BE622010A - - Google Patents

Description

       

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    Manufacture of premium gasoline and diesel fuel * by hydrocracking refractory cycling oil.



   The present invention relates to cracking. It relates in particular to a process for converting refractory charges into high quality gasoline and diesel fuel.



   It is argued that the r # fracary cycling charges obtained by catalytic cracking only find relatively limited applications as such. 'They are sometimes recycled for cracking, but cracking is difficult due to the retractable nature of these products.

   These materials are also used to obtain diesel fuel and household fuel oil. These uses are not, however, advantageous because the cycling products are of relatively poor quality and must be subjected to other treatments before they can be used. .

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  In the hydroeracking operations described by exea-j, Pal @ # da "the deâ" dto US patents: tins 51-151 (1953) pie, in 1 * $ dMttahdes of US patents # 351,151 (1953) and 9yr 418,166 (1954), a fraction of rtlati # em64tr raé grade eye fuel is usually obtained. * The gasoline obtained during this operation, however, has a relatively low Octane Number.

   Therefore, it must be reformed to bring its octane number up to the value demanded by modern engines. Obviously it would be very desirable to obtain high octane gasoline and fuel oil having a high octane number. high decetane number in one operation and find a way to convert product $ '
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 of cycling refraetalres in useful products.



  It has now been discovered that refractory cyclane products can be converted into useful products by a relatively simple process and suitable for industrial performance.
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 the. It has been found that a refractory cycling feed can be made into gasolines having an octane number of at least 95 (Y-1 +) d3 TEPB) and has a diesel fuel having a cetane number of at least And excellent storage stability by contacting it with a catalyst containing a metal of the platinum or palladium series in the presence of hydrogen under carefully controlled conditions,
An object of the invention is to provide a method for converting refractory fillers into useful materials.

   Another object is to provide a process for producing high-grade gasoline and high quality diesel fuel in the same.
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 surgery. A particular object is to provide a process for converting refractory fillers in a single operation into gasoline
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 having an octane number of at least 95 (F-1 + 3 TEPb)

   and a diesel fuel having a cetane number of at least 35 and improved storage stability. Another more particular object is to provide a process for converting refractory cycling charges into high octane gasoline and high quality diesel fuel by contacting them, in the presence of hydrogen, with.

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 a catalyst containing a metal of the platinum or palladium series under carefully controlled conditions.



   Other objects and advantages of the present invention will emerge from the detailed description given below with reference to the drawings in which;
Fig. 1 is a diagram showing the relationship between the octane number "of leaded gasoline and the conversion, in volume percent, to products boiling at temperatures below about 410 F (210 C) obtained in contacting a typical refractory cydizing charge with a platinum-containing catalyst according to the process of the invention;

     
Fig. 2 graphically relates the cetane number of diesel fuel to the conversion by volume percent to products boiling at temperatures below about 410 * F (210 C) obtained by contacting a refractory cycling charge typical with a platinum-containing catalyst according to the process of the invention? and, Fig, 3 graphically relates the conversion by volume percent to products boiling at temperatures below about 410 F (210 C) and the temperature upon contact of a typical gas oil with a catalyst containing carbon. stage at two different space speeds, according to the process of the invention.



   In general, the invention provides a process for converting refractory fillers into gasoline having an octane rating, with lead of at least 95 and diesel fuel having a cetane number of at least 35 and improved stability. in storage, whereby a refractory charge is brought into contact with an initial boiling point of between approximately 300 and 500 F (149 and 260 ° C) and a final boiling point of between approximately 600 and 900 "F (316 and 482 C) and which contains at least 1% by weight sulfur, with a catalyst which comprises about 0.05% to 20% by weight, based on the catalyst, of at least one Metal selected from the group formed by metals having an atomic number from 44 to 46 inclusive,

   

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 40 76 z 78 inclusive, on an synthetic composite material formed by the solid oxides of at least two elements of groups IX4. IHN and IV of the periodic table of the elements, this composite material having an activity index of at least 25, in.prr $ ounce of hydrogen in quantities expressed by the molar ratio of hydrogen-hydrocarbon introduced varying between approximately 10 and 80, at an hourly liquid space velocity varied between about 0.25 and $ jumps a hydrogen pressure varying between about 500 pounds /
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 square inch (35 kg / cm) and 3000 deliver / square inch (210 icg / ea)

   with a manometer and at a temperature between about 600 çt OOOOP (316 and 4Z7 * C) j the temperature is chosen and the liquid hourly space quickly to maintain the degree of conversion into product?
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 boiling at temperatures below 4100? (210 * C) approximately between about 5 and 25 volume percent *
In the description and the claims, the held
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 .cutlyer.1on. is a general term designating the quantity of product boiling at temperature. less than about 410 F (210 "C) (recycling 100), gasoline or diesel fuel, obtained in the dice process.

     The conversion is expressed in percent by volume of the initial charge transformed in the process. The amount of boiled product
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 lant at temperatures below approximately 43O * F (2iq "c) is calculated by subtracting the percentage by volume of cycling charge (diesel fuel) from 100% $ i.e. from the initial volume of the charge,

   L $ expresolon "recycling 1009 is an abbreviation for this subtraction. As the cycling charge obtained in the process is an excellent diesel fuel * the conversion to diesel fuel is the% by volume of products boiling in temperatures.
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 greater than approximately 410 * P (ZIOOC). Dry gas "denotes methane, ethane, propane, ethylene and propylene obtained in the cracking process, expressed in percent by weight of the initial charge.
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 t1lo.

   Light naphtha is the product that boils between 125 and 170 * <f (52 and 77 * C) oar, Wnapht. heavy is the product stirring between 70 and 4109F (77 and 2100C) env1rQn..L'1adit de çéta4em, du

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 diesel fuel is a measure of its combustion qualities and
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 is unearthed by the process described in the appendix in Esla:! .. AS.



    D975-53T. The cracking activity of a carrier is expressed in teraes of percent by volume of a normal hydrocarbon feed cracked under conditions specified in the "Category A" test. This
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 test is described by Alexander and tlh1tnp in National Petroleum Nova 36, page R-537 (August 2, 1944) * The unit for evaluating the cracking activity of the material is called the "activity index" (IAA.) .



  The catalysts which can be used are those described
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 in U.S. Patent Applications Nos. 3 $ lt15l (1953) and nt 418,166 (1954). Briefly, these catalysts comprise about 0.05 to 20% by weight - based on the final catalyst, preferably 0.1 to 5% by weight of at least one metal of the platinum and pilla series -
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 said, that is, those which have atomic numbers from 44 to 6 inclusive and from 76 to 78 inclusive, deposited on materials
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 synthetic composites forced from two or more rrac tary oxides.

   The support is a synthetic composite material of two or more refractory oxides of the metals of the groups ttA, 8! IVA and IVB of the Periodic Table of the Elements CE, Chem. Ed. 2 & 409 (1937) J, These synthetic composite materials of refractory oxides should have an activity index of at least about 25. They may also contain halogens and other materials known to act as catalyst activators. cracking or small amounts of alkali metals added to adjust the activity index of the support.



  Non-limiting examples of the composite materials envisaged are
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 silica-alumina, silica-circonia, s11ica * glUM1nZ1rcone, alumina-boron oxide, silica-alumina-fluorine, etc. The preferred support is a synthetic composite of silica and alumina containing about 1% to 90% by weight of alumina. These synthetic composite materials of two or more refractory oxides can be prepared by any of the known catalyst preparation methods. Examples of preparation processes are given in the aforementioned patent applications.

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     The following example illustrates a process for preparing a platinum-containing catalyst suitable for the process of the invention.



  EXAMPLE 1 - A synthetic silica-alumina support containing 10% by weight of alumina is prepared by mixing an aqueous solution of sodium silicate (containing 158 g per liter of silica) with a
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 equal weight of an acidic aqueous solution of aluminum sulphate coiltto ning 39.4 g of A12 (so and 26.6 <of H 2 804 concentrated per liter. Ctt mixture of solutions drop by drop into an oil column where the hydrogel gels into perlas.

   The beaded hydrogel is soaked
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 in hot water (about 120 * F (49 * C)) for about 3 hours The sodium in the hydrogel is then removed by exchange using: an, aqueous solution of aluminum sulfate, 1, , 5 of A12 (80 4) 3 by weight% j7 containing a small amount (0.2% by weight) of ammonium sulfate. The hydrogel beads thus exchanged are washed with water.

   Then they are steam treated to superheat about 50,340 F (138-171 * C)) for about 3 hours and finally calcined at 4pfftt 1300 * F (704 * C) under a low partial voltage of water vapor for about 10 hours,
An aqueous solution of chloroplatinic acid is then sprayed onto a calcined support, the concentration of the solution being sufficient to introduce the desired amount of metal into the completed catalyst. The support thus impregnated is in *
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 then aged in a covered container at; 31 "F; (J: xC C) for 24 hours.

   The catalyst is heated to 4500F (232 ° C) in a nitrogen atmosphere then treated with hydrogen for 2 hours at .0P '(232 ° C) t Before use, it is activated in hydrogen for 2 hours at 900 *? (48260) approx. The catalyst thus prepared contains 0.53% platinum, by weight of the catalyst, and the silica-alumina support has an activity index of 46.



   The fillers used in the process of the invention are the so-called refractory materials, that is to say the fractions

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 hydrocarbons normally resistant to conventional cracking. The generally preferred charges are the refractory cycling charges which are obtained by conventional cracking of gas oils, for example by cracking in the presence of silica-alumina or clay catalysts. It is also possible, under certain circumstances, to use coker gas oils and thermal gas oils. Direct distillation gasoline, however, cannot be used.

   The feed should have an initial boiling point of approximately 300 to 500 F (149 and 260 * C) and a final boiling point of approximately 600 to 900 * F (316 and 482 * C). A preferred refractory cycling charge obtained by conventional cracking boils between about 400 and 700 F (204 and 371 ° C). It is essential for the process of the invention that the feed contains at least 1% sulfur by weight and preferably more.



   The process of the invention should be carried out at a liquid hourly space velocity varying between about 0.25 and 5, preferably between about 0.5 and 3. The quantity of hydrogen introduced must be sufficient to obtain the refining of diesel fuel.



  To avoid the reduction of the octane content of the naphtha produced, however, the amount of hydrogen cannot be too high. Consequently, the quantity of hydrogen introduced is expressed by the molar ratio of hydrogen: hydrocarbon feed, which should be between 10 and 40 approximately and preferably between 10 and 30 approximately. The temperature should be chosen according to the hourly liquid space velocity in order to maintain the degree of conversion of products boiling below about 410 ° F (210 C) between about 5 and 25 volume percent. These conditions emerge from the following example.



  EXAMPLE 2. -
The feed used in the tests described in this example is a refractory cycling feed obtained by cracking a refinery gas oil in a “thermofor” catalytic cracking apparatus in the presence of a silica-alumina catalyst.

   This cycling load has the following properties:

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 Doutt4 Àepozo z0 Dla è1U. tlon ASTM
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<tb> Boiling point <SEP> <SEP> initia <SEP> F <SEP> 419 <SEP> (215 C)
<tb>
<tb>
<tb>
<tb>
<tb>
 
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 50% *? 538 (283, * C) Final doibullitton point 'F 634 (3346c)
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<tb> Cutaneous <SEP> <SEP> index <SEP> 31.8
<tb>
<tb> $ addition, <SEP> weight <SEP> percent <SEP> 1.55
<tb>
   For a series of tests, this load is put in contact
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 with the catalyst described in Example 1, in the presence of hydrogen * Each * osai is run under a pressure of about 1000 pounds /
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 square inch (70 lIe # 2)

   with a Twiometer at an hourly space velocity Iiquid ': 1 J 1' f using a hydrogen t hydrocerbi4m 1 molar ratio of% Each test is performed at a different temperature. They appear in Table I.



  Urie Auttg par'de of the load is contacted with the c ... t1l7UUJ: describes 4ana * 9xeMpJLe 1 at a temperature of 76, ..., (407 ° C) using a liquid hourly space velocity of 2. The pressure and the hydrogen molar ratio:

   hydrocarbons are the mines that in the previous paragraph. Information for this test is given in Table I.
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 llsoa'4 1 2 4 V3HL Vif ",, 'ji Average catalyst temperature, 673, .712,! 745, 765N (356) (378) (396) (407) CQn \ l'1I: 1!" d ± l {(10049 *? (; 31'3-I'UO ;; :) 8.6 2.6 19.5 Convic rM (10 <00 "F (M- * 0" C) 8s6 2.1 '24e6 1985 W & hJte Cé-170aF (77 * 0), vol u ia our-citf 0.5 | 1.0 '1.8 3 Volume percent 10.6 14..4 z, 2 M, 5 Density APl 36 # 1 138.6 414 A0, $ Index 4 # oCtune CJ93 of TF.Pb) 97 <4 if95,, 5 93eo 94..2 Cw.rStI of cJc'laie, 41Q P # (2J.O'C *) t

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 AT THE WATER. 1.

   (pt4jbe>
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<tb> Test <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4
<tb>
 
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 Volume Percent 91> 4 87.9 75.4 80.5 Specific Gravity 6, API 3004 31.9 32.9 30.0 Dtaniline Point. * F (, le) 123.0 12501 123.6 U7.9 ( 506) 2.00.9 (47.72) Cetane number z0.2 42.0 42.3 38.9
Figs. 1, 2 and 3 are based on the figures in Table I. There Fig. 1 shows the relationship between the octane number, with lead, of gasoline and the conversion in percent by volume of products boiling at temperatures below about 410 F (210 * C) which one obtains in putting contacting the cycling feed with the platinum catalyst.

   It will be appreciated that at conversion rates greater than about 15 volume percent, the octane number drops below 95, when using the charge of the example. At conversion temperatures of less than 15 volume percent, the octane number increases inversely with the degree of conversion.
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 When other fillers are used, however, the maximum degree of conversion may be higher. Thus, in order to satisfy one of the conditions of the process of the invention, the rate of conversion should generally not exceed more than 25 volumes. percent according to the particular load.



   To. to ensure at the same time the production of a diesel fuel having a high cetane number, greater than 35 and preferably 37, the degree of conversion to gasoline in the process must be at least 5 volumes per- a hundred or so. This emerges from FIG. 2 which shows the relationship between the cetane number of diesel fuel and the percent conversion by volume of products boiling at temperatures below about 410 * F (2lO * C) which are obtained together with the gasoline, as shown in Fig. 1.

   Note that as the conversion rate increases,? cetane number rises above 35, for a conversion rate of about 3 Tolum percent and above 37 for a conversion rate of about

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 5 volume percent * Therefore, to simultaneously obtain gasoline with an octane number with lead of at least 95 and diesel fuel with a cetane number greater than 37, the degree of conversion in the process should be kept between 5 and 25 volumea percent approximately and preferably between 5 and 15 volum percent approximately *
In order to achieve the desired degree of conversion, a close correlation between liquid hourly space velocity and temperature must be established.

   This correlation is illustrated by the curves of FIG. 3. Curve 1 shows the relationship between temperature and degree of conversion to products boiling at temperatures below about 410 F (210 C) when the refractory cycling charge is contacted with the platinum-containing catalyst. at a space speed of 1. Curve 2 represents a similar relationship, but for a space speed of 2. Note that at the highest space speed, a temperature not exceeding 750 F (399 * C) can be used to keep the conversion rate below 15 volume percent. At the lower space speed (curve 1), the maximum temperature that can be used is approximately 720 F (382 * C).

   On the other hand, in order to maintain a conversion of at least 5% by volume, the temperature at the lower space speed should be at least about 625 ° F, (329 C).



   For other space velocities, the temperature-conversion relationships vary as shown in Fig. 3, with an increase or decrease in space speed. In general, therefore, the range of temperatures useful in establishing a relationship with space velocity to obtain favorable results from the process of the invention ranges from about 500 to 800 F (260 to 427 C), and preferably about 650 to 800 F (343 to 427 C).



  EXAMPLE 3. -
To show the storage stability of the products of the invention, the products of tests 1 to 4 of Example 2 are subjected to the following storage test:

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 . A 500 cc sample of the fuel being tested is placed in a convection oven maintained at 110 F (43 C) for 12 weeks. The sample is then filtered through a tared asbestos filter (Gooch crucible) to separate the insoluble matter. The weight of these materials in milligrams is the amount of sediment.



   Samples of the products of runs 1 to 4 are subjected to this test and compared to a typical fuel oil obtained from cracked distillation oil. The values obtained are shown in Table II.



   TABLE II
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<tb> Fuel <SEP> oil <SEP> from <SEP> Test <SEP> Test <SEP> Test <SEP> Test
<tb> distillation <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4
<tb> cracked
<tb>
<tb> Initial <SEP> color
<tb> N.P.A. <SEP> D-l <SEP> L-3 <SEP> D-2 <SEP> L / 2 <SEP> L-3 <SEP> L-4
<tb>
<tb> 12 <SEP> weeks. <SEP> 110 F
<tb> (43 C)
<tb>
<tb> Color <SEP> N.P.A. <SEP> L-5 <SEP> D-2 <SEP> D-2 <SEP> 1/2 <SEP> D / 2 <SEP> 1/2 <SEP> L-31/2
<tb> Sediment, <SEP> mg / liter <SEP> 243 <SEP> 26 <SEP> 39 <SEP> 37 <SEP> 43
<tb>
 
It appears from Table II that the fuel oils obtained by the process of the invention have excellent storage stability.



  The good storage stability and the high cetane number make these materials much superior to current eyelash fuel.



   -Although certain embodiments and details of execution have been described to illustrate the invention, it goes without saying that the latter is susceptible of numerous variations and modifications without departing from its scope.



  CLAIMS.

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Claims (1)

1.- Process for hydroracking refractory cycling charges originating from a conventional catalytic cracking and containing at least 1% by weight of sulfur, with a view to directly obtaining a gasoline having an octane content, with lead (3 cm3), of at least 95 without reforming and a diesel fuel having a cetane number of at least 35, characterized in that the re-cycling charge is brought into contact. <Desc / Clms Page number 12> fractional from conventional catalytic cracking and having a sulfur content of at least 1% by weight, an initial boiling point of between about 300 and 500 F (149 and 260 C) and a final boiling point of between approximately 600 and 900 F (316 and 482 C), with a catalyst comprising 0.05% to 20%, by weight of the catalyst of at least one metal selected from the group consisting of metals having atomic numbers from 44 to 46 inclusive and from 76 to 78 inclusive, deposited on a synthetic composite material formed by the solid oxides of at least two elements of groups IIA, IIIB and IV of the Periodic Table of the Elements, this composite material having an activity index of at least 25, in the presence of hydrogen in quantity * * expressed by the hydrogen molar ratio: hydrocarbons which is 10 to 40, at a liquid hourly space velocity of between about 0.25 and $ under a hydrogen pressure of between about 500 and 3000 psi (35 and 210 kg / cm) at a pressure gauge and at a Turkish temperature between about 600 and 900 F (316 and 482 C) while maintaining a relationship between temperature and space speed to ensure a degree of conversion into products boiling below 410 F (210 C) in the range of about 5 to 25 percent volume. Process according to Claim 1, characterized in that platinum is used as the metal in the catalyst, in an amount varying between 0.1 and 5%, the composite material having an activity index of at least 28.