CA1292977C - Oxidation of hydrocarbons with v-zr or v-ti catalyst - Google Patents
Oxidation of hydrocarbons with v-zr or v-ti catalystInfo
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- metallic glass
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Abstract
ABSTRACT OF THE DISCLOSURE
A process is disclosed for the oxidation of cyclic hydrocarbons in the presence of a catalytically-active metallic glass containing titanium and vanadium or zirconium and vanadium, the metallic glass being activated by oxidative treatment prior to the oxidation step or in situ during the oxidation.
A process is disclosed for the oxidation of cyclic hydrocarbons in the presence of a catalytically-active metallic glass containing titanium and vanadium or zirconium and vanadium, the metallic glass being activated by oxidative treatment prior to the oxidation step or in situ during the oxidation.
Description
1~92~';7 The invention relates to a process for catalytically oxidizing cyclic hydrocarbons using catalytically-active metallic glasses.
Gertain amorphous metal alloys catalyze 6 hydrogenation reactions, for ex~mple, those of cyGlohexene derivatives rG.V. Smith et al., J. of Catalysis 83 (1~83) 23~ or of carbon monoxide ti.e.~ Fisher-TrcpsGh ~eaction) [A. YokoYama et al., Chemistry Letters ~1988), 195]. The catalytic action is based on the amorphous state of the metals. However, it has also been described that, in the case of the system Pd80Si20, no significant differences exist concerning the selectivity in the case of hydrogenation reactions between the amorphous state and the crystalline state ~B. Giessen et al., Mater Res. Soc.
Symp. Proc., Vol. 1~ (1982), 255].
For the most part, the surfaces and the state of order of catalysts consisting of amorphou~ metals have not been investigated sufflclently, ~o that the ~ompari~on be~ween amorphou~ and cry~talline ~yB~em~ i8 not of any significant meaning. It turned out, for example, that the catalytical effectivene~s could n~t be deduce~ because of a lack of knowledge of the connections between amorphous and crystalline systems.
An object of the invention is to provide an improved process for the oxidation of cyclic hydrocarbons.
A further object of the invention i8 to provide catalytically-active metallic glasses for use in such process.
It is to be noted that the term "metallic glasses" as used herein is intended to have the same meaning as the term "amorphous metals".
Accordingly, one aspect of the invention provides a process for the oxidation of a cyclic hydrocarbon, which comprises oxidizing said hydrocar~on in ~5 the presence of an activated, vitreou~ly-rigidif~ed, metallic glass containing of ~i) titanium or zirconium and (ii) vanadium, ~aid metalllc ~lass bein~ activated by ~k ~IZ~29~77 being subjected to an oxidative treatment prior to the oxidation step or in situ during said oxidation.
Another aspect of the invention provides an oxidation catalyst for use in the oxidation of cyclic 5 hydrocarbons, compri.sing an aGtivated, vitreously-rigidified, metallic glass containing titanium or zirconium and vanadium.
This application is a divisional of our copending Application Serial No. 4~,421, filed ~uly 24, 1985, which describes and claims a process for catalytically synthesizing ammonia from nitrogen and hydrogen, which comprises using a vitreously-rigidified metallic glass consisting of (i) Fe and Zr or (ii) Fe, Zr and Mo, as the catalyst, as well as a process for the production of an activated, vitreously-rigidified metallic glass consisting of ~i) Fe and Zr or ~ii) Fe, Zr and Mo, which comprises: ~a) producing the metalliç glass from (i) Fe and Zr or ~il) Fe, Zr and Mo; and ~) without any preactlvation treatment, activating ~he metallic glass in situ using the ammonia-synthesis stream of hydrogen and nitrogen, thereby providing the activated, vitreously-rigidified metallic glass catalyst.
The metallic glasses change in such a way that the transformation products, the nature of which has not yet been exactly determined, show unexpected catalytic effectiveness. Possibly, amorphous and crystalline regions lie side by side in highly dispersed forms. It is further noteworthy that the composition of the surface in many cases is not the same as that of the catalyst body.
Starting out from amorphous alloys, cataly~ts according to the invention can be produced which are not obtainable according to hitherto known method~ for the production of catalysts or from the corresponding crystalline alloys.
The advantage of using amorpholls metals a~
starting materials for the production of çatalysts for use in the invention lies, among other thin~s, ln the fact that the metals in their am~rphou~ state are distri~uted lZ9Z977 in an extraordinarily highly-dispersed manner; they may be aggregations of only a few atoms. In the case of the processes used hitherto for the production of catalysts, .it i8 true that with regard to the degree of dispersion c3reat advance~ have been achieved. However, none of the industrially used processes leads to a similarly high degree of dispersion as that achieved for the catalysts u~ed in the invention.
The catalytically-active metallic glasses contain at least one element from a subgroup of the periodic system and at least one element from a main group of the periodic system. In the invention, the elements of Group VA are also counted as being in a main group.
The metallic glasses preferably contain an 16 element from Group IVA of the periodic system and at least one element of Group IB, Group VA or Group VIII of the periodic system. From group IV, ~he elements Ti and especially Zr are preferred, while from Group IB the element ~u, from Crollp VA, the element V ~vanadlum), and from ~roup VIII, the elements Co, Ni, Pd and especially Fe, are preferred.
The deslgnation of the groups of the psriodic system utilized herein is based on the table of "The Periodic System of the Elements" from "Roempps Chemical Dictionary," Vol. 4, 7th Ed., (1974), page 25.~7.
Examples of suitable metallic glasses may ~e chosen from those containing Zr and Fe, Ti and Fe, Zr and Cu, Ti and Cu, Zr and V, Ti and V, Zr and Ni, or Ti and Ni. Preferred examples are alloys with the formula Feg1Zr9, FeglTi9~ Fe24Zr76, Fe24Ti76~ Ni24Zr76~ Ni24Ti76~
cu70zr30, Cu70Ti30, V36Zr64~ V36Ti64~ Ni64Zr~6 and Ni64 Ti36 The so-called metallic ~lasses, amorphous metals, glassy metal~ or vitreou~ly-ri~idified metals are amorphous metal alloys with a non-arranged ~tr~çture which are not in thermodynamic equilibrium. Metallic gla~es are inclined to recrystallization whenever the reaotion temperature of the catalytic ~onver~ion lies a~ove the 1'~929~7 vitreous conversion temperature. A~ a result of component.s of the alloy, with up to 5 atom percent, for example, of molybdenum or tungsten, the glas~ conVersiQn temperature can be raised sufficiently so that a ~tabillzation of the actual catalyst is achieved without significantly influencin~ its activity. Stabilized metallic glasses consist, for example, of Zr or Ti, Fe and Mo, preferably with the formula (Fe~lTig)~5Mo5 or ~ FP9 1zr~)gsMo5 The catalytically-active, metallic glasses Gan be used as such as catalysts since they often activate themselves, partly with an enlargement of the surface.
Examples of such alloys have the formula FeglZr~ and FeglTig.
It can, however, also be effective for various metallic glAsses, for example Ni64Zr36 or Ni64Ti36, to conduct catalyst activation. Catalyst activation comprises processe~ such AS treatment with acid, effectively dllute ac~d, pre~er~ly aqueous HN03, :In ord~r to remove layer~ of oxide, ~hen ~ubsequent treatmçnt with oxygen and after that treatment with hydrogen.
Consequently, the activation consists of treatment in an oxidizing atmosphere and subsequently treatment in a reducing atmosphere. Corresponding to the intended purpose of use, the treatment can also be reversed.
The metallic glasses are also ~uitable as starting product.s for catalysts without carriers. For example, one of the phases can be converted by chemical conversion in such a way that it açts like a carrier in the conventional sense. As a possible di.sadvantage, there is a smaller specific surface which results from the various production processes.
The metallic gla~se.s can he produced in known manner, for example, by the melt spinning process, as flat or separated lamellae, and by the splat-cooling process, It turned out, however, that the ribbons obtained according to the melt-spinning process are also easily reduced to powder at low temperAture and so can 1;29Z977 also be u~ed in powdery form. Metallis glasses or amorphous metals, however, can also be produced directly a.s a powder. From ribbons or foils of metallic glass or amorphous metal, molded bodies, for example, filles of columns, can also be produced and then activated to a catalyst state, being used as such.
In a series of cases, for example, with Cu70Zr30 or Cu70Ti30, the catalysts from metallic glasses show activity already at temperatures lower than the corresponding catalysts based on crystalline starting material. It is important that the reaction temperature be sufficiently lower than the glass conversion temperature of the metallic glass.
The metallic glasses of the formula ~u70Zr30 can be ac~ivated in a hydrogen stream and then are suitable as hydration catalysts, for example, for the hydration of 1,3-butadiene. For this reaction, it is ~dvantageous to reduce the metallic glaffse~ wlth the formula Cu70Zr30 for ab~lAt 2 to 8 hou~ in a hydrogen stream at 160 to 240C.
Durin~ the hydration a ratio of butadiçne to hydrogen of 2:1 to 1:1 and a temperature of 90 to 200C, preferably 9.~ to 130C, i8 maintained.
The catalytically active metallic glasses are su~table for hydrogenation reactions, for example, the synthesis of ammonia from hydrogçn and nitrogen, or hydrocarbons from olefins or the hydrogenation from nitroaromatics, for the oxidation of cyclic hydrocarbons, such as ~oluene, and for the isomerization of hydrocarbons, for example, methylcyclopentane.
~y way of summary, the invention involves catalytically-active metallic glasses composed of at least one element from Group IVA of the periodic system, for example, Zr or Ti, and at lea~t one elçment from Group IB, for Example, Cu, or Group VA, for example, V, or Grol~p VIII, for example, Co, Ni, Pd or Fe. Thç mçtallic glassçs have been self-activated or activated by an oxidative and/or reductlve treatment. The metalllc ~lasse~ Gan bç
l~Z~7 used as catalysts, for example, for hydrogenation, oxidation or isomerization.
The following Examples illustrate the invention or are included for reference purposes. As used herein, all ratios, proportions, parts and percentages are on a weight basis unless otherwise stated herein or otherwise obvious to one skilled in the art.
Synthesis of ammonia from nitrogen and hydrogen 10For the conversion, a gas of 75 percent of hydrogen and 25 percent of nitrogen was used. The gas mixture was free of carbon monoxide. The pressure was 9 bar. In a microcontinuous reactor, 2 g of catalyst was inserted. The length of the catalyst bed was 20 mm, and 15the through-flow quantity was between 20 and 200 micromole sec ~quilibrium turnover nanomol~ sec~l Startina Material .380C. 400C. 420C. Remarks Conventional Halder- 250 450 ~00 after 2000 Top~oe catalyst hrs. not stable FeglZrg-crystalline 800 1400 2000 stable after 2000 hrs .
FeglZrg-crystalline 140 260 400 stable after 2000 hrs.
~Fegl Zr9 )gsMs glass 180 330 S00 stable Ni64Zr36 glass 190 340 600 A nickel-zircon catalyst produced in the conventional manner showed no effectiveness under these conditions. Under equilibrium turnover, the turnover is given per contact time standardized on the surface of the starting materials (equals average duratlon of stay of a gas molecule in the contact volume). The Halder-Top~oe l~Z9~77 catalyst i~ more ~ensitive vis-a-vi~ oxygen than the Feg1Zr9 glass.
Synthesis of ammonia 6 The conversion was carried out in an integral reactor made of stainless steel (40 cm long, 1.5 cm diameter) with purified gases. Analysis of the reaction products was done by means of an IR-gas analyzer. The pressure was 4 bar. The total through-flow of gas was 30 to 40 mlN.min 1 with a catalyst quantity of 8 to 10 g.
The ribbons of metalliç glass or amorphous metal were degreased and cut into piecçs of a length of 1 to 2 cm.
TABLE II
Conversion grade ~ =
~N~ 1 Starting Material Temp., C tNH3] (e q) Feg1Zr9, amorphou6 350 0.001704 Fe91Zr9, crystalline 350 0.001309 Fe, pur~ crystalline .330 0.000144 20 Fe91Zr9, amorphous 330 0.0050~9 Fe91Zr9, crystalline 380 0.004~01 Fe, pure crystalline 450 0.00835 Fe91Zrg, crystalline 450 0.0326~
Fe24Zr7fi, amorphous 450o 0.08170 25 Fe24Zr76, amorphous 380 0.002830 Note: Ratio N2:H2 = 1:2 That alternating effects exist between the metals in the actual effective catalyst is shown in the comparison of the conversion figures for the ammonium synthesis in the case of the system iron-zirconium.
Whereas pure iron does not result in an active çatalyst ~t 350C., Fe9Zr91 and Fe24Zr76 glasses form active catalysts. Whereas Fe91Zr9 i8 more active at 400C than 35 Fe24Zr76, Fe24Zr7fi surpasses the activity of Fe~1Zr~ at higher tem~eratures. Many highly active catalytic systems can be obtained by way of amorphous metals.
~XAMPL~ 3 lZ~Z977 Hydrogenation of ethylene The investigation was carried out in a circulatory reactor, and the products were analyzed by means of ga.s chromatography. The metallic glasses or amorphous metals were used as strips of about 1 cm length after they had been degreased. The reaction mixture consisted of ethylene and hydrogen. Amorphous Ni64Zr~6 was first treated with diluted nitric acid, then treated with oxygen and subsequently treated with hydrogen. After this pretreatment, the material showed catalytic activity.
Feg1Zrg glass showed no activity even after the pretreatment. Cu70Zr30 glass showed a clear enlargement of its surface and extraordinary catalytic activity by means of treatment with hydrogen.
TABLE III
CatalYst Reduction ActivitY
Cu70Zr30 200C very active amorphous H~, 4 hrs. even a~ ~0C
~0 CU70zr3 200C
cry~tal~ine H2, 4 hr~
H2, 8 hrs, ---Cu 200C.
H2, 4 hrs. ---With amorphous Cu70Zr30, after activation at 200C, a parallel quantitative conversion was measured in 24 minutes. In the same period of time, the conversion already was 40 percent at 80C. The difference between amorphous and crystalline starting material showed itself very clearly in the case of hydrogenation of ethylene by means of Cu70Zr30. Only the amorphous starting material resulted in an active catalyst.
Oxidation of toluene The conversion was carried out with a mlcropul~e reactor at 300C. The reactor was coated with 2 g of amorphous V36Zr64, which previou~ly had been tr~ated with diluted HN03. A stream of air was saturated with toluene and was pa~ed through the micropulse reactor. After 2 lZ~Z~77 hours, the catalyst had açtivated itself; per passage, 12.5 perçent of the toluene quantity used was oxidized into benzoic acid.
Under identical conditions, a V205 catalyst on 6 .Sio2 resulted in a conver~ion of 8.~ percent.
Hydrogenation of 1,3-butadiene The reactions were carried out in a batsh-circulation reactor and the products consisting of 1-butene, cis-2-butene, trans-2-butene and butane were analyzed by means of gas chromatography. Amorphous and crystalline samples of the composltion Cu70Zr30 were reduced at 200C for 4 hours in a stream of hydrogen.
This pretreatment caused an enlargement of the surface of 0.015 m2/g on 0.56 m2/~ with the amorphous sample, while the 6urface of the crystalline sample remained unchanged at O.OOB m2/g.
In order to be able to çompare the activity of the~e sample~, catalyst ~uantitie~ were ~elected 6uch that e~ually large curface~ were pre~en~ ln the reactor. TJnder identical conditisn~ (T = 130C., p = 0.8 bar, butadiene:H2 = 1:1), thece experiments clearly showed that amorphous Cu70Zr30 was much more active than the corresponding cry6talline sample.
TABLE IV
0.12 g of amorphous 8.0 ~ of crystalline t(min)conversion, ~ercent conversion, ~ercent 4.59 0.0 13.04 o,o ~o 16.76 0.0 130 23.00 o.g 130 2~.00 1.1 The selectlvlty a~ to butene wa~ more closely investigated with the amorphous sample. In the ca~e of 90 percent conversion, the selectivity w~s 75 percent at 130C and 96 percent at 95C.
lZ9Z977 EXAMPLE ~
';elective hydrogenation of butadiene Dienes, especially 1,3-butadiene, cause cleactivation of the catalyst in the case of hydroformylation and form polymers in cracking operations.
Therefore, they should be removed from olefins.
According to Example 5, 4 g of amorphous Cu70Zr30 was used as catalyst. The hydrogenation of the mixture with the composition: ~3 percent of 1-butene, 24 percent of cis-2-butene and 3 percent of 1~3-butadiene, was examined at various temperatures. At temperatures higher than 90C, olefins were hydrated and large quantities of ~utane developed. At 75C butadiene was hydrated selectively and the product distribution 15 consisted of~ 1.63 percent of butane, 1.35 percent of trans-2-butene, 22.6 percent of cis-2-butene, 74.41 percent of 1-butene and 0.0 percent of butadlene, after a reaction time of ~0 minutes. The hydro~en concentration at the ~ame time was 2 to 4 t~.me~ greater than the butadiene concentration. In thi~ area, the hydrogen concentration had no greater influence on the selectivity.
The selective hydrogenation of butadiene in the mixture of ethylene and butadiene also took place at lower temperatures. The reaction temperature of 7SC made possible the hydrogenation of butadiene with 93 percent selectivity on butene; ethylene was not hydrated at all.
Higher temperatures however also cause the hydrogenation of ethylene.
Gertain amorphous metal alloys catalyze 6 hydrogenation reactions, for ex~mple, those of cyGlohexene derivatives rG.V. Smith et al., J. of Catalysis 83 (1~83) 23~ or of carbon monoxide ti.e.~ Fisher-TrcpsGh ~eaction) [A. YokoYama et al., Chemistry Letters ~1988), 195]. The catalytic action is based on the amorphous state of the metals. However, it has also been described that, in the case of the system Pd80Si20, no significant differences exist concerning the selectivity in the case of hydrogenation reactions between the amorphous state and the crystalline state ~B. Giessen et al., Mater Res. Soc.
Symp. Proc., Vol. 1~ (1982), 255].
For the most part, the surfaces and the state of order of catalysts consisting of amorphou~ metals have not been investigated sufflclently, ~o that the ~ompari~on be~ween amorphou~ and cry~talline ~yB~em~ i8 not of any significant meaning. It turned out, for example, that the catalytical effectivene~s could n~t be deduce~ because of a lack of knowledge of the connections between amorphous and crystalline systems.
An object of the invention is to provide an improved process for the oxidation of cyclic hydrocarbons.
A further object of the invention i8 to provide catalytically-active metallic glasses for use in such process.
It is to be noted that the term "metallic glasses" as used herein is intended to have the same meaning as the term "amorphous metals".
Accordingly, one aspect of the invention provides a process for the oxidation of a cyclic hydrocarbon, which comprises oxidizing said hydrocar~on in ~5 the presence of an activated, vitreou~ly-rigidif~ed, metallic glass containing of ~i) titanium or zirconium and (ii) vanadium, ~aid metalllc ~lass bein~ activated by ~k ~IZ~29~77 being subjected to an oxidative treatment prior to the oxidation step or in situ during said oxidation.
Another aspect of the invention provides an oxidation catalyst for use in the oxidation of cyclic 5 hydrocarbons, compri.sing an aGtivated, vitreously-rigidified, metallic glass containing titanium or zirconium and vanadium.
This application is a divisional of our copending Application Serial No. 4~,421, filed ~uly 24, 1985, which describes and claims a process for catalytically synthesizing ammonia from nitrogen and hydrogen, which comprises using a vitreously-rigidified metallic glass consisting of (i) Fe and Zr or (ii) Fe, Zr and Mo, as the catalyst, as well as a process for the production of an activated, vitreously-rigidified metallic glass consisting of ~i) Fe and Zr or ~ii) Fe, Zr and Mo, which comprises: ~a) producing the metalliç glass from (i) Fe and Zr or ~il) Fe, Zr and Mo; and ~) without any preactlvation treatment, activating ~he metallic glass in situ using the ammonia-synthesis stream of hydrogen and nitrogen, thereby providing the activated, vitreously-rigidified metallic glass catalyst.
The metallic glasses change in such a way that the transformation products, the nature of which has not yet been exactly determined, show unexpected catalytic effectiveness. Possibly, amorphous and crystalline regions lie side by side in highly dispersed forms. It is further noteworthy that the composition of the surface in many cases is not the same as that of the catalyst body.
Starting out from amorphous alloys, cataly~ts according to the invention can be produced which are not obtainable according to hitherto known method~ for the production of catalysts or from the corresponding crystalline alloys.
The advantage of using amorpholls metals a~
starting materials for the production of çatalysts for use in the invention lies, among other thin~s, ln the fact that the metals in their am~rphou~ state are distri~uted lZ9Z977 in an extraordinarily highly-dispersed manner; they may be aggregations of only a few atoms. In the case of the processes used hitherto for the production of catalysts, .it i8 true that with regard to the degree of dispersion c3reat advance~ have been achieved. However, none of the industrially used processes leads to a similarly high degree of dispersion as that achieved for the catalysts u~ed in the invention.
The catalytically-active metallic glasses contain at least one element from a subgroup of the periodic system and at least one element from a main group of the periodic system. In the invention, the elements of Group VA are also counted as being in a main group.
The metallic glasses preferably contain an 16 element from Group IVA of the periodic system and at least one element of Group IB, Group VA or Group VIII of the periodic system. From group IV, ~he elements Ti and especially Zr are preferred, while from Group IB the element ~u, from Crollp VA, the element V ~vanadlum), and from ~roup VIII, the elements Co, Ni, Pd and especially Fe, are preferred.
The deslgnation of the groups of the psriodic system utilized herein is based on the table of "The Periodic System of the Elements" from "Roempps Chemical Dictionary," Vol. 4, 7th Ed., (1974), page 25.~7.
Examples of suitable metallic glasses may ~e chosen from those containing Zr and Fe, Ti and Fe, Zr and Cu, Ti and Cu, Zr and V, Ti and V, Zr and Ni, or Ti and Ni. Preferred examples are alloys with the formula Feg1Zr9, FeglTi9~ Fe24Zr76, Fe24Ti76~ Ni24Zr76~ Ni24Ti76~
cu70zr30, Cu70Ti30, V36Zr64~ V36Ti64~ Ni64Zr~6 and Ni64 Ti36 The so-called metallic ~lasses, amorphous metals, glassy metal~ or vitreou~ly-ri~idified metals are amorphous metal alloys with a non-arranged ~tr~çture which are not in thermodynamic equilibrium. Metallic gla~es are inclined to recrystallization whenever the reaotion temperature of the catalytic ~onver~ion lies a~ove the 1'~929~7 vitreous conversion temperature. A~ a result of component.s of the alloy, with up to 5 atom percent, for example, of molybdenum or tungsten, the glas~ conVersiQn temperature can be raised sufficiently so that a ~tabillzation of the actual catalyst is achieved without significantly influencin~ its activity. Stabilized metallic glasses consist, for example, of Zr or Ti, Fe and Mo, preferably with the formula (Fe~lTig)~5Mo5 or ~ FP9 1zr~)gsMo5 The catalytically-active, metallic glasses Gan be used as such as catalysts since they often activate themselves, partly with an enlargement of the surface.
Examples of such alloys have the formula FeglZr~ and FeglTig.
It can, however, also be effective for various metallic glAsses, for example Ni64Zr36 or Ni64Ti36, to conduct catalyst activation. Catalyst activation comprises processe~ such AS treatment with acid, effectively dllute ac~d, pre~er~ly aqueous HN03, :In ord~r to remove layer~ of oxide, ~hen ~ubsequent treatmçnt with oxygen and after that treatment with hydrogen.
Consequently, the activation consists of treatment in an oxidizing atmosphere and subsequently treatment in a reducing atmosphere. Corresponding to the intended purpose of use, the treatment can also be reversed.
The metallic glasses are also ~uitable as starting product.s for catalysts without carriers. For example, one of the phases can be converted by chemical conversion in such a way that it açts like a carrier in the conventional sense. As a possible di.sadvantage, there is a smaller specific surface which results from the various production processes.
The metallic gla~se.s can he produced in known manner, for example, by the melt spinning process, as flat or separated lamellae, and by the splat-cooling process, It turned out, however, that the ribbons obtained according to the melt-spinning process are also easily reduced to powder at low temperAture and so can 1;29Z977 also be u~ed in powdery form. Metallis glasses or amorphous metals, however, can also be produced directly a.s a powder. From ribbons or foils of metallic glass or amorphous metal, molded bodies, for example, filles of columns, can also be produced and then activated to a catalyst state, being used as such.
In a series of cases, for example, with Cu70Zr30 or Cu70Ti30, the catalysts from metallic glasses show activity already at temperatures lower than the corresponding catalysts based on crystalline starting material. It is important that the reaction temperature be sufficiently lower than the glass conversion temperature of the metallic glass.
The metallic glasses of the formula ~u70Zr30 can be ac~ivated in a hydrogen stream and then are suitable as hydration catalysts, for example, for the hydration of 1,3-butadiene. For this reaction, it is ~dvantageous to reduce the metallic glaffse~ wlth the formula Cu70Zr30 for ab~lAt 2 to 8 hou~ in a hydrogen stream at 160 to 240C.
Durin~ the hydration a ratio of butadiçne to hydrogen of 2:1 to 1:1 and a temperature of 90 to 200C, preferably 9.~ to 130C, i8 maintained.
The catalytically active metallic glasses are su~table for hydrogenation reactions, for example, the synthesis of ammonia from hydrogçn and nitrogen, or hydrocarbons from olefins or the hydrogenation from nitroaromatics, for the oxidation of cyclic hydrocarbons, such as ~oluene, and for the isomerization of hydrocarbons, for example, methylcyclopentane.
~y way of summary, the invention involves catalytically-active metallic glasses composed of at least one element from Group IVA of the periodic system, for example, Zr or Ti, and at lea~t one elçment from Group IB, for Example, Cu, or Group VA, for example, V, or Grol~p VIII, for example, Co, Ni, Pd or Fe. Thç mçtallic glassçs have been self-activated or activated by an oxidative and/or reductlve treatment. The metalllc ~lasse~ Gan bç
l~Z~7 used as catalysts, for example, for hydrogenation, oxidation or isomerization.
The following Examples illustrate the invention or are included for reference purposes. As used herein, all ratios, proportions, parts and percentages are on a weight basis unless otherwise stated herein or otherwise obvious to one skilled in the art.
Synthesis of ammonia from nitrogen and hydrogen 10For the conversion, a gas of 75 percent of hydrogen and 25 percent of nitrogen was used. The gas mixture was free of carbon monoxide. The pressure was 9 bar. In a microcontinuous reactor, 2 g of catalyst was inserted. The length of the catalyst bed was 20 mm, and 15the through-flow quantity was between 20 and 200 micromole sec ~quilibrium turnover nanomol~ sec~l Startina Material .380C. 400C. 420C. Remarks Conventional Halder- 250 450 ~00 after 2000 Top~oe catalyst hrs. not stable FeglZrg-crystalline 800 1400 2000 stable after 2000 hrs .
FeglZrg-crystalline 140 260 400 stable after 2000 hrs.
~Fegl Zr9 )gsMs glass 180 330 S00 stable Ni64Zr36 glass 190 340 600 A nickel-zircon catalyst produced in the conventional manner showed no effectiveness under these conditions. Under equilibrium turnover, the turnover is given per contact time standardized on the surface of the starting materials (equals average duratlon of stay of a gas molecule in the contact volume). The Halder-Top~oe l~Z9~77 catalyst i~ more ~ensitive vis-a-vi~ oxygen than the Feg1Zr9 glass.
Synthesis of ammonia 6 The conversion was carried out in an integral reactor made of stainless steel (40 cm long, 1.5 cm diameter) with purified gases. Analysis of the reaction products was done by means of an IR-gas analyzer. The pressure was 4 bar. The total through-flow of gas was 30 to 40 mlN.min 1 with a catalyst quantity of 8 to 10 g.
The ribbons of metalliç glass or amorphous metal were degreased and cut into piecçs of a length of 1 to 2 cm.
TABLE II
Conversion grade ~ =
~N~ 1 Starting Material Temp., C tNH3] (e q) Feg1Zr9, amorphou6 350 0.001704 Fe91Zr9, crystalline 350 0.001309 Fe, pur~ crystalline .330 0.000144 20 Fe91Zr9, amorphous 330 0.0050~9 Fe91Zr9, crystalline 380 0.004~01 Fe, pure crystalline 450 0.00835 Fe91Zrg, crystalline 450 0.0326~
Fe24Zr7fi, amorphous 450o 0.08170 25 Fe24Zr76, amorphous 380 0.002830 Note: Ratio N2:H2 = 1:2 That alternating effects exist between the metals in the actual effective catalyst is shown in the comparison of the conversion figures for the ammonium synthesis in the case of the system iron-zirconium.
Whereas pure iron does not result in an active çatalyst ~t 350C., Fe9Zr91 and Fe24Zr76 glasses form active catalysts. Whereas Fe91Zr9 i8 more active at 400C than 35 Fe24Zr76, Fe24Zr7fi surpasses the activity of Fe~1Zr~ at higher tem~eratures. Many highly active catalytic systems can be obtained by way of amorphous metals.
~XAMPL~ 3 lZ~Z977 Hydrogenation of ethylene The investigation was carried out in a circulatory reactor, and the products were analyzed by means of ga.s chromatography. The metallic glasses or amorphous metals were used as strips of about 1 cm length after they had been degreased. The reaction mixture consisted of ethylene and hydrogen. Amorphous Ni64Zr~6 was first treated with diluted nitric acid, then treated with oxygen and subsequently treated with hydrogen. After this pretreatment, the material showed catalytic activity.
Feg1Zrg glass showed no activity even after the pretreatment. Cu70Zr30 glass showed a clear enlargement of its surface and extraordinary catalytic activity by means of treatment with hydrogen.
TABLE III
CatalYst Reduction ActivitY
Cu70Zr30 200C very active amorphous H~, 4 hrs. even a~ ~0C
~0 CU70zr3 200C
cry~tal~ine H2, 4 hr~
H2, 8 hrs, ---Cu 200C.
H2, 4 hrs. ---With amorphous Cu70Zr30, after activation at 200C, a parallel quantitative conversion was measured in 24 minutes. In the same period of time, the conversion already was 40 percent at 80C. The difference between amorphous and crystalline starting material showed itself very clearly in the case of hydrogenation of ethylene by means of Cu70Zr30. Only the amorphous starting material resulted in an active catalyst.
Oxidation of toluene The conversion was carried out with a mlcropul~e reactor at 300C. The reactor was coated with 2 g of amorphous V36Zr64, which previou~ly had been tr~ated with diluted HN03. A stream of air was saturated with toluene and was pa~ed through the micropulse reactor. After 2 lZ~Z~77 hours, the catalyst had açtivated itself; per passage, 12.5 perçent of the toluene quantity used was oxidized into benzoic acid.
Under identical conditions, a V205 catalyst on 6 .Sio2 resulted in a conver~ion of 8.~ percent.
Hydrogenation of 1,3-butadiene The reactions were carried out in a batsh-circulation reactor and the products consisting of 1-butene, cis-2-butene, trans-2-butene and butane were analyzed by means of gas chromatography. Amorphous and crystalline samples of the composltion Cu70Zr30 were reduced at 200C for 4 hours in a stream of hydrogen.
This pretreatment caused an enlargement of the surface of 0.015 m2/g on 0.56 m2/~ with the amorphous sample, while the 6urface of the crystalline sample remained unchanged at O.OOB m2/g.
In order to be able to çompare the activity of the~e sample~, catalyst ~uantitie~ were ~elected 6uch that e~ually large curface~ were pre~en~ ln the reactor. TJnder identical conditisn~ (T = 130C., p = 0.8 bar, butadiene:H2 = 1:1), thece experiments clearly showed that amorphous Cu70Zr30 was much more active than the corresponding cry6talline sample.
TABLE IV
0.12 g of amorphous 8.0 ~ of crystalline t(min)conversion, ~ercent conversion, ~ercent 4.59 0.0 13.04 o,o ~o 16.76 0.0 130 23.00 o.g 130 2~.00 1.1 The selectlvlty a~ to butene wa~ more closely investigated with the amorphous sample. In the ca~e of 90 percent conversion, the selectivity w~s 75 percent at 130C and 96 percent at 95C.
lZ9Z977 EXAMPLE ~
';elective hydrogenation of butadiene Dienes, especially 1,3-butadiene, cause cleactivation of the catalyst in the case of hydroformylation and form polymers in cracking operations.
Therefore, they should be removed from olefins.
According to Example 5, 4 g of amorphous Cu70Zr30 was used as catalyst. The hydrogenation of the mixture with the composition: ~3 percent of 1-butene, 24 percent of cis-2-butene and 3 percent of 1~3-butadiene, was examined at various temperatures. At temperatures higher than 90C, olefins were hydrated and large quantities of ~utane developed. At 75C butadiene was hydrated selectively and the product distribution 15 consisted of~ 1.63 percent of butane, 1.35 percent of trans-2-butene, 22.6 percent of cis-2-butene, 74.41 percent of 1-butene and 0.0 percent of butadlene, after a reaction time of ~0 minutes. The hydro~en concentration at the ~ame time was 2 to 4 t~.me~ greater than the butadiene concentration. In thi~ area, the hydrogen concentration had no greater influence on the selectivity.
The selective hydrogenation of butadiene in the mixture of ethylene and butadiene also took place at lower temperatures. The reaction temperature of 7SC made possible the hydrogenation of butadiene with 93 percent selectivity on butene; ethylene was not hydrated at all.
Higher temperatures however also cause the hydrogenation of ethylene.
Claims
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the oxidation of a cyclic hydrocarbon, which comprises oxidizing said hydrocarbon in the presence of an activated, vitreously-rigidified, metallic glass containing of (i) titanium or zirconium and (ii) vanadium, said metallic glass being activated by being subjected to an oxidative treatment prior to the oxidation step or in situ during said oxidation.
2. A process as claimed in claim 1, wherein the metallic glass consists of V36Zr64 or V36Ti64 and is activated by treatment with an acid.
3. A process as claimed in claim 2, wherein the acid is HNO3.
4. A process according to claim 1, 2 or 3, wherein the hydrocarbon is toluene.
5, An oxidation catalyst for use in the oxidation of cyclic hydrocarbons, comprising an activated, vitreously-rigidified, metallic glass containing titanium or zirconium and vanadium .
6. A catalyst as claimed in claim 5, wherein the metallic glass consists of V36Zr64 or V36Ti64 and is activated by treatment with an acid.
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the oxidation of a cyclic hydrocarbon, which comprises oxidizing said hydrocarbon in the presence of an activated, vitreously-rigidified, metallic glass containing of (i) titanium or zirconium and (ii) vanadium, said metallic glass being activated by being subjected to an oxidative treatment prior to the oxidation step or in situ during said oxidation.
2. A process as claimed in claim 1, wherein the metallic glass consists of V36Zr64 or V36Ti64 and is activated by treatment with an acid.
3. A process as claimed in claim 2, wherein the acid is HNO3.
4. A process according to claim 1, 2 or 3, wherein the hydrocarbon is toluene.
5, An oxidation catalyst for use in the oxidation of cyclic hydrocarbons, comprising an activated, vitreously-rigidified, metallic glass containing titanium or zirconium and vanadium .
6. A catalyst as claimed in claim 5, wherein the metallic glass consists of V36Zr64 or V36Ti64 and is activated by treatment with an acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000601832A CA1292977C (en) | 1989-06-05 | 1989-06-05 | Oxidation of hydrocarbons with v-zr or v-ti catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000601832A CA1292977C (en) | 1989-06-05 | 1989-06-05 | Oxidation of hydrocarbons with v-zr or v-ti catalyst |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000487421A Division CA1262718A (en) | 1984-07-27 | 1985-07-24 | Process for the production of catalytically-active metallic glasses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1292977C true CA1292977C (en) | 1991-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000601832A Expired - Fee Related CA1292977C (en) | 1989-06-05 | 1989-06-05 | Oxidation of hydrocarbons with v-zr or v-ti catalyst |
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| Country | Link |
|---|---|
| CA (1) | CA1292977C (en) |
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1989
- 1989-06-05 CA CA000601832A patent/CA1292977C/en not_active Expired - Fee Related
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