CA1224199A - Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene - Google Patents
Process for preparing inorganic metal oxygen composition capable of dehydrocoupling tolueneInfo
- Publication number
- CA1224199A CA1224199A CA000444985A CA444985A CA1224199A CA 1224199 A CA1224199 A CA 1224199A CA 000444985 A CA000444985 A CA 000444985A CA 444985 A CA444985 A CA 444985A CA 1224199 A CA1224199 A CA 1224199A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- metal
- oxygen
- organic alcohol
- toluene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for preparing a metal oxygen composition capable of dehydrocoupling toluene wherein metal oxides such as Sb2O3, PbO, and Bi2O3 are admixed with an organic media such as isobutanol and heated to form a metal oxygen precursor composition which is recovered and calcined is disclosed.
A process for preparing a metal oxygen composition capable of dehydrocoupling toluene wherein metal oxides such as Sb2O3, PbO, and Bi2O3 are admixed with an organic media such as isobutanol and heated to form a metal oxygen precursor composition which is recovered and calcined is disclosed.
Description
~4~9 BACKGROUND OF T~E INVENTION
2 The present invention is directed to a process
3 for preparing a metal~oxygen composition which composition
4 is capable of dehydrocoupling toluene to stilbene.
Styrene is currently commercially produced from 6 benzene in a two-step process. In the first step benzene 7 is alkylated with ethylene to for~ ethylbenzene, and in 8 the second step, the ethylbenzene is dehydrogenated to g form styrene.
One of the known alternative routes for forming 11 styrene in~olves the oxidati~e coupling of toluene to form 12 1, 2-diphenyl e~hylene ~stilbene) followed by the dispro-13 portionation of the stilbene with ethylene in ~he presence 14 Of a catalyst to ~orm styrene. The economic significance o the overall procesg scheme o the toluene-stilbene route 16 is that styrene can be produced from 0.5 mole of ethylene 17 and one mole of toluene. This compar~s with the con~en-18 tional ethylbenzene route wherein styrene is produced from one 19 mole of ethylene and one mole of benzene. In light o~ the rising costs of benzene and ethylene and the environmental 21 problems of benæene, the toluene-based process will become 22 a more attractive route than the existing ben2ene-based 23 process ~or styrene manuf-acture.
24 In addition to its utility as an intermediate in production of styrene, stilbene, because of its unsaturated 26 character, iS very reactive and may be employed in various 27 organic synthesss. Derivatives of stilbene are useful in 28 the production of chemicals which may be used in the manu-2gi facture of dyes, paints, and resins. It is also use~ul in optical bri~hteners, in pharmaceutic~ls and as an organic 31 intermediate~
32 Thus, there is substantial economic incantive to develop an economical process for producing stilbene.
34 The oxidative coupling o toluene to 1, 2-diphenyl etbane (i.e., bibenzyl) and sti}bene has bee~ known for 36 many years.
;
., ~
.:. . ..
. ., :.- ' . ~
~24~
1 The ideal reaction to stilbene from toluene is 2 the direct dehydrocoupling reaction summarized as follows:
6 H3+0,-~ ~ CH=CH ~ +~2 (eq.l) toluene stilbene Such a selective reaction in practice is difficult to 9 achieve. More often, the overall reaction involves the dehydrocoupling of toluene to stilbene as well as bibenzyl~
11 Bibenzyl however can be dehydrogenated to stilbene. Thus, 12 a commercial process for producing stilbene could include 13 an overall reaction scheme summarized as follows:
16 4 ~ C~3 ........ ~ ~ 82-CH ~
~:: 17 ~ Bibenzyl (eq.2) - ~ S ilben 2i 22 although the greater selectivity of the reaction to stil-23 bene, the more ef~icient the process.
24 The reaction of Equation 1, employing oxygen as the oxidant in the ab5:ence of a catalyst, is extremely 26 inefficient because of the preponderance of non-selective 27 free-radical reactions~le:ading to complete combustion of.
28 the h.ydrocarbons and the formation of oxygenated by-products.
29 Consequently, attempts:have been made to improve the selec-tivity of the reaction:using oxidants, such as metal or 31 non-metal oxides as stoichiometric reactants~providing 32 lattice oxygen which is depleted during the reaction.
33 Such metal oxides can also function as catalysts for a ~ 34 prima.ry oxidant such as oxyg:en. Becau5e of the oxyge:n :`~ 35 depletion.of metal oxide stoichiometric oxidantsi their .
~z~9 1 use requires that they be either very inexpensive and 2 therefore disposable, or they must be capable of being 3 regenerated by replacing the lattice oxygen l~st during 4 the reaction. Since many o~ the conventional stoichio-metric metal oxide oxidants are expensive, their use re-6 quires extensive plant equipment and engineering design to 7 provide proper regeneration. This has led to two alter-8 native approaches; namely, fixed bed and fluidized bed 9 sy~tems. In the fixed bed system, two or three reactors 1~ with staggered cycles typically are employed to achieve 11 continuous operation. This system is very costly in terms 12 of plant equipment. In the fluidized system a single 13 reactor can be ~mployed and a portion of the metal-oxide 14 can be constantly removed, regeneratedl and returned to the reactor. Fluidi~ed systems, however, lead to attrition 16 of the metal oxide and in many instances the metal of the 17 metal oxide can be lost as fines which coat the walls of 18 the reactors.
19 Another difficulty with stoichiometric oxidants and/or catalysts is t~lat those producing relatively good 21 selectivity usually result in a slow reaction rate. In 22 addition the oxygen-carrying capacity is usually very low 23 leading to a short active life.
24 Representative examples of conventional metal oxide oxidants and/or catalysts are disclosed in U.S.
26 Patent Nos. 3,694,518; 3,739,038; 3,868,427; 3,965,206;
27 3,980,580; 4,091jO44; 4,183,828; 4,243,825; 4,247,~27;
~8 4,254,293; 4,255,60`2; 4,255,603; 4,255,604; 4,268,703;
29 4,268,704; 4,278,824; 4,278,825; and 4/278,826. These patents disclose various metal/oxide compositions which can 31 be p~epared by a variety of methods. For example, the sim-32 plest me*hod involves intimately mixing the powdered metal 33 oxides in the dry state and calcining. Another method i~-34 volves adding the metal oxides to water with stirring, fil-tering to remove excess water or, alternatively, heating to 36 evaporate the water, drying, and calcining. In ¬her 37 method of pre~aration, the powdered metal ~xides ca-n be '``' ~2~
1 intimately mixed before fonming a paste with water and fur-2 ther mixing the paste. The paste can be dried in air, after 3 which it can be calcined in air. The calcined product can 4 then be crushed and sieved to the desired mesh size. In still another method o~ preparation, the powdered metal ox-6 ides can be mixed in the dry state together. A further 7 method of preparation involves intLmately mixing the pow-8 dered metal oxides in water and spray drying the resulting 9 sLurry or solution to produce relatively dust-free a~d free-flowing ~pherical particles which are also calcined prior 11 to use. In an alternative method of preparation, suitable in-12 organic metal/oxygen composition precursor salts such as 13 nitrates, carbonates,and acetates are intimately mixed or 14 dissolved in water or nitric acid and heated to thenmally decompose the precursor salts to form the corresponding ox 16 ides and/or oxygen complexe The oxides and/or oxygen com-17 plexes can then be treated as described hereinabove prior 18~ to use.
1~ - Thus, a majority of these preparative methods employ water and are referred to herein as aqueous pre-21 parations. None of these patents disclose th~ use of 22 organic liquids to prepare the metal oxide compositions.
23 ?he metal oxide compositions disclosed in these 24 patents prepared by an aqueous method exibit an extremely short active life. For example, Example 6 in U.S. Patent 26 No. 4,091,044 illustrates the use of a Sb/Pb/Bi oxide 27 oxidant prepared by the aqueous method. When run for 1 28 minute at 580C (run 3, Table 6) the conversion is 47.3~
2;9 and a selectivity for cis and trans stilbene plus bibenzyl is 81.2~. However, after 7 minutes reaction time (run 6, 31 Table 6) the conversion drops to 9.7~ at a corresponding 32 selectivity of 87.5~. The substantial drop in conversion 3~3 over a period of S minutes indicates that the oxidant is 34 quic~ly dea¢tivated and implies that it is not an efficient oxygen carrier. It is for this reason that the oxidant 36 is typicalIy regenerated for 30 to 60 minutes after each 37 one-minute run (iee Exam~le 1, lines 34 et. s;eq.). Thus, ,~
~4~
l not only is the oxidant quickly deactivated but its regen-2 eration time is also ~uite long.
3 It is known that vanadium phosphorus oxygen catalysts for the oxidat~on o~ hydrocarbons, e.g. butane, to form, for example, maleic anhydride, can be prepared 6 using an organic medium, such as isobutanol, as illustrated 7 by U.S. Patent Nos. 3,864,280; 4,132,670 and commonly 8 assigned U.S. Patent ~o. 4,392,986. However these 9 catalyst~ are not employed for the conversion of toluene to stilbene.
11 The search has there~ore continued for metal 12 oxide compositions for use in conjunction with the conver-13 sion o toluene by oxidative dehydrocoupling to stilbene 14 which possess the characteristics of (1) high activity and 15 selectivity ~o minimize toluene recycle and loss to unde-16 sired by-products, (2) high oxygen-carrying capacity, (3) `~ 17 high reoxidation or regeneration rate to minimize the 18 amount of composition employed, ~4) high a~trition resis-19 tance under`c~n~itions o~ repeated oxidation a~d reduction, 20 a~ (g~) h~i~h; reaction r~te. The present invention was de-2~ veloped in.~e~spo,n~e to thi~. se&rch.
'.~
., .
. ~' ' ~ ' ~ ,' .
4~
2 In one aspect of the present invention there is 3 provided a process for preparing a precursor metal oxygen 4 composition capable of dehydrocoupling toluene when calcined which comprises:
6 (i) reacting a mixture of metal oxides in the 7 presence of at least one organic media comprising 8 at least one member selected from the group g consisting of organic: alcohol~ aldehyde, ketone, ether, amine, amide and thiol, to form a metal 11 oxygen precursor composition the metals of said 12 ~etal oxide mixture having (a) at least one 13 member selected from the group consisting of Tl, 14 . Bi, Pb, Co, and Th and (b) at least one member lS selected from the group consisting of Li, Na, K, 16 Rb, Cs, Fr, Be, Mg, Ca, Sr, ~a, Ra, In, Tl, Ge, 17 P, As, Sb, Ag, Au, ~u, Zn, Cd, Hg, Sc, Y, La, 1.8 Ac, Ti, Zr, ~f, ~b, Ta, Mn, Tc, Re, Fe, Ru, Os, 19 Rh, Ir, Ni, Pd, ~t, Ce, Pr, Nd, Pm, Sm, Eu, Gd, . Tb, Py, Er, Tm, Yb, ~u, and U;
21 ~ii) se~parating the precursor composition from 22 the organic media-23 In another aspect of the present invention there 24 is provided a psocess for preparing a metal oxygen compo-sition capable of dehydrocoupling toluene which comprises 26 ca}cining the above described precursor metal oxygen compo-27 sition.
28 In a further aspect of the present invention there 29 is provided a process for dehydrocoupling toluene and/or toluene derivatives using the metal oxygen composition pre-pared by the aQredescribed process.
32 }n still another aspect of:the present invention 33 there is provi~ed a metal oxy$en composition prepared by :4 the afore:de~scribe.~ p~r~ee$s..
.
~ ~ .
.
s ~.. , ~ `' .
-2 A majority of the metals employed to prepare the 3 metal oxide composition capable of dehydrocoupling toluene 4 to stilbene are conventional in the ~rt. More specifically,
Styrene is currently commercially produced from 6 benzene in a two-step process. In the first step benzene 7 is alkylated with ethylene to for~ ethylbenzene, and in 8 the second step, the ethylbenzene is dehydrogenated to g form styrene.
One of the known alternative routes for forming 11 styrene in~olves the oxidati~e coupling of toluene to form 12 1, 2-diphenyl e~hylene ~stilbene) followed by the dispro-13 portionation of the stilbene with ethylene in ~he presence 14 Of a catalyst to ~orm styrene. The economic significance o the overall procesg scheme o the toluene-stilbene route 16 is that styrene can be produced from 0.5 mole of ethylene 17 and one mole of toluene. This compar~s with the con~en-18 tional ethylbenzene route wherein styrene is produced from one 19 mole of ethylene and one mole of benzene. In light o~ the rising costs of benzene and ethylene and the environmental 21 problems of benæene, the toluene-based process will become 22 a more attractive route than the existing ben2ene-based 23 process ~or styrene manuf-acture.
24 In addition to its utility as an intermediate in production of styrene, stilbene, because of its unsaturated 26 character, iS very reactive and may be employed in various 27 organic synthesss. Derivatives of stilbene are useful in 28 the production of chemicals which may be used in the manu-2gi facture of dyes, paints, and resins. It is also use~ul in optical bri~hteners, in pharmaceutic~ls and as an organic 31 intermediate~
32 Thus, there is substantial economic incantive to develop an economical process for producing stilbene.
34 The oxidative coupling o toluene to 1, 2-diphenyl etbane (i.e., bibenzyl) and sti}bene has bee~ known for 36 many years.
;
., ~
.:. . ..
. ., :.- ' . ~
~24~
1 The ideal reaction to stilbene from toluene is 2 the direct dehydrocoupling reaction summarized as follows:
6 H3+0,-~ ~ CH=CH ~ +~2 (eq.l) toluene stilbene Such a selective reaction in practice is difficult to 9 achieve. More often, the overall reaction involves the dehydrocoupling of toluene to stilbene as well as bibenzyl~
11 Bibenzyl however can be dehydrogenated to stilbene. Thus, 12 a commercial process for producing stilbene could include 13 an overall reaction scheme summarized as follows:
16 4 ~ C~3 ........ ~ ~ 82-CH ~
~:: 17 ~ Bibenzyl (eq.2) - ~ S ilben 2i 22 although the greater selectivity of the reaction to stil-23 bene, the more ef~icient the process.
24 The reaction of Equation 1, employing oxygen as the oxidant in the ab5:ence of a catalyst, is extremely 26 inefficient because of the preponderance of non-selective 27 free-radical reactions~le:ading to complete combustion of.
28 the h.ydrocarbons and the formation of oxygenated by-products.
29 Consequently, attempts:have been made to improve the selec-tivity of the reaction:using oxidants, such as metal or 31 non-metal oxides as stoichiometric reactants~providing 32 lattice oxygen which is depleted during the reaction.
33 Such metal oxides can also function as catalysts for a ~ 34 prima.ry oxidant such as oxyg:en. Becau5e of the oxyge:n :`~ 35 depletion.of metal oxide stoichiometric oxidantsi their .
~z~9 1 use requires that they be either very inexpensive and 2 therefore disposable, or they must be capable of being 3 regenerated by replacing the lattice oxygen l~st during 4 the reaction. Since many o~ the conventional stoichio-metric metal oxide oxidants are expensive, their use re-6 quires extensive plant equipment and engineering design to 7 provide proper regeneration. This has led to two alter-8 native approaches; namely, fixed bed and fluidized bed 9 sy~tems. In the fixed bed system, two or three reactors 1~ with staggered cycles typically are employed to achieve 11 continuous operation. This system is very costly in terms 12 of plant equipment. In the fluidized system a single 13 reactor can be ~mployed and a portion of the metal-oxide 14 can be constantly removed, regeneratedl and returned to the reactor. Fluidi~ed systems, however, lead to attrition 16 of the metal oxide and in many instances the metal of the 17 metal oxide can be lost as fines which coat the walls of 18 the reactors.
19 Another difficulty with stoichiometric oxidants and/or catalysts is t~lat those producing relatively good 21 selectivity usually result in a slow reaction rate. In 22 addition the oxygen-carrying capacity is usually very low 23 leading to a short active life.
24 Representative examples of conventional metal oxide oxidants and/or catalysts are disclosed in U.S.
26 Patent Nos. 3,694,518; 3,739,038; 3,868,427; 3,965,206;
27 3,980,580; 4,091jO44; 4,183,828; 4,243,825; 4,247,~27;
~8 4,254,293; 4,255,60`2; 4,255,603; 4,255,604; 4,268,703;
29 4,268,704; 4,278,824; 4,278,825; and 4/278,826. These patents disclose various metal/oxide compositions which can 31 be p~epared by a variety of methods. For example, the sim-32 plest me*hod involves intimately mixing the powdered metal 33 oxides in the dry state and calcining. Another method i~-34 volves adding the metal oxides to water with stirring, fil-tering to remove excess water or, alternatively, heating to 36 evaporate the water, drying, and calcining. In ¬her 37 method of pre~aration, the powdered metal ~xides ca-n be '``' ~2~
1 intimately mixed before fonming a paste with water and fur-2 ther mixing the paste. The paste can be dried in air, after 3 which it can be calcined in air. The calcined product can 4 then be crushed and sieved to the desired mesh size. In still another method o~ preparation, the powdered metal ox-6 ides can be mixed in the dry state together. A further 7 method of preparation involves intLmately mixing the pow-8 dered metal oxides in water and spray drying the resulting 9 sLurry or solution to produce relatively dust-free a~d free-flowing ~pherical particles which are also calcined prior 11 to use. In an alternative method of preparation, suitable in-12 organic metal/oxygen composition precursor salts such as 13 nitrates, carbonates,and acetates are intimately mixed or 14 dissolved in water or nitric acid and heated to thenmally decompose the precursor salts to form the corresponding ox 16 ides and/or oxygen complexe The oxides and/or oxygen com-17 plexes can then be treated as described hereinabove prior 18~ to use.
1~ - Thus, a majority of these preparative methods employ water and are referred to herein as aqueous pre-21 parations. None of these patents disclose th~ use of 22 organic liquids to prepare the metal oxide compositions.
23 ?he metal oxide compositions disclosed in these 24 patents prepared by an aqueous method exibit an extremely short active life. For example, Example 6 in U.S. Patent 26 No. 4,091,044 illustrates the use of a Sb/Pb/Bi oxide 27 oxidant prepared by the aqueous method. When run for 1 28 minute at 580C (run 3, Table 6) the conversion is 47.3~
2;9 and a selectivity for cis and trans stilbene plus bibenzyl is 81.2~. However, after 7 minutes reaction time (run 6, 31 Table 6) the conversion drops to 9.7~ at a corresponding 32 selectivity of 87.5~. The substantial drop in conversion 3~3 over a period of S minutes indicates that the oxidant is 34 quic~ly dea¢tivated and implies that it is not an efficient oxygen carrier. It is for this reason that the oxidant 36 is typicalIy regenerated for 30 to 60 minutes after each 37 one-minute run (iee Exam~le 1, lines 34 et. s;eq.). Thus, ,~
~4~
l not only is the oxidant quickly deactivated but its regen-2 eration time is also ~uite long.
3 It is known that vanadium phosphorus oxygen catalysts for the oxidat~on o~ hydrocarbons, e.g. butane, to form, for example, maleic anhydride, can be prepared 6 using an organic medium, such as isobutanol, as illustrated 7 by U.S. Patent Nos. 3,864,280; 4,132,670 and commonly 8 assigned U.S. Patent ~o. 4,392,986. However these 9 catalyst~ are not employed for the conversion of toluene to stilbene.
11 The search has there~ore continued for metal 12 oxide compositions for use in conjunction with the conver-13 sion o toluene by oxidative dehydrocoupling to stilbene 14 which possess the characteristics of (1) high activity and 15 selectivity ~o minimize toluene recycle and loss to unde-16 sired by-products, (2) high oxygen-carrying capacity, (3) `~ 17 high reoxidation or regeneration rate to minimize the 18 amount of composition employed, ~4) high a~trition resis-19 tance under`c~n~itions o~ repeated oxidation a~d reduction, 20 a~ (g~) h~i~h; reaction r~te. The present invention was de-2~ veloped in.~e~spo,n~e to thi~. se&rch.
'.~
., .
. ~' ' ~ ' ~ ,' .
4~
2 In one aspect of the present invention there is 3 provided a process for preparing a precursor metal oxygen 4 composition capable of dehydrocoupling toluene when calcined which comprises:
6 (i) reacting a mixture of metal oxides in the 7 presence of at least one organic media comprising 8 at least one member selected from the group g consisting of organic: alcohol~ aldehyde, ketone, ether, amine, amide and thiol, to form a metal 11 oxygen precursor composition the metals of said 12 ~etal oxide mixture having (a) at least one 13 member selected from the group consisting of Tl, 14 . Bi, Pb, Co, and Th and (b) at least one member lS selected from the group consisting of Li, Na, K, 16 Rb, Cs, Fr, Be, Mg, Ca, Sr, ~a, Ra, In, Tl, Ge, 17 P, As, Sb, Ag, Au, ~u, Zn, Cd, Hg, Sc, Y, La, 1.8 Ac, Ti, Zr, ~f, ~b, Ta, Mn, Tc, Re, Fe, Ru, Os, 19 Rh, Ir, Ni, Pd, ~t, Ce, Pr, Nd, Pm, Sm, Eu, Gd, . Tb, Py, Er, Tm, Yb, ~u, and U;
21 ~ii) se~parating the precursor composition from 22 the organic media-23 In another aspect of the present invention there 24 is provided a psocess for preparing a metal oxygen compo-sition capable of dehydrocoupling toluene which comprises 26 ca}cining the above described precursor metal oxygen compo-27 sition.
28 In a further aspect of the present invention there 29 is provided a process for dehydrocoupling toluene and/or toluene derivatives using the metal oxygen composition pre-pared by the aQredescribed process.
32 }n still another aspect of:the present invention 33 there is provi~ed a metal oxy$en composition prepared by :4 the afore:de~scribe.~ p~r~ee$s..
.
~ ~ .
.
s ~.. , ~ `' .
-2 A majority of the metals employed to prepare the 3 metal oxide composition capable of dehydrocoupling toluene 4 to stilbene are conventional in the ~rt. More specifically,
5 the inorganic metal oxide composition prepared in accor-
6 dance with the present invention comprises a material which
7 can be represented by the empirical formula:
9 Aa~bx (I) 12 wherein ~ is at least one metal selected from the group 13 consisting of Tl, Bi, Pb, Co, and Th; and B at least one 14 ~etal selected from the group consisting of Li, Na, K, Rb, Cs, and Fr of Group lA (of the periodic chart) Be, Mg, Ca, 16 Sr, Ba, and Ra of Group 2a; In, and Tl of Group 3a; Ge of 17 Group 4a; P, As~ and Sb, o~ Group SA; Ag~ Au, and Cu, of 18 Group Ib; Zn, Cd, and ~ of Group 2b; Sc, Y, La, and Ac of 19 Group 3b; Ti, Zr~ and Hf of Group 4b; Nb and Ta of Group Sb; Mn, Tc, and Re of Group 7b; Fe, Ru, Os, Rh, Ir, ~i, Pd, 21 and Pt of Group 8; Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, 22 Tm, Yb, and Lu, of the Lanthanides or rare earths; and Th 23 and U of the actinides. Also in formula I, "a" is a num- -24 ber o~ about l, "b" is a number of from about .01 to about 100, preferably from about .01 to 10, most pre~erably .1 26 to 10; and "x" is a numbe~ taken to satisfy the average 27 valences of metals A and B in the oxidation states in which 28 they exi-qt in the composition.
29 It is~ to be understood that while the abov2 ~for-3Q mula Iand formulae which ~ollow hereinafter are referred 31 to ~s empirical formulae, they are not considered to be 32 em~irical formulae in the conventional sense. The precise 33 structure of the metal oxide catalysts of the present 34 invention has not yet been determined and X in these ~ormu-3; lae in fact has no fixed deteminate value since it can 3~ vary widely de~ending on the various possible co~binations 37 within the cata~lyst. l~hat there is oxygen present is-kno~n , 4~9~
1 a~d the x in these formulae is representative of this.
Z However, these formulae are significant in that they repre-3 sent the gram atom ratio of the metal components of the 4 catalvst.
Subgeneric classes of suita~ble metal oxide compo-6 sitions falling wi~hin the ~cope of formula I include those 7 represented by the following ~mpirical formulae:
9 Aa~bx (I) 12 wherein ~ is at least one metal selected from the group 13 consisting of Tl, Bi, Pb, Co, and Th; and B at least one 14 ~etal selected from the group consisting of Li, Na, K, Rb, Cs, and Fr of Group lA (of the periodic chart) Be, Mg, Ca, 16 Sr, Ba, and Ra of Group 2a; In, and Tl of Group 3a; Ge of 17 Group 4a; P, As~ and Sb, o~ Group SA; Ag~ Au, and Cu, of 18 Group Ib; Zn, Cd, and ~ of Group 2b; Sc, Y, La, and Ac of 19 Group 3b; Ti, Zr~ and Hf of Group 4b; Nb and Ta of Group Sb; Mn, Tc, and Re of Group 7b; Fe, Ru, Os, Rh, Ir, ~i, Pd, 21 and Pt of Group 8; Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, 22 Tm, Yb, and Lu, of the Lanthanides or rare earths; and Th 23 and U of the actinides. Also in formula I, "a" is a num- -24 ber o~ about l, "b" is a number of from about .01 to about 100, preferably from about .01 to 10, most pre~erably .1 26 to 10; and "x" is a numbe~ taken to satisfy the average 27 valences of metals A and B in the oxidation states in which 28 they exi-qt in the composition.
29 It is~ to be understood that while the abov2 ~for-3Q mula Iand formulae which ~ollow hereinafter are referred 31 to ~s empirical formulae, they are not considered to be 32 em~irical formulae in the conventional sense. The precise 33 structure of the metal oxide catalysts of the present 34 invention has not yet been determined and X in these ~ormu-3; lae in fact has no fixed deteminate value since it can 3~ vary widely de~ending on the various possible co~binations 37 within the cata~lyst. l~hat there is oxygen present is-kno~n , 4~9~
1 a~d the x in these formulae is representative of this.
Z However, these formulae are significant in that they repre-3 sent the gram atom ratio of the metal components of the 4 catalvst.
Subgeneric classes of suita~ble metal oxide compo-6 sitions falling wi~hin the ~cope of formula I include those 7 represented by the following ~mpirical formulae:
8 Al~lOX CII) wherein Al is Tl (o Group 3a); Bl is at least one member 11 selected from the group consisting of Sc, Y, La, Ac (of 12 Group 3b); Ti, Zr, and H~ (of Group 4b); N~, and Ta ~of 13 Group 5~); Mn, Tc, Re (of Group 7b)7 As and Sb (of &roup 14 5a); Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, and Lu (of the Lanthanides or rare earths); Th, and U
16 (of the actinides); preerably ~1 is selected from Ta, 17 Sb, Ti, Zr, and Hf and mixtures; "a" is a number of about 18 1, ~b" is a number of from about .01 to about 10; preferably 19 from about .05 to about 5, and "x~ is as described above;
. ~ B~Ox (III) 2:2 wherein A2 is Bi; 82 is at least one member selected 23 from the group consisting of Be, Mg, Ca, Sr, Ba, and 24 Ra (of Group 2a); In (of Group 3a); ~g (of Group lb);
preferably 32 is Ag, Mg, Ca, Sr or Ba and mixtures thereof;
26 "h" is a numbe~r of about I, "j" is a number of from about 27 .01 to about I00, preferably from about Ool to about 2~8. 10, and ~x" is: as described above;
AkBl x (IV) 31 wherein A3 is Bi; B3 is at least one mèmber selected 3~ from the group consisting of Li~ Na, K, Rb, Cs, and Fr 33 (of Group la); Sc, Y, La~, and Ac (of Group 3b); Ti, Zr, 3:4 and Hf (of.Gr~up 4b); Fe, Ru, Os, Co, Rh, Ir, Ni, ~d, and Pt (of Goup 8), Zn~(of Group 2b); Ge (of Group 4a);
.
' -;
. . .:
. . :, :. ' ' ~:, .. :. ..... .
1 Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, and Lu 2 (of the Lanthanides or rare earths); Th (of the actinides);
3 preferably 83 is selected from Zn, Ce, Li, Na, K, Cs, 4 and Zr and mixtures; "k" is a number of about 1, "1"
5 is a number of from about 0.01 to about 10, preferably 6 from about O.S to about S, and "x" is as described above;
8 AmBnOX (V) 10 wherein A4 is cobalt, B4 is La, "m" is a number of about 1, 11 "b" is a number of from about 1 ~o about 10, preferably 12 from about 1 to about S, and "x" is as described above:
i4 AoBSOx (VI) 16 wherein A5 iq Th; ~5 is at least one member selected from 17 the group consisting of Cu (of Group lb); Zn, Cd, and Hg 18 (of Group 2b); preferably B5 is Zn; "o" is a number of about 19 1, "p" ig a number of from about 0.01 to about 10, prefer-20 ably from abo~t 0.5 to about 5; and "x" is as described 21 above;
23 A696O tVII) 24 wherein A6 is~ Pb; B6 is at least one member selected 25 from the group consisting of Li, Na, R, Rb, C9, Fr (of 26 Group la); Sc, Y, La, and Ac (of Group 3b); Ti, Zr, and 27 Hf (of Group 4b); Fe~, Ru, Qs, Co, Rh, Ir, Ni, Pd, and 28 Pt (of Group 8), kg (of Group lb); Zn (o Group 2b);
23 Ge (of Group 4a), P.and As (of Group Sa); Ce, Pr, Nd, 3a Pm, Sm, Eu, Gd, Tb, Py, Er, Tm~ Yb, and Lu tof the Lan~ha-31 ni~es or rare earths); Th (of the actinides); (preferably 32 B6 is se}ected from Ag, Zn, As, Li, Na, g, Rb, Cs, Zr, 33 and mixtures, most preferably Ag, Zn, K, and Zr); "g~
34 is a number of about 1, "r" is a~number of from ahout 35 .01 to about lQ, pre~fera~b.ly from about 0.5 to about S, 36 a~nd "x" is a;s described a~ove;
"': ' ' .
.';. ' .:
....
., '.,~: .,.,. ~ `
~2~4~
1 ~ 7 AsBtx (VIII) 3 wherein A7 is Pb; B7 is at least one member selected 4 from the group consisting of Be, Mg, Ca, Sr, Ba, Ra (of Group 2a); Tl (of Group 3a) (preferably B7 is selected 6 from Ba, Ca, Sr and mixtures); ~s" is a number of about 7 ,; "t" is a number of from about 0.01 to about 10, preferably 8 from about 0.5 to about 5; and ~x'l is as described above;
Sbc d ie x (IX) 1~ wherein "c" is a number of about 1, "d" is a number of from 12 ~bout 0.1 to about 10, preferably from about 0.5 to about 13 5, ne" is a number from about O ~o about 5, preferably from 14 about O to about 1, and "x" is as defined in co~nection with formula I as it pertains to the oxidation state of Sb, Pb, 16 and Bi metals in the formula; and 17 DuEvSbyBizx (X) 19 wherein D is at least one member selected ~rom the group 23 consisting of Li, Na, R, Rb, Cs, Fr, ae, ~g, Ca, Sr, Ba, and 2:1 Ra; preferably D is Cs; E is at least one member selected 22 from the group consisting of Pb, Au, Agj Pt, Pd, Cu, Zn, Cd, 23 and Hg; preferably E is Pb, Au, or Cu; most ~referably ~u; "u"
24 is a number which can vary rom about O to a-bout 10, pre-ferably from about 0.5 to about 5; "v" is a number which 26 can vary from about O to about 10, pre~erably from about 27 0.5 to about 5; "y" is a~number which can vary from about O
28 to about 10, pre~feFaby` from abou~ 0.5 to about 5; ''z" is a 29 number which can vary from about 0.01 to about 10, prefe~r-3~ ably from:about .01 to about 5; and ''x" is as aefined in 31 connection:with formula I as it pertains to the oxldation 32 state o~ D, E, Sb, and BL.
33 Representative~examples of empirical formulas 34. (based on formula I) of metal oxygen compositions which can 3~s be prepared in accordance with the present invention are 36 d~scribed below. The l~-tters "a" and "b" in each formula 37 co~llectively repr~s:en~ the gra~m atom ratios o each m~tal , i: .: .. ,.,,,.,.. , ~ ~ :
", ; ~ ~
1 in the composition. The letter "x" of each of these formu-2 las is as described above is indeterminate although its the-3 oretical value can be calculated from the representative ox-4 idation states o~ each metal as also provided. Futhermore, the o~idation states of each of the metals of the calcined 6 metal oxygen composition may vary between the highest and 7 lowes~ pcssible oxidation states in a sin~le composition.
....... ........
:
, :: ~ :
. ~....... .
~ :- :
, . , ~: :
~az24~
13~s~i3g~ a b +3 ~3 2 Tl S~ o 1 .3 a bx 3 1 .5 4 n 6 n 1 3 7 Tl Ti40 1 . 2 a b x 8 1 .3 n 1 . 5 W
}I . n 1 ;~
12 ~I 1 3 13 Tl~3T +50 a }~ x 14 Tla 3M~b2o }5 Tl 31;ab30x 16 Tla3Ub50X ~1. 5 17 Bi l 3Cab20x 10.1 18 n 10~3 19 n 10.5 20` n 21 n 22 ~ 1 lQ
23 ~ ` 1lOa ;
. ~ - . ..
::,. ::
: , , ~2;;~
-- l3_ 1E:mpirical Formula a b 2Bi+3Srb x 1 . 3 ~ - n 1 5 4 "
5 1~ 1 4 Bi+3I +30 a b x 7Bia3AgblO 1 . l n 1 ~16
16 (of the actinides); preerably ~1 is selected from Ta, 17 Sb, Ti, Zr, and Hf and mixtures; "a" is a number of about 18 1, ~b" is a number of from about .01 to about 10; preferably 19 from about .05 to about 5, and "x~ is as described above;
. ~ B~Ox (III) 2:2 wherein A2 is Bi; 82 is at least one member selected 23 from the group consisting of Be, Mg, Ca, Sr, Ba, and 24 Ra (of Group 2a); In (of Group 3a); ~g (of Group lb);
preferably 32 is Ag, Mg, Ca, Sr or Ba and mixtures thereof;
26 "h" is a numbe~r of about I, "j" is a number of from about 27 .01 to about I00, preferably from about Ool to about 2~8. 10, and ~x" is: as described above;
AkBl x (IV) 31 wherein A3 is Bi; B3 is at least one mèmber selected 3~ from the group consisting of Li~ Na, K, Rb, Cs, and Fr 33 (of Group la); Sc, Y, La~, and Ac (of Group 3b); Ti, Zr, 3:4 and Hf (of.Gr~up 4b); Fe, Ru, Os, Co, Rh, Ir, Ni, ~d, and Pt (of Goup 8), Zn~(of Group 2b); Ge (of Group 4a);
.
' -;
. . .:
. . :, :. ' ' ~:, .. :. ..... .
1 Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, and Lu 2 (of the Lanthanides or rare earths); Th (of the actinides);
3 preferably 83 is selected from Zn, Ce, Li, Na, K, Cs, 4 and Zr and mixtures; "k" is a number of about 1, "1"
5 is a number of from about 0.01 to about 10, preferably 6 from about O.S to about S, and "x" is as described above;
8 AmBnOX (V) 10 wherein A4 is cobalt, B4 is La, "m" is a number of about 1, 11 "b" is a number of from about 1 ~o about 10, preferably 12 from about 1 to about S, and "x" is as described above:
i4 AoBSOx (VI) 16 wherein A5 iq Th; ~5 is at least one member selected from 17 the group consisting of Cu (of Group lb); Zn, Cd, and Hg 18 (of Group 2b); preferably B5 is Zn; "o" is a number of about 19 1, "p" ig a number of from about 0.01 to about 10, prefer-20 ably from abo~t 0.5 to about 5; and "x" is as described 21 above;
23 A696O tVII) 24 wherein A6 is~ Pb; B6 is at least one member selected 25 from the group consisting of Li, Na, R, Rb, C9, Fr (of 26 Group la); Sc, Y, La, and Ac (of Group 3b); Ti, Zr, and 27 Hf (of Group 4b); Fe~, Ru, Qs, Co, Rh, Ir, Ni, Pd, and 28 Pt (of Group 8), kg (of Group lb); Zn (o Group 2b);
23 Ge (of Group 4a), P.and As (of Group Sa); Ce, Pr, Nd, 3a Pm, Sm, Eu, Gd, Tb, Py, Er, Tm~ Yb, and Lu tof the Lan~ha-31 ni~es or rare earths); Th (of the actinides); (preferably 32 B6 is se}ected from Ag, Zn, As, Li, Na, g, Rb, Cs, Zr, 33 and mixtures, most preferably Ag, Zn, K, and Zr); "g~
34 is a number of about 1, "r" is a~number of from ahout 35 .01 to about lQ, pre~fera~b.ly from about 0.5 to about S, 36 a~nd "x" is a;s described a~ove;
"': ' ' .
.';. ' .:
....
., '.,~: .,.,. ~ `
~2~4~
1 ~ 7 AsBtx (VIII) 3 wherein A7 is Pb; B7 is at least one member selected 4 from the group consisting of Be, Mg, Ca, Sr, Ba, Ra (of Group 2a); Tl (of Group 3a) (preferably B7 is selected 6 from Ba, Ca, Sr and mixtures); ~s" is a number of about 7 ,; "t" is a number of from about 0.01 to about 10, preferably 8 from about 0.5 to about 5; and ~x'l is as described above;
Sbc d ie x (IX) 1~ wherein "c" is a number of about 1, "d" is a number of from 12 ~bout 0.1 to about 10, preferably from about 0.5 to about 13 5, ne" is a number from about O ~o about 5, preferably from 14 about O to about 1, and "x" is as defined in co~nection with formula I as it pertains to the oxidation state of Sb, Pb, 16 and Bi metals in the formula; and 17 DuEvSbyBizx (X) 19 wherein D is at least one member selected ~rom the group 23 consisting of Li, Na, R, Rb, Cs, Fr, ae, ~g, Ca, Sr, Ba, and 2:1 Ra; preferably D is Cs; E is at least one member selected 22 from the group consisting of Pb, Au, Agj Pt, Pd, Cu, Zn, Cd, 23 and Hg; preferably E is Pb, Au, or Cu; most ~referably ~u; "u"
24 is a number which can vary rom about O to a-bout 10, pre-ferably from about 0.5 to about 5; "v" is a number which 26 can vary from about O to about 10, pre~erably from about 27 0.5 to about 5; "y" is a~number which can vary from about O
28 to about 10, pre~feFaby` from abou~ 0.5 to about 5; ''z" is a 29 number which can vary from about 0.01 to about 10, prefe~r-3~ ably from:about .01 to about 5; and ''x" is as aefined in 31 connection:with formula I as it pertains to the oxldation 32 state o~ D, E, Sb, and BL.
33 Representative~examples of empirical formulas 34. (based on formula I) of metal oxygen compositions which can 3~s be prepared in accordance with the present invention are 36 d~scribed below. The l~-tters "a" and "b" in each formula 37 co~llectively repr~s:en~ the gra~m atom ratios o each m~tal , i: .: .. ,.,,,.,.. , ~ ~ :
", ; ~ ~
1 in the composition. The letter "x" of each of these formu-2 las is as described above is indeterminate although its the-3 oretical value can be calculated from the representative ox-4 idation states o~ each metal as also provided. Futhermore, the o~idation states of each of the metals of the calcined 6 metal oxygen composition may vary between the highest and 7 lowes~ pcssible oxidation states in a sin~le composition.
....... ........
:
, :: ~ :
. ~....... .
~ :- :
, . , ~: :
~az24~
13~s~i3g~ a b +3 ~3 2 Tl S~ o 1 .3 a bx 3 1 .5 4 n 6 n 1 3 7 Tl Ti40 1 . 2 a b x 8 1 .3 n 1 . 5 W
}I . n 1 ;~
12 ~I 1 3 13 Tl~3T +50 a }~ x 14 Tla 3M~b2o }5 Tl 31;ab30x 16 Tla3Ub50X ~1. 5 17 Bi l 3Cab20x 10.1 18 n 10~3 19 n 10.5 20` n 21 n 22 ~ 1 lQ
23 ~ ` 1lOa ;
. ~ - . ..
::,. ::
: , , ~2;;~
-- l3_ 1E:mpirical Formula a b 2Bi+3Srb x 1 . 3 ~ - n 1 5 4 "
5 1~ 1 4 Bi+3I +30 a b x 7Bia3AgblO 1 . l n 1 ~16
9 n 1 ~2 n 1 ~3 11 I~ 1 ~5 B~i 3Ca 2Ag lx l . 3 1Bi+3C;a~2Inb30 1Ca- . 3, In~ . 8 L4~3i t 3Cab25~2ox 1. S
+2 +2 l .1 a~ b x 16 " 1 . 3 17 n 1 5 18 n Lg n 1 2 n 1 3 P~+2Mg+20 22Pb+2~ab20 x 2_Pb~a2'rl~ x 1 2 2.4 Bi 3Znb20 l .1 ~5` '` 1 .I7 26 " 1 . 2S
~7 " 1 .5 28~
.
., .
, . -2~ 9 Empirical Fo~mula a b 2 l 2 3 n l 3 4 Bi~ R~; x 1 . 013 n l .2I
6 1 .43 7 n 8Bi 1 3Nib2o x 1 . 2 n l 3 n l 5 11 n 12 n 1 2 ~ ~ n 1 3 14Bi+3Zr.b4OX 1 .17 lS n. 1 .3 1~ n 1 3 lg Bi ~eb 1 .17 2Q n ~ l .7 21 1~ 1 3. Q
2~ Bi Ceb40 : l .1 ?
2 3 n ~ 1 .- 3 3 24 ni 1 .S
n :
21~ n 1 2 r 1 3 ,~ ~
-- , ., - -.
~2~4~9~
-- 15 -- .
L ~irical Fors~ula A b 2 B~+3Lab3~ 1 .3 3 1~ 1 .5 4 n 6 n 1 2 3i31'h 4æ 1 . 3 a 9 ~ 1 .5 "
n 1 2 2 ~ 1 3 1-3 Bi~3mb4Zn~2OX 1 ~h- .16,Zn~ . 5 14 8i+3~,a+3X I lo 1 La~ . 5 a b b x ~i+3Geb4Nib20 1 Gec . 25,2~i~ . 5 16 ~1~3Zn+2Zr+4O 1 Zn= 1, Zr- 1 a b b x 17 Bi+3Ce~4m 1 Ce- .~, m-a b b x 18 Co 6Lab3O
19 " 1 2 20 " 1 3 +4; +2 21 ~ Z~ O 1 .3 a b x 2~2 ~ ~ ~5 ~4. " 1. 2 n . 1 3 25Th+4CU~20~ 1 1 a ~. x :; :
.
.. .,: , , .
: . :.~. , :, ... .
~z~ 9 -- i6 --E~npi~ical For;nula a b 2 Th~4cd+20 a b x 3 pb+2z~+40 1 . 3 a b x 3 1 .5 4 n 6 n 1 3 7 pb+2~+10 1 2 a b x 8 pb+2y+30 1 . 3 a b x n 1 5 1 01 n 11 n 1 6 ~:
12 n 1 10 .13 Pb 2Co~2o a b x 14.p~;l 2T~40 a b x lS a b x 1 . 2 : n 1 .-3 n 1 D5 1~ `
l g n 1 2 1~ 1 3 ~3 22 Pb 2P+50X
a b 23 Pb 2Asb;O x ` 24 Pb ~A~b10 x` 1 .1 : .~ 1 . ~ 3 . 2~
n ` 1 .17 ~6 .
. -. .
, ~Z;~4~
1 E~irical Formula a b 1 .2S
3 " 1 ~
4 Pba2AgblZrb4Ox 1 Ag= .7, Zr- .3 5 pb+2K+lzr+4O g= .8, Zr-- .3 a b b x 6 Pb~2Yb32rb4Ox Y= .3, Zr= .35 7 Pb+2Zn+2Th+4O Zn= .4, Th= .01 8 Pb~2Znb2Cob2ox Zn= .3, Co= .17 Representative examples of empirical formulas of 11 metal oxide compositions, based on formula IX, are illus-12 trated below. In these formulas, the letters "c", ~d" and 13 ~e" as provided collectively represent gram atom ratios of 14 the respective metals. The letter "x" is as described above.
16 Empirical Formula c d e 17sbc3pb~2~i~3~ I 1.5 0 18 ~ 1 2 .~5 19 ~` 1 2 0 2~0 " 1 3 0 21 " 1 4 0 22 " 1 5 0 23 " 1 1.5 .25 24 Representative examples of empirical formulas of metal cxide comDositions, based on structural formula X
26 are illustrated below. In these formulas the letters "u", 27 "v", "y" and "z", collectively represent gram atom ratios 28 of the respective metals. The letter "x" is às described 29 above.
30 Em~irical Por ~ a u v ~ z 31 SbyBizOX
32 " 0 0 0.25 33 " 0 0 1.0 0.25 34 CsuSbyBizOx 0-05 1.0 0.25 35- ~ 0.1 0 1.0 0.25 36 " 0.5 0 1.0 0.25 37 " 1.0 0 1.0 0.25 '~
.
~2~ 9 - 18 ~
1 Em~irical Formula u v ~ z 2CsuPbvShyBizOx .S 1.51.0 0.25 3 " 0.1 1.51.0 0.25 4 " 0.5 1.51.0 0.25 " 1.0 1.51.0 0.25 6CuvSbyBizOx 0 0.251.0 0.25 7 " 0 0.51.0 0.25 8 n 0 0.51. 0 0.5 9 n 0 0.5O.S 1.0 10AuvSbyBizOx 0 0.051.0 0.25 11 " 0 0.051.0 0.50 12 " 0 0.11.0 0.25 13 " 0 0.11.0 0.50 14CSuCUvSbyBizx .S 0.250 1.0 n 0.1 0~250 1.0 16 " 0.5 0.250 1.0 17 1.0 0.250 1.0 18KvSbyBizOx 0.051.0 0.25 19 " 0 0.11.0 0.25 " 0 ~.5 0 1.0 21 n O 1.0 0 1.0 22RbuAu~SbyBizOx 0.05 0. 05 1. O O . 25 2~3 " 0.1 0.051.0 0.25 24 " 0.5 0.051.0 0.25 " 1.0 0.0S1.0 0.25 26 Representative starting materials in metal oxide 27 form, from which the metal oxide composltion of the present 28 invention can be prepared include Sb2O3,PbO, Bi2O3, T12O3, 2 5 23' T12O3, U3O8, CaO, In2O3, SrO, BaO MgO ZnO
ZrO2, GeO3~ CeO2~ Y2O3-31 However, included within the ~erm metal oxides 32 are precursors~of said metal oxide such as nitrates, car-33 bonates, and acetates which can be converted to their cor-34 re-spon~ing metal oxides by heat treatment~
Representative illustrations of such precursor 36 metal oxide,s include l~n(NO3)2, Bi(NO3)3, AgN03, ~h(NO3)4, 3 3)2' CU(~3)2~ Na~¢o3, Na2Co3, ..
`' , ` . ~' , . . .
, ~" ,.'. ~
4~9 1 The process for preparing the metal oxide compo-~ si~ions o~ the ~resent invention is conducted by reacting 3 at least two of the oxides of said metals in the presence 4 of at least one organic media, e.g., alcohol, under condi-tions and in a manner sufficient to ~orm a catalyst pre-6 cursor co~position. m e term "media" i used herein in a 7 collective sense to signi~y singular and/or plural.
8 When an alcohol is em~loyed as the liquid organic 9 media, water and other organio by-products, such as ethexs, esters and the like, are formed as a result of this reaction ll and there are essentially no other detectable by-products 12 therefrom. While not wishing to be bound by any particular 13 theory, thiC occurence has led to the conclusion that the 14 organic alcohol participates in thi~ reaction, although to an undetermined extent, through the hydroxy functional 16 group thereby releasing water. More specifically, it is 17 fu~ther believed that the alcohol may react with at least 18 the qur~ace o tha metal oxide particles to form an alkoxide 19 which in turn may become an active intermediate for further reaction to form the complex metal oxide catalyst matrix.
21 An organic media with reducing properties may facilitate 22 this intermediate forming reaction.
23 In any event, the metal oxides are eventually 24 reacted with each o~her and the precursor catalyst com-position is not belie~ed to be a mere mixture of oxides.
26 The above rea~tion can be conducted bv admixing 27 at least two of said metal oxides with at least one orga~ic 28 media and heating t~e admixture. Since most metal oxide~
29 a~e generally at ieast partially insoluble in the organic media, a slurry or suspension will result and the reaction 31 is conducted in a heterogeneous phase. However, an organic 32 media whi¢h dis~solves the met~l oxides can also be employed 33 although this complicates the recovery procedure. Accord-34 ingly, it is contemplated to employ-organic metal oxides such as~a~timony butoxide and ma;gnesium methaxide which are 36 s~-luble i~ the o~r~anic ~è~ia, a~s starting materials in the 37 process of the present in~e~nti3~.
: .
:
. .
.:: '' ' ; ' ~Z~4~9~
1 ~hus, the organi~ media functions as a solvent and/or 2 suspending medium for the metal oxides, as a solvent and/or 3 suspending agent for the catalyst precursor composition, as 4 a medium for providing uniform heating of the metal oxides, and optionally as a reactant.
6 The organic m~dia is comprised of carbon, hydrogen, 7 and at least one hetero-atom such as oxygen, nitrogen or 8 sulfur.
9 Included within the scope of organic media are alcohols, aldehydes, ketones, ethers, amines, arnides, 11 and thiols, and mixtures thereof, containing typically 12 from about 1 to about 20, preferably ~rom about 1 to 13 about 10, and most preferably from about 1 to about 5 14 carbon atoms.
lS More specifically, the organic moiety to which 16 the alcohol, aldehyde, ketone, ether, amine, amide, and 17 thiol functional groups can be attached includes alkyl, 18 typically about Cl to about C20, preferahly Cl to C10, 19 most preferably Cl to C5 alkyl; aryl, typically about C6 to a~out CI4, preferably about C6 to about C10, most 21 preferably C6 aryl, cycloalkyl, typically about C4 to 22 about Czo~ preferably about C6 to about C12, most preferably 23 about C6 to C10 cycloalkyl, aralkyl and alkaryl wherein 24 the alkyI and aryl groups thereof are described above.
Each class o liquid organic media can contain 26 one or more, typically 1 to 3, functional groups.
27 The preferred organic compounds are the primary 2~ and secondary alcohols. AlcohoIs which con~ain 1, 2 29 or 3 hydroxyl substituent groups are especially preferred 3a because these, in general, are readily liquiied at useful 31 temperatures in the process range. Representative hydro~y-32~ lic compounds useful in the process include monoalcohols, 33 such as methanol, ethanol, isopropanol, }-propanol, 1-34 butanol, isobutanol, 2-butanol, t-butan~ Pentanol, cyclohexanol, 1-o¢tanol, 2-octanol, 3-octanol , 4-octanol, 36 2-hexadecanal, 2-eicosanol, ~-ethyl-l- hexanol, 37 phenol, ~en~yl alcohol, etc.; di-alcohols, such as ethylene ,.
, .
,:
. . . . . .
.-. -~ ., ~
; ,. ., - ' :
: . ~ , : ~
~Z2~9 .
} glycol, 1,4-butanediol, 1,2-propanediol; trialcohol suoh 2 as glycerine, 2,2-dimethylol ~ propanol; ether alcohols 3 such as diethylene glycol, triethylene glycol, 2-butoxy-4 ethanol, 4-methoxybutanol, tetrahydrofurfuryl alcohol;
and mixtures thereof.
6 Representative aldehydes include benzaldehyde, 7 formaldehyde, acetaldehyde, propionaldehyde, m-~olualdehyde, 8 2-ethylh~anol, trioxane, valeraldehyde and mixtures g thereof.
Representative ketones include acetone, methyl-11 ethylketone, cyclohexanone, dimethyl ketone, diethyl 12 ketone, dibutyl ketone, methyl isopropyl ketone, methyl 13 sec butyl ketone, benzophenone, and mixtures thereof.
14 Representative ethers include diethyl ether, lS di~utyl ether, tetrahydrofuran, anisole, dioctyl ether, 16 1,2-dimethoxyethane, 1,4~-dimethoxybutane, diethylene 17 ether, and mixtures thereof.
18 Representative amines include ethylene diamine, 19 hexylamine, cyclohexyl a~ine, diethylamine, 1,3 butadia~ine ethylene triamine, n-phenylbenzamine and mixtures thereof.
21 Representative amides include formamide~, dimethyl 22 ormam~ide, acetamide, 3-butaneamide, n-phenyl acetamide, 23 azacyclohexan-2-one, hexanediamide and mixtures thereof.
24 Representative thiols include phenylmethanethiol, ethanethiol, pentanethiol, 1,4-butanedithiol, cyclohexane-26 thiol, benzylthiol, l,S-pentane dithiol; and mixtures 27 thereof.
28 The~primary and secondary alkanols (ROH~ having 29 a carbon atom content in the range from 3 to 6 are a prefe-rred class of liquid organic media for reason or 31 cost and~avàil~ability and because of their convenient 32 boiling points. I-sobutanol is the optimum liquid.
3-3 In sh~rt, any~ of the aforenoted organic compounds 34 a~lone or in any~combïn-ation can be~employed as the organic 3S media.
T~e o~ga~ic m~diia may als~ contain non-oxygenated ~7 unreactive dil~ents w~hich-a~re in the liquid ~has~e at . :.
:~
, .. -:
.
, . .. . . ..
:~ - :., :. ,,, .:.
. ~ . ~ : :
~Z~ 9~
1 reaction temperature. The5e include hydrocarbons, mono-2 and polychlorinated hydrocarbons, and the like diluents.
3 The diluents which can be most advantageously 4 employed are less expensive than the organic media and help to reduce the cost o the overall process. However, a min-6 imum amount of hetoro-atom containing organic media is 7 employed as described herein to form the precursor com-8 position.
g Repre entative compounds which can function as a ln diluent in the organic media include hexane, heptane, 11 octane, cyclohexane, methylcyclopentane, 2,2,4-trimethylpen-12 tane, dodecane, 2-ethylhexane, 3-octene, cyclohexene; ben-13 zene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, 14 trimethylbenzene, 2-propylbenzene; methylene chloride, chloroform, carbon tetrabromide, carbon tetrachloride 3-16 ahlorohexane, 2,3-dichlorooctane, chlorocyclohexane, 1,2-l? dichloropentane, 1,2-dichloroheptane, 1,1,2-trichloroethane;
18 chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichloro-19 benzene, 2-chlorotoluene, 4-chlorotoluene, 2,4-dichloro-- 2:0 toluene, 1,3-dimethyI-4-chlorobenzene, butyl bromide, and 21 the like hydrocarbons and halogenated hydrocarbons.
22 The proportion of each metal oxide added to the 23 reaction mixture i9 selected to achieve the gram atom 24 metal ratios employed to yield a metal oxygen composition caRable of dehydrocoupling toluene such as described above 26 in the final composition in conjunction with the a~ore-27` mentione~d formulas.I and II~
28 Thè amount of` orqanic madia which is admixed with 29 the metal:oxides i~ any amount suffi~ient to permit uniform heating and mixing. o the reaction mixture and formation of 31 the precursor comFosition. Generally, the number of moles 32 of organic med`ia is at lea~st equal t~ the sum of the number 33 of moles of each met21 in the me.tal oxide mixture multiPlied 34 by the oxidation state of each metal in said mixture. Thus, while any effe~tive amount of organic media can be employed, 36 su¢h efi~etive amQunts will: constitute a ratio of moles of 37 me--tal iB the metal= ox-ide mi~tu;~e pe~ mole of oLganic media o ,:
: : :
`' "
.
:
~Z~24~
1 typically at leas~ 1:1, preferably at least 1:3, and most 2 preferably at lea~t 1:8. The preferred amount of organic 3 media i9 calculated according to the formula:
4 ~oles of organic media = ~i Mi x Vmax,i 5 wherein Mi is the moles of ith metal in the catalyst system 6 and U max,i is the maximum possible oxidation state of metal 7 M. Most preferably about 5 to about 10 times the moles of 8 organic media calculated from the above equation is employed g initially and the excess over the calcula~ed quantity is gradually rem~ved.
11 Alternatively, the amount of organic media and 12 metal oxides can be expressed as a percentage of the reaction 13 mixture. Thus, the reaction mlxture wiLl comprise typically 14 from about 1 to about 60%, preferably from about 10 to about 50%, and most pxe~erably from about 10 to about 30~, by 16 weight, metal oxides, and typically from about 40 to about 17 99%, preferably from about 50 to about 90~, and mQst:pre-18 fe~ably from about~70 to ~out gQ%, by ~eight~ organic media,19 based on the weight of the reaction mixture.
The reaction mixture comprising organic media and 21 metal oxides is heated to any temperature sufficient to form 22 the precursor composition. ~hus, while any effective temper-23 ature may be employed, such e~fective temperatures typicaLly 24 wLll be at least 20C, preferably at least 75C, and most pre~erably at least 105C, and can vary typically from about 26 20 to about 200C, preferably from about 75 to about 150C, 27 a~d most pre~ferably from about 100 to about 110C.
28 Preferably, the organic media is selected so tnat 29 it will ~oil at the sA}ected reaction temperature. This permits ref}uxing of the reaction mixture.
31 During heating of the reaction mix~ure, an~
3~ wa~er and/or volatile organic by-products such as es~ers, 33 ethers, aldehydes~, ketones and acids~ formed in-situ are pre-34 ferably removed, for exampIet by azeotropic distillation.
Thus, the rea~tion mixture is preferably heated ~nder s~b-36 stæntially ain~hYdirous ~onditions.
37 3y "~ubst-anitially aDhy~rous~" as u~ed herein is meant .- ,, . :. .
: '' '~ ' ~
. ~ .- . .
~,.; - .
.: -,; . . .
:. .; , :' ' .
-~2Z~9 1 typically less than about 10~, preferably less than about 2 5%, and most preferably less than about 1~, by weight water, 3 based on the weight of the organic media in the reaction mix-4 ture.
As stated above,the reaction r~uxture typically 6 will axist as a slurry or suspended material during heating.
7 The term "slurry" as used in connection with the 8 cataLy5t precursor forming step is defined herein to mean a g suspension wherein the solid components thereof are present therein at a solids content of typically not greater than 11 about 60, preferably not greater than about 40, and most 12 preferably not greater than about 2S~, by weight, based on 13 the weight of the suspension.
14 The order of addition of the metal oxides to the organic me~ia is not critical.
16 The reaction time is selected in conjunction with 17 the reaction temperature to permit substantially complete 18 reaction at the above reaction temperatures. Such reaction 19 times typically will ~ary from about 2 to about 48 hours, preerably from about 10 to about 30 hours, and most pre-21 fsrably from about 16 to about 24 hours.
22 Upon completion of the reaction,the precurqor 23 composition is separated from the reaction mixture by any 24 means capable of achieviNg this goal. Since the precursor composition typically is insoluble in the reaction mixture, 26 bulk se~aration can be accomplished by simple filtration 27 techniques. Alternately, the residual organic media can 28 be distiIled to orm a wet paste. Residual liquid is pre-29 ferably removed from the filtrand ~i.e., the insoluble m~ate~rial removed from the filtrate) or paste by drying the 31 same, tvpically at temperatures of from about 25 to about 32 210C, preferably from about 80 to about 160C, and most 33 preferably from about 100 to about 150C.
34 The isolated precuxsor composition is then cal-cined to form the metal oxygen composition capable of de-36 hydrocoupling toluene. Calcination ca~ be conduct~d in a 3~ sepa~ate step or in-situ in the reactor and involve~s :..... : ~.
1 heating the metal oxygen com~osition to at least reaction 2 temperature.
3 Accordingly, calcination is conducted at tem-4 peratures of ty~ic~lly from about 300 to about 1200C, pre-ferably from about 400 to about 1000C (e.g. 500 to 1000C), and most preferably from about 600 to about 900C for a 7 period of typically from about 0.5 to about 24 hours, pre-8 ferably from about 1 to about 10 hours, and most preferably 9 from about 1 to about 4 hours.
The atmospheDe under which calcinationis conducted 11 is capable of oxadizing, where possible, the metal(s) in 12 the metal oxygen composition. Such atmospheres include 13 oxygen or an oxygen containing gas s~ch as air; a gaseous 14 mixture of air and minor amounts of at least one of the inert gases such as helium, argon and the like; and a 16 mixture of air and minor amounts of at least one other 17 gas such as CO2~ CO, H2, and hydrocarbon (e.g. toluene).
l8 The preferred calcination atmosphere is air. While the l9 calcination atmosphere may be passed as a moving stream ~0 over the precursor composition, it is preferred that the 21 ca}cination atmosphere be static in nature.
22 A~ter calcination is conducted the metal oxygen 23 composition can optionally be activated. Activation in-2~ volves preconditioning the metal oxygen composition with 2~ ~ir or other atmosphere descr~bed in connection with 2; calcination beore selecting the final operating conditions.
27 Activation is therefore typically conducted by contacting 23 the metal oxygen com~osition with said gaseous atmosphere 2~ at temperatures of t~pically from about 350 to about 700, 30 oreferably from about 400 to about 650, and most preferably 3l from about 400 to about 600C.
32 Acti~ation times can vary typically from about l 33 to about 24, pre~erably from about 2 to about 20, and most 3I preferably from akout lO to about 16 hours. While activa-3~ tion may be conducted in a static atmos~here it is pre-ferred that sueh atmosi~here~be dynamic and pass over the -:, ..
:
.
., ': ~ ~.' ' . ~' . ... ':~ ,.: .
~4~9~
1 the catalyst as a fluid tream.
2 The attrition resistance of the metal oxide com-3 position can be sub~tantially improved by incorporating at 4 least one: alkali or alkaline earth metal oxide, prefer-S ably alkali metal oxide, most Dreferably cesium oxide into 6 the final composition. This can be achieved by selecting 7 the a~propriate alkali or alkaline earth metal oxide as one 8 of the initial metal oxides which i9 admixed with the 9 organic media. Alternatively, and most preferably, ~he
+2 +2 l .1 a~ b x 16 " 1 . 3 17 n 1 5 18 n Lg n 1 2 n 1 3 P~+2Mg+20 22Pb+2~ab20 x 2_Pb~a2'rl~ x 1 2 2.4 Bi 3Znb20 l .1 ~5` '` 1 .I7 26 " 1 . 2S
~7 " 1 .5 28~
.
., .
, . -2~ 9 Empirical Fo~mula a b 2 l 2 3 n l 3 4 Bi~ R~; x 1 . 013 n l .2I
6 1 .43 7 n 8Bi 1 3Nib2o x 1 . 2 n l 3 n l 5 11 n 12 n 1 2 ~ ~ n 1 3 14Bi+3Zr.b4OX 1 .17 lS n. 1 .3 1~ n 1 3 lg Bi ~eb 1 .17 2Q n ~ l .7 21 1~ 1 3. Q
2~ Bi Ceb40 : l .1 ?
2 3 n ~ 1 .- 3 3 24 ni 1 .S
n :
21~ n 1 2 r 1 3 ,~ ~
-- , ., - -.
~2~4~9~
-- 15 -- .
L ~irical Fors~ula A b 2 B~+3Lab3~ 1 .3 3 1~ 1 .5 4 n 6 n 1 2 3i31'h 4æ 1 . 3 a 9 ~ 1 .5 "
n 1 2 2 ~ 1 3 1-3 Bi~3mb4Zn~2OX 1 ~h- .16,Zn~ . 5 14 8i+3~,a+3X I lo 1 La~ . 5 a b b x ~i+3Geb4Nib20 1 Gec . 25,2~i~ . 5 16 ~1~3Zn+2Zr+4O 1 Zn= 1, Zr- 1 a b b x 17 Bi+3Ce~4m 1 Ce- .~, m-a b b x 18 Co 6Lab3O
19 " 1 2 20 " 1 3 +4; +2 21 ~ Z~ O 1 .3 a b x 2~2 ~ ~ ~5 ~4. " 1. 2 n . 1 3 25Th+4CU~20~ 1 1 a ~. x :; :
.
.. .,: , , .
: . :.~. , :, ... .
~z~ 9 -- i6 --E~npi~ical For;nula a b 2 Th~4cd+20 a b x 3 pb+2z~+40 1 . 3 a b x 3 1 .5 4 n 6 n 1 3 7 pb+2~+10 1 2 a b x 8 pb+2y+30 1 . 3 a b x n 1 5 1 01 n 11 n 1 6 ~:
12 n 1 10 .13 Pb 2Co~2o a b x 14.p~;l 2T~40 a b x lS a b x 1 . 2 : n 1 .-3 n 1 D5 1~ `
l g n 1 2 1~ 1 3 ~3 22 Pb 2P+50X
a b 23 Pb 2Asb;O x ` 24 Pb ~A~b10 x` 1 .1 : .~ 1 . ~ 3 . 2~
n ` 1 .17 ~6 .
. -. .
, ~Z;~4~
1 E~irical Formula a b 1 .2S
3 " 1 ~
4 Pba2AgblZrb4Ox 1 Ag= .7, Zr- .3 5 pb+2K+lzr+4O g= .8, Zr-- .3 a b b x 6 Pb~2Yb32rb4Ox Y= .3, Zr= .35 7 Pb+2Zn+2Th+4O Zn= .4, Th= .01 8 Pb~2Znb2Cob2ox Zn= .3, Co= .17 Representative examples of empirical formulas of 11 metal oxide compositions, based on formula IX, are illus-12 trated below. In these formulas, the letters "c", ~d" and 13 ~e" as provided collectively represent gram atom ratios of 14 the respective metals. The letter "x" is as described above.
16 Empirical Formula c d e 17sbc3pb~2~i~3~ I 1.5 0 18 ~ 1 2 .~5 19 ~` 1 2 0 2~0 " 1 3 0 21 " 1 4 0 22 " 1 5 0 23 " 1 1.5 .25 24 Representative examples of empirical formulas of metal cxide comDositions, based on structural formula X
26 are illustrated below. In these formulas the letters "u", 27 "v", "y" and "z", collectively represent gram atom ratios 28 of the respective metals. The letter "x" is às described 29 above.
30 Em~irical Por ~ a u v ~ z 31 SbyBizOX
32 " 0 0 0.25 33 " 0 0 1.0 0.25 34 CsuSbyBizOx 0-05 1.0 0.25 35- ~ 0.1 0 1.0 0.25 36 " 0.5 0 1.0 0.25 37 " 1.0 0 1.0 0.25 '~
.
~2~ 9 - 18 ~
1 Em~irical Formula u v ~ z 2CsuPbvShyBizOx .S 1.51.0 0.25 3 " 0.1 1.51.0 0.25 4 " 0.5 1.51.0 0.25 " 1.0 1.51.0 0.25 6CuvSbyBizOx 0 0.251.0 0.25 7 " 0 0.51.0 0.25 8 n 0 0.51. 0 0.5 9 n 0 0.5O.S 1.0 10AuvSbyBizOx 0 0.051.0 0.25 11 " 0 0.051.0 0.50 12 " 0 0.11.0 0.25 13 " 0 0.11.0 0.50 14CSuCUvSbyBizx .S 0.250 1.0 n 0.1 0~250 1.0 16 " 0.5 0.250 1.0 17 1.0 0.250 1.0 18KvSbyBizOx 0.051.0 0.25 19 " 0 0.11.0 0.25 " 0 ~.5 0 1.0 21 n O 1.0 0 1.0 22RbuAu~SbyBizOx 0.05 0. 05 1. O O . 25 2~3 " 0.1 0.051.0 0.25 24 " 0.5 0.051.0 0.25 " 1.0 0.0S1.0 0.25 26 Representative starting materials in metal oxide 27 form, from which the metal oxide composltion of the present 28 invention can be prepared include Sb2O3,PbO, Bi2O3, T12O3, 2 5 23' T12O3, U3O8, CaO, In2O3, SrO, BaO MgO ZnO
ZrO2, GeO3~ CeO2~ Y2O3-31 However, included within the ~erm metal oxides 32 are precursors~of said metal oxide such as nitrates, car-33 bonates, and acetates which can be converted to their cor-34 re-spon~ing metal oxides by heat treatment~
Representative illustrations of such precursor 36 metal oxide,s include l~n(NO3)2, Bi(NO3)3, AgN03, ~h(NO3)4, 3 3)2' CU(~3)2~ Na~¢o3, Na2Co3, ..
`' , ` . ~' , . . .
, ~" ,.'. ~
4~9 1 The process for preparing the metal oxide compo-~ si~ions o~ the ~resent invention is conducted by reacting 3 at least two of the oxides of said metals in the presence 4 of at least one organic media, e.g., alcohol, under condi-tions and in a manner sufficient to ~orm a catalyst pre-6 cursor co~position. m e term "media" i used herein in a 7 collective sense to signi~y singular and/or plural.
8 When an alcohol is em~loyed as the liquid organic 9 media, water and other organio by-products, such as ethexs, esters and the like, are formed as a result of this reaction ll and there are essentially no other detectable by-products 12 therefrom. While not wishing to be bound by any particular 13 theory, thiC occurence has led to the conclusion that the 14 organic alcohol participates in thi~ reaction, although to an undetermined extent, through the hydroxy functional 16 group thereby releasing water. More specifically, it is 17 fu~ther believed that the alcohol may react with at least 18 the qur~ace o tha metal oxide particles to form an alkoxide 19 which in turn may become an active intermediate for further reaction to form the complex metal oxide catalyst matrix.
21 An organic media with reducing properties may facilitate 22 this intermediate forming reaction.
23 In any event, the metal oxides are eventually 24 reacted with each o~her and the precursor catalyst com-position is not belie~ed to be a mere mixture of oxides.
26 The above rea~tion can be conducted bv admixing 27 at least two of said metal oxides with at least one orga~ic 28 media and heating t~e admixture. Since most metal oxide~
29 a~e generally at ieast partially insoluble in the organic media, a slurry or suspension will result and the reaction 31 is conducted in a heterogeneous phase. However, an organic 32 media whi¢h dis~solves the met~l oxides can also be employed 33 although this complicates the recovery procedure. Accord-34 ingly, it is contemplated to employ-organic metal oxides such as~a~timony butoxide and ma;gnesium methaxide which are 36 s~-luble i~ the o~r~anic ~è~ia, a~s starting materials in the 37 process of the present in~e~nti3~.
: .
:
. .
.:: '' ' ; ' ~Z~4~9~
1 ~hus, the organi~ media functions as a solvent and/or 2 suspending medium for the metal oxides, as a solvent and/or 3 suspending agent for the catalyst precursor composition, as 4 a medium for providing uniform heating of the metal oxides, and optionally as a reactant.
6 The organic m~dia is comprised of carbon, hydrogen, 7 and at least one hetero-atom such as oxygen, nitrogen or 8 sulfur.
9 Included within the scope of organic media are alcohols, aldehydes, ketones, ethers, amines, arnides, 11 and thiols, and mixtures thereof, containing typically 12 from about 1 to about 20, preferably ~rom about 1 to 13 about 10, and most preferably from about 1 to about 5 14 carbon atoms.
lS More specifically, the organic moiety to which 16 the alcohol, aldehyde, ketone, ether, amine, amide, and 17 thiol functional groups can be attached includes alkyl, 18 typically about Cl to about C20, preferahly Cl to C10, 19 most preferably Cl to C5 alkyl; aryl, typically about C6 to a~out CI4, preferably about C6 to about C10, most 21 preferably C6 aryl, cycloalkyl, typically about C4 to 22 about Czo~ preferably about C6 to about C12, most preferably 23 about C6 to C10 cycloalkyl, aralkyl and alkaryl wherein 24 the alkyI and aryl groups thereof are described above.
Each class o liquid organic media can contain 26 one or more, typically 1 to 3, functional groups.
27 The preferred organic compounds are the primary 2~ and secondary alcohols. AlcohoIs which con~ain 1, 2 29 or 3 hydroxyl substituent groups are especially preferred 3a because these, in general, are readily liquiied at useful 31 temperatures in the process range. Representative hydro~y-32~ lic compounds useful in the process include monoalcohols, 33 such as methanol, ethanol, isopropanol, }-propanol, 1-34 butanol, isobutanol, 2-butanol, t-butan~ Pentanol, cyclohexanol, 1-o¢tanol, 2-octanol, 3-octanol , 4-octanol, 36 2-hexadecanal, 2-eicosanol, ~-ethyl-l- hexanol, 37 phenol, ~en~yl alcohol, etc.; di-alcohols, such as ethylene ,.
, .
,:
. . . . . .
.-. -~ ., ~
; ,. ., - ' :
: . ~ , : ~
~Z2~9 .
} glycol, 1,4-butanediol, 1,2-propanediol; trialcohol suoh 2 as glycerine, 2,2-dimethylol ~ propanol; ether alcohols 3 such as diethylene glycol, triethylene glycol, 2-butoxy-4 ethanol, 4-methoxybutanol, tetrahydrofurfuryl alcohol;
and mixtures thereof.
6 Representative aldehydes include benzaldehyde, 7 formaldehyde, acetaldehyde, propionaldehyde, m-~olualdehyde, 8 2-ethylh~anol, trioxane, valeraldehyde and mixtures g thereof.
Representative ketones include acetone, methyl-11 ethylketone, cyclohexanone, dimethyl ketone, diethyl 12 ketone, dibutyl ketone, methyl isopropyl ketone, methyl 13 sec butyl ketone, benzophenone, and mixtures thereof.
14 Representative ethers include diethyl ether, lS di~utyl ether, tetrahydrofuran, anisole, dioctyl ether, 16 1,2-dimethoxyethane, 1,4~-dimethoxybutane, diethylene 17 ether, and mixtures thereof.
18 Representative amines include ethylene diamine, 19 hexylamine, cyclohexyl a~ine, diethylamine, 1,3 butadia~ine ethylene triamine, n-phenylbenzamine and mixtures thereof.
21 Representative amides include formamide~, dimethyl 22 ormam~ide, acetamide, 3-butaneamide, n-phenyl acetamide, 23 azacyclohexan-2-one, hexanediamide and mixtures thereof.
24 Representative thiols include phenylmethanethiol, ethanethiol, pentanethiol, 1,4-butanedithiol, cyclohexane-26 thiol, benzylthiol, l,S-pentane dithiol; and mixtures 27 thereof.
28 The~primary and secondary alkanols (ROH~ having 29 a carbon atom content in the range from 3 to 6 are a prefe-rred class of liquid organic media for reason or 31 cost and~avàil~ability and because of their convenient 32 boiling points. I-sobutanol is the optimum liquid.
3-3 In sh~rt, any~ of the aforenoted organic compounds 34 a~lone or in any~combïn-ation can be~employed as the organic 3S media.
T~e o~ga~ic m~diia may als~ contain non-oxygenated ~7 unreactive dil~ents w~hich-a~re in the liquid ~has~e at . :.
:~
, .. -:
.
, . .. . . ..
:~ - :., :. ,,, .:.
. ~ . ~ : :
~Z~ 9~
1 reaction temperature. The5e include hydrocarbons, mono-2 and polychlorinated hydrocarbons, and the like diluents.
3 The diluents which can be most advantageously 4 employed are less expensive than the organic media and help to reduce the cost o the overall process. However, a min-6 imum amount of hetoro-atom containing organic media is 7 employed as described herein to form the precursor com-8 position.
g Repre entative compounds which can function as a ln diluent in the organic media include hexane, heptane, 11 octane, cyclohexane, methylcyclopentane, 2,2,4-trimethylpen-12 tane, dodecane, 2-ethylhexane, 3-octene, cyclohexene; ben-13 zene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, 14 trimethylbenzene, 2-propylbenzene; methylene chloride, chloroform, carbon tetrabromide, carbon tetrachloride 3-16 ahlorohexane, 2,3-dichlorooctane, chlorocyclohexane, 1,2-l? dichloropentane, 1,2-dichloroheptane, 1,1,2-trichloroethane;
18 chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichloro-19 benzene, 2-chlorotoluene, 4-chlorotoluene, 2,4-dichloro-- 2:0 toluene, 1,3-dimethyI-4-chlorobenzene, butyl bromide, and 21 the like hydrocarbons and halogenated hydrocarbons.
22 The proportion of each metal oxide added to the 23 reaction mixture i9 selected to achieve the gram atom 24 metal ratios employed to yield a metal oxygen composition caRable of dehydrocoupling toluene such as described above 26 in the final composition in conjunction with the a~ore-27` mentione~d formulas.I and II~
28 Thè amount of` orqanic madia which is admixed with 29 the metal:oxides i~ any amount suffi~ient to permit uniform heating and mixing. o the reaction mixture and formation of 31 the precursor comFosition. Generally, the number of moles 32 of organic med`ia is at lea~st equal t~ the sum of the number 33 of moles of each met21 in the me.tal oxide mixture multiPlied 34 by the oxidation state of each metal in said mixture. Thus, while any effe~tive amount of organic media can be employed, 36 su¢h efi~etive amQunts will: constitute a ratio of moles of 37 me--tal iB the metal= ox-ide mi~tu;~e pe~ mole of oLganic media o ,:
: : :
`' "
.
:
~Z~24~
1 typically at leas~ 1:1, preferably at least 1:3, and most 2 preferably at lea~t 1:8. The preferred amount of organic 3 media i9 calculated according to the formula:
4 ~oles of organic media = ~i Mi x Vmax,i 5 wherein Mi is the moles of ith metal in the catalyst system 6 and U max,i is the maximum possible oxidation state of metal 7 M. Most preferably about 5 to about 10 times the moles of 8 organic media calculated from the above equation is employed g initially and the excess over the calcula~ed quantity is gradually rem~ved.
11 Alternatively, the amount of organic media and 12 metal oxides can be expressed as a percentage of the reaction 13 mixture. Thus, the reaction mlxture wiLl comprise typically 14 from about 1 to about 60%, preferably from about 10 to about 50%, and most pxe~erably from about 10 to about 30~, by 16 weight, metal oxides, and typically from about 40 to about 17 99%, preferably from about 50 to about 90~, and mQst:pre-18 fe~ably from about~70 to ~out gQ%, by ~eight~ organic media,19 based on the weight of the reaction mixture.
The reaction mixture comprising organic media and 21 metal oxides is heated to any temperature sufficient to form 22 the precursor composition. ~hus, while any effective temper-23 ature may be employed, such e~fective temperatures typicaLly 24 wLll be at least 20C, preferably at least 75C, and most pre~erably at least 105C, and can vary typically from about 26 20 to about 200C, preferably from about 75 to about 150C, 27 a~d most pre~ferably from about 100 to about 110C.
28 Preferably, the organic media is selected so tnat 29 it will ~oil at the sA}ected reaction temperature. This permits ref}uxing of the reaction mixture.
31 During heating of the reaction mix~ure, an~
3~ wa~er and/or volatile organic by-products such as es~ers, 33 ethers, aldehydes~, ketones and acids~ formed in-situ are pre-34 ferably removed, for exampIet by azeotropic distillation.
Thus, the rea~tion mixture is preferably heated ~nder s~b-36 stæntially ain~hYdirous ~onditions.
37 3y "~ubst-anitially aDhy~rous~" as u~ed herein is meant .- ,, . :. .
: '' '~ ' ~
. ~ .- . .
~,.; - .
.: -,; . . .
:. .; , :' ' .
-~2Z~9 1 typically less than about 10~, preferably less than about 2 5%, and most preferably less than about 1~, by weight water, 3 based on the weight of the organic media in the reaction mix-4 ture.
As stated above,the reaction r~uxture typically 6 will axist as a slurry or suspended material during heating.
7 The term "slurry" as used in connection with the 8 cataLy5t precursor forming step is defined herein to mean a g suspension wherein the solid components thereof are present therein at a solids content of typically not greater than 11 about 60, preferably not greater than about 40, and most 12 preferably not greater than about 2S~, by weight, based on 13 the weight of the suspension.
14 The order of addition of the metal oxides to the organic me~ia is not critical.
16 The reaction time is selected in conjunction with 17 the reaction temperature to permit substantially complete 18 reaction at the above reaction temperatures. Such reaction 19 times typically will ~ary from about 2 to about 48 hours, preerably from about 10 to about 30 hours, and most pre-21 fsrably from about 16 to about 24 hours.
22 Upon completion of the reaction,the precurqor 23 composition is separated from the reaction mixture by any 24 means capable of achieviNg this goal. Since the precursor composition typically is insoluble in the reaction mixture, 26 bulk se~aration can be accomplished by simple filtration 27 techniques. Alternately, the residual organic media can 28 be distiIled to orm a wet paste. Residual liquid is pre-29 ferably removed from the filtrand ~i.e., the insoluble m~ate~rial removed from the filtrate) or paste by drying the 31 same, tvpically at temperatures of from about 25 to about 32 210C, preferably from about 80 to about 160C, and most 33 preferably from about 100 to about 150C.
34 The isolated precuxsor composition is then cal-cined to form the metal oxygen composition capable of de-36 hydrocoupling toluene. Calcination ca~ be conduct~d in a 3~ sepa~ate step or in-situ in the reactor and involve~s :..... : ~.
1 heating the metal oxygen com~osition to at least reaction 2 temperature.
3 Accordingly, calcination is conducted at tem-4 peratures of ty~ic~lly from about 300 to about 1200C, pre-ferably from about 400 to about 1000C (e.g. 500 to 1000C), and most preferably from about 600 to about 900C for a 7 period of typically from about 0.5 to about 24 hours, pre-8 ferably from about 1 to about 10 hours, and most preferably 9 from about 1 to about 4 hours.
The atmospheDe under which calcinationis conducted 11 is capable of oxadizing, where possible, the metal(s) in 12 the metal oxygen composition. Such atmospheres include 13 oxygen or an oxygen containing gas s~ch as air; a gaseous 14 mixture of air and minor amounts of at least one of the inert gases such as helium, argon and the like; and a 16 mixture of air and minor amounts of at least one other 17 gas such as CO2~ CO, H2, and hydrocarbon (e.g. toluene).
l8 The preferred calcination atmosphere is air. While the l9 calcination atmosphere may be passed as a moving stream ~0 over the precursor composition, it is preferred that the 21 ca}cination atmosphere be static in nature.
22 A~ter calcination is conducted the metal oxygen 23 composition can optionally be activated. Activation in-2~ volves preconditioning the metal oxygen composition with 2~ ~ir or other atmosphere descr~bed in connection with 2; calcination beore selecting the final operating conditions.
27 Activation is therefore typically conducted by contacting 23 the metal oxygen com~osition with said gaseous atmosphere 2~ at temperatures of t~pically from about 350 to about 700, 30 oreferably from about 400 to about 650, and most preferably 3l from about 400 to about 600C.
32 Acti~ation times can vary typically from about l 33 to about 24, pre~erably from about 2 to about 20, and most 3I preferably from akout lO to about 16 hours. While activa-3~ tion may be conducted in a static atmos~here it is pre-ferred that sueh atmosi~here~be dynamic and pass over the -:, ..
:
.
., ': ~ ~.' ' . ~' . ... ':~ ,.: .
~4~9~
1 the catalyst as a fluid tream.
2 The attrition resistance of the metal oxide com-3 position can be sub~tantially improved by incorporating at 4 least one: alkali or alkaline earth metal oxide, prefer-S ably alkali metal oxide, most Dreferably cesium oxide into 6 the final composition. This can be achieved by selecting 7 the a~propriate alkali or alkaline earth metal oxide as one 8 of the initial metal oxides which i9 admixed with the 9 organic media. Alternatively, and most preferably, ~he
10 appropriate metal oxide is impregnated into the precursor
11 composition after removal of the organic media therefrom
12 by any suitable method. In accordanca with the preferred
13 me~hod of impregnationO the appropriate alkali or alkaline
14 earth metal oxide is dissolved in water to form a solution,
15 e.g., of CsO~/~20, and the precursor composition is admixed
16 with the solution to form a slurry.
17 The resulting slurry is then stirred ~or a time
18 of typically from about 1 to about 24, preferably from
19- about 2 to 16, and most preferably from about 4 to about 10
20 h~urs, at temperatures of typically from about 2S to about
21 lU0, preferably ~rom abou* 60 to about 80, and most pre-
22 ferably from about 65 to ahout 7SC to effect impregnation.
23 The impresnated precur~or composition solids are
24 then recovered by, for example, evaporating the water to
25 form a thick paste which i5 then dried in an oven at the
26 aforedescribed drying temPeratureS. The impregnated pre-
27 c~rsor composition is then calcined as deRcribed herein.
28 The attrition resistance effect has been found to
29 be imparted to the final composition by the alkali or alka~
3~ line earth metal oxide when pre~ent ~herein in amounts of 31 typicallv from about 0.01 to about 100, pre~erably 0.1 to 32 about 10, and most preferably from about 1.0 to about 5.0 33 mole ~ a;ttrition resistance modifying metal, based on the 34 total number of moles of metals in the metal oxygen com-35 position.
36 ~he s~urfaee ar~ea of the metal oxide composition 37 after calcination typic~llv will vary from ahout 0.1 to ... :.: .
,: .: .,: , .
~Z~
1 about 10, preferably from about 0.1 to about 2.0, and most 2 preferably from about 0.1 to about 1.0 m2/gm, as de~ermined 3 by the B.E,T. method.
4 The metal oxide composition resulting after caL-cination exhibits improved activity and selectivity vis-a-6 vis the dehydrocoupling of toluene to stilbene relative to 7 metal oxide composition derived from similar metal oxides 8 prepared by prior art techniques, particularly the aqueou~
9 slurry techniques discussed above. In addition, the metal oxide composition of the present invention deactivates at 11 a slower rate than those prepared by prior art techniques .
12 and is more attrition resistant. Thus, while the metal 13 oxide compocition of the present invention may possess an 14 ampirical formula similar to that of the prior art, the particular method of preparation described herein is 16 believed to alter both the precursor and final composition's 17 basic physical and/or chemical characteristics in terms of 18 crystal structure, porosity and surface area relative to 19 prior art com~ositions to the extent that improved effects are obser~ed as described herein.
21 The inorganic metal oxygen composition of the 22 present invention can function in a catalytic mode, a 23 stoichiometric mode ~also referred to herein as the cyclic 24 mode because of the need for regeneration o~ lattice oxygen) as an oxidant or oxygen carrier, or a combined catalytic/
26 stoichiometric mode for the dehydrocoupling of toluene~
27 In the catalytic mode of operation, oxygen-or an 28 oxyqen-containing gas such as air or oxygen-enriched air is 29 reacted with toluene in an amount suficient for the dehy-drocoupling reaction,said reaction being catalyzed by and 31 conductedin the presence of the metal oxygen composition.
32 In the stoichiometric mode of operation, the 33 metal oxygen composition is the sole source of oxygen.
34 That is, in the latter instance the dehydrocoupling of toluene is conducted in the substantial absence of added 36 free oxygen such as would be obtained from air. Consequently, 37 the metal oxygen composition when operating in this mode is ' : - -.. - "', ~' ~ :
:: . . ,~, .
~ .: : ' :
4~
1 eventually depleted of oxygen and must be regenerated as 2 described hereinafter.
3 I~ the combined catalytic/stoichiometric mode of 4 operation, oxygen or an oxygen-containing gas is added as a reactant in a manner similar to that noted herelnabove for 6 the catalytic mode of operation. However, the amount of 7 added oxygen i- not suficient by itself to meet the 8 stoichiometric oxygen re~uirements of the d~hydrocoupling 9 reaction. Conqequently, additional oxygen must be supplied by the inorganic metal oxygen compo~ition. The amount of 11 added free oxygen is typical~y controlled and limited by 12 diluting the atmosphere in contact with the metal o~ygen 13 composition with a suitable inert gas such as nitrogen.
14 Of these three modes of operation, the stoichio-metric mode is generally preerred although this preference 16 may change depending on the particular metal oxygen com-17 position elected.
18 The term "dehydrocoupling n and related terms 19 are employed herein to mean that the toluene molecules are coupled or dimerized, with carbon-carbon bond formation 21 occurring between the methyl group carbons, and the coupled 22 molecules have lost eLther one or two hydrogen atoms 23 from the ~ethyl group of each toluene molecule. When 24 two hydrogen atoms per molecule of toluene are lost r the carbon-carbon bond at the coupling or dimerization 26 site is uns~aturated as by dehydrogenation, that is, stilbene 27 is the product. On the other hand, bibenzyl, having 28 a saturated carbon-carbon bond at the coupling site, 29 is the product when only one hydrogen atom per molecule o toluene is lost.
31 In general, the production of stilbene as the 32 dehydrocoupled toluene product is preferred over the 33 production of bibenzyl. This stated preference is due 34 to the unsaturated character of stilbene as opposed to the saturated character of bibenzyl. As is well 36 known in the art, the presence of the unsaturated olefinic 37 carbon-carbon double bond causes the stilbene to exhibit .
- 2~ -1 high reactivity, thereby facilitating its direct use 2 as an organic intermediate in numerous organic syntheses.
3 The process of this invention is conveniently 4 carried out in an apparatus of the type suitable for carrying out chemical reactions in the vapor phase.
6 It can be conducted in a single reactor or in multiple 7 reactors using either a fixed bed, a moving bed, or a 8 fluidized bed system to effect contacting of the reactant g or reactants and metal oxygen composition. The reactant toluene or toluene derivatives will generally be heated 11 and introduced into the reactor as a vapor. However, 12 the reactant may be introduced to the reactor as a liquid 13 and then vaporized.
14 The oxidative dehydrocoupling reaction is prefer-ably carried out in the vaDor ~hase and under the influence l; of heat. The temperature ranqe under which the reaction can 17 be carried out ranges from about 300 to about 650C, te.g.
18 400 to 650C), preferablY from about 450 to about 600C, 19 and mo~t preferably from about 500 to about 580C.
2~ Pressure is not critical in the dehydrocoupling 21 process of this invention. The reaction ma~ be carried Z2 out at subat spheric, atmospheric, or superatmospheric 23 pressures as desired. It will be generally preferred, 24 however, to conduct the reaction at or near atmospheric pressure. Generally, pressures from about 1 to about 2S 10, preferably from about 1 to about 5, and most prefer-27 ably from about I to about 2 atmospheres can be conveniently 2~ employed.
29 The reaction time for the contact of the reactant 3~ with the metal oxygen composition in the present invention 31 may be selected from a broad`operab}e range which may 32 vary from about 0.5 to about 10, preferably from about 33 1 to about 8, and most preferably from about 1 to about 34 4 seconds. The reaction time maY be defined as the length of time in seconds which the reactant gasses 36 measured under reaction conditions are in ~ontact with 37 the inorganic metal oxygen com~osition in the reactor.
. .
.
' ~z~
3~ line earth metal oxide when pre~ent ~herein in amounts of 31 typicallv from about 0.01 to about 100, pre~erably 0.1 to 32 about 10, and most preferably from about 1.0 to about 5.0 33 mole ~ a;ttrition resistance modifying metal, based on the 34 total number of moles of metals in the metal oxygen com-35 position.
36 ~he s~urfaee ar~ea of the metal oxide composition 37 after calcination typic~llv will vary from ahout 0.1 to ... :.: .
,: .: .,: , .
~Z~
1 about 10, preferably from about 0.1 to about 2.0, and most 2 preferably from about 0.1 to about 1.0 m2/gm, as de~ermined 3 by the B.E,T. method.
4 The metal oxide composition resulting after caL-cination exhibits improved activity and selectivity vis-a-6 vis the dehydrocoupling of toluene to stilbene relative to 7 metal oxide composition derived from similar metal oxides 8 prepared by prior art techniques, particularly the aqueou~
9 slurry techniques discussed above. In addition, the metal oxide composition of the present invention deactivates at 11 a slower rate than those prepared by prior art techniques .
12 and is more attrition resistant. Thus, while the metal 13 oxide compocition of the present invention may possess an 14 ampirical formula similar to that of the prior art, the particular method of preparation described herein is 16 believed to alter both the precursor and final composition's 17 basic physical and/or chemical characteristics in terms of 18 crystal structure, porosity and surface area relative to 19 prior art com~ositions to the extent that improved effects are obser~ed as described herein.
21 The inorganic metal oxygen composition of the 22 present invention can function in a catalytic mode, a 23 stoichiometric mode ~also referred to herein as the cyclic 24 mode because of the need for regeneration o~ lattice oxygen) as an oxidant or oxygen carrier, or a combined catalytic/
26 stoichiometric mode for the dehydrocoupling of toluene~
27 In the catalytic mode of operation, oxygen-or an 28 oxyqen-containing gas such as air or oxygen-enriched air is 29 reacted with toluene in an amount suficient for the dehy-drocoupling reaction,said reaction being catalyzed by and 31 conductedin the presence of the metal oxygen composition.
32 In the stoichiometric mode of operation, the 33 metal oxygen composition is the sole source of oxygen.
34 That is, in the latter instance the dehydrocoupling of toluene is conducted in the substantial absence of added 36 free oxygen such as would be obtained from air. Consequently, 37 the metal oxygen composition when operating in this mode is ' : - -.. - "', ~' ~ :
:: . . ,~, .
~ .: : ' :
4~
1 eventually depleted of oxygen and must be regenerated as 2 described hereinafter.
3 I~ the combined catalytic/stoichiometric mode of 4 operation, oxygen or an oxygen-containing gas is added as a reactant in a manner similar to that noted herelnabove for 6 the catalytic mode of operation. However, the amount of 7 added oxygen i- not suficient by itself to meet the 8 stoichiometric oxygen re~uirements of the d~hydrocoupling 9 reaction. Conqequently, additional oxygen must be supplied by the inorganic metal oxygen compo~ition. The amount of 11 added free oxygen is typical~y controlled and limited by 12 diluting the atmosphere in contact with the metal o~ygen 13 composition with a suitable inert gas such as nitrogen.
14 Of these three modes of operation, the stoichio-metric mode is generally preerred although this preference 16 may change depending on the particular metal oxygen com-17 position elected.
18 The term "dehydrocoupling n and related terms 19 are employed herein to mean that the toluene molecules are coupled or dimerized, with carbon-carbon bond formation 21 occurring between the methyl group carbons, and the coupled 22 molecules have lost eLther one or two hydrogen atoms 23 from the ~ethyl group of each toluene molecule. When 24 two hydrogen atoms per molecule of toluene are lost r the carbon-carbon bond at the coupling or dimerization 26 site is uns~aturated as by dehydrogenation, that is, stilbene 27 is the product. On the other hand, bibenzyl, having 28 a saturated carbon-carbon bond at the coupling site, 29 is the product when only one hydrogen atom per molecule o toluene is lost.
31 In general, the production of stilbene as the 32 dehydrocoupled toluene product is preferred over the 33 production of bibenzyl. This stated preference is due 34 to the unsaturated character of stilbene as opposed to the saturated character of bibenzyl. As is well 36 known in the art, the presence of the unsaturated olefinic 37 carbon-carbon double bond causes the stilbene to exhibit .
- 2~ -1 high reactivity, thereby facilitating its direct use 2 as an organic intermediate in numerous organic syntheses.
3 The process of this invention is conveniently 4 carried out in an apparatus of the type suitable for carrying out chemical reactions in the vapor phase.
6 It can be conducted in a single reactor or in multiple 7 reactors using either a fixed bed, a moving bed, or a 8 fluidized bed system to effect contacting of the reactant g or reactants and metal oxygen composition. The reactant toluene or toluene derivatives will generally be heated 11 and introduced into the reactor as a vapor. However, 12 the reactant may be introduced to the reactor as a liquid 13 and then vaporized.
14 The oxidative dehydrocoupling reaction is prefer-ably carried out in the vaDor ~hase and under the influence l; of heat. The temperature ranqe under which the reaction can 17 be carried out ranges from about 300 to about 650C, te.g.
18 400 to 650C), preferablY from about 450 to about 600C, 19 and mo~t preferably from about 500 to about 580C.
2~ Pressure is not critical in the dehydrocoupling 21 process of this invention. The reaction ma~ be carried Z2 out at subat spheric, atmospheric, or superatmospheric 23 pressures as desired. It will be generally preferred, 24 however, to conduct the reaction at or near atmospheric pressure. Generally, pressures from about 1 to about 2S 10, preferably from about 1 to about 5, and most prefer-27 ably from about I to about 2 atmospheres can be conveniently 2~ employed.
29 The reaction time for the contact of the reactant 3~ with the metal oxygen composition in the present invention 31 may be selected from a broad`operab}e range which may 32 vary from about 0.5 to about 10, preferably from about 33 1 to about 8, and most preferably from about 1 to about 34 4 seconds. The reaction time maY be defined as the length of time in seconds which the reactant gasses 36 measured under reaction conditions are in ~ontact with 37 the inorganic metal oxygen com~osition in the reactor.
. .
.
' ~z~
- 30 -1 The sele¢ted reaction time may vary depending upon the re-2 actio~ temperature and the de~ired toluene conversion level.
3 At higher temperatures and lower toluene conversion levels, 4 shorter contact times are required.
In addition to the toluene and/or toluene deriva-6 tives, other inert substances such as nitrogen, helium and 7 the like may be present inthe reactor~ Such inert materials 8 may be introduced to the process alone or may be combined 9 with ~he other materials as feed.
Water has been found to play a signi~icant role 11 in the dehydrocoupling process. ~igher toluene conversions 12 and selectivities to desired products can be obtained by 13 including water, preferably in the form of steam,in the 14 t~luene feed stream. However, care should be taken to avoid introducing too much steam, since steam cracking of 16 tha toluene can occur thereby yie}ding a product effluent 17 having an undesirably hi~gh benzene and C02 by-product con-18 tent. Thus,~ suitable steam to hydrocarbon mole ratios~ in 19 the feed stream are selected in conjunction with a p~rticu-2n lar metal oxygen composition to effect improved selectivi-21 tie~s to stilbene and diphenylethane, and toluene conversions 22 relative to the absence of steam. Accordingly, while any 23 effe~tive steam-to-hydrocarbon mole ratios may be employed 24 it is contemplated that such mole ratios constitute typically from about 0:1 to about 10:1, preferably 1:1 to about 5:1, 2~6 and most preferably 2:1 to about 4:1.
27 ~he metal oxygen composition may be employed in 28 the present invention alone or in association with a support 29 or carrier. The use of a support may be particularly ad-vantageous to further improve attrition resistance during 3-1 reactor charging and/ox under reaction conditions encoun-32 tered during the course of the re~ction process. Suitable 33 su~ports, typically employed in sphe~rical, tablet, or cylin-34 drical form, for the composition are, for example, siL-ca, aIumina, silica-alumina, metal aluminates such as magnesium 36 alumina~e, calcium aluminate, titania, zirconia, acti~ated 37 car~on, zeolites~ a~d the li~e.
,~
., ~ : .... . ,: .
. . .
.. .... ..
. ::. .
4~
3 At higher temperatures and lower toluene conversion levels, 4 shorter contact times are required.
In addition to the toluene and/or toluene deriva-6 tives, other inert substances such as nitrogen, helium and 7 the like may be present inthe reactor~ Such inert materials 8 may be introduced to the process alone or may be combined 9 with ~he other materials as feed.
Water has been found to play a signi~icant role 11 in the dehydrocoupling process. ~igher toluene conversions 12 and selectivities to desired products can be obtained by 13 including water, preferably in the form of steam,in the 14 t~luene feed stream. However, care should be taken to avoid introducing too much steam, since steam cracking of 16 tha toluene can occur thereby yie}ding a product effluent 17 having an undesirably hi~gh benzene and C02 by-product con-18 tent. Thus,~ suitable steam to hydrocarbon mole ratios~ in 19 the feed stream are selected in conjunction with a p~rticu-2n lar metal oxygen composition to effect improved selectivi-21 tie~s to stilbene and diphenylethane, and toluene conversions 22 relative to the absence of steam. Accordingly, while any 23 effe~tive steam-to-hydrocarbon mole ratios may be employed 24 it is contemplated that such mole ratios constitute typically from about 0:1 to about 10:1, preferably 1:1 to about 5:1, 2~6 and most preferably 2:1 to about 4:1.
27 ~he metal oxygen composition may be employed in 28 the present invention alone or in association with a support 29 or carrier. The use of a support may be particularly ad-vantageous to further improve attrition resistance during 3-1 reactor charging and/ox under reaction conditions encoun-32 tered during the course of the re~ction process. Suitable 33 su~ports, typically employed in sphe~rical, tablet, or cylin-34 drical form, for the composition are, for example, siL-ca, aIumina, silica-alumina, metal aluminates such as magnesium 36 alumina~e, calcium aluminate, titania, zirconia, acti~ated 37 car~on, zeolites~ a~d the li~e.
,~
., ~ : .... . ,: .
. . .
.. .... ..
. ::. .
4~
- 31 -1 As noted hereinabove, the dehydrocoupling reaction 2 may be conducted in the presence or absence of added 3 free oxygen. When oxygen is not added to the system, 4 that is, the reaction is conducted in the stoichiometric mode of operatïon; the oxygen required for the reaction 6 is provided by the metal oxygen composition which enters 7 into the reaction and is consequently reduced (or, in 8 actual practice, partially reduced~ during the course 9 of the reaction. This necessitates rPgeneration or reoxida-tion which can be easily effected by heating the material 11 in an oxygen containin~ gas such as air or oxygen at reac-12 tion temperatures reci~ed herein, e.g. prefera~ly from about 13 500C ~o about 600C for a period of time ranging fromabout 14 5 minutes to about 2 hours. In a semi-continuous operation, regeneration can be effected by periodic interruption 16 of the reaction for reoxidation of the reduced composition, 17 that is, periods of reaction are ~ycled with perlodq 18 of regeneration. Operation, howeqer, can be on a continuou~
19 basis whereby a portion of the metal oxygen composition can be continuously or intermittently removed, reoxidized 2~ and the reoxidized material can ~hereafter be continuously 22 or intermittently returned to the reaction. The latter 23 method is particularly adapted to operations in which 24 the metal oxygen composition is fed in the form of a fluidized bed or a moving bed system.
26 The~metai oxygen compositlon typically can be oper-27 ated~at conversions of from about 1 to about 40~ a~d selectivi-28i ties to stilbene and bibenzyl o~ from aDOUt 10 to abou~ 95%, ior ~9 periods of ~rom about 5 to ahout 40 minutes, preferably from about l0 to about 30 minutes, and most preferably from 31 abou~ 20 to about 30 minutes before having to be regener-
19 basis whereby a portion of the metal oxygen composition can be continuously or intermittently removed, reoxidized 2~ and the reoxidized material can ~hereafter be continuously 22 or intermittently returned to the reaction. The latter 23 method is particularly adapted to operations in which 24 the metal oxygen composition is fed in the form of a fluidized bed or a moving bed system.
26 The~metai oxygen compositlon typically can be oper-27 ated~at conversions of from about 1 to about 40~ a~d selectivi-28i ties to stilbene and bibenzyl o~ from aDOUt 10 to abou~ 95%, ior ~9 periods of ~rom about 5 to ahout 40 minutes, preferably from about l0 to about 30 minutes, and most preferably from 31 abou~ 20 to about 30 minutes before having to be regener-
32 ate~. ~
j3 When oxygen is employed as a reactant, the reac-34 tion may be conducted in~either a catalytic mode or opera-tion or a combined catalytic/stoichiometric mode of opera-36 tion, depending on the amount of oxygen supplied. In the catalytie mode of o~eratiQn, oxysen is sup~lied in an amount 38 su~icie~nt f~r the dehydrocou~ling rea¢tion. The actu~l am~u~t : ; ~
`' ~ `, ' ;, .: ' '`
;;. :; . .. .
~;224~
1 of oxygen supplied m2y be specified as a function o the 2 amount of the toluene o~ other suitable hydrocarbon com-3 ponent. On this basis the amount of oxygen supplied is 4 ordinarily selected to provide a hydrocarbon-to-oxygen mole ratio from about 0.2:1 to about 10:1, preferably from 6 about 0.5:1 to about 5:1, and most preferably from about 7 0.8:1 to about 2:1.
8 In the combined catalytic/stoichiometric mode 9 of operation, the amount of oxygen supplied as a reactant is not sufficient for the dehydrocoupling reaction, thereby 11 requiring an additional source of oxygen. The required 12 additional oxygen will be supplied by the metal oxygen 13 compogition, that is, the composition will serve as the 14 additional source of oxygen. As a result, the metal oxygen composition enters into the reaction a~d is conse-16 quently reduced during the course of the reaction. This 17 necessitates regeneration or reoxidation of the reduced 18 composition which can be easily effected as described 19 hereinabove for the stoichiometric mode of operation.
In either mode of operation employing added oxygen 21 as a reaatant, w~ether catalytic or combined catalvtic~
22 stoichiometric, the added free oxygen may be supplied 23 either as oxygen or an oxygen~containing gas such as 24 air or oxygen-enriched air.
The dehydrocoupled toluene products, stilbene 26 and bibenzyl, may be recovered and purified by any appropri-27 ate method and means known to the art. As noted previously, 2~ stil~ene, of course, is the preferred product. If desired, 29 bibenzyl can subsequently be converted to stilbene also 30 b~ ~ethods well known In the art or recycle~ back to the 31 toluene coupling reactor.
3-2 The followin~ examples are given as specific
j3 When oxygen is employed as a reactant, the reac-34 tion may be conducted in~either a catalytic mode or opera-tion or a combined catalytic/stoichiometric mode of opera-36 tion, depending on the amount of oxygen supplied. In the catalytie mode of o~eratiQn, oxysen is sup~lied in an amount 38 su~icie~nt f~r the dehydrocou~ling rea¢tion. The actu~l am~u~t : ; ~
`' ~ `, ' ;, .: ' '`
;;. :; . .. .
~;224~
1 of oxygen supplied m2y be specified as a function o the 2 amount of the toluene o~ other suitable hydrocarbon com-3 ponent. On this basis the amount of oxygen supplied is 4 ordinarily selected to provide a hydrocarbon-to-oxygen mole ratio from about 0.2:1 to about 10:1, preferably from 6 about 0.5:1 to about 5:1, and most preferably from about 7 0.8:1 to about 2:1.
8 In the combined catalytic/stoichiometric mode 9 of operation, the amount of oxygen supplied as a reactant is not sufficient for the dehydrocoupling reaction, thereby 11 requiring an additional source of oxygen. The required 12 additional oxygen will be supplied by the metal oxygen 13 compogition, that is, the composition will serve as the 14 additional source of oxygen. As a result, the metal oxygen composition enters into the reaction a~d is conse-16 quently reduced during the course of the reaction. This 17 necessitates regeneration or reoxidation of the reduced 18 composition which can be easily effected as described 19 hereinabove for the stoichiometric mode of operation.
In either mode of operation employing added oxygen 21 as a reaatant, w~ether catalytic or combined catalvtic~
22 stoichiometric, the added free oxygen may be supplied 23 either as oxygen or an oxygen~containing gas such as 24 air or oxygen-enriched air.
The dehydrocoupled toluene products, stilbene 26 and bibenzyl, may be recovered and purified by any appropri-27 ate method and means known to the art. As noted previously, 2~ stil~ene, of course, is the preferred product. If desired, 29 bibenzyl can subsequently be converted to stilbene also 30 b~ ~ethods well known In the art or recycle~ back to the 31 toluene coupling reactor.
3-2 The followin~ examples are given as specific
33 illustrations of the claimed invention. It should be un~er-
34 stood, however, that the invention is not limited to the
35 specific details set forth in the examples. All parts and
36 percentages in the examples as well as in the remainder of
37 the q~ecification are by wei~ht u~less otherwise sipecified.
, ' : ,:~
`.
~4~9 l Futhermore, while the following examples may be written in 2 the present tense it is to be understood that such examples 3 represent-wor~ actually per~ormed.
4 In the following examples, selectiYity and con-version are calculated as follows:
6 . gms. of cArbon of desired product 96 selectlvity ~ x 100 ~ms~ of car~on o feed % conve~sion , gms- of carbon in feed reacted x 100 ~ gms. of carbo~ in feed 9 All product analysis is conducted by gas chroma-tography 11 While the present in~ention i9 described in con-12 junction with the dehydrocoupling Or toluene, it will be 13 understood by thase sXilled in the art that methyl substi-14 tuted derivatives of toluene can also be employed as the hydrocarbon feed s~urce. Thus, the hydrocarbon feed source 16 which can be employed in the process of the present inven-17 tion comprises at least~o~e compound represented by he I8 5tructural formula ~
~ (C~3)n ~XI) 21 wherein n is a number from 1 to 6, preferably l to 4, most 22 preferably l to about 3 (e.~. 2). Representative examples 23 of such hydrocarbon feed sources in addition to toluene, 24 include, o-xylene, m-xylene, p-xylene, 1,3,5-trimethyl-benzene, 1,2,4-trimethylbenzene, 1,2,4,6-tetramethylbenzene, 26 hexamethylbenzene, pentamethylbenzene and the like. The 27 most preferred toluene derivatives are the xylenes.
28 Generally, when a hydrocarbon feed source other 29 than toluene is employed the dehydrocoupled product will 3~ be the appro~riate methyl substituted stilbene or diphenyl 31 ethane products, e.g. the methyl groups in excess of 1 are 32 carrie~ along and rem~i~ une~ected by the dehydrocoupling 33 reactions.
34 The term "toluene~ derivative" is therefore de~ined herein to be at least one compound represented by formula 36 X~I w~herein n is betwee~ 2 and 6.
37 The followin~ examples illust~ate the per~orma~ce ", .~ , ..
. .
~',',. '', -: ~ , `
:. ~
1 of the metal oxygen composition when operating in either 2 the stoichiometric mode, the catalytic mode or combined 3 catalytic/stoichiometric mode. As described above, when 4 operating in the stoichiometric mode, the metal oxygen composition is allowed to contact with toluene, steam 6 and nitrogen for a certain length of time during which the 7 oxygen of the metal oxygen composition depletes due to it~
8 stoichiometric reaction with toluene in the coupling proces~.
g The mstal oxygen composition, therefore, would need to be regenerated in air (or oxygen) in-situ cyclically between 11 tests when employed commercially in this mode.-Consequently, 12 some of the runs pro~ided herein illustrate the per~ormance 13 of the metal oxygen composition ater regeneration.
I4 To illustrate the performance of the metal oxygen lS com~osition when operating in the catalytic mode, said 16 composition is allowed to contact continually with toluene, 17 steam and air. Sufficient air is supplied in the feed to 18 maintai~ the oxygen content of the composition needed for 19 efficient dehydrogenation. Consequently, the metal oxygen composition actg as a catalyst in the toluene dehydrocoupl-21 ing process and its cyclic regeneration in air is no longer 22 necessary.
23 Nhen reporting the data in Table 1, an asterisk 24 in the column reporting toluene conversion signifies the run is within the scope of the present invention.
27 A slurry is prepared by adding 58.3~ Sb2O3, 134.0g 28 PbO; and 23.3g Bi203 sequentially to 200 ml o~ iso~utanol 29 in a suitable container at room temperature. The resuIting slurry is heated, stirred and refluxed at 108C ror 24 31 hours to remo~e water as it is formed. Durlng the reflux, 32 the color of the slurry changes from light yellow to orange.
33 The mix~ure is then cooled to room temperature (about 25C) 34 filtered, and the filter cake air dried at rOQm temperature for about l6 hours. The resulting air dried ~ilter cake is 36 then further drisd in air at 150C for 48 hours in an oven.
37 The resulting precursor composition is then calcined in air
, ' : ,:~
`.
~4~9 l Futhermore, while the following examples may be written in 2 the present tense it is to be understood that such examples 3 represent-wor~ actually per~ormed.
4 In the following examples, selectiYity and con-version are calculated as follows:
6 . gms. of cArbon of desired product 96 selectlvity ~ x 100 ~ms~ of car~on o feed % conve~sion , gms- of carbon in feed reacted x 100 ~ gms. of carbo~ in feed 9 All product analysis is conducted by gas chroma-tography 11 While the present in~ention i9 described in con-12 junction with the dehydrocoupling Or toluene, it will be 13 understood by thase sXilled in the art that methyl substi-14 tuted derivatives of toluene can also be employed as the hydrocarbon feed s~urce. Thus, the hydrocarbon feed source 16 which can be employed in the process of the present inven-17 tion comprises at least~o~e compound represented by he I8 5tructural formula ~
~ (C~3)n ~XI) 21 wherein n is a number from 1 to 6, preferably l to 4, most 22 preferably l to about 3 (e.~. 2). Representative examples 23 of such hydrocarbon feed sources in addition to toluene, 24 include, o-xylene, m-xylene, p-xylene, 1,3,5-trimethyl-benzene, 1,2,4-trimethylbenzene, 1,2,4,6-tetramethylbenzene, 26 hexamethylbenzene, pentamethylbenzene and the like. The 27 most preferred toluene derivatives are the xylenes.
28 Generally, when a hydrocarbon feed source other 29 than toluene is employed the dehydrocoupled product will 3~ be the appro~riate methyl substituted stilbene or diphenyl 31 ethane products, e.g. the methyl groups in excess of 1 are 32 carrie~ along and rem~i~ une~ected by the dehydrocoupling 33 reactions.
34 The term "toluene~ derivative" is therefore de~ined herein to be at least one compound represented by formula 36 X~I w~herein n is betwee~ 2 and 6.
37 The followin~ examples illust~ate the per~orma~ce ", .~ , ..
. .
~',',. '', -: ~ , `
:. ~
1 of the metal oxygen composition when operating in either 2 the stoichiometric mode, the catalytic mode or combined 3 catalytic/stoichiometric mode. As described above, when 4 operating in the stoichiometric mode, the metal oxygen composition is allowed to contact with toluene, steam 6 and nitrogen for a certain length of time during which the 7 oxygen of the metal oxygen composition depletes due to it~
8 stoichiometric reaction with toluene in the coupling proces~.
g The mstal oxygen composition, therefore, would need to be regenerated in air (or oxygen) in-situ cyclically between 11 tests when employed commercially in this mode.-Consequently, 12 some of the runs pro~ided herein illustrate the per~ormance 13 of the metal oxygen composition ater regeneration.
I4 To illustrate the performance of the metal oxygen lS com~osition when operating in the catalytic mode, said 16 composition is allowed to contact continually with toluene, 17 steam and air. Sufficient air is supplied in the feed to 18 maintai~ the oxygen content of the composition needed for 19 efficient dehydrogenation. Consequently, the metal oxygen composition actg as a catalyst in the toluene dehydrocoupl-21 ing process and its cyclic regeneration in air is no longer 22 necessary.
23 Nhen reporting the data in Table 1, an asterisk 24 in the column reporting toluene conversion signifies the run is within the scope of the present invention.
27 A slurry is prepared by adding 58.3~ Sb2O3, 134.0g 28 PbO; and 23.3g Bi203 sequentially to 200 ml o~ iso~utanol 29 in a suitable container at room temperature. The resuIting slurry is heated, stirred and refluxed at 108C ror 24 31 hours to remo~e water as it is formed. Durlng the reflux, 32 the color of the slurry changes from light yellow to orange.
33 The mix~ure is then cooled to room temperature (about 25C) 34 filtered, and the filter cake air dried at rOQm temperature for about l6 hours. The resulting air dried ~ilter cake is 36 then further drisd in air at 150C for 48 hours in an oven.
37 The resulting precursor composition is then calcined in air
38 at 900 for 2 hours and sleved to a -12+20 mQsh size (U.S.
39 Sie~e Series).
~ .
, , ~
~z~ 9 1 Forty grams of the sieved metal oxygen composi-2 tion are then placed in a 20 cc stainless steel U-shaped 3 reactor tube (OoD~ 3~8n, I.D. 5/16") immersed in a sand 4 bath to supply heat to the reactor. The inlet portion of the reactor tube is horizontal, located in the sand bath, 6 and of sufficient length to vaporize the li~uid toluene 7 and any water before it is introduced into the reactor 8 portion. The empty heated horizon~al inlet tube therefore 9 functions as a preheating zone. The composition is then heated in the reactor tube at 450C while passing air ll through the tube at a flow rate sufficient to achleve a 12 contact time of about 2 sec., for a period o~ about 16 13 hours to activate the composition. During activation, re-14 sidual moisture and volatile impurities are removed from the metal oxygen composition and the metal oxidation states 16 are elevated to impart cptimum activity. A liquid mixture 17 con~aining toluene, ~2~ and ~2 in a I:2:1 molar ratio is 18 then introduced into the preheating zone of the reactor I9 tube whereupon the toluene and water are vaporized. The gaseous mixture is then passed through the remainder o~
21 the reacto~ tube.
22 The flow rate through the reactor is sufficient 23 to achieve a contact time with the metal oxygen composition 24 o 4.2 seconds. The temperature of the reactor during the 25 contact is 565C. The gaseous mixture is allowed to flow ~6 through the reactor for a period deRignated by "on-stream 27 time" before product samples are removed for ~nalysis.
28 Several runs are conducted in series and in each run 29 reactor effluent is scrubbed for 30 minutes with an ace-tone trap at 0C. The metal oxygen composition i9 not 31 regenerated between each run. Samples for analysis are 32 removed fr~m the reactor ef~luent after 0.5, 1.0, and 2.0 33 hours of on-stream time.
34 The results are ;summari ed in Table 1 (runs 3-5) sele~tivity to stilbene plus diphenyl ethane (i.e., DPE) 36 ran~es ~rom 81.7~ to 84.8~ at toluene conversions of 13.6%
37 and 16.2% resPectively.
, .
.
~ , ..
. ~ ;
4~
2 Example 1 i~ repeat~d with the exception that 3 the contact time between the feed gas mixture and the metal 4 oxygen composition is reduced to 3.5 seconds, and the feed gas contains a small amount of air sufficient to provide ~
6 molar ratio between toluene-stream-~2 and air of 1:2sl;0.87 7 respectively. This example is therefore conducted in the 8 combined catalytic/stoichiometric mode. On-stream time 9 before removing a product sample for analysis is two hours.
The results are summari~ed at Table 1, (run 9). Selectivity 11 to stilbene plus DPE is 72.2~ at a toluene conversion of 12 10.3~.
13 ~XAMPLE 3 14 A metal oxygen composition is prepared in accordance with Example 1 (including drying, calcination and activation 16 conditions), and tested in accordance with the same with the 17 exception that before each recovery run is made, the metal 18 oxygen composition is regeneraged at reaction temperature~
19 (560-565C~ by passin~ air through the reactor for 30 minutes at about 200 cc per minute. The re3ults are summarized ~i at Table l,truns 11 and 12). Selectivity to stilbene plus 22 DPE range~s from 90.4% to 89.7~ at respective toluene con-23 versions of L7.3% and 15.6% with respective on-stream times 24 o~ 0.5 in 1 hour.
26 ~he me-tal oxygen composition employed in this 27 example is prepared in aocordance with the proc@dure de-28 scribed in Example 1 (including drying, and activation) with 29 the exception tha~ the composition is caIcined at 600C for 2 hours. 9.0g of the metal oxysen composition are evaluated 31 in a 5cc micnsreactor immersed in a heated salt bath at553C.
32 The same feed stream employed in Example 1 is used and the 33 contact time is control}ed ~o be about 1.7 seconds. The 34 catalyst is regenerated in air at 553C for 0.5 hours prior to each recovery run. The~ reactor effluent is scrubbed in dual traps at ice temperature (OC). Samples of reactor 37 ef1ue~nt are removed~ after on-stream times of 0.5, 1.0, and .
, ' :
., '. ~ `' " '`' ,-:
: - :
- .
~29~
1 2.0 hours for analysis. The reRults are summa~ized at 2 Table 1, (runs 15-18). Selectivity to stilbene plus DPE
3 ranges from 88.8 to 91.0~ at toluene conversions at from 4 18.4 to 17.5% respectively.
-6 The metal oxygen com~osition for this example is 7 prepared in accordance with the procedures of Example 4 with 8 the exception that the precursor composition after drying 9 in accordance with Example 1 is placed in a ball mill jax and ball-milled for four hours. The ball mill precursor 11 composition is then calcined at 6~0C for two hours in an 12 oven and sieved to a mesh size of -20+40 (U.S. Series).
13 ~all-milliny is employed to improve the uniformity of the 14 metal oxygen precursor composition. The metal oxygen com-position is activated in accordance with Example 1, and 16 tested in accoraance with the procedures of Example 4. On-17 stream times are varied from 5 to 20 minutes and regenera-18 tion in air at 553C for 0.5 hours,at 2 sec. contact time 19 i~ conducted before each recovery run. The results are 20 summarized at Table 1, runs 21 to 24. Selectivity to stil-21 bene plus DPE ranges from 85.1 to 86.9% a~ respective 22 toluene c~nversions of 32.8 and 20.8%.
23 EX~UPLE 6 24 The metal oxygen composition prepared and tested in accordance with Example 5 tincluding drying, activation, 26 and regeneration) using a feed stream compri ing toluene, 27 water and nitrogen at a molar ratio of 1:3:1 and 2 seconds 28 contact time. Two runs are conducted with on-stream times 29 of 20 minutes for each run. The results are summarized at Table 1, lruns 25-2~). The average selectivity to stilbene 31 plus DPE of these runs- is 84.1~ and an average toluene con-32 version of 26.1%. Comparing these results with selectivity 33 and con~ersion obtained in run 24, it can be seen that the 34 use of additional water in the feed stream improves toluene conversion substantially from 20.8% to 26.15% while the 36 stilbene plus DPE selec~ivity i5 reduce~ only slightly fro~
37 86.9% to 84.1%.
:, , .
, ~lZ2~
1 EX~PLE_7 2 Par~ A
3 ln this example, attrition resistance of the 4 metal oxygen composi~ion is improved by impregnating the same with cesium hydroxide while maintaining stilbene 6 selectivity a~ moderately high levels. More specifically, 7 the metal oxygen precursor prepared in accordance with 8 Example 1 after being dried but uncalcined is impregnated 9 with cesium hydroxide in the following manner. In a l-liter beaker, 2.56g of CsOH is added to 250 cc of ~2 11 and the mixture is stirred~to yield a uniform solution.
12 A slurry is made by adding to this CsOH solution, 150 g 13 of the dried metal oxide precursor. The slurry is constantly 14 stirred while it is heated for about five ho~rs and finally evaporated to a thick paste. The paste is dried in the 16 oven at 150C for about 48 hours. The resulting metal 17 oxygen composition slurry is boiled down to a paste and 18 dried at 150C for about 48 hours. The dry composition 19 is then calcined in air at 600C ~or two hours. The re-sulting calcined composition pos~esses the empirical formula:
21 ~90,o3~ Pbl.0' S~0.67' Bio.l7~ O4 5~ and a bulk density of 22 2.02 g/cc.
23 A portion of this composition is then tested for 24 attrition resistance in the following manner:
A~ter sieving the composition to a mesh size of 26 -20+40 (U.S. Series), 10 g of the composition are dropped 27 through a 10 ft. pipe of 1/2" I.D. onto a hzrd surface. The 28 particles are then sieved through a 20 mesh screen (U.S.
29 Series) and the particles los~ throu~h the screen is between about 2 to 5~, based on the total initial weight.
31 The remainder of the metal oxygen composition not 32 tested for attrition resistance is then sieved to a mesh 33 size of -20+40 (U.5. Sieve~ Series).
34 Part ~
10.1 g of the -20+40 sie~ed metal oxygen composi-3~ tion is then placed into the reactor employed in Example 1, 37 activated for 15 hrs. in air at 450C, 2 sec. contact ti~e .
"
... .
.:
.- .~ , .
~2Z431 ~39 1 and then contacted *ith a vaporized feed mixture of toluene:
2 ~2O:N2 (1:2:1 mo}ar ratio) which is passed thr~ugh the re-3 actor tube at 550C and 2 second contact time. Before 4 recovering product for analysis, the composition is regener-at~d in air in accordance with Example 4. The reaction 6 conditions and results are summarized at Table 1, run 41.
7 The products are scrubbed in acetone traps at ice tempera-8 ture and non-condensibles are collected in a sampling tube.
9 The products are analyzed by means of gas chromatography.
The same metal oxygen composition of run 41 after 11 regeneration and sample testing,are tested again after an 12 additional on-stream time of 20 minutes at 512C reaction 13 temperature, 2 second contact time, using a vaporized feed 14 mlxture of toluene:H20:N2 (1:4:1 molar ratio). Before pro^
duct recovery and analysis, the composition is regeneratad 16 in ~ccordance with Example 4. The reaction conditions and 17 results are summarized at Table 1, run 42.
18 The above procedure of run 42 is repeated again 19 at 522C reaction temperature, 2 second contact time,with a vaporized feed mixture of toluene:H2O:N2 (1:5:1 molar 21 ratio). The reaction condi*ions, and results are summarized 22 at Table 1, run 43. As may be seen from the results of runs 23 41 to 43, increasing the amount of steam in the feed gas 24 results in increased selectivity to desired products with only slight decreases in conversion upon regenexation.
26 Part C
27 To illustrate the performance of the metal oxyyen 28 composition when operating in the catalytic mode, 10.1 g 29 of the used and regene~aged metal oxygen composition from run 43~, Part B is contacted with a vaporized feed mixture 31 of toluene:~2O:air (1:4:1 molar ratio) which is continuously 32 passed through the tube at a reaction temperature of 550C
33 and 2 second contact time until a steady state is attained, 34 i.e., about 3 hours. Product is then recovexed without regeneration by the aforedescribed scrubbing procedure for 36 an additional 20 minutes and analyzed. The reaction is then 37 allowe~ to proceed until the to~al on-stream tim~ is about ~,:
:`
' . ,. '' :~LZ~4
~ .
, , ~
~z~ 9 1 Forty grams of the sieved metal oxygen composi-2 tion are then placed in a 20 cc stainless steel U-shaped 3 reactor tube (OoD~ 3~8n, I.D. 5/16") immersed in a sand 4 bath to supply heat to the reactor. The inlet portion of the reactor tube is horizontal, located in the sand bath, 6 and of sufficient length to vaporize the li~uid toluene 7 and any water before it is introduced into the reactor 8 portion. The empty heated horizon~al inlet tube therefore 9 functions as a preheating zone. The composition is then heated in the reactor tube at 450C while passing air ll through the tube at a flow rate sufficient to achleve a 12 contact time of about 2 sec., for a period o~ about 16 13 hours to activate the composition. During activation, re-14 sidual moisture and volatile impurities are removed from the metal oxygen composition and the metal oxidation states 16 are elevated to impart cptimum activity. A liquid mixture 17 con~aining toluene, ~2~ and ~2 in a I:2:1 molar ratio is 18 then introduced into the preheating zone of the reactor I9 tube whereupon the toluene and water are vaporized. The gaseous mixture is then passed through the remainder o~
21 the reacto~ tube.
22 The flow rate through the reactor is sufficient 23 to achieve a contact time with the metal oxygen composition 24 o 4.2 seconds. The temperature of the reactor during the 25 contact is 565C. The gaseous mixture is allowed to flow ~6 through the reactor for a period deRignated by "on-stream 27 time" before product samples are removed for ~nalysis.
28 Several runs are conducted in series and in each run 29 reactor effluent is scrubbed for 30 minutes with an ace-tone trap at 0C. The metal oxygen composition i9 not 31 regenerated between each run. Samples for analysis are 32 removed fr~m the reactor ef~luent after 0.5, 1.0, and 2.0 33 hours of on-stream time.
34 The results are ;summari ed in Table 1 (runs 3-5) sele~tivity to stilbene plus diphenyl ethane (i.e., DPE) 36 ran~es ~rom 81.7~ to 84.8~ at toluene conversions of 13.6%
37 and 16.2% resPectively.
, .
.
~ , ..
. ~ ;
4~
2 Example 1 i~ repeat~d with the exception that 3 the contact time between the feed gas mixture and the metal 4 oxygen composition is reduced to 3.5 seconds, and the feed gas contains a small amount of air sufficient to provide ~
6 molar ratio between toluene-stream-~2 and air of 1:2sl;0.87 7 respectively. This example is therefore conducted in the 8 combined catalytic/stoichiometric mode. On-stream time 9 before removing a product sample for analysis is two hours.
The results are summari~ed at Table 1, (run 9). Selectivity 11 to stilbene plus DPE is 72.2~ at a toluene conversion of 12 10.3~.
13 ~XAMPLE 3 14 A metal oxygen composition is prepared in accordance with Example 1 (including drying, calcination and activation 16 conditions), and tested in accordance with the same with the 17 exception that before each recovery run is made, the metal 18 oxygen composition is regeneraged at reaction temperature~
19 (560-565C~ by passin~ air through the reactor for 30 minutes at about 200 cc per minute. The re3ults are summarized ~i at Table l,truns 11 and 12). Selectivity to stilbene plus 22 DPE range~s from 90.4% to 89.7~ at respective toluene con-23 versions of L7.3% and 15.6% with respective on-stream times 24 o~ 0.5 in 1 hour.
26 ~he me-tal oxygen composition employed in this 27 example is prepared in aocordance with the proc@dure de-28 scribed in Example 1 (including drying, and activation) with 29 the exception tha~ the composition is caIcined at 600C for 2 hours. 9.0g of the metal oxysen composition are evaluated 31 in a 5cc micnsreactor immersed in a heated salt bath at553C.
32 The same feed stream employed in Example 1 is used and the 33 contact time is control}ed ~o be about 1.7 seconds. The 34 catalyst is regenerated in air at 553C for 0.5 hours prior to each recovery run. The~ reactor effluent is scrubbed in dual traps at ice temperature (OC). Samples of reactor 37 ef1ue~nt are removed~ after on-stream times of 0.5, 1.0, and .
, ' :
., '. ~ `' " '`' ,-:
: - :
- .
~29~
1 2.0 hours for analysis. The reRults are summa~ized at 2 Table 1, (runs 15-18). Selectivity to stilbene plus DPE
3 ranges from 88.8 to 91.0~ at toluene conversions at from 4 18.4 to 17.5% respectively.
-6 The metal oxygen com~osition for this example is 7 prepared in accordance with the procedures of Example 4 with 8 the exception that the precursor composition after drying 9 in accordance with Example 1 is placed in a ball mill jax and ball-milled for four hours. The ball mill precursor 11 composition is then calcined at 6~0C for two hours in an 12 oven and sieved to a mesh size of -20+40 (U.S. Series).
13 ~all-milliny is employed to improve the uniformity of the 14 metal oxygen precursor composition. The metal oxygen com-position is activated in accordance with Example 1, and 16 tested in accoraance with the procedures of Example 4. On-17 stream times are varied from 5 to 20 minutes and regenera-18 tion in air at 553C for 0.5 hours,at 2 sec. contact time 19 i~ conducted before each recovery run. The results are 20 summarized at Table 1, runs 21 to 24. Selectivity to stil-21 bene plus DPE ranges from 85.1 to 86.9% a~ respective 22 toluene c~nversions of 32.8 and 20.8%.
23 EX~UPLE 6 24 The metal oxygen composition prepared and tested in accordance with Example 5 tincluding drying, activation, 26 and regeneration) using a feed stream compri ing toluene, 27 water and nitrogen at a molar ratio of 1:3:1 and 2 seconds 28 contact time. Two runs are conducted with on-stream times 29 of 20 minutes for each run. The results are summarized at Table 1, lruns 25-2~). The average selectivity to stilbene 31 plus DPE of these runs- is 84.1~ and an average toluene con-32 version of 26.1%. Comparing these results with selectivity 33 and con~ersion obtained in run 24, it can be seen that the 34 use of additional water in the feed stream improves toluene conversion substantially from 20.8% to 26.15% while the 36 stilbene plus DPE selec~ivity i5 reduce~ only slightly fro~
37 86.9% to 84.1%.
:, , .
, ~lZ2~
1 EX~PLE_7 2 Par~ A
3 ln this example, attrition resistance of the 4 metal oxygen composi~ion is improved by impregnating the same with cesium hydroxide while maintaining stilbene 6 selectivity a~ moderately high levels. More specifically, 7 the metal oxygen precursor prepared in accordance with 8 Example 1 after being dried but uncalcined is impregnated 9 with cesium hydroxide in the following manner. In a l-liter beaker, 2.56g of CsOH is added to 250 cc of ~2 11 and the mixture is stirred~to yield a uniform solution.
12 A slurry is made by adding to this CsOH solution, 150 g 13 of the dried metal oxide precursor. The slurry is constantly 14 stirred while it is heated for about five ho~rs and finally evaporated to a thick paste. The paste is dried in the 16 oven at 150C for about 48 hours. The resulting metal 17 oxygen composition slurry is boiled down to a paste and 18 dried at 150C for about 48 hours. The dry composition 19 is then calcined in air at 600C ~or two hours. The re-sulting calcined composition pos~esses the empirical formula:
21 ~90,o3~ Pbl.0' S~0.67' Bio.l7~ O4 5~ and a bulk density of 22 2.02 g/cc.
23 A portion of this composition is then tested for 24 attrition resistance in the following manner:
A~ter sieving the composition to a mesh size of 26 -20+40 (U.S. Series), 10 g of the composition are dropped 27 through a 10 ft. pipe of 1/2" I.D. onto a hzrd surface. The 28 particles are then sieved through a 20 mesh screen (U.S.
29 Series) and the particles los~ throu~h the screen is between about 2 to 5~, based on the total initial weight.
31 The remainder of the metal oxygen composition not 32 tested for attrition resistance is then sieved to a mesh 33 size of -20+40 (U.5. Sieve~ Series).
34 Part ~
10.1 g of the -20+40 sie~ed metal oxygen composi-3~ tion is then placed into the reactor employed in Example 1, 37 activated for 15 hrs. in air at 450C, 2 sec. contact ti~e .
"
... .
.:
.- .~ , .
~2Z431 ~39 1 and then contacted *ith a vaporized feed mixture of toluene:
2 ~2O:N2 (1:2:1 mo}ar ratio) which is passed thr~ugh the re-3 actor tube at 550C and 2 second contact time. Before 4 recovering product for analysis, the composition is regener-at~d in air in accordance with Example 4. The reaction 6 conditions and results are summarized at Table 1, run 41.
7 The products are scrubbed in acetone traps at ice tempera-8 ture and non-condensibles are collected in a sampling tube.
9 The products are analyzed by means of gas chromatography.
The same metal oxygen composition of run 41 after 11 regeneration and sample testing,are tested again after an 12 additional on-stream time of 20 minutes at 512C reaction 13 temperature, 2 second contact time, using a vaporized feed 14 mlxture of toluene:H20:N2 (1:4:1 molar ratio). Before pro^
duct recovery and analysis, the composition is regeneratad 16 in ~ccordance with Example 4. The reaction conditions and 17 results are summarized at Table 1, run 42.
18 The above procedure of run 42 is repeated again 19 at 522C reaction temperature, 2 second contact time,with a vaporized feed mixture of toluene:H2O:N2 (1:5:1 molar 21 ratio). The reaction condi*ions, and results are summarized 22 at Table 1, run 43. As may be seen from the results of runs 23 41 to 43, increasing the amount of steam in the feed gas 24 results in increased selectivity to desired products with only slight decreases in conversion upon regenexation.
26 Part C
27 To illustrate the performance of the metal oxyyen 28 composition when operating in the catalytic mode, 10.1 g 29 of the used and regene~aged metal oxygen composition from run 43~, Part B is contacted with a vaporized feed mixture 31 of toluene:~2O:air (1:4:1 molar ratio) which is continuously 32 passed through the tube at a reaction temperature of 550C
33 and 2 second contact time until a steady state is attained, 34 i.e., about 3 hours. Product is then recovexed without regeneration by the aforedescribed scrubbing procedure for 36 an additional 20 minutes and analyzed. The reaction is then 37 allowe~ to proceed until the to~al on-stream tim~ is about ~,:
:`
' . ,. '' :~LZ~4
- 40 -1 9 hour5. At thi5 tLme, the product is recovered without 2 regeneration by the scrubbing technique and analyzed. The 3 reaction conditions and test results are summarized at 4 Table 1 runs 44 and 45 respectively.
As may be seen from the data of runs 44 and 45 6 while the conversion drops to some extent relative to the 7 cyclic mode, the com~ined stilbene and DPE selectivity re-8 mains high, i.e. about 80%.
The metal oxygen composition of this example 11 is prepared and tested in general acco~dance with the 12 procedures described in Example 1. However, in this 13 example 135.09 Bi2O3 and 94.5g ZnO are introduced into 14 and slurried with 500 cc of isobutanol. The resulting slurry is heated and refluxed at 107.5C for 20 hours.
16 The mixture i5 then cooled to a temperature of 25C, 17 filtered and the filter cake dried in an over at }10C for 1~ 24 hours. The dry precursor composition i5 then calcined 1~ at 400C ~or two hours and 800C for one hour in an oven.
2b The calcined composition i~ then crushed and sieved to 21 a ~ 20 mesh size (U.S. Series) and placed in a 20cc stain-22 less steel reac~or using a sand bath as a heat source. The 23 comDosition is then activated in air at 450C for 16 hr3.
24 'rhe ~ed mixture of toluene, H2O and N2 employed in ~xample 1 is then Passed throu~h the reactor which is maintained at 26 550C. Con~act time of the Seed gas with the metal oxygen 27 ¢omPosition is 4 seconds. The reactor effluent is scrubbed 28 in acetone for 30 minutes a~ter each run. Two runs are con-29 duc~ed and samples are removed immediately after start-up and after 0.5 hours of on-stream tLme for analysis. In 31 between each o these runs, the catalyst is regenerated in 32 air at a temperature of 550~ for a period of 0.5 hours.
33 Results are summarized at Table 1.(runs 27-28).
34 ~XAMPLES 9-12 A metal oxygen composition is prepared and tested 36 in accordance with Example 4. Such com~osition is use~ to 37 conduGt several runs at varying toluene:water:N2 molar ' `' ' ~ ' ` :
'' ' ' ` :' -` ~:
~LZ~4L31 ~39
As may be seen from the data of runs 44 and 45 6 while the conversion drops to some extent relative to the 7 cyclic mode, the com~ined stilbene and DPE selectivity re-8 mains high, i.e. about 80%.
The metal oxygen composition of this example 11 is prepared and tested in general acco~dance with the 12 procedures described in Example 1. However, in this 13 example 135.09 Bi2O3 and 94.5g ZnO are introduced into 14 and slurried with 500 cc of isobutanol. The resulting slurry is heated and refluxed at 107.5C for 20 hours.
16 The mixture i5 then cooled to a temperature of 25C, 17 filtered and the filter cake dried in an over at }10C for 1~ 24 hours. The dry precursor composition i5 then calcined 1~ at 400C ~or two hours and 800C for one hour in an oven.
2b The calcined composition i~ then crushed and sieved to 21 a ~ 20 mesh size (U.S. Series) and placed in a 20cc stain-22 less steel reac~or using a sand bath as a heat source. The 23 comDosition is then activated in air at 450C for 16 hr3.
24 'rhe ~ed mixture of toluene, H2O and N2 employed in ~xample 1 is then Passed throu~h the reactor which is maintained at 26 550C. Con~act time of the Seed gas with the metal oxygen 27 ¢omPosition is 4 seconds. The reactor effluent is scrubbed 28 in acetone for 30 minutes a~ter each run. Two runs are con-29 duc~ed and samples are removed immediately after start-up and after 0.5 hours of on-stream tLme for analysis. In 31 between each o these runs, the catalyst is regenerated in 32 air at a temperature of 550~ for a period of 0.5 hours.
33 Results are summarized at Table 1.(runs 27-28).
34 ~XAMPLES 9-12 A metal oxygen composition is prepared and tested 36 in accordance with Example 4. Such com~osition is use~ to 37 conduGt several runs at varying toluene:water:N2 molar ' `' ' ~ ' ` :
'' ' ' ` :' -` ~:
~LZ~4L31 ~39
- 41 -1 ratios. Thus, in Example 9 (runs 31-32), such ratio is 1:0:
2 1; in Example 10 (runs 33, 34, 36),1:1:1; in Example 11 3 (runs 37-38), 1:2:1: and in Exampla 12 (runs 39-40), 1:3:1.
4 The test conditions and results of Examples 9-12 are sum-S marized at Table 1 (runs 31-40). The on-stream time before 6 product analysis is taken for each of these runs is twenty 7 minutes. Except for run 35 of EY.amP1e 10, each of the runs 8 31 to 40 are conducted in the cyclic mode. Run 35, however, 9 is conducted in the catalytic mode using air in place of N2 but because of an obviously incorrect material balance, the 11 product~ were not properly recovere~ and the results had to 12 be ignored. All of runs 31 to 40 are conducted on the same 13 metal oxygen composition, and upon completion of each run 14 co~ducted in the cyclic mdde the composition is regenerated in air fQX 0.5 hours at 553C prior to sample recovery. As 16 may be seen rom the data of ~uns 31 to 34, and 36-40, in-17 creasing- tbe steam content substantially improves both the 18 selectivity to desired products and conversion of toluene.
19 The following comparative examples are intended to illustrate the difference in results obtainable by com-21 paring metal oxygen compositions prepared in accordance with 22 the aqueous procedures described in the prior art. U.S.
23 Patent No~. 4,091,044 and 4,254,293 are used to illustrate 24 the aqueous preparation.
COMPARATIVE EX~MPLE 1 26 Example 6 of U.S. Patent No. 4,091,04~ is repeated 27 using the~ same amaunts o Sb203, PbO, and ~i203 employed 28 in Example 1 (described above) with the exception that each 2;9 of these components are sequentially added to 250 ml of watsr. The resulting slurry is heated with constant stir-31 ring and boiled down to a paste, which is then dried in an 32 oYe~ at 110C for 24 hours. The dried product possesses a 33 light green color-. A p~rtion of the dried product is 3-4 calcined at 900C for 2 hours~ and the calcined catalyst sieved to -12+20 mesh sizè (U.S. Sieve Series) for evalua-36 tion. 20cc of the resulting mixed oxide composition are 37 evaluate~ in the 2Qcc stainless steel reactor tube of -: , :;, '`: ' ,:. :
~- ... ., ~ : - .
.~ ~: .: :
. ", ' ~
'~2Z9~
2 1; in Example 10 (runs 33, 34, 36),1:1:1; in Example 11 3 (runs 37-38), 1:2:1: and in Exampla 12 (runs 39-40), 1:3:1.
4 The test conditions and results of Examples 9-12 are sum-S marized at Table 1 (runs 31-40). The on-stream time before 6 product analysis is taken for each of these runs is twenty 7 minutes. Except for run 35 of EY.amP1e 10, each of the runs 8 31 to 40 are conducted in the cyclic mode. Run 35, however, 9 is conducted in the catalytic mode using air in place of N2 but because of an obviously incorrect material balance, the 11 product~ were not properly recovere~ and the results had to 12 be ignored. All of runs 31 to 40 are conducted on the same 13 metal oxygen composition, and upon completion of each run 14 co~ducted in the cyclic mdde the composition is regenerated in air fQX 0.5 hours at 553C prior to sample recovery. As 16 may be seen rom the data of ~uns 31 to 34, and 36-40, in-17 creasing- tbe steam content substantially improves both the 18 selectivity to desired products and conversion of toluene.
19 The following comparative examples are intended to illustrate the difference in results obtainable by com-21 paring metal oxygen compositions prepared in accordance with 22 the aqueous procedures described in the prior art. U.S.
23 Patent No~. 4,091,044 and 4,254,293 are used to illustrate 24 the aqueous preparation.
COMPARATIVE EX~MPLE 1 26 Example 6 of U.S. Patent No. 4,091,04~ is repeated 27 using the~ same amaunts o Sb203, PbO, and ~i203 employed 28 in Example 1 (described above) with the exception that each 2;9 of these components are sequentially added to 250 ml of watsr. The resulting slurry is heated with constant stir-31 ring and boiled down to a paste, which is then dried in an 32 oYe~ at 110C for 24 hours. The dried product possesses a 33 light green color-. A p~rtion of the dried product is 3-4 calcined at 900C for 2 hours~ and the calcined catalyst sieved to -12+20 mesh sizè (U.S. Sieve Series) for evalua-36 tion. 20cc of the resulting mixed oxide composition are 37 evaluate~ in the 2Qcc stainless steel reactor tube of -: , :;, '`: ' ,:. :
~- ... ., ~ : - .
.~ ~: .: :
. ", ' ~
'~2Z9~
- 42 -1 Example 1 using a sand bath to sup~ly heat. Toluene, steam, ~ and N2 in a 1:2O1 molar ratio are fed throu~h and vaporized 3 in the reactor, said reactor being at 565C, while control-4 ling the flow rate to achieve a contact time of 1.4 seconds.
5 Two runs are conducte~ at on-stream tLmes of 0.5 and 1.0 hour 6 and after each recovery run, the reactor effluent is scrubbed 7 for 30 minutes in acetone. The metal oxygen composition is 8 not regenerated between each of these runs. The results 9 are summarized in Table 1 (runs 1 and 2).
iO COr~PARATIVE EXAMPLE 2 11 The metal oxygen composition of this example is 12 Prepared in accordance with with the procedures of Compara-13 tive Example 1 with the exception that the compo~ition is 14 activated in air at 450ac for 16 hours, 2 second contact time and eva~uation of the same is conducted in accordance 16 with the procedures of Example 1 to obtain a comparison.
17 The re ults are summarized at Table 1 (run~ 6-8).
18 COMPARATIV~ _XAMPLE 3 19 A me~al oxvgen composition is Drepared in accord-2~0 ance with the procedures of ComDarative Example Z. Prior 21 to ~roduct analysis, however, the composition is allowed 22 to remain on-stream without regeneration prior to the re-23 covery run for a period of 2 hours. Reactor testing 24 pro¢edure is conducted in accordance with the procedure o~
Example 2. The results are summarized at Table 1 (run 10).
26 CO~ARATIVE EXAMPLE 4 27 A metal oxygen composition i5 prepared in accord-28 ance with Comparative Example I with the exception that 29 activation is conducted in accordance wi~h Comparative Example 2. The raactor testing and regeneration procedure 31 is conducted in accordance with Exam~le 3 to ~rovide a 32 basi~ o~ a comparison therewith The results are summarized 33 at Table 1 (runs 13 and 14).
34 COMPARATIVL EX~MPLE 5 A metal oxygen com~osition is prepared in accord-36 ance with the procedures or Comparati~e Example 1 with the 37 e~ce~tion that calcination is conducted at 60QC for 2 hours ~ ., . . , -, - , ~
5 Two runs are conducte~ at on-stream tLmes of 0.5 and 1.0 hour 6 and after each recovery run, the reactor effluent is scrubbed 7 for 30 minutes in acetone. The metal oxygen composition is 8 not regenerated between each of these runs. The results 9 are summarized in Table 1 (runs 1 and 2).
iO COr~PARATIVE EXAMPLE 2 11 The metal oxygen composition of this example is 12 Prepared in accordance with with the procedures of Compara-13 tive Example 1 with the exception that the compo~ition is 14 activated in air at 450ac for 16 hours, 2 second contact time and eva~uation of the same is conducted in accordance 16 with the procedures of Example 1 to obtain a comparison.
17 The re ults are summarized at Table 1 (run~ 6-8).
18 COMPARATIV~ _XAMPLE 3 19 A me~al oxvgen composition is Drepared in accord-2~0 ance with the procedures of ComDarative Example Z. Prior 21 to ~roduct analysis, however, the composition is allowed 22 to remain on-stream without regeneration prior to the re-23 covery run for a period of 2 hours. Reactor testing 24 pro¢edure is conducted in accordance with the procedure o~
Example 2. The results are summarized at Table 1 (run 10).
26 CO~ARATIVE EXAMPLE 4 27 A metal oxygen composition i5 prepared in accord-28 ance with Comparative Example I with the exception that 29 activation is conducted in accordance wi~h Comparative Example 2. The raactor testing and regeneration procedure 31 is conducted in accordance with Exam~le 3 to ~rovide a 32 basi~ o~ a comparison therewith The results are summarized 33 at Table 1 (runs 13 and 14).
34 COMPARATIVL EX~MPLE 5 A metal oxygen com~osition is prepared in accord-36 ance with the procedures or Comparati~e Example 1 with the 37 e~ce~tion that calcination is conducted at 60QC for 2 hours ~ ., . . , -, - , ~
- 43 -l and activation is conducted in accordance with Comparati~e 2 Example 2. The resultins composition is tested in accord-3 ance with the procedures of Example 4 to provide a basis 4 for comparison ~herewith. The results are summarized at Table 1 (ru~s 19 and 20).
6 ~
7 A metal oxygen romposition is prepared in accord-8 ance with U.S. Patent No. 4,254,293 by slurrying 135.0g 9 Bi2O3 and 94.5g ZnO with 500cc of water, The resulting slurry is constantly stirred while being boiled down to a 11 ~aste. The paste is then dried in an oven at 110C for 24 12 hours. The dried produc~ is calcined at 400C for 2 hours 13 and subsequently at 800C for 1 hour. The calcined catalyst 14 is crushed and sieved to a -1~+20 mesh size (U.S. ~ieve Series) for evalu~tion. Testing of the metal oxygen comr 16 position in a 20cc reactor is conducted in accordance with 17 the procedure~ of Example 8,including activation,to provide 18 a basis fo~ comparison therewith. Results are s~mmarized 19 at ~able 1 ~runs 24-30~.
SUMMARY OF EX~MP~ES AND COMPA~ATIVE EXAMPLES
21 The following is a summary of the conclusions 22 which can be drawn from the various examples and comparative 23 examples provided in Table 1.
74 Comparing runs 3, 4 and 5 (Example 1) with runs ~5 6, 7, and 8 (Comparative Example 2) respectively it can Z6 be seen that at comparable on-stream times metal oxygen 27 compositions prepared by the organic method yield substan-28 tially better stilbene selectivities than metal oxygen 2~ composi~ions prepared by the aqueous procedure, e.g., 49.8~ vs. 29.8~, 47.8~ vs. 27.4% and 50.6% vs. 19.0%.
31 Furthermore, as on-stream time increases to 2 hours the 32 activity of the compositions prepared by the aqueous 33 method is reduced by more than 50% (toluene conversion 34 drops from 6.4~ to 2.9~) and a major proportion of this reduction is due to a substantial dro~ in stilbene selectlv-36 ity (i.e., ~electivity drops from 29.8~ to 19.0%). In con-37 ~rast, the organicallv prepared compositions of the present ' . ~ ,.... .. . . , :
- .;. - ~
. , , . .. : : -, :
::: ~,. . .:
: : .. - ' : - .
'~' ": . :
4~
6 ~
7 A metal oxygen romposition is prepared in accord-8 ance with U.S. Patent No. 4,254,293 by slurrying 135.0g 9 Bi2O3 and 94.5g ZnO with 500cc of water, The resulting slurry is constantly stirred while being boiled down to a 11 ~aste. The paste is then dried in an oven at 110C for 24 12 hours. The dried produc~ is calcined at 400C for 2 hours 13 and subsequently at 800C for 1 hour. The calcined catalyst 14 is crushed and sieved to a -1~+20 mesh size (U.S. ~ieve Series) for evalu~tion. Testing of the metal oxygen comr 16 position in a 20cc reactor is conducted in accordance with 17 the procedure~ of Example 8,including activation,to provide 18 a basis fo~ comparison therewith. Results are s~mmarized 19 at ~able 1 ~runs 24-30~.
SUMMARY OF EX~MP~ES AND COMPA~ATIVE EXAMPLES
21 The following is a summary of the conclusions 22 which can be drawn from the various examples and comparative 23 examples provided in Table 1.
74 Comparing runs 3, 4 and 5 (Example 1) with runs ~5 6, 7, and 8 (Comparative Example 2) respectively it can Z6 be seen that at comparable on-stream times metal oxygen 27 compositions prepared by the organic method yield substan-28 tially better stilbene selectivities than metal oxygen 2~ composi~ions prepared by the aqueous procedure, e.g., 49.8~ vs. 29.8~, 47.8~ vs. 27.4% and 50.6% vs. 19.0%.
31 Furthermore, as on-stream time increases to 2 hours the 32 activity of the compositions prepared by the aqueous 33 method is reduced by more than 50% (toluene conversion 34 drops from 6.4~ to 2.9~) and a major proportion of this reduction is due to a substantial dro~ in stilbene selectlv-36 ity (i.e., ~electivity drops from 29.8~ to 19.0%). In con-37 ~rast, the organicallv prepared compositions of the present ' . ~ ,.... .. . . , :
- .;. - ~
. , , . .. : : -, :
::: ~,. . .:
: : .. - ' : - .
'~' ": . :
4~
- 44 -1 invention yield only a slight drop in conversion (19.6% to 2 16.2~) and an increase in stilbene selectivity ti.e., 49.8%
3 ~o 50.6%).
4 Comparing run 9 (Example 2) with run 10 (Compara-tive Example 3) wherein a minor quantity o~ air is added 6 to the feed s~ream and contact time i9 reduced to 3.5 sec-7 onds, it can be seen that stilbene selectivity of the or-8 ganicall-y prepared compositions is higher than the aqueous 9 preparation (i.e., 72.2% vs. 60.9%). These runs therefore illustrate the superior performance of compositions pre-11 pared by the organic method when run in the catalytic/
12 stoichiometric mode.
13 Comparing runs 11 and 12 (Example 3) with runs 14 1~ and 14 (Comparative Example 4) it can be seen that lS after regene~ration, ~tilbene selectivities of runs 11 and 16 12 remain higher than runs 13 and 14 ~i.e., 49.0~ vs.
17 43.3%, and 49.9% vs. 44.0~ at re~pective on-stream times 18 of 0.5 and 1 hours).
I9 Comparing runs 15 and 16 (Example 4) with runs 19 and 20 (Comparative Example 5) at on-stream times of 21 0.5 and 1.0 hour respectively and a calcination temperature 22 of 600C, it can be seen that stilbene selectivities, 23 toluene conv~rsions, and stilbene and DPE selectivities of 24 ~he organically prepared compositions are or the most part substantially better than those of the aqueous pre-26 pared compositions (i.e., stilbene salectivities: 65~9% vs.
27 46.6%, 66.1~ V5. 46.6~; toluene conversions: 18.4~ vs.
28 6.6~, 20.2% vs~. 8.6~, stilbene and D~E selectivities: 88.8 z9 vs. 85.1%, ~0.2% vs. 91.1%).
Comparing runs 27 and 28 (Example 8) with xuns 29 31 and 30 ~Comparative Example 6). It can be seen that an 32 even greater improvement in perfo~mance of the organically 33 prepared metal oxygen compositions is achieved using a 34 Bi/Zn metal oxygen composition.
For example~, the above noted runs yield the 36 ~ollowing com~aris~ns:
..
.: -:~ .... .
. . " ~ , .. ~
3 ~o 50.6%).
4 Comparing run 9 (Example 2) with run 10 (Compara-tive Example 3) wherein a minor quantity o~ air is added 6 to the feed s~ream and contact time i9 reduced to 3.5 sec-7 onds, it can be seen that stilbene selectivity of the or-8 ganicall-y prepared compositions is higher than the aqueous 9 preparation (i.e., 72.2% vs. 60.9%). These runs therefore illustrate the superior performance of compositions pre-11 pared by the organic method when run in the catalytic/
12 stoichiometric mode.
13 Comparing runs 11 and 12 (Example 3) with runs 14 1~ and 14 (Comparative Example 4) it can be seen that lS after regene~ration, ~tilbene selectivities of runs 11 and 16 12 remain higher than runs 13 and 14 ~i.e., 49.0~ vs.
17 43.3%, and 49.9% vs. 44.0~ at re~pective on-stream times 18 of 0.5 and 1 hours).
I9 Comparing runs 15 and 16 (Example 4) with runs 19 and 20 (Comparative Example 5) at on-stream times of 21 0.5 and 1.0 hour respectively and a calcination temperature 22 of 600C, it can be seen that stilbene selectivities, 23 toluene conv~rsions, and stilbene and DPE selectivities of 24 ~he organically prepared compositions are or the most part substantially better than those of the aqueous pre-26 pared compositions (i.e., stilbene salectivities: 65~9% vs.
27 46.6%, 66.1~ V5. 46.6~; toluene conversions: 18.4~ vs.
28 6.6~, 20.2% vs~. 8.6~, stilbene and D~E selectivities: 88.8 z9 vs. 85.1%, ~0.2% vs. 91.1%).
Comparing runs 27 and 28 (Example 8) with xuns 29 31 and 30 ~Comparative Example 6). It can be seen that an 32 even greater improvement in perfo~mance of the organically 33 prepared metal oxygen compositions is achieved using a 34 Bi/Zn metal oxygen composition.
For example~, the above noted runs yield the 36 ~ollowing com~aris~ns:
..
.: -:~ .... .
. . " ~ , .. ~
- 45 -1 Stilbene selectivity: 28.3~ vs. 11.5%
2 48.q% vs. 11.6%
3 Stilbene + DP 93.2~ vs. 72.3%
4 se}ectivity 92.7% vs. 77.,5%
Toluene Conversion: 3.6~ vs. 2.6%
3.1% vs. 3.4 , ,:
, '` ~
.~
'.~
., , ~
.
.
.
~ . :
,.: : :-:
- ; ::~ -:
: ~., ~ : :. - , - ' : '~:': ' ': ,` ' ~z~
I ~ ~ ! ~ _ _ r ~ O~ ~ O . _ ~ ~ æ _ 7 rO~
~i _ _ _ _ ~0 10 ~ _ _ r~ ~i, N
~~ h I!i ~ ~~ ~ a -- i æ ~ ~ ~
~ I ~ O ~ _ G. r~ 0 u~ _ o ~ r ¦~ ~
_ _ ~ c ¦-- ~ 3 o 3 ~ _ ~ ~ N N W 10 N 0 4~ ~ " I N "
:; _. _ I__ IA 0 0 _ ¦ ~ O _ ~ N N O ~_ ~ Cl _ ~ _ _ O _ ~1 ~ U~ 1- ~ 0~ '.0 0 1 0 ~ 8 ,, ~ ~ 0 ~' ~ _ N ~ ~1 ~ 11 In 10 1 N ~ I . 8 o ~ 8 ~ a, ~ 2 ~i ¦ ~ . . ~ . ~
~ ~ ~ ~
Z 1~ ~ ~
0 -- N _ I .
, ~ ~ """ ' ~' ' .. .:
,'"~;'"~,, ,, ' ' , ~1 224~ 99 ~. ~ ~ 3~ la ~
~^ I ~ ;a ~ 3 _ _____'A O, l~n _IIN Q ~0 _ Jo~ o ~O ~O ~a ~e I ~ ~ ~ A ~ 0 ~~~ ~ ~ 1~o!o a 0 ~ ~ .
~ ~ o 31_~ , ~ ~ a7 ~ n i 4~' r~ ~ ~ ~ ~ ~ ~ , æ ~ ~cV u . ~ ~ . .
O ~ . . . . . . ~ s3c~ . .
ut ~ ~ ~ ~ t~l ~ ~ ~ ~ ~ ~ _ . ~ r~ ~ 0,, 0 ., ~ 3 ~ ~a 33 ~ I a a~ a~
1!_ ~. ~ j o o ~ ~ 5~ S i o 3 _ ~ O~
~ ~ I' ~ 30 ~ C~ o ` z ~C' 1~ ~ - ~ - 2 ~ a R ~. ~ .o ~ c~ g .- . . : . .~ ` :.,` .:
.. - . . .~ ~ : ..
-,le / ~ ,' 1 `
'1- 1~ ~ 3~ i i~
~ ,,,' ~,:, ,Oo-,~l , . : , ' ~ ~ ~ ~ S X
~ .
~ _~ 2. o o. ~ ~
~ ~ ~ ~ _ ~ .
M ~ W ~0 O d ~ 'O
, o ~ 3 ~ ~
~o~ ~`
.~ oL~-~ ~ ~, ~ ......... ~ .
~io ~ ~-. ~o ~ V~
. ~ ~,~c a 9 ~ & 5--~
~ W~ . . ~ . ~ .
~ ~ ~ Y ~ C
. ~ ~ o~Y~ _ ~ 3 ~ ~ ,, .
~ ~ 1~ 9 ~I ~ il~
____ . j~
_ '-~;! ~ ~ . ~ ~ o :~ :~
. e .~ '~' .~ '~' V~
24~
1 The principles, preferred embodiments, and modes 2 of operation of the present invention have been described 3 in the foregoing specification. The invention which 4 is intended to be protected herein, however, i5 not .o be construed as limited to the particular forms disclosed, 6 since these are to be regarded as illustrative rather 7 ~han restrictive. Variations and cbanges may be made 8 by those s~il}ed in the a,rt without depar~ing from the 9 spirit of the i~vention.
.
, ~
, ,:
:
2 48.q% vs. 11.6%
3 Stilbene + DP 93.2~ vs. 72.3%
4 se}ectivity 92.7% vs. 77.,5%
Toluene Conversion: 3.6~ vs. 2.6%
3.1% vs. 3.4 , ,:
, '` ~
.~
'.~
., , ~
.
.
.
~ . :
,.: : :-:
- ; ::~ -:
: ~., ~ : :. - , - ' : '~:': ' ': ,` ' ~z~
I ~ ~ ! ~ _ _ r ~ O~ ~ O . _ ~ ~ æ _ 7 rO~
~i _ _ _ _ ~0 10 ~ _ _ r~ ~i, N
~~ h I!i ~ ~~ ~ a -- i æ ~ ~ ~
~ I ~ O ~ _ G. r~ 0 u~ _ o ~ r ¦~ ~
_ _ ~ c ¦-- ~ 3 o 3 ~ _ ~ ~ N N W 10 N 0 4~ ~ " I N "
:; _. _ I__ IA 0 0 _ ¦ ~ O _ ~ N N O ~_ ~ Cl _ ~ _ _ O _ ~1 ~ U~ 1- ~ 0~ '.0 0 1 0 ~ 8 ,, ~ ~ 0 ~' ~ _ N ~ ~1 ~ 11 In 10 1 N ~ I . 8 o ~ 8 ~ a, ~ 2 ~i ¦ ~ . . ~ . ~
~ ~ ~ ~
Z 1~ ~ ~
0 -- N _ I .
, ~ ~ """ ' ~' ' .. .:
,'"~;'"~,, ,, ' ' , ~1 224~ 99 ~. ~ ~ 3~ la ~
~^ I ~ ;a ~ 3 _ _____'A O, l~n _IIN Q ~0 _ Jo~ o ~O ~O ~a ~e I ~ ~ ~ A ~ 0 ~~~ ~ ~ 1~o!o a 0 ~ ~ .
~ ~ o 31_~ , ~ ~ a7 ~ n i 4~' r~ ~ ~ ~ ~ ~ ~ , æ ~ ~cV u . ~ ~ . .
O ~ . . . . . . ~ s3c~ . .
ut ~ ~ ~ ~ t~l ~ ~ ~ ~ ~ ~ _ . ~ r~ ~ 0,, 0 ., ~ 3 ~ ~a 33 ~ I a a~ a~
1!_ ~. ~ j o o ~ ~ 5~ S i o 3 _ ~ O~
~ ~ I' ~ 30 ~ C~ o ` z ~C' 1~ ~ - ~ - 2 ~ a R ~. ~ .o ~ c~ g .- . . : . .~ ` :.,` .:
.. - . . .~ ~ : ..
-,le / ~ ,' 1 `
'1- 1~ ~ 3~ i i~
~ ,,,' ~,:, ,Oo-,~l , . : , ' ~ ~ ~ ~ S X
~ .
~ _~ 2. o o. ~ ~
~ ~ ~ ~ _ ~ .
M ~ W ~0 O d ~ 'O
, o ~ 3 ~ ~
~o~ ~`
.~ oL~-~ ~ ~, ~ ......... ~ .
~io ~ ~-. ~o ~ V~
. ~ ~,~c a 9 ~ & 5--~
~ W~ . . ~ . ~ .
~ ~ ~ Y ~ C
. ~ ~ o~Y~ _ ~ 3 ~ ~ ,, .
~ ~ 1~ 9 ~I ~ il~
____ . j~
_ '-~;! ~ ~ . ~ ~ o :~ :~
. e .~ '~' .~ '~' V~
24~
1 The principles, preferred embodiments, and modes 2 of operation of the present invention have been described 3 in the foregoing specification. The invention which 4 is intended to be protected herein, however, i5 not .o be construed as limited to the particular forms disclosed, 6 since these are to be regarded as illustrative rather 7 ~han restrictive. Variations and cbanges may be made 8 by those s~il}ed in the a,rt without depar~ing from the 9 spirit of the i~vention.
.
, ~
, ,:
:
Claims (95)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a precursor metal oxygen composition capable of dehydrocoupling toluene when calcined which comprises:
(i) reacting a mixture of metal oxides in the presence of at least one alcohol under substantially anhydrous conditions of less than about 1%, by weight water, based on the weight of organic alcohol present, said organic alcohol being present in an amount of at least 3 moles of said alcohol per mole of metal in the metal oxide mixture, the metals of said metal oxide mixture having (a) at least one member selected from the group consisting of Bi, and Pb, and (b) at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (ii) separating the precursor composition from the organic alcohol.
(i) reacting a mixture of metal oxides in the presence of at least one alcohol under substantially anhydrous conditions of less than about 1%, by weight water, based on the weight of organic alcohol present, said organic alcohol being present in an amount of at least 3 moles of said alcohol per mole of metal in the metal oxide mixture, the metals of said metal oxide mixture having (a) at least one member selected from the group consisting of Bi, and Pb, and (b) at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (ii) separating the precursor composition from the organic alcohol.
2. The process of claim 1 wherein the precursor metal oxygen composition is calcined at a temperature of from about 300° to about 1200°C.
3. The process of claim 1 wherein the precursor metal oxygen composition is calcined at a temperature of about 600° to about 900°C and activated at a temperature of from about 350°C to about 700°C.
4. The process of claim 1 wherein said organic alcohol is selected from the group consisting of methanol, ethanol, isopropanol, l-propanol, isobutanol, l-butanol, 2-butanol, t-butanol, l-pentanol, cyclohexanol, l-octanol, 2-octanol, 3-octanol, phenol, ethylene elycol, 1,4-butane diol, diethylene glycol, triethylene glycol, 4-methoxy butanol.
5. The process of claim 4 wherein the organic alcohol is isobutanol.
6. The process of claim 1 wherein said reaction of Step (i) is conducted by refluxing a reaction mixture comprising from about l to about 60%, by weight, metal oxide mixture, and from about 99 to about 40%, by weight, of at least one organic alcohol in a manner and under conditions sufficient to remove water as it forms.
7. The process of claim 6 wherein said refluxing is conducted for a period of from about 2 to about 48 hours.
8. The process of claim 1 wherein the number of moles of organic alcohol present during said reaction is at least equal to the sum of the moles of each metal oxide in the metal oxide mixture multiplied by the oxidation state of each metal in said mixture.
9. The process of claim 1 wherein the metals of said metal oxide mixture comprise Bi and Zn.
10. The process of any one of claims 1, 2 and 3, wherein the composition of said metal oxide mixture is controlled to yield a metal oxygen composition having a gram atom ratio of said metals present therein represented by the formula:
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b" independently represents a number of from about 0.01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition.
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b" independently represents a number of from about 0.01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition.
11. The process of any one of claims 4, 5, or 6, wherein the composition of said metal oxide mixture is controlled to yield a metal oxygen composition having a gram atom ratio of said metals present therein represented by the formula:
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, X, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about i, "b" independently represents a number of from about 0.01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition.
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, X, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about i, "b" independently represents a number of from about 0.01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition.
12. The process of any one of claims 7 and 8, wherein the composition of said metal oxide mixture is controlled to yield a metal oxygen composition having a gram atom ratio of said metals present therein represented by the formula:
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b" independently represents a number of from about 0:01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition.
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b" independently represents a number of from about 0:01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition.
13. A process for preparing a metal oxygen composition capable of dehydrocoupling toluene said metal oxygen composition comprising metals having a gram atom ratio represented by the formula:
AaBbOx wherein in said formula A and B, are different and;
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb;
(ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Cs, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b" independently represents a number of from about 0.01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition, which comprises:
(1) admixing at least two metal oxides with at least one organic alcohol to form a reaction mixture having present therein at least 3 moles of organic alcohol per mole of metal in the metal oxide mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition;
(2) heating said reaction mixture to a temperature of at least 75°C to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions of less than about 1%, by weight water, based on the weight of the organic alcohol;
(3) separating said precursor composition from the organic alcohol, and (4) calcining said precursor composition to yield said metal oxygen composition.
AaBbOx wherein in said formula A and B, are different and;
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb;
(ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Cs, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b" independently represents a number of from about 0.01 to about 100, and "x" represents a number which satisfies the average valences of metals A and B as they exist in said composition, which comprises:
(1) admixing at least two metal oxides with at least one organic alcohol to form a reaction mixture having present therein at least 3 moles of organic alcohol per mole of metal in the metal oxide mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition;
(2) heating said reaction mixture to a temperature of at least 75°C to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions of less than about 1%, by weight water, based on the weight of the organic alcohol;
(3) separating said precursor composition from the organic alcohol, and (4) calcining said precursor composition to yield said metal oxygen composition.
14. The process of claim 13 wherein the reaction mixture is a slurry which is heated at a temperature of from about 25° to about 130°C for a period of from about 2 to about 48 hours; the metal oxygen precursor composition after separation from the reaction mixture is dried at a temperature of from about 25° to about 210°C; and calcination is conducted in air at a temperature of from about 400° to about 1000°C for a period of from about 0.5 to about 24 hours.
15. The process of claim 14 wherein the metal oxygen composition is calcined at a temperature of from about 600° to about 900°C.
16. The process of claim 13 wherein the organic alcohol is isobutanol.
17. A process for dehydrocoupling a hydrocarbon feed selected from toluene, toluene derivative, and mixtures thereof which comprises contacting said hydrocarbon in the vapor phase at a temperature of from about 300° to about 650°C with a metal oxygen composition, said metal oxygen composition being prepared by the process which comprises:
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions of less than about 1%, by weight, water based on the weight of the organic alcohol present, said organic alcohol being present in an amount of at least 3 moles of said alcohol per mole of metal in the metal oxide mixture to form a metal oxygen precursor composition, the metals of said metal oxide mixture having (a) at least one member selected from the group consisting of Bi, and Pb and (b) at least one member selected from the group consisting of Li, Na, R, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu;
(ii) separating the precursor composition from the organic alcohol; and (iii) calcining said precursor composition.
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions of less than about 1%, by weight, water based on the weight of the organic alcohol present, said organic alcohol being present in an amount of at least 3 moles of said alcohol per mole of metal in the metal oxide mixture to form a metal oxygen precursor composition, the metals of said metal oxide mixture having (a) at least one member selected from the group consisting of Bi, and Pb and (b) at least one member selected from the group consisting of Li, Na, R, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu;
(ii) separating the precursor composition from the organic alcohol; and (iii) calcining said precursor composition.
18. The process of claim 17 wherein the contacting between said hydrocarbon and the metal oxygen composition is effected at a temperature of from about 400° to about 650°C for a period between about 0.5 and about 10 seconds.
19. The process of claim 17 wherein steam is admixed with the hydrocarbon during said contact in an amount sufficient to provide a steam to hydrocarbon feed mole ratio of from about 1:1 to about 5:1.
20. The process of claim 11 wherein the reaction temperature is from about 500° to about 580°C.
21. The process of claim 17 wherein the dehydrocoupling reaction is conducted in a stoichiometric mode of operation in the absence of added free oxygen.
22. The process of claim 17 wherein a reactant selected from the group consisting of oxygen and an-oxygen containing gas is introduced with said hydrocarbon feed.
23. The process of claim 22 wherein the oxygen and oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a catalytic mode of operation.
24. The process of claim 22 wherein the oxygen and oxygen containing gas is introduced in an amount sufficient to provide a toluene to oxygen mole ratio of from about 0.2:1 to about 10:1.
25. The process of claim 22 wherein the oxygen or oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a combined catalytic/stoichiometric mode of operation.
26. The process of claim 17 wherein the metal oxygen composition is admixed with a support material.
27. The process of any one of claims 17, 18 or 19, wherein the hydrocarbon feed comprises toluene.
28. The process of any one of claims 20, 21 or 22, wherein the hydrocarbon feed comprises toluene.
29. The process of any one of claims 23, 24 or 25, wherein the hydrocarbon feed comprises toluene.
30. The process of claim 26, wherein the hydrocarbon feed comprises toluene.
31. A process for preparing a precursor metal oxygen composition capable of dehydrocoupling toluene when calcined which comprises:
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) at least two of Sb, Pb and Bi; of (b) Bi and Zn, to form a catalyst precursor metal oxygen composition; and;
(ii) separating the precursor metal oxygen composition from said organic alcohol.
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) at least two of Sb, Pb and Bi; of (b) Bi and Zn, to form a catalyst precursor metal oxygen composition; and;
(ii) separating the precursor metal oxygen composition from said organic alcohol.
32. The process of claim 31 wherein the precursor metal oxygen composition is calcined at a temperature of from about 300° to about 1200°C.
33. The process of claim 31 wherein the precursor metal oxygen composition is calcined at a temperature of about 600° to about 900°C and activated at a temperature of from about 300°C to about 700°C.
34. The process of claim 31 wherein said organic alcohol is selected from the group consisting of methanol, ethanol, isopropanol, l-propanol, isobutanol, l-butanol, 2-butanol, t-butanol, l-pentanol, cyclohexanol, l-octanol, 2-octanol, 3-octanol, phenol, ethylene glycol, 1,4-butane diol, diethylene glycol, triethylene glycol, 4-methoxy butanol.
35. The process of claim 34 wherein the organic alcohol is isobutanol.
36. The process of claim 31 wherein said reaction of Step (i) is conducted by refluxing a reaction mixture comprising from about 1 to about 60%, by weight, metal oxide mixture, and from about 99 to about 40%, by weight, of at least one organic alcohol in a manner and under conditions sufficient to remove water as it forms.
37. The process of claim 36 wherein said refluxing is conducted for a period of from about 2 to about 48 hours.
38. A process for preparing a metal oxygen composition capable of dehydrocoupling toluene, said metal oxygen composition comprising metals having a gram atom ratio represented by the formula:
SbcPdBieOx wherein "c" represents a number of about 1, "d" represents a number of from about 0.2 to about 10, "e" represents a number of from 0 to about 5, and "x"
represents a number which satisfies the average valences of the metals Sb, Pb, Bi, as they exist in said composition, which comprises:
(1) admixing at least two metal oxides with at least one organic alcohol to form a reaction mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition;
(2) heating said reaction mixture to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions;
(3) separating said precursor composition from the organic alcohol; and (4) calcining said precursor composition to yield said metal oxygen composition.
SbcPdBieOx wherein "c" represents a number of about 1, "d" represents a number of from about 0.2 to about 10, "e" represents a number of from 0 to about 5, and "x"
represents a number which satisfies the average valences of the metals Sb, Pb, Bi, as they exist in said composition, which comprises:
(1) admixing at least two metal oxides with at least one organic alcohol to form a reaction mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition;
(2) heating said reaction mixture to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions;
(3) separating said precursor composition from the organic alcohol; and (4) calcining said precursor composition to yield said metal oxygen composition.
39. The process of claim 38 wherein the reaction mixture is a slurry which is heated at a temperature of from about 20° to about 200°C for a period of from about 2 to about 48 hours; the metal oxygen precursor composition after separation from the reaction mixture is dried at a temperature of from about to about 210°C; and calcination is conducted in air at a temperature of from about 400 to about 1000 C for a period of from about 0.5 to about 24 hours.
40. The process of claim 39 wherein the metal oxygen composition is calcined at a temperature of from about 600° to about 900°C.
41. The process of claim 38 wherein the organic alcohol is isobutanol.
42. A process for dehydrocoupling a hydrocarbon feed selected from toluene, toluene derivative, and mixtures thereof which comprises contacting said hydrocarbon in the vapor phase at a temperature of from about 300° to about 650°C with a metal oxygen composition, said metal oxygen composition being prepared by the process which comprises:
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) at least two of Sb, Pb, and Bi; or (b) Bi and Zn; in a manner and under conditions sufficient to form a catalyst precursor composition;
(ii) separating the precursor composition from the organic alcohol; and (iii) calcining said precursor composition.
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) at least two of Sb, Pb, and Bi; or (b) Bi and Zn; in a manner and under conditions sufficient to form a catalyst precursor composition;
(ii) separating the precursor composition from the organic alcohol; and (iii) calcining said precursor composition.
43. The process of claim 42 wherein said metal oxygen composition is prepared in a manner sufficient to yield a gram atom ratio of said metals present therein represented by the formula:
SbcPbdBieOx wherein "c" represents a number of about 1, "d" represents a number of from about 0.2 to about 10, "e" represents a number of from 0 to about 5, "x"
represents a number which satisfies the average valences of the metals Sb, Pb, Bi, and they exist in said composition.
SbcPbdBieOx wherein "c" represents a number of about 1, "d" represents a number of from about 0.2 to about 10, "e" represents a number of from 0 to about 5, "x"
represents a number which satisfies the average valences of the metals Sb, Pb, Bi, and they exist in said composition.
44. The process of claim 43 wherein the contacting between said hydrocarbon and the metal oxygen composition is effected at a temperature of from about 500° to about 650°C for a period between about 0.5 and about 10 seconds.
45. The process of claim 43 wherein steam is admixed with the hydrocarbon during said contact in an amount sufficient to provide a steam to hydrocarbon feed mole ratio of from about 1:1 to about 5:1.
46. The process of claim 43 wherein the reaction temperature is from about 500° to about 580°C.
47. The process of claim 43 wherein the dehydrocoupling reaction is conducted in a stoichiometric mode of operation in the absence of added free oxygen.
48. The process of claim 43 wherein a reactant selected from the group consisting of oxygen and an oxygen containing gas is introduced with said hydrocarbon feed.
49. The process of claim 48 wherein the oxygen and oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a catalytic mode of operation.
50. The process of claim 48 wherein the oxygen and oxygen containing gas is introduced in an amount sufficient to provide a toluene to oxygen mole ratio of from about 0.2:1 to about 10:1.
51. The process of claim 48 wherein the oxygen or oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a combined catalytic/stoichiometric mode of operation.
52. The process of claim 43 wherein the metal oxygen composition is admixed with a support material.
53. The process of claim 43 wherein the hydrocarbon feed comprises toluene.
54. A process for preparing a metal oxygen composition capable of dehydrocoupling toluene, said metal oxygen composition comprising metals having a gram atom ratio represented by the formula:
DuEvSbyBizoOx wherein:
(i) "D" represents at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Si and Ba;
(ii) "E" represents at least one member selected from the group consisting of Pb, Au, Ag, and Cu; and (iii) "u" represents a number which can vary from about 0 to about 10;
"v" represents a number which can vary from about 0 to about 10; "y"
represents a number of which can vary from about 0.5 to about 5; "z"
represents a number which can vary from about 0.01 to about 10; and "x" is a number which satisfies the average valences of metals "D", "E", Sb, and Bi, and they exist in said composition, which comprises:
(1) admixing at least two metal oxides with at least one organic alcohol to form a reaction mixture having present therein at least 3 moles of organic alcohol per mole of metal in the metal oxide mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition (2) heating said reaction mixture to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions of less than about 1%, by weight, water, based on the weight of the organic alcohol;
(3) separating said precursor composition from the organic alcohol; and (4) calcining said precursor composition to yield said metal oxygen composition.
DuEvSbyBizoOx wherein:
(i) "D" represents at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Si and Ba;
(ii) "E" represents at least one member selected from the group consisting of Pb, Au, Ag, and Cu; and (iii) "u" represents a number which can vary from about 0 to about 10;
"v" represents a number which can vary from about 0 to about 10; "y"
represents a number of which can vary from about 0.5 to about 5; "z"
represents a number which can vary from about 0.01 to about 10; and "x" is a number which satisfies the average valences of metals "D", "E", Sb, and Bi, and they exist in said composition, which comprises:
(1) admixing at least two metal oxides with at least one organic alcohol to form a reaction mixture having present therein at least 3 moles of organic alcohol per mole of metal in the metal oxide mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition (2) heating said reaction mixture to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions of less than about 1%, by weight, water, based on the weight of the organic alcohol;
(3) separating said precursor composition from the organic alcohol; and (4) calcining said precursor composition to yield said metal oxygen composition.
55. The process of claim 54 wherein the precursor metal oxygen composition is impregnated with cesium prior to calcination to improve attrition resistance of the metal oxygen composition.
56. The process of claim 54 wherein the precursor metal oxygen composition is calcined at a temperature of from about 300° to about 1200°C.
57. The process of claim 54 wherein the precursor metal oxygen composition is calcined at a temperature of about 600° to about 900°C and activated at a temperature of from about 350° to about 700°C.
58. The process of claim 54 wherein said organic alcohol is selected from the group consisting of methanol, ethanol, isopropanol, l-propanol, isobutanol, l-butanol, 2-butanol, t-butanol, l-pentanol, cyclohexanol, l-octanol, 2-octanol, 3-octanol, phenol, ethylene glycol, 1,4-butane diol, diethylene glycol, triethylene glycol, 4-methoxy butanol.
59. The process of claim 58 wherein the organic alcohol is isobutanol.
60. The process of claim 54 wherein said reaction of Step (i) is conducted by refluxing a reaction mixture comprising from about 1 to about 60%, by weight, metal oxide mixture, and from about 99 to about 40%, by weight, of at least one organic alcohol in a manner and under conditions sufficient to remove water as it forms.
61. The process of claim 60 wherein said refluxing is conducted for a period of from about 2 to about 48 hours.
62. The process of claim 54 wherein the number of moles of organic alcohol present during said reaction is at least equal to the sum of the moles of each metal oxide in the metal oxide mixture multiplied by the oxidation state of each metal in said mixture.
63. The process of claim 54 wherein the reaction mixture is a slurry which is heated at a temperature of from about 20° to about 200°C for a period of from about 2 to about 48 hours; the metal oxygen precursor composition after separation from the reaction mixture is dried at a temperature of from about to about 210°C; and calcination is conducted in air at a temperature of from about 400° to about 1000°C for a period of from about 0.5 to about 24 hours.
64. The process of claim 63 wherein the metal oxygen composition is calcined at a temperature of from about 600° to about 900°C.
65. A process for dehydrocoupling feed selected from toluene, toluene derivative, and mixtures thereof which comprises contacting said hydrocarbon in the vapor phase at a temperature of from about 300° to about 650°C with a metal oxygen composition, said metal oxygen composition comprising metals having a gram atom ratio represented by the formula:
DuEvSbyBizOx wherein:
(i) "D" represents at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba;
(ii) "E" represents at least one member selected from the group consisting of Pb, Au, Ag, and Cu; and (iii) "u" represents a number which can vary from about 0 to about 10;
"v" represents a number which can vary from about 0 to about 10; "y"
represents a number which can vary from about 0.5 to about 5; "z" represents a number which can vary from about 0.01 to about 10; and "x" is a number which satisfies the average valences of metals "D", "E", Sb, and Bi, and they exist in said composition, and said metal oxygen composition being prepared by the process comprising:
(1) admixing at least two metal oxides with at least one organic alcohol to form a resection mixture having present therein at least 3 moles of organic alcohol per mole of metal in the metal oxide mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition;
(2) heating said reaction mixture to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions of less than about 1%, by weight, water, based on the weight of the organic alcohol;
(3) separating said precursor composition from the organic alcohol; and (4) calcining said precursor composition to yield said metal oxygen composition.
DuEvSbyBizOx wherein:
(i) "D" represents at least one member selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba;
(ii) "E" represents at least one member selected from the group consisting of Pb, Au, Ag, and Cu; and (iii) "u" represents a number which can vary from about 0 to about 10;
"v" represents a number which can vary from about 0 to about 10; "y"
represents a number which can vary from about 0.5 to about 5; "z" represents a number which can vary from about 0.01 to about 10; and "x" is a number which satisfies the average valences of metals "D", "E", Sb, and Bi, and they exist in said composition, and said metal oxygen composition being prepared by the process comprising:
(1) admixing at least two metal oxides with at least one organic alcohol to form a resection mixture having present therein at least 3 moles of organic alcohol per mole of metal in the metal oxide mixture, the identity and molar ratio of said metal oxides in the reaction mixture being selected to yield a gram atom relationship in accordance with said formula in the metal oxygen composition;
(2) heating said reaction mixture to form a metal oxygen precursor composition and water, said heating being conducted under substantially anhydrous conditions of less than about 1%, by weight, water, based on the weight of the organic alcohol;
(3) separating said precursor composition from the organic alcohol; and (4) calcining said precursor composition to yield said metal oxygen composition.
66. The process of claim 65 wherein the contacting between said hydrocarbon feed and the metal oxygen composition is effected at a temperature of from about 400° to about 650°C for a period between about 0.5 and about 10 seconds.
67. The process of claim 65 wherein steam is admixed with the hydrocarbon during said contact in an amount sufficient to provide a steam to hydrocarbon feed mole ratio of from about 1:1 to about 5:1.
68. The process of claim 65 wherein the reaction temperature is from about 500° to about 580°C.
69. The process of claim 65 wherein the dehydrocoupling reaction is conducted in a stoichiometric mode of operation in the absence of added free oxygen.
70. The process of claim 65 wherein a reactant selected from the group consisting of oxygen and an oxygen containing gas is introduced with said hydrocarbon feed.
71. The process of claim 70 wherein the oxygen and oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a catalytic mode of operation.
72. The process of claim 70 wherein the oxygen and oxygen containing gas is introduced in an amount sufficient to provide a toluene to oxygen mole ratio of from about 0.2:1 to about 10:1.
73. The process of claim 70 wherein the oxygen or oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a combined catalytic/stoichiometric mode of operation.
74. The process of claim 65 wherein the metal oxygen composition is admixed with a support material.
75. The process of claim 65 wherein the hydrocarbon feed comprises toluene.
76. A process for preparing a precursor metal oxygen composition capable of dehydrocoupling toluene when calcined which comprises:
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) Sb, Pb, and Bi, (b) Bi and Zn, (c) Pb and K, (d) Bi and Ag, (e) Au, Sb, and Bi (f) Pb and Ba, and (g) mixtures thereof to form a catalyst precursor metal oxygen composition; and (ii) separating the precursor metal oxygen composition from said organic alcohol.
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) Sb, Pb, and Bi, (b) Bi and Zn, (c) Pb and K, (d) Bi and Ag, (e) Au, Sb, and Bi (f) Pb and Ba, and (g) mixtures thereof to form a catalyst precursor metal oxygen composition; and (ii) separating the precursor metal oxygen composition from said organic alcohol.
77. The process of claim 76 wherein the precursor metal oxygen composition is calcined at a temperature of from about 300° to about 1200°C.
78. The process of claim 76 wherein the precursor metal oxygen composition is calcined at a temperature of about 600° to about 900°C and activated at a temperature of from about 350° to about 700°C.
79. The process of claim 76 wherein said organic alcohol is selected from the group consisting of methanol, ethanol, isopropanol, l-propanol, isobutanol, l-butanol, 2-butanol, t-butanol, l-pentanol, cyclohexanol, l-octanol, 2-octanol, 3-octanol, phenol, ethylene glycol, 1,4-butane diol, diethylene glycol, triethylene glycol, 4-methoxy butanol.
80. The process of claim 79 wherein the organic alcohol is isobutanol.
81. The process of claim 76 wherein said reaction of Step (i) is conducted by refluxing a reaction mixture comprising from about 1 to about 60%, by weight, metal oxide mixture, and from about 99 to about 40%, by weight, of at least one organic alcohol in a manner and under conditions sufficient to remove water as it forms.
82. The process of claim 81 wherein said refluxing is conducted for a period of from about 2 to about 48 hours.
83. A process for dehydrocoupling a hydrocarbon feed selected from toluene, toluene derivative, and mixtures thereof which comprises contacting said hydrocarbon in the vapor phase at a temperature of from about 300° to about 650°C with a metal oxygen composition, said metal oxygen composition being prepared by the process which comprises:
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) Sb, Pb, and Bi, (b) Bi and Zn, (c) Pb and K, (d) Bi and Ag, (e) Au, Sb, and Bi, (f) Pb and Ba, and (g) mixtures thereof in a manner and under conditions sufficient to form a catalyst precursor composition;
(ii) separating the precursor composition from the organic alcohol; and (iii) calcining said precursor composition.
(i) reacting a mixture of metal oxides in the presence of at least one organic alcohol under substantially anhydrous conditions, the metals of said metal oxide mixture comprising those represented by a member selected from the group consisting of (a) Sb, Pb, and Bi, (b) Bi and Zn, (c) Pb and K, (d) Bi and Ag, (e) Au, Sb, and Bi, (f) Pb and Ba, and (g) mixtures thereof in a manner and under conditions sufficient to form a catalyst precursor composition;
(ii) separating the precursor composition from the organic alcohol; and (iii) calcining said precursor composition.
84. The process of claim 83 wherein the contacting between said hydrocarbon and the metal oxygen composition is effected at a temperature of from about 400 to about 650 C for a period between about 0.5 and about 10 seconds.
85. The process of claim 83 wherein steam is admixed with the hydrocarbon during said contact in an amount sufficient to provide a steam to hydrocarbon feed mole ratio of from about 1:1 to about 5:1.
86. The process of claim 83 wherein the reaction temperature is from about 500° to about 580°C.
87. The process of claim 83 wherein the dehydrocoupling reaction is conducted in a stoichiometric mode of operation in the absence of added free oxygen.
88. The process of claim 83 wherein a reactant selected from the group consisting of oxygen or an oxygen containing gas is introduced with said hydrocarbon feed.
89. The process of claim 88 wherein the oxygen or oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a catalytic mode of operation.
90. The process of claim 88 wherein the oxygen or oxygen containing gas is introduced in an amount sufficient to provide a toluene to oxygen mole ratio of from about 0.2:1 to about 10:1.
91. The process of claim 88 wherein the oxygen or oxygen containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reaction in a combined catalytic/stoichiometric mode of operation.
92. The process of claim 83 wherein the metal oxygen composition is admixed with a support material.
93. The process of claim 83 wherein the hydrocarbon feed comprises toluene.
94. The process of any one of claims 4, 5 or 6, wherein the composition of said metal oxide mixture is controlled to yield a metal oxygen composition having a gram atom ratio of said metals present therein represented by the formula:
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b"
independently represents a number of from about 0.01 to about 100, and "x"
represents a number which satisfies the average valences of metals A and B as they exist in said composition.
AaBbOx wherein in said formula, A and B are different and:
(i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b"
independently represents a number of from about 0.01 to about 100, and "x"
represents a number which satisfies the average valences of metals A and B as they exist in said composition.
95. The process of any one of claims 7 or 8 wherein the composition of said metal oxide mixture is controlled to yield a metal oxygen composition having a gram atom ratio of said metals present therein represented by the formula:
wherein in said formula, A and B are different and:
AaBbOx (i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b"
independently represents a number of Prom about 0.01 to about 100, and "x"
represents a number which satisfies the average valances of metals A and B as they exist in said composition.
wherein in said formula, A and B are different and:
AaBbOx (i) "A" represents at least one metal selected from the group consisting of Bi, and Pb and (ii) "B" represents from 1 to 3 of the metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sb, Ag, Au, and Cu; and (iii) "a" independently represents a number of about 1, "b"
independently represents a number of Prom about 0.01 to about 100, and "x"
represents a number which satisfies the average valances of metals A and B as they exist in said composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000444985A CA1224199A (en) | 1984-01-10 | 1984-01-10 | Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000444985A CA1224199A (en) | 1984-01-10 | 1984-01-10 | Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1224199A true CA1224199A (en) | 1987-07-14 |
Family
ID=4126914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000444985A Expired CA1224199A (en) | 1984-01-10 | 1984-01-10 | Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1224199A (en) |
-
1984
- 1984-01-10 CA CA000444985A patent/CA1224199A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0253522B1 (en) | Boron-promoted reducible metal oxide and methods for their use | |
| USRE35632E (en) | Methane conversion process | |
| US5599510A (en) | Catalytic wall reactors and use of catalytic wall reactors for methane coupling and hydrocarbon cracking reactions | |
| CA1249603A (en) | Methane conversion process | |
| US5336826A (en) | Oxidation of methane over heterogeneous catalysts | |
| US4629718A (en) | Alkali promoted manganese oxide compositions containing silica and/or alkaline earth oxides | |
| CA1289125C (en) | Upgrading low molecular weight alkanes | |
| US4751248A (en) | Preparation of alcohols from synthesis gas | |
| US5095161A (en) | Process and catalyst for upgrading methane to higher carbon number hydrocarbons | |
| EP0099715A1 (en) | Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas | |
| NZ216388A (en) | Catalytic conversion of methane into hydrogen and higher hydrocarbons | |
| US4769508A (en) | Alkali promoted manganese oxide compositions containing titanium | |
| US4891467A (en) | Selective synthesis of pseudocumene and durene | |
| US5026945A (en) | Perovskite catalysts for oxidative coupling | |
| US4454363A (en) | Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene | |
| US4788372A (en) | Methane conversion process | |
| US4769509A (en) | Reducible metal oxide compositions containing zirconium | |
| CA1224199A (en) | Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene | |
| US4795842A (en) | Methane conversion process | |
| US4429174A (en) | Process for dehydrocoupling toluene using a modified faujasite zeolite catalyst composition | |
| US5026947A (en) | Methane conversion process | |
| JP2002539180A (en) | Method for producing cyclic α, β-unsaturated ketone | |
| EP0148544A1 (en) | Process for preparing inorganic metal oxygen composition capable of dehydrocoupling toluene | |
| EP0639548A1 (en) | Catalytic wall reactors and use of catalytic wall reactors for methane coupling and hyxdrocarbon cracking reactions | |
| US4767738A (en) | Lead aluminum borate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |