DE4233763A1 - Reactivation of noble metal activated carbon catalyst - by e.g. reforming or platforming catalyst by pyrolysis, activation and opt. redn without burning carbon support - Google Patents

Reactivation of noble metal activated carbon catalyst - by e.g. reforming or platforming catalyst by pyrolysis, activation and opt. redn without burning carbon support

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Publication number
DE4233763A1
DE4233763A1 DE19924233763 DE4233763A DE4233763A1 DE 4233763 A1 DE4233763 A1 DE 4233763A1 DE 19924233763 DE19924233763 DE 19924233763 DE 4233763 A DE4233763 A DE 4233763A DE 4233763 A1 DE4233763 A1 DE 4233763A1
Authority
DE
Germany
Prior art keywords
activation
catalyst
pyrolysis
reactivation
activated carbon
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Withdrawn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
DE19924233763
Other languages
German (de)
Inventor
Hasso Von Bluecher
Ernest De Dr Ruiter
Original Assignee
Hasso Von Bluecher
Ruiter Ernest De
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 Hasso Von Bluecher, Ruiter Ernest De filed Critical Hasso Von Bluecher
Priority to DE19924233763 priority Critical patent/DE4233763A1/en
Publication of DE4233763A1 publication Critical patent/DE4233763A1/en
Withdrawn legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation
    • B01J23/96Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/02Heat treatment
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G35/00Reforming naphtha
    • C10G35/04Catalytic reforming
    • C10G35/06Catalytic reforming characterised by the catalyst used
    • C10G35/085Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof

Abstract

Reactivation of catalysts (I) based on activated C (II) charged with noble metal (III) comprises pyrolysis, activation and opt. redn. (II) is extremely attrition-resistant spherical C black (IIA) with a dia. of 0.1-1.0mm. Pyrolysis is carried out at up to 350 deg. C in a slightly oxidising atmos.; and activation at 750-900, pref. 800-850 deg C in an inert gas contg. 1-5% steam. USE/ADVANTAGE - (I) are used in petrochemistry, e.g, in reforming and platforming. In many cases, (I) can be reactivated without burning (II) and the cost of recovering (III) from the ash and impregnating a new (II) charge. Organic cpds. blocking the pores vaporise, 6-10% of the original (II) is lost and 90-95% of (III) (partly as oxides) remains on (II), whilst almost the remaining 5-10% can be recovered.

Description

Precious metal catalysts, especially based on palladium and platinum, are widely used in petrochemicals. Known processes, such as Refor Ming and platforming, for example, increase knock resistance by straightening chain hydrocarbons are isomerized, cyclized or flavored. Because of the high price, precious metal catalysts are always with you Carrier manufactured so that large with relatively small amounts of metal Surfaces can be achieved. A special case is with precious metals impregnated activated carbon because the adsorption on the coal is the concentra tion in the immediate vicinity of the catalyst increased, so that higher sales ten can be achieved. But as with any catalytic converter, it happens over time ner deactivation, which can have two causes: on the one hand Block the pores of the activated carbon and on the other hand the classic poison processing of the precious metal.

The current method of processing deactivated, with precious metals loaded activated carbon is the combustion with recovery of the noble talls from the ashes. In addition to the loss of a few percent of the precious metal and the total loss of activated carbon also bears the cost of the refurbishment treatment and the impregnation of a new batch of activated carbon. This The object of the present invention was to reduce costs.

The solution to the problem is that when using highly abrasion-resistant grain coal, in particular spherical coal, post-activation and possibly egg A subsequent reduction in many cases restores the activity can be.

Surprisingly, it was found that a thermal after treatment under slightly oxidizing conditions, for example a short one Reactivation in the range of approx. 800-850 ° C under nitrogen, something Water vapor is added

  • a) organic material that clogs the pores evaporates
  • b) about 6-10% of the original activated carbon is lost
  • c) about 90-95% of the precious metal (partly as oxides) on the coal remain, but the remaining 5-10% to a very large extent can be recovered.

If existing precious metal oxides are undesirable, they can be by a reduction, for example by adding hydrogen in the Cooling phase after activation, very easy to convert into pure metal.

One has proven to be particularly well suited for the proposed method Ball coal with a diameter of 0.1-1 mm on petroleum pitch basis (see at  for example, DE 29 32 571 C3) proved. Your particular advantages are one very hard shell that is extremely abrasion-resistant and also when reactivated is preserved, as well as an extremely high flow resistance and relatively good gas permeability in a compact layer, which means reactivation in the rotary kiln allowed. Because of the extremely low abrasion and the low mass ratio Funny when reactivated, the loss of precious metal is less than 10%. However, the greater part of this is found in the "dust" and can be recovered. A spherical carbon is also very suitable by pyrolysis of polysulfonated "porous polymers" based on styrene and Divinylbenzene can be obtained. They also have a very hard exterior Bowl.

The following basically applies to the temperatures of the reactivation: The Akti vation is always associated with a certain erosion and should also be used in Take place inside the activated carbon. If the temperature is too high, for example 950 ° C, the rate of the combustion reaction is so high that the Ab Fire mainly affects the outer areas because of the oxidizing water vapor reacts before it can diffuse inside. Because of course every impregnation the outer layers are loaded much more, a preferred erosion of these layers would be extremely disadvantageous. At the Ku Gelcoal also affects the hard shell, which opposes the burnup very cheap. 1-5% water vapor proved to be particularly suitable in nitrogen at a temperature of 800-850 ° C.

example

A spherical coal based on a petroleum residue with a diameter of 0.5-0.65, an inner surface of 1200 m 2 / g, a micropore volume of 0.54 ml / g, a best pressure of 600 g / sphere and a bulk weight of 600 g / l was loaded with platinum in a known manner. Platinum share 0.8%, based on coal. The catalytic activity was checked with the dehydrogenation of cyclohexane (vertical tube, 20 mm ⌀, ball bed height 30 mm, flow velocity 10 mm / sec, temperature 260 ° C, offer: 10% mol in N 2 ). The catalyst was then poisoned by styrene vapors, some of which resinified, and additionally exposed to H 2 S. After this treatment, cyclohexane dehydration was almost 95% prevented. The catalyst was then in a rotary kiln under N 2 in the presence of 1% O₂ in 30 min. heated to 350 ° C, then under N 2 in 30 min. to 750 ° C and with the addition of 5% water vapor in 10 min. brought to 800 ° C and 60 min. long reactivated. The cooling took place under N 2 , from 350 ° C with addition of H 2 . The original catalytic activity was exceeded by 20% in the regenerated material.

Claims (5)

1. A process for reactivating catalysts based on activated carbon loaded with noble metals, characterized in that pyrolyzed, activated and optionally reduced.
2. The method according to claim 1, characterized in that the activated carbon an extremely abrasion-resistant spherical carbon with a diameter of 0.1 to 1.0 mm is.
3. The method according to one or more of the preceding claims, characterized in that the pyrolysis easily oxidize up to 350 ° C in the atmosphere.
4. The method according to one or more of the preceding claims, characterized in that the activation in the range 750-900 ° C, preferably 800-850 ° C is carried out.
5. The method according to one or more of the preceding claims, characterized in that the activation in inert gas, the 1-5% Water vapor are added is carried out.
DE19924233763 1992-10-07 1992-10-07 Reactivation of noble metal activated carbon catalyst - by e.g. reforming or platforming catalyst by pyrolysis, activation and opt. redn without burning carbon support Withdrawn DE4233763A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19924233763 DE4233763A1 (en) 1992-10-07 1992-10-07 Reactivation of noble metal activated carbon catalyst - by e.g. reforming or platforming catalyst by pyrolysis, activation and opt. redn without burning carbon support

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19924233763 DE4233763A1 (en) 1992-10-07 1992-10-07 Reactivation of noble metal activated carbon catalyst - by e.g. reforming or platforming catalyst by pyrolysis, activation and opt. redn without burning carbon support

Publications (1)

Publication Number Publication Date
DE4233763A1 true DE4233763A1 (en) 1994-04-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
DE19924233763 Withdrawn DE4233763A1 (en) 1992-10-07 1992-10-07 Reactivation of noble metal activated carbon catalyst - by e.g. reforming or platforming catalyst by pyrolysis, activation and opt. redn without burning carbon support

Country Status (1)

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DE (1) DE4233763A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19522063A1 (en) * 1995-06-17 1996-12-19 Ald Vacuum Techn Gmbh Method and apparatus for recovery of noble metals from activated carbon@

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2512089A1 (en) * 1974-03-21 1975-09-25 Inventa Ag A method for increasing the activity and selectivity of platinum metal-containing catalysts
SU519214A1 (en) * 1974-08-13 1976-06-30 Институт Органической Химии Им. Зелинского Ан Ссср Catalyst for the conversion of cyclic hydrocarbons
SU523707A1 (en) * 1974-08-13 1976-08-05 Иститут Общей И Неорганической Химии Ан Белорусской Сср Method of preparation of catalyst for the conversion of cyclic hydrocarbons

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2512089A1 (en) * 1974-03-21 1975-09-25 Inventa Ag A method for increasing the activity and selectivity of platinum metal-containing catalysts
DE2512089B2 (en) * 1974-03-21 1978-02-09 A process for the reactivation of platinum / activated-carbon and platinum / graphite catalysts
SU519214A1 (en) * 1974-08-13 1976-06-30 Институт Органической Химии Им. Зелинского Ан Ссср Catalyst for the conversion of cyclic hydrocarbons
SU523707A1 (en) * 1974-08-13 1976-08-05 Иститут Общей И Неорганической Химии Ан Белорусской Сср Method of preparation of catalyst for the conversion of cyclic hydrocarbons

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19522063A1 (en) * 1995-06-17 1996-12-19 Ald Vacuum Techn Gmbh Method and apparatus for recovery of noble metals from activated carbon@
DE19522063C2 (en) * 1995-06-17 1999-02-25 Ald Vacuum Techn Gmbh Method and device for recovering precious metals from activated carbon

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OM8 Search report available as to paragraph 43 lit. 1 sentence 1 patent law
8139 Disposal/non-payment of the annual fee