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EP0204750A1 - Reactivation d'un catalyseur desactive - Google Patents

Reactivation d'un catalyseur desactive

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Publication number
EP0204750A1
EP0204750A1 EP85905984A EP85905984A EP0204750A1 EP 0204750 A1 EP0204750 A1 EP 0204750A1 EP 85905984 A EP85905984 A EP 85905984A EP 85905984 A EP85905984 A EP 85905984A EP 0204750 A1 EP0204750 A1 EP 0204750A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
metal
solution
aqueous solution
rejuvenating
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Withdrawn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
EP85905984A
Other languages
German (de)
English (en)
Other versions
EP0204750A4 (fr
Inventor
Dennis L. Holtermann
Rodolfo V. Panopio
Sue D. Pandey
Leslie A. Field
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron Research and Technology Co
Chevron Research Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Research and Technology Co, Chevron Research Co filed Critical Chevron Research and Technology Co
Publication of EP0204750A1 publication Critical patent/EP0204750A1/fr
Publication of EP0204750A4 publication Critical patent/EP0204750A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/20—Regeneration or reactivation
    • 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
    • B01J29/90—Regeneration or reactivation

Definitions

  • the present invention concerns a method for rejuvenatinq a zeolitic catalyst.
  • Catalytic reforming is a well known process that . m is used to raise the octane rating of a naphtha for gasoline.
  • the reactions that occur during reforming include: dehydrocyciization of acyclic hydrocarbons, dehydroqenation of cyclohexanes , dehydroiso erization of alkylcyclopentanes , isomerization of paraffins, dealky- i lation of alkylbenzenes, and hydrocrackinq of paraffins.
  • the hydrocrackinq reaction should be suppressed because that reaction lowers the yield of hydrogen and lowers the yield of liquid products.
  • Reforming catalysts must be selective for 0 dehydrocyciization in order to produce high yields of liquid product and low yields of light qases. These cata ⁇ lysts should possess good activity, so that low tempera ⁇ tures can be used in the reformer. Also they should possess good stability, so that they can maintain a high activity and a high selectivity for dehydrocyciization over a long period of time. Furthermore, they should be regenerable, so that they can be reqenerated without loss of performance.
  • a new catalyst that comprises: a large-pore zeolite, a Group VIII metal, and an alkaline earth metal.
  • This catalyst has a very hiqh selectivity for dehydrocyciization, but it is hard to 0 regenerate.
  • S ⁇ MMARY OF THE INVENTION The present invention is based on the discovery that a catalyst can be rejuvenated by contacting the cata ⁇ lyst with an aqueous media selected from the group con ⁇ sisting of water, an aqueous solution, and a saturated water vapor. This method of reiuvenation works for large-pore zeolitic catalysts that contain at least one Group VIII metal -
  • At least 10 cc of aqueous media must be used per cc of catalyst, and the aqueous media must be in the liquid phase.
  • at least 500 cc of aqueous media is used per cc of catalyst.
  • oxidizing conditions preferably at a temperature of from about 200°C to about 450°C.
  • reducinq conditions preferably in the presence of hydrogen at a temperature of from about 200°C to about 700°C.
  • a basic solution (i.e., r>H greater than 7) can be used instead of water or a saturated water vapor.
  • the catalyst is contacted with a basic solution at a temperature of from about 70°C to about 80°C.
  • the basic solution can be an alkali metal hydroxide solution, such as potassium hydroxide solution having a pH of at least 10.
  • a zeolitic catalyst in a second embodiment, can be rejuvenated, and the stability of that catalyst can be improved, by contacting the catalyst with an aqueous solu ⁇ tion of a metal salt or metal hydroxide, wherein the metal is either an alkali metal and an alkaline earth metal.
  • a zeolitic catalyst can be rejuvenated by washinq the catalyst with either a neutral" or an acidic solution, contacting the washed cata ⁇ lyst with an aqueous solution of a metal salt or metal hydroxide (the metal is either an alkali metal and an alkaline earth metal) , washing the contacted catalyst with a neutral solution; and dryinq the twice washed catalyst.
  • This method is useful for both sulfur-contaminated cata ⁇ lysts and catalysts deactivated by other means.
  • the concentration of the aqueous solution should be from 0.1% to 10% by weight of metal.
  • a more preferred concen ⁇ tration range is from 0.1% to 3% by weight of metal.
  • the metal salt or hydroxide is either a metal halide, metal nitrate, metal carbonate, metal phosphate, or metal hydroxide.
  • the preferred metal salt is a metal hydroxide, such as potassium hydroxide.
  • the contacting occurs at a temperature of from 25°C to 100°C (more preferably, about 80°C) , then the catalyst that has been contacted with the aqueous solution is washed with from 10 to 200 cc of water per gram of cata ⁇ lyst to remove excess metal, and the washed catalyst is dried.
  • the catalyst is contacted with an oxidizing gas at conditions which favor oxidation before the first washing step.
  • the present invention involves rejuvenating a catalyst by contacting the cata ⁇ lyst with a large guantity of an agueous media in the liquid phase.
  • This contacting step is an essential ele ⁇ ment of the present invention.
  • the aqueous media must be in the liquid phase. If water in the liquid phase is not present then the con ⁇ tacting step does not show the surprising regeneration of the present invention.
  • a large quantity of aqueous media is required. At least 10 cc of aqueous media should be used per cc of catalyst. Preferably, at least 500 cc of aqueous media should be used per cc of catalyst.
  • This regeneration procedure is not only useful for sulfur-contaminated catalysts, but is also useful for catalysts deactivated by other means.
  • a basic solution can be used to contact the . n sul ur-contaminated catalyst at a temperature of from about 70°C to about 80°C.
  • the basic solution is an alkali metal hydroxide solution, such as a potassium hydroxide solution having a pH of at least 10.
  • This embo ⁇ diment has the advantaqe of minimizinq the formation of l ⁇ acid sites on the catalyst.
  • a saturated water vapor in the liquid phase can be used to contact the sulfur-contamina ed catalyst, pre ⁇ ferably at a temperature of from about 120°C to about 180 °C.
  • This embodiment has the advantage of allowing in situ treatment without having to remove or handle the. catalyst.
  • the present invention rejuvenates the catalyst without removing all the sulfur from the catalyst. While it is not fully understood how the present invention achieves its surprising rejuvenation of sulfur-contami ⁇ nated catalysts, one theory is that the washing might be converting the sulfur present in the catalyst to a state which is easier to be removed from the catalyst during the reduction and reforming process or a state which does not 0 interfere wi h the desired catalytic reactions.
  • the catalyst can be exposed to oxidizing condi ⁇ tions prior to contacting the catalyst with an aqueous media. While the contacting step causes a sizable rejuve ⁇ nation of the catalyst, the combination of the oxidizing 5 step and the contacting step causes a still more sizable rejuvenation.
  • the oxidation step occurs in the presence of oxygen .at a temperature of from about 200°C to about 450°C. The oxidation step alone does not rejuvenate the catalyst. 0 * It is thought that the oxidation step changes the sulfur to a water-soluble form and/or weakens the association between platinum and sulfur. This could be effected with other oxidizing agents besides oxygen, such as KMnO ⁇ , Cr0 3 , etc. This could be applied to other metal-containing catalysts where sulfur is known to harm activity.
  • the catalyst can be exposed to reducing condi ⁇ tions after contacting the catalyst with an aqueous media.
  • the reduction step occurs in the presence of hydrogen at a temperature of from 200°C to 700 °C. Note that no rejuvenation occurs from the reduction step alone, or from reduction following oxidation without including the water step.
  • the ef ectiveness of this reducing step may depend on whether the solvent molecules shielding the platinum are removed faster than the sulfur is reduced. In this context, we have discovered that if the water treatment employs wet hydrogen, a more stable rejuvenated catalyst is obtained. Other reducing agents, such as water-soluble hydrazine-hydrate , NaBH ⁇ , and KBH 4 , could also be used for this step.
  • the combination of the oxidizing step, the soak ⁇ ing step, and the reducing step causes a still more sizable rejuvenation than the combination of the soaking step with either only the oxidizing step or only the reducing step. These three steps can be repeated, as needed, until the catalyst is rejuvenated to the desired level .
  • a sul ur-contaminated catalyst can be exposed to oxidizing conditions in the presence of oxygen at a tem ⁇ perature of from about 200°C to about 450°C, the oxidized catalyst is contacted with at least 500 cc of a saturated water vapor in the liquid phase per cc of catalyst at .? temperature of from about 120 °C to about 180 °C, then the catalyst is exposed to reducing conditions in the presence of hydrogen at a temperature of from 200 °C to about 700 °C. These steps are repeated until the catalyst is rejuvenated to the desired level. — ⁇ —
  • a large-pore zeolitic catalyst that contains at least one Group VIII metal is
  • the metal salt or hydroxide may be either a metal halide, metal nitrate, metal carbonate, metal phosphate, or metal hydroxide.
  • the metal salt or hydroxide is
  • the catalyst is con ⁇ tacted with from 2 to 30 cc of aqueous solution per gram of catalyst at a temperature o-f from 25°C to 100°C, more preferably at a temperature of about 80°C.
  • the aqueous solution should have a concentration of from 0.1% to 10%
  • metal 20 by weight of metal, preferably from 1%. to 8% by weight of metal .
  • the catalyst is washed with from 10 to 200 cc of water per gram of catalyst to remove excess
  • the sulfur-contaminated catalyst can comprise a type L zeolite containing from 8% to 10% by weight barium and from 0.1% to 1.5% by weight platinum; and an inorganic
  • This sulfur-con ⁇ taminated catalyst is contacted at a temperature of about 30°C with from 2 to 30 cc of an aqueous potassium hydroxide solution per gram of catalyst.
  • the agueous solu- -J tion has a concentration of from 1% to 8% by weiqht of metal. After the catalyst is contacted with a solution, it is washed with from 10 to 200 cc of water per gram of catalyst to remove excess metal, and then it is dried.
  • the catalyst can be washed with a neutral or • Q acidic ⁇ solution, then contacted with an aqueous solution of an alkali metal salt or alkaline earth metal salt, then washed with a neutral solution, and dried.
  • the present invention involves rejuvenating a large-pore zeolitic catalyst that contains at least one Group VIII metal by washing the catalyst with a non-basic solution, contacting the washed ._ catalyst with an aqueous solution of a salt of a metal selected from the group consisting of an alkali metal and an alkaline earth metal, washing the contacted catalyst with a neutral solution; and drying the washed catalyst.
  • This regeneration procedure i ' s useful, not only for sul- j c fur-contaminated catalysts, but also for catalysts deac ⁇ tivated by other means.
  • the present invention rejuvenates the catalyst without removinq all the sulfur from the catalyst.
  • the catalyst is washed with from 10 to 200 cc of either a neutral solution or an acidic solution per qram of catalyst-.
  • An essential step of this embodiment is that the catalyst must be contacted with an aqueous solution of a salt or hydroxide of a metal selected from the group con ⁇ sisting of an alkali metal and an alkaline earth metal.
  • the metal salt or hydroxide may be either a metal halide, metal nitrate, metal carbonate, metal phosphate, or metal 0 hydroxide.
  • the catalyst is contacted with from 2 to 30 cc of aqueous solution per gram of catalyst at a temperature of from 25°C to 100°C, more preferably at a temperature of about 80 °C.
  • the aqueous solution should have a concentration of from 0.1% to 10% by weiqht of 5 metal, preferably from 0.1% to 8% by weight of metal.
  • the catalyst has been contacted with the agueous solution, the catalyst is washed with from 10 to 200 cc of water per gram of catalyst to remove excess metal, then the washed catalyst is dried.
  • the catalyst is contacted with an oxidizing gas at conditions which favor oxidation before the first washing step.
  • the deactivated catalyst is a sulfur-contaminated catalyst that comprises a type zeolite containing from 8% to 10% by weight barium and from 0.1% to 1.5% by weight platinum; and an inorganic binder selected from the group consisting of silica, alumina, aluminosilicates, and clays.
  • This sulfur-contaminated catalyst is contacted with an oxidizing gas at conditions which favor oxidation, then the catalyst is washed with a neutral solution, then the catalyst is contacted at a temperature of about 80 °C with from 2 to 30 cc of an agueous potassium hydroxide solution per -gram of catalyst.
  • the aqueous solution has a concen ⁇ tration of from 0.1% to 8% by weight of alkali or alkaline earth metal.' After the catalyst is contacted with a solu ⁇ tion, it is washed with from 10 to 200 cc of water per gram of catalyst to remove excess metal, then it is dried.
  • One reforming catalyst that can be regenerated by the present invention is a large-pore zeolite charged with one or more dehydrogenating constituents.
  • the term "large-pore zeolite” is defined as a zeolite having an effective pore diameter of 6 to 15 Angstroms.
  • Type L zeolite, zeolite X, zeolite Y and faujasite are thought to be the best large-pore zeolites for this operation and have apparent pore sizes on the order of from 7 to 9 Angstroms.
  • the preferred catalyst is a type L zeolite charged with one or more dehydrogenating constituents.
  • An alkaline earth metal can be present in the catalyst. That alkaline earth metal can be either barium, strontium or calcium.
  • the alkaline earth metal can be incorporated into the zeolite by synthesis, impregnation or ion exchanqe.
  • Barium is preferred to the other alkaline earths because the resulting catalyst has high activity, high selectivity and hiqh stability.
  • the barium should preferably constitute from about 0,1% to about 35% of the weight of the zeolite, more preferably from about 1% to about 20% by weight.
  • the reforming catalysts according to the inven ⁇ tion are charged with one or more Group VIII metals, e.g., nickel, ruthenium, rhodium, palladium, iridium or platinum.
  • Group VIII metals e.g., nickel, ruthenium, rhodium, palladium, iridium or platinum.
  • the preferred Group VIII metal is platinum, which is more selective with regard to dehydrocyciization and is also more stable under the reforming reaction con ⁇ ditions than other Group VIII metals.
  • the preferred per- centa ⁇ e of platinum in the catalyst is between 0.1% and 5%, more preferably from 0.1% to 1.5%.
  • An inorganic oxide can be used as a.carrier to bind the large pore size zeolite.
  • the carrier can be a natural or a synthetically produced inorganic oxide or combination . of inorganic oxides. Preferred loadings of inorganic' oxide are from 5% to 50% by weight of the cata ⁇ lyst.
  • Typical inorganic oxide supports which can be used include silica, alumina, and aluminosilicates.
  • the first embodiment of the present invention will be further illustrated by the following examples which set forth a particularly advantageous method and composition embodiments. While the examples are provided to illustrate the present invention, they are not intended to limit it.
  • a catalyst was prepared by (1) ion exchanging a potassium-type L zeolite with a sufficient volume of 0.17 molar barium nitrate solution to contain an excess of barium compared to the ion exchange capacity of the zeolite; (2) drying the resulting barium-exchanged type L zeolite catalyst; (3) calcining the catalyst at 590°C; (4) impreqnatinq the catalyst with 0.8% platinum using tetrammineplatinu (II) nitrate; (5) drying the catalyst; (6) calcining the catalvst at 260°C; and (7) reducing the catalyst in hydrogen at 480°C to 500°C.
  • the catalyst of Exampl e I wa s used in a pilot plan t to re form n-hexane that had been hydrof ined to remove sul f ur , oxygen and nitrogen .
  • the re forming occurred a t 860 °F , 100 ps ig , 17 LHSV, and 5 H 2 /HC .
  • Example I The catalyst of Example I was used in a pilot plant to reform naphtha that had been hydrofined to remove sulfur, oxygen and nitrogen and then to which sulfur com ⁇ pounds were deliberately added in order to generate a sulfur-contaninated catalyst.
  • the reforming occurred at 860°F, 100 psiq - 1.5 LHSV, and- 6 H 2 /HC for 3 weeks to produce a sulfided catalyst, then the sulfided catalyst was tested by the procedures of Example II. The results of that test after ten and twenty hours are listed in Table I.
  • the sulfided catalyst of Example III was oxidized at one atmosphere with 1% oxygen in nitrogen for one half hour at 400°F, one hour at 500°F, and 5 hours at 750°F ; then the catalyst was tested by the procedures of Example II. The results of that test after ten and twenty hours are listed in Table I.
  • Example Til The sulfided catalyst of Example Til was washed with 80°C water at 2cc/min for one hour, then the catalyst was tested by the procedures of Example II. The results of that test after ten and twenty hours are listed in Table I.
  • Example VI The sulfided catalyst of Example III was oxidized at one atmosphere with 1% oxygen in nitrogen for one half hour at 400°F, one hour at 500°F, and 5 hours at 750 °F; then washed with 100% steam at 212°F for 3 hours, then the catalyst was tested by the procedures of Example' II. The results of that test after ten and twenty hours are listed in Table I.
  • Example VIII The sulfided catalyst of Example III was oxidized at one atmosphere with 1% oxygen in nitrogen for one half hour at 400°F, one hour at 500°F, and 5 hours at 750 °F ; then washed with 100% steam at 212 °F for 3 hours; then reduced at 900°F in H 2 for 1-1/2 hours, then oxidized at one atmosphere with 1% oxygen in nitrogen for one half hour at 400°F, one hour at 500°F, and 5 hours at 750°F; then washed with 100% steam at 212°F for 3 hours; then reduced at 900°F in H 2 for 1-1/2 hours, then oxidized at one atmosphere with 1% oxygen in nitrogen for one half hour at 400°F, one hour at 5.00°F and 5 hours at 750°F; then washed with 100% steam at 212°F for 3 hours; then the catalyst was tested by the procedures of Example II. The results of that test after ten and twenty hours are listed in Table I. Table I Relative Rate Constants for
  • Examples V, VI, VII, and VIII are examples of the present invention. They show that washing, either alone or in conjunction with oxidation, rejuvenated deactivated catalysts.
  • Fresh reforminq catalyst was prepared by (1) ion exchanging a potassium-type L with a sufficient volume of 0.17 molar barium nitrate solution to contain an excess of barium compared to the ion exchange capacity of the zeolite: (2) drying the resulting barium-exchanged type L zeolite catalyst; (3) calcining the catalyst at 590°C;
  • a second portion of the fresh reforming catalyst was deactivated by contacting the catalyst with a sulfur- containing light straight run until about 200 ppm sulfur
  • the deactivated catalyst was rejuvenated by contacting the catalyst for two hours at a temperature of about 80°##?C with an aqueous solution of potassium hydroxide having a concentration of 5% by weight of metal, wherein there was 30 cc of aqueous solu ⁇
  • a type L zeolite reforming catalyst was treated with a sulfur-containing hydrocarbon feed until the cata ⁇ lyst was substantially deactivated.
  • the catalyst had been prepared by (1) extruding the catalyst with 20 wt. % of an - j , alumina inorganic oxide binder in the shape of l/16th inch extrudate; (2) ion exchanging a potassium-type L zeolite wi h a sufficient volume of 0.3 molar barium nitrate solu ⁇ tion to contain an excess of barium compared to the ion exchanqe capacity of the zeolite; (3) drying the resulting 0 barium-exchanged type L zeolite; (4) calcining the cata ⁇ lyst at 590°C; (5) impregnating the catalyst with 0.8% platinum based on the weight of L zeolite using tetrammineplatinum (II) nitrate; (6) drying the catalyst;
  • 0.356 Grams of catalyst screened to 24 to 80 mesh was placed in a tubular reactor. A low surface area alpha alumina was placed above and below the catalyst. The catalyst was treated at 400 °F in hydrogen flowing at 500 cc/min. for one-half hour, then at 880 °F in hydrogen for 10 mi ⁇ utes, then at 920 °F in hydrogen for on,e hour. After one hour at 920°F- the flow of hydrogen was cut back to 60 cc/min. and the pressure was built up from atmos ⁇ pheric pressure to 100 psiq. At this point, n-hexane was introduced at 3 cc/hr.
  • Example X The catalyst in this example was not treated to any regeneration procedures.
  • Example XI The catalyst in this example was placed into a quartz reactor tube in a furnace, then 1% oxygen in nitro ⁇ gen was passed over the catalyst at a rate of 2 cc/gram catalyst/min. The catalyst was treated at 600 °F for one hour, then the catalyst was treated at 780 °F for five hours. The flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature. Then the catalyst was, for three times: (1) treated with a ten-fold excess of deionized water for 30 minutes at 165°F, (2) cooled, and (3) filtered. Then the catalyst was dried in air at 250 °F for two hours and treated in flowing air at 500°F for two hours.
  • the catalyst in this example was placed into a guartz reactor tube in a furnace, then 1% oxygen in nitro ⁇ gen was passed over the catalyst at a rate of 2 cc/gram catalyst/min.
  • the catalyst was treated at 600°F for one hour, then the catalyst was treated at 780°F for five hours_•
  • the flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature.
  • the catalyst was, for three times: (1) treated for 30 minutes at 165°F with a en-fold excess of an aqueous solution of hydrogen chloride having a pH of 3, (2) cooled, and (3) filtered. '
  • the catalyst was dried' in air at 250°F for two hours and treated in flowing air at 500 °F for two hours.
  • the catalyst of this example was placed into a guartz reactor tube in a furnace, then 1% oxygen in nitro ⁇ gen was passed over the catalyst at a rate of 2 cc/gram catalyst/min.
  • the catalyst was treated at 600 °F for one hour, then the catalyst was treated at 780°F for five hours.
  • the flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature.
  • the catalyst was heated to 176°F for two hours, and occasionally stirred, in the presence of a twenty-fold excess of an aqueous solution of 4 wt. % KOH, then cooled and filtered.
  • the catalyst was for nine times: (1) mixed with a ten-fold excess of water at room temperature for one minute, (2) allowed to settle for three minutes, and (3) filtered. At this point, the pH of the effluent water was 7.5. Then the catalyst was dried in air at 250°F for 20 hours and treated in flowing air at 500 °F for two hours. Table II shows the effect of the regeneration procedures of Examples X through XIII. From this table.
  • Example XIV The catalyst of this example was placed into a guartz reactor tube in a furnace, then 1% oxygen in nitro-
  • Example XV The catalyst of this example- was heated to 176°F for two hours, and occasionally stirred, in the presence of a -twenty-fold excess of an aqueous solution of 4 wt. % KOH, then cooled and filtered. Then the catalyst was, for nine times: (1) mixed with a ten-fold excess of water at room temperature for one minute, (2) allowed to settle for three minutes, and (3) filtered. At this point, the pH of the effluent water was 7.5. Then the catalyst was dried in air at 250°F for 20 hours and treated in flowing air at 500 °F for two hours.
  • Example XVI The catalyst of this example- was heated to 176°F for two hours, and occasionally stirred, in the presence of a -twenty-fold excess of an aqueous solution of 4 wt. % KOH, then cooled and filtered. Then the catalyst was, for nine times: (1) mixed with a ten-fold excess of water at room temperature for one minute, (2) allowed to settle for
  • the catalyst of this example was, for three times: (1) treated for 30 minute at 165°F in a ten-fold excess of an aqueous solution of hydrogen chloride havinq a pH of 3, (2) then cooled and filtered. Then the cata- lyst was, for three times: ( 1) mixed with a ten-fold excess of a solution of 0. IN KOH, (2) treated with the KOH solution for one hour at 135°F, (3) cooled, and (4) fil ⁇ tered. Then the catalyst was treated with a ten-fold excess of deionized water at 135°F, cooled, and filtered. Then the catalyst was dried in air at 250°F for two hours and treated in flowing air at 500 °F for two hours.
  • Example XVII
  • the cata-lyst of this example was placed into a quartz reactor tube in a furnace, then 1% oxygen in nitro ⁇ gen was passed over the catalyst at a rate of 2 cc/gram catalyst/min.
  • the catalyst was treated at 600°F for one hour, then the catalyst was treated at 780°F for five hours.
  • the flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature.
  • the catalyst was, for three times: (1) treated with a ten-fold excess of deionized water for 30 minutes at 165°F. (2) cooled, and (3) filtered. Then the catalyst was, for three times: (1) treated for one hour at 135°F in a ten-fold excess of a solution of 0.
  • the catalyst of this example was placed into a quartz reactor tube in a furnace, then 1% oxygen in nitro ⁇ gen was passed over the catalyst at a rate of 2 cc/gram catalyst/min.
  • the catalyst was treated at 600°F for one hour, then the catalyst was treated at 780°F for five hours.
  • the flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature.
  • the catalyst was, for three times: (1) treated for 30 minutes at 165°F with a ten-fold excess of an aqueous solution of hydrogen chloride having a pH of 3, (2) cooled, and (3) filtered.
  • the catalyst was, for three times: (1) treated for one hour at 135°F with a seven-fold excess of a solution of 0.
  • Example XIX The catalyst of this example was heated to 176°F for two hours, and occasionally stirred, in the presence of a twenty-fold excess of an agueous solution of 4 wt . % KOH, then cooled and filtered. Then the catalyst was, for nine times: (1) mixed with a ten-fold excess of water at room temperature for one minute, (2) allowed to settle for three minutes, and (3) filtered. ⁇ t this point, the pH of the e f flue n t wa ter wa s 7. 5. Then the catalyst was dried in a ir at 250 °F for 20 hours .
  • the catalyst of this example was placed into a guartz reactor tube in a furnace, then 1% oxygen in nitro ⁇ gen was passed over the catalyst at a rate of 2 cc/gram catalyst/min.
  • the catalyst was treated at 600°F for one
  • the catalyst was treated at 780°F for five hours.
  • the flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature.
  • the catalyst was heated to 176°F for two hours, and occasionally stirred, in the presence of a twenty-fold excess of an
  • Example XXI The catalyst of this example was, for three times: (1) treated for 30 minutes at 165°F with a ten-
  • Table V shows the importance of using a pre- oxidation step. It sets forth pairs of data obtained with and without this step.
  • Example XXII The catalyst of this example was placed into a quartz reactor tube in a furnace, then 1% oxygen in nitrogen was passed over the catalyst at a rate of 2 cc/gram catalyst/min. The catalyst was treated at 600 °F for one hour, then the catalyst was treated at 780°F for five hours. The flow of oxygen was then stopped and the catalyst was. cooled to room temperature. Then the cata ⁇ lyst was, for three times: (1) treated for 30 minutes at 165°F with a ten-fold excess of an aqueous solution of hydrogen chloride having a pH of 3, (2) cooled, and (3) filtered. Then the catalyst was, for three times: (1) treated for one hour at 135 °F with a seven-fold excess of a solution of 0.
  • Example XXIII The catalyst of this example was placed into a quartz reactor tube in a furnace, then 1% oxygen in nitro- age was passed over the catalyst at a rate of 2 cc/grams catalyst/min. The catalyst was treated at 600 °F for one hour, then the catalyst was treated at 780°F for five hours. The flow of oxygen was then stopped and the cata ⁇ lyst was cooled to room temperature. Then the catalyst was, for three times: (1) treated with a ten-fold excess of deionized water for 30 minutes at 165°F, (2) cooled,
  • the catalyst was, for three times: (1) treated for one hour at 135°F with a ten-fold excess of a solution of O.IN magnesium nitrate, (2) cooled, and (3) filtered. Then the catalyst was, for three times: (1) treated for one hour at 140°F with a ten-fold excess of deionized water, (2) cooled, and (3) filtered. Then the catalyst was dried in air at 250°F for two hours and treated in flowing air at 500°F for two hours.
  • Table VI shows two unsuccessful treat ⁇ ments, one with a preliminary acidic treatment, and the other without.

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Abstract

Dans un mode de réalisation, un catalyseur contaminé avec du soufre est réactivé par un processus cyclique qui consiste à: (1) exposer le catalyseur à des conditions d'oxydation en présence d'oxygène à une température comprise entre 200oC et 450oC; (2) mettre en contact le catalyseur oxydé avec au moins 10cc d'un milieu aqueux dans sa phase liquide par cc de catalyseur; le milieu aqueux étant sélectionné dans le groupe composé d'eau, d'une solution aqueuse, et de vapeur d'eau saturée; et (3) exposer le catalyseur humide à des conditions de réduction en présence d'hydrogène à une température comprise entre 200oC et 700oC. Dans un autre mode de réalisation, le catalyseur est mis en contact avec une solution aqueuse d'un sel d'un métal sélectionné dans le groupe composé d'un métal alcalin et d'un métal alcalino-terreux. Dans un troisième mode de réalisation, le catalyseur est lavé avec une solution neutre ou acide, mis en contact avec une solution aqueuse d'un sel d'un métal sélectionné dans le groupe composé d'un métal alcalin et d'un métal alcalino-terreux, puis lavé avec une solution neutre et séché.
EP19850905984 1984-11-08 1985-11-07 Reactivation d'un catalyseur desactive. Withdrawn EP0204750A4 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US66948484A 1984-11-08 1984-11-08
US66948784A 1984-11-08 1984-11-08
US66948684A 1984-11-08 1984-11-08
US669487 1984-11-08
US669484 1984-11-08
US669486 1984-11-08

Publications (2)

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EP0204750A1 true EP0204750A1 (fr) 1986-12-17
EP0204750A4 EP0204750A4 (fr) 1987-12-02

Family

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Application Number Title Priority Date Filing Date
EP19850905984 Withdrawn EP0204750A4 (fr) 1984-11-08 1985-11-07 Reactivation d'un catalyseur desactive.

Country Status (8)

Country Link
EP (1) EP0204750A4 (fr)
KR (1) KR870700404A (fr)
AU (1) AU5201686A (fr)
CA (1) CA1257245A (fr)
DE (1) DE3590575T1 (fr)
GB (1) GB2176716A (fr)
NL (1) NL8520394A (fr)
WO (1) WO1986002861A1 (fr)

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USRE34250E (en) * 1986-12-19 1993-05-11 Chevron Research And Technology Company Process for regenerating sulfur contaminated reforming catalysts
GB2211756A (en) * 1987-10-30 1989-07-12 Shell Int Research Process for the preparation of paraffinic hydrocarbons and of a catalyst for said process
US4994423A (en) * 1990-05-25 1991-02-19 Amoco Corporation Process for regenerating spent heavy hydrocarbon hydroprocessing catalyst
US5270272A (en) * 1992-05-26 1993-12-14 Uop Sulfur removal from molecular-sieve catalyst
US6521791B1 (en) * 2001-11-09 2003-02-18 Air Products And Chemicals, Inc. Process for regenerating a monolith hydrogenation catalytic reactor
US8912108B2 (en) 2012-03-05 2014-12-16 Chevron Phillips Chemical Company Lp Methods of regenerating aromatization catalysts
US8716161B2 (en) 2012-03-05 2014-05-06 Chevron Phillips Chemical Company Methods of regenerating aromatization catalysts
US9387467B2 (en) 2012-09-26 2016-07-12 Chevron Phillips Chemical Company Lp Aromatization catalysts with high surface area and pore volume
KR101369021B1 (ko) * 2012-10-25 2014-02-28 한국화학연구원 수분 안정성이 향상된 유독성 가스 제거용 저온산화촉매
US10226761B2 (en) 2016-12-20 2019-03-12 Chevron Phillips Chemical Company, Lp Aromatization catalyst preparation with alkali metal present during a washing step
US10118167B2 (en) * 2016-12-20 2018-11-06 Chevron Phillips Chemical Company Lp Methods for regenerating sulfur-contaminated aromatization catalysts

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Also Published As

Publication number Publication date
GB2176716A (en) 1987-01-07
WO1986002861A1 (fr) 1986-05-22
AU5201686A (en) 1986-06-03
GB8612723D0 (en) 1986-07-02
KR870700404A (ko) 1987-12-29
EP0204750A4 (fr) 1987-12-02
DE3590575T1 (de) 1986-11-20
NL8520394A (fr) 1986-10-01
CA1257245A (fr) 1989-07-11

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