JPS62500710A - Regeneration of deactivated catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Regeneration of deactivated catalyst Background of the invention The present invention relates to a method for regenerating a zeolite catalyst.

Catalytic reforming is a well-known process used to increase the octane number of naphtha or gasoline. be. Reactions that occur during reforming include dehydrocyclization of acyclic hydrocarbons and cyclohexane dehydrogenation. Dehydrogenation, dehydroisomerization of alkylcyclopentane, isomerization of paraffins, alkyl Includes dealkylation of rubenzene, and cyclocracking of paraffins. of Therefore, the iron cracking reaction should be suppressed because it lowers the yield of hydrogen and the yield of liquid product. It should be controlled.

Reforming catalysts dehydrogenate to produce high yields of liquid products and low yields of light gases. Must be selective for cyclization. These catalysts can be used at low temperatures in the reforming reactor. It should have good activity so that it can be used. They also dehydrogenate over long periods of time. Good stability should be maintained to maintain high yield and selectivity of the cyclization reaction. It is. Furthermore, they are reproducible so that they can be regenerated without loss of performance. It should be of.

Most reforming catalysts contain platinum on an alumina support, but some, such as large-pore zeolites, Other catalyst supports have been proposed. These large pore zeolites are gasoline It has pores large enough to allow the passage of hydrocarbons in the boiling range. These ze Catalysts based on oleite supports have been commercially unsuccessful.

Recently, two new catalysts have been developed, which include large pore zeonites, group II metals and Composed of alkaline earth metals.

This catalyst has extremely high selectivity for dehydrocyclization, but is difficult to regenerate. .

The present invention provides a catalyst with an aqueous medium selected from the group consisting of water, an aqueous solution and saturated steam. It is based on the discovery that catalysts can be regenerated by contacting them. This way of playing The method also works with large pore zeolitic catalysts containing at least one Group 1M metal.

In the first embodiment, at least 10 aC of aqueous medium is used per cc of catalyst. The aqueous medium must be in liquid phase. Preferably, at least 50ocI of aqueous medium is used per cc of catalyst.

Prior to contacting the catalyst with the aqueous medium, the catalyst is subjected to oxidizing conditions, preferably at about 200'C. The exposure should be at a temperature of about 450°C. Contact the catalyst with an aqueous medium. Once exposed, the catalyst is subjected to reducing conditions, preferably in the presence of hydrogen, at about 200'C. It should also be exposed at a temperature of about 700'C. The process of oxidizing the catalyst, its The steps of contacting the catalyst with an aqueous medium and reducing the catalyst are It can be repeated if necessary until it is regenerated to the desired level.

Basic solution (i.e. - (greater than 7)) in place of saturated water or saturated steam Can be used for In this embodiment, the catalyst is mixed with a basic solution at a temperature of about 70°C to about 80°C. Contact is made at a temperature of 0.00. This basic solution has at least 10 - It can be an alkali metal hydroxide solution, such as a potassium chloride solution.

In a second embodiment, the catalyst is contacted with a metal salt or metal hydroxide, in which case Zeo Light catalysts can be regenerated and their stability can be improved.

In a third embodiment, the catalyst is washed with a neutral or acidic solution; The catalyst is a metal salt or metal hydroxide (metals are alkali metals and alkaline earth metals). ), and the contacted catalyst is treated with a neutral solution. Regenerate the zeolite catalyst by washing and drying this twice washed catalyst. be able to. This method is deactivated by sulfur-polluting catalysts and other means. It is useful for both types of catalysts.

Preferably, in the second and third embodiments, the aqueous solution concentration is by weight of metal. It should be between 0.1 inch and 10 inch. A more preferable concentration range is 0 by weight of metal. 8% from 1st. Preferably, in each washing step, catalyst 1F! water-based per The solution is 2 to 30 a1. It is.

Preferably, in the second and third embodiments, the metal salt or hydroxide is gold. Heronides, metal nitrates, metal carbonates, metal phosphates, or metal hydroxides Either. Preferred metal salts are metal hydroxides such as potassium hydroxide.

Preferably, in the second and third embodiments, the contact is between 25°C and 1°C. 00°C (more preferably about 80'C) and then the The catalyst in contact with the aqueous solution is washed with 10 to 200 heads of water per gram of catalyst. to remove excess metal and dry the washed catalyst. Preferably the catalyst is an oxidizing contact with a toxic gas under conditions favorable to oxidation before the first cleaning step.

In its broadest aspects, the invention involves contacting a catalyst with a bulk aqueous medium in a liquid phase. Includes catalyst regeneration by This contacting step is an essential element of the invention.

The aqueous medium must be in liquid phase. Contact with liquid water in the absence of water The stage does not show the extraordinary regeneration of the present invention.

It also requires large amounts of aqueous media. At least 10 cc of aqueous medium per cc of catalyst You should use your body. Preferably, at least 500 CC of aqueous medium is added to the catalyst IC. should be used for r-.

This regeneration method is not only useful for sulfur-polluted catalysts, but also It is also useful for deactivated catalysts.

The basic solution is contacted with the sulfur-contaminated catalyst at a temperature of about 70°C to about 80'C. Can be used. Preferably, the basic solution is potassium hydroxide with at least 10 - It is an alkali metal hydroxide solution like solution. This embodiment is based on the acidic points on the catalyst. It has the advantage of minimizing formation.

Saturated steam in the liquid phase with a sulfur-contaminated catalyst, preferably from about 120°C to about 180°C. It can be used for contacting at a temperature of C. This embodiment can be used to remove or remove the catalyst. has the advantage of allowing on-the-spot processing without manual handling.

The present invention regenerates the catalyst without removing all the sulfur from the catalyst. present invention It is not well understood how this achieves its remarkable regeneration of sulfur-polluted catalysts. Although not true, one theory is that the scrubbing reduces the sulfur present in the catalyst or during reforming. Does not become easily removed from the catalyst during the reaction or interfere with the desired catalytic reaction In other words, it is a transformation into a state.

The catalyst can be exposed to oxidizing conditions before contacting it with the aqueous medium. this Although the contacting step provides significant regeneration of the catalyst, the combination of the oxidation and contacting steps Even more remarkable regeneration is achieved. Preferably, the oxidation step is in the presence of oxygen. Occurs at temperatures between about 200°C and about 450°C. The oxidation stage alone regenerates the catalyst do not.

This oxidation step converts the sulfur to a water-soluble form and/or the association between platinum and sulfur. It is thought to weaken the

This is not affected by other oxidizing agents other than oxygen, such as KIAn04 and CrO3. can be This is because sulfur is known to impair the activity of other metal-containing catalysts. Applicable to

The catalyst can be exposed to reducing conditions after contacting it with the aqueous medium.

Preferably, the reduction step takes place at a temperature of 200°C to 700°C in the presence of hydrogen.

Regeneration does not occur from a reduction step alone or follows an oxidation that does not include an aqueous step. You should know that this does not occur from reduction.

The effect of this reduction step is that the solvent molecules that screen the platinum are removed faster than the sulfur is reduced. It may depend on whether it is removed or not. In this regard, wet hydrogen is used for water treatment. We have discovered that a more stable regenerated catalyst can be obtained when using

Other reducing agents such as water-soluble hydrazine hydrate, NaBH4 and KBH, are also available. Can be used at this stage.

The only combination of oxidation stage, soaking stage and reduction stage is this soaking stage and oxidation stage. This causes even more pronounced regeneration than the combination with the reduction stage alone. these The six steps can be repeated as necessary until the catalyst is regenerated to the desired level.

The sulfur-contaminated catalyst is subjected to oxidizing conditions in the presence of oxygen at temperatures of about 20,000 to about 450°C. The oxidized catalyst is exposed at a temperature of at least 500 CC per cc of catalyst. Contact with saturated water vapor in liquid phase at a temperature of about 120°C to about 180°C, and then The catalyst is then subjected to reducing conditions in the presence of hydrogen at a temperature of 200°C to about 700°C. can be exposed. These steps are repeated until the catalyst is regenerated to the desired level. returned.

In a second embodiment, a large pore zeolite catalyst containing at least one Group The medium is an aqueous solution of a metal salt selected from the group consisting of alkali metals and alkaline earth metals. It is regenerated by bringing the liquid into contact with a catalyst.

The essential step in this embodiment is to prepare the catalyst consisting of an alkali metal and an alkaline earth metal. contact with an aqueous solution of a salt or hydroxide of a metal selected from the group consisting of: It is. The metal salts or hydroxides are metal halobides, metal nitrates, metal carbons. It may be an acid salt, a metal phosphate, or a metal hydroxide. Preferably, The metal salt or hydroxide is potassium hydroxide. Preferably, the catalyst is more preferably about Contact is made at a temperature of 80°C. The aqueous solution is from 0.1 inch to 1 inch by weight of metal. It should have a concentration of 0%, preferably 1% to 8%.

After contacting the catalyst with the aqueous solution, the catalyst is After washing with water to remove excess metal, the washed catalyst is dried.

The sulfur-contaminated catalyst contains 8 to 10 wt% barium and 0.1 to 1.5 wt% platinum. consisting of L-type zeolite, silica, alumina, aluminosilicate and clay. and an inorganic binder selected from the group. This sulfur-polluted catalyst is about 80 In contact with 2 to 50 cc of potassium hydroxide aqueous solution per gram of catalyst at a temperature of °C. Let me touch it. This aqueous solution contains 1 to 8% by weight of metal.

After contacting the catalyst with the solution, wash it with 200cc of water per 1g of catalyst. It is washed to remove excess metal and then dried.

The catalyst is washed with a neutral or acidic solution and then treated with an alkali metal salt or alkali. Contact with an aqueous solution of a lithium metal salt, then wash with a neutral solution and dry. can be done.

In a third embodiment, the invention comprises at least one Group 1'III metal. The large pore zeolitic catalyst is washed with a non-basic solution, and the washed catalyst is washed with an alkali solution. Contact with an aqueous solution of a salt of a metal selected from the group consisting of metals and alkaline earth metals The contacted catalyst is washed with a neutral solution, and the washed catalyst is dried. Including reproducing by doing. This regeneration method is useful for sulfur-polluted catalysts. It is also useful for catalysts that have been deactivated by other means.

In regenerating sulfur-contaminated catalysts, the present invention does not remove all sulfur from the catalyst. Regenerate the catalyst.

After contacting the catalyst with the aqueous solution, the catalyst is heated at 10 to 200 CC per gram of catalyst. Wash with either a neutral or acidic solution.

The key step in this embodiment is to select the catalyst from the group consisting of alkali metals and alkaline earth metals. This means that the metal must be brought into contact with an aqueous solution of a metal salt or hydroxide. Ru. Metal salts or hydroxides include metal halides, metal nitrates, metal carbonates, gold It may be either a metal phosphate or a metal hydroxide. Preferably, the catalyst an aqueous solution of 2 to 50 Cr per catalyst 11 and a temperature of 25°C to 100°C, preferably or at a temperature of about 80°C. This aqueous solution contains 0.1 to 1 It should have a concentration of 0% by weight, preferably 0.1 to 8% by weight.

After contacting the catalyst with the aqueous solution, it is heated at 10 to 200 CC per cc of catalyst. Excess metal is removed by washing with water and the washed catalyst is then dried.

Preferably, the catalyst is subjected to an initial cleaning step under oxidizing gas and conditions favorable to oxidation. contact before.

In one preferred method in this embodiment, the deactivated catalyst is to 10% by weight of L-type zeolite, 0.1 to 1.5% by weight of platinum, and silica. an inorganic binder selected from the group consisting of silica, alumina, aluminosilicate and clay; It is a sulfur-polluting catalyst consisting of

This sulfur-contaminated catalyst is contacted with an oxidizing gas under conditions favorable to oxidation, and then The medium is washed with a neutral solution and the catalyst is then washed with 1 g of catalyst at a temperature of about 80°C. Or 2 to 30CF1. of potassium hydroxide.

This aqueous solution has a concentration of 0.1 to 8% by weight of alkali metal or alkaline earth metal. have degree. After contacting the catalyst with the solution, it is added at a concentration of 10 to 200 Wash with CC water to remove excess metal and then dry it.

A reforming catalyst that can be regenerated by the present invention can produce one or more dehydrogenation catalysts. It is a large pore zeolite loaded with ingredients for The term "large pore zeolite" starts from 6 It is defined as a zeolite with an effective pore size of 15 angstroms.

L-type zeolite, X-type zeolite, Y-type zeolite and faujasite are It is considered to be the best large pore zeolite for the operation of 7 to 9 Å It has an apparent pore size of about 100 ml. Preferred catalysts are one which can react with more than one desorption. This is an L-type zeolite loaded with hydrogen components.

Alkaline earth metals can be present in the catalyst. The alkaline earth metals are barium, sulfur It can be trontium or calcium. Alkaline earth metals are synthesized, It can be incorporated into zeolites by impregnation or ion exchange. Baliu Because the resulting catalyst has high activity, high selectivity, and high stability, it can be compared with other alkalis. Preferable than earth. Barium accounts for about 0.1 to about 65% of the weight of zeolite. More preferably, it should constitute from about 1 to about 20% by weight.

The reforming catalyst according to the invention contains one or more Group II metals, such as nickel. loaded with metal, ruthenium, rhodium, palladium, iridium or platinum. Ru.

The preferred Group I metal is platinum, which is more selective with respect to dehydrocyclization. , it is also more stable than other Group I metals under reforming reaction conditions. Preferable platinum in catalyst The percentage is between 0.1 and 5%, more preferably between 0.1 and 1.5%. It is.

Inorganic oxides can be used as carriers to bind large pore size zeolites. Ru. The carrier is a natural or synthetic inorganic oxide or a combination of inorganic oxides. 5 to 50% by weight. Typical inorganic oxide supports that can be used are silica and alumina. , and aluminosilicates The first embodiment of the invention provides particularly advantageous method and composition embodiments. This is further illustrated by the following examples, in which the formulation is presented. These examples are based on the original It is provided for illustrative purposes only and is not intended to be limiting.

Example I The catalyst consists of (1) potassium L-type zeolite in excess compared to its ion exchange capacity; Ion exchange with a 0.17M barium nitrate solution in an amount sufficient to contain barium. (') Dry the obtained barium-exchanged zeolite catalyst, and (6) dry the catalyst. (4) Using tetramine platinum(II) nitrate as a catalyst, (5) drying the catalyst, (6) calcining the catalyst at 260°C, (7) Reducing the catalyst in hydrogen at 480°C to 500°C. The catalyst of I was hydrofined to remove sulfur, oxygen and nitrogen. d) was used in a pilot plant to reform the produced n-hexane. So The modification is 860'F, 100 psig, 17 LH8V, and 5 H2/ This was done at HC. The results after 10 and 20 hours are shown in Table I.

Example III Using the catalyst of Example I in a pilot plant to remove sulfur, oxygen and nitrogen Hydrorefining and sulfur compounds are intentionally added to produce sulfur-polluting catalysts. The naphtha was reformed. The modification is 860°F, 100 psig, 1-5 LH3V, and 6H2/tonne (catalyst sulfided for 6 weeks at C) The sulfurized catalyst was then tested according to the procedure of Example H. 10 hours later The results of that test after 20 hours are shown in Table I.

Example■ The sulfidation catalyst of Example 2 was heated to 400'''F with 1 liter of oxygen in nitrogen at 1 atm. ’ for about half an hour, 500°F for 1 hour, and 750″F′ After oxidation for 5 hours, the catalysts were tested according to the procedure of Example H. 1 The results of the test after 0 and 20 hours are shown in Table 3.

Example V The sulfurized catalyst of Example III was washed with water at 80° C. for 1 hour at 2 aC/min, then the catalyst Tested according to the procedure of Example H. The test results after 10 hours and 20 hours The sulfidation catalyst of Example I■ in nitrogen at 1 atmosphere (1%) oxygen a-c', 4 000F' for half an hour, 5[] 0'FIC for 1 hour, and 750 oxidized for 5 hours and then tested the catalysts according to the procedure of Example ■. did. The test results after 10 and 20 hours are shown in Table I.

The sulfidation catalyst of Example III was heated at 400° with 1% oxygen in nitrogen at 1 atm. 1/2 hour at 500″F, 1 hour at 500″F, and 5 o’clock at 750″F oxidize for 6 hours, then wash with 10 rounds of steam at 212"F' for 6 hours. , then reduced in H2 at 1 ÷ h 900), then reduced in nitrogen at 1 atm. 1 hour at 400'F and 1 hour at 500'F with 1 g of oxygen. and 750°F for 5 hours, then the catalyst was treated according to the procedure of Example H. Tested. The test results after 10 hours and 20 hours are shown in Table 3.

The sulfidation catalyst of Example III was heated to 400' with 1% oxygen in nitrogen at 1 atm. F for half an hour, 5[ ] O”F’ for one hour, and 750’F Oxidize for 5 hours at 100°C, then wash for 6 hours at 212'F with 100°C steam. then reduced in H2 at 900"F for 1 hour, then reduced in nitrogen at 1 atm. 1 hour at 400"F' and 1 hour at 500°F with 1 g of oxygen in the base. time and oxidize for 5 hours at 750'F, then 100% steam at 212"F. Wash with a team for 3 hours, then reduce in H2 at 9001 for 1 ÷ hour, Then heated at 4000F for 1/2 hour at 500F with 1H oxygen in nitrogen at 1 atm. 'F for 1 hour and 7500F for 5 hours, then 212 After washing with 100 °F steam for 6 hours, the catalyst was washed according to the procedure of Example H. I tested it. The test results after 10 hours and 20 hours are shown in Table 3.

Table I Example 111 1 1 1 8685 Example III C1,080,090,010,011112 Example IV O, 210,180,100,094045 Example V O, 190, 19' 0.1 0 0.10 45 45 Example Vl O, 710, 740, 530, 5675 76 Examples ■ 0.81 0.80 0.80 0.76 84 81 Examples ■ 0.81 0.80 0.80 0.76 84 81 Example V, Vl, ■O and ■ are examples of the present invention.

They indicate that washing alone or together with oxidation regenerated the deactivated catalyst. There is.

Example■ A second embodiment of the invention is the following implementation which shows a particularly advantageous embodiment of the method and composition. Let us further illustrate by example. These examples are provided to illustrate the invention. It is not intended to be limiting.

A new reforming catalyst is developed by using (1) potassium L type with the ion exchange capacity of its zeolite. A 0.17 molar solution of barium nitrate with a volume sufficient to contain an excess of barium compared to (2) The resulting barium-exchanged zeolite catalyst was dried. , (3) calcining the catalyst at 590°C, and (4) injecting the catalyst by pore-filling impregnation method. impregnated with 0.8% platinum using tetramine platinum(II) nitrate, (5) dry the catalyst, (6) calcinate the catalyst at 26,000 ℃, and (7) soak the catalyst in water. It was made by reducing in water at 48[3'C to 500°C] .

Supply oil of n-hexane which has been hydrotreated to remove sulfur, oxygen and nitrogen is 920% at °F', 100 psig, 10HLSV, and 5 H2/HC , was brought into contact with a portion of this new reforming catalyst. Benzene selection for its operation The conversion rate and hexane conversion rate are shown in Figures 1 and 2.

A second portion of this new reforming catalyst is combined with a sulfur-containing light straight distillate fraction of about 2 Deactivated by contacting until 0.00 ppm of sulfur is deposited on the catalyst. Ta.

This deactivation catalyst is prepared by combining it with an aqueous solution of potassium hydroxide at a concentration of 5% by weight of the metal. 0°##? The aqueous solution was kept in contact for 2 hours at a temperature of 30CC, and the catalyst contacted with the aqueous solution was treated with 20CH of water per 1g of catalyst. Wash the catalyst 10 times (total of 2 CIOCC) to remove excess metal and dry the washed catalyst. Regenerated by drying. Hydrorefined to remove sulfur, oxygen and nitrogen The n-hexane feed oil was heated to 920°F, 100 psig, 10 LH3V, and 5 H2/HC was brought into contact with this regenerated reforming catalyst.

Example X - Separate ■ [ The following implementation illustrates a particularly advantageous method and composition embodiment of a third embodiment of the present invention. Let us further illustrate by example. These examples are provided to illustrate the invention. and is not intended to limit it.

Using a sulfur-containing hydrocarbon feedstock as an L-type zeolite reforming catalyst, the catalyst is substantially deactivated. Processed until sexualized.

The catalyst was prepared by: (1) mixing the catalyst with 20% by weight of an alumina inorganic oxide binder at 1/6; (2) Potassium L-type zeolite is extruded as an inch extrudate. Sufficient volume of barium nitrate containing excess barium compared to the ion exchange capacity of the nitrate. Ion exchange with a 0.3 molar solution, (6) the resulting barium exchanged zeolite (4) Calcinate the catalyst at 590°C; (5) Dissolve the catalyst in tetranitrate. Impregnated with 0.8% platinum based on L-type zeolite using Min platinum (n). (6) Dry the catalyst (in air or 50% steam at 260 °C). (8) the catalyst with 20 wt% alumina inorganic oxide binder at 1/2; (9) catalyst in hydrogen at 480'C; It was prepared by reducing from 500°C. Calm this catalyst Modification conditions (100 psig, 870 Yen, 2H2/HC, 1,5LH8V) Operation with sulfur-containing naphtha feedstock (1.5 ppm dimethyl disulfide) It was deactivated by the following method. The catalyst is subjected to various regeneration procedures and then tested by the test.

0.656 g of catalyst sieved into 24 to 80 ml was placed in a tubular reactor. . Low surface area alpha alumina was placed above and below the catalyst. Smell the catalyst at 400'F and treated in hydrogen flowing at 500 CC/min for 1 hour.

After 1 hour at 920 cc, the hydrogen flow was reduced to 60 cc/min and the pressure was reduced from atmospheric to 1 cc/min. I set it to 00 psig. At this point, n-hexane was introduced at 3 ac/hr. Ta. Initial data and final data were collected approximately 2 hours and 18 hours after the introduction of n-hexane. I took it. Conversion rate, selectivity for dehydrocyclization reaction, and feed oil molarity. The aromatic yield in the product as was calculated at those times.

Example X The catalyst of this example was not subjected to any regeneration procedure.

Example M The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1 tiooxygen in nitrogen was poured onto the catalyst. It was passed at a rate of 2 cC/g of catalyst for 7 minutes. Treat the catalyst at 600”F for 1 hour, then The catalyst was treated at 780"F for 5 hours. The oxygen flow was then stopped and the catalyst was allowed to cool to room temperature. It was cooled to Then apply the catalyst three times: (1) 1 for 60 minutes with a 10-fold excess of deionized water; Processed at 65°F', (2) cooled, and (3) filtered. Next, the catalyst Dry for 2 hours at 250'F' in air and 5000F in flowing air. It was treated for 2 hours.

The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1% oxygen in nitrogen was added to the catalyst. 2Cr:, 7 g/catalyst 7 min. Catalyst at 600°F' for 1 hour The catalyst was then processed for 5 hours at 780°C. stop the flow of oxygen, The catalyst was cooled to room temperature. The catalyst was then heated 6 times: (1130 minutes at 165°F') p) Treat with a 10-fold excess of aqueous hydrochloric acid in 13, cool (21), and (6) filter. Ta. The catalyst was then dried in air at 250°F for 2 hours and then dried in flowing air at 500°F for 2 hours. Time processed.

The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1% oxygen in nitrogen was added over the catalyst. was passed through at a rate of 2 cC/g of catalyst for 7 minutes. Treat the catalyst at 600°F for 1 hour and then and 780°F for 5 hours. The flow of oxygen was then stopped and the catalyst was cooled to room temperature. . The catalyst was then heated to 176'F' for 2 hours and a 20x excess of 4wt 4KOH water was added. The solution was stirred occasionally, then cooled and filtered. Next, the catalyst is 9 times :( 1) Mix for 1 minute at room temperature with a 10-fold excess of water, (2) Allow to settle for 6 minutes, (6) Filter did. At this point, the - of the effluent was 7.5. Next, place the catalyst in the air. Dry at 250'F' for 20 hours and dry at 500°F' for 2 hours in flowing air. Processed in between.

Table ■ shows the effect of the regeneration procedure of the lesson from Example X.

From this table it can be seen that preliminary oxidation is carried out followed by contact with water or an aqueous solution followed by drying. It has been shown that regeneration by calcination and calcination provides substantial regeneration of the deactivated catalyst. It is clear. Among these four examples, the example layer (KOH cleaning) has the best results. gave.

X 4.96 43.27 2.15! 1.93 62.29 2.45XI 4.2.07 85.79 66.0928.78 87.25 25.11 XI 14.58 68. 9.8510.58 73. 7.67X [II] 40.72 87.49 35.6336.29 90.64 52.90 actual The example catalyst was placed in a quartz reaction tube in a furnace and then 1% oxygen in nitrogen was added to the catalyst. It was passed through at a rate of 2 CL/g of catalyst for 7 minutes. The catalyst was treated at 600'F for 1 hour and then The sample was treated at 780OF for 5 hours. The oxygen flow was stopped and the catalyst was cooled to room temperature. Next The catalyst was heated to 165''F' for 30 minutes with a 1H excess of deionized water for 6 times. (2) cooled, and (3) filtered. Next, apply the catalyst 5 times (111!5″ F' for 1 hour in the presence of a 10-fold excess of Q,iN KOH aqueous solution (2 ) cooled and (3) filtered. The catalyst was then washed with a 10-fold excess of deionized water to 1400 ml. Washed with F' for 1 hour, then cooled and filtered. Next, place the catalyst in air for 2 Dry at 50°C for 2 hours and process in flowing air at 500°F for 2 hours.

Table In shows the improvements obtained when treating the catalyst with a neutral solution before KOH washing. ing. From the table, it is clear that washing the catalyst with a neutral washing solution before KOH washing It can clearly be seen that it gives better results than without.

X[II 40.72 87.49 35.65 36.29 90.64 3 2.90XIV 56.73 93.13 52.83 54.15 95.1 0.51.49 The catalyst of this example was heated to 176°F for two hours and It was stirred occasionally in the presence of % KOH aqueous solution, then cooled and filtered. Next, touch The medium was mixed 9 times: (1) with a 10-fold excess of water for 1 minute at room temperature, allowed to settle for 3 minutes (2J , (6) filtered. At this point, the - of the effluent was 7.5.

The catalyst was then dried in air at 250'JP for 20 hours and in flowing air at 500'JP. Processed for 2 hours at °F'.

Example layer The catalyst of this example was tested 6 times: (10 times pH 3 at 165°F' for 1130 minutes) Treated in excess aqueous hydrochloric acid (2) then cooled and filtered. Next, the catalyst is 6 Times: (1) 0. I NK, mixed with 10 times excess of OH solution, ('2J that K Treat with OH solution for 1 hour at 165°F, (6) cool, (4) filter. Ta. The catalyst was then treated with a 10x excess of deionized water at 1350F and cooled. and filtered. The catalyst was then dried in air at 25 D'F for 2 hours and drained. Processed for 2 hours at 500°F in aeration.

Examples &■ The catalyst of the present invention is placed in a quartz reaction tube in a furnace, and then 1% oxygen in nitrogen is placed over the catalyst. 2CI:,/j! - The catalyst was passed through at a speed of 7 minutes. Catalyst at 600°F for 1 hour treated and then treated at 780″F for 5 hours. The oxygen flow was then stopped and the catalyst was cooled to room temperature. The catalyst was then washed 6 times: (30 Treated at 165° F' for minutes, (2) cooled, and (6) filtered. Then apply the catalyst 6 times - (1) in a 10-fold excess of 0.1N sodium carbonate at 135°F for 1 hour. (2) cooled, and (6) cooled. Then the catalyst 6 times: (IN time 135 (2) and (6) were treated in a 10-fold excess of deionized water at F. . The catalyst was then dried for 2 hours at 250'F in air and 500'F in flowing air. 'F for 2 hours.

Example XVI11 The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1% oxygen in nitrogen was added over the catalyst. 2CLli.catalyst at a rate of 7 minutes. Treat the catalyst at 600″F for 1 hour. 780) for 5 hours. The flow of oxygen is then stopped and the catalyst is brought to room temperature. Cooled. Then apply catalyst 6 times: (1) 10 times excess...6 at 165↑ for 30 minutes (2) cooled and (filtered). Then the catalyst 6 times: (7-fold excess of 0.1 tq carbonate at 155'F' for 111 hours) - thorium solution Then, it is treated with C, (2) cooled, and (3) filtered. Then apply the catalyst 6 times: (1) 1 treated with a 7x excess of deionized water for 1 hour at 35°F; (2) cooled; (6) Filtered. The catalyst was then dried in air at 250°F for 2 hours and distributed. Processed for 2 hours at 500'F in air.

Table 1■ shows the further improvement obtained with a preliminary treatment with an acidic solution. Two sets of de the first one in each case before treatment with the salt solution. treated with a neutral solution or no solution treatment at all; in each case the second was first treated with an acidic solution. The first set of data and the second set of data In the difference between It is also worth noting the benefits that can be obtained if

XV 27.53 82.13 22.61 8.42 65.45 5.51 XVI 56.84 93.48 53.1358.52 96.08 56. 25 When performing pre-oxidation Cold n 47.96 89.29 42.82 41.77 91.84 38. 36 The catalyst of this example was heated to 176°F for 2 hours and treated with 4% by weight of an aqueous OH solution. Stir occasionally in the presence of a 20-fold excess, then cool and filter. Then the catalyst 9 times: (1) mixed for 1 minute at room temperature with a 10-fold excess of water, (2) allowed to settle for 5 minutes. (6) Filtration 1~. At this point, the pH of the effluent was 7.5. Next The catalyst was then dried in air at 250T for 20 hours.

Example beans The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1 liter of oxygen in nitrogen was added to the catalyst. was passed through at a rate of 2 CL/jj catalyst 7 minutes. Heat the catalyst at 600’F for 1 hour. and then treated at 780”F for 5 hours. The oxygen flow was stopped and the catalyst was cooled to room temperature. did. The catalyst was then heated to 176'F for 2 hours and 20% of the 4 wt. Stir occasionally in the presence of a two-fold excess, then cool and filter.

The catalyst was then mixed 9 times: (2) with an IHO-fold excess of water for 1 min at room temperature and (2) allowed to settle for 6 min. (6) filtered. At this point, the pH of the effluent was 7.5. Next The catalyst was then dried in air at 250"F' for 20 hours.

Example W The catalyst of this example was tested 6 times: (10 times excess p in j6S oven for 1130 minutes) (3 (2) cooled, and (6) filtered. Next, the catalyst is : (treated with 0.IN aqueous sodium carbonate solution at IN time 135 minutes, (21) cooled and (6) filtered. The catalyst was then heated three times: (1) 140°F for 1 hour. with a 10-fold excess of deionized water, (2) cooled, and (6) filtered. . The catalyst was then dried for 2 hours at 250'F in air and 500'F in flowing air. 00 for 2 hours.

Table V shows the importance of using a pre-oxidation step. The table uses this stage. A pair of data obtained with and without is shown.

Beans 24.75 83.68 20.69 18.86 82.67 15.59 XX 39.86 8B, 53 35.29 1.31 89.29 27. 95Xfl 55.26 88.85 49.5049.88 92.90 4 6.34Xi 61.92 88.01 54゜4955.66 91.12 50.72 Example ■ The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1 liter of oxygen in nitrogen was poured onto the catalyst. 2 (f knee/& catalyst passed at a speed of 7 minutes. Catalyst at 600"F' Processed for 1 hour, then 5 hours at 780°F. Stop the flow of oxygen and touch The medium was cooled to room temperature. Next, the catalyst was heated 6 times (1+30 minutes at 165″F’ treated with a 10-fold excess of pH 3 aqueous hydrochloric acid, (2) cooled, and (6) filtered. .

The catalyst was then washed with a 7x excess of 0.1N nitric acid at 5'F for 6 times: Treat with nesium solution, (2) cool, and (6) filter. Then the catalyst 6 times: (treated with 7x excess deionized water for 1 hour at 11135″F, (2) Cool and (3) filter. The catalyst was then dried in air at 250″F for 2 hours ( Dry for 2 hours at 500 g in -1 flowing air.

The catalyst of this example was placed in a quartz reaction tube in a furnace, and then 1 liter of oxygen in nitrogen was placed on the catalyst. It was passed through at a rate of 2 cr, 7 g/7 minutes of catalyst. The catalyst was treated with 6001 for 1 hour and then and 780° F' for 5 hours. Stop the flow of oxygen and cool the catalyst to room temperature did. The catalyst was then washed 6 times: 165 times for 30 minutes with a 1110-fold excess of deionized water. In Process 1-1(2), the mixture was cooled and filtered. Then apply the catalyst 6 times: (1113 treated with a 10-fold excess of deionized water for 1 hour at 5°T, (2) cooled and ( 6) Filtered. The catalyst was then dried in air at 250°F and in flowing air for 50 minutes. 00°F' for 2 hours; -.

Finally, Table ■ shows two unsuccessful treatments, one for the preliminary acid treatment. The other case is when there is no such processing.

XXII 6.10 27.41 1.67 3.05 30.00 1.19 XXIII5.78 21.82 1.26 This invention is too low to calculate Although described in terms of specific embodiments, this application does not require a person skilled in the art to understand the spirit of the appended claims. I intend to include changes that can be made without going out of scope.

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Claims (15)

[Claims] 1. contacting the catalyst with at least 10 cc of aqueous medium in liquid phase per cc of catalyst; , wherein said aqueous medium is selected from the group consisting of water, an aqueous solution and saturated steam. , and the catalyst is from a large pore zeolite containing at least one Group VIII metal. A method for regenerating a catalyst. 2. Sulfur contamination consisting of large pore zeolites containing at least one Group VIII metal A method for regenerating a catalyst, the method comprising: (a) subjecting the catalyst to oxidizing conditions at about 200°C in the presence of oxygen; (b) the above oxidized catalyst to catalyst 1c. contact with at least 500 cc of aqueous medium in liquid phase per c to form a wet catalyst. except that the aqueous medium is from the group consisting of water, an aqueous solution, and saturated steam. (c) subjecting the above wet catalyst to reducing conditions from about 200°C in the presence of hydrogen; (d) steps (a) to (c) are carried out at a temperature of about 700° C. when the catalyst is desired; Repeat until level is reached again A method consisting of things. 3. Claim 2, wherein the large pore zeolite is an L-type zeolite. A method for regenerating sulfur-polluted catalysts. 4. The aqueous medium is a basic solution, and the catalyst is mixed with the basic solution at about 70°C. The sulfur-contaminated catalyst of claim 2, wherein the catalyst is contacted at a temperature of about 80°C. How to play. 5. A method for regenerating a catalyst and improving the stability of the catalyst, the method comprising: Salts or hydroxides of metals selected from the group consisting of alkali metals and alkaline earth metals contact with an aqueous solution of a catalyst, wherein said catalyst is A method comprising a large pore zeolite containing a Group III metal. 6. The above aqueous solution has a metal concentration of 1 to 8% by weight, and per gram of catalyst. Regenerating the catalyst according to claim 5, wherein from 2 to 30 cc of aqueous solution is present. and how to improve its stability. 7. Claim 5, wherein the metal salt or hydroxide is potassium hydroxide. A method of regenerating a catalyst and improving its stability as described. 8. Claim 5, wherein said contact occurs at a temperature of 25°C to 100°C. A method for regenerating a catalyst and improving the stability of the catalyst, as described in . 9. The catalyst in contact with the aqueous solution is then treated at a concentration of 10 to 200 c/g of catalyst. The catalyst according to claim 5, wherein excess metal is removed by washing with water of c. A method for regenerating and improving the stability of the catalyst. 10. Claim 5, wherein the large pore zeolite is an L-type zeolite. A method for regenerating a catalyst and improving the stability of the catalyst. 11. A method for regenerating a sulfur-contaminated catalyst and improving the stability of the catalyst, the method comprising: (a) Contacting the above catalyst with an aqueous potassium hydroxide solution at a temperature of about 80°C; except that the aqueous solution has a metal concentration of 1% to 8% by weight, and (b) 10 to 30 cc of the above catalyst per gram of catalyst; Remove excess metal by contacting with 200cc of water, (c) drying the washed catalyst; It is a method consisting of and the above catalyst is (A) L-type zeolite containing 0.1% to 1.5% platinum by weight; (B) an element selected from the group consisting of silica, alumina, aluminosilicate and clay; A method comprising a biological binder. 12. The above method (a) contacting the catalyst with a solution selected from the group consisting of a neutral solution and an acidic solution; (b) the above washing catalyst is selected from the group consisting of alkali metals and alkaline earth metals; contact with an aqueous solution of a metal salt or hydroxide to be exposed, (c) washing the contacted catalyst with a neutral solution; (d) drying said twice-washed catalyst, wherein said catalyst is Catalyst regeneration method comprising a large pore zeolite containing at least one Group VIII metal Law. 13. Claim 12, wherein the metal salt or hydroxide is potassium hydroxide. Catalyst regeneration method described in section. 14. Claim 12, wherein the large pore zeolite is an L-type zeolite. Catalyst regeneration method as described. 15. A method for regenerating a sulfur-contaminated catalyst, the method comprising: (a) oxidizing the catalyst with an oxidizing gas; contact under convenient conditions, (b) washing the catalyst with a solution selected from the group consisting of neutral solutions and acidic solutions; , (c) contacting the washed catalyst with an aqueous solution of potassium hydroxide at a temperature of about 80°C; At that time, the above aqueous solution of potassium hydroxide has a metal concentration of 0.1 to 8% by weight. Mochi, and 2 to 30 cc of aqueous solution exists per 1 g of catalyst, (d) 10 to 200 cc of the above contacted catalyst of step (c) per gram of catalyst; Rinse with water to remove excess metal. (e) drying the washed catalyst of step (d); (f) treating the dried catalyst with an oxidizing gas; Contact under conditions favorable for oxidation, A method comprising the steps of: (A) containing 0.1 to 1.5% by weight of the catalyst; L-type zeolite containing platinum, (B) an element selected from the group consisting of silica, alumina, aluminosilicate and clay; A method comprising a biological binder.