EP0319626A1 - Procédé de déparaffinage catalytique avec un lit adsorbant à haute température - Google Patents

Procédé de déparaffinage catalytique avec un lit adsorbant à haute température Download PDF

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Publication number
EP0319626A1
EP0319626A1 EP87310908A EP87310908A EP0319626A1 EP 0319626 A1 EP0319626 A1 EP 0319626A1 EP 87310908 A EP87310908 A EP 87310908A EP 87310908 A EP87310908 A EP 87310908A EP 0319626 A1 EP0319626 A1 EP 0319626A1
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EP
European Patent Office
Prior art keywords
sorbent
catalyst
dewaxing
alumina
day
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.)
Withdrawn
Application number
EP87310908A
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German (de)
English (en)
Inventor
David Said Shihabi
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Publication date
Priority to US06/853,384 priority Critical patent/US4719003A/en
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Priority to EP87310908A priority patent/EP0319626A1/fr
Publication of EP0319626A1 publication Critical patent/EP0319626A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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

Definitions

  • This invention relates to improvements in processes for the catalytic hydrodewaxing of hydrocarbon chargestocks.
  • Particularly effective catalysts for catalytic dewaxing include ZSM-5 and related zeolites as described in U.S. Reissue Patent No. 28,398. Drastic reductions in pour point are achieved by selective conversion of the wax with hydrogen in the presence of ZSM-5.
  • the present invention provides a process for preparing a high Quality lube base stock oil from a waxy chargestock by contacting the chargestock and hydrogen gas with a zeolite dewaxing catalyst comprising a zeolite having a constraint index of 1-12 to produce dewaxed lube base stock and deactivated dewaxing catalyst characterized by contacting the chargestock with a sorbent at temperatures greater than 177°C (350°F) before dewaxing.
  • a zeolite dewaxing catalyst comprising a zeolite having a constraint index of 1-12 to produce dewaxed lube base stock and deactivated dewaxing catalyst characterized by contacting the chargestock with a sorbent at temperatures greater than 177°C (350°F) before dewaxing.
  • the feed may be any waxy hydrocarbon oil that has a pour point which is undesirably high.
  • Petroleum distillates such as atmospheric tower gas oils, kerosenes, jet fuels, vacuum gas oils, whole crudes, reduced crudes, and propane deashalted residual oils are contemplated as suitable feeds.
  • oils derived from tar sands, shale, and coal are contemplated as suitable feeds.
  • a particular embodiment of this invention is applicable to lube oil stocks in which the process of the present invention is used to prepare low pour point lube oil stocks with superior oxidation resistance.
  • Lubricating oils are based on petroleum fractions boiling above 232°C (450°F). The molecular weight is high. These fractions include almost all conceivable structures. This complexity and its consequences are referred to in "Petroleum Refinery Engineering,” by W. L. Nelson, McGraw Hill Book Company, Inc., New York, New York, 1958 (4th Ed.)
  • the first step of the process of this invention requires that the feed be treated by contact with a sorbent to remove some of the deleterious impurity. These conditions may cover a fairly wide range of time, temperature and pressure, and may be conducted in the presence of hydrogen. The conditions, both broad and preferred, for this step of the process are indicated in Table 1.
  • the sorbents used as the guard bed include alumina, clay, bauxite, spent catalysts, etc.
  • a sorbent having a surface area of at least 50 m2/g and at least l0% of the pores being in the range of 30-l00°A is useful in this invention.
  • Gamma-alumina, eta-­alumina, or mixtures thereof are effective sorbents.
  • the sorbent may consist of molecular sieve type zeolites with or without exchange capacities having pores with an effective diameter of at least 5 Angstroms.
  • Another class of sorbents that could be used also include a family of crystalline microporous aluminophosphates (U.S. Patent 4,385,994) and silicoaluminophosphate (U.S. Patent 4,440,871). These sorbents can be used alone or in combination with other refractory inorganic oxides.
  • zeolites with pores of 5 Angstroms Illustrative of zeolites with pores of 5 Angstroms are zeolite A in the calcium salt form, chabazite and erionite, which sorb normal paraffins but exclude all other molecules of larger critical diameter.
  • Other zeolites which may be used which have larger pore diameters include zeolite X, zeolite Y, offretite and mordenite. The last group of zeolites sorbs molecules having critical diameters up to about 13 Angstroms, and all of them sorb cyclohexane freely.
  • any zeolites useful as dewaxing catalysts also may be used as sorbents.
  • the zeolite sorbent and dewaxing catalysts may have the same crystal structure.
  • the pretreated feed is separated from the sorbent and passed to the catalytic dewaxing step.
  • the feed is contacted with a dewaxing catalyst under sorption conditions after which a pretreated feed is recovered and passed to storage.
  • the sorbent is now treated, for
  • the catalytic dewaxing process is illustrated in U.S. Reissue 28,398 and U.S. 3,956,102 and 4,137,148.
  • the dewaxing step may be conducted with or without hydrogen, although use of hydrogen is preferred. It is contemplated to conduct the dewaxing step at the dewaxing conditions shown in Table II.
  • Useful dewaxing catalysts include zeolites having a constraint index of 1-12. Preferred are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 ZSM-38, ZSM-48, and other similar materials.
  • ZSM-5 is described in US 3,702,866 and Re. 29,948.
  • ZSM-23 is described in U.S. 4,076,842.
  • ZSM-35 is described in U.S. 4,016,245.
  • ZSM-48 is described in U.S. 4,397,827.
  • the zeolite When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form.
  • the hydrogen form In addition to the hydrogen form, other forms of the zeolite wherein the original alkali metal has been reduced to less than about 1.5 percent by weight may be used.
  • the original alkali metal of the zeolite may be replaced by ion exchange with other suitable metal cations of Groups I through VIII of the Periodic Table, including, by way of example, nickel, copper, zinc, palladium, calcium or rare earth metals.
  • Useful matrix materials include both synthetic and naturally occurring substances, as well as inorganic materials such as clay, silica and/or metal oxides.
  • the matrix may be in the form of a cogel.
  • the relative proportions of zeolite component and inorganic oxide gel matrix, on an anhydrous basis, may vary widely with the zeolite content ranging from 1 to 99 percent by weight and more usually in the range of 5 to 80 percent by weight of the dry composite.
  • Bright stock raffinate having the properties set forth in Table 3 was dewaxed at 1 LHSV, 2900 kpa (400 psig), 450 n.l.l ⁇ 1 H2 (2500 SCFB) over catalyst comprising 65% ZSM-5/35% alumina. Properties of the dewaxing catalyst are shown in Table 4. The catalyst was used for seven processing cycles with hydrogen reactivation in between the first four cycles (120 days) and oxygen regeneration, with air, for all subsequent cycles. In all cases air regeneration was carried out in situ circulating gas containing less than 1% 02 during initial coke burn. Final coke burn was accomplished by a stream containing 50% air at 510° (950°F).
  • the experiments were carrier out in stainless steel micro-units.
  • the reactor was 5.3 mm (5/8 ⁇ ) ID with a 3.2 mm (1/8 ⁇ ) axial thermowell containing 15 cc (8.6 grams) of the as received extrudate catalyst diluted with 15 cc of 0.84 to 1.41 mm (14/20 mesh) vycor chips.
  • Fig. 1 summarize the reults of this study. Aging rates of 2.8°C/day (5°F/day), 4.7°C/day (8.5°F/day), and 5.6°C/day (l0°F/day) following first, second and third air regenerations were obtained. In addition, start of cycle temperature increased 2.8-5.6°C (5-l0°F) following every air regeneration.
  • the catalyst was air regenerated and submitted for alpha and acid sites density mearsurements. The alpha values were evaluated after H2S treatment of the fresh and spent catalysts. The reported alpha values were 120 and 140 for fresh and spent catalysts, respectively. Acid site densities of the fresh catalyst and the air regenerated spent catalyst are essentially the same at 0.202 and 0.221 MEQ N/g CAT, respectively.
  • Example 1 Bright stock of Example 1 was dewaxed in a micro-unit similar to the one used in Example 1.
  • the reactor had a 5.3 mm (5/8 ⁇ ) ID and contained 15 cc of the as received extrudate catalyst mixed with 10 cc of fine sand.
  • the axial thermocouple was removed to maximize feed distribution throughout the catalyst bed.
  • the catalyst was used for seven processing cycles with hydrogen reactivation in between the first four cycles and air regeneration for all subsequent cycles.
  • aging curves for fresh and air regenerated catalyst are shown in Fig. 2. Aging rate increased from 1.3°C/day (2.3°F/day) for fresh catalyst to 2.3°C/day (4.1°F/day) and 3.1°C/day (5.5°F/day) for first and second air regeneration.
  • alpha value and acid site density of the spent and fresh catalysts were measured.
  • the catalyst was air regenerated in a procedure similar to that used for the second air regeneration and submitted for analysis.
  • Alpha values were evaluated after H2S treatment of the fresh and spent catalysts. The reported alpha values were 125 and 115 for fresh and spent catalysts, respectively. Acid site densities of the fresh catalyst and the air regenerated spent catalyst are essentially the same at 0.23 and 0.24 MEQ N/g CAT, respectively.
  • the experiments were carried out in stainless steel two-stage reactor.
  • the first reactor 5.3 mm (5/8 ⁇ ) I.D. contained 30 cc of American Cynamid alumina (surface area 200m2/g) mixed with 20cc sand.
  • the second reactor 5.3 mm (5/8 ⁇ ) I.D. contained 15 cc of the as-received 101 alpha dewaxing catalyst of Example 1 mixed with 15 cc of the same sand.
  • the experiments consisted of seven processing cycles with air regeneration in between the first four cycles. Standard hydrogen activation before the fifth cycle and air regeneration before the last two cycles.
  • Hydrogen activation was done at 482°C (900°F) for 24 hours at 2200 kPa (305 psig) in once-through hydrogen circulation 450 n.l.l ⁇ 1 (2500 SCF/B), based on 1 LHSV.
  • a fresh alumina guard bed was used with each new cycle (the alumina was dried by purging with hydrogen at 149°C (300°F).
  • Fresh and air regenerated catalyts were presulfided prior to catalytic evaluation.
  • the guard bed which was changed at the end of each cycle, was bypassed during high temperature purging, oxygen regeneration and presulfiding. Bypassing the guard bed kept desorbed materials from the dewaxing catalyst.
  • Hydrogen and feed were passed over the alumina guard bed at 0.5 LHSV 288°C (550°F) and 2900 kPa (400 psig), and the product was cascaded over the dewaxing catalyst.
  • Dewaxing conditions over the catalyst were 0.9 LHSV, 2900 kPa (400 psig) and 450 n.l.l ⁇ 1 (2500 SCF H2/B).
  • the guard bed temperature was held constant at 288°C (550°F), while the dewaxing reactor temperature was set to maintain specification pour point on the product.
  • Cycle No. 6 lasted 42 days.
  • the catalyst aged at 1.6°C/day (2.9°F/day).
  • the catalyst was then air regenerated.
  • Then bright stock was processed over this seventh cycle for seven days.
  • the catalyst aging rate was 1.6°C/day (2.9°F/day).
  • the guard bed stabilizes the cycle to cycle dewaxing performance of dewaxing catalysts.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP87310908A 1984-06-18 1987-12-11 Procédé de déparaffinage catalytique avec un lit adsorbant à haute température Withdrawn EP0319626A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US06/853,384 US4719003A (en) 1984-06-18 1986-04-16 Process for restoring activity of dewaxing catalysts
EP87310908A EP0319626A1 (fr) 1987-12-11 1987-12-11 Procédé de déparaffinage catalytique avec un lit adsorbant à haute température

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP87310908A EP0319626A1 (fr) 1987-12-11 1987-12-11 Procédé de déparaffinage catalytique avec un lit adsorbant à haute température

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EP0319626A1 true EP0319626A1 (fr) 1989-06-14

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE508479A (fr) *
US4269694A (en) * 1979-10-01 1981-05-26 Phillips Petroleum Company Method of removing contaminant from a feedstock stream
US4357232A (en) * 1981-01-15 1982-11-02 Mobil Oil Corporation Method for enhancing catalytic activity
US4534855A (en) * 1983-01-03 1985-08-13 Tenneco Oil Company Shale oil demetallization process
EP0175799A1 (fr) * 1983-06-20 1986-04-02 Ashland Oil, Inc. Immobilisation de vanadium déposé sur des adsorbants pendant la viscoréduction d'huiles contenant des métaux et des précurseurs de carbone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE508479A (fr) *
US4269694A (en) * 1979-10-01 1981-05-26 Phillips Petroleum Company Method of removing contaminant from a feedstock stream
US4357232A (en) * 1981-01-15 1982-11-02 Mobil Oil Corporation Method for enhancing catalytic activity
US4534855A (en) * 1983-01-03 1985-08-13 Tenneco Oil Company Shale oil demetallization process
EP0175799A1 (fr) * 1983-06-20 1986-04-02 Ashland Oil, Inc. Immobilisation de vanadium déposé sur des adsorbants pendant la viscoréduction d'huiles contenant des métaux et des précurseurs de carbone

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