CA1156588A - Catalytic dewaxing of hydrocarbon oils - Google Patents

Catalytic dewaxing of hydrocarbon oils

Info

Publication number
CA1156588A
CA1156588A CA000350630A CA350630A CA1156588A CA 1156588 A CA1156588 A CA 1156588A CA 000350630 A CA000350630 A CA 000350630A CA 350630 A CA350630 A CA 350630A CA 1156588 A CA1156588 A CA 1156588A
Authority
CA
Canada
Prior art keywords
oil
dewaxing
catalyst
oils
zsm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000350630A
Other languages
French (fr)
Inventor
Alan W. Peters
Emmerson Bowes
Thomas R. Stein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Application granted granted Critical
Publication of CA1156588A publication Critical patent/CA1156588A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium

Abstract

Abstract:

An improved process for catalytically dewaxing a hydrocarbon oil is disclosed. In this process the waxy oil is contacted in the presence of hydrogen with a dense zeolitic dewaxing catalyst associated with a nickel-tungsten hydrogenation component. The dewaxed oil has unexpectedly good stability and a low bromine number compared with oils processed with prior art catalyst. The process may be used to dewax crude oils, fuel oil fractions and lubricating oils.

Description

~ F-0137 Catalytic dewaxing of hydrocarbon oils This invention is concerned with a process for catalytically dewaxing a hydrocarbon oil. In particular, it is concerned with dewaxing a petroleum oil such as a whole crude, a reduced crude, or a distillate fraction thereof by contact with a zeolite catalyst exemplified by ZSM-5 associated with a nickel-tungsten hydrogenation component. It is further concerned with a process for manufacturing low pour point distillate fuels. It is still further concerned with a catalytic dewaxing process for manufacturing a high V.I.
distillate lubricating oil stock of low pour point and good stability. Products produced by the method of this invention need less severe or no hydrofinishing, or less amounts of stabilizing additives, since they are inherently of improved stability.
Catalytic dewaxing of hydrocarbon oils to reduce the tem-perature at which separation of waxy hydrocarbons occurs is a known process. A process of that nature developed by British Petroleum is described in The Oil and Gas Journal dated January 6, 1975, at pages 69-73. See also U.S. Patent 3,668,113, which describes dewaxing followed by hydro-finishing.

Reissue Patent 28,398 to Chen et al, reissued April 23, 1975, describes a process for catalytic dewaxing with a catalyst comprising a zeolite of the ZSM-5 type. A hydro-genation/dehydrogenation component may be present.

A process for dewaxing a gas oil is described in U.S. Patent 3,956,102 issued May 11, 1976.

A mordenite catalyst containing a Group VI or a Group VIII
metal is used to dewax a low V.I. distillate from a waxy ~k tl56588 crude, as described in U.S. Patent 4,110,056 issued July 11, 1978.

U.S. Patent 3,755,138 to Chen et al describes a process for mild solvent dewaxing to remove high quality wax from a lube stock, which is then catalytically dewaxed to specification -pour point.

The patents and publications cited above are illustrative of the dewaxing art as applied to various hydrocarbon oils, including crude petroleum.
.
Petroleum products generally are required to have some specified stability properties consistent with intended use.
This requirement is in addition to the requirement that the pour point or freeze point for certain oils be low enough to cause no flow problem. Thus, hydrocarbon oil products intended for use as jet fuel, lubricating oils, or as fuel oil, are sometimes treated with additives to improve oxidation stability, reduce deposit formation, or both. In other cases these oils are "hydrofinished" for the same reason. In still other cases both "hydrofinishing" and additives may be required to achieve the required stability.

Catalytic dewaxing followed by catalytic hydrofinishing is described in U.S. Patent 3,894,938 issued July 15, 1975.

As is evident from the foregoing references, problems as-sociated with waxy constituents in a hydrocarbon oil may occur with crude oil, jet fuel, home heating oil, and the distillate or residual fractions used to prepare lubricants.
The resistance to low temperatures required for each of these products depends on the type of exposure encountered.
For example, the permissible pour point of a crude to be transported by pipeline in Saudi Arabia may be considerably :
!

higher than that of a crude to be transported in Alaska.
Furthermore, a jet fuel is required not to separate waxy material at a temperature above about -40C (-40F), for example, while a pour point for the common home heating oil of about -6.7C (+20F) would be satisfactory in a temperate climate. As a result of this diversity of requirements, a number of specifications have been developed which apply to different products. Some of these specifications, and the method by which they are determined, include: Pour Point, determined by ASTM Standard D97; Cloud Point, ASTM D-2500;
Freeze Point, ASTM D-2836; and Cold Filter Plugging Point ~CFPP), DIN 51428, SIS-155122, and AFNOR 549 Standards.
Throughout this specification, it will be understood that - when the term Pour Point is used, the comparable Cloud Point, Freeze Point, or CFPP value may be substituted when appropriate.

Lubricating oils for use in automotive and aircraft engines must not vary too much in viscosity as temperature changes.
This requirement is in addition to the requirements for satisfactory pour point and stability. Since the present invention is useful in the preparation of high quality lubricating oils, a brief summary of this highly developed and complex art is now given.

Although the broad principles involved in refining of lubri-cating oils are qualitatively understood, the art is en-cumbered by quantitative uncertainties which require con-siderable resort to empiricism in practical refining.
Underlying these quantitative uncertainties is the complexity of the molecular constitution of lubricating oils. Because lubricating oils for the most part are based on petroleum fractions boiling above about 232C (450F), the molecular weight of the hydrocarbon constituents is high and these constituents display almost all conceivable structures and structure types. This complexity and its consequences are referred to in "Petroleum Refinery Engineering", by W.L.
Nelson, McGraw Hill Book Company, Inc., New York, N.Y., 1958 (Fourth Edition).
In general, the basic notion in lubricant refining is that a suitable crude oil, as shown by experience or by assay, contains a quantity of lubricant stock having a predetermined set of properties such as, for example, appropriate viscosity, oxidation stability, and maintenance of fluidity at low temperatures. The process of refining to isolate that lubricant stock consists of a set of subtractive unit op-erations which removes the unwanted components. The most important of these unit operations include distillation, solvent refining, and dewaxing, which basically are physical - separation processes in the sense that if all the separated fractions were recombined one would reconstitute the crude oil.

A refined lubricant stock may be used as such as a lubricant, or it may be blended with another refined lubricant stock having somewhat different properties. Or, the refined lubricant stock, prior to use as a lubricant, may be com~
pounded with one or more additives which function, for example, as antioxidants, extreme pressure additives, and V.I. improvers. As used herein, the term "stock", regardless whether or not the term is further qualified, will refer only to a hydrocarbon oil without additives. The term "raw stock" will be used herein to refer to a viscous distillate fraction of crude petroleum oil isolated by vacuum distil-lation of a reduced crude from atmospheric distillation, and before further processing, or its equivalent. The term "solvent-refined stock" will refer to an oil that has been solvent refined, for example with furfural. The term "dewaxed stock" will refer to an oil whlch has been treated by any method to remove or otherwise convert the wax contained therein and thereby reduce its pour point. The term "waxy", as used herein will refer to an oil of sufficient wax content to result in a pour point greater than -3.9C (+25F). The term "stock", wnen unqualified, will be used herein generi-cally to refer to the viscous fraction in any stage of refining, but in all cases free of additives.

The novel process of this invention is concerned with cata-lytic dewaxing of hydrocarbon feeds~ocks. The term "dewaxing"
as used in the specification and claims is used in its broadest sense and is intended to mean the conversion or removal of those hydrocarbons which readily solidify (waxes) from petroleum stocks.

Briefly, for the preparation of a high grade distillate lubricating oil stock, the current practice is to vacuum distill an atmospheric tower residuum from an appropriate crude oil as the first step. This step provides one or more raw stocks within the boiling range of about 232 to 566C
(450 to 1050F). After preparation of a raw stock of suitable boiling range, it is extracted with a solvent, e.g. furfural, phenol, or chlorex, which is selective for aromatic hydro-carbons, and which removes undesirable components. `The raffinate from solvent refining is then dewaxed, for example by admixing with a solvent such as a blend of methyl ethyl ketone and toluene. The mixture is chilled to induce crystal-lization of the paraffin waxes which are then separated from the dissolved oil, and the dewaxed raffinate is then recovered by removal of the solvent.

Other processes such as hydrofinishing or clay percolation may be used if needed to reduce the nitrogen and sulfur content or improve the color and stability of the lubricating oil stock. Bright stocks are often deasphalted, e.g. by treatment with propane.
, :, 1156~88 Viscosity Index (V.I.) is a quality parameter of considerable importance for distillate lubricating oils to be used in automotive engines and aircraft engines which are subject to wide varations in temperature. This Index is a series of numbers ranging from 0 to 100 or more which indicate the rate of change of viscosity with temperature. A viscosity index of 100 indicates an oil that does not tend to become viscous at low temperture or become thin at high temperatures.
Measurement of the kinematic viscosities of an oil at 40 and 100C, and referral to established correlations, provides a measure of the V.I. of the oil. For purposes of the present invention, whenever V.I. is referred to it is meant the V.I.
as determined by the ASTM Method D2270-77, published by ASTM, 1916 Race Street, Philadelphia 3, Pa., or equivalent, and accom'panying tables.

To prepare high V.I. automotive and aircraft oils the refiner usually selects a crude oil relatively rich in paraffinic hydrocarbons, since experience has shown that crudes poor in paraffins, such as those commonly termed "naphthene-base"
crudes yield little or no refined stock having a V.I. above about 40. Suitable stocks for high V.I. oils, however, also contain substantial quantities of waxes which result in solvent-refined lubricating oil stocks of high pour point, i.e. a pour point substantially greater than -3.9C (+25F).
Thus, in general, the refining of crude oil to prepare acceptable high V.I. distillate stocks ordinarily includes dewaxing to reduce the pour point to not greater than -3.9C
(+25F). The refiner, in this step, often produces saleable paraffin wax by-product, thus in part defraying the high cost of the dewaxing step.

Raw distillate lubricating oil stocks usually do not have a particularly high V.I. However, solvent-refining, as with furfural for example, in addition to removing unstable and `` 1156~88 sludge-forming components from the crude distillate, also removes components which adversely affect the V.I. Thus, a solvent refined stock prior to dewaxing usually has a V.I.
well in excess of specifications. Dewaxing, on the other hand, removes paraffins which have a V.I. of about 200, and thus reduces the V.I. of the dewaxed stock. Minimal loss of V.I. on dewaxing is desirable.

It has now been found that catalytic dewaxing of a hydrocarbon oil is advantageously done by contacting said oil and hydrogen with a dewaxing catalyst comprising a dense crystalline zeolite having an effective pore diameter greater than 5 Angstroms and having associated therewith, as more fully described hereinbelow, a nickel-tungsten hydrogenation component. The dewaxed product produced by the method of this invention is unexpectedly stable, ~.e. it is more resistant to oxidation or sludge formation or both. When the catalytic dewaxing method of this invention is applied in the refining of distillate lube oil stocks, this same improved stability and color is achieved and in addition the dewaxing may be effected with reduced loss of V.I.

In all cases, i.e. whether manufacturing high quality lubes or other products, the product produced by the method of this invention is surprisingly stable and requires less post-treatment by hydrofinishing, or lesser amount of ad-ditives, or both, to match the stability of prior-art cata-lytically dewaxed product. Thus, in a sense the process of this invention provides a combination of catalytic hydro-dewaxing and hydrotreating.

The catalyst use~ul in this invention comprises a dense crystalline zeolite having an effective pore diameter greater than 5 Angstroms and a nickel-tungsten hydrogenation component.
These components are intimately associated in a catalyst ... .

particle. Mordenite may be used as the crystalline zeolite.
The preferred crystalline zeolite is a member of a novel class of zeolites having a silica to alumina ratio of at least 12, and a Constraint Index of 1 to 12. By a dense zeolite we mean a zeolite that has a density in the dry ; hydrogen form of not substantially less than 1.6 grams per cubic centimeter. The catalyst contains about 0.7 to about 7 wt. ~ nickel and about 2.1 to about 21 wt.% tungsten, - expressed as metal, which functions as hydrogenation component. The zeolite and hydrogenation component may be dispersed in a matrix such as alumina or clay. A particularly preferred dense zeolite is ZSM-5 having a crystallite size of less than about 0.05 microns.

The preferred crystalline aluminosilicate zeolites utilized herein are members of a novel class of zeolites that exhibits unusual properties.

Briefly, the preferred type zeolites useful in this invention possess, in combination: a silica to alumina mole ratio of at least about 12; a dried crystal density of not less than about 1.6 grams per cubic centimeter and a constraint index of about 1 to about 12. Crystal density constraint index and the measurement thereof are described in U.S. 4,118,431.
An important characteristic of the crystal structure of this class of zeolites is that it provides constrained access to and egress from the intracrystalline free space by virtue of having an effective pore size intermediate between the small pore Linde A and the large pore Linde X.

Although zeolites with a silica to alumina ratio of at least 12 are useful, it is preferred to use zeolites having hiyher ratios of at least about 30. Such zeolites, after activation, acquire an intracrystalllne sorption capacity for normal !

hexane which is greater than that for water, i.e. they exhibit "hydrophobic" properties. It is believed that this hydrophobic character is advantageous in the present invention.

The class of zeolites defined herein is exemplified by ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35 and ZSM-38, defined respectively by the Xray diffraction data presented in U.S.
3,702,886, U.S. 3,709,979, U.S. 3,822,449, U.S. 4,076,842, U.S. 4,016,245 and U.S. 4,046,859. The preferred zeolite is ZSM-5.

In practicing the desired conversion process, it may be desirable to incorporate the above described crystalline aluminosilicate zeo].ite in another material resistant to the temperature and other conditions employed in the pro-cess. Such matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and/or metal oxides.

The nickel-tungsten hydrogenation component may be incorp-orated with catalyst by impregnation or by any other known means. Pellets of the hydrogen form zeolite, for example, may be impregnated with aqueous solutions of ammonium metatungstate and nickel nitrate to associate the zeolite with the hydrogenation component. The method by which the hydrogenation component is brought into association with the zeolite is not believed to be critical.

The dewaxing process preferably comprises contacting the hydrocarbon oil to be dewaxed and hydrogen with the above-described catalyst at a temperature of about 232 to 510C
(450 to 950F), a pressure of 446 to 20,785 kPa (50 to 3000 psig) and at a space velocity of 0.1 to 20 LHSV
(Liquid Hourly Space Velocity, i.e. volumes of oil per volume of catalyst per hour) to effect the desired reduction , .j 156~88 of pour point, freeze point, or other measure of wax content as required. The recovered dewaxed product is characterized by unusual stability, indicated by a low bromine number relative to such oil treated comparably with a prior-art catalyst. Bromine number, being a measure of unsaturation and reactivity, is believed also to be a good index of stability, higher numbers indicating;less resistance to oxidation, sludge formation, or both.

Any hydrocarbon oil, regardless of source, that boils above 177C (350F) and has an unacceptable content of waxy hydro-carbons such that its pour point is unacceptable, may be benefited by the process of this invention. Thus hydro-cracked oils, oils derived from coal or tar sands, and most particularly petroleum oils, may be treated to produce, for example, jet fuel, heating oil, diesel fuel, or even crude oil of reduced pour point.

The process of this invention is well-suited to producing high quality distillate lubricating oils from petroleum fractions. In the description which follows, particular reference will be made to the preparation of hydrocarbon lubricating oil stocks from suitable crude petroleum fractions.
Within this context, a suitable crude petroleum, for purposes of this invention, is one from which may be prepared (i.e.
contains) a dewaxed lubricating oil having a V.I. of at least about 85, and a pour point not greater than -3.9C
(+25F), by conventional methods of distillation, solvent refining and dewaxing. Also contemplated as within the scope of this invention for use as feed thereto is any hydrocarbon lubricating oil stock boiling within the range of from 232C (450F), and preferably from about 316C to about 566C (600F to about 1050F), and capable of yielding significant amounts of dewaxed lubricating oil having a V.I.
of at least about 85 and a pour point not greater than t - ~156588 1l -3.9C (+25F). Thus, hydrocracked petroleum oils having the foregoing characteristics are included within the scope of this invention, as well as are other processed heavy oils whether derived from tar sands, coal, or from other sources.
The boiling points herein referred to are boiliny points at atmospheric pressure, and may be determined by vacuum assay in the manner known to those skilled in the art.
. .
In a preferred embodiment of this invention, the raw stock hereinabove described is solvent refined by countercurrent extraction with at least an equaI volume (100 vol.~) of a selective solvent such as furfural. It is preferred to use 1.5 to 2.5 volumes of solvent per volume of oil. The raf-finate is subjected to catalytic dewaxing by mixing with hydrogen and contacting at 260C to about 399C (500F to about 750F) with the above-described catalyst. The catalytic dewaxing preferably is conducted at a liquid hourly space velocity (LHSV) of 0.1 to 5.0 volumes of charge oil per volume of catalyst per hour.
In some instances it may be desirable to partially dewax the solvent-refined stock by conventional solvent dewaxing techniques, say to a pour point from -6.7C to about +10C
(20F to about 50F), and preferably to a pour point greater than about -3.9C (+25F), prior to catalytic dewaxing. The higher melting point waxes so removed are those of greater hardness and higher market value than the waxes removed in taking the product to a still lower pour point.

The cracked fragments from cracking wax molecules in the catalytic dewaxer will have adverse effects on flash and fire points of the product and preferably are therefore removed by distillation of the product to flash and fire point specifications.
.~

The catalytic dewaxing step of this invention may be conducted by contacting the feed to be dewaxed with a fixed stationary bed of catalyst, with a fixed fluidized bed, or with a transport bed, as desired. A simple and therefore preferred configuration is a trickle-bed operation in which the feed is allowed to trickle through a stationary fixed bed, pre-ferably in the presence of hydrogen. With such configuration, it is of considerable importance in order to obtain maximum benefits from this invention to initiate the reaction with fresh catalyst at a relatively low temperature such as 260C
to 316C (500 to 600F). This temperature is of course raised as the catalyst ages, in order to maintain catalytic activity. In general, for lube oil base s-tocks the run is terminated at an end-of-run temperature of about 399C
(750F), at which time the catalyst may be regenerated by contact at elevated temperature with hydrogen gas, for example, or by burning in air or other oxygen-containing gas.

In general, for the purpose of manufacturing a refined lubricating oil stock according to this invention, the dewaxing step preferably is conducted at a LHSV of from 0.1 - to 5.0, a temperature from about 260C to about 399C (500F
to about 750F), and at a pressure of about 1480 to 13890 kPa (200 to 2000 psig). As indicated above, however, reaction conditions for the dewaxing step broadly include, in com-bination, a temperature of about 260C to 510C (450 to 950F), a pressure of 1480 to 20785 kPa (200 to 3000 psig), and a LHSV of 0.1 to 20 with a hydrogen circulation rate of 500 to 20,000 SCF/bbl ~standard cubic feet per barrel of feed). The combination of reaction conditions are chosen such as to effect a reduction of the pour point, or the freeze point, or the cloud point, or the CFPP (cold filter plugging point) of the feed of at least -15C (5F), and preferably at least -12.2C (10F). The terms pour point, , . _ cloud point, and CFPP refer to those characteristics of the feed or product as defined by test procedures currently specified by the American Society for Testing Materials or equivalent.

The precise process conditions selected for the process of this invention will of course depend on the nature and wax content of the feed, and the specifications for the product.
In general, however, it is a feature of this invention that most usually not more than about 20 wt.% of the feed is converted to dewaxed product boiIing lower than the feed.

- The improved process of this invention will now be il-lustrated by examples. All parts and proportions in these examples are by weight unless explicitl~ stated to be other-wise.

.
; 20 This example illustrates the preparation of a catalyst useful in this invention.

A mixture of 65 wt.% ZSM-5 having a framework density of ;1.79 g/cc and a crystallite size of less than 0.05 microns and 35 wt.% alumina on an anhydrous basis was extruded to form 1.6mm (1/16 inch) pellets. The pellets were calcined at 538C (1000F) in nitrogen, ammonium exhanged, and then calcined in air.

100 grams of the air-calcined~extrudate was impregnated with 13.4 grams of ammonium metatungstate (72.3% W) in 60 cc of water, followed by drying at 240C and calcination in air at 538C (1000F). The extrudate was then impregnated with 15.1 grams of nickel hexahydrate in 60 cc of water, and the wet pellets dried and again calcined at 538C ~1000F).

11~6588 The final catalyst had a calculated nickel content of about 3.4 wt.~ as NiO and a calculated tungsten content of about 10.5 wt~ as W03.

Example 2 A mixture of Nigerian and Arab Light gas oils was dewaxed with the catalyst of Example 1 and with a prior art Ni-ZSM-5 (Nickel-ZSM-5) catalyst. The gas oil feed had the following properties:
Gravity, API 27.0 Bromine No. 1.6 Hydrogen, wt.% 12.77 ~Sulfur, wt.~ 1.26 Nitrogen, ppm 600 Pour Pointj C 26.7 (80F) The dewaxing conditions and the yield and properties of the product are shown in Table I.
~, .
TABLE I
Catalyst Example 1Prior Art Ni/ZSM-5 Pressure, kPa 2859 t400 psig) 2859 (400 psig) ` LHSV .87 .87 Temperature, C 351 (663F) 350(661F) 25 H2 Circulation, scf/B 5151 5151 H2 Consumption, scf/B (Est'd.) 250 170 Product Prope~ties, 166C+ (330 F ) 30 Yield, vol. ~ 86.3 85.78 Gravity, API 25.7 24.5 Bromine No. 1.4 4.5 Hydrogen, wt.~ (Est'd) 12.71 12.50 Sulfur, wt.~ 0.36 1.27 Nitgrogen, ppm 460 480 Pour Point, C -3.9 (25F) -9.4 (15F) l 15B588 Product Properties, C5-166C
Yield, vol. ~ 6.54 6.92 Density, g/cc.6826 .6962 Bromine No. 15.1 84.8 R+O 85.2 91.8 - 5 M~O 74.9 80.0 Paraffins, vol. ~79.8 47.3 Olefins, vol. ~9.0 42.4 Naphthenes, vol. % 9.8 8.5 Aromatics, vol.%1.4 1.8 Yields, 10 H S, wt.% 1.00 0.15 N~ , wt.% .04 0.03 C 3C wt.% 2.82 3.36 C14, ~ol. ~ 7.04 6.56 C , vol % 92.84 92.70 T5tal, vol. ~99.88 99.26 48-Hour Accelerated Storage Stability, 166C+
Initial Color 3.0 4.0 48-Hour Color L4.0 5.5 Color Change ~ 1.0 1.5 ., ~ i I Initial Sediment, mg/l 2.4 14.2 ~ 20 48-Hour Sediment, mg/l 6.4 - 12.8 I

Example 3 i An Arab Light heavy neutral waxy lube oil stock was dewaxed with the catalyst of Example 1. For comparison, a prior-art Ni-ZSM-5 catalyst was also used. The waxy lube oil stock had the following properties:
Gravity, API28.9 Bromine No. 0.7 Hydrogen, wt.%13.72 Sulfur, wt.%0.79 Nitrogen, ppm31 ` 30 Pour Point, C44 (110F) The dewaxing conditions and the properties of the dewaxed oil9 are summarired in Table II

, ~- l 156588 .

TABLE II

Catalyst . Example 1 Prior Art Ni-ZSM-5 _ 5 ; Days On-Stream 12.011.5 LHSV 0.971.06 Temperature, C 331 (619F)313 (595F) 8~ Pressure, kPa H2 1430 ~200psig) 1430 (200psig) : ~ H2 Circulation, scf/Bbl 5233 5222 H2 Consumption, scf/Bbl . 247 56 Produc~t Properties, 166C+
: Gravity,~API ; 28.6 28.1 Bromine No. :: ~1.3 4.0 -Hydrogenl wt.~ : 13.45 -13.44 Sulfur,: wt.~% 15 0.38 0.86 Nitrogen~, ppm :. ~ 30 35 Pour~Point, C : -15 (5F) -12.2 (10F) : 15 : ProductlProperties,~ 232C
EV @ 100C, cs 10.29~ : 10~.71 KV @ 40C, cs~: : 91.76 99.50 i- :- V.I. ~ 92.2 89.3 Po~r Poi~t, C~ -9.4 (15F) - -17.8 (0F) 20 ~ yieldS ; ~

C -C ~, wt. % 4.6: ~ : 2.4 : cl v~ :: :: : 11.8 6.5 66C, vol.~ 8.0 9.3 6C+~, vol.%~ 84 0 ~ 5 :., ,: - .

: ~ ' ', .

:~: : ' ~: :

' ~ ' ' ' ' , I
;_ '-.

Claims (5)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for dewaxing a hydrocarbon oil boiling above 177°C which process comprises contacting said oil and hydrogen with a catalyst at dewaxing conditions, character-ized in that said catalyst comprises a crystalline zeolite having an effective pore diameter greater than 5 Angstroms and a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centimeter and a nickel-tungsten hydrogenation component.
2. The process of Claim 1 wherein said dewaxing conditions include a temperature of about 232 to 510°C, a pressure of 446 to 20 785 kPa, a space velocity of 0.1 to 20 LHSV and an H2 circulation rate of 500 to 20,000 SCF/Bbl.
3. The process of claim 1 or 2 wherein said hydrogenation component consists of 0.7 to about 7 wt.% nickel and 2.1 to about 21 wt.% tungsten expressed as metal based on said catalyst, and said crystalline zeolite is ZSM-5.
4. The process of claim 1 or 2 wherein said crystalline zeolite is ZSM-5 having a crystalline size of less than about 0.85 microns.
5. The process of claim 1 or 2 wherein said crystalline zeolite is contained in an alumina matrix.
CA000350630A 1979-04-27 1980-04-24 Catalytic dewaxing of hydrocarbon oils Expired CA1156588A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US033,775 1979-04-27
US06/033,775 US4229282A (en) 1979-04-27 1979-04-27 Catalytic dewaxing of hydrocarbon oils

Publications (1)

Publication Number Publication Date
CA1156588A true CA1156588A (en) 1983-11-08

Family

ID=21872370

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000350630A Expired CA1156588A (en) 1979-04-27 1980-04-24 Catalytic dewaxing of hydrocarbon oils

Country Status (8)

Country Link
US (1) US4229282A (en)
EP (1) EP0018778B1 (en)
JP (1) JPS55145793A (en)
AU (1) AU540098B2 (en)
CA (1) CA1156588A (en)
DE (1) DE3061987D1 (en)
ES (1) ES490892A0 (en)
ZA (1) ZA802411B (en)

Families Citing this family (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743355A (en) * 1979-10-15 1988-05-10 Union Oil Company Of California Process for producing a high quality lube oil stock
US4419271A (en) * 1979-10-15 1983-12-06 Union Oil Company Of California Hydrocarbon conversion catalyst
US4743354A (en) * 1979-10-15 1988-05-10 Union Oil Company Of California Process for producing a product hydrocarbon having a reduced content of normal paraffins
US4305808A (en) * 1980-04-14 1981-12-15 Mobil Oil Corporation Catalytic hydrocracking
US4428865A (en) 1981-01-13 1984-01-31 Mobil Oil Corporation Catalyst composition for use in production of high lubricating oil stock
US4372839A (en) * 1981-01-13 1983-02-08 Mobil Oil Corporation Production of high viscosity index lubricating oil stock
US4357232A (en) * 1981-01-15 1982-11-02 Mobil Oil Corporation Method for enhancing catalytic activity
US4358363A (en) * 1981-01-15 1982-11-09 Mobil Oil Corporation Method for enhancing catalytic activity
US4358362A (en) * 1981-01-15 1982-11-09 Mobil Oil Corporation Method for enhancing catalytic activity
US4343692A (en) * 1981-03-27 1982-08-10 Shell Oil Company Catalytic dewaxing process
US4600497A (en) * 1981-05-08 1986-07-15 Union Oil Company Of California Process for treating waxy shale oils
US4790927A (en) * 1981-05-26 1988-12-13 Union Oil Company Of California Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
US4877762A (en) * 1981-05-26 1989-10-31 Union Oil Company Of California Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
JPS588790A (en) * 1981-07-02 1983-01-18 Idemitsu Kosan Co Ltd Preparation of high-quality naphthene base oil
US4440630A (en) * 1982-02-08 1984-04-03 Mobil Oil Corporation Process for simultaneous hydrodesulfurization and hydrodewaxing with a catalyst of controlled pore size and metals content
FR2524481B1 (en) * 1982-04-05 1985-12-13 Elf France CATALYTIC HYDROTREATMENT OF OIL CUTTINGS
US4448270A (en) * 1982-05-10 1984-05-15 Hughes Tool Company Variable diameter earth boring bit
US5254770A (en) * 1982-09-01 1993-10-19 Mobil Oil Corp. Isomerization of aromatic compounds over ZSM-22 zeolite
US4472266A (en) * 1982-09-27 1984-09-18 Mobil Oil Corporation Hydrodewaxing with Mo, Ni-Mo, or Co-Mo on Zsm-5 type catalysts
US4436614A (en) 1982-10-08 1984-03-13 Chevron Research Company Process for dewaxing and desulfurizing oils
US4579647A (en) * 1982-10-15 1986-04-01 Mobil Oil Corporation Multiphase catalytic process with improved liquid distribution
US4589977A (en) * 1983-05-13 1986-05-20 Chevron Research Company Zeolite SSZ-19
JPS60212487A (en) * 1984-03-19 1985-10-24 モ−ビル オイル コ−ポレ−ション Catalytic dewaxing process using zsm-11 zeolite
DE3587895T2 (en) * 1984-05-03 1994-12-01 Mobil Oil Corp Catalytic dewaxing of light and heavy oils in two parallel reactors.
US4575416A (en) * 1984-07-16 1986-03-11 Mobil Oil Corporation Hydrodewaxing with mixed zeolite catalysts
GB8425837D0 (en) * 1984-10-12 1984-11-21 Shell Int Research Manufacture of lubricating base oils
US4919788A (en) * 1984-12-21 1990-04-24 Mobil Oil Corporation Lubricant production process
US4728415A (en) * 1984-12-24 1988-03-01 Amoco Corporation Process for the manufacture of lubricating oils
US4642176A (en) * 1985-01-09 1987-02-10 Mobil Oil Corporation Catalytic dewaxing process
US4749467A (en) * 1985-04-18 1988-06-07 Mobil Oil Corporation Lube dewaxing method for extension of cycle length
US4647369A (en) * 1985-06-14 1987-03-03 Mobil Oil Corporation Catalyst dewaxing process using a slurry phase bubble column reactor
US4597854A (en) * 1985-07-17 1986-07-01 Mobil Oil Corporation Multi-bed hydrodewaxing process
US4612108A (en) * 1985-08-05 1986-09-16 Mobil Oil Corporation Hydrocracking process using zeolite beta
US4808296A (en) * 1985-10-18 1989-02-28 Mobil Oil Corporation Process for dewaxing hydrocarbon feedstock
US4975177A (en) * 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US4804647A (en) * 1985-12-06 1989-02-14 Uop Dewaxing catalysts and processes employing titanoaluminosilicate molecular sieves
US4686029A (en) * 1985-12-06 1987-08-11 Union Carbide Corporation Dewaxing catalysts and processes employing titanoaluminosilicate molecular sieves
US4678556A (en) * 1985-12-20 1987-07-07 Mobil Oil Corporation Method of producing lube stocks from waxy crudes
LU86288A1 (en) * 1986-02-03 1987-09-10 Labofina Sa GASOILS TREATMENT PROCESS
JPH07116452B2 (en) * 1986-06-23 1995-12-13 株式会社ジャパンエナジー Method for producing highly aromatic base oil
US4812246A (en) * 1987-03-12 1989-03-14 Idemitsu Kosan Co., Ltd. Base oil for lubricating oil and lubricating oil composition containing said base oil
US4828678A (en) * 1987-07-09 1989-05-09 Mobil Oil Corporation Catalytic cracking
US5021142A (en) * 1987-08-05 1991-06-04 Mobil Oil Corporation Turbine oil production
US4846959A (en) * 1987-08-18 1989-07-11 Mobil Oil Corporation Manufacture of premium fuels
US4908120A (en) * 1987-08-20 1990-03-13 Mobil Oil Corporation Catalytic dewaxing process using binder-free zeolite
US4814543A (en) * 1987-12-28 1989-03-21 Mobil Oil Corporation Nitrogen resistant paraffin hydroisomerization catalysts
US4923591A (en) * 1988-01-04 1990-05-08 Mobil Oil Corporation Continuous lubricating oil dewaxing process
US4853104A (en) * 1988-04-20 1989-08-01 Mobil Oil Corporation Process for catalytic conversion of lube oil bas stocks
US4877581A (en) * 1988-09-01 1989-10-31 Mobil Oil Corporation Catalyst for dewaxing hydrocarbon feedstock
US5015361A (en) * 1989-01-23 1991-05-14 Mobil Oil Corp. Catalytic dewaxing process employing surface acidity deactivated zeolite catalysts
US5236880A (en) * 1989-12-11 1993-08-17 W. R. Grace & Co.-Conn. Catalyst for cracking of paraffinic feedstocks
US5053117A (en) * 1990-07-25 1991-10-01 Mobil Oil Corporation Catalytic dewaxing
US5157183A (en) * 1990-12-10 1992-10-20 Cotterman Ronald L Aromatization process using an improved catalyst
US5332490A (en) * 1992-09-28 1994-07-26 Texaco Inc. Catalytic process for dewaxing hydrocarbon feedstocks
US5365003A (en) * 1993-02-25 1994-11-15 Mobil Oil Corp. Shape selective conversion of hydrocarbons over extrusion-modified molecular sieve
US5391286A (en) * 1993-11-03 1995-02-21 Texaco Inc. Process for catalytic dewaxing of hydrocarbon feedstocks
US5961815A (en) * 1995-08-28 1999-10-05 Catalytic Distillation Technologies Hydroconversion process
US5833837A (en) * 1995-09-29 1998-11-10 Chevron U.S.A. Inc. Process for dewaxing heavy and light fractions of lube base oil with zeolite and sapo containing catalysts
US5935416A (en) * 1996-06-28 1999-08-10 Exxon Research And Engineering Co. Raffinate hydroconversion process
US5911874A (en) * 1996-06-28 1999-06-15 Exxon Research And Engineering Co. Raffinate hydroconversion process
US6099719A (en) * 1996-12-17 2000-08-08 Exxon Research And Engineering Company Hydroconversion process for making lubicating oil basestocks
US6096189A (en) * 1996-12-17 2000-08-01 Exxon Research And Engineering Co. Hydroconversion process for making lubricating oil basestocks
US5935417A (en) * 1996-12-17 1999-08-10 Exxon Research And Engineering Co. Hydroconversion process for making lubricating oil basestocks
FI102767B1 (en) 1997-05-29 1999-02-15 Neste Oy Process for the production of high quality diesel fuel
CN1102642C (en) * 1997-12-08 2003-03-05 中国石油化工集团总公司抚顺石油化工研究院 Catalyst for small crystal granule ZSM-5 molecular sieve catalystic dewaxing
US6051129A (en) * 1998-07-24 2000-04-18 Chevron U.S.A. Inc. Process for reducing haze point in bright stock
US6602405B2 (en) * 2000-01-21 2003-08-05 Bp Corporation North America Inc. Sulfur removal process
US6599417B2 (en) * 2000-01-21 2003-07-29 Bp Corporation North America Inc. Sulfur removal process
US6773578B1 (en) 2000-12-05 2004-08-10 Chevron U.S.A. Inc. Process for preparing lubes with high viscosity index values
US6699385B2 (en) 2001-10-17 2004-03-02 Chevron U.S.A. Inc. Process for converting waxy feeds into low haze heavy base oil
US20070187292A1 (en) * 2001-10-19 2007-08-16 Miller Stephen J Stable, moderately unsaturated distillate fuel blend stocks prepared by low pressure hydroprocessing of Fischer-Tropsch products
US20070187291A1 (en) * 2001-10-19 2007-08-16 Miller Stephen J Highly paraffinic, moderately aromatic distillate fuel blend stocks prepared by low pressure hydroprocessing of fischer-tropsch products
US6627779B2 (en) * 2001-10-19 2003-09-30 Chevron U.S.A. Inc. Lube base oils with improved yield
US6702937B2 (en) 2002-02-08 2004-03-09 Chevron U.S.A. Inc. Process for upgrading Fischer-Tropsch products using dewaxing and hydrofinishing
US6605206B1 (en) 2002-02-08 2003-08-12 Chevron U.S.A. Inc. Process for increasing the yield of lubricating base oil from a Fischer-Tropsch plant
JP4325843B2 (en) * 2002-12-20 2009-09-02 株式会社日立製作所 Logical volume copy destination performance adjustment method and apparatus
FR2852865B1 (en) 2003-03-24 2007-02-23 Inst Francais Du Petrole CATALYST AND USE THEREOF FOR IMPROVING THE FLOW POINT OF HYDROCARBON LOADS
RU2261266C1 (en) * 2004-04-01 2005-09-27 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Diesel fuel production process
FI20085400A0 (en) 2007-11-09 2008-04-30 Upm Kymmene Oyj Method for integrated waste water treatment
FI20075794L (en) * 2007-11-09 2009-05-10 Upm Kymmene Oyj An integrated process for the production of diesel fuel from biological material and products, uses and devices associated with the process
BRPI0822791A2 (en) * 2008-06-17 2017-05-09 Upm-Kymmene Oyj integrated process for producing diesel fuel from biological material, use of lignocellulosic material, method for narrowing the chain length distribution of a fischer-tropsch-derived diesel fuel, biological intermediate distillate fraction, and use of intermediate distillate fraction biological
US9290703B2 (en) 2010-04-23 2016-03-22 Exxonmobil Research And Engineering Company Low pressure production of low cloud point diesel
WO2012143613A1 (en) 2011-04-18 2012-10-26 Upm-Kymmene Corporation Catalytic process and apparatus for producing hydrocarbons from biooils
US9039892B2 (en) 2012-09-05 2015-05-26 Syed Tajammul Hussain Nano catalytic dewaxing of heavy petroleum wastes (>C-23 alkanes)
US10538950B2 (en) * 2015-11-05 2020-01-21 Mansfield Engineered Components, Inc. Lid hinge assembly with snubber and counterbalance spring
US11041129B2 (en) 2016-12-20 2021-06-22 Uop Llc Processes for producing a fuel range hydrocarbon and a lubricant base oil
WO2020131492A1 (en) 2018-12-21 2020-06-25 Exxonmobil Research And Engineering Company Catalytic dewaxing of hydrocarbon feedstocks
BR102019027610B1 (en) 2019-12-20 2022-03-08 Petróleo Brasileiro S.A. – Petrobras SELECTIVE PROCESS FOR THE PRODUCTION OF RENEWABLE AND FUEL AND HIGH MOLECULAR WEIGHT PARAPHINIC FUEL AND DISTILLATE
BR102020017281A2 (en) 2020-08-24 2022-03-08 Petróleo Brasileiro S.A. - Petrobras CATALYSTS AND SELECTIVE PROCESS FOR PRODUCTION OF RENEWABLE AVIATION FUELS AND PRODUCED BIOFUEL

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3539498A (en) * 1966-06-20 1970-11-10 Texaco Inc Catalytic dewaxing with the use of a crystalline alumino zeolite of the mordenite type in the presence of hydrogen
US3663430A (en) * 1967-12-22 1972-05-16 Texaco Inc Hydrocarbon dewaxing with a mordenite-type alumino-silicate
GB1242889A (en) * 1968-11-07 1971-08-18 British Petroleum Co Improvements relating to the hydrocatalytic treatment of hydrocarbons
USRE28398E (en) 1969-10-10 1975-04-22 Marshall dann
US3700585A (en) * 1969-10-10 1972-10-24 Mobil Oil Corp Dewaxing of oils by shape selective cracking and hydrocracking over zeolites zsm-5 and zsm-8
US3755138A (en) * 1969-10-10 1973-08-28 Mobil Oil Corp Lube oils by solvent dewaxing and hydrodewaxing with a zsm-5 catalyst
US3853742A (en) * 1971-10-20 1974-12-10 Union Oil Co Selective midbarrel hydrocracking
USRE29857E (en) * 1972-05-18 1978-12-05 Mobil Oil Corporation Conversion with ZSM-5 family of crystalline aluminosilicate zeolites
GB1404406A (en) * 1973-02-08 1975-08-28 British Petroleum Co Production of lubricating oils
US3926782A (en) * 1973-02-09 1975-12-16 Mobil Oil Corp Hydrocarbon conversion
GB1402821A (en) * 1973-02-09 1975-08-13 British Petroleum Co Production of lubricating oils
US3968024A (en) * 1973-07-06 1976-07-06 Mobil Oil Corporation Catalytic hydrodewaxing
US3970544A (en) * 1974-05-06 1976-07-20 Mobil Oil Corporation Hydrocarbon conversion with ZSM-12
US3929616A (en) * 1974-06-26 1975-12-30 Texaco Inc Manufacture of lubricating oils
US3992466A (en) * 1975-08-13 1976-11-16 Mobil Oil Corporation Hydrocarbon conversion
CA1108084A (en) * 1976-12-20 1981-09-01 Philip D. Caesar Gas oil processing

Also Published As

Publication number Publication date
US4229282A (en) 1980-10-21
AU540098B2 (en) 1984-11-01
AU5774880A (en) 1980-10-30
DE3061987D1 (en) 1983-03-24
EP0018778A1 (en) 1980-11-12
EP0018778B1 (en) 1983-02-16
ZA802411B (en) 1981-08-26
ES8102180A1 (en) 1980-12-16
JPS55145793A (en) 1980-11-13
ES490892A0 (en) 1980-12-16

Similar Documents

Publication Publication Date Title
CA1156588A (en) Catalytic dewaxing of hydrocarbon oils
US4259170A (en) Process for manufacturing lube base stocks
EP0163449B1 (en) Catalytic dewaxing of lubricating oils
CA1133412A (en) Production of high v.i. lubricating oil stock
US4259174A (en) Catalytic dewaxing of hydrocarbon oils
EP0016554B1 (en) Production of high viscosity index lubricating oil stock
US5885438A (en) Wax hydroisomerization process
US4437975A (en) Manufacture of lube base stock oil
CA1110192A (en) Specialty oils by solvent refining, zeolite catalytic dewaxing and hydrotreating
US4181598A (en) Manufacture of lube base stock oil
AU717101B2 (en) Process for highly shape selective dewaxing which retards catalyst aging
US4372839A (en) Production of high viscosity index lubricating oil stock
US5976351A (en) Wax hydroisomerization process employing a boron-free catalyst
US4610778A (en) Two-stage hydrocarbon dewaxing process
US4437976A (en) Two-stage hydrocarbon dewaxing hydrotreating process
CA1187827A (en) Method for enhancing catalytic activity
US4541919A (en) Shape selective dewaxing using coke modified large pore zeolites
AU706864B2 (en) Wax hydroisomerization process
US4269695A (en) Reclaiming wax contaminated lubricating oils
CA1252410A (en) Combination process for making improved lubricating oils from marginal crudes
US4376036A (en) Production of high V. I. lubricating oil stock
US4952303A (en) Process for preparing a very high quality lube base stock oil
US4428865A (en) Catalyst composition for use in production of high lubricating oil stock
AU615679B2 (en) Catalytic hydrodewaxing process
EP0134637B1 (en) Viscosity index improvement in dewaxed lube basestock by partial desulfurization in hydrotreat bed

Legal Events

Date Code Title Description
MKEX Expiry