US2405996A - Process of averaging hydrocarbons - Google Patents

Description

Patented Aug. 20, 1946 PROCESS OF AVERAGING HYDROCARBON S Robert E. Burk, Cleveland Heights, Ohio, assignor to The Standard Oil Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application April 5, 1944,

Serial No. 529,681

20 Claims. 1

This invention relates to the treatment of light and heavier molecular weight hydrocarbons with a catalyst comprising primarily hydrogen fluoride promoted by a minor proportion of boron trifluoride to produce hydrocarbons of intermediate molecular Weight, a process herein termed averaging.

A preferred and important embodiment of the invention comprises the use of n-butane as the light hydrocarbon, and a liquid hydrocarbon boiling above the gasoline range as the heavier hydrocarbon, to produce gasoline of desirable properties.

It is one of the objects of the invention to utilize the relatively unreactive normal hydrocarbons, such as n-butane, as one of the raw materials in making more valuable hydrocarbon products.

A further object of the invention is to utilize heavier hydrocarbon fractions, such as kerosene or naphthas, in the formation of hydro-carbons of lower molecular weight, such as gasoline, without the production of large amounts of unsaturates or fixed gases, and also without the destructive influences and losses incident to conventional methods of cracking.

It is also an object of the invention to provide a process in which a Wide variety of light and heavier stocks of diverse nature may be used as the raw materials.

:An additional object of the invention is to utilize both a light hydrocarbon and a heavier hydrocarbon simultaneously in a single reaction to produce valuable products resulting from a net consumption of both of them at the same time.

Still a further object of the invention is to carry out the above reactions in the liquid phase in the presence of a liquid catalyst comprising primarily hydrogen fluoride and promoted by a minor proportion of boron trifluoride, and if desired, also promoted by the presence of an unsaturate.

Another object is the provision of a process in which fluorides containing the impurities present in commercial grades may be used.

Still another object of the invention is to carry out th averagin reaction in the presence of an amount of the li ht hydrocarbon in excess of that entering into the reaction so as to form products of enhanced value, and in which the excess of the lower molecular weight hydrocarbon may be recycled to the averaging reaction in a continuous or semi-continuous process.

A further object of the invention i to carry out the above process, utilizing a normal hydrocarbon, such as n-butane or n-pentane in excess of that entering into the reaction, fractionating the excess to remove all or a portion of the isomer which is formed during the averaging reaction, and recycling the unisomerized normal hydrocarbon together with any portion of the isomer not fractionated.

An additional object of the invention is to carry out the averaging process under conditions of temperature and pres-sure not lower nor higher than can be obtained conveniently in ordinary plant operations,

The invention has as a. further object the provision of a process of the character described in which the activity of the catalyst, in addition to being controlled by variations in temperature, pressure and other factors ordinarily employed in catalytic operations, also can be controlled readily by means of the partial pressure and boron trifluoride constituent of the catalyst.

Still a further object is the provision of a process of averaging as described in which the catalyst can be readily recovered and reused.

Other objects of the invention will appear from the following description.

In carryin out the process of the invention a light hydrocarbon, such as butane, is mixed with the heavier boiling fraction, such as a normally liquid'hydrocarbon. These are caused to react preferably in a liquid state, in the presence of a liquid catalyst and under conditions of temperature and pressure as will be pointed out more particularly hereinafter, to produce products heavier than the light hydrocarbon and lighter than the heavier hydrocarbon starting materials. At the conclusion of the treatment the hydrocarbons are separated as one phase and ma be fractionated, and the catalyst is separated as another phase. The catalyst phase may be reused as such or may be regenerated and reused.

The light hydrocarbon may be methane through hexanes, preferably propane through hexane. Methane and ethane are more diflicult to react. If the operation is to be in the liquid 1 phase the difficulty in liquefying ethane and methane also suggests that they would be less desirable for practicing the invention on a commercial scale. Pentanes and butanes are preferred, especially the latter. Mixed propane and butanes and mixed butanes and pentanes may be used, or all three in admixture. Pentanes and hexanes are reasonably valuable as such, or can be used advantageously in other processes. Butane is readily reacted in accordance With the invention and since it is not suitable in itself as 3 a motor fuel and there is an ample amount, the invention assumes particular importance with reference to its use as the lower molecular weight raw material. For this reason the invention will be described employing butane as an illustrative example.

The light hydrocarbon may be obtained from natural gas or from any refinery operation; it is immaterial if it contains small amounts of other constituents, and for this reason it need not be highly purified. It is also immaterial, and in fact it is an advantage as .pointed out later, if it contains a small amount of unsaturates. For this reason it is not necessary to fractionate the unsaturates and other ingredients from the light fraction. When a butane fraction is used,

it may comprise normal butane, but no harm isdone if isobutane is present. Under some conditions the reaction is facilitated by the presence of isobutane. However, since isobutane is useful in other reactions, such as alkylation, the ability to use normal butane as the starting material in the averaging process is of great importance. If the process is practiced with pentanes or hexanes as the light hydrocarbon, the ability to use the normal hydrocarbon similarly is an important advantage. z

,In a continuous operation in which an excess of butane is used, a part of the excess may be isomerized to isobutane. When the excess butane is recycled the amount of isobutane in the recycled fraction may be varied and this becomes a controllable variable. Larger amounts of isobutane are helpful, under some conditions, in producing higher yields.

The heavier fraction should be selected with reference to the light hydrocarbons. In .general the heavier fraction should have at least vtwo more carbon atoms than the light hydrocarbons. For example, propane may be averaged with pentane or any heavier hydrocarbon; Butane may be averaged with hexane or any heavier hydrocarbon. Generally the heavier fraction will have a molecular weight higher than hexane.

While the heavier fraction may be a pure hydrocarbon, generally it will be a mixture, such as natural gasoline, light naphtha (YO-300 F), heavier naphthas (250400 F.), kerosenes (350- 550 F.), light gas oils MOO-625), heavy gas oils (500-710" F.), mixtures of light and heavy gas oils (400-710" F), deasphaltized'and dearomatized residues (above 700 F.) the portion of crude boiling to 550 F., the portion of crude boiling to 700 F., the portion of crude oil boiling between 250-"110 F., mixtures of natural .gasoline, or naphthas with kerosenes and fractions boiling higher than 825 F. Other stocks that may be used are Fischer-Tropsch (Hz-l-CO) stock, Houdry cycle stock and thermal cycle stock. Some of the above fractions may require aromatic extraction because the stock should be relatively low in aromatics as explained hereinafter. The heavier fractions described may contain normal hydrocarbons, isomers, naphthenes or small amounts of other hydrocarbons otherthan normal or unsaturates. The latter may be beneficial as mentioned heretofore. Q

In some instances both the light and the heavier fractions to be reacted in the averaging process may be in the form of a single fraction. vFor example, a stock boiling from 70? to above 350 F., or crude oil or reduced crude as such, may be averaged. Since the avera ing oi heavie'r hydrocarbons tends to promotethe averagingof lighter hydrocarbons, it may be desirable to use a frac- 4 tion boiling over a broader range. The stock to be operated on in a commercial embodiment will depend upon a number of factors and may depend largely on the economics involved. For example, if a plant is equipped to practice isomerization, that process may be practiced on certain light fractions and the heavier stocks may be averaged. Other stocks may be preferred for operating existing catalytic cracking units and the remainder may be used in averaging. The versatility of the process with reference to the stocks that may be employed is an important advantage of the process of the invention.

case of averagin with butane, it is more difiicult to obtain a net consumption of the light fraction, when less than 1 mol of the light fraction per mol of the heavier fraction is used as raw materials, except when other variables are very closely controlled. Contrary to what might be expected, a corresponding increase in yield is not obtained with a, pronounced increase in the light fraction. It has been found that with 2 to 6 mols of the light fraction per mol of the heavier fraction the reaction gives maximum yield and maximum consumption of the light fraction. Less than 3 mols gives somewhat lower yields, but this disadvantage may be offset by the advantage incident to lower amounts of the excess that need be recycled. Since the yields do not improve markedly when more than 8 mols of the light fraction is used, there is no object in having'present more of this fraction than will reflect an improvement, since there is no point in recycling a large excess which does not accomplish a corresponding improvement in the reaction.

The catalyst used in the process comprises hydrogen fluoride promoted with a minor proportion of boron trifluoride therein,and in some instances with an olefin. It is used preferably in the liquid phase. 7 Hydrogen fluoride boils at about 67 F. and is therefore a liquid at temperatures just under room temperature and may be kept liquid at higher temperatures by moderate pressures. The temperatures and pressures used in the process of the invention are conveniently those that maintain the hydrogen fluoride liquid. Boron trifluoride boils at l50 F. and is a gas at the temperatures and pressures conveniently employed in hydrocarbon treating processes. However, boron trifluoride dissolves in liquid hydrogen fluoride to a given extent and the amount which dissolves at any given temperature depends on the partial pressure of boron trifluoride. At higher partial pressures, a larger amount of boron trifluorideis dissolved.

The boron trifluoride in the hydrogen fluoride in the liquid phase possibly may react at least to some extent, but an understanding of the chemistry involved is not necessary to practice my invention, and I do not intend to be bound by any theory. At any eventv the amount of the boron trifluoride in the hydrogen fluoride, which controls the activity of the catalyst, is a function of the partial pressure of the boron trifiuoride.

The amount of boron trifluoride dissolved in the hydrogen fluoride, at any given temperature, may be expressed conveniently in terms. of the partial pressure of boron trifluoride. This may vary, in accordance with the invention, from 5 to 1000 pounds per square inch; generally ,about50 to 300 pounds per square inch will be used. However, the partial pressure should under no circumstances be such that the amount of boron trifiuoride exceeds 50 mol per cent of the fluorides. With the partial pressures usually used the amount does not exceed 25 mol per cent. The words dissolved and solution are used as generic to both a physical admixture and a reaction product.

One of the advantages of the process of the invention is the ability to control the reaction by adjusting :the activity of the catalyst through control of its composition. This may be accomplished by varying the partial pressure of the boron trifluoride, because a change in this partial pressure results in a change in the amount of boron trifluoride dissolved. If the partial pressure of the boron trifluoride is increased, by admitting boron trifiuoride to the reaction zone from a high pressure source of supply, the activity of the catalyst is greater under conditions otherwise the same. If this partial pressure is decreased, by bleeding boron trifluoride, the activity of the catalyst is reduced.

If an olefin is added, or is present in the reaction zone in an amount less than that which acts as a poison, the olefin appears to act as a promoter. The available evidence indicates that the olefin acts as a hydrogen acceptor and that the hydrogen fluoride-boron trifluoride solution or the reaction product may form a new compound or chemical complex with the olefin. Since olefins may be formed in the process, especially when heavier stocks are used, the addition of an olefin as a separate added ingredient to the stocks may not reflect a separate improvement.

The catalyst to be used in practicing the invention, therefore, may be viewed as hydrogen fluoride promoted by a minor proportion of boron trifluoride; or it may be viewed as hydrogen fluoride promoted by both boron trifluoride and an olefin; or a combination of both fluorides promoted by the olefin. The presence of an olefin generally gives somewhat better results.

The hydrogen fluoride and boron trifluoride may be the available commercial grades. It is not necessary to have chemically pure fluorides. The impurities in the commercial grades, including water, which are generally present in an amount of about A; to 5 per cent, do not interfere materially withthe operation of the catalyst. In view of the economic advantage of using the commercial grade, it is preferred, and was used in the following examples. Reference to the fluorides hereinafter is intended to include such commercial grades and their normal impurities or their equivalent in composition.

The conditions under which the process is carried out are selected within convenient ranges so as to produce maximum yields. In general the temperature may vary from 30 to 400 F., preferably from about 20 to 212 F. Averaging with kerosene as the heavier stock shows that the process can be carried out conveniently at a temperature within a range of about 20 to 150 F. It is an advantage of the process that extreme temperatures in either direction are not necessary. A single temperature may be used throughout the reaction, or it may be varied durin the reaction. If the catalyst is reused a somewhat higher temperature may be desirable than is the case when the catalyst is fresher. It may be desirable, for this reason, to operate with ascending temperatures in the direction of flow. This may enable a reduction in the amount of catalyst per unit of the product formed, and it 6 may also have a beneficial effect in 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 considered with reference to both of the fluoride ingredients comprising it. The amount of the hydrogen fluoride may be 5 to 300 volume per cent based on the hydrocarbons to be treated when in liquid form, preferably the amount should be about 25 to 100 volume per cent. Amounts as low as 1 volume per cent may be used in a multistage 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 yield drops somewhat with a decrease in the amount of hydrogen fluoride. In view of this fact the amount used may depend to a large extent upon the economics involved and the maximum conversion 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.

The amount of the boron fluoride used, as expressed in terms of partial pressure, has been indicated heretofore in describing the composition of the catalyst.

When an olefin is added separately as an ingredient it may Vary from extremely small amounts to 100 or more mol per cent based on the amount of the boron trifluoride dissolved in the hydrogen fluoride. Expressed in practical terms, the amount of the olefin may be /2 to 25% based on the hydrocarbons being treated.

The total pressure should be suflicient to keep the hydrogen fluoride in the liquid phase, and preferably also to keep all the hydrocarbons in the liquid phase. It must, of course, exceed the partial pressure of the boron trifiuoride. The 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 advantage is gained (unless hydrogen is used as described later) by having a total pressure greater than the sum of the partial pressure of the boron trifiuoride and the partial pressures of the hydrogen fluoride and the hydrocarbons at the temperature utilized.

The time of contact between the hydrocarbon and the catalyst may vary with the temperature, thoroughness of contact or mixing between the hydrocarbon and the catalyst, and other factors. Depending upon such other factors, the time should be selected to give optimum yields. This may be from 5 minutes to 3 hours, although in the higher temperature ranges and with very thorough mixing, as might be accomplished with the best commercial mixing apparatus available, the time might be reduced to the order of a minute. In a commercial operation, it is desirable, of course, to keep the reaction time as short as possible since this decreases the size of the reactor necessary to produce a given amount of product. Observations indicate that the reaction proceeds quite quickly, and readily reaches a condition where more time does not materially alter the distribution of the products to such an extent that it is of economic advantage to continue the reaction longer.

The agitation may be accomplished with any type of a mechanical agitator or stirrer, or it may be accomplished by induced flow such as by the introduction of one of the ingredients from an orifice 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 mean that any temperature'may be used with any length of time or any composition of catalyst to obtain the identical result. For example, if a lower temperature is used, a somewhat larger amount of catalyst may be present or a somewhat higher partial pressure of boron trifluoride may be used, or the treating time may be longer, or mixing better, or any or all of them, to obtain about the same result that would be obtained with a higher temperature and with a lesser amount of catalyst, or a lower partial pressure of boron trifluoride, or with a shorter treating time. Thus, for example, any temperature within the range may be employed and the other variables may be adjusted within their ranges so as to obtain averaging.

It is a particularly important part of the procass that in addition to varying the time of contact, the amount of catalyst, and the temperature, which are the variables with which the prior art has had to work, it is possible, in accordance with the process to vary the composition of the catalyst by varying the partial pressure of the boron fluoride. Thus, for any given temperature, time of contact, etc., at which it is desirable to operate because of plant equipment or economic reasons, the rate of the reaction and the activity for the catalyst can be varied simply by adjustingthe partial pressure of the boron trifluoride.

The process may also be carried out in the presenceof hydrogen, which may be introduced into the reaction in an amount to provide a partial pressure of hydrogen of 100 to 1000 pounds per square inch. This tends to minimize th amount of hydrocarbons entering the lower layer.

The process is adapted either for batch operation or for continuous operation. In either type of operation the feed stocks may be dried, if desired, by suitable driers. In a batch operation the hydrocarbons and the fluorides are brought together in the desired amounts in a closed container or autoclave where they are pref erably subjected to agitation and maintained under the desired temperature and pressure for the required length of time, In a continuous process the fluorides and the hydrocarbons to be treated are fed into a continuous type mixer, for example, a three-stage mixer, and maintained at the desired temperature and under the appropriat pressure. 'The flow through the mixer may be intermittent or continuous and may be adjusted so that the hydrocarbons are in contact with the catalyst for the desired length of time.

In either the batch or continuous operation, if an olefin is to be added as a promoter, this may be contained in either of the raw materials or may be introduced separately or absorbed in the fluorides. If hydrogen is to be used, this may be introduced from a separat high pressure source of the supply.

The order of mixing the components is not critical. The light and heavy hydrocarbons may be fed separately or mixed and introduced into the fluorides or vice .versa. Alternatively the light component may be mixed with the fluorides and this mixture fed gradually to the heavier hydrocarbons or vice versa in one or more'stages.

In either a batch or continuous process, the fluorides may be introduced in increments at different intervals during the total reaction period. When using a continuous mixer having a plurality of stages, the fluorides may be introduced at each stage. The operation may be countercurrent or concurrent.

After the hydrocarbons and the catalyst have been mixed under the selected conditions for the desired time, the agitation will be discontinued and the catalyst phase and the hydrocarbon phase, being mutually insoluble in each other, will separate by gravity. If desired, forces greater than gravity, such as centrifuging, can be used in effecting the separation. The lighter or upper layer will contain the averaged hydrocarbons and the unreacted raw materials, and the lower layer will comprise the catalyst phase. Preferably this separating operation is carried out under the pressure used in effecting the reaction.

If fluorides are separated from the hydrocarbons at such a temperature and pressure that the catalyst remains as a distinct liquid phase, in accordance with the preferred embodiment, the catalyst phase may be recycled and reused alone for the treatment of a fresh supply of raw materials or in admixture with a fresh supply of the catalyst, such as in a countercurrent system. The used catalyst may also be employed in other averaging operations which require a less active catalyst. For example, the catalyst may be used initially on a stock which is diflicult to react and after separation from said stock, it may be reused with stocks that are easier to react.

Certain hydrocarbons, notably unsaturates and aromatics, tend to accumulate in the catalyst phase in the form of a complex during the averaging reaction. A small amount of a complex with an unsaturate is thought to be helpful as a promoter, and for this reason the presence of an olefin has been indicated as desirable. But the accumulation of too much hydrocarbon in the catalyst phase exerts a poisoning effect. Therefore, if the amount of hydrocarbon in the catalyst phase is kept at the optimum value, the reaction will proceed more rapidly and less of the catalyst will be required. To overcome this poisoning effect, a part or all of th used or reused catalyst may be withdrawn at any stage of the operation and subjected to a relatively high temperature, for example, 250-600" F. This may be by way of a pot still, or by means of flashdistillation. Preferably a two-stage treatment is employed, the first stage using a flash distillation at a somewhat lower temperature, followed by distillation in a stripper at a higher temperature. At this temperature substantially all of the fluorides are liberated as gases, These can be collected and condensed and/or compressed and returned to the mixing zone or stored or otherwise used.

Alternatively, instead of distilling the fluorides, the lower layer or catalyst phase may be treated with a material which exerts a solvent action on the fluorides and which is immiscible with the hydrocarbons in the lower layer, or which forms a chemical compound or complex with the fluorides, and from which the fluorides may be released later, for example, by heating. It may also be possible to introduce this material into the catalyst phase before separation, whereupon the hydrocarbons in the catalyst phase would be shifted to the hydrocarbon phase.

Another alternative is to distill off a part or most of the fluorides from the lower layer'at a relatively lower temperature and remove the rest of the fluorides by extraction with such a material. Substantially all of the fluorides can be recovered by any of these processes and reused.

The hydrocarbons in the upper layer can be treated with a material to extract fluorides therefrom if this is desired, for example, an oxyfluoboric acid, such as H3BF202 or I-I4BF3O2.

The upper phase from the separation, comprising the hydrocarbons, may be sent to a primary fractionating column and the excess of butanes and any fluorides dissolved in the upper phase may be separated at the top of the column and recycled to the reaction zone. Since an excess of butanes in th reaction zone is preferable, a part of the feed may comprise the recycled butanes fraction and fresh feed. The amount of the fresh feed stock need be only equal to that which is consumed in the averaging reaction.

During the averaging process the normal butane fed into the averaging reaction zone may become at least partially isomerized and the butanes that are taken from the top of the primary fractionating column may be further fractionated in a secondary fractionating column to separate a portion or all of the isobutane for use in other processes, such as alkylation, and the remainder of the excess of the butane fraction may be returned to the averaging zone. Thus the invention contemplates the ability not only to utilize the normal butane and convert it into a higher molecular weight hydrocarbon, but at the same time to convert normal butane to isobutane, a portion of which may be withdrawnand used in other reactions.

The butanes separated for recycling may be depropanized by fractional distillation, absorption, or any other fractionation or suitable method before recycling, if the propane builds up to an undesirable level.

The wanted products may be withdrawn from intermediate plates in the primary fractionating column.

The heavier unconverted products may be withdrawn from the bottom of the column. These may or may not be recycled to the reaction zone, depending upon their character, or they may be further fractionated and a part returned to the reaction zone.

Alternatively, the upper layer may be sent to a debutanizer and the heavier material from the bottom of the debutanizer may be treated to remove fiuorides by any known means and this treated stock then fractionated into gasoline and unreacted heavier stock in a separate column.

If desired, a single product, such as isopentane or neo-hexane or a mixture of the two (since little if any normal pentane is formed in the process) may be withdrawn from the fractionating column and all of the lighter and all of the heavier materials may be recycled to the averaging reaction zone. This will shift the conditions in the averaging reaction so as to form primarily the product being Withdrawn. The averaging process thus may be used essentially for making a single wanted product with the return of all other products as raw materials.

If fixed gases should accumulate beyond the point where they may be reacted under the conditions employed, they may be removed at any point in the process.

The presence of aromatics in the feed stocks, particularly in the higher molecular weight fraction where they are more apt to be present, is undesirable because these aromatics are transferred to the lower layer and form a complex with the catalyst and thus decrease its activity. For this reason it is desirable that 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 suitably, it will be generally preferable to reduce the aromatic content of the stock of a dearomatization process. This may be done by any means conventional in the art, such as solvent extraction, or the fluorides may be used for dearomatizing in accordance with the process described in my Patent No. 2,343,744, granted March 7, 1944. In a multiple treatment process the first treatment with the catalyst may be largely one of dearomatizing and subsequent treatments may be responsible for the major portion of the averaging reaction. Although the catalyst may be reduced in activity during the averaging reaction so as to render it ineffective for further averaging, it may still be used to dearomatize and the dearomatization of the feed stock with the used catalyst from the averaging reaction is an important aspect of the invention. This could be accomplished, fOr example, in a two-stage countercurrent treatment. The catalyst containing the aromatics may then be subjected to a regenerating action in accordance with any of the processes indicated heretofore, and the fluorides returned to the averaging zone.

For example, the lower layer from a first stage reactor (which may accomplish primarily dearomatizing if the feed stock is not sufliciently dearomatized or otherwise may accomplish a part of the averaging) and the lower layer from a second stage reactor (which may act upon the upper layer from the first stage to accomplish averaging) may be combined and fed to a catalyst recovery tower from which the fluorides are removed at the top by distillation and returned to the first and/or second stage reactors.

The following examples are given merely as illustrative of the results that may be accomplished when the invention is practiced on a laboratory scale. This may be transformed on a commercial basis, with the incidental improvements as described heretofore:

Example 1 A kerosene fraction and isobutane gas in the ratio of '7 mols of the latter per mol of the kerosene are treated under a total pressure of 250 pounds per square inch for 10 hours at C. with the liduid HF and BFs, the latter in amount of 50 pounds partial pressure persquare inch. Thirty to fifty per cent of the kerosene is converted into hydrocarbons of gasoline range, depending upon the duration of treatment.

Ewample 2 A de-aromatized Pennsylvania kerosene was averaged with a mixture of normal butane and isobutane containing 16 per cent of the latter, by liquid hydrofluoric acid as catalyst in which boron fluoride is dissolved to partial pressure of 150 pounds per square inch, 6 mols of butanes being employed per mol of kerosene, the temperature being 32 C. The total pressure was 210 pounds per square inch. After two hours per cent by weight of kerosene was converted to liquid products 80 per cent of which consisted of a gasoline boiling in the range 70-410 F. and having an unleaded A. S. T. M. octane number 84. 20 per cent of the total charge was converted to isopentane.

aeoaoec The butanes remaining contained 65 per cent by volume of isobutane.

Example 3 A similar kerosene stock was averaged with a mixture of butanes, by liquid HF as catalyst and BF: dissolved to partial pressure of 150 pounds per square inch, th temperature being 'C. The total pressure was 190 pounds per square inch. After about 2 hours 83.6 volume per centof gasoline was obtained.

Example 4 Butane containing 16% isobutane was averaged with dearomatized Pennsylvania kerosene. The volume of the butane fraction based on the hero sene was 212% and the weight of the kerosene based on the total charge of hydrocarbon was 39.2%. The reaction was continued with agitation at a temperature of 40 F. for two hours. The amount of the hydrogen fluoride employed was 33 volume per cent based on the total hydrocarbon charge, and the amount of the boron trifiuoride was such as to provide a partial pressure of 150 pounds per square inch. The total pressure was 220 pounds per square inch. At the conclusion of the reaction the hydrocarbon phase was separated from the catalyst phase and the hydrocarbon phase was fractionated. It was found to contain 0.23% propane and lighter products, 38.8% butanes, of which 64.6% was isobutone. The recovered butane fraction was 63.8% of the butane charge, indicating that 36.2% of the butane fraction had entered into the reaction. The products boiling within the range of 70 to 300 F. amounted to 28.7%. The products boiling from 300 F. to 400 F. amounted to 8%, and the products above 400 F. amounted to 17.6%. The hydrocarbons in the catalyst phase amounted to 6.2%.

If the butanes recovered are recycled, the gasoline fraction based on the heavy stock and the butanes reacted would amount to about 47%.

Example 5 A butane fraction containin 11% isobutane was averaged with a dearomatized Illinois naphtha. The volume of the butane fraction based upon the naphtha was 262% and the weight of the naphtha based on the total hydrocarbon charge was 3l.05%. The amount of hydrogen fluoride based on the hydrocarbon charge was 28.4 volume per cent and the amount of boron trifiuoride was such as to provide a partial pressure of 150 pounds per square inch. The total pressure was 220 pounds per square inch. The reaction was continued at a temperature of 122 F. for two hours, following which the phases were separated and the hydrocarbon phase fractionated. The amount of hydrocarbons lighter than C4 was found to be 6.5%. The butanes amounted to 53.1%, of which 41.8% was isobutane. The fraction from 70 to 300 F. amounted to 25.7%, and the hydrocarbons above this boiling range amounted to 0.6%. The catalyst phase contained 8.9% hydrocarbons. Calculation showed that 15.5% of' the butane fed into the reaction zone had reacted with the naphtha to form products in the gasoline range. The recovered butanes which. amounted to 58.1% of the charge were recycled and the gasoline formed, based on the remaining 41.9%,amountedto about 62%.

Example 6 A butane fraction containing 15.7% isobutane was averaged with dearomatized Pennsylvania kerosene. The volume of the butane fraction based on the kerosene was 200% and the weight of the kerosene based on the total hydrocarbon charge was 40.6%. The amount of the hydrogen fluoride based on the total hydrocarbon charge was 33.7 volume per cent, and the amount of the boron trifluoride was such as to provide a partial pressure of 150 pounds per square inch. The total pressure was 200 pounds per square inch. The hydrocarbons and the catalyst were agitated under these conditions at a temperature of F. for one hour. The hydrocarbon phase. upon its separation from the catalyst, was found to contain 0.8% of hydrocarbons lighter than C4, 53.2% butanes of which 54.4% was isobutane. The hydrocarbons boiling within the range of 70 to 300 F. amounted to 21.6%. The hydrocarbons boiling within the range of 300 to 400 F. amounted to 3.4%, and those boiling above 400 F. amounted to 10.2%. 8.6% of hydrocarbons was found in the catalyst phase.

Calculations showed that about 11% of the butane feed entered into the reaction.

The recovered butane fraction and the fraction boiling above 300 F. may be recycled to the averaging zone, resulting in a net consiunption of 39.2% of the charge. Of this, 55% is converted into hydrocarbons in the gasoline range.

Example 7 A butane fraction containing 60.9% of isobutane was averaged with an Illinois kerosene having a boiling range of 340 to 520 F. The aromatics in the kerosene had been reduced to less than 2% by treatment with hydrogen fluoride and boron trifiuoride followed by treatment with silicon dioxide. The volume of the butane fraction, based on the kerosene, was about 400% and the weight of the kerosene, based on the total hydrocarbon charged, was 26.6%. The amount of hydrogen fluoride was volume per cent, based on the kerosene charged, and the amount of boron trifluoride was such as to provide a partial pressure of 190 pounds per square inch. Thehydrocarbons and the catalyst were agitated in the liquid phase at a temperature of 90 F. for 1 hour. The hydrocarbon phase, upon its separation from the catalyst phase, was found to contain 1.5% hydrocarbons lighter than C4, 63.6% butanes of which 66.1% was isobutane. The hydrocarbons boiling within the range of isopentane to 300 F. amounted to 14.7% and the hydrocarbons boiling above 300 amounted to 9.5%. The catalyst phase contained 5.7% hydrocarbons. The recovered butane fraction and the fraction boiling above 300 F. may be recycled, resulting in a net consumption of 21.9% of the charge. Of this 67.1% is converted into hydrocarbons in the gasoline range.

Example 8 A butane fraction containing 60.3% isobutane was averaged with a, dearomatized Pennsylvania kerosene, all of the constituents of which boiled above 300 F. The volume of the butane fraction based on the kerosene, was about 400% and the weight of the kerosene, based on the total hydrocarbon charge, was 26.2%. The amount of the hydrogen fluoride was 100 volume per cent, based on the kerosene charged. The amount of boron trifluoride was such as to provide a partial pressure of pounds per square inch. The hydroca-rbons and the catalyst were agitated under 13 these conditions at a temperature of 90 F. for 1 hour, following which the hydrocarbon phase was stratified and separated from the catalyst phase. The hydrocarbon phase was found to contain 0.8% of hydrocarbons lighter than C4, 66.5% of butanes, of which 68.3% was isobutane. The hydrocarbons boiling in the gasoline range, namely from isopentane to 300 F. amounted to 19.6% and the hydrocarbons boiling above 300 F. amounted to 9.3%. The catalyst phase contained 3.8% hydrocarbons. Upon recycling of the recovered butane fraction and the fraction boiling above 300 F. the resulting net consump tion of butanes was 7.3% and the kerosene was 16.9% or a total of 24.2%. Of this 81% was converted into hydrocarbons in the gasoline range.

The above examples are given merely as illustrative of the results that may be accomplished and not as a limitation upon the scope of the invention as described heretofore.

From the above explanation it seems likely that the normal hydrocarbon in the lower molecular weight hydrocarbon feed is isomerized, that the higher hydrocarbon fraction is cracked, and that the unsaturates formed in the cracking are used in alkylating the isomer. It is surprising that all three of the reactions can be effected simultaneously under the same conditions, since it has been thought that more vigorous conditions are required for isomerization than for alkylation, and also that conditions which crack the upper fraction would prevent the alkylation (i. e. crack the alkylate as fast as it is formed). That the averaging is possible is attributed to the catalyst used in this particular reaction and the ability to control its activity in relation to the other conditions so as to obtain the averaging reaction.

It will be apparent that the control of the process is an important aspect of the invention and that it is not possible to interrelate the variables mathematically. However, it is believed that one skilled in the art, in view of the disclosure in this application, will be able to adjust the conditions without difiiculty so as to obtain the desired new results.

The reference to a hydrocarbon fraction is intended to refer to a pure hydrocarbon as well as a mixture of hydrocarbons.

This application is a continuation-in-part of applications Serial Nos. 423,073 and 458,769, filed December 15, 1941 and September 18, 1942, respectively.

It will be apparent that the invention is capable of many applications and variations and I intend all of them to be included as are within the following claims.

I claim:

1. A process of catalytically averaging hydrocarbons which comprises reacting a light hydrocarbon fraction comprising normal hydrocarbons of not over six carbon atoms and a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in said light fraction in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said light and said heav- 14' ier fractions resulting from a net consumption of said light normal hydrocarbons and said heavier hydrocarbons.

2. A process of catalytically averaging hydrocarbons, which comprises reacting a normally liquid hydrocarbon fraction comprising parafiinic hydrocarbons, and a normally gaseous hydrocarbon fraction comprising a normally gaseous normal parafiinic hydrocarbon, in the presence of a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mol per cent of boron trifiuoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said liquid and said gaseous hydrocarbon fractions resulting from a net consumption of said liquid hydrocarbon fraction and said normally gaseous normal parafiinic hydrocarbon.

3. A process of catalytically averaging hydrocarbons which comprises reacting a normally liquid hydrocarbon fraction comprising parafiinic hydrocarbons, and a normally gaseous hydrocarbon fraction comprising'normal butane, in the presence of a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mol per cent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifiuoride to produce hydrocarbons intermediate said liquid and said gaseous hydrocarbon fractions resulting from a net consumption of said. liquid hydrocarbon fraction and said normal butane.

4. A process of catalytically averaging hydrocarbons which comprises reacting a butane fraction containing normal butane and a heavier hydrocarbon fraction higher than gasoline in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce gasoline resulting from a net consumption of said normal butane and said heavier fraction.

5. A process of catalytically averaging hydrocarbons, which comprises reacting kerosene and a normally gaseous hydrocarbon fraction comprising normal butane, in the presence of a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mol per cent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said kerosene and said gaseous hydrocarbon fraction resulting from a net consumption of said kerosene and said normal butane.

6. A process of catalytically averaging hydrocarbons, which comprises reacting a normally liquid hydrocarbon fraction comprising paraffinic hydrocarbons, and a normally gaseous hydrocarbon fraction comprising normal and isobutanes, in the presence of a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mol per cent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said liquid and said butanes resulting from a net consumption of said liquid hydrocarbon fraction and said normal butane.

7. A process of catalytically averaging hydrocarbons, which comprises reacting kerosene and a normally gaseous hydrocarbon fraction comprising normal and isobutanes, in the presence of a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mol per cent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said kerosene and said butane resulting from a net consumption of said kerosene and said normal butane. l

8. A process of catalytically averaging hydrocarbons which comprises reacting a light hydrocarbon fraction comprising normal hydrocarbons of not over six carbon atoms and a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in said light fraction in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride s the primary inorganic catalytic ingredients, and in the presence of a complex in said liquid catalyst phase formed by the action of the fluorides upon unsaturated hydrocarbons, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said light and said heavier fractions from a net consumption of said light and said heavier fractions.

9. A process of catalytically averaging hydrocarbons, which comprises reacting a normally liquid hydrocarbon fraction comprising paraffinic hydrocarbons, and a normally gaseous hydrocarbon fraction comprising a normally gaseous normal parafimic hydrocarbon, in the presence of an unsaturated hydrocarbon and a liquid catalyst the inorganic ingredients ofwhich comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mo] per cent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said liquid and said gaseous hydrocarbon fractions resulting from a net consumption of said liquid hydrocarbon fraction and said normally gaseous normal paraffinic hydrocarbon.

; A process of catalytically averaging hydrocarbons which comprisesreacting a butane fraction and a heavier hydrocarbon fraction having at least six carbon atoms in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and in the presence or" a complex in said liquid catalyst phase formed by the action of the fluorides upon unsaturated hydrocarbons, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a. period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said butane and said heavier fractions resulting from a net consumption of said butane and said heavier fractions.

11. A process of catalytically averaging hydrocarbons, which comprises reacting kerosene and a normally gaseous hydrocarbon fraction com prising normal butane, in the presence of an unsaturated hydrocarbon and a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbonsintermediate said kerosene and said gaseous hydrocarbon fraction resulting from a net consumption of said kerosene and said normal butane.

12. A process of catalytically averaging hydrocarbons, which comprises reacting gas oil and a normally gaseous hydrocarbon fraction comprising a normally gaseous normal paraflinic hydrocarbon, in the presence of a liquid catalyst the inorganic ingredients of which comprise essentially liquid hydrogen fluoride in whichis dissolved not over 50 mol per cent of boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said gas oil and said gaseous hydrocarbon fraction resulting from a net consumption of said gas oil and said normally gaseous normal parafiinic hydrocarbon.

13. A process of catalytically averaging hydrocarbons, which comprises reacting a light hydrocarbon fraction comprising normal hydrocaricons of not over six carbon atoms and a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in said light fraction in a reaction zone in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the pridro'carbon phase, and'recycling the catalystphase to the averaging reactionKzon'e. i e V 7 14. A process of catalytically averaging hydrocarbons, which comprises reacting a light hydrocarbon fraction comprising normal hydrocarbons of not over six carbon atoms and a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in said light fraction in a reaction zone in the presence of a liquidcatalyst; said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said light and said heavier fractions from a net consumption of said light and said heavier fractions, separating the fluorides from the catalyst phase and recycling the separated fluorides to the averaging reaction zone.

15. A process of catalytically averaging hydrocarbons which comprises reacting a butane fraction and a heavier hydrocarbon fraction having at least six carbon atoms in a reaction zone in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said butane and said heavier fractions resulting from a net consumption of said butane and said heavier fractions, separating the fluorides from the catalyst phase, and recycling the separated fluorides to the averaging reaction zone.

16. A process of catalytically averaging hydrocarbons, which comprises reacting a light hydrocarbon fraction comprising normal hydrocarbons of not over six carbon atoms and a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in said light fraction in a reaction zone in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol percent of boron trifluoride as the primary inorganic catalytic ingredients, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said light and said heavier fractions from a net consumption of said light and said heavier fractions, separating the catalyst phase, fractionating the hydrocarbon phase and recycling any unreacted light hydrocarbon fraction to the averaging reaction zone.

1'7. A process of catalytically averaging hydrocarbons which comprises reacting a butane fraction and a heavier hydrocarbon fraction having at least six carbon atoms in a reaction zone in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride whichis dissolved less than 5011101 per cent and said heavier fractions resulting-from a net consumption of said butane and said heavier fractions, separating the hydrocarbons from the catalyst phase, fractionating the hydrocarbons and recycling the unreacted butane fraction to the averaging reaction zone.

18. A process of catalytically averaging hydrocarbons, which comprises reacting a light hydrocarbon fraction comprising normal hydrocarbons of not over six carbon atoms and a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in said light fraction in a reaction zone in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said light and said heavier fractions from a net consumption of said light and heavier fractions, separating the catalyst phase and the hydrocarbon phase, fractionating the hydrocarbon phase to separate a single wanted close boiling fraction, and recycling at least part of'the light and the heavier hydrocarbons to the averaging reaction zone.

19. A process of catalytically averaging hydro-- carbons which comprises mixing 1 to 6 mols of a light hydrocarbon fraction comprising normal hydrocarbons of not over six carbon atoms with 1 mol of a heavier hydrocarbon fraction comprising primarily hydrocarbons having at least two more carbon atoms than contained in the light fraction in a reaction zone in the presence of a liquid catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifluoride as the primary inorganic catalytic ingredients, and in the presence of a complex in said liquid catalyst phase formed by the action of the fluorides upon unsaturated hydrocarbons, and continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydrocarbons liquid and at a temperature and for a period of time while regulating the activity of the catalyst by adjusting the partial pressure of the boron trifluoride to produce hydrocarbons intermediate said light and said heavier fractions resulting from a net consumption of said normal 'hydrocarbons and said heavier hydrocarbons,

separating the hydrocarbon and. the catalyst phase, fractionating the hydrocarbons to sepa- 19 carbons, which comprises mixing 1 to 6' mols of abutane fraction containing normal butane with l molof a heavier hydrocarbon fraction higher than gasoline in a reaction zone in the presence of a liquid; catalyst, said catalyst comprising essentially liquid hydrogen fluoride in which is dissolved less than 50 mol per cent of boron trifiuoride as the primary inorganic catalytic ingredients, and in the presence of a complex in said liquid catalyst phase formed by the action of the fluoride upon unsaturated hydrocarbons, and

continuing the reaction under a pressure to maintain the hydrogen fluoride and the hydro-