DE4200790A1 - Catalyst for hydrogenating halo-hydrocarbon cpds. to hydrocarbon - has hydrogen halide resistant support comprising iron@-nickel@-chromium@ alloy coated with titanium di:oxide - Google Patents
Catalyst for hydrogenating halo-hydrocarbon cpds. to hydrocarbon - has hydrogen halide resistant support comprising iron@-nickel@-chromium@ alloy coated with titanium di:oxideInfo
- Publication number
- DE4200790A1 DE4200790A1 DE19924200790 DE4200790A DE4200790A1 DE 4200790 A1 DE4200790 A1 DE 4200790A1 DE 19924200790 DE19924200790 DE 19924200790 DE 4200790 A DE4200790 A DE 4200790A DE 4200790 A1 DE4200790 A1 DE 4200790A1
- Authority
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- Germany
- Prior art keywords
- catalyst
- hydrocarbon
- nickel
- hydrogen halide
- hydrogenation
- 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- Withdrawn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 31
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 title claims description 11
- 239000012433 hydrogen halide Substances 0.000 title claims description 11
- 229910052742 iron Inorganic materials 0.000 title claims description 4
- 229930195733 hydrocarbon Natural products 0.000 title abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 5
- 150000005826 halohydrocarbons Chemical class 0.000 title abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title 1
- 239000010936 titanium Substances 0.000 title 1
- 229910052719 titanium Inorganic materials 0.000 title 1
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 150000008282 halocarbons Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000967 As alloy Inorganic materials 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract 2
- 229910000640 Fe alloy Inorganic materials 0.000 abstract 1
- 229910000990 Ni alloy Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052762 osmium Inorganic materials 0.000 abstract 1
- 229910052702 rhenium Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 hexachloroplatinum (IV) Chemical compound 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
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- 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft einen Katalysator und ein Verfahren zur hydrierenden Entsorgung von Halogenkohlenwasserstof fen.The invention relates to a catalyst and a method for the hydrogenating disposal of halogenated hydrocarbon fen.
Es ist allgemein bekannt, Halogenkohlenwasserstoffe durch Verbrennung zu entsorgen. Nachteilig an dieser Verfahrens weise ist einerseits die Tatsache, daß wertvolle Kohlen wasserstoffbestandteile zu Kohlenoxiden vernichtet werden, die letztlich die Umwelt belasten. Andererseits besteht beim oxidativen Abbau von Halogenkohlenwasserstoffen die Gefahr der Dioxinbildung.It is well known to go through halogenated hydrocarbons Dispose of incineration. A disadvantage of this method One wise thing is the fact that valuable coal hydrogen components are destroyed to form carbon oxides, that ultimately pollute the environment. On the other hand, there is in the oxidative degradation of halogenated hydrocarbons Danger of dioxin formation.
Aus diesem Grund heraus wurden mehrere Lösungen ent wickelt, um Halogenkohlenwasserstoffe hydrierend zu ent sorgen ( DE 35 10 033; DD 2 35 630; DD 2 40 741; DD 2 40 740; US 39 27 131 FR 26 09 652). Die technisch interessanteste Lösung ist in DE 21 64 074 von SCHARFE und WILHELMS aufgezeigt worden.For this reason, several solutions have been developed wraps to hydrogenate halogenated hydrocarbons worry (DE 35 10 033; DD 2 35 630; DD 2 40 741; DD 2 40 740; US 39 27 131 FR 26 09 652). The most technically interesting The solution is in DE 21 64 074 from SCHARFE and WILHELMS been shown.
Bei Temperaturen um 180 bis 250°C wurde an einem Rh/Al2O3- Katalysator Dichlorpropan mit Wasserstoff im Molverhältnis von 1:3,5 vollständig zu Propan und Chlorwasserstoff umge setzt. Der Katalysator verlor seine Aktivität nach 400 h. Diese Katalysatorstandzeit ist technisch unbefriedigend.At temperatures around 180 to 250 ° C., dichloropropane was completely converted to propane and hydrogen chloride on a Rh / Al 2 O 3 catalyst using hydrogen in a molar ratio of 1: 3.5. The catalyst lost its activity after 400 hours. This catalyst life is technically unsatisfactory.
Eigene Versuche an Pt/Al2O3-Katalysatoren bestätigten die gefundenen Resultate und zeigten zugleich, daß der gebildete Chlorwasserstoff den Al2O3-Katalysatorträger irreversibel schädigt. Noch stärker tritt eine Schädigung auf, wenn Fluorkohlenwasserstoffe hydrierend entsorgt werden.Our own tests on Pt / Al 2 O 3 catalysts confirmed the results found and at the same time showed that the hydrogen chloride formed irreversibly damages the Al 2 O 3 catalyst support. Damage occurs even more when hydrofluorocarbons are disposed of in a hydrating manner.
Die Erfindung verfolgt das Ziel, Halogenkohlenwasserstoffe unter Rückgewinnung der Kohlenwasserstoffkomponente und der Halogenwasserstoffkomponenten hydrierend in einfacher und ökonomischer Weise zu entsorgen.The invention aims at halogenated hydrocarbons with recovery of the hydrocarbon component and of the hydrogen halide components in simple hydrogenation and dispose of it economically.
Der Erfindung liegt die Aufgabe zugrunde, einen Katalysa torträger zu entwickeln, der eine gute Verteilung der hydrieraktiven Komponente ermöglicht, eine geringe Neigung zur Verkokung zeigt und gegen Halogenwasserstoffe weitest gehend inert ist.The invention has for its object a catalytic converter To develop goal carriers that have a good distribution of the hydration-active component allows a slight incline for coking and as far as possible against hydrogen halide is inert.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß auf einen gegen Halogenwasserstoff beständigen Katalysator träger - bestehend aus einer mit Titaniumoxid beschichte ten Eisen-und/oder Nickelbasislegierung - 1 bis 10 Gew.% - bezogen auf die TiO2-Komponente - einer bekannten Hydrier komponente wie Pt, Pd, Rh, Ru und/oder Gemische derselben, gegebenenfalls unter Zusatz von Os und/oder Re und/oder Ir, aufgebracht werden.The object is achieved in that on a catalyst resistant to hydrogen halide - consisting of a titanium oxide-coated iron and / or nickel-based alloy - 1 to 10 wt.% - Based on the TiO 2 component - 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, can be applied.
Der erfindungsgemäße Katalysator wird von dem gebildeten Halogenwasserstoff nicht angegriffen.The catalyst of the invention is formed by the Hydrogen halide not attacked.
Er kann in bekannter Weise regeneriert werden. Eine irre versible Alterung durch den Angriff des Halogenwasser stoffs, wie auf den dem bekannten Stand der Technik ent sprechenden Al2O3-Träger, tritt bei diesem Katalysator nicht auf.It can be regenerated in a known manner. Irreversible aging due to the attack of the hydrogen halide, as on the Al 2 O 3 supports corresponding to the known prior art, does not occur with this catalyst.
Überraschend wurde gefunden, daß die erfindungsgemäßen Effekte ohne die Al2O3-Komponente erzielbar sind.It has surprisingly been found that the effects according to the invention can be achieved without the Al 2 O 3 component.
Als Eisen- und/oder Nickelbasislegierungen sind solche geeignet, die einen Chromgehalt von mehr als 15% aufweisen. Beispielsweise können Legierungen eingesetzt werden, die folgenden DIN-Werkstoffnummern entsprechen: 1.4335; 1.4529; 1.4876; 2.4816.Such as iron and / or nickel-based alloys suitable, which have a chromium content of more than 15%. For example, alloys can be used that correspond to the following DIN material numbers: 1.4335; 1.4529; 1.4876; 2.4816.
Diese Legierungen können in Blechform, aber auch in anderen Formen mit großer spezifischer Oberfläche einge setzt werden. Beispielsweise kann die Legierung Nicrofer 7216 (Werkstoffnr.: 2.4816) der Fa. Krupp VDM AG verwendet werden.These alloys can be in sheet form, but also in other forms with a large specific surface be set. For example, the Nicrofer alloy 7216 (material no .: 2.4816) from Krupp VDM AG will.
Bei Temperaturen im Bereich von 800 bis 1200°C werden die Legierungen oberflächlich verzundert. Anschließend wird die Metallegierung mit einer phosphorsauren TiO2-Auf schlämmung imprägniert und 0,5 bis 4 h bei Temperaturen von 500 bis 1000°C getempert.At temperatures in the range of 800 to 1200 ° C, the alloys are scaled on the surface. The metal alloy is then impregnated with a phosphoric acid TiO 2 slurry and annealed at temperatures of 500 to 1000 ° C. for 0.5 to 4 h.
Der erfindungsgemäß hergestellte Katalysatorträger wird in allgemein bekannter Weise mit 1 bis 10 Gew.%, bezogen auf die TiO2-Komponente, an hydrieraktiver Edelmetallkomponen te imprägniert.The catalyst support produced according to the invention is impregnated in a generally known manner with 1 to 10% by weight, based on the TiO 2 component, of hydrogenation-active noble metal components.
Mit diesem erfindungsgemäßen Katalysator können dann Halo genkohlenwasserstoffe nach folgendem Verfahren zu Kohlen wasserstoff und Halogenwasserstoff mit nahezu 100%iger Selektivität umgesetzt werden.Halo can then be used with this catalyst according to the invention hydrocarbons to coal according to the following procedure hydrogen and hydrogen halide with almost 100% Selectivity.
Der Halogenkohlenwasserstoff wird, sofern er nicht dampf förmig vorliegt, verdampft, wobei die dafür erforderliche Energie von der freiwerdenden Reaktionswärme aufgebracht werden kann, und zusammen mit Wasserstoff im Molverhältnis von H2/Halogenatom von 2:1 bis 6:1 in den mit erfindungs gemäß hergestellten Katalysator gefüllten Reaktor gelei tet.The halogenated hydrocarbon, unless it is in vapor form, is evaporated, the energy required for this being able to be applied by the heat of reaction liberated, and together with hydrogen in a molar ratio of H 2 / halogen atom from 2: 1 to 6: 1 in accordance with the invention prepared catalyst filled reactor is tet.
Bei Temperaturen von 150 bis 300°C und Drucken von 1 bis 100 atm erfogt die Umsetzung zu Halogenwasserstoff und Kohlenwasserstoff. Das den Reaktor verlassende Gemisch enthält als weitere Komponente nichtumgesetzten Wasser stoff und Halogenkohlenwasserstoff.At temperatures from 150 to 300 ° C and pressures from 1 to The conversion to hydrogen halide and Hydrocarbon. The mixture leaving the reactor contains unreacted water as a further component fabric and halogenated hydrocarbon.
Dieses Gemisch kann in allgemein bekannter Weise destil lativ und/oder absorptiv aufgearbeitet werden, wobei der Kohlenwasserstoff in bekannter Weise noch über Alkali hydroxid von Resten an Halogenwasserstoff befreit werden kann.This mixture can be distilled in a generally known manner be worked up latively and / or absorptively, the Hydrocarbon in a known manner over alkali hydroxide of residues of hydrogen halide are freed can.
Die nicht umgesetzten Reaktionsprodukte werden wieder in den Reaktor zurückgeführt.The unreacted reaction products are in again returned the reactor.
Die Erfindung wird durch nachstehendes Beispiel näher erläutert.The invention is illustrated by the example below explained.
50 g der Krupp VDM-Legierung Nicrofer 7261 wurden als Blech mit 0,12 mm Dicke in Form von spiralförmig aufge wickelten Röllchen mit einer Kantenlänge von 1,5 bis 2 mm eingesetzt. Die Oberfläche betrug ca. 1000 cm2. Dieses Blech wurde 2 h bei 1000°C in Luft thermisch behandelt.50 g of the Krupp VDM alloy Nicrofer 7261 were used as sheet with a thickness of 0.12 mm in the form of spirally wound rolls with an edge length of 1.5 to 2 mm. The surface was approx. 1000 cm 2 . This sheet was thermally treated in air at 1000 ° C. for 2 hours.
Danach wurden 30 g TiO2 in 80 ml 10%iger Phosphorsäure aufgeschlämmt. Die metallischen Festkörper wurden mit dieser Aufschlämmung imprägniert und anschließend 1 h bei 600°C erhitzt. Der fertige Katalysatorträger enthält 7,5 g TiO2. Sein Schüttgewicht beträgt 1 g/ml.30 g of TiO 2 were then slurried in 80 ml of 10% phosphoric acid. The metallic solids were impregnated with this slurry and then heated at 600 ° C for 1 h. The finished catalyst carrier contains 7.5 g TiO 2 . Its bulk density is 1 g / ml.
Dieser Katalysator wurde mit 0,88 g Hexachlorplatin(IV)- säurehexahydrat, gelöst in 50 ml Wasser, imprägniert und anschließend in bekannter Weise reduktiv mit Wasserstoff behandelt.This catalyst was treated with 0.88 g of hexachloroplatinum (IV) - acid hexahydrate, dissolved in 50 ml water, impregnated and then reductively with hydrogen in a known manner treated.
Der Katalysator wurde in einem Strömungsrohrreaktor (Länge: 300 mm; Innendurchmesser: 32 mm) so eingebaut, daß vor und nach der Katalysatorschicht inerte keramische Formkörper lagen. Als Halogenwasserstoff wurde Dichlorpro pan verwendet, wie es bei der Herstellung von Propylenoxid nach dem Chlorhydrinverfahren anfällt. Pro Stunde wurden 113 g Dichlorpropan mit der fünffachen molaren Menge an Wasserstoff bei einem Druck von 9 atü und einer Temperatur von 250°C über den Katalysator geleitet. In einem Reak tordurchgang wurde ein 47%iger Umsatz zu Propan und HCl erhalten.The catalyst was in a flow tube reactor (Length: 300 mm; inner diameter: 32 mm) installed so that inert ceramic before and after the catalyst layer Shaped bodies were. As a hydrogen halide was dichlorpro pan used as it is in the manufacture of propylene oxide after the chlorohydrin process. Per hour 113 g dichloropropane with five times the molar amount of Hydrogen at a pressure of 9 atm and a temperature passed from 250 ° C over the catalyst. In a reak gate passage was a 47% conversion to propane and HCl receive.
Im Vergleich zum aluminiumoxidgeträgerten Katalysator traten bei Verwendung des erfindungsgemäßen Katalysators keine Schädigungen des Katalysatorträgers durch HCl auf und es fiel weniger als 1/10 an Kohlenstoffablagerungen auf dem Katalysator an, bezogen auf den Vergleichsversuch mit aluminiumoxidgeträgerten Katalysator. Weitere Produkte entstanden nicht.Compared to the alumina-supported catalyst occurred when using the catalyst of the invention no damage to the catalyst carrier by HCl and less than 1/10 of carbon deposits fell on the catalyst, based on the comparison test with alumina-supported catalyst. Further products did not arise.
Das nicht umgesetzte Dichlorpropan wurde destillativ von den anderen Produkten getrennt und, ergänzt durch frisches Dichlorpropan, in den Reaktor zurückgeführt.The unreacted dichloropropane was distilled from the other products separately and, supplemented by fresh Dichloropropane, returned to the reactor.
Der Chlorwasserstoff wurde mittels wäßriger Lösung aus dem verbleibenden Gasgemisch absorbiert.The hydrogen chloride was removed from the remaining gas mixture absorbed.
Auf eine Auftrennung des Propan/H2-Gemisches wurde ver zichtet.The propane / H 2 mixture was not separated.
Analoge Ergebnisse wurden auch mit Fluorchlorkohlenwasser stoffen erzielt, wo bei neben HCl im entsprechenden Ver hältnis HF anfiel.Analogous results were also obtained with chlorofluorocarbons substances achieved where in addition to HCl in the corresponding ver ratio HF was incurred.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924200790 DE4200790A1 (en) | 1992-01-15 | 1992-01-15 | Catalyst for hydrogenating halo-hydrocarbon cpds. to hydrocarbon - has hydrogen halide resistant support comprising iron@-nickel@-chromium@ alloy coated with titanium di:oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924200790 DE4200790A1 (en) | 1992-01-15 | 1992-01-15 | Catalyst for hydrogenating halo-hydrocarbon cpds. to hydrocarbon - has hydrogen halide resistant support comprising iron@-nickel@-chromium@ alloy coated with titanium di:oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4200790A1 true DE4200790A1 (en) | 1993-07-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19924200790 Withdrawn DE4200790A1 (en) | 1992-01-15 | 1992-01-15 | Catalyst for hydrogenating halo-hydrocarbon cpds. to hydrocarbon - has hydrogen halide resistant support comprising iron@-nickel@-chromium@ alloy coated with titanium di:oxide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4200790A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4426390C1 (en) * | 1994-07-26 | 1995-08-17 | Leuna Werke Gmbh | Gas phase catalytic hydro-dechlorination of chloro:hydrocarbons |
| DE4426391C1 (en) * | 1994-07-26 | 1995-12-14 | Leuna Katalysatoren Gmbh | Complete gas-phase hydrodechlorination of chloro-hydrocarbon(s) |
| US5625110A (en) * | 1994-07-26 | 1997-04-29 | Leuna-Katalysatoren Gmbh | Hydrodehalogenation catalyst |
| US5811628A (en) * | 1994-07-26 | 1998-09-22 | Leuna-Katalysatoren Gmbh | Method for the complete hydrodechlorination of chlorinated hydrocarbons |
-
1992
- 1992-01-15 DE DE19924200790 patent/DE4200790A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4426390C1 (en) * | 1994-07-26 | 1995-08-17 | Leuna Werke Gmbh | Gas phase catalytic hydro-dechlorination of chloro:hydrocarbons |
| DE4426391C1 (en) * | 1994-07-26 | 1995-12-14 | Leuna Katalysatoren Gmbh | Complete gas-phase hydrodechlorination of chloro-hydrocarbon(s) |
| US5625110A (en) * | 1994-07-26 | 1997-04-29 | Leuna-Katalysatoren Gmbh | Hydrodehalogenation catalyst |
| US5811628A (en) * | 1994-07-26 | 1998-09-22 | Leuna-Katalysatoren Gmbh | Method for the complete hydrodechlorination of chlorinated hydrocarbons |
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