JPS60166387A - Hydrofinishing process for catalytic dewaxed lubricating oil - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for hydrofinishing a catalytically hydrodewaxed lubricating oil feedstock by hydroisomerizing the residual wax content.

Catalytic dewaxing processes for hydrocarbon oils to reduce the temperature at which waxy hydrocarbons are separated are known processes and are described, for example, in The Oil and Gas Journal (t
he Oil a'and ()asJournal)
J (T9?!R, January 6th edition), page 69~
This is described on page 3. Many patents have also been issued describing catalytic dewaxing methods, such as U.S. Reissue Patent No.
g. J f 1 describes a catalytic membrane waxing process incorporating a ZSM-4 type zeolite and a catalyst containing hydrogenation/dehydrogenation components. ZSM again! The hydrogenation membrane waxing method for gas oil using type zeolite is described in US Patent No. 3.
9k 4/01. Mordenite catalysts containing metals from group ■ or group ■ of the periodic table are disclosed in US Patent No. Q/00. 0! r As described in Specification A, low viscosity index (V,
1. ) can be used to dewax the distillate. U.S. Patent No. 3. 7 1 g. / j The specification of No. 1 completely describes a method of performing mild solvent dewaxing to remove all of the high quality wax content from lubricating oil raw materials, followed by catalytic film waxing to the pour point specified in the specifications.

The catalytic membrane waxing operation may be followed by any other operational steps such as hydrodesulfurization and denitrification processes to improve the quality of the product. For example, U.S. Patent No. J. A A ff.
/ / No. J describes a complete method for carrying out a catalytic membrane waxing operation using a mordenite dewaxing catalyst followed by a catalytic hydrodesulfurization step over an alumina-based catalyst. U.S. Patent No. 7. t 9 II, 9, 7g specification is ZSM-! A method is described in which a hydromembrane waxing operation using a type catalyst is followed by a conventional hydrodesulfurization operation of the dewaxed intermediate product.

In catalytic membrane waxing processes using shape-selective catalysts such as zsu-, type zeolites, the waxy components, particularly 1cn-paraffins, are reduced by the zeolites to light gases such as 08 to 08C, and some that fall within the lubricating oil boiling point range. The heavier olefinic segment of the These olefinic fractions are combined and hydrogenated to improve the oxidative stability of the oil. The catalyst is CO MO / Al2
It is a medium hydrogenation catalyst such as the Os type. The color of the oil is also improved upon hydrofinishing.

The waxy components in bright stock in heavy lubricating oil category, %, include not only n-baraffins but also slightly branched baraffins and cyclono (roughins). Bright stock contains microcrystalline wax and contains so-called n-baraffins, while slightly branched baraffins and cyclono-(roughfins) contain so-called petrolatum wax (amorphous wax). Crystalline wax is cranked faster than petrolatum wax. As a result, even if enough microcrystalline wax is cranked to meet the pour point requirement 1, e.g. -7c, there is still some undecomposed petrolatum. A wax remains. This small amount of petrolatum wax does not compromise the pour point specification, but - Night Cloud Point ((,1NC) Test (ASTMD-,2 & 00-66)
) to reject the oil.

- Night cloud point test tests the final product oil at a specified pour point, e.g. -7C (,20F)! ;, j7): (10p)
This is done by placing the unit in a freezer set at a high temperature. If the sample oil remains clear and shiny, the sample oil passes the above test, but some oils, especially hydrodewaxed oils, develop a tinge due to the growth of wax crystals and fail the above test. will be failed. Wax crystal nuclei are generated o, o
The oil fails the overnight test as soon as it grows to a sufficient size of r~0.3 microns.

By greatly increasing the severity of the dewaxing reaction, the resulting product can pass the overnight cloud point (ONC) test. For example, by increasing the dewaxing temperature or decreasing the space velocity, the pour point of the product -2-s, ? U
(−t OF ) by decreasing to −/C(
All products can be produced that pass the ONC test of 30FI. However, this total lowering of the pour point leads to an increase in cost due to the severity of the reaction and especially a decrease in yield.

Therefore, without incurring the disadvantages of high severity dewaxing operations (ON
It would be desirable to develop a method for improving the quality of catalytic dewaxing products so as to pass the C test, and in particular to avoid all yield losses associated with the high severity treatments.

It has now been found that large amounts of hetrolatum wax can be converted to more soluble isomers by hydroisomerization under mild conditions with little loss in yield. Is the overnight cloud point (low cloud point temperature) significantly improved by this treatment? A product with a certain amount is obtained. Hydrofinished products are also characterized by improved oxidative stability and a relative absence of colored substances. Moreover, these improvements are obtained with minimal loss in final product oil yield.

Accordingly, the present invention provides a process for hydrofinishing catalytically dewaxed oils comprising isomerizing the residual wax content of the dewaxed oil over a hydroisomerization catalyst. The catalyst used in the present invention is a co-functional catalyst having both hydrogenation and acid activity. The acid functionality is provided by an amorphous material such as alumina-silica-alumina or more preferably by a crystalline zeolite. The hydrogenation component is a metal such as platinum, palladium, nickel, cobalt or molybdenum or a mixture of these metals.

Isomerization is performed under heating and pressure isomerization conditions, typically at a temperature of 20
0C~II! rOc (392F-491F), pressure kl
'a 't00~It, θ00 →(!rza~3 A, 2
A, psig) and 0.1. It is carried out in the presence of hydrogen at a liquid time intermediate rate 1j (LH8V) of IQ time-1.

The feedstock for the isomerization process of the present invention is typically a catalytically dewaxed oil with a boiling point range above the distillate range (3a3C(6so1r)1). This type of product has a low content of n-halaffins. A lubricating oil feedstock having all the characteristics, but also containing small amounts of residual oils of slightly branched paraffins and cycloparaffins, which give unacceptable results due to the NC test.These petrolatum The content of waxes is typically θ,!r~5% by weight of the oil (said product).
However, slightly higher or slightly lower contents are encountered depending on the nature of the feedstock for the dewaxing step and the conditions used for the dewaxing (catalyst severity).

The typical boiling point range of lubricating oil raw materials depends on the grade, but 31
1 SoC or higher.

The present invention is applicable to feedstocks other than lubricating oil feedstocks where a low wax content is desired in the final product and especially where a product that passes a test similar to ○NC is desired. The invention is therefore also applicable to catalytically derotated distillate range materials such as heating oils, jet fuels and diesel fuels.

Catalytically dewaxed oils can be processed using various catalytic membrane waxing methods such as U.S. Pat. A A &, / /, No. 7 and No. 1 At.
io, ost.

However, zsu-r, ZSM-/t, ZSM--2
It is particularly useful to use oils produced by dewaxing operations using shape-selective catalysts such as 7°ZSM-3,'- or ZSM-3g. Dewaxing processes using catalysts of this type are known, for example, in U.S. Reissue Patent No. 21139.
No. g, U.S. Patent No. 7. ? , t4/02 issue.

It is described in the specifications of Ilt. No. 131 and Ilt. 31g9 and No. 73g, respectively, and please refer to the above-mentioned patent specifications @ for details of the operation. Since this type of dewaxing process is always carried out in the presence of hydrogen, these processes are often called hydrogenated membrane waxing processes, and for this reason dewaxed oils are often used in catalytic membrane waxing processes or catalytic hydrogenated membrane waxing processes. It can be obtained from the method described as either. For convenience, the term "catalytic membrane waxing method" in this specification includes both the catalytic membrane waxing process and the catalytic hydrogenation membrane waxing process, so it is referred to as vr-(
Used for vl. When the hydrofinishing method of the present invention and the contact membrane waxing process are used in combination, the contact membrane waxing process can be applied to all specifications of the product, especially the pour point specification and the ONC.
There is no need to conduct the process under the harsh conditions that were previously necessary in order to pass the standard. This is because the process of the invention improves the quality of the product, especially the pour point and ONC performance and stability. But if desired, will it adversely affect catalyst performance? In order to remove the heterocyclic contaminants that affect the oil, the catalytically dewaxed oil may be completely hydrodesulfurized or denitrified before the hydrofinisosing step (according to the present invention). Hydrotreating steps of this type are described, for example, in U.S. Pat. Please refer to these specifications for details of these steps.

The catalyst used in the hydrofinishing method of the present invention is a hydroisomerization catalyst containing an acidic component and a hydrogenation←dehydrogenation component (hereinafter abbreviated as hydrogenation component for convenience); Normal Periodic World CIUPAC and U.S. National Standard rU,s, National Bureau
, of 5 standards) approved by Fischer M-Scientific Camba =
-(Fisher Scientific Compa.
ny) Catalog number! -702-7O of Group IB, Group IIB, Group VA, Group MA or Group ■A of the periodic table
metal or two or more metals.

The preferred hydrogenation component is a noble metal from Group IA of the Periodic Table, especially platinum, but other noble metals such as palladium, gold, silver, rhenium or rhodium can also be used. Combinations of noble metals such as platinum-rhenium, platinum-palladium, platinum-iridium or platinum-iridium-rhenium as well as the above-mentioned noble metals and non-precious metals (base metals), especially periodic ones such as cobalt, nickel, vanadium, tungsten, titanium and molybdenum. Combinations of Group MA and Group A Metals 1 Examples of important combinations include platinum-tungsten, platinum-nickel, or platinum-nickel-tungsten.

Base metal hydrogenation components can also be used, especially nickel, cobalt, molybdenum, tungsten, copper or zinc.

Base metal combinations such as cobalt-nickel, cobalt-molybdenum, nickel-tungsten, cobalt-nickel-tungsten or cobalt-nickel-titanium can also be used. More active noble metals such as platinum and palladium are usually preferred over less active base metals because the desired isomerization is favored by the residual hydrogenation activity of the catalyst.

The metals are incorporated into the catalyst by any suitable method such as impregnation onto zeolites or ion exchange. The metals can be incorporated in the form of complex cations or anions such as pt (NH,)4 or neutral complexes, and complex cations of the type pt (NH8)," can be incorporated on the zeolite. complex anions are also useful as impregnations into zeolites.

The amount of the hydrogenation-dehydrogenation component is suitably Q, Q/-10% by weight, usually 0.17 to 5% by weight, and of course this can vary depending on the nature of the component, with high activity noble metals such as platinum being replaced by low activity base metals. Less is better.

The acidic component zeolite may be a porous amorphous material such as acid clay, alumina or even silica-alumina, but porous crystalline zeolites are preferred. The crystalline zeolite catalyst used in the catalyst contains a three-dimensional lattice of 5104 tetrahedra bridged by covalent oxygen atoms.

The crystalline zeolite catalyst may also optionally contain other atoms in the lattice, in particular K AIO, aluminum in the form of tetrahedrons; the crystalline zeolite also has sufficient Contains complementary cations. Zeolites have a crystalline structure that allows control of entry into and exit from intracrystalline free space. This control, exerted by the crystal structure itself, depends on the form of the molecules that must or must not enter the internal structure of the zeolite, and also on the structure of the zeolite itself. The pores of zeolite are in the form of rings formed by the regular arrangement of tetrahedra that make up the anion skeleton structure of crystalline alumino2/licade, and the oxygen atom itself is connected to the silicon or aluminum atom in the center of the tetrahedron. are combined. A convenient measure of the degree of control that a zeolite gives to molecules of various sizes over their entry into the zeolite's internal structure is provided by the zeolite's control index: very restricted entry into the zeolite's internal structure and its internal structure. Zeolites with very limited emissions have a high control index value, and these types of zeolites usually have pores of small size. On the contrary, zeolites that have relatively free access to the internal structure of the zeolite have low control index values.
It is described in detail in the specification of AO14:l1g.

Reference is made to the above-referenced US patent specification for detailed methods for measuring control index as well as examples of control index for some representative zeolites. The control index is related to the crystal structure of the zeolite, but since it is measured by a test method that takes advantage of the ability of the zeolite to engage in cracking reactions, the control index is related to the zeolite's acid sites and acid functions. The sample used in the test is representative of the zeolite structure for determining the control index, as it is measured by a reaction that depends on the properties of the zeolite, and also contains the acid functionality necessary for the test. It is something you own. Of course, the acid functionality can be changed by methods including base exchange, steaming, or adjusting the silica/alumina ratio.

Naturally produced fauja stone, mordenite, zeolite
, large pore zeolites such as zeolite Y% Z8M-:10 and zeolite beta, small pore zeolites such as zeolite A and characterized by a control index / , / and a silica/alumina ratio of at least l co/l A variety of acidic zeolites can be used in the present invention, including zeolites. Control index /% / u and at least l co /
A zeolite with a silica/alumina ratio of l is ZSM-J
%ZSM-/ /, ZSM-/u, ZSM-J!
r and ZSM-3tf, the zeolites each contain U.S. Pat. ?
No. 79; same No. 3. t3! No. 449; Same No. 1A0
11. It is disclosed in the Oyumi issue and the specifications of the same issue, ottt and trrq. Among the zeolites, ZSM-,5-
is suitable.

The high silica content form of ZSM-// is European Patent Publication No. 11
40g9 and high silica-containing forms of ZSM-/- are described in European Patent Publication No. 131,30, respectively. For more information on zeolites and methods of making them, please refer to the above-cited patent.

The silica/alumina ratio described herein is the structural ratio, that is, the crystal skeleton structure ratio, that is, the SiO
, /AIO, is the tetrahedral ratio. This ratio may differ from the silica/alumina ratio determined by various physical and chemical methods. For example, the total chemical analysis may include aluminum present in the form of cations bound to acid sites on the zeolite, thereby resulting in a low silica/alumina ratio. Similarly, when this ratio is determined by thermogravimetric analysis of ammonia desorption (7GA), a low ammonia titration value is obtained because the aluminum cations prevent any ion exchange of ammonium ions to the acid sites. This difference becomes particularly troublesome when processes such as the dealumination process described below, which result in a zeolite structure free of ionic aluminum, are used. Therefore, care should be taken to accurately measure the silica/alumina ratio of the crystalline framework.

Large pore zeolites such as Zeolite I-Y, ZSM-:10 and Zeolite Beta are useful in the present invention.

Zeolites of this type usually have a control index of less than 1.

The zeolite may be used alone or with control index / , / p
, ? It has been found that the combinations Y and ZSM-3 are particularly good with the zeolite.

Zeolite Beta is US Patent No. 3.30 & 06? For details of zeolite beta and its preparation, please refer to the above-mentioned US patent specification.

When zeolites are prepared in the presence of organic cations, the prepared zeolites have no catalytic activity, probably because the intracrystalline free space is occupied by the organic cations of the zeolite-forming solution.

The zeolite is activated by heating for 1 hour at 5 lIoC in an inert atmosphere, followed by base exchange with an ammonium salt, followed by calcination for 1 hour with SOC in air. The presence of organic cations in the zeolite-forming solution is not absolutely necessary for the formation of zeolites, but appears to be advantageous for the formation of this particular type of zeolite.

Some naturally occurring zeolites can sometimes be converted to desired types of zeolites by various activation methods such as base exchange, steaming, alumina extraction and calcination and other treatments.

When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form by calcining the ammonium type intermediate, usually obtained by ammonium ion exchange.

Although hydrogen-type zeolites promote the reaction with good results, the zeolites may also be partially of the alkali metal type. However, type zeolites have low selectivity for α-picoline.

Zeorai)? It is desirable to mix it with other materials (matrix) that are resistant to the temperatures and other conditions used in the present invention.

The matrix includes synthetic or naturally occurring materials as well as inorganic materials consisting of seven or more types of clay, silica, and metal oxides. The latter may be naturally occurring or may be in the form of a gelatinous precipitate or a gel containing a mixture of silica and metal oxides.A0 naturally occurring clays may be complexed with zeolites, and the clays may be as mined. In raw form or in advance! Can be used after acid treatment or chemical modification. Also, zeolite is alumina,
Silica alumina, silica madanesia, silica zirconia, silica thoria, silica beryllia, silica
Titania and ternary compositions such as silica-alumina
The matrix may be in the form of a cogel, which can be composited with a porous matrix such as thoria, silica-alumina-zirconia, silica-alumina-magnesia or silica-magnesia-zirconia. The relative proportions of the zeolite component and the inorganic oxide gel matrix may vary depending on the zeolite content over a range of 7 to 99% by weight of the composite, and more commonly from 7 to 99% by weight of the composite. The matrix itself has acidic catalytic properties, contributing to the functionality of the catalyst. Zeolites can also be composited with amorphous catalysts or other porous materials such as alumina. ) Y and ZSM-, t
We have found that the combination of aluminum and alumina is particularly desirable.

Isomerization reactions are reactions that require a relatively low degree of acid functionality on the catalyst. For this reason, zeolites are those with very high silica/alumina ratios, which are less than 0.0 because the silica/alumina ratio is inversely proportional to the acid site density of the catalyst. Therefore, structural silica/alumina ratios of SO/l or higher are preferred; in fact, such ratios may be, for example, 100
//, ,200/I, ! r00/l, 100θ/
1 or more. Since zeolites are known to have acid-functionalized metals even at very high silica/alumina ratios of about 000/l, even ratios of θ00//l or higher are not intended. Ru.

If the selected zeolite can be produced by direct synthesis into the desired high silica content form, this is often the most convenient way to obtain the zeolite. For example, zeolite beta is covered by US Patent No. J, ? It is possible to directly synthesize the silica/alumina ratio/00 as described in detail in U.S. Pat. No. 0,069 and US Pat. It is well known.

On the other hand, zeolite Y can only be synthesized in a form with a silica/alumina ratio up to S/l;
Various techniques are used to remove alumina in the zeolite structure to obtain a higher silica content zeolite structure. A similar technique is used for mordenite, which in its natural form is directly synthesized and has a silica/alumina ratio of about 10//. Zeolite ZSM
-10 is silica/alumina ratio/l or more;
What is typical? Direct synthesis is possible within the range of //-/θ/l. The preparation method and properties of ZSM-10 are described in detail in U.S. Pat. No. 39'729tJ and U.S. Pat. Tai. Zeolite Z8M-J
O can also be treated by various methods to increase the overall silica/alumina ratio.

Control of the silica/alumina ratio of the zeolite in the as-synthesized form can be carried out by appropriate selection of the starting materials, the relative proportions of silica and alumina precursors in %, and relatively small amounts of alumina precursors can be used up to the limit of the synthesized product. The entire production of zeolite products with higher silica/alumina ratios. If a high silica/alumina ratio is desired and alternative syntheses that yield the desired high silica/alumina ratio are not available, other techniques such as those described below may be used to prepare the desired high silica-containing zeolite. can.

Many methods are known for increasing the total structural silica/alumina ratio of zeolites.

Many of these methods involve the removal of aluminum from the zeolite framework by appropriate chemicals at the ends of the zeolite. Many studies on the preparation of faujasites with low aluminum content have been previously carried out and are described in the book "Atopan 7th in Chemistry Series" by C.T.
/ (Advances in Chemistry
5eries A/Col)'s "Molecular Thieves (
Molecular 5ieves) J (American Chemical Society
It has been reviewed in the publication ``ciety''). A special method for the preparation of dealuminated zeolites is described below.
Further details of the method are described in the following references: Catalysis by Zeolite.
Zeolites) (International Symposium on Zeolites)
alSymposium on Zeolites,
Dealumination treatment of zeolite Y using silicon tetrachloride; Lyon / September 9-II, 9tO), published by Elsepia Scientific φ Publishing Corporation (TQGO), Amsterdam; US Patent No. , 4'l, 2. '7
? , S- and British Patent Nos. 1.03 to 7g (hydrolysis and removal of aluminum by chelation); British Patent No. 10 Allda 7 (acid extraction of aluminum); US Patent No. J, 49 J, , lt/No. 9 [Removal of aluminum by steaming and chelation]; US Patent No. J,! r? 4ggg No. C Removal of Aluminum by Steaming); US Patent No. 1A4? ,? ,
No. 733 C dealumination with silicon halides and silicon oxyhalides); US Pat.
zbtto Dede No. C acid extraction of aluminum); US Patent No. 'A 093. r No. 40 (dealumination treatment by salt treatment); U.S. Patent No. 3.93'l') 9/
No. (Aluminum removal using Or(II) solution);
U.S. Patent No. 3. ! No. 04400 (post-steaming chelation); U.S. Pat. If j
& 3 A/No. (removal of aluminum using acid);
West German Patent Application No. λ & / 0.74' 0
(Processing of zeolites using chlorine or chlorine-containing gases at high temperatures; Dutch Patent No. 7, AO Co. 21, 1)
No. 4 (acid extraction); Japanese Patent Application Publication J3-101003
No. (Treatment with EDTA or other substances for aluminum removal) and Journal of Catalysis Vol.

Convenient? For practical purposes, a preferred dealumination method for the preparation of high silica-containing zeolites for use in the present invention is acid extraction of aluminum from the zeolite by contacting the zeolite with an acid, preferably an inorganic acid such as hydrochloric acid. It's a method. In the case of zeolite beta, dealumination can be carried out easily and with minimal loss of crystallinity at ambient or slightly heated temperatures to produce a high silica form of zeolite beta with a silica/alumina ratio of at least 100//. A silica/alumina ratio of θ0// or even higher can be easily achieved.

High-silica forms of zeolite Y can be prepared by steaming of structural aluminum and/or acid extraction; It is necessary to change it to a new form. Methods for doing this are known and the most common form of acid-resistant zeolite (Y) is known as Ultrastable Y (USY). Ultrastable Y is described in U.S. Patent No. 2.293. /No. 9- and No. 3, Hiro Oλ de 9
Specification No. 6 and C.V.
McDaniel) and B.K. Maher (P.
K. Maher) Co-authored Monograph Molecular Thieves
5ieves) 1st El, p.
Chemical Engineering) London, 19611]. Please refer to these documents for details. In general, "ultra-stable" means high resistance to reduction in crystallinity due to high temperature and steam treatment, and R of less than 7% by weight, preferably less than 7%.
Y characterized by an O content (wherein R is Na, K or other alkali metal ion), a unit cell size of less than or equal to 4', jA, and a silica/alumina molar ratio of J, S/l to //or above. - type zeolide. Ultrastable forms of Y-type zeolides are obtained primarily by alkali metal ions and a substantial reduction in unit cell size. Ultrastable zeolites are identified both by smaller unit cells in their crystal structure and by low alkali metal content.

The ultra-stable form of Y-type zeolide is produced by continuous base exchange of Y-type zeolide with an aqueous solution of an ammonium salt such as ammonium nitrate until the alkali metal content of Y-type zeolide is reduced to less than 2% by weight. Can be prepared. Next, to produce ultrastable zeolite Y, the base-exchanged zeolite was heated to a temperature of saoc-g. oC for several hours, cooled and subjected to continuous base exchange with aqueous solutions of ammonium salts until the alkali metal content is reduced to below 7% by weight, then washed and again at temperature sg oC-toor; Ultra-stable zeolite (Y) can be obtained by using the claw arm. The ion exchange and heat treatment procedures substantially reduce the alkali metal content of the initial zeolite and also shrink the unit cell, which is believed to lead to the ultrastability of the resulting Y-type zeolide.

The ultrastable zeolite Y is then extracted with acid to obtain a high silica content form of the zeolite. Acid extraction is carried out in the same manner as described for zeolite beta above.

A method for increasing the silica/alumina ratio of zeolite Y by acid extraction is disclosed in the US Patent No. No. 07, No. J,
! ; 9 lQ g No. 8 and No. 3.1.9 < 099
It is stated in the specification of the No. Please refer to these patent specifications for the details.

Zeolite ZSM-CoO can be converted to a higher silica-containing form by methods similar to those used for zeolite Y. That is, the zeolite is first transformed into an ultrastable form and then dealuminated by acid extraction. Conversion to the ultrastable form is conveniently accomplished by the same procedure used to prepare ultrastable Y. That is, the zeolite is continuously base-exchanged to the ammonium type and converted to iron at a temperature usually above 70.00°C. j
[Calcination is carried out in a deep bed to prevent removal of gaseous products as recommended in the aforementioned Atopansis in Chemistry Series, Volume 1.] Ultra-stable ZSM-:IO
The acid extraction of is carried out similarly to the method for zeolite beta described above.

High silica forms of mordenite are described, for example, in U.S. Pat.
No. 1099 and the same No. J, j? Other dealumination techniques used for mordenite, carried out by acid extraction operations of the type described in US Pat.
It is disclosed in No. 1931/9 and the specification of the same No. a≠Dayukta J. Please refer to these patent specifications for details.

Another 7% of the zeolite used in the catalyst of the present invention
One property is the hydrocarbon sorption capacity of zeolites. The zeolite used in the catalyst of the present invention must have a hydrocarbon sorption capacity of n-hexane of at least 6% by weight SOC, preferably at least 6% by weight SOC. Hydrocarbon sorption capacity is soc.

Colo AAPa(2) in an inert carrier such as helium
Determined by measuring hydrocarbon sorption at a hydrocarbon pressure of 0 tm Hg).

Sorption tests are conveniently carried out by thermogravimetric analysis (TGA, ) using helium as carrier gas flowing over zeolites at SOC. The hydrocarbon of interest, e.g. n-hexane, is introduced into the gas stream adjusted to a hydrocarbon pressure of 20 tmHg and the hydrocarbon uptake, measured as the increase in weight of the zeolite, is recorded as a zeolite hydroisomerization catalyst. are usually used in the cationic form with the required acidity and stability under the reaction conditions used. Zeolites are at least partially in the hydrogen form, such as the H form of H28M-3, zeolite) Y, to provide the acid functionality necessary for isomerization, but they also contain other cations, especially alkaline earth metal cations. ions such as calcium and magnesium, and rare earth cations such as tf/tan,
Cation exchange with cerium, praseodymium and neodymium is used to control the proportion of cationized sites in the zeolite and thus the acidity. Rare earth forms of large pore zeolites zeolite X and zeolite) Y, namely RKX (rare earth exchanged zeolite
) are useful as well as alkaline earth metal types of ZSM-j type zeolites such as MgZSM-3.

The isomerization reaction requires both an acid function and a hydrogenation-dehydrogenation function in the catalyst, and in order to obtain the best performance, a catalyst with an appropriate balance between these two functions is required. ,
It is desirable to use more active hydrogenating components such as platinum and higher acidity components. Conversely, however, if the acidity component has a low acidity activity, it becomes possible to use a less active hydrogenation component such as nickel or nickel-tungsten.

The feedstock is isomerized over a hydroisomerization catalyst in the presence of hydrogen under warm and pressure isomerization conditions. The reaction temperature must be high enough to obtain sufficient isomerization activity, but low enough to reduce cracking activity to avoid loss of product yield. The reaction temperature is usually θ0C-1130C (392F-r Hiroko F)
, preferably 2!0C-3'15C (41:JF~707
p). When using catalysts with higher acidity,
Relatively low temperatures in the above range are usually used to minimize conversion to lower boiling range products, with kPα 3,300 to 1000 to 17000
ig). Space velocity is usually liquid hourly space velocity (LH8V) 0. / ~ / maintained within the range of 0 hours - 1. Typical hydrogen circulation speed is 30-700n
t/1 (: /Ig~J9JkoSCF/Bb1 (Standard cubic feet/Gare/X/)], Normal cooo~5oOn
t/4 (ttko3~Jg/OSCF/Bbl
). The hydrogen partial pressure is usually at least S of the total working pressure.
O%, more generally go~deO% of the total working pressure. Isomerization reactions produce products in the low boiling range, especially gases (C,~C
4) in a manner that minimizes conversion to 4). During the isomerization reaction, petrolatum wax (slightly branched paraffins and cycloparaffins of at least 70 carbon atoms, usually 016-C4O) is converted to more soluble branched chain isoparaffins at low temperatures. . Conversion to products in the lower boiling range is usually less than 70% by weight, and in good cases less than % by weight S, such as 1% Jai.

The present invention will be explained below with reference to examples. Unless otherwise specified, proportions and percentages are based on amounts.

Example/~Here Equipment: A laboratory continuous downflow reactor was used.

The reactor is equipped with a feed stock reservoir and pump, reactor temperature control and monitoring equipment, gas regulator, flow control equipment and pressure gauge. The product was discharged into a sample receiver via a globe loader that controlled the operating pressure. The quality product was collected in a dry ice cooling trap downstream of the sample receiver. The uncondensed gas first passes through a gas sampling device, then NaOH, before passing through the gas meter.
passed through the scrubber.

Operation start operation: The reactor was charged with catalyst/θcc. The catalyst was heated at 3.5% at H1 circulation rates and pressures similar to the experimental design described above.
Activation was achieved by passing hydrogen through for two hours at 70'C. After n hours of setting up the reaction, starting the charging of raw materials.

The operating conditions and catalysts used in the examples are shown in Table 1.

Sample preparation and test method: Collected oil products/cosC
Vacuum stripping was performed for 1 hour at /b, lea (0, OA; tmHg) to remove water and volatile fractions. Yields were calculated based on the final stripped product. The product! , 7 cr11A/filled into a vial with a screw cap and 1/2 to determine the degree of haze.
It was left in a freezer maintained at 76°C for 76 hours.

To clearly assess the haze of each oil product -
A set of standards were prepared. These are catalytic hydrogenated membrane waxed and then monosolvent dewaxed brightstocks (this material passed the ONC test) and hydrogenated membrane waxed brightstocks (this material failed the ONC test).
It is a kind of mixture with. /component is 0 with respect to other components
-100% of the mixture. The set of standards provides a full range of haze from 0 to 100%. Some dark coloration of the solvent-dewaxed oil was removed by passing it through a basic alumina column to make the kernel oil the same color as that of the hydrogenated membrane waxed bridestock before being used for standard preparation.
To score the clarity-haze of the product oil, the product oil and standard were filled into vials of the above dimensions and placed side by side in a -/C freezer for 76 hours. The clarity-haze of the product was then compared to a standard. A quality number corresponding to the 70 content of the solvent-dewaxed oil component in the specified standard was assigned to the oil sample to indicate the clarity of the product oil.

For example, a go number means that a particular oil sample has the same clarity as that of a standard containing 110% solvent-dewaxed oil.

The conditions used for the hydroisomerization and the results obtained are shown in Table 7 below. All experiments were carried out at a pressure of 1I030 kPa.
(Left 1fll! psig).

Chapter/Table A: pt/Al, O, (O, 3%Pt) B: p
'd/zeolite Y-H type C: l't/Mg zeolite beta/Al, O, (1
7,,7% PitSO%Mg Zeolite Beta/30%
Al, O,; Zeolite Beta SiO, /Al, O,:
/ 00: /)D,' p d/REY/Hz
SM-j /Alt Os (0-j 3%Pd;so
%REY//, t%HzSM-j, 8%Al, O,
) These results show that a high degree of improvement in the ONC test is achieved by the hydroisomerization operation with little loss of yield.

Claims (1)

[Scope of Claims] l A method for hydrofinishing a catalytic hydrogenated membrane wax hydrocarbon oil, characterized in that in η, the catalytic hydrogenation membrane wax hydrocarbon oil is hydroisomerized. Thing method. U. Hydroisomerizing a catalytic membrane wax hydrocarbon oil under hydroisomerization conditions to convert the petrolatum wax in the catalytic membrane wax hydrocarbon oil to more soluble components at low temperatures. The method described in EJ. 3. The method according to claim 2, wherein petrolatum wax containing slightly branched paraffins and cycloparaffins is converted into paraffins having more soluble branched chains. q Catalytic Hydrogenation The method according to claim 1, wherein the wax hydrocarbon oil is hydroisomerized by contacting it with a hydroisomerization catalyst containing an acidic component and a hydrogenation component. 9. The method according to claim 9, wherein the hydrogenation component comprises a metal component of group MA and group A of the periodic table. The method according to claim 1, wherein the acidic component comprises crystalline zeolite. 2. The method of claim 6, wherein the acidic component comprises a large pore zeolite having a control index of less than 1. 7. The method of claim 6, wherein the acidic component comprises a zeolite having a silica/alumina ratio of at least 1/1 and a control index of /-/2. The method according to claim 1, wherein the catalytic hydrogenated membrane wax hydrocarbon oil is a lubricating oil. IQ, catalytic hydrogenation membrane wax hydrocarbon oil at temperature 200'C
~aso'6. Pressure 1t00'kcr, n A-: 1s
2. The process according to claim 1, wherein the hydroisomerization is carried out at a space velocity of 0.000, f'a and 0.7-/OLH8V. /i The method according to claim 1, wherein the conversion rate of the catalytic hydrogenated membrane wax hydrocarbon oil to lower boiling point components is less than or equal to IQ% by weight. 8. The method according to claim 7, wherein the conversion rate of the catalytic hydrogenated membrane wax hydrocarbon oil to lower boiling point components is 5% by weight or less. i3. In the method for producing a lubricating oil with completely improved clarity and stability, (1) the hydrocarbon charge material is subjected to catalytic hydrogenation membrane waxing to remove all the waxy paraffinic components, and (11) the resulting catalytic hydrogenation membrane wax is contacting a hydrocarbon oil with a co-functional hydroisomerization catalyst under hydroisomerization conditions;
A method for producing lubricating oil characterized by hydroisomerizing residual wax components into more soluble components. /4f Claim 13, wherein the conversion rate of the catalytic hydrogenation membrane wax hydrocarbon oil to lower boiling point components is 3% by weight or less
The method described in section. /& The method according to claim 13, wherein the conversion rate of the catalytic hydrogenated membrane wax hydrocarbon oil to lower boiling point components is 3% by weight or less.