Patent Application
20190358613
The present invention relates to a composition comprising a ternary intermetallic compound X2YZ supported on a support material, wherein X, Y, and Z are different from one another. Further, the present invention relates to a process for preparing said ternary intermetallic compound. Yet further, the present invention relates to the use of said ternary intermetallic compound.
Heusler phases are intermetallic compounds with X2YZ composition wherein X and Y are transition metals and Z is a third/fourth row main group element. Since their discovery, the main interest for said compounds mainly focused on ferromagnetic applications such as in spintronics, thermoelectrics, and giant magnetoresistance. In particular, their catalytic properties were barely touched such as in Hedin et al. which is a study on how changes in ferromagnetism may influence catalytic reactions such as the hydrogenation of carbon monoxide and ethylene over nickel and the oxidation of carbon monoxide to carbon dioxide over the Heusler alloy MnAlCu2. Kojima et al. disclose the catalytic properties of specific Heusler phases. Therefore, there remains a need for new ternary intermetallic compounds having the X2YZ composition which can be used in particular in various fields of catalysis. Accordingly, it was an object of the present invention to provide new ternary intermetallic compounds having the X2YZ composition which can be used in catalytic reactions.
Senanayake et al. “Exploring Heusler alloys as catalysts for ammonia dissociation”, August 2016, ISBN: 978-1-369-00770-1, discloses activation energy of ammonia cracking on the surfaces of various compositions of Heusler alloys, like NiMnGa and CoCrGe.
Okamura et al. “Structural, magnetic, and transport properties of full-Heusler alloy Co2(Cr1-x Fex)Al thin films” J. Appl. Phys. vol. 96, no. 11, 1 Dec. 2004, pages 6561-6564, discloses the structural, magnetic, and transport properties of full-Heusler alloy Co2(Cr1-xFex)Al thin films sputtered on thermally oxidized Si substrates at room temperature.
Kelekar et al. “Epitaxial growth of the Heusler alloy Co2Cra-xFexAl” J. Appl. Phys. Vol. 96, no 1, 1 Jul. 2004, pages 540-543, discloses a method for the growth of single-phase epitaxial thin films of compounds from the family of Heusler alloys Co2Cr1-xFexAl.
Ko et al. “Half-metallic Fe2CrSi and non-metallic Cu2CrAl Heusler alloys for currentperpendicular-to-plane giant magneto-resistance: First principle and experimental study” J. Appl. Phys. Vol 109, no. 7, 17 Mar. 2011, pages 7B1031-7B1033, discloses Fe—Cr—Si and CuCr—Al films on Cr-buffered MgO substrates.
Therefore, the present invention relates to a composition comprising a ternary intermetallic compound X2YZ, wherein
X, Y, and Z are different from one another;
X being selected from the group consisting of Mn, Fe, Co, Ni, Cu, and Pd;
Y being selected from the group consisting of Cr, Co, and Ni; and
Z being selected from the group consisting of Al, Si, Ga, Ge, In, Sn, Zn, and Sb; wherein the ternary intermetallic compound is supported on a porous oxidic support material.
The term “X2YZ” as used in the present invention refers to compositions having a composition XaYbZc wherein a is in the range of from 1.9 to 2.1 such as in the range of from 1.90 to 2.05 or from 1.95 to 2.10 or from 1.95 to 2.05; wherein b is in the range of from 0.9 to 1.1 such as in the range of from 0.90 to 1.05 or from 0.95 to 1.10 or from 0.95 to 1.05; and wherein c is in the range of from 0.9 to 1.1 such as in the range of from 0.90 to 1.05 or from 0.95 to 1.10 or from 0.95 to 1.05.
Generally, any conceivable porous oxidic support material can be used. Preferably, the porous oxidic support material comprises one or more of silica, alumina, titania, zirconia, a mixed oxide of one or more Si, Al, Ti, and Zr, and a mixture of two or more thereof. Preferably, at least 99 weight-%, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the porous oxidic support material consist of one or more of silica, alumina, titania, zirconia, a mixed oxide of one or more Si, Al, Ti, and Zr, and a mixture of two or more thereof.
According to a preferred embodiment of the present invention, the intermetallic compound comprises Co. Therefore, preferably either X or Y is Co. While generally all respective combinations of X, Y, and Z are conceivable, it is preferred that if X is Co, Y is Cr and, if Y is Co X is Cu. In particular for these combinations of X and Y, it is preferred that Z is selected from the group consisting of Al, Ga, In, and Zn.
Therefore, the ternary intermetallic compound is preferably selected from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoIn, Cu2CoZn, and Cu2CoGa. More preferably, the ternary intermetallic compound is selected from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoZn, and Cu2CoGa.
With regard to said Co-based intermetallic compounds, the porous oxidic support material preferably comprises Si. More preferably, the porous oxidic support material comprises silica or a mixed oxide of Si and Al. More preferably, the porous oxidic support material comprises a mixed oxide of Si and Al. Preferably at least 99 weight-%, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the porous oxidic support material consist of the mixed oxide of Si and Al.
Generally, every porous mixed oxide of Si and Al can be employed. Preferably, porous mixed oxide of Si and Al is a zeolitic material. Zeolites are microporous, aluminosilicate minerals, occur naturally and are also produced industrially, in some instances on a large scale. Zeolites are the aluminosilicate members of the family of microporous solids known as “molecular sieves” mainly consisting of Si, Al, O. A microporous material is a material containing pores with diameters less than 2 nm. Preferably, the zeolitic material has a framework type which is ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVL, AWO, AWW, BCT, BEA, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEl, EMT, EON, EPI, ERI, ESV, ETL, ETR, EUO, *-EWT, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, *-ITN, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, *MRE, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POS, PSI, PUN, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, *SFV, SFW, SGT, SIV, SOD, SOF, SOS, SSF, *-SSO, SSY, STF, STI, *STO, STT, STW, -SVR, SVV, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YUG, ZON, a mixture of two or more of these framework types, or a mixed framework type thereof. Such three letter code abbreviations and the respective explanations can be found, for example, under “www.iza-structure.org”, in section “Framework Type”, or in “Atlas of Zeolite Framework Types, 6th revised edition, Elsevier, 2007”, accessible online via “http://www.iza-structure.org/databases/books/Atlas_6ed.pdf”. More preferably, the zeolitic material comprises framework type MFI. More preferably, the zeolitic material has framework type MFI. More preferably, the zeolitic material comprises a zeolite ZSM-5. More preferably, the zeolitic material is a zeolite ZSM-5.
Therefore, the present invention preferably relates to a composition comprising a ternary intermetallic compound X2YZ, wherein the ternary intermetallic compound is selected from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoIn, Cu2CoZn, and Cu2CoGa, preferably from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoZn, and Cu2CoGa, wherein the ternary intermetallic compound is supported on a zeolitic material preferably having framework type MFI, more preferably being a zeolite ZSM-5.
The loading of the porous oxidic support materials with the Co-based ternary intermetallic compound X2YZ is not subject to any specific restrictions. Preferably, in the composition of the present invention, the weight ratio of the ternary intermetallic compound relative to the porous oxidic compound is in the range of from 0.5:99.5 to 30:70, preferably in the range of from 1:99 to 20:80, more preferably in the range of from 2:99 to 10:90, more preferably in the range of from 3:97 to 7:93. Preferably, the present invention relates to a composition wherein the ternary intermetallic compound is selected from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoIn, Cu2CoZn, and Cu2CoGa, preferably from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoZn, and Cu2CoGa, wherein in the composition, the weight ratio of the ternary intermetallic compound relative to the porous oxidic compound is in the range of from 3:97 to 7:93, preferably in the range of from 4:96 to 6:94. More preferably, the present invention relates to a composition wherein the ternary intermetallic compound is selected from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoIn, Cu2CoZn, and Cu2CoGa, preferably from the group consisting of Co2CrAl, Co2CrIn, Co2CrZn, Co2CrGa, Cu2CoAl, Cu2CoZn, and Cu2CoGa, wherein in the composition, the weight ratio of the ternary intermetallic compound relative to the porous oxidic compound is in the range of from 3:97 to 7:93, preferably in the range of from 4:96 to 6:94, wherein the ternary intermetallic compound is supported on a zeolitic material preferably having framework type MFI, more preferably being a zeolite ZSM-5.
According to a preferred embodiment of the present invention, Y is Ni. In this regard, it is preferred that X is Cu. Therefore, preferred compositions of the present comprise Cu as X and Ni as Y. Further in this regard, it is preferred that Z is Al, Si, Ga, In, Sn, or Sb. More preferably, Z is Sn. Therefore, preferred compositions of the present comprise Al, Si, Ga, In, Sn, or Sb as Z, more preferably Sn as Z, and Ni as Y. More preferably, the composition of the present invention comprises a ternary intermetallic compound which is Cu2NiSn.
With regard to said Ni-based intermetallic compounds, the porous oxidic support material preferably comprises Si. More preferably, the porous oxidic support material comprises silica or a mixed oxide of Si and Al. With regard to preferred mixed oxides of Si and Al and in particular preferred zeolitic materials, reference is made to the disclosure above. More preferably, the porous oxidic support material comprises silica. Preferably at least 99 weight-%, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the porous oxidic support material consist of silica.
The loading of the porous oxidic support materials with the Ni-based ternary intermetallic compound X2YZ is not subject to any specific restrictions. Preferably, in the composition of the present invention, the weight ratio of the ternary intermetallic compound relative to the porous oxidic support is in the range of from 1:99.5 to 70:30, preferably in the range of from 5:99 to 60:40, more preferably in the range of from 10:90 to 50:50, more preferably in the range of from 10:90 to 45:55, more preferably in the range of from 10:90 to 40:60.
Preferably, the present invention relates to a composition wherein the ternary intermetallic compound is Cu2NiSn, wherein in the composition, the weight ratio of the ternary intermetallic compound relative to the porous oxidic compound is in the range of from 20:80 to 40:60, preferably in the range of from 25:75 to 35:65, preferably in the range of from 28:72 to 32:68. More preferably, the present invention relates to a composition wherein the ternary intermetallic compound is Cu2NiAl, wherein in the composition, the weight ratio of the ternary intermetallic compound relative to the porous oxidic compound is in the range of from 20:80 to 40:60, preferably in the range of from 25:75 to 35:65, preferably in the range of from 28:72 to 32:68, wherein the ternary intermetallic compound is supported on a porous oxidic support material which comprises, preferably is silica.
Within the meaning of the present invention, the terms “D10”, “D50”, and “D90” respectively refer to the particle size by number of the particles, formed by the ternary intermetallic compound of the present invention, wherein D10 refers to the particle size wherein 10% of the particles, formed by the ternary intermetallic compound, by number lie below said value, D50 refers to the particle size wherein 50% of the particles, formed by the ternary intermetallic compound, by number lie below said value, and D90 accordingly refers to the particle size wherein 90% of the particles, formed by the ternary intermetallic compound, by number lie below said particle size.
The mean particle size “D50” as well as the particle sizes “D90” and “D10” as used herein may readily be measured by known methods, wherein preferably they are determined by Transmission Electron Microscopy (TEM), preferably wherein the samples for TEM, preferably a powder, are prepared on ultra-thin carbon TEM carriers, preferably by dispersing the powder in ethanol, preferably by applying one drop of the dispersion between two glass objective slides which is then dispersed, preferably wherein the TEM carrier film is then subsequently dipped on the resulting thin film, wherein more preferably the TEM images are recorded on a Tecnai Osiris machine operated at 200 keV under bright-field as well as high-angle annular dark-field scanning TEM (HAADF-STEM) conditions. Preferably Chemical composition maps are acquired by energy-dispersive x-ray spectroscopy (EDXS), wherein more preferably images and elemental maps are evaluated using the iTEM as well as the Esprit software packages. Preferably, the particle size distributions are evaluated using the ParticleSizer plugin for FIJI. According to the present invention it is more preferred that the mean particle size D50 as well as the particle sizes D90 and D10 as used herein are determined according to the method described herein under the examples, more preferably as described in reference example 1.1.
Preferably, the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size, determined via TEM as described in Reference Example 1.1 herein, in the range of from 0.1 nm to 2 micrometer, preferably of from 0.5 nm to 2 micrometer, more preferably of from 1 nm to 2 micrometer, and more preferably of from 2 nm to 2 micrometer, wherein at least 10 weight-%, preferably from 10 to 30 weight-% of the composition consist of these particles.
Preferably, the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D10 in the range of from 0.5 to 10 nm, preferably from 1 to 9 nm, more preferably from 2 to 8 nm, more preferably from 3 to 7 nm, and more preferably from 4 to 6 nm.
Preferably, the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D50 in the range of from 1 to 13 nm, preferably from 2 to 12 nm, more preferably from 3 to 11 nm, more preferably from 4 to 10 nm, more preferably from 5 to 9 nm, and more preferably from 6 to 8 nm.
Preferably, the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D90 in the range of from 7 to 19 nm, preferably from 8 to 18 nm, more preferably from 9 to 17 nm, more preferably from 10 to 16 nm, more preferably from 11 to 15 nm, and more preferably from 12 to 14 nm.
Preferably, the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D10 in the range of from 2 to 8 nm, preferably from 3 to 7 nm, and more preferably from 4 to 6 nm;
wherein the particle size D50 is in the range of from 4 to 10 nm, preferably from 5 to 9 nm, and more preferably from 6 to 8 nm; and
wherein the particle size D90 in the range of from 10 to 16 nm, preferably from 11 to 15 nm, and more preferably from 12 to 14 nm.
It is alternatively preferred that the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D10 in the range of from 35 to 59, preferably from 37 to 57 nm, more preferably from 39 to 55 nm, more preferably from 41 to 53 nm, more preferably from 43 to 51 nm, and more preferably from 45 to 49 nm.
It is alternatively preferred that the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D50 in the range of from 55 to 79 nm, preferably from 57 to 77 nm, more preferably from 59 to 75 nm, more preferably from 61 to 73 nm, more preferably from 63 to 71 nm, and more preferably from 65 to 69 nm.
It is alternatively preferred that the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D90 in the range of from 108 to 152 nm, preferably from 112 to 148 nm, more preferably from 116 to 144 nm, more preferably from 120 to 140 nm, more preferably from 124 to 136 nm, and more preferably from 128 to 132 nm.
It is alternatively preferred that the Ni-based composition of the invention comprises particles, formed by the ternary intermetallic compound, having a particle size D10 in the range of from 41 to 53 nm, preferably from 43 to 51 nm, and more preferably from 45 to 49 nm;
wherein the particle size D50 is in the range of from 61 to 73 nm, preferably from 63 to 71 nm, and more preferably from 65 to 69 nm; and
wherein the particle size D90 in the range of from 120 to 140 nm, preferably from 124 to 136 nm, and more preferably from 128 to 132 nm.
Preferably, in the Ni-based composition of the invention, the crystallite size, determined via XRD using the Scherer equation as described in Reference Example 1.2 herein, is in the range of from 8 to 30 nm. Preferably, the Ni-based composition of the invention has a BET specific surface area, determined as described in Reference Example 1.3 herein, in the range of from 150 to 400 m2/g.
Generally, the composition of the present invention may comprise, in addition to the ternary intermetallic compound and the porous oxidic support material, one or more further compounds.
Preferably, the composition of the present invention essentially consists of the ternary intermetallic compound and the porous oxidic support material. Therefore, preferably at least 99 weight %, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the composition consist of the ternary intermetallic compound and the porous oxidic support material.
Among others, it is preferred that the intermetallic compound of the composition of the present invention is a Heusler phase.
Preferably, the intermetallic compound is supported on the porous oxidic material in the form of particles.
Generally, the composition of the present invention can be prepared by any suitable process.
Preferably, it is prepared by a process comprising
Preferably, the source of X is selected from the group consisting of salts of X. Said salts of X are preferably selected from the group consisting of acetates, acetylacetonates, nitrates, nitrites, sulfates, hydrogensulfates, dihydrogensulfates, sulfites, hydrogensulfites, phosphates, hydrogenphosphates, dihydrogenphosphates, halides, cyanides, cyanates, isocyanates, and mixtures of two or more thereof. More preferably, said salts are selected from the group consisting of acetates, acetylacetonates, nitrates, chlorides, bromides, fluorides, and mixtures of two or more thereof. More preferably, said salts are selected from the group consisting of acetates, acetylacetonates, nitrates and chlorides.
Preferably, the source of Y is selected from the group consisting of salts of Y. Said salts of Y are preferably selected from the group consisting of acetates, acetylacetonates, nitrates, nitrites, sulfates, hydrogensulfates, dihydrogensulfates, sulfites, hydrogensulfites, phosphates, hydrogenphosphates, dihydrogenphosphates, halides, cyanides, cyanates, isocyanates, and mixtures of two or more thereof. More preferably, said salts are selected from the group consisting of acetates, acetylacetonates, nitrates, chlorides, bromides, fluorides, and mixtures of two or more thereof. More preferably, said salts are selected from the group consisting of acetates, acetylacetonates, and nitrates.
Preferably, the source of Z is selected from the group consisting of salts of Z. Said salts of Z are preferably selected from the group consisting of C1-C4 alkoxides, acetates, nitrates, nitrites, sulfates, hydrogensulfates, dihydrogensulfates, sulfites, hydrogensulfites, phosphates, hydrogenphosphates, dihydrogenphosphates, halides, cyanides, cyanates, isocyanates, and mixtures of two or more thereof. More preferably, said salts are selected from the group consisting of C2-C3 alkoxides, acetates, nitrates, chlorides, bromides, fluorides, and mixtures of two or more thereof. More preferably, said salts are selected from the group consisting of ethoxides, acetates, nitrates, and chlorides.
Therefore, it is preferred that the source of X is an acetate, an acetylacetonate, a nitrate or a chloride of X, the source of Y is an acetate, an acetylacetonates, or a nitrate of Y, and the source of Z is an ethoxide, an acetates, a nitrates or a chloride of Z.
Preferably, the source of the porous oxidic support material comprises one or more of silica, alumina, titania, zirconia, a mixed oxide of one or more Si, Al, Ti, and Zr, and a mixture of two or more thereof. Preferably at least 99 weight-%, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the porous oxidic support material consist of one or more of silica, alumina, titania, zirconia, a mixed oxide of one or more Si, Al, Ti, and Zr, and a mixture of two or more thereof.
According to a preferred embodiment of the present invention according to which the ternary intermetallic compound is a Co-based compound, the source of the porous oxidic support material comprises silica or a mixed oxide of Si and Al, preferably a mixed oxide of Si and Al. More preferably, at least 99 weight-%, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the porous oxidic support material consist of the mixed oxide of Si and Al.
Generally, every porous mixed oxide of Si and Al can be employed as source of the porous oxidic support material. Preferably, porous mixed oxide of Si and Al is a zeolitic material. Zeolites are microporous, aluminosilicate minerals, occur naturally and are also produced industrially, in some instances on a large scale. Zeolites are the aluminosilicate members of the family of microporous solids known as “molecular sieves” mainly consisting of Si, Al, O. A microporous material is a material containing pores with diameters less than 2 nm. Preferably, the zeolitic material has a framework type which is ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVL, AWO, AWW, BCT, BEA, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEl, EMT, EON, EPI, ERI, ESV, ETL, ETR, EUO, *-EWT, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, *-ITN, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, *MRE, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POS, PSI, PUN, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, *SFV, SFW, SGT, SIV, SOD, SOF, SOS, SSF, *-SSO, SSY, STF, STI, *STO, STT, STW, -SVR, SVV, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YUG, ZON, a mixture of two or more of these framework types, or a mixed framework type thereof. Such three letter code abbreviations and the respective explanations can be found, for example, under “www.izastructure.org”, in section “Framework Type”, or in “Atlas of Zeolite Framework Types, 6th revised edition, Elsevier, 2007”, accessible online via “http://www.izastructure.org/databases/books/Atlas_6ed.pdf”. More preferably, the zeolitic material comprises framework type MFI. More preferably, the zeolitic material has framework type MFI. More preferably, the zeolitic material comprises a zeolite ZSM-5. More preferably, the zeolitic material is a zeolite ZSM-5.
Therefore, the present preferably relates to the process described above, wherein the source of X is an acetate, an acetylacetonate, a nitrate or a chloride of X, the source of Y is an acetate, an acetylacetonates, or a nitrate of Y, and the source of Z is an ethoxide, an acetates, a nitrates or a chloride of Z, and the source of the porous oxidic compound is a zeolitic material preferably having framework type MFI, more preferably being a zeolite ZSM-5.
According to a preferred embodiment of the present invention according to which the ternary intermetallic compound is a Ni-based compound, it is preferred that the source of the porous oxidic compound comprises silica or a mixed oxide of Si and Al, preferably silica. More preferably, at least 99 weight-%, more preferably at least 99.5 weight-%, more preferably at least 99.9 weight-% of the porous oxidic support material consist of silica.
Generally, any suitable silica can be employed, including both colloidal silica and so-called “wet process” silica and so-called “dry process” silica can be used. More preferably, the silica is amorphous silica. Colloidal silica, preferably as an alkaline and/or ammoniacal solution, more preferably as an ammoniacal solution, is commercially available, inter alia, for example as Ludox®, Syton®, Nalco® or Snowtex®. “Wet process” silica is commercially available, inter alia, for example as Hi-Sil®, Ultrasil®, Vulcasil®, Santocel®, Valron-Estersil®, Tokusil® or Nipsil®. “Dry process” silica is commercially available, inter alia, for example as Aerosil®, Reolosil®, Cab-O-Sil®, Fransil® or ArcSilica®. Inter alia, an ammoniacal solution of colloidal silica can be used according to the present invention. More preferably, the silica comprises, preferably is fumed silica. Preferably, the silica has a BET specific surface area, determined as described in Reference Example 1.3, in the range of from 300 to 500 m2/g, more preferably in the range of from 350 to 450 m2/g. Preferably, the silica has a total pore volume, determined as described in Reference Example 1.3, in the range of from 0.4 to 0.5 ml/g, more preferably in the range of from 0.42 to 0.48 ml/g. Preferably, the silica has an average pore size, determined as described in Reference Example 1.3, in the range of from 4 to 5 nm, more preferably in the range of from 4.2 to 4.8 nm.
Preferably, step (i) of the process of the present invention comprises
As solvent according to (i.1), it is preferred to employ a polar solvent, more preferably one or more polar protic solvents. More preferably, the one or more solvents are selected from the group consisting of water, C1 alcohols, C2 alcohols, C3 alcohols, C4 alcohols, and mixtures of two or more thereof, more preferably selected from the group consisting of water, C1 alcohols, C2 alcohols, C3 alcohols, and mixtures of two or more thereof. More preferably, the solvent is one or more of water, methanol and ethanol, wherein more preferably, the solvent according to (i.) comprises, preferably is, methanol.
According to (i.2), it is preferred to prepare a liquid mixture comprising a solvent and the source of the porous oxidic support material and admixing the liquid mixture with the mixture prepared in (i.1). As solvent according to (i.2), it is preferred to employ a polar solvent, more preferably one or more polar protic solvents. More preferably, the one or more solvents are selected from the group consisting of water, C alcohols, C2 alcohols, C3 alcohols, C4 alcohols, and mixtures of two or more thereof, more preferably selected from the group consisting of water, C1 alcohols, C2 alcohols, C3 alcohols, and mixtures of two or more thereof. More preferably, the solvent is one or more of water, methanol and ethanol, wherein more preferably, the solvent according to (i.2) comprises, preferably is, methanol. Preferably, the solvent according to (i.2) is the solvent according to (i.1).
According to (ii), the liquid phase is removed from the mixture. Generally, this can be accomplished by every suitable method or combination of methods. According to the present invention, it is preferred to remove the liquid phase either by suitably heating the mixture, or by suitably subjecting the mixture to evaporation, or by suitably heating the mixture and by suitably subjecting the mixture to evaporation. If heating and evaporation are carried out, it is possible to subject the mixture to evaporation and subsequently subject to respectively obtained mixture to heating. Further, it is possible to subject the mixture to heating and subsequently subject to respectively obtained mixture to evaporation. Yet further, it is possible that evaporation and heating are carried out at least partially simultaneously.
Therefore, it is preferred that removing the liquid phase from the mixture according to (ii) comprises heating the mixture prepared in (i), preferably heating to a temperature of the mixture in the range of from 70 to 150° C., preferably in the range of from 80 to 140° C., more preferably from 90 to 130° C., more preferably from 100 to 120° C. Further, it is preferred that the mixture prepared in (i) is subjected to evaporation, preferably at a pressure in the range of from 2 to 500 mbar(abs), more preferably in the range of from 5 to 200 mbar(abs), more preferably in the range of from 10 to 100 mbar(abs). It is more preferred that according to (ii) and prior to heating, the mixture prepared in (i) is subjected to evaporation, preferably at a pressure in the range of from 2 to 500 mbar(abs), more preferably in the range of from 5 to 200 mbar(abs), more preferably in the range of from 10 to 100 mbar(abs). During evaporation, it is preferred to adjust the temperature of the mixture to a value in the range of from 20 to 60° C., preferably in the range of from 30 to 50° C.
With regard to the reducing according to (iii), it is preferred that the reducing atmosphere according to (iii) comprises hydrogen) preferably comprises hydrogen and an inert gas, such as argon or nitrogen, preferably nitrogen. Preferably in the reducing atmosphere, the volume ratio of hydrogen relative to the inert gas, preferably nitrogen, is in the range of from 30:70 to 70:30, preferably in the range of from 40:60 to 60:40.
According to (iii), it is preferred to heat the mixture to a temperature of the reducing atmosphere in the range of from 400 to 1,100° C., preferably in the range of from 500 to 1,000° C. More preferably, according to (iii), the mixture is heated to a temperature of the reducing atmosphere in the range of from 800 to 1,000° C., more preferably in the range of from 850 to 1000° C.
Generally, the mixture can be heated to said temperature using any suitable temperature ramp or heating rates. Preferably, according to (iii), the mixture is heated at a temperature ramp in the range of from 0.1 to 15 K/min, preferably in the range of from 0.3 to 12 K/min. According to a first embodiment, the mixture is heated at a temperature ramp preferably in the range of from 0.4 to 7 K/min, more preferably in the range of from 0.5 to 5 K/min. According to a second embodiment, the mixture is heated at a temperature ramp preferably in the range of from 8 to 12 K/min, preferably in the range of from 9 to 11 K/min. During heating, the temperature ramp can be varied; for example, the mixture can be heated at a first temperature ramp to a first temperature, heated at a second temperature ramp to a second temperature, optionally heated at a third temperature ramp to a third temperature, wherein at least one of the first, second and third temperature ramp is different from at least of the other temperature ramps. Further, it is possible that, once the first or the second temperature is reached, the mixture is kept at this temperature for a certain period of time. Once the desired maximum temperature as described above is reached, it is preferred to keep the mixture at the temperature for a period of time in the range of from 0.5 to 20 h, preferably in the range of from 1 to 15 h, more preferably in the range of from 2 to 10 h.
After said heat treatment, it is preferred to cool the heat-treated mixture, preferably to a temperature in the range of from 10 to 50° C., more preferably in the range of from 20 to 30° C. Therefore, the process of the present invention preferably further comprises
Yet further, the present invention relates to the composition as described above, which is obtainable or obtained or preparable or prepared by a process as described above, preferably comprising steps (i) to (iiii), more preferably steps (i) to (iv).
Still further, the present invention relates to the use of the composition of the present invention as a catalytically active material, preferably for an oxidation reaction, a hydrogenation reaction, a dehydrogenation reaction, and/or a condensation reaction. Also, the present invention relates to a method for catalytically converting an organic compound, comprising bringing the organic compound in contact with a catalyst which comprises the composition of the present invention as a catalytically active material, wherein the converting of the organic compound comprises an oxidation reaction, a hydrogenation reaction, a dehydrogenation reaction, and/or a condensation reaction. Preferably, the hydrogenation reaction comprises the hydrogenation of an aldehyde, preferably cinnamaldehyde. Preferably, the dehydrogenation reaction comprises the dehydrogenation of an alkane, preferably propane. Preferably, the oxidation reaction comprises the oxidation of an alkane, preferably a cyclic alkane, more preferably cyclohexane. Preferably, the condensation reaction comprises the condensation of a carbonyl compound with a methylene group containing compound, wherein the condensation reaction is preferably a Knoevenagel condensation reaction.
Generally, the composition of the present invention may be used as such as a catalyst. Further, it is possible that in addition to the composition of the invention, the catalyst may comprise one or more further catalytically active materials and/or one or more inert materials including, but not restricted to, one or more matrix materials, for example one or more binder materials.
The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as “The catalyst of any one of embodiments 1 to 4”, every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to “The catalyst of any one of embodiments 1, 2, 3, and 4”.
The present invention is further illustrated by the following examples, comparative examples, and reference examples.
Samples for Transmission Electron Microscopy (TEM) were prepared on ultra-thin carbon TEM carriers. The powder was therefore dispersed in ethanol. One drop of the dispersion was applied between two glass objective slides and gently dispersed. The TEM carrier film was subsequently dipped on the resulting thin film. The samples were imaged by TEM using a Tecnai Osiris machine (FEI Company, Hillsboro, USA) operated at 200 keV under bright-field as well as high-angle annular dark-field scanning TEM (HAADF-STEM) conditions. Chemical composition maps were acquired by energy-dispersive x-ray spectroscopy (EDXS). Images and elemental maps were evaluated using the iTEM (Olympus, Tokyo, Japan, version: 5.2.3554) as well as the Esprit (Bruker, Billerica, USA, version 1.9) software packages. Particle size distributions were evaluated using the ParticleSizer plugin for FIJI.
The X-ray powder diffraction (XRD) measurements were carried out with a D 5005 type diffractometer of Siemens/Bruker AXS using a Cu Kalpha Source (lambda=0.15405 nm). The source was operated at 35 kV and 25 mA and the data were collected in a 2theta range from 3 to 110° with a step size of 0.1° (2theta). The crystallite sizes were determined by the Scherer equation using peaks at 79° 2theta. A Gaussian fit was used to determine the full width at half maximum (FWHM).
The BET specific surface area was determined according to DIN 66131 via nitrogen adsorption/desorption at a temperature of 77 K. The total pore volume was determined via mercury intrusion porosimetry according to DIN 66133. The average pore size was determined via mercury intrusion porosimetry according to DIN 66133.
1.4.1 Metal Sources
The following materials were employed for preparing the intermetallic compounds (see Table 1 below):
1.4.2 Porous Oxidic Materials
According to Example 1, the following ternary intermetallic compounds supported on a porous oxidic support were prepared (see Table 2 below). In Example 1.1, the typical process is disclosed.
Co(NO3)2.6H2O (1.57 g, 5.39 mmol), Cr(NO3)3.9H2O (1.08 g, 2.69 mmol) and Al(NO3)3.9H2O (1.01 g, 2.69 mmol) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 minutes. ZSM-5 (2.15 g) and 100 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40° C. The residue was dried at 110° C. for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 minutes at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at 900° C. The maximum temperature was achieved by heating rate of 10 K/min−1 and kept constant for 8 h. Finally, the samples were cooled to room temperature. The crystal structure of the prepared ternary intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co2CrAl/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1.
The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co2CrGa/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co2CrIn/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co2CrZn/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Cu2CoAl/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 wt.-% Cu2CoGa/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 wt.-% Cu2CoIn/ZSM-5 for the range 2theta=3-100° is shown in
The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Cu2CoZn/ZSM-5 for the range 2theta=3-100° is shown in
All combinations prepared by the procedure as described in Example 2.1.1 below were prepared with a total metal content of 30 weight-% and a metal stoichiometry of X:Y:Z=2:1:1.
Cu(NO3)2.2.5H2O (1.96 g, 8.44 mmol), Ni(NO3)2.6H2O (1.23 g, 4.22 mmol) and SnCl2.2H2O (0.95 g, 4.22 mmol) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 min. Fumed silica (3.00 g, 7 nm) and 10 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40° C. The residue was dried at 110° C. for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 min at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at 880° C. The detailed temperature program for the reducing method is given in Table 3 below. Finally, the samples were cooled to room temperature.
The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiAl/SiO2 for the angle range 2theta=15-100° is shown in
The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiGa/SiO2 for the angle range 2theta=15-100° is shown in
The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiIn/SiO2 for the angle range 2theta=15-100° is shown in
The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSbISiO2 for the angle range 2theta=15-100° is shown in
The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern of 30 weight-% Cu2NiSi/SiO2 for the range 2theta=15-100° is shown in
The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern of 30 weight-% Cu2NiSn/SiO2 for the range 2theta=15-100° is shown in
All combinations prepared by the procedure as described in Example 2.2 were prepared with a total metal content of 30 weight-% and a metal stoichiometry of X:Y:Z=2:1:1 and varying reduction temperatures.
Cu(NO3)2.2.5H2O (1.96 g, 8.44 mmol) Ni(NO3)2.6H2O (1.23 g, 4.22 mmol) and SnCl2.2H2O (0.95 g, 4.22 mmol) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 min. Fumed silica (3.00 g, 7 nm) and 10 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40° C. The residue was dried at room temperature for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 min at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at the respective temperature indicated in the Examples 2.2.1 to 2.2.6. The maximum temperature was achieved using a heating rate of 10 K/min and kept constant for 3 h. Finally, the samples were cooled to room temperature.
The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
All combinations prepared by the procedure as described in Example 2.3 were prepared with a metal stoichiometry of X:Y:Z=2:1:1 and varying metal content, as shown in Table 4 below:
The compositions were prepared as follows: Cu(NO3)2.2.5H2O (respective amount according to Table 4) Ni(NO3)2.6H2O (respective amount according to Table 4) and SnCl2.2H2O (respective amount according to Table 4) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 min. Fumed silica (3.00 g, 7 nm) and 10 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40° C. The residue was dried at room temperature for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 min at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at 800° C. The maximum temperature was achieved at a heating rate of 10 K/min and kept constant for 3 h. Finally, the samples were cooled to room temperature. The L21 structure cannot be undoubtedly verified for metal content below 10 wt.-%. The signal broadening is assumed to be resulting from decreasing the crystallite sizes. In
The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The particle size distribution of the Heusler compound, determined according to reference example 1.1, afforded a D10 value of about 47 nm, a D50 value of about 68 nm, and a D90 value of about 129 nm (see
The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 20 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 15 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 10 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The particle size distribution of the Heusler compound, determined according to reference example 1.1, afforded a D10 value of about 5 nm, a D50 value of about 7 nm, and a D90 value of about 13 nm (see
The crystal structure of the intermetallic compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 5 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the intermetallic compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 2 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The crystal structure of the intermetallic compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 1 weight-% Cu2NiSn/SiO2 for the angle range 2theta=15-100° is shown in
The catalytic activities of the intermetallic compounds supported on ZSM-5 prepared according to Examples 1.1 to 1.4 (Co2CrAl/ZSM-5, Co2CrGa/ZSM-5, Co2CrIn/ZSM-5, Co2CrZn/ZSM-5) and Examples 1.5 to 1.8 (Cu2CoAl/ZSM-5, Cu2CoGa/ZSM-5, Cu2CoIn/ZSM-5, Cu2CoZn/ZSM-5) were tested in the oxidation of cyclohexane with molecular oxygen.
The oxidation of cyclohexane was carried out in a stainless steel autoclave with Teflon inlay, which was filled with 25 ml cyclohexane, 50 ml acetone as solvent and 250 mg of the supported intermetallic compound. Then the autoclave was pressurized with 2 MPa of synthetic air (20.5% O2 in N2) and heated up. After the reaction temperature of 150° C. was reached the reaction was carried out under stirring for 6 h. Product samples were analyzed in a gas chromatograph (HP 6890 Series) with integrated mass selective detector (HP 5973). For this purpose, 10 microL of the samples were mixed with 2 microL toluene (external standard) and diluted in 1000 microL acetone. The conditions for the gas chromatographic analysis of the products from the cyclohexane oxidation were chosen as follows:
sample volume: 4 microL
injector temperature: 200° C.
heating rate: start at 35° C., 10 min isothermal, heating rate 30 K/min to 200° C.
eluent: He
flow rate: 139.3 ml/min
column head pressure: 1.2 bar (abs)
split ratio: 50:1
column: CP-SIL 5 CB, 100% dimethylpolysiloxane
detector: MS
As products, cyclohexanone (CHO) and cyclohexanol (CHOL) were identified.
The yields of cyclohexanone and cyclohexanole obtained when using the intermetallic compounds of Examples 1.1 to 1.4 (Co2CrAl/ZSM-5, Co2CrGa/ZSM-5, Co2CrIn/ZSM-5, Co2CrZn/ZSM-5) are shown in
The yields of cyclohexanone and cyclohexanole obtained when using the intermetallic compounds of Examples 1.5 to 1.8 (Cu2CoAl/ZSM-5, Cu2CoGa/ZSM-5, Cu2CoIn/ZSM-5, Cu2CoZn/ZSM-5) are shown in
An overview of the results of the cyclohexane oxidation is shown in
The catalytic activities of the synthesized supported intermetallic compounds were tested in the cinnamaldehyde hydrogenation reaction. In particular, the compounds of Examples 2.1.6 (30 weight-% Cu2NiSn/SiO2), Example 2.3.1 (30 weight-% Cu2NiSn/SiO2) and Example 2.3.4 (10 weight-% Cu2NiSn/SiO2) were tested.
A batch autoclave with magnetic stirring was supplied with 150 ml cyclohexane, 5 ml cinnamaldehyde, 1 ml tetradecane as internal standard and 0.5 g of the respective supported intermetallic compound. The autoclave was sealed and afterwards flushed 3 with 7 bar of nitrogen. After 3 times flushing with 20 bar(abs) hydrogen, the reactor was heated up to 150° C. By reaching 150° C., hydrogen was used to set the pressure to 50 bar(abs), which was defined as the start time of the reaction. At regular time intervals, the reaction mixture was analyzed by gas chromatography. The conditions for the gas chromatographic analysis of the products from the hydrogenation of cinnamaldehyde were chosen as follows:
stationary phase: CP-SIL 5 CB
length: 25 m
inner diameter: 250 micrometer
film thickness: 0.25 micrometer
oven temperature: start: 120° C. 1 min
inlet temperature: 220° C.
split ratio: 30:1
total flow rate: 32.6 ml/min
eluent: N2
velocity: 30 cm/s
detector: flame ionization detector
makeup flow: 45 ml/min
hydrogen flow: 40 ml/min
air flow: 450 ml/min
In
In
In
The catalytic activities of the synthesized supported intermetallic compound of Example 2.1.6 (30 weight-% Cu2NiSn/SiO2) was tested in the dehydrogenation of propane. The time-on-stream experiment was carried out in a fixed-bed flow-type reactor at 650° C. The catalyst particle size was set to 255-355 micrometer by grounding and sieving. 250 mg of catalyst were tested in a mixture of flowing propane (3 ml/min) and nitrogen (27 ml/min) at atmospheric pressure. At regular time intervals, the product mixture was analyzed by gas chromatography. The conditions for the gas chromatographic analysis of the products from the dehydrogenation of propane were chosen as follows:
stationary phase: HP-Plot
length: 50 m
inner diameter: 530 micrometer
film thickness: 0.15 micrometer
oven temperature: 120° C.
inlet temperature: 200° C.
split ratio: 10:1
total flow rate: 81.6 ml/min
eluent: N2
velocity: 56 cm/s
detector: flame ionization detector
makeup flow: 45 ml/min
hydrogen flow: 40 ml/min
air flow: 450 ml/min
It was found that after a reaction time of 21 h, the tested supported intermetallic compound shows a conversion of 42%, a selectivity with respect to propene of 40%, a selectivity with respect to ethene of 37.5%, a selectivity with respect to ethane of 2%, and a selectivity with respect to methane of 20.5%
The catalytic activities of the synthesized supported intermetallic compound of Examples 2.1.1 to 2.1.6 (30 weight-% Cu2NiZ/SiO2) were tested in the Knoevenagel condensation reaction.
Malononitrile (0.52 g, 8 mmol), benzaldehyde (0.84 g, 8 mmol), 20 ml toluene as a solvent and 0.2 g of 1,4-dichlorbenzene as internal standard were mixed in a 50 ml two-necked flask equipped with a reflux condenser. The mixture was heated in an oil bath and 0.4 g of the respective supported intermetallic compound were added when the maximum temperature of 80° C. was reached. At regular time intervals, the reaction mixture was analyzed by gas chromatography. The conditions for the gas chromatographic analysis of the products from the hydrogenation of cinnamaldehyde were chosen as follows:
stationary phase: CP-SIL 5 CB
length: 25 m
inner diameter: 250 micrometer
film thickness: 0.25 micrometer
oven temperature: start: 55° C. 1 min
inlet temperature: 245° C.
split ratio: 50:1
total flow rate: 53.3 ml/min
eluent: He
velocity: 40 cm/s
detector: mass selective (MS) detector
In
| Number | Date | Country | Kind |
|---|---|---|---|
| 17160332.7 | Mar 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/055900 | 3/9/2018 | WO | 00 |
