferably a two-stage treatment ‘is em uid and at a temperature and for a period of ployed, the ?rst stage using a ?ash distillation 70 time while regulating the activity of the catalyst at a somewhat lower temperature, preferably at by adjusting the partial pressure of the boron system pressure followed by distillation in a tri?uoride to result in a net production of hydro stripper at a higher temperature and lower pres carbons intermediate said kerosene and said pen sure. At this temperature substantially all of tanes. 4. A process of catalytically averaging hydro the ?uorides are liberated as gases, These can 75 13 2,405,997 14 carbons, which comprises reacting a normally liquid hydrocarbon fraction comprising paraf?nic catalyst phase from the hydrocarbon phase, frac tionating the hydrocarbon phase and recycling hydrocarbons having at least seven carbon atoms and a butanes-pentanes hydrocarbon fraction comprising normal pentane, in the presence of a liquid catalyst the inorganic ingredients of at least part of the unreacted lighter hydrocar bon fraction to the reaction zone. 8. A process of catalytically averaging hydro carbons, which comprises reacting a lighter hy drocarbon fraction comprising normal pentane which comprise essentially liquid hydrogen ?uo ride in which is dissolved not over 50 mol per and a heavier hydrocarbon fraction comprising cent of boron tri?uoride, and continuing the re primarily hydrocarbons having at least seven action under a pressure to maintain the hydro 10 carbon atoms in a reaction zone in the presence gen ?uoride liquid and at a temperature and for of a liquid catalyst, said catalyst comprising es a period of time while regulating the activity sentially liquid hydrogen ?uoride in which is dis of the catalyst by adjusting the partial pressure solved less than 50 mol per cent of boron tri of the boron tri?uoride to result in a net con ?uoride as the primary inorganic catalytic in sumption of said liquid hydrocarbon fraction and 15 gredients, and continuing the reaction under a said normal pentane, and to produce hydrocar bons intermediate said liquid hydrocarbon frac pressure to maintain the hydrogen ?uoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the tion and said pentanes. 5. A process of catalytically averaging hydro activity of the catalyst by adjusting the partial carbons, which comprises reacting a petroleum 20 pressure of the boron tri?uoride to result in a fraction boiling higher than gasoline and a bu net production of isopentane and hexanes, sep tanes-pentanes hydrocarbon fraction comprising arating the catalyst phase and the hydrocarbon a normal pentane, in the presence of a liquid catalyst the inorganic ingredients of which com prise essentially liquid hydrogen ?uoride in which 25 is dissolved not over 50 mol per cent of boron tri?uoride, and continuing the reaction under a pressure to maintain the hydrogen ?uoride liquid phase, iractionating the hydrocarbon phase to separate a single wanted fraction boiling between isopentane and hexane isomers, and recycling at least part of the remaining heavier hydrocar bons to the reaction zone. 9. A process of catalytically averaging hydro and at a temperature and for a period of time carbons, which comprises reacting a lighter hy while regulating the activity of the catalyst by 30 drocarbon fraction comprising normal pentane adjusting the partial pressure of the boron tri and a heavier hydrocarbon fraction comprising ?uoride to result in a net consumption of said primarily hydrocarbons having at least seven petroleum fraction and said normal pentane, and carbon atoms in the presence of a liquid catalyst, to produce hydrocarbons intermediate said petro said catalyst comprising essentially liquid hydro leum fraction and said pentane. 35 gen ?uoride in which is dissolved less than 50 6. A process of catalytically averaging hydro mol per cent of boron tri?uoride as the primary carbons, which comprises reacting a lighter hy inorganic catalytic ingredients, and continuing the drocarbon fraction comprising normal pentane reaction under a pressure to maintain the hydro and a heavier hydrocarbon fraction comprising gen ?uoride and the hydrocarbons liquid and at primarily hydrocarbons having at least seven 40 a temperature and for a period of time while carbon atoms in a reaction zone in the presence regulating the activity of the catalyst by adjust of a liquid catalyst, said catalyst comprising es ing the partial pressure of the boron tri?uoride sentially liquid hydrogen ?uoride in which is to result in a net production of isobutane and dissolved less than 50 mol per cent of boron tri hydrocarbons intermediate the pentane and said ?uoride as the primary inorganic catalytic in heavier fraction, separating the catalyst phase gredients, and continuing the reaction under a pressure to maintain the hydrogen ?uoride and the hydrocarbons liquid and at a temperature and for a period time while regulating the activ ity of the catalyst by adjusting the partial pres sure of the boron tri?uoride to result in a net production of hydrocarbons intermediate said normal pentane and said heavier fraction, sep arating the catalyst phase from the hydrocar and the hydrocarbon phase, fractionating the hydrocarbon phase to separate isobutane as one fraction and said intermediate hydrocarbons as 50 another fraction. 10. A process of catalytically averaging hydro carbons which comprises reacting a butanes pentanes hydrocarbon fraction comprising nor mal pentane and a petroleum fraction boiling above gasoline in a reaction zone in the presence , bons, separating the ?uorides from the catalyst 55 of a liquid catalyst, said catalyst comprising es phase, and recycling the separated ?uorides to the, sentially liquid hydrogen ?uoride in which is dis reaction zone. solved less than 50 mol per cent of boron tri 7. A process of catalytically averaging hydro ?uoride as the primary inorganic catalytic in carbons, which comprises reacting a lighter hy gredients, and continuing the reaction under a drocarbon fraction comprising normal pentane 60 pressure to maintain the hydrogen ?uoride and and a heavier hydrocarbon fraction comprising the hydrocarbons liquid and at a temperature primarily hydrocarbons having at least seven car and for a period of time while regulating the ac bon atoms in a reaction zone in the presence of tivity of the catalyst by adjusting the partial a liquid catalyst, said catalyst comprising essen pressure of the boron tri?uoride to result in a net tially liquid hydrogen ?uoride in which is dis 65 consumption of said normal pentane and said solved less than 50 mol percent of boron tri?uo petroleum fraction, and to produce hydrocarbons ride as the primary inorganic catalytic ingredi intermediate said normal pentane and said pe ents, and continuing the reaction under a pres troleum fraction, separating the catalyst phase sure to maintain the hydrogen ?uoride and the from the hydrocarbon phase, separating ?uorides hydrocarbons liquid and at a temperature and for 70 from the catalyst phase and recycling the sepa a period of time while regulating the activity of rated ?uorides to the reaction zone, fractionat the catalyst by adjusting the partial pressure of ing the hydrocarbon phase and recycling to the the boron tri?uoride to result in a net production reaction zone at least part of the hydrocarbons of hydrocarbons intermediate said normal pen lighter than said intermediate hydrocarbons. tane and said heavier fraction, separating the 75 ROBERT E. BURK.