DE3930145A1 - Supported catalyst for low-temp. oxidn. of organic cpds. etc. - comprises support loaded with transition metal phthalocyanine and amine, activated by heating in nitrogen etc. - Google Patents

Abstract

Supported catalyst (I) for low-temp. oxidn. of organic cpds. and/or CO is obtd. by loading a catalyst support (II) simultaneously or consecutively with a transition metal phthalocyanine (III) and an amine (IV) so as to form the amine-phthalocyanine complex, and converting this into the active catalyst by treatment at 20-200 deg.C in a stream of N2 and/or O2 and/or air and/or CO and/or hydrocarbons and/or alcohols, with displacement of some of the complexed amine. (III) is Fe, Mn and/or Co phthalocyanine. (IV) is ammonia, mono-, di- or tri- methylamine, methylimidazole, pyridine, bipyridyl, pyrazole or polymeric amine, esp. aliphatic amine and such amines on polyethylene or styrene-DVB copolymer. (II) is aluminosilicate, silicate, SiO2, Al2O3 or zeolite, esp. a cordierite or mullite honeycomb material or Al oxide minimonoliths (wagon wheels). When (IV) is a polymeric amine based on synthetic resin or ion exchange resin, this itself serves at a catalyst support with a large surface area. USE/ADVANTAGE - (I) enables oxidn. at lower temps. (50-150 deg.C) than with prior-art catalysts (e.g. 200-600 deg.C depending on the cpd. to be oxidised). (I) gives high conversion yields and is selective for prods. of partial oxidn.

Description

The invention relates to supported catalysts made from transition metal phthalocyanine amine complexes for the oxidation of organic compounds or CO at low temperatures as well as the use of these catalysts for the oxidative change in organic compounds and the oxidation of CO CO₂.

Compared to the prior art, there is the task of known catalysts to be replaced by others and developed in such a way that a the highest possible conversion is achieved at low temperatures, and that the products of partial oxidation are obtained selectively. For the production thermally sensitive products through partial oxidation of organic Starting materials are more concerned with a gentle working temperature than on a high turnover.

According to the invention, this object is achieved by a supported catalyst for the oxidation of organic compounds and / or CO at low Temperatures, characterized in that by loading a support with a transition metal phthalocyanine and a Amine - at the same time or in succession - from the transition metal phthalocyanine and the amine-the phthalocyanine complex is prepared and this at temperatures between 20 and 200 ° C by treatment in one Gas flow from nitrogen and / or oxygen and / or air and / or carbon monoxide and / or hydrocarbons and / or alcohols with displacement part of the complexed amine is converted into the active catalyst becomes.

The di-amine complexes of the metal phthalocyanines are known and in the literature described. These diamine-phthalocyanine complexes are not catalytic active. The catalyst according to the invention differs from the prior art Technique in that the di-amine complexes by treatment with suitable Gases or gas mixtures are converted into the mono-amine complexes. According to the invention, this conversion can also be carried out by treatment at temperatures between 20 ° C and 200 ° C in a stream of nitrogen; better results is obtained by displacement or substitution of the one amine ligand by one of the reactants of the proposed catalytic conversion, usually oxygen, organic compounds, preferably alcohols or Hydrocarbons, and / or carbon monoxide.

Compared to the prior art, the catalysts are based on of amine complexes of the metal phthalocyanines in that the temperatures the oxidation reaction compared to those previously used in the oxidation Catalysts can be lowered to between 50 and 150 ° C can. Previously used catalysts work at 220 ° C and 300 ° C (2-propanol) or 600 ° C (methanol). Due to the very low working temperatures can, in particular, use thermally labile components as starting materials or can be achieved as products.

The chemical interaction between the components of the invention Catalysts are detected by IR spectroscopy. Compared to the the interaction with the amines is due to pure metal phthalocyanines characterized characteristic band shifts. This for metal phthalocyanine amine catalysts typical band shifts are related with the catalytic activity. The manufactured according to the invention Metal phthalocyanine and amine catalyst has specific catalytic Properties that differ from those of the non-complexed metal phthalocyanines are different. The catalytic inactivity of the di-amine complexes was already highlighted.

The invention further relates to a method for producing a carrier-based Catalyst for the oxidation of organic compounds and / or CO at low temperatures, characterized in that by loading a support with a transition metal phthalocyanine and a Amine - at the same time or in succession - from the transition metal phthalocyanine and the amine-the phthalocyanine complex is prepared and this at temperatures between 20 and 200 ° C by treatment in one Gas flow from nitrogen and / or oxygen and / or air and / or carbon monoxide and / or hydrocarbons and / or alcohols with displacement part of the complexed amine is converted into the active catalyst becomes.  

The porous carrier is preferably loaded by soaking Solutions or suspensions. All three options are applicable and Different advantages depending on the amines used: A) Manufacture of the di-amine-phthalocyanine complex in solution and watering the carrier with this, b) impregnation of the carrier with phthalocyanine and subsequent transfer in the di-amine complex, c) impregnating the support with amine or Using a polymer-based polymer amine - and producing the Amine complex on the support by introducing phthalocyanine. Subsequently the active catalyst must be generated from the diamine. Using polymeric amines arise from the outset for steric reasons Mono-amine complex.

Suitable solvents for the production processes according to the invention in particular chlorobenzene, chloronaphthalene, bromonaphthalene, pyridine, pyrrole, organic Amines, liquid ammonia, sulfuric acid, formic acid, acetic acid, Propionic acid, alkanoic acids, chlorosulfonic acids, mono-, di- and trichloroacetic acid, Benzophenone, N-ethyl carbazole, liquid sulfur dioxide and dimethyl sulfoxide, Alcohols, water, hydrocarbons and mixtures of the above Fabrics.

The solubility is sometimes very low and is only a few mg per liter. This is for the production of amine bound with metal phthalocyanine but sufficient. The application temperatures go from the freezing point up to the boiling point of the solvent.

Ammonia, mono-, di- and trimethylamine are used as amines typical representatives for aliphatic amines and methylimidazole, pyridine and bipyridine, Pyrazole as a typical representative of aromatic amines.

Furthermore, the amines can be covalently attached to organic supports, synthetic resins and ion exchangers, in particular hydrocarbon chains, polyethylene, copolymers from styrene and divinylbenzene, and bound to dextrans. These Carriers can be used as powders, granules, compacts and moldings will.

The catalysts can also be produced at normal temperatures gaseous amines are used. For this purpose, the metal phthalocyanines as Powder bed or the carrier loaded with phthalocyanine presented in one Vacuum equipment by alternately applying a vacuum and loading with amine vapor and amine, even at elevated temperature reacted with amines for a few hours. Then the catalysts represented by treatment with the appropriate gas mixture.  

According to the invention, the catalyst can also be synthesized by passing it over a gas stream loaded with amine (nitrogen, oxygen, helium or air) over a powder bed of the metal phthalocyanine or with Carrier loaded with phthalocyanine. The metal phthalocyanine is increased Temperature thermostated to increase the rate of catalyst formation enlarge. The catalysts are then treated with a gas mixture shown.

Polymeric metal phthalocyanines can also be reacted with amines to form catalysts will. The polymeric metal phthalocyanines are obtained by extraction cleaned with suitable organic solvents. Here, the Catalysts by reaction with amines and subsequent treatment produced.

The di-amine complexes can also be produced by sublimation. The metal phthalocyanine and the amine are in a vacuum apparatus submitted under vacuum. Then the metal phthalocyanine and the amine sublimated by thermostated heating and on a cooled surface of the Di-amine complex deposited or directly on the cooled carrier material sublimated. Thereafter, the catalysts are treated with the appropriate one Shown gas.

All known and customary from the prior art can be used as carriers Materials and materials are used, especially those in DE-A-35 22 637 and EP-A-02 28 398 described and used substances and mixtures.

Preferred carriers are diatomaceous earth, silicon dioxide, cordierite, steatite, mullite, aluminum oxide, Clay, kaolin and perlite, also aluminosilicates, especially zeolites of type A, X, Y or ZSM as well as natural zeolites and feldspars. Also suitable are graphite, magnesium silicates, magnesium oxide, zinc oxide, Zirconium silicate, zirconium oxide, titanium dioxide, silicon carbide as well as synthetic resins, plastics and ion exchangers with amine groups.

The carrier materials used according to the invention preferably have a microporous one Structure.

In principle, the phthalocyanines can be used for the catalysts according to the invention all transition metals are used. Such transition metals that are characterized by high price or toxicity, but do not necessarily have to be used. The phthalocyanines are particularly preferred the metals iron, manganese and cobalt.

Examples

Used abbreviations:
FePc: iron phthalocyanine
CoPc: cobalt phthalocyanine
MnPc: manganese phthalocyanine
Bipy: 4 ′, 4-bipyridine
N (Me) ₃: trimethylamine
MeOH: methanol
2-PrOH: 2-propanol

Carrier body:
Aluminum oxide mini monoliths (wagon wheels) or cordierite honeycomb body, volume 30 cm³.

1. FePc (Bipy) on mini monoliths or honeycomb bodies

Presentation:
3.8 g FePc in 150 ml chlorobenzene. 15 ml of a 0.5 molar bipyridine solution in pentane are added. Then boiling under reflux at 110 ° C. for 6 h.

Impregnation:
Directly from the solution subsequently obtained at room temperature until a loading of 5.5% by weight, based on the weight of the carrier body, is achieved.
Between the impregnations drying at 20 ° C. At the end, soak in ethanol to remove excess bipyridine. If the chlorobenzene is stripped off beforehand and the complex is added to a pentane / ethanol mixture and the support is impregnated therefrom, the catalyst shows the same activity.

Activation:
3 h at 100 ° C in the reaction gas

Activity: Methanol oxidation to formaldehyde:
SV = 30 h ^-1 , MeOH: 150 hPa, O₂: 150 hPa.
Sales:
15% at 150 ° C
24% at 180 ° C
2-propanol oxidation to acetone:
SV = 30 h ^-1 , 2-PrOH: 50 hPa O₂: 100 hPa.
Sales:
17% at 150 ° C
25% at 185 ° C

2. FePc (Bipy) on mini monoliths or honeycomb bodies

Presentation:
As in Example 1, however, solvent is stripped off and dried at 50 ° C. and excess bipyridine is washed out with ethanol.

Impregnation:
The complex obtained is suspended in formic acid. Impregnation until a load of 7 wt .-% is reached.

Activation:
3 h at 100 ° C in the reaction gas

Activity:
2-propanol oxidation to acetone:
SV = 30 h ^-1 , 2-PrOH: 50 hPa O₂: 100 hPa.
Sales:
9% at 150 ° C
10% at 185 ° C

3. FePc (Bipy) represented in ethanol / pentane 10: 1 on mini monoliths

Presentation:
Like Ex. 1; Boil under reflux at a significantly lower temperature.

Impregnation:
From the reaction solution until a loading of 2.2% by weight is reached. Between the impregnations dry at room temperature.

Activation:
3 h at 100 ° C in the reaction gas

Activity:
2-propanol oxidation to acetone:
SV = 30 h, 2-PrOH: 50 hPa O₂: 100 hPa.
Sales:
4% at 150 ° C
3% at 185 ° C

4. FePc on Amberlite LA-2 on mini monoliths or honeycomb bodies

Presentation:
3.8 g of FePc are placed in 150 ml of chlorobenzene. Then 15 ml of a 25% Amberlite LA-2 solution in hexane are added and both are boiled under reflux for 6 h.

Impregnation:
From the reaction solution until a loading of 7-8% by weight is reached. Between the impregnations dry at room temperature. Excess Amberlite LA-2 is then washed out with ethanol.

Activation:
not applicable

Activity:
2-propanol oxidation to acetone:
SV = 30 h, 2-PrOH: 50 hPa O₂: 100 hPa.
Sales:
6% at 150 ° C
7% at 185 ° C

5. MnPc (Bipy) on mini monoliths or honeycomb bodies

Presentation:
4 g of MnPc are placed in 150 ml of chlorobenzene. After warming to 50 ° C, 30 ml of a 0.5 molar bipyridine solution in pentane are added. The solution is brought to boiling under reflux for 24 h.

Impregnation:
The reaction solution is soaked at 50 ° C. until a loading of 3% by weight is reached. Excess bipyridine is removed by soaking in ethanol.

Activation:
4 h at 120 ° C in the reaction gas

Activity:
Methanol oxidation to formaldehyde:
SV = 30 h ^-1 , MeOH: 150 hPa, O₂: 150 hPa.
Sales:
5% at 150 ° C
16% at 180 ° C
2-propanol oxidation to acetone:
SV = 30 h ^-1 , 2-PrOH: 50 hPa O₂: 100 hPa.
Sales:
6% at 150 ° C
25% at 185 ° C

6. CoPc (Bipy) on mini monoliths or honeycomb bodies

Presentation:
Analogous to example 1.

Impregnation:
From the reaction solution at room temperature until a load of 10% by weight is reached.

Activation:
3 h at 140 ° C in the reaction gas

Activity:
Methanol oxidation to formaldehyde:
SV = 30 h ^-1 , MeOH: 150 hPa, O₂: 150 hPa.
Sales:
4% at 150 ° C
8% at 180 ° C
2-propanol oxidation to acetone:
SV = 30 h ^-1 , 2-PrOH: 50 hPa
O₂: 100 hPa.
Sales:
3% at 150 ° C
6% at 185 ° C

7. CoPc on ion exchanger Merck-II

Presentation:
4 g of CoPc are placed in 150 ml of chlorobenzene. 50 g of Merck-II ion exchanger dried at 105 ° C. are added and the two are heated together at 100 ° C. for 6 hours.
It is then filtered hot and the residue washed several times with chlorobenzene until only the loaded ion exchanger can be seen. This is dried at 50 ° C. The loading is 1-2% by weight.

Activation:
At 120 ° C in the reaction gas

Activity:
Methanol oxidation to formaldehyde:
SV = 30 h ^-1 ,
MeOH: 150 hPa,
O₂: 150 hPa.
Sales:
6% at 150 ° C
7% at 180 ° C
2-propanol oxidation to acetone:
SV = 30 h ^-1 , 2-PrOH: 50 hPa
O₂: 100 hPa.
Sales:
2% at 150 ° C
5% at 185 ° C

8. CO oxidation on FePc-N (Me) ₃

Presentation:
Sublimate the FePc to a support in a vacuum at 10 ° C Pa. Evaporation of the FePc with trimethylamine at 90 ° C.

Activation:
Annealing at 100 ° C in the reaction gas stream.

Activity:
CO oxidation:
SV = 30 h ^-1 O₂, CO: 100 hPa
Sales:
20% at 100 ° C

9. FePc on Merck II ion exchanger

Presentation:
As in Example 7 but with FePc

Activation:
At 100 ° C in the reaction gas stream

Activity:
Methanol oxidation to formaldehyde:
SV = 30 h ^-1
O₂: 90 hPa
MeOH: 140 hPa
Sales:
4% at 120 ° C
10% at 140 ° C

10. FePc pyridine

Presentation:
FePc is placed in a loader tube. Saturated pyridine vapor is passed over the FePc at 65 ° C. for 19 h.

Activation:
At 100 ° C in the reaction gas stream

Activity:
Methanol oxidation to formaldehyde:
SV = 30 h ^-1
O₂: 100 hPa
MeOH: 120 hPa
Turnover: 2% at 105 ° C

11. FePc (bipy) by cosublimation

Presentation:
FePc is sublimed at 510 ° C in a vacuum on a cooled surface. Subsequently, bipyridine is sublimed to the FePc at 25 ° C.

Activation:
3 h at 100 ° C in the reaction gas

Activity:
Methanol oxidation to formaldehyde:
SV = 30 h ^-1 ,
MeOH: 150 hPa,
O₂: 150 hPa.
Sales:
12% at 130 ° C
19% at 140 ° C
2-propanol oxidation to acetone:
SV = 30 h ^-1 , 2-PrOH: 35 hPa
O₂: 100 hPa.
Sales:
12% at 120 ° C
19% at 140 ° C

Claims (8)

1. Supported catalyst for the oxidation of organic compounds and / or CO at low temperatures, characterized in that the amine-phthalocyanine complex is prepared by loading a support with a transition metal phthalocyanine and an amine - simultaneously or in succession - from the transition metal phthalocyanine and the amine and this at temperatures between 20 and 200 ° C by treatment in a gas stream from nitrogen and / or oxygen and / or air and / or carbon monoxide and / or hydrocarbons and / or alcohols with displacement of part of the complexed amine in the active catalyst. 2. Catalyst according to claim 1, characterized in that as transition metal phthalocyanine at least one of iron, manganese or Is cobalt phthalocyanine. 3. Catalyst according to claim 1, characterized in that as amine at least one of ammonia, mono-, di-, trimethylamine, methylimidazole, Pyridine, bipyridine, pyrazole or polymeric amines, especially aliphatic Amines and those on polyethylene, styrene and divinylbenzene, or dextrans to be used. 4. A catalyst according to claim 1, characterized in that as carrier material aluminosilicates, silicates, silicon dioxide, aluminum oxides or Zeolites are used.   5. A catalyst according to claim 1, characterized in that a cordierite or mullite honeycomb body or aluminum oxide minimonolite as the carrier (wagon wheels) can be used. 6. Catalyst according to claim 1, characterized in that when using a polymeric amine based on synthetic resin or ion exchanger this itself serves as a surface-rich carrier. 7. Process for the preparation of a supported catalyst for oxidation of organic compounds and / or CO at low temperatures one of claims 1 to 6, characterized in that by loading a support with a transition metal phthalocyanine and a Amine - at the same time or in succession - from the transition metal phthalocyanine and the amine-the phthalocyanine complex is prepared and this at temperatures between 20 and 200 ° C by treatment in one Gas flow from nitrogen and / or oxygen and / or air and / or carbon monoxide and / or hydrocarbons and / or alcohols with displacement part of the complexed amine is converted into the active catalyst becomes. 8. Use of the catalysts of one of claims 1 to 6 for oxidation of organic compounds and / or CO at low temperatures.