DE1645737A1 - Improved Hydroisomerization Catalyst - Google Patents

Description

DR. EULE DR. BERG DIPL, -ING.

PATENTANWÄLTE 8 MÜNCHEN 2. HILBLESTRASSE 2O. f V Hf 5/3

Dr. Owl dr Berg Dipl.-Ing. Stopf, 8 Munich 2, Hilblestraße 20 Our sign 'date

Attorney File 16 631
Be / Sch -

Esso Research and Engineering Company, Elizabeth,

N, J. 0720.7 / USA

"Improved Hydrochlorination Catalyst"

This invention relates to an improved combination process in which a middle distillate is both isoranized and removed. In particular, this invention relates to a method for the simultaneous reduction of the ice and cloud points §, as well as for the desulfurization of

000862 / 200.8 -2-

Middle distillates. It can do this selectively with little. Side effects are caused by the middle distillate. Only slight changes in the properties, such as the specific gravity of the middle distillate, are found. This © results are achieved by dividing the middle distillate into two fractions, one low-boiling Fraction and a higher boiling fraction. the The higher-boiling fraction is then brought into contact with an acidic solid carrier, which is impregnated contains introduced or otherwise dispersed and reduced metal of group YIII. Optionally, the acidic carrier, which reduced that introduced by impregnation Metal of group YIII contains, eibenso oxides or Sulphides of mixtures of metals of group YIII and YIb, such as nickel * contain cobalt, tungsten and molybdenum, introduced by impregnationj * These metal sulfides can be used for Increase, the effectiveness of what is arranged on an acidic carrier Group YIII metal for hydroisomerization and Desulfurization of the middle distillates, which contain high amounts of sulfur, can be added. Such high amounts of sulfur are a poison to Group VIII metals such as platinum, especially when used alone

The high stick and exercise points of the various waxy middle distillate fractions are for use as diesel fuels ι heating oils, etc. »in different

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0098B2 / 2006

Locations of cold climates unsuitable because high floor and Cloud points with the content of normal paraffin waxes If such distillates are interrelated, a process for converting the normal paraffins into the corresponding branched isomers would be highly desirable. However, must the conversion of normal paraffins into their branched ones Isomers are made selectively. Waxy normal Paraffins are those which weigh C, - "be ^ start. When these long-chain normal paraffins are cracked into small pieces or fragments of intermediate sizes, the product would not meet the quality requirements because the specific weight and the boiling range (doho the molecular weight) of the distillate fraction must be maintained. A process that is essentially cracking Long paraffin chains would be complete for this purpose be unacceptable,

A variety of methods for lowering the pour point however, of middle distillates has heretofore been proposed do they bring limited overall success. One of the most widely used methods is one To add pour point depressant to the middle distillate «. It was found in the past that for the pour point depression only certain types of oils responding to them are suitable through additives and that the cloud points of all Distillates essentially through the pour point lowering

009052/2006 ~ ⁴ ~

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remains unaffected additively. Since the median temperature flow problems not-only with the pour point alone in Be-_ Stand drawing but it? with both the opacity and even with the sticking point, there is a need for one Procedure that would humiliate the two. The use of an Ötock depressant is not such a method.

Other methods were used as well. Under these Mention should be made of the use of a molecular sieve to separate the normal wax-containing paraffins from the middle distillates. This technique has had limited success but still poses several serious problems. Among these the sieve deactivation after repeated cycles, In addition, there is the problem of contamination, such as sulfur, which is absorbed on the normal paraffins and so contaminate the paraffins that they cannot be used without further processing. It is Of course, it is just as true that the selective physical removal of normal paraffins from waxy ones The upper boiling fraction would serve to reduce the specific gravity of the new mixture of a total distillate .so disadvantageous to influence that it becomes too unsatisfactory. In the similar way is urea adduction, in which the Waxy straight-chain paraffins form adducts with urea and then preferably from the upper boiling fraction

00985272006

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dea middle detail a & tfern% warden, just as unsatisfiedendo Like in. Case of the molecular aiebipjig. ti eat the use. the Urnatoff adducts of the removal of the heavy, langet figs normal. Paraffins, from the middle distillate and the is like. already mentioned above, not satisfactory. In addition, the conventional molecular sieving is required, and urinary adduction a careful and expensive Vex * - driving guide; compared to simple catalytic hydrolysis: the together, with the. Taestenendeii hydrodesulfurization to deposit before; to be fat

A method is therefore required that has a. Lowering the stick and! Rüfeungspunkte zum.'Ergebnis has "but does not affect elm on the weight of the apazifisoha Geaamtmitteldestillats. For this purpose, the isomerization of the horizontal aormilea paraffins was irorgesöheiti, but the sulfur present in the middle detachate constitutes an important problem. The metal catalysts of Srupie VIII which are diapered on acidic solids, such as Kiakel on silicon dioxide aluminum oxide, platinum ai | f aluminum oxide, are deactivated when used with normal sulfur en-slow materials because

I ·. ■■ '. ■

the. aktit-eja Hetallstelleii, which is a hyoration-dehydration; Perceive puncture activity, are converted into relatively inactive sulfide * It is generally accepted that a 'minimal hy ^ ration-hydration functional activity bti »ineis & -% Αν $ £ ίίαι Hydroiaömerittifiningskatalysator

is required * On the one hand, this can be necessary for the formation of olefinic intermediates which are suitable for entering into the ekeletal isomerization at the active acidic sites of the catalyst support and on the other hand to reduce the catalyst deactivation by coking in a hydrogen gas atmosphere. Therefore, the presence of sulfur in a middle distillate can cause severe deactivation in isomerization catalysts. Be these are also catalysts that are sulfur-tolerant. They include sulfides on metals of groups YIII and VIb ₁ which are deposited on acidic solids. Unfortunately, these catalysts, which are sulfur tolerant, tend to be inactive during normal paraffin hydroisomerization.

According to the invention, it has unexpectedly been found that the use of a single process satisfactorily enables the hydroisomerization of the waxy normal paraffins of a middle distillate * without the problem of severe catalyst deactivation. It has been found that when the middle distillate is divided into two fractions, a light-boiling fraction and a heavier, higher-boiling fraction, only the higher-boiling fraction requires a lowering of the stook point, because the lighter fraction prepares at temperatures from -20 ° to 20 ⁰ F (-29 ° -7 ⁰ C) is pourable or flowable,

009852/2006

the temperatures required in colder climates » The higher-boiling fraction can be mixed directly with an acidic '' like aluminum oxide, on which a precious metal is impregnated was to be brought into contact »These" precious metals are from group VIII of the periodic table and the most preferred precious metals are platinum and palladium. It is an important object of the present invention that no prior desulfurization is required before the heavy higher boiling stream is brought into contact with the isomerization catalyst. In a particular embodiment of the present invention it may be desirable to have the heavier stream up at a level of about 0.4 weight percent sulfur mild to desulfurize «This is the case with the present invention not essential, although it may be desirable down to a 0.4 weight percent sulfur level Treat with hydrogen because certain fuels stipulate this as a tolerable maximum sulfur content make necessary. In addition, this hydrogen treatment serves for a general purification of the starting material and can be desirable in this regard. It must be emphasized that the catalyst is the present invention operates successfully at sulfur levels found in the middle distillate stream available. Should be a hydrogen treatment stage may be required, one in the trade

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available Nalco Esso cobalt molybdate on Aluminiumoxidfcatalysator under typical Verfshrensbedi43.gungen of 600 ° to 75O ⁰ B ¹ (316 ^o to 599 ° G) temperature, 4-00 to 800 psig (29 to 57kg / ci3§ pressure, residence time between 0 , 5 and 2.0 v / h / v and hydrogen gas rates between 500 and 2000 SOE per barrel (14.16-56.64 nr) of oil being processed The low boiling fraction will in all likelihood not require a hydrogen refining treatment.

In a particular embodiment of this invention, the acidic carrier with a metal of Group VIII, such as Platinum or palladium and, in addition, with oxides or sulfides of other metals of Group VIII and VIb, such as Nickel, oobalt, molybdenum and tungsten. This way both stick and cloud point can be achieved of · the middle distillate can be lowered while at the same time the precious metal components slightly ahead of the sulfur poisoning caused deactivation can be protected. This will only be necessary in certain cases and it It must be emphasized that the noble metal, acidic supported catalyst works satisfactorily in all cases «

The acidic support can be any of a wide variety of catalyst supports be known to those skilled in the art. These are, for example, aluminum oxide, halogen-treated alurainium

ΟΟ'98 62 / ΐΦΟ *

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oxide, Silioiiimdioxiä-AliMinitu ^ oxiä, boron oxide-AluaniniiimQxid, such as wide-pore sieves such as molecular sieves of the type X and Y ₀ It should be noted that a molecular sieve orientation with pore sizes of 8 to 15 $ unit, is satisfactory. The acidic carrier can be either one or a combination of these above-mentioned materials as well as others for hydrois omerization; known acidic carriers. The catalysts can be prepared by impregnating the carrier by precipitating the catalyst components, by cation exchange in the form of crystalline zeolite carriers, by making intimate mixtures of two catalyst components or by combinations of these techniques, for example using mixtures of platinum supported on aluminum oxide with Mckel - Tungsten sulfide supported on silicon dioxide - 'aluminum oxide »Preferably, a Hiokelsulfld or Kiekel tungsten sulfide catalyst is impregnated on the acidic, solid support, for example aluminum oxide, with a platinum salt solution and, after drying, the platinum metal is reduced in a hydrogen atmosphere. In this way, precious metal sites are made available for normal paraffin dehydration. This is a preferred embodiment ₀

The catalyst used in the process according to the invention can be an acidic carrier that is a refractory oxide and a hydrogenation resistance part, the acidic carrier '

ΟΟΘ8Ε2 / 2008 '-to-

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may be of the "most similar" type in manufacture; catalytic agent is used for hydrocarbon conversion reactions xmd will contain hydroxyl groups distributed over the surface, the surface covering a fairly wide range, for example from about 50 to about 1000 square meters per gram. the · acidic! Interrogator / is a solid and can be made of different refractory oxides, high surface area are selected, these oxides of use are equivalent to the carrier thus designated as regards not necessarily in the preparation of these catalysts. for AEEN suitable acidic carriers include various substances, such as silica, alumina, titania, zirconia, zinc oxide, silica-alumina, silica-alumina-magnesia, silica-alumina-magnesia, ghrome-alumina, alumina-boron oxide, silica-zirconia, silica-alumina-zirconia, etc. d as well as various acidic carriers of different degrees of purity occurring in nature, such as bauxite, kaolin or clay (which may or may not have been acid-treated), diatomaceous earth such as kieselguhr, montmorillonite, spinels such as magnesium oxide-aluminum oxide spinels or zinc oxide spinels, etc. » Of the above refractory oxides, alumina is preferred, and Q-amma synthetically produced alumina having a high purity x11 is particularly preferred

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All of these "" carriers mentioned above, either synthetic manufactured or naturally occurring, contain both chemically bound as well as physically absorbed water. Various known methods such as drying and / or calcining can make the water content of these refractory Oxides are lowered or decreased while at the same time a surface can be developed, whereby the surface either as such or together with others Materials useful as contact for accelerating reactions such as catalyzed hydrocarbon conversion reactions is “It is known that excessive temperatures cause this Surfaces can destroy and they must therefore be avoided. When drying and / or galvanizing a suitable refractory oxide, such as alumina, is used initially physically absorbed water removed from it. Then, at even higher temperatures, the chemically linked ones begin Hydroxyl groups escape from the surface. This is achieved by joining the two hydroxyl groups, for example with the formation of a water molecule and a new oxide bond. In the case of aluminum oxide, this results in complete removal of chemically linked hydroxyl groups from the surface under the calcination conditions, the conversion of the aluminum oxide to the known anhydrous Alpha aluminum oxide, which acts as a catalyst carrier, is generally unsatisfactory or inert. These -

009852/2006 -12-

unsatisfactory or inert properties so far the small surface area, alpha aluminum oxide but it is now believed to be in addition to the. Loss of the chemically bound Hydroxyl groups related. While, therefore, as indicated above, many refractory oxides are used as carriers suitable for the catalysts of the process according to the invention these refractory oxides are characterized by the presence of chemically bound hydroxyl groups. The presence of such chemically bonded hydroxyl groups can be determined by treating these refractories Oxides after drying and / or calcining with anhydrous hydrogen chloride, which tends to have hydroxyl groups to react with elimination of water and replacement of the hydroxyl groups by chlorine atoms. It can then Chlorine content of such refractory oxides can easily be determined by known analytical methods »This chlorine content can then be addressed as equal to the hydroxyl equivalents on the surface of the refractory Oxides.

In those used in the method of the present invention Catalysts are composed of the acidic supports described above with a hydrogenation component. Suitable Hydrogenation components include metals from subgroup VIb and group VIII of the periodic table.

009852/2006 ~ ¹³ ~

borrowed chromium, molybdenum, tungsten, iron, cobalt, nickel, platinum, Palladium, ruthenium, rhodium, osmium and iridium. These metals are not necessarily considered hydrogenation components in the catalysts as used in the process of the present invention, equivalent and of of these metals, platinum and palladium and the latter are particularly preferred.

These hydrogenation components can be combined with the above-mentioned acidic carriers in any desired manner, such as by impregnation, reprecipitation, etc. The impregnation techniques are known as such and in such a process is a compound of the desired hydrogenation component, such as the platinum compound chloroplatinic acid, in a suitable solvent dissolved and the refractory oxide brought into contact with it, { subsequently dried and calcined. While synethetically prepared, high purity refractory oxides are used, it is sometimes desirable or preferable to precipitate the platinum group metal along with the refractory oxide. After such co-precipitation, the resulting preparation is dried and calcined. V / i θ already indicated above, of the metals that are combined with a refractory oxide, platinum and palladium are preferred, with platinum being particularly preferred. As previously described, it becomes 0098B2 / 2006

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the platinum group metal and refractory oxide preparation made by impregnation, precipitating, etc., then dried and calcined.This calcination is normally carried out under carefully controlled conditions to remove physically absorbed solvents such as water therefrom, but under sufficiently mild conditions Conditions so that the chemically bound hydroxyl groups are not completely excreted or lost. The Galcinierungstemperaturen in the range of about 35O ⁰ G to about 700 G ⁰ are usually satisfactory. As previously stated, the presence of the chemically bonded hydroxyl groups in these platinum group metal and refractory oxide preparations is a necessary precondition for the preparation of the catalytic agents intended for use in the process according to the invention »

Elevated temperatures and pressures can occur during the Hydrois omerization-hydrodesulfurization processes can be used. These serve to activate the catalyst prevent «dwell times and hydrogen circulation rate en can also be changed within wide ranges within the scope of the present invention.

The present one deals in more detail; Invention with the hydroisomerization of middle distillates, which as

009852/2006

Motor vehicle and marine diesel oils, domestic heating oils, light heating oils, etc. can be used. These middle distillates boiling between 300 ° and 800 ⁹ P (149 ° and 427 ° 0), preferably 350 ° and 75O ⁰ F (177 ° and 399 ⁰ O). They contain approximately 100 ppm to 3 percent by weight sulfur. Be in the Hegel

waxy middle distillates have a pour point between (-23 and 21 ⁰ C) (-20 ° to 24 ° ~ C)

-10 ° and 70 F / and a cloud point of / -5 to 75 F. The reason for this high pour point is the large number of G ^ ₇ plus normal paraffins contained in the putty distillate. The middle distillate treated by the process of the present invention will contain about 3 to 30 weight percent w / w plus normal paraffins. The specific gravity of the middle distillates to be treated according to the present invention will vary between 0.82 and 0.88; specific gravity below 0.81 are usually unsuitable for use as fuels. Particular middle distillates to be treated according to the process of the present invention are those derived from the following crude oils: Brega, Aramco, Safaniya, Iran, Kuwait, "Eastern Hediterranean Iraq", Louisiana-Mississippi and middle distillates from synthetic crude oil sources, for example Shale oil, tar sands or coal.

The middle distillate is separated into at least two components, a lighter fraction between 300 ° and 700 ⁰ F (149 ° and 371 ⁰ O) boils particular between 375 ° and

009852/2006

60O ⁰ F (190 and 316 ⁰ G), makes up from about 50 to 95 percent by weight, preferably 70 to 90 percent by weight of the total middle distillate. A heavier fraction with a boiling range between 500 and 800 ⁰ P (260 and 427 C), especially between 550 and 700 ⁰ F (288 and 371 ⁰ O), contains approximately 0.1 to 4 percent by weight of sulfur and represents 5

up to 50% by weight of middle distillate. “This sulfur content is unacceptable in contrast to that of the lighter fraction, which contains approximately 100 to 10,000 parts per million sulfur. The heavier fraction also contains between 50 and 95 $ 0> ₇ plus normal paraffins contained in the middle distillate.

Accordingly, the lighter fraction did not have to be subjected to the hydroisomerization process of the present invention. This means that the lower fraction already has the desired sulfur and pour point heights and that only the heavier fraction, which ^{boils between 500 and 800 ° F (260 and 427 0} O), is treated by hydroisomerization ß

Established via Yur-Eiisgeheiid, the acidic carrier for the hydroisomeri- -5isrimg üsT ^ r-sugte! Carrier is aluminum oxide or an AIu- ^ ίιώι ^ ί ^ νΙ ^ ο ^ ΙτΛΛ such as aluminum oxide with halogen promoter, SiIi v.iMTjdrl;>:; : li - i Ix ^ 'a / airimoxla, boron oxide-Al'aminiuisaxid, aluminum · » we * t: -: ° r? ry: -. ΐ ^ Λ γ; ^ϊ:; litiecher K-ristalloti'iiktur. "the Molecular SiSC; -c-UifL. J - :: - :: ■ BZ'uve carrier is then with a metal

^ 08852/2006 -17-

the 'group YIII impregnated, preferably with platinum or palladium. In a "preferred embodiment, in addition to platinum or palladium, the acidic carrier is also impregnated with oxides or sulfides of other metals from group VIII and TIb, such as cobalt, kickel, molybdenum and tungsten. This can be done according to known, conventional methods a

The separation of the feed material into an easy and The heavier boiling fraction is an important subject of the present invention. If desired, a mild one can be used Hydrotreatment of the heavier fraction take place, however, this will not be necessary, and it should additionally, if used, the threshold content no more than Be 0.4 percent by weight. As such, it goes without saying that the invention is equally satisfactory works with lower sulfur content, but it is desirable

Worth seeing to avoid extra spending to make this small Sulfur content to be obtained when the catalyst is in completely satisfactory catfish, in the presence of higher amounts of sulfur, works »

The solidification and cloud points of the hydrotreated higher boiling. Fraction are then reduced duroh iJl - Contact-bring with an acidic support on which one Precious metal catalyst was impregnated. Danaoh can do that

009852/2006 ~ ¹⁸ ~

treated heavier fraction with the untreated low-boiling fraction to be mixed again. The combined Fraction now has satisfactory stick and cloud points, specific gravity and sulphurous levels. In a particular embodiment, the higher boiling fraction is brought into contact with an acidic carrier which contains a noble metal and a Desulfurization type catalyst, satisfactory results are also obtained. Optionally, the entire middle distillate with the combined desulphurisation precious metal catalyst be treated without separation into lighter and heavier boiling fractions.

The desulfurization catalyst can also serve this purpose to enlarge the hydroisoric reaction. This can be done by distributing additional for the hydroisomerization process required metal points can be achieved. This would bring all of the middle distillate into contact with an acidic carrier with a noble metal impregnated therein in addition to the "desulfurization catalyst.

Hydrogen is released together with the middle distillate via the noble metal and desulfurization catalyst stored on an acidic carrier, containing the catalytic agent. The presence of hydrogen serves to To avoid coke formation, to initiate dehydration and in the formation of active chemical intermediates,

009852/2006

which are essential to the procedure to help. It has been found that the temperature above the catalyst is important. Satisfactory results have been achieved with temperatures in the range of 55 "~ * ds- ^s 1000 F (288 ° - 538 ° G). However, it is generally preferred to use temperatures of 800 ⁰ Jj ¹ (427 ° C) or higher. * In fact, superior results will be obtained with temperatures from 800 ⁰ P (427 ° C) up to about 1000 ⁰ F (538 ° 0) achieved. In addition, the specific weight of the middle distillate obtained is improved considerably at temperatures in the range of 800 ° to 1000 ⁰ F (427 ° to 538 ° C) above the Hyöroisomsrisierungszone. The pressure can vary between 50 and 1000 si, ( ^{4.5-71 I: r- / cm 2} ), preferably 200 to 800 psig '.15 57 kg / cm), the dwell time also changes in a wide range. A range from 0.2 to 10 Tol / StcL / Tel can be used, preferably from 5 to 10? Oil / StcL / ¹ FoI ₅ The water flow resistance can be between J0j väi & 15,000 bG3f per barrel (14.16 and 424.8 ιϊΡ) oil ^ scias-sln, preferably you can change awisciien 1000 iiaü. 10 OGv fcCF pr-c barrel (26.52 and 28J _f 2 m ^) Gl _i bescnclsra be ^ or-svi

the «; assei-material circulation between 2CQC mi-i.

rel ς56.64 and 283.2 al ⁵ ) oil.

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0098B2 / 2006

heavier fraction mixed again with the lighter fraction. The combined fractions now have a ütockpunkt from -20 ° to 30 ⁰ F (-29 ° to -1 ⁰ C) in contrast to -10 ° to 70 ⁰ F (-23 ° to 21 ° C), the output had the middle distillate. In addition, the specific gravity of the middle distillate now changes between 0.810 and 0.88 and is thus essentially the same as the specific gravity of 0.820 to 0.880 that it originally had. Furthermore, the cloud point of the Wittel distillate is now -15 ° to 35 ° ί ^Ί (-26 ° to 2 ° C) and is therefore a good comparison with the cloud point of -5 ° to 75 ⁰ F (-21 ° to 24 ⁰ C) it initially had.

In a specific embodiment of the present invention is a middle distillate having a boiling range between 375 ° and 685 ° F (192 ° and 363 ⁰ C), resulting the light tents-from a Arabia crude oil, into two fractions, a lighter and a heavier, separated. The middle distillate contains 4,000 to 7,000 parts per million sulfur prior to separation, which is an acceptable level in the present invention and no hydrotreatment is necessary. Additionally, the middle distillate contains from 7 to 10 wt # ⁰ ^ n ₊ normal paraffins, has a specific gravity of 0.8 to 0.9 and a cloud point of 5 ° to -15 ⁰ F (-15 ° to ⁰ C). The lighter fraction has a boiling point between 375 ° to 585 ° F (192 ° to 307 ⁰ C)

and forms 60 to 80 wt.% of the total middle distillate, üie 0 09 852/2006

has a pour point of -15 ° to -5O ⁰ F (-26 ° to -3 a cloud point of -20 ° to -JO ⁰ F (-29 ° to and contains 3 "000 to 4000 parts per million sulfur. They are these acceptable levels. The heavier fraction contains more than 11 000 parts per million of sulfur and has a pour point of 30 ° to 5O ⁰ F (-1 ° to 1O ⁰ O). As previously, it was unexpectedly found that successful working method iochwefelhöhen even in these The lighter fraction is stored for subsequent mixing. The heavier fraction is brought into contact with the hydroisomerization catalyst of the present invention. In this embodiment the hydroisomerization catalyst comprises an acidic carrier which is alumina, on which carrier is impregnated a platinum or palladium salt solution. the preparation of the catalyst may change in a wide range. Approximately 0.1 to 1.0 wt.% platinum or palladium on the carrier absorbier t.

The heavier fraction is passed over the hydroisomerization catalyst at a rate or residence time of 0.5 to 10 vol / hour / vol and a hydrogen flow rate of 1000 to 10,000 SGF per barrel (28.32 to 283.2 nr) Oil is used. The temperature above the hydroisomerization zone can be between 850 ° to 1GOG ⁰ F (454 ⁰ to 538 ⁰ G), preferably between 875 ° to 95O ⁰ F

; ⁰ : A. '-AQ ⁰ C) WvOUBwLu and the jJruck I: i vj; t Aryan C \) Γ P f ^: * ■' ^ '06

50 to 1000 psig (4.5 to 71 kg / cm). After this treatment, the heavier fraction of the lighter fraction is added together again. The combined middle distillate has now ⁰ F (-18 ⁰ O -29 °), a l'rübungspunkt of -1Ö ° to 2 ° F contains a pour point of -20 ° to O (-28 ° to -17 ° C) and essentially the same amount of sulfur. In addition, the specific gravity of the middle distillate is essentially the same as before the heavy fraction treatment. Dei? C / io, normal paraffin content of the middle distillate has now been reduced from 8.6 wt / o to approximately 3 to 6.5 wt%. The middle distillate is now for a colder climate.

example 1

In this example, a middle distillate was made from 1/3 tents, 2/3 "light Arabian" mixed crude with a boiling point

between 375 ° and 685 ⁰ F (191 ° and 363 ° C) treated according to the methods described herein. The middle distillate had a specific gravity of 0.832 and a sulfur content

oa.
of o.66 wt. ^. It contained 9 »6 wt. # C * o ₊ normal paraffins

and had a pour point of 10 ⁰ F (-12 ⁰ C) and an cloud point of 14 ⁰ F (-10 ⁰ O). The middle distillate was divided into two fractions, a lighter fraction which unge ferry 69 $ of the total middle distillate amounted with a boiling point between 375 ° and 585 ° F (191 ° and 307 ⁰ G) and a heavier fraction having a boiling point between 585 and

009852/2006 .- ,, ..

⁰ F (307 ° and 363 ⁰ G) which was approximately 31% by weight of the total middle distillate. The lighter fraction was approximately 4.7 barrels and the heavier fraction was approximately 2.0 barrels of the middle distillate.

The lighter fraction was stored and a sample of the heavier fraction was ^{hydrotreated under mild conditions at a temperature of 650 0} F (343 ⁰ O) J a pressure of 4 psig (29 kg / cm) over a Co-Mo / AlpO ^ catalyst, until a sulfur content of 0.4 wt. <p was obtained. Thereafter "the heavier fraction was brought into contact with a hydroisomerization catalyst.

The catalyst used was a commercially available ketjene platinum to alumina conversion catalyst. It contained 0.61 wt% Pt and 0.72 wt % Gl. The catalyst was made in the form of 1/8 "(3 * 1 mm) tablets, which in turn were made by grinding and tableting the chain-fed 1/16" (1.6 mm) extrudate. The initial extradate had a major

surface area of I72 m / g. The Ketgen catalysts were made by the chloroplatinic acid impregnation of gamma-alumina.

The heavier fraction was then over the platinum catalyst at a speed of 1.3 wt / od / wt (W / Hr. / W)

009852/2008 -24-

and a hydrogen circulation rate of 13,000 SCi? per barrel (368.16 m ^) middle distillate used. The temperature across the catalyst zone was 800 ⁰ F. (427 ⁰ C) and the pressure was 200 psig (15 kg / cm ^2). The results obtained are shown in Table I. As expected, the catalyst was noticeably deactivated by the high sulfur feedstock at 800 ⁰ E ¹ (427 ° C).

At the end of 30 dtunden the temperature (482 ⁰ C) was increased. The surprisingly high and stable activity achieved in this way is explained in Table II. It is therefore to work at about 900 ⁰ F (482 ⁰ C) is critical for useful activity sizes when a Beschiekungsmaterial is used with high öchwefelgehalt.

Table I. Liquid yield
(Wt. ^) hours of oil
Dispatch Product tests
Cloud point (F)
(° ü) Specific weight (10ü) (Feed) (42) (6) (0.851) 88 10-12 20 (-6) 0.856 88 12-14 24 (-4) 0.854 93 14-30 30 (-1) 0.851

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hours υΐ-
feed Cloud point F
(° C) ... Spe2 »wt. (6) (0.851) (Peed) (42) (-28) 0.870 33 * 36 -18 (-2?) 0.870 36-38 -16 0.868 38-54 -16

Table II

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Liquid yield

(100)

75 77 76

Tables I and II contain figures relating to the treatment of the heavier fraction. It can be seen that a significant lowering of the cloud point was achieved by working at 90O ⁰ P (482 ⁰ C). Remixing the heavier fraction, which was ^{treated at 900 0} F (482 ⁰ O) into the lighter fraction gave a middle distillate with a pour point of -20 ⁰ F (-29 ⁰ O) and a cloud point of -18 ⁰ F (-28 ⁰ G). It, this represents a substantial improvement over the Anfangsstock- and cloud points of 10 ⁰ F (-12 ⁰ O) and 14 ⁰ F (-10 ⁰ C). The specific weight of the middle distillate was now 0,830. On analysis it was found that the normal paraffins of C ^ ₇ only make up 3.4% by weight of the middle distillate compared to 9.6% by weight at the beginning. This demonstrates the success of the present process in reducing the pour and cloud points without affecting the other properties of the middle distillate. The re-mixing of the treated at 800 ⁰ F (427 ° C) fraction with the lighter fraction yielded a

009852/2006 -26-

Middle distillate with a pour point of O ⁰ F (-18 ° 0) and a cloud point of 4- ⁰ F (-16 ⁰ G). The specific gravity in this case was 0 _f 82? and the normal paraffins were $ 7.1 of the middle distillate.

Example 2

In this example, the same starting material was treated again, but not mild hydrogen treatment was carried out and the starting material, which was passed over the catalyst of the present invention, contained about 1.2 wt.% Sulfur. A temperature of 900 ⁰ I (482 ⁰ O) was used during the sulfur contact. It should be reiterated that no hydrotreatment took place prior to contacting the portion of the middle distillate with the catalyst of the present invention. Substantially the same results as in Example 1 were obtained. Pour point is now -2O ⁰ I ¹ (-29 ⁰ O) and the cloud point of -18 ⁰ F (-28 ⁰ O) .in comparison to an output pour point of 10 ⁰ F (-12 ⁰ O) and an output cloud point of 14 ⁰ F (-10 ⁰ O). The specific weight is now 0,830 and there were about 3 »4 wt. # ^ An, normal paraffins present.

009862/2006

Claims (1)

Patent claims: J Procedure for lowering the dock and cloud point of a middle distillate, characterized in that the middle distillate is divided into a lighter and a heavier fraction divides, the heavier fraction in the presence of hydrogen with a catalyst in contact, wherein the catalyst comprises an acidic support impregnated with a Group VIII metal, then the lighter one and remixing the heavier fraction after contacting the heavier fraction with the catalyst and thus a middle distillate with a significantly lowered pour point and cloud point is obtained. 2. The method according to claim 1, characterized in that the acidic carrier made of aluminum oxide, silicon dioxide-aluminum oxide, ßoroxid-aluminum oxide, halogen-treated aluminum oxide and / or large-pore molecular sieves. 5. The method according to claim 1 and 2, characterized in that the catalyst has a metal of group VIII impregnated acidic carrier and a desulfurizing agent. 4. The method according to any one of claims 1 to 3, characterized in that that the Group VIII metal is a noble metal. 009852/2006 5. The method according to any one of claims 3 and 4, characterized in that that the desulfurizing agent comprises oxides and sulfoxides of metals of Group VIII and / or VIB. 6. The method according to any one of claims 1 to 5, characterized in that that the acidic carrier is impregnated with 0.1 to 1.0 wt. # Platinum and / or palladium. 7. The method according to any one of claims 4 to 6, characterized in that the acidic carrier is impregnated with 0.1 to 1.0 wt. $ Platinum and / or palladium and 0.1 to 20 wt. % Desulfurizing agent namely the oxides and sulfoxides of metals of groups VIII and / or VIB. 8. A method according to any one of claims 1 to 7 characterized in that the lighter fraction is between 300 ° and 700 ° F (149 ° and 371 ° O) boils and 50 to 90 wt.% Makes up the middle distillate and heavier fraction between 500 ° and 800 ° F (260 ° and 427 ° C) and boiling is 10 to 50 wt.% of the middle distillate. 9. The method characterized according to one of claims 1 to 8, that the heavier fraction is treated with hydrogen in order to reduce the sulfur content to a maximum value of about 0.4 wt.% Before the heavier fraction subjected to the contact with the catalyst will, 0.098B2 / 2006 -29- 10. The method characterized according to one of claims 1 to 9, wherein said contacting at a temperature of at least about 900 ⁰ F (482 ⁰ G) and a pressure zwisehen 500 and 1000 psig (36 and 71 kg / cm) is performed. 11. The method according to claim 10, characterized in that A the bringing into contact is carried out at a temperature between 900 ° and 1000 ⁰ I ¹ (482 ° and 538 ° 0), a pressure between 500 and 1QQO psig (36 and 71 kg / cm) , a throughput rate or residence time of 0.5 to 10 vol / hour / vol (V./Hr./V.) and a hydrogen circulation rate between 1000 and 10,000 SGI ¹ (per barrel) (28.32 and 283.2 m ⁵ ) oil. 12. Procedure for lowering the pour point and cloud point of a middle distillate, characterized in that the " Contacting middle distillate in the presence of hydrogen with a catalyst, the catalyst comprising an acidic carrier impregnated with a Group VIII metal and a desulfurizing agent of oxides and sulfoxides of metals of Group VIII and / or VIB. 13 Process for lowering the pour point and the sulfur content of a middle distillate essentially as above described with special reference to the examples. . 009852/2006 j