US3912620A - Lubricating oil production utilizing hydrogen in two catalytic stages - Google Patents

Lubricating oil production utilizing hydrogen in two catalytic stages Download PDF

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US3912620A
US3912620A US45288774A US3912620A US 3912620 A US3912620 A US 3912620A US 45288774 A US45288774 A US 45288774A US 3912620 A US3912620 A US 3912620A
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James P Gallagher
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Atlantic Richfield Co
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    • 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
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12Noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/12Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
    • 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil

Abstract

Lubricating oil of increased viscosity index and reduced aromatic hydrocarbon content is prepared by contacting a heavy lubricating oil fraction with hydrogen in the presence of a sulfur-resistant catalyst (e.g., nickel molybdate on alumina) to form an effluent oil and further contacting the effluent oil with hydrogen in the presence of a hydrogen- or rare-earth-exchanged, faujasite catalyst containing a platinum group metal to produce a product from which a lubricating oil having a reduced aromatic hydrocarbon content relative to the feedstock can be recovered.

Description

Umted States Patent 11 1 1111 3,912,620 Gallagher Oct. 14, 1975 54] LUBRICATING OIL PRODUCTION 3,159,568 12/1964 Price et a1 208/89 UTILIZING HYDROGEN IN TWO 3,494,854 2/1970 Gallagher et a1. 208/89 3,506,568 4/1970 Annesser et a1. 208/89 CATALYTIC STAGES 3,528,908 9/1970 Bowles et a1 208/89 James P. Gallagher, Park Forest, 111.

Atlantic Richfield Company, Philadelphia, Pa.

Filed: Mar. 20, 1974 App]. No.: 452,887

Related U.S. Application Data Continuation-in-part of Ser. No. 5,963, Jan. 26, 1970, abandoned.

Inventor:

Assignee:

U.S. Cl 208/210; 208/89 Int. Cl. C10G 23/04; ClOG 23/02 Field of Search 208/89, 212, 210, 59

References Cited UNITED STATES PATENTS 7/1964 Plank et a1. 252/455 Z 12/1964 Kelley et a1 208/89 Primary ExaminerDelbert E. Gantz Assistant E.xaminerG. J. Crasanakis Attorney, Agent, or FirmFrank J. Uxa

[ ABSTRACT Lubricating oil of increased viscosity index and reduced aromatic hydrocarbon content is prepared by contacting a heavy lubricating oil fraction with hydrogen in the presence of a sulfur-resistant catalyst (e.g., nickel molybdate on alumina) to form an effluent oil and further contacting the effluent oil with hydrogen in the presence of a hydrogenor rare-earthexchanged, faujasite catalyst containing a platinum group metal to produce a product from which a lubricating oil having a reduced aromatic hydrocarbon content relative to the feedstock can be recovered.

11 Claims, N0 Drawings LUBRICATING OIL PRODUCTION UTILIZING HYDROGEN IN TWO CATALYTIC STAGES This application is a continuation-in-part of application Ser. No. 5,963, filed Jan. 26, 1970, now abandoned.

This invention relates to a process employing two distinct catalyst types to produce high quality lubricating oil stocks from raw, mineral lubricating oil fractions. More particularly, this invention concerns a catalytic hydroconversion process for the production of a refined mineral lubricating oil having an increased viscosity index and a reduced content of aromatic hydrocarbons.

Raw heavy lubricating oil fractions often require additional refining for quality improvement. It is often desirable to increase the viscosity index of such raw fractions, as well as to reduce the aromatic hydrocarbon content of these materials. However, since these raw lubricating oil fractions are valuable, it is also desirable to increase the viscosity index and reduce the aromatic hydrocarbon content while minimizing the losses of lubricating oil to, for example, lower boiling components.

Therefore, one of the objects of the present invention is to provide a method for producing a lubricating oil having an increased viscosity index from a raw, mineral lubricating oil fraction.

Another object of the present invention is to provide a process for producing a lubricating oil having a reduced aromatic hydrocarbon content from a raw, mineral lubricating oil fraction.

A still further object of the present invention is to provide a process for producing a lubricating oil having an increased viscosity index and a reduced aromatic hydrocarbon content from a raw, mineral lubricating oil fraction while minimizing the loss of this fraction to lower boiling hydrocarbon components. Other objects and advantages of the present invention will become apparent hereinafter.

An improved process has now been discovered using a raw, mineral lubricating oil feedstock to produce a lubricating oil with an increased viscosity index and a reduced content of aromatic hydrocarbons, relative to the feedstock, without undue cracking and yield loss of the feedstock to lighter materials, such as gasoline, i.e., less than about preferably less than about 15%, by weight of the feedstock is converted to material boiling lower than 400F. The raw, mineral lubricating oil feedstock is derived from a waxy mineral crude oil and contains at least about 0.3% by weight of sulfur and at least about 1000 ppm. by weight of nitrogen. The present improvement comprises first contacting this raw feedstock with hydrogen in the presence of a sulfurresistant hydrogenation catalyst at a temperature of from about 600F. to about 800F. to form an effluent oil and second contacting this effiuent oil with hydrogen in the presence of a second catalyst at a temperature of from about 500F. to about 800F. to improve the viscosity index of the effiuent oil. The second catalyst comprises (1) a major amount, preferably at least about 70% by weight, of a faujasite in which at least 50% of the cations are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof and the faujasite has a silica-to-alumina mole ratio of greater than about 3:1; (2) a minor, catalyticallyeffective amount of at least one platinum group metal; and (3) a minor amount of at least one refractory inorganic oxide effective to improve the mechanical strength of the second catalyst. The first and second contactings described above are carried out at conditions so that less than about 20%, preferably less than about 15%, by weight of the feedstock is converted by hydrogen materials boiling below 400F. The first and second contactings of the present invention can be conducted either with or, preferably without, intermediate processing, for example, separation of gases, e.g., H 5 and NH from the effluent oil prior to the second contacting. The material obtained from the second contacting may be further processed using conventional methods, e.g., flashing distillation, and the like, to obtain a lubricating oil having increased viscosity index and reduced aromatic hydrocarbon content relative to the raw mineral lubricating oil feedstock. In addition, at least a portion of the material obtained from the second contacting step may be dewaxed, as by solvent dewaxing, to remove any wax present.

The raw, mineral lubricating oil fractions or feedstocks suitable in the process of the instant invention are typically heavy lubricating oil fractions, such as deasphalted residual lubricating oil fractions having a 5% boiling point of greater than about 800F. Such heavy lubricating oil fractions can be deasphalted, for instance, by distillation or by a solvent treatment of the residual fraction obtained from the vacuum distillation of a waxy mineral crude oil. These raw, mineral lubricating oil feedstocks often possess a viscosity of equal to or greater than about 25 K.V. at F., for example, from about 30 K.V. to about 50 K.V. at 120F. These feedstocks typically contain small amounts of sulfur and nitrogen, e.g., at least about 0.3%, often from about 0.3% to about 1%, by weight of sulfur, and at least about 1000 ppm. (parts per million), often from about 1000 ppm. to about 2000 ppm. by weight of nitrogen. These raw, mineral oil feedstocks also contain aromatic compounds, for example, in an amount such that the feedstock has a specific dispersion of at least about 1 10, preferably at least about 130.

The first contacting step of the present process is conducted at temperatures from about 600F. to about 800F., preferably from about 675F. to about 775F. The other first contacting conditions preferably include pressures of from about 500 psig., to about 5000 psig., more preferably from about 1000 psig.; to about 3000 psig.; weight hourly space velocities (WHSV) of from about 0.1 to about 2, preferably from about 0.25 to about 1; and molecular hydrogen to feedstock ratios of from about 5,000 SCF/B (i.e., standard cubic feet of hydrogen per barrel of feedstock) to about 20,000 SCF/B, more preferably, from about 10,000 SCF/B to about 15,000 SCF/B. This first contacting step func tions to produce an effluent oil. At least a portion, pref erably at least a major portion, of both the sulfur and the nitrogen contained in the raw, mineral lubricating oil feedstock is chemically converted to H S and NH respectively, in this first contacting step.

The effiuent oil from the first contacting step is subjected to a second contacting step wherein a substantially hydrocarbon product is produced. The catalyst in the second contacting step is especially chosen to effect selective aromatic hydrocarbon hydrogenation and bydrocracking. This second contacting step occurs at conditions, e.g., temperature, so as to provide a substantially hydrocarbon product from which lubricating oil having an increased viscosity index and reduced aromatic hydrocarbon content relative to the raw mineral lubricating oil feedstock without undue cracking and loss to lighter materials can be recovered. Temperatures in the second contacting step can range, for example, from about 500F. to about 800F., with temperatures of from about 600F. to about 750F. being preferred. Other second contacting conditions preferably include pressures of from about 500 psig. to about 5000 psig., more preferably from about 1000 psig. to about 3000 psig.; weight hourly space velocities of from about 0.1 to about 2, preferably from about 0.25 to about 1; and molecular hydrogen to effluent oil ratios of from about 5,000 SCF/B to about 20,000 SCF/B, more preferably, from about 10,000 SCF/B to about 15,000 SCF/B.

The catalyst used in the first contacting step of the present process can be any of the sulfur-resistant or sulfur-active, non-precious metal hydrogenation catalyst, such as those conventionally employed in the hydrogenation of heavy mineral oils. Examples of suitable catalytic ingredients are tin, vanadium, members of Group VIB in the Periodic Table, i.e., chromium, molybdenum and tungsten, and metals of the iron group, i.e., iron cobalt and nickel, metals of Group VIII in the Periodic Table. These metals are present in catalyticallyeffective amounts, for instance, from about 2% to about 30% by weight, and may be present in the elemental form or in combined form such as the oxides or sulfides, with the sulfide form being preferred. Mixtures of these metals can be employed, for example,

mixtures of the iron group metal oxides or sulfides with the oxides or sulfides of Group VIB providing very satisfactory catalysts. Examples of such mixtures are nickel molybdate, tungstate or chromate (or thiomolybdate, thiotungstate or thiochromate) or mixtures of nickel or cobalt oxides with molybdenum, tungsten or chromium oxides. As the art is aware, and as the specific examples below illustate, these catalytic ingredients are generally employed while disposed on a suitable carrier of the solid metal oxide type, e.g., a predominantly calcined or activated alumina. Commonly employed catalysts have about 1% to about 10% by weight of an iron group metal (calculated as the elemental metal) and about 5% to about 25% by weight of a Group VIB metal (calculated as the oxide). Advantageously, the catalyst is sulfided nickel-molybdena supported on alumina. Such preferred catalysts can be prepared by the method described in US. Pat. No. 2,938,002.

The catalyst employed in the second contacting step of the present invention comprises: (1) a major amount, preferably at least about 70%, by weight (based on the total catalyst) of a faujasite in which at least about preferably at least about 70%, of the cations are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof; (2) a minor, catalytically-effective amount, preferably from about 0.1% to about 5% and more preferably, from about 0.3% to about 2%, by weight (based on the total catalyst) of at least one platinum group metal; and (3) a minor amount, preferably from about 5% to about 25% by weight (based on the total catalyst) of at least one refractory inorganic oxide effective to improve the mechanical strength of the catalyst. In certain instances, during activation and/or use of the catalyst employed in the second contacting step, at least a portion of the hydrogen cations of the faujasite are removed.

The remaining faujasite thus includes cation vacancies and may be termed a decationized" faujasite. Such decationized faujasites are, by definition, within the class of faujasites suitable for use in the catalyst of the second contacting step provided that they are derived from faujasites in which at least 50%, preferably at least of the cations are hydrogen ion.

The faujasite component of the catalyst in the second contacting step may be synthetic or naturallyoccurring. This component has pore openings of from about SA to about 15A in diameter, preferably from about 10A to about 14A. Usually, with a given material, the pores are relatively uniform in size. Suitable faujasites have silica-to-alumina mole ratios of greater than about 3:1, usually not above about 12:1. In a preferred embodiment, the faujasite component has a silica-to-alumina mole ratio of from about 4:1 to about 6:1. The faujasite is at least about 50%, preferably at least about 70%, hydrogenor rare-earth-exchanged. That is, at least about 50% of the cations present in the faujasite are hydrogen or one or more of the rare-earth metals or mixtures thereof. Included among the suitable rare-earth metals are cerium, lanthanum, neodymium and the like. Hydrogen exchange often is carried out by exchange of the cations of the synthetic or naturally-occurring faujasites with ammonium ions, for instance, through contact with an aqueous solution of ammonium chloride or other water soluble ammonium compound and subsequently calcining the faujasite, for instance at a temperature of about 500F. to about 1500F., preferably from about 700F. to about II00F. Similarly, rare-earth metal exchange is commonly carried out by exchange of the cations with a water-soluble rare-earth metal compound followed by calcination.

The platinum group metals of the catalyst of the second contacting step include such Group VIII metals as, for example, platinum, palladium, ruthenium, osmium, rhodium and iridium. The platinum group metal, preferably platinum, palladium and mixtures thereof, more preferably platinum, may be present in the metallic form or as a sulfide, oxide or other combined form. The metal may interact with other constituents of the catalyst, but, if during use, the platinum group metal is present in metallic form, then it is preferred that it be so finely divided that it is not detactable by Xray diffraction means, i.e., that it exist as crystallites of less than about 50A in size. The platinum group metal may be combined with the faujasite before or after the calcination of the hydrogenor rare-earth metal-exchanged faujasite, by for example, ion exchange or impregnation. Ion exchange is preferred. In any event, after the platinum group metal is added, the platinum group metal-containing faujasite can be activated, e.g., calcined at the temperatures, e.g., from about 500F. to about I500F., described above.

One method for combining the platinum group metal by ion exchange comprises contacting the faujasite with an aqueous solution containing a water-soluble form of the metal to be deposited in the crystal structure of the faujasite. The metal ion-exchanges with the cations present in the faujasite. The exchanged material is then removed from the solution, dried and calcined or otherwise activated. The platinum group metal may also be added by impregnation. Thus, the faujasite, either with or without previous evacuation, can be soaked in either a dilute or concentrated aqueous solution of a water-soluble platinum group metal compound, often in an amount just sufficient to wet the material and be completely absorbed. Examples of such water-soluble platinum group metal compounds in- The process of the present invention is illustrated by the following examples which are not to be considered as limiting.

EXAMPLE I clude chloroplatinic acid, chloropalladic acid, ammo- 5 nium hexathiocyanoplatinate (IV), hexathiocyanate- A waxy mlxed base deflsphalted lubncatmg Q platinic acid and the like. The solid material from this feedstock havmg the properties of the feefjstock m impregnation can be calcined or otherwise activated. Table below was Contact? m thfee runs hydro Although various refractory inorganic oxides known gen the presence of a Calcmed mckel'inolybdena in the art may be utilized as a component in the catalyst alumma catalyst temperature of 750 a pressure employed in the second contacting step to improve the of 1500 a weght hourly Space velocity of and mechanical stability of the catalyst, the preferred oxide a hydrogen to ,ratlo rate of 12090 SCF/B' comprises a major amount of calcined or otherwise ac- The catalyst wh'ch colltamed percent mckel (cal' tivated alumina. The oxide comprises a minor amount, Eulated as i gd d f y preferably from about 5% to about 25%, more preferal5 enum, g as me y ena) hesdsupporteld bly from about 5% to about by weight of the total g; gg% pretleate g gfii catalyst. Other suitable oxides, for example, include sil- I e or Ours one 2 r/ ica, silica-alumina, zirconia, magnesia and the like. It is grams of catalyst The total produc.t from this first f preferred that the alumina have a surface area of from non zone was sewn? corltacted m a sfcond reaftlon about mzi/gm to about 600 mzhlgm The alumina 20 zone at temperatures varying from 624 F. to 663 F., a may be derived from hydrous alumina predominating pressure of 1500 pslg" a we'ght hourly Space velocity phous hydrous alumina and mixtures thereof which alucine; reduced lagnum comainin fauhsite mina has a surface area from about 50 m ./gm. to about h p J 500 m2 g The useful aluminas y Contain in addi 25 boe mite catalyst. The catalyst used in the second con- I tactin st m ris t f' tion, minor proportions of other well-known refractory Site i sfgg i f gg jf g z f ag 253: inorganic oxides such as silica, zirconia, magnesia and the like However the preferred oxide for use in this mum (derived from coifwentlonal exchange) the faujasite having pores o a diameter of about 12A and gatalyst sLlbstannzny p i i from a silica-to-alumina mole ratio of about 4:1, about 0.5% salsa: z'y2?:;;" ..:."m;: 22:22.; by of by of boehmite alumina. The catalyst was calcined so that f 1 z i i m i f g the ammonium cations of the faujasite were converted a umma pre Omma mg m a mono to hydrogen ions. At least a portion of these hydrogen ra e.

The catalysts of either contacting step of the present Ions r g frpm this faujaslte leavmg d d b f d t d cancies. e boehmite alumma was included prior to. mvenlion can, 1 esrre lle orme 1n oi a fl extrusion of the catalyst to improve the mechanical Fi f i 1 t t s t l t 3n t h strength of the catalyst. The product from the second 1 6 OX] e,componen 0 e use reaction zone was distilled to remove lighter hydrocarsecond contacting step may, along with improving the 0 bon components mechanical stabil ty of the catalyst, providea catalyst The properties 0f the product obtained in each of wh'ch more eas 1ly Such macros'zed these runs is set forth in Tables [I and Ill. The products cles. The macrosized particles of the catalysts useful in were dewaxed and found to have the properties Set the present Invention can have any shape and be of any forth in Table form, e.g., size, compatible with the environment in 4 TABLE] which such catalysts are to be used. Generally, these 5 macrosized particles have a minimum linear dimension Feedstock of at least about 0.01 inches. For example, these particles may have a cylindrical configuration, typically of Gravity. AP! 23.6 from about H64 in. to about A in. or more, in diameter Kv a! 1200!, 229 and from H16 in. to about 1 in. or more in length. Al- P 1", F, though formation of macrosized particles often occurs PPM before calcination of the final compounded catalyst, it spccmppispersion 4 can be performed at any time found most convenient. 5% Bollmg Poinl 5F.

TABLE ll RUN NO. l 2 3 PRODUCT Wt. 71 Vol. 71 Wt. 57; Vol. 7( Wt. 92 Vol. '7: ANALYSIS DRY GAS 0.65 0.95 1.18 2.23 0.07 0.09 TOT. C4 0.70 1.08 0.87 1.35 0.07 0.1 l TOT. C5 0.33 0.48 0.0 0.0 0.03 0.04 C5+ 98.56 98.51 100.35 H25 0.51 0.51 0.54 NH 0.l6 0.16 0.17 H O 0.02 0.02 0.02 COl IVERSlON To 550F. Minus l4.33 27.00 32.57

ll0-400F. 5.61 5.34 13.99 14.57 l8.76 I954 400550F. 7.28 7.58 ll.53 12.00 l4.l5 l4.73 to 550F. Plus 85.67 89.20 73.00 76.01 67.43 70.22

TABLE II-Continued RUN NO. 1 2 3 PRODUCT Wt. 74 Vol. 72 Wt. Vol. 7: Wt. 7: Vol. 7! ANALYSIS H2 CONSUMPTION S62/SCF/B 744/SCF/B 747/SCF/B WT. YIELDS N FEED CONVERTED To 550F. MINUS DRY GAS 4.55 4.36 0.21

TOT. C4 4.89 3.21 0.2!

TOT. CS 2.3] 0.0 0.09

ll0-400F. 39.12 51.81 57.62

TABLE means that a higher yield of higher viscosity oil is ob tained. This is reflected in the measured KV of the total Analysis of Total Liquid Product 550 1 dewaxed fraction. It ShOLlld also be noted that Run Number I 2 3 all of the above runs were made at 1500 psig. pressure Carbon 8704 3644 35796 which is significantly lower than the usual pressure of ygt 3- 1392 prior art processes, e.g., 2500 psig. It thus appears that ppm mogn 4 the process herein disclosed permits the use of a lower Analysis of the 550F+Fraction pressure during the reaction while maintaining good 1:; Nsmber 86157 8 2 3 product characteristics. These examples also illustrate c ar on 6.16

% Hydrogen 1367 I180 that the outstanding benefits, e.g., lubricating oils hav- Refractive mg increased viscosity index and reduced hydrocarbon index at 80F. 1.46150 1.45695 AH Gravity 309 29-6 33.4 30 aromatic content, of the present inventionare achieved without undue yield losses to lower boiling components. For example, in each of Runs 1, 2 and 3, the

TABLE IV amount of feedstock converted to material boiling a 400F. and lower, was less than 20 by weight. This is an important advantage of the present process since Run Number Lubncatmg 'L l 2 high yields of high quality lubricating oils are obtained. While this invention has been described with respect g f Analysis to various specific examples and embodiments, it is to m 5 be understood that the invention is not limited thereto Wax 40 and that it can be variously practiced within the scope API Gravity 35.7 34.8 34.1

PMP, F. 166.0 |69.9 166.9 of the following clams on 1,842 3,623 5 The embodiments of the invention in which an exclusive ro ert or rivile e is claimed are defined as fol- API Gravity 32.3 29.7 28.1 I p y p g Flash Point, F. 359 425 440 ire Point. F. 420 465 490 1. In a process for producing a hydrocarbon lubricat- HO H0 in oil of increased viscosit index and reduced aro KV/100F. 65.10 128.1 164.2 matic hydrocarbon content from a raw, mineral lubri- KV/2l0F. 8.864 13.16 14.92

Carbon Res (COM 082 0, 914 cat ing oil feedstock containing at least about 0.3% by S ifi pistpegsion W276 101,8 |07 weight of sulfur and at least about 1000 ppm. by weight ASTM Dlslllgg o 580 437 536 of nitrogen derived from a waxy mineral crude oil, the

5% 619 624 626 improvement which comprises first contacting said 10 637 689 698 feedstock with hydrogen and with a sulfur-resistant hy- 5g 53g 3;; 3% drogenation catalyst at a temperature of about 600F. 40 874 984 980 to about 800F. to form a first effluent oil and second 50 960 1026 55 contacting said first effluent oil with hydrogen and with 1016 1055 at 1059 O 58% a second catalyst at a temperature of about 500 F. to 53 about 800F., to produce a a second effluent oil, recov- Viscoshy Index E 106 T ering said hydrocarbon lubricating oil having an inwi. '71 Yield of creased viscosity index and reduced aromatic hydrog i' z x g 7300 85m 60 carbon content relative to said feedstock from said sec- Dcwaxed on 529 55-3 645 0nd effluent oil, said second catalyst comprising a major amount of a faujasite in which at least 50 of the cations are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof, said faujasite having a silica-to-alumina mole ratio of greater than about 3:1, a minor catalytically-effective amount of at least one platinum group metal and a minor amount of at least one refractory inorganic oxide effective to improve the mechanical strength of said second catalyst, said first and second contacting producing less than about 20% by weight of hydrocarbon material boiling below 400F. based upon the weight of said feedstock.

2.'The process of claim 1 wherein said first contacting is conducted at a pressure of from about 500 psig. to about 5000 psig., a weight hourly space velocity of about 0.1 to about 2 and a hydrogen to feedstock ratio of from about 5000 SCF/B to about 12,000 SCF/B.

3. The process of claim 2 wherein said second contacting is conducted at a pressure of about 500 psig. to about 5000 psig., a weight hourly space velocity of about 0.l to about 2 and a hydrogen to effluent oil ratio of from about 5000 SCF/B to about 20000 SCF/B.

4. The process of claim 3 wherein at least 70% of the cations in said faujasite are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof.

5. The process of claim 4 wherein the platinum group metal is platinum and is present in said second catalyst in an amount from about 0.1% to about 5.0% by weight of the total catalyst.

6. The process of claim 5 wherein the sulfur-resistant catalyst contains molybdenum and an ion group metal.

7. The process of claim 6 wherein the iron group metal is nickel.

8. The process of claim 1 wherein said first contacting is conducted at a temperature of about 675F. to about 775F., a pressure of about 1000 psig. to about 3000 psig., a weight hourly space velocity of about 0.25 to about 1 and a hydrogen to feedstock ratio of from about 10,000 SCF/B to about 15,000 SCF/B, and said second contacting is conducted without intermediate separation of gas at a temperature of from about 600F. to about 750F., a pressure of from about 1000 psig. to about 3000 psig., a weight hourly space velocity of from about 0.25 to about 1 and a hydrogen to effluent oil ratio of from about 10,000 SCF/B to about 15,000 SCF/B.

9. The process of claim 8 wherein at least of the cations in said faujasite are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof.

10. The process of claim 9 wherein the platinum group metal is platinum and is present in said second catalyst in an amount from about 0.3% to about 2% by weight of the total catalyst.

11. The process of claim 10 wherein the sulfurresistant catalyst contains molybdenum and nickel on UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PAT ENT NO. I 3,912,620

DATED October 14, 1975 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9, line 25; delete the word "ion" and substitute therefore -iron- Signed and Sealed this tenth D3) 0f February 1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParenrs and Trademarks

Claims (11)

1. IN A PROCESS FOR PRODUCTING A HYDROCARBON LUBRICATING OIL OF INCREASED VISCOSITY INDEX AND REDUCED AROMATIC HYDROCARBON CONTENT FROM A RAW, MINERAL LUBRICATING OIL FEEDSTOCK CONTAINING AT LEAST ABOUT 0.3% BY WEIGHT OF SULFUR AND AT LEAST ABOUT 1000 PPM BY WEIGHT OF NITROGEN DERIVED FROM A WAXY MINERAL CRUDE OIL THE IMPROVEMENT WHICH COMPRISES FIRST CONTACTING SAID FEEDSTOCK WITH HYDROGEN AND WITH A SULFURRESISTANT HYDROGENATION CATALYST AT A TEMPERATURE OF ABOUT 600*F. TO ABOUT 800*F. TO FORM A FIRST EFFLUENT OIL AND SECOND CONTACTING SAID FIRST EFFLUENT OIL WITH HYDROGEN AND WITH A SECOND CATALYST AT A TEMPERATURE OF ABOUT 500*F. TO ABOUT 800*F. TO PRODUCE A A SECOND EFFLUENT OIL, RECOVERING SAID HYDROCARBON LUBRICATING OIL HAVING AN INCREASED VISCOSITY INDEX AND REDUCED AROMATIC HYDROCARBON CONTENT RELATIVE TO SAID FEEDSTOCK FROM SAID SECOND EFFLUENT OIL, SAID SECOND CATALYST COMPRISING A MAJOR AMOUNT OF A FAUJASTIE IN WHICH AT LEAST 50% OF THE CATIONS ARE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN ION, EARTH ION AND MIXTURES THEREOF, SAID FAUJASITE HAVING A SILICA-TO-ALUMINA MOLE RATIO OF GREATER THAN ABOUT 3:1, A MONOR CATALYTICALLY-EFFECTIVE AMOUNT OF AT LEAST ONE PLATINUM GROUP METAL AND A MONOR AMOUNT OF AT LEAST ONE REFRACTORY INORGANIC OXIDE EFFECTIVE TO IMPROVE THE MECHANICAL STRENGHT OF SAID SECOND CATALYST, SAID FIRST AND SECOND CONTACTING PRODUCING LESS THAN ABOUT 20% BY WEIGHT OF HYDROCARBON MATERIAL BOILING BELOW 400*F. BASED UPON THE WEIGHT OF SAID FEEDSTOCK.
2. The process of claim 1 wherein said first contacting is conducted at a pressure of from about 500 psig. to about 5000 psig., a Weight hourly space velocity of about 0.1 to about 2 and a hydrogen to feedstock ratio of from about 5000 SCF/B to about 12,000 SCF/B.
3. The process of claim 2 wherein said second contacting is conducted at a pressure of about 500 psig. to about 5000 psig., a weight hourly space velocity of about 0.1 to about 2 and a hydrogen to effluent oil ratio of from about 5000 SCF/B to about 20000 SCF/B.
4. The process of claim 3 wherein at least 70% of the cations in said faujasite are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof.
5. The process of claim 4 wherein the platinum group metal is platinum and is present in said second catalyst in an amount from about 0.1% to about 5.0% by weight of the total catalyst.
6. The process of claim 5 wherein the sulfur-resistant catalyst contains molybdenum and an ion group metal.
7. The process of claim 6 wherein the iron group metal is nickel.
8. The process of claim 1 wherein said first contacting is conducted at a temperature of about 675*F. to about 775*F., a pressure of about 1000 psig. to about 3000 psig., a weight hourly space velocity of about 0.25 to about 1 and a hydrogen to feedstock ratio of from about 10,000 SCF/B to about 15,000 SCF/B, and said second contacting is conducted without intermediate separation of gas at a temperature of from about 600*F. to about 750*F., a pressure of from about 1000 psig. to about 3000 psig., a weight hourly space velocity of from about 0.25 to about 1 and a hydrogen to effluent oil ratio of from about 10,000 SCF/B to about 15,000 SCF/B.
9. The process of claim 8 wherein at least 70% of the cations in said faujasite are selected from the group consisting of hydrogen ion, rare earth ion and mixtures thereof.
10. The process of claim 9 wherein the platinum group metal is platinum and is present in said second catalyst in an amount from about 0.3% to about 2% by weight of the total catalyst.
11. The process of claim 10 wherein the sulfur-resistant catalyst contains molybdenum and nickel on alumina.
US45288774 1970-01-26 1974-03-20 Lubricating oil production utilizing hydrogen in two catalytic stages Expired - Lifetime US3912620A (en)

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Cited By (12)

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US4057489A (en) * 1976-12-29 1977-11-08 Gulf Research & Development Company Process for producing a transformer oil having lower pour point and improved oxidation stability
US4113603A (en) * 1977-10-19 1978-09-12 The Lummus Company Two-stage hydrotreating of pyrolysis gasoline to remove mercaptan sulfur and dienes
US4169783A (en) * 1976-05-06 1979-10-02 Uop Inc. Hydrocarbon conversion catalytic composite
US4225418A (en) * 1979-06-07 1980-09-30 Uop Inc. Hydroprocessing of hydrocarbons
US4294687A (en) * 1979-12-26 1981-10-13 Atlantic Richfield Company Lubricating oil process
US4518485A (en) * 1982-05-18 1985-05-21 Mobil Oil Corporation Hydrotreating/isomerization process to produce low pour point distillate fuels and lubricating oil stocks
US4758544A (en) * 1985-07-17 1988-07-19 Chevron Research Company Catalyst composition and hydroprocessing of oils using same
US4801373A (en) * 1986-03-18 1989-01-31 Exxon Research And Engineering Company Process oil manufacturing process
US6103101A (en) * 1993-10-01 2000-08-15 Petroleo Brasileiro S.A.-Petrobras Process for producing lube base oils of high viscosity index and diesel oil of high cetaned number
US20100078355A1 (en) * 2008-10-01 2010-04-01 Chevron U.S.A. Inc. Process to manufacture a base stock and a base oil manufacturing plant
US20100163454A1 (en) * 2008-12-31 2010-07-01 Gala Hemant B Hydrocracking processes yielding a hydroisomerized product for lube base stocks
CN106492859A (en) * 2016-11-26 2017-03-15 新疆佳宇恒能源科技有限公司 Surface modified nickel-based sulfur resistant hydrogenation catalyst and preparation method thereof

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US3159564A (en) * 1961-10-20 1964-12-01 Union Oil Co Integral hydrofining-hydro-cracking process
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169783A (en) * 1976-05-06 1979-10-02 Uop Inc. Hydrocarbon conversion catalytic composite
US4057489A (en) * 1976-12-29 1977-11-08 Gulf Research & Development Company Process for producing a transformer oil having lower pour point and improved oxidation stability
US4113603A (en) * 1977-10-19 1978-09-12 The Lummus Company Two-stage hydrotreating of pyrolysis gasoline to remove mercaptan sulfur and dienes
US4225418A (en) * 1979-06-07 1980-09-30 Uop Inc. Hydroprocessing of hydrocarbons
US4294687A (en) * 1979-12-26 1981-10-13 Atlantic Richfield Company Lubricating oil process
US4518485A (en) * 1982-05-18 1985-05-21 Mobil Oil Corporation Hydrotreating/isomerization process to produce low pour point distillate fuels and lubricating oil stocks
US4758544A (en) * 1985-07-17 1988-07-19 Chevron Research Company Catalyst composition and hydroprocessing of oils using same
US4801373A (en) * 1986-03-18 1989-01-31 Exxon Research And Engineering Company Process oil manufacturing process
US6103101A (en) * 1993-10-01 2000-08-15 Petroleo Brasileiro S.A.-Petrobras Process for producing lube base oils of high viscosity index and diesel oil of high cetaned number
US20100078355A1 (en) * 2008-10-01 2010-04-01 Chevron U.S.A. Inc. Process to manufacture a base stock and a base oil manufacturing plant
WO2010039297A1 (en) * 2008-10-01 2010-04-08 Chevron U.S.A. Inc. A process to manufacture a base stock and a base oil manufacturing plant
US8562819B2 (en) 2008-10-01 2013-10-22 Chevron U.S.A. Inc. Process to manufacture a base stock and a base oil manufacturing plant
US9732287B2 (en) 2008-10-01 2017-08-15 Chevron U.S.A. Inc. Process to manufacture a base stock
US20100163454A1 (en) * 2008-12-31 2010-07-01 Gala Hemant B Hydrocracking processes yielding a hydroisomerized product for lube base stocks
US8231778B2 (en) 2008-12-31 2012-07-31 Uop Llc Hydrocracking processes yielding a hydroisomerized product for lube base stocks
CN106492859A (en) * 2016-11-26 2017-03-15 新疆佳宇恒能源科技有限公司 Surface modified nickel-based sulfur resistant hydrogenation catalyst and preparation method thereof
CN106492859B (en) * 2016-11-26 2019-05-17 新疆佳宇恒能源科技有限公司 A kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof

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