CA1156588A - Catalytic dewaxing of hydrocarbon oils - Google Patents
Catalytic dewaxing of hydrocarbon oilsInfo
- 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
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 17
- 239000003921 oil Substances 0.000 title abstract description 42
- 230000003197 catalytic effect Effects 0.000 title description 17
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 abstract description 23
- 239000010779 crude oil Substances 0.000 abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 239000000295 fuel oil Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 12
- 238000007670 refining Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 235000019809 paraffin wax Nutrition 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- NSVFPFUROXFZJS-UHFFFAOYSA-N nickel;hexahydrate Chemical compound O.O.O.O.O.O.[Ni] NSVFPFUROXFZJS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining 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
- C10G45/60—Refining 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
- C10G45/64—Refining 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline 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
- B01J29/48—Crystalline 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.
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
;_ '-.
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)
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.
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) |
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-
1979
- 1979-04-27 US US06/033,775 patent/US4229282A/en not_active Expired - Lifetime
-
1980
- 1980-04-22 ZA ZA00802411A patent/ZA802411B/en unknown
- 1980-04-23 AU AU57748/80A patent/AU540098B2/en not_active Ceased
- 1980-04-24 EP EP80301325A patent/EP0018778B1/en not_active Expired
- 1980-04-24 DE DE8080301325T patent/DE3061987D1/en not_active Expired
- 1980-04-24 CA CA000350630A patent/CA1156588A/en not_active Expired
- 1980-04-25 ES ES490892A patent/ES490892A0/en active Granted
- 1980-04-28 JP JP5558180A patent/JPS55145793A/en active Pending
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 |
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