|Publication number||US3755145 A|
|Publication date||Aug 28, 1973|
|Filing date||Mar 17, 1971|
|Priority date||Mar 17, 1971|
|Publication number||US 3755145 A, US 3755145A, US-A-3755145, US3755145 A, US3755145A|
|Original Assignee||Mobil Oil Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (5), Referenced by (53), Classifications (10)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 1 Orkin [4 Aug. 28, 1973 LUBE 01L HYDROCRACKING WITH zsM-s 3,494,854 2/1970' Gallagher et al. 208/59 ZEOLITE 3,620,963 1 1/197] Mulaskey 208/1 1 1 3,650,945 3/1972 Bertolacini et al. 208/1 1 I Bernard A. Orkin, Cherry Hill, NJ.
Mobil Oil Corporation, New York, NY.
Filed: Mar. 17, 1971 Appl. No.: 125,409
US. Cl 208/111, 208/18, 252/455 Z Int. Cl C10g 13/02, ClOg 37/02 Field of Search 208/1 1 l, 18
References Cited UNITED STATES PATENTS 4/1969 Morris et al. 208/87 11/1970 Morris et al. 208/111  ABSTRACT A process for preparing lube oils characterized by possessing low pour points is set forth. The process involves subjecting a lube stock to a hydrocracking operation utilizing a catalyst mixture comprising hydrogenation components, a conventional cracking catalyst which can be either crystalline or amorphous and a crystalline aluminosilicate of the ZSM-5 type.
9 Claims, No Drawings" LUBE OIL IIYDROCRACKING WITH ZSM-S ZEOLITE BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the production of lube oils of high VI and low pour points by a completely catalytic process so that solvent dewaxing can be eliminated. The above is accomplished by using a hydrocracking catalyst which contains a mixture of at least two acidic components one acidic component being a conventional cracking catalyst, e.g. silica-alumina, or a large pore zeolite such as X or Y or mixtures thereof and the other acidic component being a crystalline aluminosilicate zeolite of the ZSM-5 type. A hydrogenation/dehydrogenation component is also present either as separate discrete particles or associated with either or both of the acidic components by conventional techniques such as base exchange or impregnation.
2. Description of the prior Art It is well known in the art to form various lubricatin oils commonly referred to as lubes from hydrocarbon fractions derived from petroleum crudes. A heretofore practiced common procedure known in the art is to extract these hydrocarbon fractions with variousselective solvents for aromatic compounds so as to obtaina raffinate of a desired high visocity index, such material being resistant to changes in viscosity with changes in temperature and thus being useful under various operating conditions. Moreover, it is. particularly desired that the lube oil have a low pour point so that it can be effectively used at low temperature conditions since formation of wax'crystals at low temperatures clogs strainers and'inhibits circulation of the lubricant. This has generally been accomplished by solvent dewaxing at low temperature with solvent mixtures such as ketone plus benzene. The heretofore practiced conventioinai solvent extraction processes plus solvent dewax ing'; although accepted commercially, nevertheless, sufferfrdin' the disadvantage that the combination is relatively expensive to operate.
It has been shown that high VI lube stocks can be prepared from raw distillates and residual oils by a mild hydrocracking adequate to open aromatic ring structures without excessive conversion to naphtha and light gaseous hydrocarbons. The resultant products often have Vlhigher than solvent refined oils .from the same source, but still require dewaxing for acceptable pour point. =Solvent dewaxing is the accepted operation, since it will remove both paraffin wax'and microcrystalline wax. 4
Recently proposals have been made to accomplish dewaxing in a catalytic operation by contact with .a shape selective cracking of hydrocracking catalyst. Such materials as zeolite A and erionite will not accept the slightly branched chain compounds of microcrystalline wax. Due to their great size, parafi'in wax (straight chains of v24 carbon atoms) are admitted slowly, if at all. Mordenite tends to coke up and become inoperative during relatively short time on stream.
In an attempt to overcome the inherent difficulties when employing a crystalline aluminosilicate having a pore size of five Angstrom units for catalystic dewaxing, the prior art resorted to so-called combination processes wherein'dewaxing was carried out utilizing both solvent techniques and catalytic conversion. In pro- 20, 1970, now abandoned, a process is disclosed for the production of lube stocks utilizing a catalyst of the ZSM-S type. In said copending application, a lube stock is first subjected to mild solvent dewaxing followed by catalytic conversion over a ZSM-S type catalyst. Although the process disclosed in this application represents a significant advance over the-heretofore practiced processes with respect to the quality of wax which is produced and the yields which are obtained, nevertheless, it is still necessary to use both solvent dewaxing and catalytic conversion thereby suffering the disadvantage of the use of multiple reactors.
DESCRIPTION OF THE INVENTION It has now been found that improved results can be obtained in the catalytic hydrocracking of lube stocks to produce lube oils having high viscosity indexes and .low pour points by contacting said lube stock iinthe presence of hydrogen with a catalyst mixture which comprises a hydrogenation component and atileast two separate acidic'cracking-catalysts, one being a-conven} tional cracking catalyst of the large pore and the other being a crystalline aluminosi'licate of the ZSM-S type. As .is more fully set forth in copending application Ser. No. 56,652 the ZSM-S type zeolites which are used in combinationwith the large pore cracking cata ,=lysts can generally be started to possess a pore size which will :alow entry into their internal pore structure of normal aliphatic compounds :and slightly branched aliphatic compounds, particulady monome'thylsubstituted compounds, yet substantially exclude all compounds containing at least a quaternary carbon atom or compounds having a molecular dimension equal to or substantially greater than a quaternary carbon atom. Thus, ZSM-5 type crystalline aluminosilicates have pore sizes which are larger than the conventional 5 Angstrom type 'aluminosilicates andyet smaller than the large pore size aluminosilicates such as those of the faujasite family. I r
The second acidiccomponent employed .in the novel catalyst mixtures of this .invention is :a conventional large pore cracking catalystsuch aswsilica-a'lumina, .silif ca-titania, .silica-zirconia, silica-boria, clay, .or a large pore 'aluminosilicate of the X and Y type of any mix-, tures thereof. These'materials, as isgenerally known in the art, have pore sizes such that :they will allow entry of essentially all the components present in a lube stock.
While not :wishing'ito abe bound'by .any theoryof operation, nevertheless, .itappears that conventional acidic" component of-the hydrocrackingcatalyst hydrogenates and opens ring compounds which have low VI "whereas also appear "likely that :there is .a synergistic effect due to a mutual coaction of each acidic .component not only witheach other butalsowith-rthezfeedmaterial. In
.any event, irrespective of anytheoreticalconsideration as to why :the catalyst :system operates, it has been found that such a catalyst system results in the production of acceptable lubes from raw distillates and residuals by a completely catalytic process without necessitating solvent dewaxing.
The ZSM-S type zeolite utilized in the novel process of this invention has the characteristic x-ray diffraction pattern set forth in Table l, hereinbelow. ZSM-S compositions can also be identified, in terms of mole ratios of oxides, as follows:
0.9: 0.2 M ln O W -100 YO, 2 H O wherein M is a cation, n is the valence of said cation, W is selected from the group consisting of aluminum and gallium, Y is selected from the group consisting of silicon and germanium, and z is from 0 to 40. In a preferred synthesized form, the zeolite has a fomiula, in terms of mole ratios of oxides, as follows:
0.9 i 0.2 M /n O A1 0 5-100 SiO, 1 H 0 and M is selected from the group consisting of a mixture of alkali metal cations, especially sodium, and tetraalkylammonium cations, the alkyl groups of which preferably contain to carbon atoms.
In a preferred embodiment of ZSM5, W is aluminum, Y is silicon and the silica/alumina mole ratio is at least and ranges up to about 60.
Members of the family of ZSM-5 zeolites possess a definite distinguishing crystalline structure whose x-ray diffraction pattern shows the following significant lines:
These values as well as all other x-ray data were determined by standard techniqes. The radiation was the K-a1pl1adoublet of copper, and a scintallation counter spectrometer with a strip chart pen recorder was used. The peak'heights, I, and the positions as a function of two times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these the relative intensities, 100 l/I, where I is the intensity of the strongest line or peak, and d(obs), the interplanar spacing in A, corresponding to the recorded lines, were calculated. In Table 1 the relative intensities are given in terms of the symbols S strong, M= medium, MS medium strong, MW medium weak and VS= very strong. It should be understood that this x-ray diffraction pattern is characteristic of all the species of ZSM-5 compositions. Ion exchange of the sodium ion with cations reveals substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample, as well as if it has been subjected to thermal treatment.
ZSM-5 is disclosed and claimed in copen'ding application Ser. No. 865,472, filed Oct. 10, 1969.
Another operable zeolite falling within the above class is zeolite ZSM-8 which is described and claimed in Ser. No. 865,418, filed October 10, 1969.
ZSM-8 can also be identified, in terms of the mole ratios of oxides, as follows:
0.9 i 0.2 M O Ai,o,= 5-100 sio 2 H O wherein M is at least one cation, n is the valence thereof and z is from 0 to 40. In a preferred synthesized form, the zeolite has a formula, in terms of mole ratios of oxides as follows: I
0.9 i 0.2 M,,,,O A1,O 10-60 SiO, 2 H O and M is selected from the group consisting of a mixture of alkali metal cations, especially sodium, and tetraethylammonium cations.
The ZSM-S type zeolites used in the instant invention usually have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art. Typical replacing cations would include hydrogen, ammonium and metal cations including mixtures of the same. Of the replacing metallic cations, particular preference is given to cations of ammonium, hydrogen, rare earth, mg, Zn, Mn, Al CA, and mixtures thereof.
Typical ion exchange techniques would be to contact the particular zeolite with a salt of the desired replacing cation or cations. Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates.
Representative ion exchange techniques are disclosed in a wide variety of patents including US. Pat Nos. 3,140,249: 3,140,251; and 3,140,253.
Following contact with the salt solution of the desired replacing cation, the zeolites may be washed with water and dried at a temperature ranging from 15 0F to about 600F and thereafter heated in air or other inert gas at temperatures ranging from about 500F to 1500F for periods of time ranging from 0.1 to 48 hours or more.
As had heretofore been pointed out in one embodiment, the novel catalyst composites of this invention comprise a physical mixture of at least two difierent cracking components, a ZSM5 type zeolite and a conventibnal large pore cracking catalyst. In one embodiment, a mixture of catalyst particles is used in which each particle contains only one of the two types of cracking components. Thus, for example, a mixture of particles of ZSM-5 type crystals and particles comprising silica-alumina may be composited in a hydrocracking catalyst. Ai hydrogenation/dehydrogenation component is present in both cracking components. Alternatively, the catalyst components may be pelleted, cast, molded, spray-dried, or otherwise formed into pieces of desired size and shape such as rods, spheres, pellets, etc.
The large pore size conventional cracking catalyst includes inorganic oxides. Of these, inorganic oxides such as clay, chemically treated clay, silica, silicaalumina, etc. are particularly preferred because of their superior porosity, and stabilityunder a reaction conditions, especially those reaction conditions encountered in the hydrocracking of lube stocks.
The compositng of the ZSM-S type zeolite with an inorganic oxide cracking catalyst can be achieved by several methods wherein the aluminosilicates are reduced to a particle size less than 40 microns, preferably less than 10 microns, and intimately admixed with an inorganic oxide while the latter is in a hydrous state such as in the form of hydrosol, hydrogel, wet gelatinous precipitate, or in a dried state. or a mixture thereof. Thus, finely divided ZSM-S type aluminosilicates can be mixed directly with a siliceous gel formed by hydrolyzing a basic solution of alkali metal silicate with an acid such as hydrochloric, sulfuric, acetic, etc. The mixing of the three components can be accomplished in any desired manner, such as in ballmill or other types of mills. The aluminosilicates also may be dispersed in a hydrosol obtained by reacting an alkali rnetal silicate with an acid or alkaline coagulant. The hydrosol is then permitted to set in mass to a hydrogel sphere consisting of stream and air or a gas which isnot which. is thereafter dried and broken into pieces of desired shape or dried by conventional spray drying techniqes or dispersed through anozzle into a bath of oil or other water-immiscible suspending medium to obtain spheroidally shaped bead particles of catalyst such as described in US. Pat. No. 2,384,946. The aluminosilicate siliceous gel thus obtained is washed free of soluble salts an thereafter dried and/or calcined as desired.
combinations thereof. The preparation of plural gels is a clay mineral whichhasbeen treated with anacid medium to render it active. The aluminosilicate can be incorporated into the clay simply by blending the two and fashioning the mixture into desired shapes. Suitable clays include attapulgite, kaolin, sepiolite, polygarskite,
- kaolinite, halloysite, plastic ball clays,bentonite, montmorillonite, illite, chlorite, etc. I
The catalyst product can be heated in steam or in other atmospheres, e.g., air, near the temperature contemplated for conversion but may be heated to operating temperatures initially during use in the conversion process. Generally, the catalyst is dried between 150F and 600F and thereafter may be calcined inair, steam, nitrogen, helium, flue gas, hydrogen or other gases not harmful to the catalyst product at temperatures ranging from about 500F to 1.,600"F for periods of time ranging from 1 .to 48-hours or more. it is to be understood that the ZSM-5 aluminosilicate can also be calcined prior to incorporation into the inorganic oxide gel cracking catalyst. It is also to be understood that the ZSM-S need not be ion exchanged prior to incorporation in the inorganic oxide but can be so treated during or after said incorporation.
- The catalyst can be subjected to amild stream treatment at elevated temperatures of 800F'to 1,600F and preferably-at temperatures of about 1,000F to 1,500F
harmful to the aluminosilicates or to the hydrogenation component. The steamtreatment can'be conducted before, after, or in place of the calcination treatment. 1
The particle size of each type of cracking component 1 making up the catalyst system is not narrowly critical but should be less than IOOmicrons and particle sizes within the range of from less-than 0.1 to 10 microns are preferred. it is also to be noted that each individual component in the catalyst system need not be of the same particle size. g
The particular proportion of one component to the other in the catalyst is also not narrowly critical and can vary over an extremely wide range. However, it has been found that for most purposes the weight ratio of the- ZSM-S type aluminosilicate to the large pore cracking catalyst can range from 1:10 to -2:1 and preferably from 1:5 up to 2:1 and still more preferably 1:4 to 1:1.
The ZSM-5 type crystalline aluminosilicates and the large pore conventional cracking catalyst may be added to a hydrocracking unit as a mixture of crystallites withinthe-same particles of catalyst composite,-
whether the particles are beads, extrudate's, or spraydried microspheres. Altemately, a mixture of particles may be added to the hydrocracking unit, some particles containing only the ZSM5 type aluminosilicate crys} tallites and hydrogenation componentand the other particles containing only the large pore cracking catalyst and hydrogenation component. In eithercase, the ratio of ZSM-5 type aluminosilicates to large pore cracking catalyst should bewithin the range of 1:10 to .221. I
The amount of the hydrogenation/dehydrogenation component employed is not narrowly critical and can range from about 0.01 to about 30 weight percent based on the entire catalyst. A variety of hydrogenation components maybe combined with either or both of the cracking components in any feasible manner which affords intimate contact of the components, employing well known techniques suchas impregnation, coprecip itation, coge'llation, mechanical admixtureof one com-. ponent with the other exchange and the like. The hy drogenation component can include metals, .oxides, and sulfides of metals of the Periodic Table which fall in Group VlB including chromium, molybdenum, tungsten, and the like; Group IIB including zinc cadmium; and Group VIII including cobalt, nickel, platinum, palladium, rhenium, rhodium and the like and cornbinations of metals, sulfides and oxides of metals of Group;
VB and VIII, such as nickel-tungsten-sulfide, cobalt.
oxide-molybdenum oxide and the like.
such is desired. The. treatment may be accompished in 1 an atmosphere'of percent steam or in an atmo- The pre-treatment before use varies depending on the hydrogenation component present. For example; with components such as nickel-tungsten and cobalt molybdenum, the catalystis sulfuractivated. But with metals like platinum or palladium, a hydrogenati'on step isemployed. These techniques are well known intheart and are accomplished in a conventional-manned Although-the conventional large pore cracking comthe art and particular preferenceis given to faujasites,:
both natural and synthetic, such as zeolites X and Y. Thus, one embodiment of this invention then includes a mixture of a ZSM- type catalyst together with zeolite X or Y wherein either or both of the aluminosilicates have a hydrogenation component associated therewith. When employing zeolites such as X and Y as the cracking component, it is preferred to base exchange said materials with cations in order to reduce the sodium content thereof. Compositions of this type include techniques with Compositions of this type include techniques with their base exchange are well known in the art and are set forth in U.S. Pat Nos. 3,140,249; 3,140,251; 3,140,252; and 3,140,253.
Still another embodiment of this invention resides in the use of a matrix material in conjunction with the large pore size aluminosilicate and the ZSM-S type zeolite. Thus, by way of illustration, the process of this invention can be carried out with a ZSM-5 type zeolite which is dispersed in a matrix such as silica-alumina into which is added a large pore crystalline aluminosilicate such as zeolite X which is also dispersed in a matrix such as silica alumina. The hydrogenation component can be present in either or both of the crystalline alumino-silicates and/or either or both of the matrices.
The novel process of this invention is carried out at temperatures of below about 650 to about 1,000F, a pressure between 100 and 5000 psig, but preferably between 1250-3000 psig. The liquid hourly space velocity is generally between 0.1 and 100 and preferably between 0.5 to 20. The hydrogen to hydrocarbon mole ratio is generally between 1 to 80 and preferably between 4 and 40.
The feed stocks which can be treated according to the novel process of this invention are waxy raw distillates and residual stocks boiling above 650F and particularly boiling between about 650F to about 1 150F.
In each of the examples (except 14) below, there is used a catalyst composite of ZSM-5 with a silicazirconia-clay composite which had been impregnated with nickel and tungsten to prepare a hydrocracking catalyst. That material was prepared by adding 1,350 g. kaolin-clay (moisture free basis) to 34,800 g. water with stirring. This slurry was added 2,037 g. silica (SiO,) as sodium silicate solution and then 31.8 g. kaolin-clay (moisture free basis). A solution was made up by adding 49 g. sodium zirconium silicate powder (contains 224 g. ZrO, and 1 14 g. SiO,) to 4,880 g. water and then adding 418 g. H SO, as 93.2% wt. 1-1,SO,
An impregnation solution was prepared by dissolving 128.6 g of ammonium metatungstate (72.3 percent wt W) and 184.4 g nickel nitrate Ni(NO,),. 611,0 in 200 cc water. This was diluted with water to 330 cc. The solution was then mixed with 880 g of the silica-zirconiaclay powder (91.0. percent solids). After addition of 150 cc water to make the material extrudable, it was extruded twice through 1/16 inch hole with roller type California Pellet Mill. The extrudate was dried 16 hours at 250F and calcined in flowing air for 3 hours at 1,000F. The product had a packed density of 0.87 g/cc and crush strength averaged 15 pounds for 25 pellets. Analysis showed 4 percent of nickel and 10 percent of tungsten, by weight.
The following examples will illustrate the best mode contemplated for carrying out this invention.
EXAMPLES 1 7 1n Examples 1-7, a catalyst mixture comprising 80 cubic centimeters of the above described nickeltungsten impregnated silica-zirconia-clay and 40 cubic centimeters of ZSM-5 which had been base exchanged with zinc and ammonium cations (ZnH/ZSM-S) were used to hydrocrack a lube stock in order to produce lubes.
The lub'e stock employed as a feed material in each of these examples had the following characteristics:
Gravity, APl 29.3 Pour Point, F +80 Sulfur, Wt. 0.47 Hydrogen, Wt. 13.04 I(.V. at 210F, cs 4.31 Wax, Wt. 16.3 Vacuum Assay, F
IBP 652 5% 686 10% 700 30% 733 767 804 844 852 The procedure employed involved contacting the catalyst mixture with the charge stock at a hydrogen circulation of 8,000 SCF/bbl. Additional operating conditions, as well as the results obtained, are shown in the following table. 1
650 F.+, Pressure Temp., wt. point, KV at KV at Example (p.s.i.g.) F. LHSV percent F. 210 \1 2, 500 760 1. 0 49. 3 0 20. 27 3. 96 100 2, 500 7 1. 5 58. 4 N 24. 77 4. 46 99 2, 600 740 1. 0 66. 7 10 24. 76 4. 4O 93 1, 500 740 1. 0 71. 3 5 28.55 4. 65 80 1,500 7 1.0 70.4 10 25.80 4.46 ST 1, 500 760 1. 5 T2. 1 +20 27. 84 4. 59 S0 1, 500 760 0. 5 43. 4 21. 65 4. 06 92 solution). The above solution was added to slurry of 60 clay in water plus sodium silicate. Then was added 35 percent H,SO till pH was 44.5. The acidified slurry was spray dried and the product was exchanged with (NI-10 80 solution, then with NH OH solution. The
exchanged material was washed with water and flash 65 dried.
Theproduct is a powder with average particle size of about 64 microns. It has a packed density of 0.56 g/cc,
EXAMPLES 8-14 The procedure of Examples 1-7 was repeated with the exception that the ratio of cracking components was changed. In Examples 8-13, the catalyst mixture contained 100 cubic centimeters of the nickeltungsten-silica-zirconia-clay and 20 cubic centimeters of ZnH/ZSM-S.
in Example 14 no conventional cracking component was present in the catalyst so that .the catalyst was solely ZnH/ZSM-5. This example serves a control so as EXAMPLES 25 28 to show the improved results obtained by the composite catalyst. Note the unacceptably low Viscosity lndex These examples, taken with Examples 2931 u trate the effect of varied proportions ofthe two compo- Additional operating conditions and results are of the catalyst when Processing Stocks f y shown below: high pour point (high wax content). should be borne 650 F.+, Pour Pressure Temp., wt. point, KV at KV at Example (p.s.i.g.) F. LHSV percen F. 100 210 VI 49 +20 17.14 3. 70 112 1 i 67 +26 19.36 3.86 100 2, 500 740 1 61 +30 20. .96 4. 16 111 1, 600 740 1 68 +20 22. 17 4. 1s 9s 1, 500 760 1 62 o 21. so 4. 14 100 1,600 760 0.5 40 -30 17.01 3.57 99 1, 500 740 0. 6 49 -1o 22. 69 4. 20 95 500 700 16 7a a4. 18 4. 9s 66 EXAMPLES 15 19 20 1n mmd that hydrocrackmg with conventional catalyst gives a net production of wax by opening rings to high boiling straight or slightly branched aliphatic compounds. For examples -28, the catalyst contained 100 parts of nickel-tungsten-silica-zirconia-clay and 20 The procedure of Examples l-7 was repeated with the exception that a charge stock was used which had the following characteristics:
Gravity, API 23.2 25 parts of ZnH/ZSM-S. The charge stock had the follow- Pour Point. ing properties: Sulfur, Wt. 2.07 -Wax',*Wt. 9.0
K.V-. 100F, cs 66.72 Gravity, API 23.8 K. V. 210F, cs 7.16 Pour Point, F. l20 Vacuum Assay, F Sulfur, wt.% 0.53 lBP 721 xv at ZIO'F. cs. 16.7 5% 778 Wax. wt.% 16.2
805 30 834 50% 846 Vacuum Assay (10 mm), "F 70% 871 mp 8 90% 893 5% 9s% I 916 10% 922 Analme point, i805 30% 940 I 957 Additional er 1' ditions and r sults are Op a lng con 6 90% m2 shown below: 95% 1020 650 F. Pour Pressure Temp, t. point, KV at KV at Example (p.s.i.g.) F. LHSV percent F. 100 F. 210 F. VI
2,600 760 1. 0 62.8 0 30.13 4; 94 95 2,600 740 1.0 73. 16 39.85 6.66 85 1, 500 740 1. 0 80.8 10 46. 1s 6. 02 76 1, 600 760 1. 0 70.5 6 4o. 15 6. 70 86 1, 500 760 1. 6 4s. 5 -1o 27. 69 4. 71 96 EXAMPLES 2024 After solvent dewaxing, the stock had these characteristics: The procedure of Examples 15-19 was repeated with the exception that the ratio of cracking components 22,": i 20 25 20 1o I was changed. In Examples 20-24, the catalyst mlxture Kv 8 3629, 3643 contained 100 cubic centimeters of the nickel- Sulfur, wt.% 0.67
tungsten-silica-zirconia-clay and 20 cubic centimeters of ZnH/ZSM 5' Processing conditions with 8,000 SCF/B of hydrogen Additional operating conditions and results are and results of processing are shown in the following Tashown below: 6 ble:
650 F.+, Pour Pressure T0111p.. point. K\' at KV at Exmnplo (p.s.l.g.) F. LI'ISV percent F. 100 F. 1'10 F. \I
650 F Pressure Temp, wt Wax,wt Pour KV at KV at lfixmnplu (psig) F. LIISV percent percent pt., F. 100 F. 210 F. VI
25.. 2,500 760 1.0 85.3 5.3 Z2 12%;; 2g 20 2.500 760 0.5 70.0 5.3 l 98 g:
,. 27 1,500 760 0.5 72.0 5.0 .fg g; 28 1, 500 760 1.0 87. 6 70 169. 2 13. 77 81 Hydrocrucked product solvent dewaxed to pour point indicated.
Example 25 was run at 2,500 psig, 760F, 1.0 LI-ISV, 8,000 SCF/B hydrogen. The 650F+ product was obtained in 85.3 percent yield with 88 V1. Removal of 5.3 percent wax brought the pour point down to F. This demonstrates that the combination operation removed at least 1 1 percent wax (hydrocracking produces wax) and raised the VI by 20 units (the raw, dewaxed charge has a 65 VI). Similarly at 0.5 LI-ISV, the raw 650F+ product was obtained in 70 percent yield with a +60F pour point (and percent wax). After dewaxing, the hydrocracked oil had a 99 VI.
Examples 27 and 28 show that the operation is also feasible at 1,500 psig where the yields are higher and the Vls are lower.
EXAMPLES 29-3l Using the same charge stock as shown for Examples 25-28, runs were made with a catalyst composite of 80 parts nickel-tungsten-silica-zirconia-clay at 8,000 SCF/B hydrogen. Further processing conditions and results obtained are shown in the following table:
b. a large pore cracking catalyst, and
c. a hydrogenation/dehydrogenation component in association with at least one of catalysts (a) or (b) whereby the Viscosity Index and the Pour Point of the oil are simultaneously enhanced.
2. The process of claim 1 wherein the large pore size aluminosilicate is synthetic faujasite.
3. The process of claim 1 wherein the ZSM-S type catalyst is ZSM-8.
4. The process of claim 1 wherein the ZSM-S type catalyst has been base exchanged with hydrogen ions, ammonium ions, and mixtures thereof.
5. The process of claim 1 wherein the large pore cracking catalyst is an inorganic oxide.
6. The process of claim 5 wherein the inorganic oxide comprises silica.
7. The process of claim 1 wherein the large pore cracking catalyst is a crystalline aluminosilicate having a pore size from 6 to 15 Angstrom units.
8. The process for preparing low pour point lube oils which comprises contacting a petroleum feed stock Pressure l.e1np., wt. Wax, wt. Pour KV at KV at Example (p.s.i.g.) F. LHSV percent percent pt., F. 100 F. 210 F. VI
What is claimed is:
l. A process for preparing low pour point lube oils which comprises contacting a petroleum charge stock having a boiling point above 650 F. and a low Viscosity Index under hydrocracking conditions to produce lubricant of substantially higher Viscosity Index with a catalyst composition comprising a mixture of a. a crystalline aluminosilicate of the ZSM-5 type having a composition in terms of mole ratios of oxides as follows:
0.9 :t 0.2 M O A1 0 Y SiO, 2 11 0 wherein M is at least one cation having a valence n, Y is at least 5 and z is between 0 and 40, said aluminosilicate having the x-ray diffraction lines as set forth in Table 1 of the specification,
9. The process of claim 8 wherein M is a mixture of ammonium and zinc cations.
* t t t mgg u STATES PATENT osmcs CERTFFICATE 0F GQECTEN mm No. 3,755,1M5 Dated August 28, 1
BERNARD A. ORKIN- Inventofls) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 6%, catalysti c" should be catalytic--. Column 2, line 53, "of" should be --or--. Column 3, line 21, "to" shouldbe 2-5 --j-.
Column l, line, 58, "under a reaction" should be -under reaction--.5 column L, line 61, "compositng" should be --compositing-.
Column 5, line 19, "an" should be --and--.; column 5, line 6-3, "stream" should be --steam--.5 column 5, line 65, "1500 1 "v should be --l500F if--.
Column 6, line 1, "stream" should be --steam-- .5 column 6, line 17, "1:10 to 2:1" should be --l:lO up tov2:l--.
Column 7, lines 9-10, Delete "Compositions of this type include techniques with" column 7, line 31 "to" should be --and--.
Signed and sealed this 5th day of February 1974.
EDWARD MELETCHERJR. I RENE D. TEGTMEYER Attesting Officer Acting Commissioner of'Patem
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|Citing Patent||Filing date||Publication date||Applicant||Title|
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|US3956102 *||Jun 5, 1974||May 11, 1976||Mobil Oil Corporation||Hydrodewaxing|
|US3989617 *||Nov 22, 1974||Nov 2, 1976||Mobil Oil Corporation||Catalytic treatment of lubrication oil base stock for improvement of oxidative stability|
|US4053532 *||Dec 5, 1975||Oct 11, 1977||Mobil Oil Corporation||Method for improving the fischer-tropsch synthesis product distribution|
|US4067797 *||Jan 16, 1976||Jan 10, 1978||Mobil Oil Corporation||Hydrodewaxing|
|US4210521 *||May 2, 1979||Jul 1, 1980||Mobil Oil Corporation||Catalytic upgrading of refractory hydrocarbon stocks|
|US4211635 *||Apr 23, 1979||Jul 8, 1980||Mobil Oil Corporation||Catalytic conversion of hydrocarbons|
|US4213847 *||May 16, 1979||Jul 22, 1980||Mobil Oil Corporation||Catalytic dewaxing of lubes in reactor fractionator|
|US4247388 *||Jun 27, 1979||Jan 27, 1981||Mobil Oil Corporation||Hydrodewaxing catalyst performance|
|US4251348 *||Dec 26, 1979||Feb 17, 1981||Chevron Research Company||Petroleum distillate upgrading process|
|US4282085 *||May 21, 1979||Aug 4, 1981||Chevron Research Company||Petroleum distillate upgrading process|
|US4292166 *||Jul 7, 1980||Sep 29, 1981||Mobil Oil Corporation||Catalytic process for manufacture of lubricating oils|
|US4347121 *||Oct 9, 1980||Aug 31, 1982||Chevron Research Company||Production of lubricating oils|
|US4358397 *||Dec 31, 1980||Nov 9, 1982||Mobil Oil Corporation||Zeolite catalysts modified with group IV A metals|
|US4383913 *||Oct 9, 1981||May 17, 1983||Chevron Research Company||Hydrocracking to produce lube oil base stocks|
|US4390413 *||Oct 6, 1980||Jun 28, 1983||Chevron Research Company||Hydrocarbon upgrading process|
|US4448673 *||Sep 28, 1982||May 15, 1984||Mobil Oil Corporation||Aging resistance shape selective catalyst with enhanced activity|
|US4542117 *||Jul 11, 1983||Sep 17, 1985||The British Petroleum Company P.L.C.||Catalyst composition, method for its production|
|US4568655 *||Oct 29, 1984||Feb 4, 1986||Mobil Oil Corporation||Catalyst composition comprising Zeolite Beta|
|US4575416 *||Jul 16, 1984||Mar 11, 1986||Mobil Oil Corporation||Hydrodewaxing with mixed zeolite catalysts|
|US4585799 *||Apr 17, 1985||Apr 29, 1986||The British Petroleum Company P.L.C.||Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas|
|US4600497 *||May 8, 1981||Jul 15, 1986||Union Oil Company Of California||Process for treating waxy shale oils|
|US4601993 *||Oct 17, 1984||Jul 22, 1986||Mobil Oil Corporation||Catalyst composition dewaxing of lubricating oils|
|US4696732 *||Feb 14, 1986||Sep 29, 1987||Mobil Oil Corporation||Simultaneous hydrotreating and dewaxing of petroleum feedstocks|
|US4757041 *||Dec 16, 1986||Jul 12, 1988||Mobil Oil Corporation||Catalysts for cracking and dewaxing hydrocarbon oils|
|US4767522 *||Jul 6, 1987||Aug 30, 1988||Mobil Oil Corporation||Distillate dewaxing process with mixed zeolites|
|US4773987 *||Apr 10, 1987||Sep 27, 1988||Mobil Oil Corporation||Shape-selective conversion of organic feedstock using clathrate group tectosilicates|
|US4790927 *||Jan 9, 1984||Dec 13, 1988||Union Oil Company Of California||Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons|
|US4818739 *||Dec 18, 1984||Apr 4, 1989||Uop||Hydrocracking catalysts and processes employing non-zeolitic molecular sieves|
|US4867861 *||Jul 21, 1988||Sep 19, 1989||Union Oil Company Of California||Process and catalyst for the dewaxing of shale oil|
|US4877762 *||Aug 22, 1988||Oct 31, 1989||Union Oil Company Of California||Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons|
|US4919788 *||Oct 21, 1988||Apr 24, 1990||Mobil Oil Corporation||Lubricant production process|
|US4976847 *||Aug 24, 1989||Dec 11, 1990||Shell Oil Company||Process for the catalytic cracking of a hydrocarbon feedstock|
|US5013422 *||Feb 14, 1990||May 7, 1991||Mobil Oil Corp.||Catalytic hydrocracking process|
|US5084159 *||Jun 26, 1989||Jan 28, 1992||Union Oil Company Of California||Process and catalyst for the dewaxing of shale oil|
|US5139647 *||Aug 14, 1989||Aug 18, 1992||Chevron Research And Technology Company||Process for preparing low pour middle distillates and lube oil using a catalyst containing a silicoaluminophosphate molecular sieve|
|US5183557 *||Jul 24, 1991||Feb 2, 1993||Mobil Oil Corporation||Hydrocracking process using ultra-large pore size catalysts|
|US5236880 *||Mar 9, 1992||Aug 17, 1993||W. R. Grace & Co.-Conn.||Catalyst for cracking of paraffinic feedstocks|
|US5290744 *||Oct 5, 1992||Mar 1, 1994||Mobil Oil Corporation||Hydrocracking process using ultra-large pore size catalysts|
|US5614079 *||Sep 29, 1994||Mar 25, 1997||Mobil Oil Corporation||Catalytic dewaxing over silica bound molecular sieve|
|US5837639 *||Jul 24, 1991||Nov 17, 1998||Mobil Oil Corporation||Hydroprocessing catalyst|
|US5846503 *||May 19, 1992||Dec 8, 1998||Mobil Oil Corporation||Process for rejuvenating used alkanolamaine solutions|
|US8231778||Dec 31, 2008||Jul 31, 2012||Uop Llc||Hydrocracking processes yielding a hydroisomerized product for lube base stocks|
|US9809509||Oct 18, 2016||Nov 7, 2017||Exxonmobil Chemical Patents Inc.||Process for xylenes isomerization|
|US20060138023 *||Nov 12, 2002||Jun 29, 2006||Exxonmobile Research And Engineering Company||Process for making a lube basestock|
|US20060142142 *||Nov 12, 2002||Jun 29, 2006||Exxonmobile Research And Engineering Company||Process for improving basestock low temeperature performance using a combination catalyst system|
|US20100163454 *||Dec 31, 2008||Jul 1, 2010||Gala Hemant B||Hydrocracking processes yielding a hydroisomerized product for lube base stocks|
|CN1061679C *||Sep 10, 1997||Feb 7, 2001||中国石油化工总公司||Catalytic dewaxing catalyst for lubricating oil|
|EP0113381A1 *||Dec 31, 1982||Jul 18, 1984||Mobil Oil Corporation||Process for simultaneous desulfurization and dewaxing of petroleum oils and catalysts therefor|
|EP0641257A1 *||Jul 23, 1992||Mar 8, 1995||Mobil Oil Corporation||Hydroprocessing catalyst|
|EP0641257A4 *||Jul 23, 1992||Jul 5, 1994||Mobil Oil Corp||Hydroprocessing catalyst.|
|WO1999041334A1 *||Feb 12, 1999||Aug 19, 1999||Exxon Research And Engineering Company||Process for improving basestock low temperature performance using a combination catalyst system|
|WO2017105617A1||Oct 18, 2016||Jun 22, 2017||Exxonmobil Chemical Patents Inc.||Process for xylenes isomerization|
|U.S. Classification||208/111.1, 502/67, 208/111.25, 208/18, 208/111.15|
|International Classification||C10G47/16, C10G45/64|
|Cooperative Classification||C10G2400/10, C10G47/16|