DE4230553A1 - Catalyst with nickel aluminium spinel carrier for dehydrohalogenation - of halo-hydro-carbon cpds. e.g. chloro-benzene, with high activity, selectivity and stability, which is easy and economical to produce. - Google Patents
Catalyst with nickel aluminium spinel carrier for dehydrohalogenation - of halo-hydro-carbon cpds. e.g. chloro-benzene, with high activity, selectivity and stability, which is easy and economical to produce.Info
- Publication number
- DE4230553A1 DE4230553A1 DE4230553A DE4230553A DE4230553A1 DE 4230553 A1 DE4230553 A1 DE 4230553A1 DE 4230553 A DE4230553 A DE 4230553A DE 4230553 A DE4230553 A DE 4230553A DE 4230553 A1 DE4230553 A1 DE 4230553A1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- dehydrohalogenation
- nickel
- selectivity
- hydro
- 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- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 4
- 239000011029 spinel Substances 0.000 title claims abstract description 4
- 238000006704 dehydrohalogenation reaction Methods 0.000 title abstract description 3
- 150000005826 halohydrocarbons Chemical class 0.000 title abstract 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title 1
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- -1 nickel-aluminum-oxygen Chemical compound 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 229910018516 Al—O Inorganic materials 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
Die Erfindung betrifft einen Hydrierkatalysator, insbesondere zur hydrierenden Entsorgung von Halogenkohlenwasserstoffen.The invention relates to a hydrogenation catalyst, in particular for the hydrogenating disposal of halogenated hydrocarbons.
Es ist bekannt, Halogenkohlenwasserstoffe in ökologisch und ökonomisch vorteilhafter Weise hydrierend zu entsorgen (z. B. DE 21 64 074). Als nachteilig erweist es sich hierbei jedoch, daß der gebildete Halogenwasserstoff die üblicherweise einge setzten Hydrierkatalysatoren (z. B. Pt auf γ-Al2O3) angreift. Hieraus resultieren technisch unbefriedigende Katalysator standzeiten von ca. 400 h und weniger.It is known to dispose of halogenated hydrocarbons in an ecologically and economically advantageous manner by hydrogenation (for example DE 21 64 074). It proves disadvantageous here, however, that the hydrogen halide formed attacks the hydrogenation catalysts which are usually employed (for example Pt on γ-Al 2 O 3 ). This results in technically unsatisfactory catalyst service lives of approximately 400 hours and less.
Dieses Problem ist lösbar durch den Einsatz halogenwasser stoffresistenter, metallgeträgerter Hydrierkatalysatoren. Bei diesen wird auf einen TiO2-beschichteten Katalysatorträger eine bestimmte Menge einer bekannten Hydrierkomponente wie Pt, Pd, Rh, Ru und/oder Gemische derselben, gegebenenfalls unter Zusatz von Os und/oder Re und/oder Ir, aufgebracht. Als Träger kommen verschiedene Legierungen in Betracht.This problem can be solved by using halogen-water-resistant, metal-supported hydrogenation catalysts. In these, a certain amount of a known hydrogenation component such as Pt, Pd, Rh, Ru and / or mixtures thereof, optionally with the addition of Os and / or Re and / or Ir, is applied to a TiO 2 -coated catalyst support. Various alloys can be used as supports.
Nachteilig bei diesen Katalysatortypen ist die umfangreiche und aufwendige Vorbehandlung zur Aufbringung des TiO2 und der Hydrierkomponente, die auch mit einer mehrmaligen thermischen Behandlung verbunden ist.A disadvantage of these types of catalysts is the extensive and complex pretreatment for applying the TiO 2 and the hydrogenation component, which is also associated with repeated thermal treatment.
Dieser hohe Aufwand belastet die Ökonomie des gesamten Ver fahrens wesentlich.This high effort burdens the economy of the entire Ver driving essential.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, einen Katalysator für die hydrierende Reduktion, insbesondere die hydrierende Entsorgung von Halogenkohlenwasserstoffen zu ent wickeln, der in einfacher und ökonomisch vorteilhafter Weise hergestellt, eingesetzt und später einfach entsorgt oder an ders weiterverwendet werden kann. The present invention has for its object a Catalyst for the hydrogenating reduction, especially the hydrogenating disposal of halogenated hydrocarbons wrap in a simple and economically advantageous manner manufactured, used and later simply disposed of or at which can continue to be used.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß ein Trä germaterial für die Aktivkomponente verwendet wird, dessen Oberfläche aus einem Nickel-Aluminium-Sauerstoff-Spinell be steht. Dieser Träger wird mit 30-70 Gew.-% Nickel beladen und so behandelt, daß 30-70 Gew.-% des Nickels als metal lisches Nickel vorliegen.The object is achieved in that a Trä Germ material is used for the active component, the Nickel-aluminum-oxygen spinel surface stands. This carrier is loaded with 30-70% by weight of nickel and treated so that 30-70 wt .-% of the nickel as metal nickel.
Die Größe der Nickelkristallite beträgt erfindungsgemäß 50-150 Å.The size of the nickel crystallites is according to the invention 50-150 Å.
Der erfindungsgemäße Katalysator wird von dem während der Reaktion gebildeten Halogenwasserstoff nicht angegriffen. Der Katalysator zeigt im Vergleich zu Pt/γ-Al2O3-Katalysatoren bzw. Katalysatoren mit niedrigeren Nickelgehalten deutlich höhere Aktivitäten und eine längere Lebensdauer.The catalyst according to the invention is not attacked by the hydrogen halide formed during the reaction. Compared to Pt / γ-Al 2 O 3 catalysts or catalysts with lower nickel contents, the catalyst shows significantly higher activities and a longer service life.
Die Dehydrohalogenierung erfolgt sehr selektiv, d. h. aromati sche Kerne von aromatischen Chlorkohlenwasserstoffen werden nicht hydriert.The dehydrohalogenation is very selective, i. H. aromati cores of aromatic chlorinated hydrocarbons not hydrogenated.
Die erfindungsgemäßen Katalysatoren können unter den für tech nische Hydrierungen üblichen Bedingungen eingesetzt werden. Die Temperatur sollte jedoch 300°C nicht überschreiten. Die Erfindung wird durch nachfolgende Beispiele näher erläu tert.The catalysts of the invention can be among those for tech African hydrogenations usual conditions are used. However, the temperature should not exceed 300 ° C. The invention is illustrated by the following examples tert.
In einem Strömungsrohrreaktor wurden jeweils 100 mg Katalysa
tor gegeben. Die Austestung erfolgte bei einer Temperatur von
250°C und Normaldruck unter folgenden Bedingungen:
15 l/h H2 und 10 g Chlorbenzen pro g Katalysator und Stunde.
Die Austestung erfolgte je nach Alterung bis zu 3 Tagen.
Folgende Ergebnisse wurden erzielt:In each case 100 mg of catalyst were placed in a flow tube reactor. The test was carried out at a temperature of 250 ° C and normal pressure under the following conditions:
15 l / h H 2 and 10 g chlorobenzene per g catalyst and hour. Depending on the age, testing was carried out for up to 3 days. The following results were achieved:
Die Größe der Nickelkristallite im erfindungsgemäßen Katalysa tor betrug 90 Å, während sie in den anderen nickelhaltigen Katalysatoren kleiner 40 Å war. Überraschenderweise zeigen die größeren Nickelkristallite eine höhere und stabilere Aktivität als die kleineren. Die Selektivität der Hydrierung der C-Cl-Bindung im Verhältnis zur Hydrierung des aromatischen Kerns betrug beim erfindungsgemäßen Katalysator 100 Mol HCI/1 Mol Cyclohexan, während die anderen Katalysatoren deutlich kleine re Selektivitäten erreichten.The size of the nickel crystallites in the catalyst according to the invention Tor was 90 Å while in the others it contained nickel Catalysts was less than 40 Å. Surprisingly, the show larger nickel crystallites a higher and more stable activity than the smaller ones. The selectivity of the hydrogenation of the C-Cl bond in relation to the hydrogenation of the aromatic nucleus was 100 mol HCl / 1 mol in the catalyst according to the invention Cyclohexane, while the other catalysts are clearly small re selectivities achieved.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4230553A DE4230553A1 (en) | 1992-09-10 | 1992-09-10 | Catalyst with nickel aluminium spinel carrier for dehydrohalogenation - of halo-hydro-carbon cpds. e.g. chloro-benzene, with high activity, selectivity and stability, which is easy and economical to produce. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4230553A DE4230553A1 (en) | 1992-09-10 | 1992-09-10 | Catalyst with nickel aluminium spinel carrier for dehydrohalogenation - of halo-hydro-carbon cpds. e.g. chloro-benzene, with high activity, selectivity and stability, which is easy and economical to produce. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4230553A1 true DE4230553A1 (en) | 1994-03-17 |
Family
ID=6467808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4230553A Withdrawn DE4230553A1 (en) | 1992-09-10 | 1992-09-10 | Catalyst with nickel aluminium spinel carrier for dehydrohalogenation - of halo-hydro-carbon cpds. e.g. chloro-benzene, with high activity, selectivity and stability, which is easy and economical to produce. |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4230553A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8067661B2 (en) * | 2008-03-07 | 2011-11-29 | Asahi Glass Company, Limited | Method for decomposing water-soluble fluorinated organic compound |
| CN114029083A (en) * | 2021-12-03 | 2022-02-11 | 中国石油大学(北京) | Hydrodesulfurization catalyst and preparation method and application thereof |
-
1992
- 1992-09-10 DE DE4230553A patent/DE4230553A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8067661B2 (en) * | 2008-03-07 | 2011-11-29 | Asahi Glass Company, Limited | Method for decomposing water-soluble fluorinated organic compound |
| CN114029083A (en) * | 2021-12-03 | 2022-02-11 | 中国石油大学(北京) | Hydrodesulfurization catalyst and preparation method and application thereof |
| CN114029083B (en) * | 2021-12-03 | 2022-11-04 | 中国石油大学(北京) | Hydrodesulfurization catalyst and preparation method and application thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |