BE545706A - - Google Patents

Description

       

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   The present invention relates to a novel solvent extraction process, using lactones, preferably butyrolactone, as a solvent for improving petroleum fractions. The present invention relates more particularly to the extraction of hydrocarbons and of hydrocarbon mixtures with a solvent consisting of butyrolactone. In one of its variants, the present invention is of particular utility in the treatment of gas oil fractions derived from a crude petroleum oil, so as to significantly improve.

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 ment the characteristics of the diesel with a view to a,. a * dvrûr: laughing catalytic cracking.

   The extraction process of the present invention is remarkable in that it provides a technique for the selective extraction of metal bushings. composed of condensed 4-ring aromatic compounds and nitrogen compounds normally present in pet3β oil fractions. high boiling point.

   In another variant of the p "¯.; '11:; ,,,; - invention, the selective solvent is used in the conception of aromatic and / or olefinic hydrocarbons from r ire Paraffinic carbides, such as concentrations of aromatic hydro (: f: '' /"..::2, boiling in the range of motens fuels, from lower octane paraffinic mixtures. In another variation still, bytu rolactone is used as a selective solvent for the removal of aromatics, from kerosene, to improve the smoke point, while a further form of application of the present invention relates to the extraction. of diesel fuel to improve the cetane level.



   Significant efforts have recently been made in the petroleum refining field to increase the recovery of a catalytic feedstock from waste petiole oil fractions. Usually the feedstock to a catalytic cracking operation is a so-called diesel pull from crude oil which boils in the range of about 400 to 800 F or a little above. Portions of crude petroleum oil boiling above the boiling range of gas oil can be
 EMI2.2
 considered as residual petroleum fractions 1: '9 such residual fractions can be used zo.; - s ;: s yes these asphalt, fuel and other products i SC'L'; "3 relatively low economic value.

   It becomes), '. L'; :: ClI; ' } '1uent, interesting to provide means for successfully using portions of the residual fractions of eight b:' \, é "r as char-

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 catalytic cracking feed management.



   Attempts to use heavier crude oil fractions for catalytic cracking have heretofore been limited due to the presence of certain metallic soils in such heavy fractions. The higher boiling fractions of a crude oil contain significant portions of metallic contaminants, including compounds of nickel, vanadium and iron. Crude oil waste fractions generally contain these metallic soils in amounts of about 10 to 50 pounds of metallic soils per 1000 barrels.

   When attempting to separate the higher boiling point distillation fractions of a crude oil, some portion of these metallic soils is inherently and inevitably washed away in the distillation products. For example, in a distillation operation. vacuum distillation, in which a fraction of high boiling gas oil is separated from a crude oil, there will be about 0.5 to 10 pounds of metallic soils per 1000 barrels in the gas oil distillate in one case. particular. In this example, the gas oil distillate in question would have a boiling range of about 800 to 1100 F or more.



   Catalytic cracking operations are affected by the presence of metal soils and it is necessary to have some means to recover the high boiling point fractions of a crude oil, while removing the metal soils in question. The presence of these, especially nickel and / or vanadium, in a cracking operation. Catalytic king results in direct contamination of the catalyst by the metallic compound. Metal continues to build up on the catalyst during the life of the catalyst, resulting in serious deterioration of the catalytic properties of the catalyst.

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   One of the effects of this catalyst poisoning is to cause excessive production of hydrogen during catalytic cracking resulting in a change in the cracking characteristics of the catalyst. In the actual operations, the production of hydrogen has become so important, due to the intoxication of the catalyst, that it causes an operation or rupture of the gas compressors, due to the change in density of the gases, with for result in flooding of the light and fractionation installation. The problem of the contamination of the catalyst is, therefore, an urgent problem at present.



   The present invention, in one of these forms of application, is based on the discovery that lactones and in particular butyrolactones are remarkably effective in the selective removal of metallic soils, heavy feedstocks of food. oil. As a result, the use of butyrolactone allows for selective removal of metal soils. liques, which causes significant removal of such soils, catalytic cracking feedstocks with little loss in feedstock productions. It has also been found that lactones also exert an advantageous selective dissolving action towards other undesirable constituents normally present in the cracking feedstock.

   In particular, butyrolactone serves to remove condensed ring aromatics and nitrogen compounds, along with metallic soils, thereby significantly improving the cracking characteristics of the feedstock. .



   The mechanism by which a butyrolactone exerts these unusual dissolving properties is not known at this time. It seems probable, however, that the particular molecular structure of this compound establishes a colonic equilibrium between a hydrocarbon solubility and a dissolving power,

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 for the compounds listed, which is particularly suitable for the purposes of the invention. For example, butyrolactone has been shown to exert dissolving powers in the practice of the present invention totally distinct from those of other solvents which have been used, such as furfurale.



   At the same time, it is possible to use solvent modifiers with butyrolactone for particular applications. Such modifiers are chosen so as not to substantially affect the selective solvent of butyrolactone, while modifying somewhat its oil solubility characteristics. Solvent modifiers are of particular interest in allowing extraction with butyrolactone at above normal temperatures. Among the modifiers which can be used are water, aliphatic alcohols, acetic acid, and ethylenic glycol.

   Such compounds can be used in combination with butyrolactone in small amounts to provide a solvent composition in which the solvent modifiers are present in amounts less than about one-third of the total solvent composition.



   Solvent extractions, using a butyrolactone according to one application form of the present invention, can be carried out at temperatures in the wide range of from about 80 to 500 F. However, the selectivity properties of butyrolactone are not not critically affected by temperature, so it is generally preferable to operate at moderate temperatures selected to maintain the feedstock at a viscosity suitable for processing.



  Thus, a temperature of about 100 to 200 F is particularly interesting. Extraction can be carried out at any

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 any pressure selected from the wide range of about 15 to 750 pounds per square inch. Again, however, pressure is not particularly important in the practice of the invention, which allows the process to take place at atmospheric pressure, which is therefore normally preferred.



   The amount of solvent composition employed in the practice of the present invention will vary somewhat depending upon the feed to be treated and the degree of loading required. In general, however, the amount of solvent to be employed will be chosen from the range of 0.5 to 3 volumes of solvent per volume of oil to be treated. For most applications it is especially preferred to use about 1 volume of solvent per volume of oil to be treated.



   The solvent treatment process can be carried out by the usual solvent extraction techniques. Thus, as desired, one can use an operation providing for mixing and sedimentation in batches or a continuous operation and against the current. It is preferable, for example, to carry out the process by introducing the butyrolactone into an upper part of a treatment tower in order to circulate it downwards in countercurrent to the oil to be treated. , which is introduced near the bottom of the treatment tower. Stuffing elements, perforated trays, or other adjuvant contact means may be employed in this system. A raffinate phase consisting of oil. the processed and small portions of butyrolactone can be removed at the top of this tower.

   An extract phase, consisting primarily of butyrolactone with small amounts of constituents removed from the processed oil, can be removed from the bottom of the processing tower.



   The solvent can be recovered from the raffinate and extract phases by standard techniques.

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     Solvent extraction using butyrolactone is especially useful for improving catalytic cracking feedstocks. Such feedstocks can be defined as the gas oil fraction of a crude petroleum oil, boiling above the gasoline boiling range or above about 450 F.



   The final boiling point of this gas oil fraction can be as high as desired, ranging up to about 1050 F to 1300 F (equivalent atmospheric boiling point). It can be observed that the solvent extraction of a lubricating oil distillate boiling in the gas oil boiling range, as defined, is of particular interest. Using the process of the present invention, such solvent extraction serves to remove unwanted aromatics from lubricating oil so as to provide high yields of high quality lubricating oil.



   The invention is widely applicable to the extraction of gas oil boiling in the range of about 450 to 1300 F, and this form of application of the invention is of particular application to the portion of such fractions boiling in the hot water. -above of-. from about 900 F to 950 F. Such high boiling gas oil fractions are those in which the metallic soils are especially concentrated. For this reason, in preparing a catalytic cracking feedstock, it is especially preferable to separate the portion of the feedstock boiling above about 950 F and then subject this fraction to particular to the process of the present invention.



   The accompanying drawings illustrate a particular and preferred embodiment of the present invention, showing its application to the preparation of a catalytic cracking feedstock.

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   Referring to Figure 1, the numeral 1 @ is used to denote a fractionation system of the type usually used for the segregation of crude oil into fractions of different boilers. The fractionation system 1 may consist of a combination of a unified atmospheric distillation unit and a vacuum distillation unit, or may consist of other types of distillation plant which can supply the stored fractions to identify. The fractionation system is of the type allowing the segregation of a crude oil introduced through line 2 into products 3, 4, 5, 6 and 7.

   C4 and lighter gases can be removed at the top through line 3, and a fraction of naphtha can be removed as a by-product through line 4.



  A stream of light gas oil boiling in the range of about 450 to 950 F is preferably removed as a higher boiling side product through line 5. Finally, the side product having the highest d The boil, removed through line 6, is a heavy gas oil boiling in the range of about 950 to 1300 F. The residual heavy constituents of the oil are removed from the fractionation system through the gas line. lower removal 7.



   According to the present invention, the fraction of heavy gas oil from line 6, containing large portions of metallic soils, is subjected to solvent extraction in tower 8. The butyrolactone is introduced into the extraction system via line 9. to be brought into contact against the current to the heavy gas oil in the tower. The extraction can be carried out, for example, at a temperature of about 150 F, at atmospheric pressure and using about 1 volume of butyrolactone per volume of heavy gas oil.



   The raffinate phase consisting of the oil treated with small amounts of butyrolactone is removed at the top

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 from the extraction system 8 through line 10. The residual solvent can be removed from the treated oil in a separation or scrub zone 11, the separated butyrolactone being recycled through line 12 to line 9 The treated oil freed from the residual solvent is then sent via line 13 to the catalytic cracking system 14.



   The extract phase removed from the solvent extraction system $ 'through line 15 can also be sent to a solvent separation apparatus 16, which causes the removal of butyrolactone through upper line 17. An oil. extracted will be removed from the bottom of the device l6 by the pipe
18. This extracted oil can be mixed with a fuel oil or can be used as a source of chemicals or for other purposes.



   The treated oil from line 13 which is subjected to catalytic cracking has improved cracking characteristics due to the significant removal of metal soils. In addition, this oil has better cracking characteristics due to the removal of high molecular weight nitrogen compounds and condensed ring aromatics. This treated oil can be subjected to the usual catalytic cracking in zone 14. Thus the cracking can be of the fixed bed type, in suspension or moving or of the fluidized solids type. However, it is preferred to use the fluidized solids cracking process.



   The fluidized solids technique for cracking hydrocarbons provides for a reaction zone and a regeneration zone, used in conjunction with a fractionation zone. The reactor and the catalyst regenerator are or can be arranged at approximately the same level. The operation of the reaction zone and of the regeneration zone takes place as explained below.

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   An overflow or overflow system is provided in the regeneration zone at the desired level of catalyst. The catalyst overflows into a removal line which is preferably in the form of a U-shaped branch forming a seal, connecting the regeneration zone to the reaction zone. The feed stream introduced is usually preheated to a temperature on the order of about 500 to 650 F, by heat exchange with combustion gases from the regenerator, which are removed at the top of the regeneration zone. , or by heat exchange with cracked products. The preheated feed stream is then introduced into the reactor.

   The seal branch is usually sufficiently below the point of feed oil injection to prevent oil vapors from returning to the regenerator in normal jerks. Since there is no restriction in the overflow line from the regenerator, satisfactory catalyst circulation will occur as long as the level of catalyst in the reactor is slightly below the level of catalyst in the regenerator. when the containers are maintained at approximately the same pressure. Spent catalyst from the reactor passes through a second U-shaped, sealant branch which runs from the bottom of the reactor to the bottom of the regenerator.

   The catalyst flow rate is controlled by injecting a quantity of the air into the catalyst transfer line to the regenerator.



   The pressure in the regenerator to be adjusted to the desired level by a butterfly valve provided in the head line from the regenerator. Thus, the pressure in the regenerator can be adjusted to any desired level by a butterfly valve which can be controlled, if desired, by a differential pressure apparatus. If the pressure difference between the two receptacles is kept to a minimum, the branches forming the joints will prevent the passage of gas

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 from one container to another, in the event that the circulation of catalyst ceases in the branches.



   The reactor and regenerator can be designed for high speed operation, assuming linear surface gas speeds of about 2.5 to 4 feet per second. However, the surface velocity of the rising gases can vary from about 1 to 5 feet per second and more. Catalyst losses are minimized and practically prevented in the reactor by the use of multiple stages of cyclone separators. The regeneration zone is also equipped with cyclone separators. These usually include 2 or 3 or more floors.



   Distribution grids can be employed in the reaction and regeneration zones. The operating temperatures and pressures can vary appreciably depending on the feedstocks being processed and the products desired. Operating temperatures are, for example, on the order of about 800 to 1000 F, preferably about 850 to 950 F in the reaction zone. High pressures can be used but, in general, effective pressures of less than 100 pounds per square inch are used. We prefer effective pressures on the order of 1 to 30 pounds per square inch.



  Catalyst / oil ratios of about 3 to 10, preferably about 6 to bw by weight are used.



   The catalytic material used in the fluidized catalytic cracking operation are usual cracking catalysts. These catalysts are oxides of metals of Groups II, III, IV, and V of the Periodic Table. A preferred catalyst is silica-alumina, the weight in% of the alumina being on the order of about 5 to 20%. Another preferred catalyst is silica-magnesia with a weight percent magnesia of about 20-35%.

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   The size of the catalyst particles is usually less than about 200 microns. Usually at least 50% of the catalyst will have a micron size on the order of about 20 to 80. Under these conditions, with the surface velocity as given, a fluidized bed is maintained in which to exile. te, in the lower section of the reactor, a dense phase of catalyst, while a dispersed phase exists in the upper zone of the reactor.



   Included in the catalytic cracking system is a product fractionator, designed to separate gasoline and higher boiling fractions from the cracked product.



   In the particular embodiment of the invention, illustrated in FIG. 1, the heavy gas oil fraction is itself subjected to extraction with butyrolactone, so as to improve the cracking characteristics of the heavy gas oil. The light gas oil, removed from fractionation system 1 through line 5, can be sent directly to a catalytic cracking system 14. Or, on the other hand, some or all of this light oil can be extracted with the heavy gas oil in the extraction area. It is preferred to use a small portion of the light gas oil mixed with the heavy gas oil to reduce the viscosity of the gas oil to the desired point.



   The following examples illustrate the nature and utility of this form of application of the invention.



    EXAMPLE 1
Heavy gas oil having a 50% boiling point of 950 F and a final boiling point greater than 1100 F was subjected to the process of the present invention. This diesel contained 2.3 parts of nickel per thousand, and 0.2 part of vana @ ium per thousand before treatment. The oil was treated by batch extraction with butyrolactone in three treatments using 1 volume of butyrolactone per volume of oil.

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 in each treatment at a temperature of 180 F and at atmospheric pressure. Contacting by mechanical agitation for 5 minutes, followed by deposition for 5-10 minutes, was suitable for this batch type of extraction. Separation of the solvent from the refined product gave an 87% production of treated oil.

   This oil had a nickel concentration of only 0.25 parts per thousand and a zero concentration of vanadium. It can be seen from these results that the extraction process of the present invention is especially suitable for extensive removal of metallic soils, heavy gas oils, while giving high yields of treated oil. For comparison, it can be noted that in a similar extraction with phenol as a solvent, and with small additions of water to control the solubility of the oil, significantly poorer results were obtained. In this case, oil yields of only 72% were obtained for the same niqkel content. Extraction with furfuraldehyde up to 0.25 parts nickel per thousand gave only 77% oil.

   It can be seen, therefore, that butyrolactone is effective in reducing the nickel content of the treated oil to a very low concentration and that the yields of treated oil were much higher than those obtained when the treated oil. extraction was done with usual solvents, such as phenol or furfural.



    EXAMPLE 2
The heavy gas oil employed in Example 1 was contacted with a solvent of 90% butyrolactone and 10% water in a series of batch extractions at 1GO F. A comparison of oil yields to The same nickel content (0.25 to 1 part per thousand) shows the same selectivity as that which resulted from the use of a 100% solvent of butyrolactone.



    EXAMPLE 3
A butyrolactone extraction of the gas oil of Example 1 was carried out at 100 F, by diluting the heavy gas oil with

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 EMI14.1
 two volumes of a light hydrocarbon fraction ('..:, 7). Three batch extracts, followed by removal of the diluent, yielded 94% refined oil with a nickel content of 0.49 parts per thousand. This yield is 13% higher than that resulting from an extraction with phenol for the same nickel content.



    EXAMPLE 4
 EMI14.2
 In order to establish other properties, the solvent, of butyrolactone, a series of various hydrocarbon oils, containing nitrogen compounds, was extracted with butyrolactone. The feedstocks employed and the results of these extractions are summarized in Table I below.



   TABLE I
Extraction of oil containing nitrogen
 EMI14.3
 
<tb> Number <SEP> Tempe- <SEP> Raffinate
<tb>
 
 EMI14.4
 Extraction test, 7¯3 ïT 7 no 'Solvents oF IFende- Nu discon- F m% nt> ### tinues
 EMI14.5
 
<tb> A <SEP> ------ Oil <SEP> from <SEP> crude <SEP> <SEP> from <SEP> Colorado <SEP> 100
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 90% <SEP> of <SEP> butyrolactone
<tb>
 
 EMI14.6
 10 of water 1 95 85 1, 5.



  B ----- Shale oil partially Hydrogenated butyrolactone-¯-¯¯¯¯¯ 100 0.21 Butyrolactone 95 S5 0.03 C ----- Heavy gas oil from El Segundo -------- --- 100 $ 0.3 Butyrolactone 1 105 z; 3 $ 20 20
 EMI14.7
 
<tb> 90% <SEP> of <SEP> butyrolactone
<tb>
 
 EMI14.8
 i0tp of water 2 105 89 0.21
It will be observed from these results that butyrolactone exerted a selective dissolving action on nitrogen compounds.
 EMI14.9
 present in the various oils processed.

   As e> e ;;: x; ls of the significance of these results, it will be noted that the: r = .i dç t3on U heavy gas oil with butyrolactone gave a. Oil would go Se in yields of 83%, while achieving 85c of ornamental nickel soils, 100p of removal of vanadium impurities, and while dropping the concentration of nitrogen compounds from 0.38 to 0.20% .

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    EXAMPLE 5
In order to show the variety of dissolving properties of butyrolactone, a heavy catalytic cycle oil.
 EMI15.1
 boiling range in the range of about "7QU to} .00oF was treated with about 260% butyrolactone. It has recently been found that such heavy cycle oils boiling above the boiling range of heating oils and obtained from various feeds of mixed lubricating oils contain valuable amounts of high quality lubricating oil components. The catalytic cycle oil treatment was carried out in a batch contact apparatus at a temperature.
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 of ..00 "F and at atmospheric pressure.

   Figures showing the results of these experiments are given in the table. next .
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 XflJ3JjJiiAU XX
 EMI15.4
 
<tb> Extraction <SEP> to <SEP> multiple <SEP> batches <SEP> of a <SEP> oil <SEP> of <SEP> cycle
<tb> catalytic <SEP> heavy <SEP>
<tb> (Temperature <SEP>:

   <SEP> 200 F. <SEP> atmospheric pressure <SEP>)
<tb>
<tb>, ¯¯¯¯¯¯¯¯¯¯ Refinât¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
<tb> N <SEP>% <SEP> Vol.de <SEP> Rende- <SEP> Severity <SEP> VSO <SEP> Index <SEP> Constant
<tb>
 
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 extr, solvent ment, OAPI 100 F '10 F from Vis.-gr. total - '"" - "-'-" visco-
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<tb> weight <SEP> site
<tb>
<tb> Power supply <SEP> 0 <SEP> 100 <SEP> 17.0 <SEP> 103.3 <SEP> 38.8 <SEP> 59.1 <SEP> 0.926
<tb>
 
 EMI15.7
 ¯¯¯¯T¯¯¯¯¯.,., T¯¯., ¯¯¯¯3utyxolactoe as solvent ---------------- 1 100 57.7 33.1 71.3 37.1 127, ë $ 0 821
 EMI15.8
 
<tb> 2 <SEP> 165 <SEP> 42.5 <SEP> 35.6 <SEP> 69.8 <SEP> 37.2 <SEP> 141.2 <SEP> 0.806
<tb>
<tb> 3 <SEP> 216 <SEP> 39.9 <SEP> 37.5 <SEP> 69.8 <SEP> - <SEP> - <SEP> 0.795
<tb> 4 <SEP> 262 <SEP> 39.0 <SEP> 38.2 <SEP> 69.0 <SEP> 37.2 <SEP> 145.2 <SEP> 0,

  791
<tb>
 
 EMI15.9
 ------------------ 90% phenol as solvent ### -. # .- ##### 1 100 54.6 '25.0 58.2x 38, 1 93.0 0.870
 EMI15.10
 
<tb> 2 <SEP> 168 <SEP> 39.5 <SEP> 32.5 <SEP> 55.2 @ <SEP> 37.8 <SEP> 120.0 <SEP> 0.622
<tb>
<tb>
<tb> 216 <SEP> 34.5 <SEP> 35.9 <SEP> 53.1 @ <SEP> 37.4 <SEP> 136.0 <SEP> 0.803
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> 257 <SEP> 29.3 <SEP> 37.2 <SEP> 52.8 @ <SEP> 37.4 <SEP> 144.0 <SEP> 0.797
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> 130 <SEP> F.
<tb>
 

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   It will be seen from these results that the extraction with butyrolactone was carried out to effectively remove the undesirable constituents of the lubricating oil, so as to provide a lubricating oil of high quality and of a high viscosity index. In considering these results, it is particularly interesting to consider, by way of comparison, the extraction results obtained using phenol as an extractant. In this case, yields of lubricating oil of equivalent quality (viscosity index of 140) were obtained in amounts as low as 73% of those obtainable by the process of the present invention.

   The amount of butyrolactone required to produce a given improvement in viscosity index was much less than the amount of phenol required to achieve the same improvement. These requirements are given for comparison in the following table.



   TABLE III
 EMI16.1
 
<tb> <SEP> index of <SEP> viscosity <SEP>% <SEP> Vol. <SEP> of <SEP> solvent <SEP> required
<tb>
<tb> product <SEP> Butyrolactone <SEP> 90 <SEP> of <SEP> phenol
<tb>
<tb>
<tb>
<tb>
<tb> 59 <SEP> (power) <SEP> 0 <SEP> 0
<tb>
<tb>
<tb>
<tb> 100 <SEP> 45 <SEP> 100
<tb>
<tb>
<tb>
<tb> 115 <SEP> 70 <SEP> 140
<tb>
<tb>
<tb>
<tb> 130 <SEP> 105 <SEP> 190
<tb>
   It will be admitted from these results that the process of. The present invention is an interesting and multifaceted process for the improvement of boiling petroleum fractions in the gas oil boiling range.

   As described, the process is particularly interesting for the preparation of catalytic cracking feedstocks and for the manufacture of high quality lubricants.



   In another application form of the present invention, the selective lactone solvent, especially butyrolactone, is used in the concentration of hydrocarbons.

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 aromatics and / or olefins boiling in the boiling range of engine fuels. The high stability and high selectivity of this compound makes it particularly attractive for this use. As in the case where this solvent is used for gas oil extraction, it can be used in a relatively pure form or in admixture with other solubility modifiers.



   Thus, a mixture of aromatic and non-aromatic hydrocarbons can be extracted with the solvent at a temperature of the order of about 50 to 300 F and at pressures ranging from about atmospheric pressure up to. at 400 pounds. per square inch to form extract and raffinate phases.



   The extract phase comprises the aromatic and olefinic hydrocarbons dissolved in the solvent, while the raffinate phase comprises the non-aromatics.



   The use of -butyrolactone as a highly selective solvent is employed especially advantageously in catalytic reforming operations, in which straight and branched chain paraffins are catalytically converted in the presence of hydrogen and a. suitable catalyst, such as platinum or molybdenum-alumina, or other known agents, in a mixture containing aromatics. By this reforming, or a hydroforming phase, the octane number of the fuel is greatly increased.



   A device making it possible to carry out this operation is shown schematically in FIG. II. Virgin naphtha boiling in the range of about 200 to 325 F is sent through line 20 to a hydroforming apparatus 22 (octane number:
87.8). Hydrogen is fed through line 24. Reactor 22 is operated under customary reaction conditions. of
The effluent / hydroforming or hydroformate passes through line 26 to the distillation zone 28 in which the C4 and the material

 <Desc / Clms Page number 18>

 lighter are removed at the top through line 36 for use as needed.

   Fraction C5, taken as the side stream, is preferably separated before the solvent extraction phase, but is re-mixed with the extract via line 34. Hydroformate C6 and above is passed through the extract. Conducted 32 to the solvent extraction zone 30 where, as described above in connection with the extraction of gas oil fractions, the hydroformate is treated with [gamma] -butyrolactone. The raffinate from this process, which in the previous application form was the desired product, is preferably recycled, in the present application form, to the hydroforming stage through line 38. view of a new conversion into aromatics.

   The extract phase containing the recovered aromatics is then separated from the solvent by one of the methods or a combination of the methods described above for the heavier oils and is removed through line 40 and combined with C5 hydrocarbons separated previously, to form C5 gasoline and higher with a high octane number.



   The use of butyrolactone as an extractive gasoline solvent has been described in connection with catalytic reforming and hydroforming. Butyrolactone is also advantageously used in the extraction of thermally or catalytically cracked naphtha, in which large amounts of high octane olefins are formed. Butyrolactone has the remarkable advantage of being usable with feeds containing olefins, which heretofore could not be treated with common solvents, such as sulfur dioxide.



   The advantages of the present invention are readily apparent from the following illustrated examples.



  EXAMPLE VI
To show the highly selective nature of the

 <Desc / Clms Page number 19>

 lactone retort aromatics extractant, a mixture of 50% normal dtheptane and 50% toluene was prepared and extracted with butyrolactone and; -propiolactone. For comparison, similar extractions were carried out with diethylenic glycol which is a commercial solvent preferably used for this purpose. The extraction temperature was 80 F. These estimates of the value of the solvents were made; by discontinuous extraction. Butyrolactone shows a high selectivity, superior to that of glycol.

   In addition, the solvent capacity of β-butyrolac- tone is far superior, as shown in the following table.



   TABLE IV
 EMI19.1
 
<tb> Comparison <SEP> of <SEP> dissolving <SEP> capacities
<tb>
<tb>
<tb>
<tb> (Extractions <SEP> to <SEP> a single <SEP> <SEP> batch <SEP> with <SEP> of the <SEP> solvent <SEP> not <SEP> diluted; <SEP> re-
<tb>
<tb>
<tb>
<tb>
<tb> sultats <SEP> put <SEP> in <SEP> correlation)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>% <SEP> of <SEP> toluene <SEP> Solvent <SEP> required, <SEP>% <SEP> Vol.

   <SEP> by <SEP> report <SEP> to <SEP> l '& limen-
<tb>
<tb>
<tb> in <SEP> <SEP> tation of <SEP> toluene-heptane
<tb>
<tb>
<tb>
<tb> raffinate
<tb>
<tb>
<tb> product <SEP> Butyrolactone <SEP> @ -propiolactone <SEP> Glycol <SEP> di-
<tb>
<tb>
<tb>
<tb>
<tb> ¯¯¯¯ <SEP> thylenic
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 15 <SEP> 200 <SEP> 265 <SEP> 1500 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 25 <SEP> 110 <SEP> 150 <SEP> 640
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 35 <SEP> 55 <SEP> 80 <SEP> 260
<tb>
 
S-propiolactone also shows good selectivity, although with slightly lower solvent capacity.

   The very superior quality of these two lactones will be noted in the previous table, as we will also see in more detail in Table V.

 <Desc / Clms Page number 20>

 



  BOARD .
 EMI20.1
 
<tb>



  <SEP> evaluation of <SEP> solvents <SEP> for <SEP> a <SEP> extraction <SEP> of aromatics
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (extractions <SEP> by <SEP> batch <SEP> to <SEP> 80 F; <SEP> power supply <SEP>: <SEP>
<tb>
<tb>
<tb>
<tb> 50% <SEP> of <SEP> toluene <SEP> and <SEP> 50 <SEP> of heptane <SEP> in <SEP> volumes).
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  Report <SEP> Raffinate <SEP> - <SEP> Extract
<tb>
<tb>
<tb>
<tb>
<tb> Solvent <SEP> solvent / <SEP> conc. <SEP> Rendt., <SEP> Cone. <SEP> Rendt.,
<tb>
<tb>
<tb>
<tb>
<tb> oil <SEP> tolu- <SEP> @ <SEP> tolu-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (<SEP> extrac.) <SEP> iall, <SEP>% <SEP> Vol. <SEP> Vol. <SEP>% <SEP> Vol. <SEP> Vol.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  I.R. @@ <SEP>% <SEP> Vol. <SEP> Vol. <SEP> I.R. @@ <SEP>% <SEP> Vol. <SEP> Vol.
<tb>
<tb>
<tb>
<tb>
<tb>



  100% <SEP> of <SEP> B <SEP> (1) <SEP> l (IX) <SEP> 1.4128 <SEP> 26 <SEP> 52 <SEP> 1.4650 <SEP> 74 <SEP> 48
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> B <SEP> 2 <SEP> (IX) <SEP> 1.4025 <SEP> 15 <SEP> 37 <SEP> 1.4588 <SEP> 70 <SEP> 63
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> B <SEP> 2 (IX) <SEP> 1.4030 <SEP> 15 <SEP> 40 <SEP> 1.4610 <SEP> 71 <SEP> 60
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 95% <SEP> of <SEP> B <SEP> 2 (IX) <SEP> 1.4078 <SEP> 20 <SEP> 52 <SEP> 1.4706 <SEP> 81 <SEP> 48
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 85% <SEP> of <SEP> B <SEP> 2 (IX) <SEP> 1.4180 <SEP> 30 <SEP> 68 <SEP> 1.4797 <SEP> 89 <SEP> 32
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 75% <SEP> of <SEP> B <SEP> 2 (IX) <SEP> 1.4261 <SEP> 38 <SEP> 79 <SEP> 1,

  4837 <SEP> 93 <SEP> 21
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> ss-P <SEP> (2) <SEP> l (IX) <SEP> 1.4061 <SEP> 20 <SEP> 50 <SEP> 1.4680 <SEP > 79 <SEP> 50
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> G. <SEP> D <SEP> (3) <SEP> 2 (IX) <SEP> 1.4270 <SEP> 39 <SEP> 80 <SEP> 1, 4808 <SEP> 90 <SEP> 20
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> G.D <SEP> 4 (IX) <SEP> 1.4184 <SEP> 30 <SEP> 67 <SEP> 1.4770 <SEP> 87 <SEP> 33
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100% <SEP> of <SEP> G.D <SEP> 8 (IX) <SEP> 1.4096 <SEP> 23 <SEP> 53 <SEP> 1.4700 <SEP> 80 <SEP> 47
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 90% <SEP> of <SEP> G.D <SEP> 2 (IX) <SEP> 1.4325 <SEP> 44 <SEP> 89 <SEP> 1.4848 <SEP> 94 <SEP> 11
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 85% <SEP> of <SEP> G.D <SEP> 2 (IX) <SEP> 1.4338 <SEP> 45 <SEP> 91 <SEP> 1,

  4807 <SEP> 90 <SEP> 9
<tb>
 : dilution with water **: refractive index at 26 C (1) Butyrolactone (3) Diethylenic glycol (2) ss-propiolactone
EXAMPLE VII
A hydroformate with a Research octane number of 87.8 was released from its pentane, and the hydrocarbon fraction C6 and higher (Research octane number: 89.8) was extracted in a continuous phase extraction apparatus. multiple. Water injection was used to control the solubility of the hydrocarbons.

   Comparative results obtained from the extraction of the hydroformate with butyrolactone and with ethylene glycol as solvents show that the most

 <Desc / Clms Page number 21>

 favorable aromatics and non-aromatics were obtained.
 EMI21.1
 Naked with Butyrolactone * The high dissolving capacity found in preliminary tests for laptone was also confirmed in continuous multi-phase extractions. Diethylene glycol is less selective and requires much higher solvent / oil ratios. A summary of these comparisons is given in the following table.
 EMI21.2
 



  Solvent Butyrqlactone Glycol ¯¯¯¯¯¯¯¯¯¯ #. 5.in C, 'ecl1 diethylenic,
 EMI21.3
 
<tb> Yield <SEP> of extract <SEP> to <SEP> 100 <SEP> of in-
<tb>
<tb> dice <SEP> of octane,
<tb>
 
 EMI21.4
 eii in Vc ,. d ycrctcarbons C and
 EMI21.5
 
<tb> superior <SEP> up to <SEP> extraction <SEP> 71 <SEP> 43
<tb>
<tb> solvent / oil <SEP> ratio
<tb> to <SEP> 50,> <SEP> from <SEP> Extract <SEP> <SEP> 1.5 <SEP> 7.5
<tb>
 
More detailed results obtained in these extractions are given in Table VI.

 <Desc / Clms Page number 22>

 
 EMI22.1
 
<tb>



  TABLE <SEP> VI
<tb>
<tb> Extraction <SEP> by <SEP> solvent <SEP> of a <SEP> hydroformate <SEP> of hydrocarbons <SEP> C6 <SEP> and
<tb> upper <SEP> in <SEP> a <SEP> device <SEP> of extraction <SEP> with <SEP> stages <SEP> multiple
<tb>
 
 EMI22.2
 'and at 80 F
 EMI22.3
 
<tb> Alimenta- <SEP> Glycol
<tb>
<tb>
<tb> <SEP> tion of hy- <SEP> Butyro- <SEP> diethylenic
<tb>
<tb>
<tb> Solvent <SEP> droformat <SEP> lactone
<tb>
<tb>
<tb> Solvent <SEP> to <SEP> the appliance
<tb>
<tb>
<tb> reil <SEP> from ex-
<tb>
 
 EMI22.4
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ tration ¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯
 EMI22.5
 
<tb>% <SEP> of addition <SEP> of water <SEP> 7.5 <SEP> 0 <SEP> 0
<tb>
<tb> Solvent / oil <SEP> ratio <SEP> 2 <SEP> 4 <SEP> 8
<tb> Extract
<tb>
 
 EMI22.6
 Yield,% Vol. 66 ..-. d3 - 5
 EMI22.7
 
<tb> Octane <SEP> number, <SEP> Res.

   <SEP> 100.6 <SEP> 101.2 <SEP> 99.6
<tb>
<tb> Index <SEP> of <SEP> refraction <SEP> '(26 C) <SEP> 1.4812 <SEP> 1.4 & 73 <SEP> 1.4850
<tb>
<tb>
<tb> Raffinate
<tb>
<tb> Yield, <SEP>% <SEP> Vol. <SEP> 34 <SEP> 67 <SEP> 48
<tb>
 
 EMI22.8
 Nato Index, Res.c1air, 9, $ 36.2 72.8 54.7
 EMI22.9
 
<tb> Refractive index <SEP> <SEP> (26 C) <SEP> 1.4535 <SEP> 1.3992 <SEP> 1.4366 <SEP> 1.4198
<tb>
<tb>
<tb>
<tb>
<tb> Severity, <SEP> API <SEP> 44.4 <SEP> 65.4 <SEP> 50.1 <SEP> 56.6
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Distillation <SEP> A.S.T.M.
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>



  Initial boiling point <SEP>,
<tb>
<tb>
<tb>
<tb> F <SEP> 207 <SEP> 205 <SEP> 206 <SEP> 209
<tb>
<tb>
<tb>
<tb>
<tb> 5% <SEP> removed <SEP> to <SEP>: <SEP> 220 <SEP> 216 <SEP> 221 <SEP> 223
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 10% <SEP> "<SEP>" <SEP> 225 <SEP> 219 <SEP> 228 <SEP> 229
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 20% <SEP> "<SEP>" <SEP> 233 <SEP> 224 <SEP> 236 <SEP> 234
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 30% <SEP> il <SEP> il <SEP> 240 <SEP> 228 <SEP> 242 <SEP> 240
<tb>
 
 EMI22.10
 40% "" 250 ii34 249 247
 EMI22.11
 
<tb> 50% <SEP> "<SEP> 258 <SEP> 239 <SEP> 257 <SEP> 253
<tb>
 
 EMI22.12
 60% tr 261 z46 267 262
 EMI22.13
 
<tb> 70% <SEP> "<SEP>" <SEP> 283 <SEP> 254 <SEP> 278 <SEP> 274
<tb>
 
 EMI22.14
 60% tif u 299 b6 292 288
 EMI22.15
 
<tb> 90% <SEP> "<SEP>" <SEP> 319 <SEP> 284 <SEP> 312 <SEP>.

   <SEP> 309 <SEP>
<tb>
 
 EMI22.16
 95% "1t 330 300 330 327 final boiling point, F 385 334 387 397
 EMI22.17
 
<tb> Recovery <SEP> 98.5 <SEP> 98.5 <SEP> 99 <SEP> 99
<tb> Residue <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP>
<tb>
 

 <Desc / Clms Page number 23>

 
EXAMPLE VIII
To show the highly selective nature of other [gamma] -lactones as solvents for aromatics, a mixture of 35% mesitylene and 65% normal decane was prepared and batch extracted with angelicalactone and with [ gamma] -valerolactone. A comparison is also made with levulinic acid which can be converted into these lactones.



  These estimates of the value of solvents were made at 80 F.



  The following Table VII and Figure 3 summarize the results of these estimations and show the superior dissolving properties of lactones compared to those of related acid when the extraction is carried out to obtain a raffinate of the same aromatic content. .



   In figure '), the percentage by volume of mesitylene in the raffinate is given on the ordinate, while the percentage of solvent by volume is given on the abscissa. The curve marked with small circles (upper curve) relates to levulinic acid, while the other curve relates to angelicalactone and [gamma] -valerolactone, the small triangles relating to angelicalactone, while the diamond refers to / -valerolactone.

 <Desc / Clms Page number 24>

 



  TABLE VII
 EMI24.1
 
<tb> Extraction <SEP> to <SEP> batch <SEP> single <SEP> with <SEP> of <SEP> solvent <SEP> not <SEP> diluted <SEP> (80 F)
<tb>
 
 EMI24.2
 (feed: 35110 of mesitylene and 65) f 'of normal decane; results correlated) Solvent required, ,, j in Vol. with respect to the hydrocarbon feed; dtaromatics in the raffinate Angelicalactone -valerolctone acid produces levulini ¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯ that
 EMI24.3
 
<tb> 17 <SEP> 150 <SEP> 150 <SEP> 600
<tb>
 
 EMI24.4
 25 85 ë5 250
 EMI24.5
 
<tb> Angelicalactone <SEP>: <SEP> CH3-C-CH
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> O <SEP> CH2
<tb>
<tb>
<tb>
<tb>
<tb> # <SEP> #
<tb>
<tb>
<tb> C
<tb>
<tb>
<tb> #
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> -Valerolactone <SEP>:

   <SEP> CH3-CH-CH2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> tt
<tb>
 
 EMI24.6
 0 "C ..- GHZ
 EMI24.7
 
<tb> n
<tb> 0
<tb>
 
 EMI24.8
 Levulinic acid: CHJCO (GH2) 2GOOH CLAIMS
1. The process of segregating petroleum oils into their relatively more aromatic constituents and into their relatively more paraffinic constituents, comprising contacting these petroleum oils with a lactone under conditions such as to form a phase. solvent extract and a raffinate phase, and separation of the respective phases.


    

Claims (1)

2. The process of claim 1 which comprises contacting such oils at a temperature of from about 80 to about 500 F with a lactone, and separating a treated oil. of 3. The process of claim 1 or / claim 2, wherein the lactone is [gamma] -butyolactone. 4. The process according to claim 1, when used to improve a hydroformate of naphtha prepared in <Desc / Clms Page number 25> a hydro.rming zone by bringing virgin naphtha vapors into contact with a gas containing hydrogen at high temperatures and pressures and a hydroforming catalyst, which comprises the separation of the C5 fraction from this hydroformate, the extraction of naphtha C6 and higher at a temperature of about 50 to 300 F with [gamma] -butyrolactone to form an extract phase and a raffinate phase, the separation of these phases. recovering the solvent; and recycling at least a portion of the raffinate to the hydroforming zone. 5. The process of claim 2 for the freshening of an oil boiling in the range of about 400 to 1300 F, which comprises contacting this oil with about 50 to 300% by volume of a lactone. , said oil constituting the gas oil fraction of a crude oil comprising constituents boiling above about 950 F. 6. The process of claim 1, wherein said lactone comprises solvent modifiers selected from the group consisting of water, water soluble alphatic alcohols, acetic acid and ethylenic glycol. 7. The process of claim 1 using about 100 to 300% by volume butyrolactone. 8. The process according to claim 1, comprising the stages of fractionation of a crude petroleum oil to obtain high-boiling gas oil constituents, in particular those of the boiling range of about 950 to 1300 F, from treatment of this high boiling point fraction with said butyrolactone, separation of a treated oil produced, and then catalytic cracking of this treated oil. 9. The process of claim 1 for the production of a high quality lubricating oil from boiling gas oil in the range of about 700 to 1100 F, which includes contacting. of this diesel with around 100 to 300 <Desc / Clms Page number 26> % butyrolactone volumes, and the separation of a refined oil of improved viscosity index. 10. The process as described above and illustrated by the examples.