CA1139321A - Dehydrocoupling of toluene - Google Patents
Dehydrocoupling of tolueneInfo
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- CA1139321A CA1139321A CA000366376A CA366376A CA1139321A CA 1139321 A CA1139321 A CA 1139321A CA 000366376 A CA000366376 A CA 000366376A CA 366376 A CA366376 A CA 366376A CA 1139321 A CA1139321 A CA 1139321A
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Abstract
20-21-0143A DEHYDROCOUPLING OF TOLUENE ABSTRACT OF THE DISCLOSURE Toluene dehydrocoupled products are produced by heating toluene in the vapor phase with an inorganic metal/ oxygen composition which functions as an oxygen carrier and has the empirical formula: where M1 is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups 1a, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is 0 to 10, and x is a num-ber taken to satisfy the average valences of lead, M1 and M2 in the oxidation states in which they exist in the com-position to yield the toluene dehydrocoupled toluene pro-duct, with the proviso that when M2 is bismuth, M1 cannot be gallium or thallium; and when M2 is antimony, M1 can-not be indium, thallium, germanium, phosphorus, or thorium. Alternatively, the same inorganic metal/oxygen composition can be employed as a catalyst or as a combination catalyst/ oxygen carrier for the dehydrocoupling reaction when oxy-gen or an oxygen-containing gas is heated with the toluene.
Description
i~39~Zl DEHYDROCOUPLIN~ 0~ ~OLUENE
BA~KGROUND'OF THE INVENTION
Field of't~e Invent on ' This invention relates to the production of S dehydrocoupled toluene productsO It is particularly related to the oxidative synthesis of 1,2-diphenylethylene (stilbene) from toluene and to'ir.organic metal/oxygen compositions effective ~or oxidatively coupling toluene to produce stilbene.
Stilbene, because of its unsaturated character, is very reactive and may be employed in various organic syntheses. Derivatives of stilbene are useful in the production of products which may be used in the manu-facture of dyes, paints, and resinsO It is also useful in optical brighteners, in pharmaceuticals, and as an organic intermediateO
DescrIption'of th'e_P'rior Art Dehydrocoupling of ~oluene by the reaction with lead oxide to form stilbene has been reported by Behr and Van Dorp,' Che~.'B'er., 6~ 753 (1873) and Lorenz, ChemO Ber., 7 ~ 1996 Cl874) o In this reported work, stilbene is obtain-ed by~ conveying toluene over lead oxide maintained at or about at a dark red glo~O T~e coupling of toluene using elemental sulfur as the coupling agent has been reported by Renard, Bul'l'. S'o'cO Ch'im.''France, 3~ 958 ~1889); 5~ 278 (1891~ and t~e types of products produced by such coupling reactions ha~e been discussed by Horton,'3, Org. Chem., 14, 761 C1949~o ~ore recently, UOS. Patent No. 3~476~747 discloses arsenic pentoxide, antimony tetroxide, antimony pentoxide, bismuth trioxide, and manganese arsenate as oxidants for the oxidative dehydrocoupling of toluene to form 1,2-bis(aryl)ethylenes. Similarly, U.SO Patent No.
3,494,956 discloses lead oxide, cadmium oxide, and thallium oxide as suitable oxidants, and in Example 9 a mixture of toluene and oxygen passed over heated lead oxide produced bibenzylO In UOS. Patent NoO 3,557,235 the stoichiometric toluene coupling reaction is taught using an oxide of bismuth, lead, tellurium, barium, thallium, cadmium, or mixtures thereof which serves as the source of oxygen in the reactionO UOSO Patent No. 3,963,7g3 teaches the use of bismuth trioxide and thallium trioxide or mixtures thereof supported on basic carrier materials selected from the oxides of Group 2a elements and having a minimum surface area of 20 m /g as suitable for toluene coupling to produce bibenzylO The addition to the supported catalyst of small amounts of silver as a promoter is also disclosedO In UOSO Patent NoO 3,965,206 oxides of lead, cadmium, bismuth, and mixtures thereof are taught as suit-able oxidants for toluene coupling. This patent alsoteaches the disproportionation of the stilbene with ethylene to produce styrene~ U.SO Patent No. 3,980,580 discloses an oxygen composition of lead, magnesium, and aluminum as an oxidant for toluene couplingO Also, U.S.
Patent NoO 4,091,044 discloses oxygen compositions of lead and antimony and optionally with bismuth as oxidants for toluene coupling to form stilbene.
SUMMARY OF THE INVENTION
This invention is directed to a pTocess for the oxidative dehydrocoupling of toluene and toluene deriv-atives to stil~ene and stilbene derivativesO In another aspect, this invention is directed to inorganic metal/-oxygen compositions which are useful as the oxygen source for the oxidative dehydrocoupling of toluene to produce stilbene, or alternatively as catalysts or combination catalysts/oxygen source for the dehydrocoupling reaction ~3~
,, when oxygen or an oxygen-containing gas is heated with the toluene.
Accordingly, typical objects of this invention are to provide (1) inorganic metal/oxygen compositions useful as the oxygen source in oxidative dehydrocoupling of toluene and toluene derivatives, (2) inorganic metal/- -oxygen compositions useful as catalysts in the oxidative dehydrocoupling of toluene and toluene derivatives, (3) -inorganic metal/,oxygen compositions useful as combination catal~sts/oxygen source in the oxidative dehydrocoupling .of toluene and toluene derivatives, ~4) a one-step vapor phase process for the production of stilbene and stilbene derivatives and bibenzyl and bibenzyl derivatives, and (5) a one-step, Yapor phase dehydrocoupling process for converting toluene and toluene derivatives to stilbene and stilbene derivatives characterized by high toluene conversions and high. stilbene selectivities.
These and other objects and advantages of this invention are achieved by the process disclosed herein for deh~drocoupling toluene and toluene derivativesO
Toluene deh~drocoupled products are produced by heating toluene Cand toluene derivatives) in the presence of an --inorganic metal/oxygen composition which functions in a catal~tic mode, a stoichiometric mode as an oxidant or oxygen carrier, or a combined catalytic/stoichiometTic mode for the dehydrocoupling reaction.
DESCRIP~ION UF THE PREFERRE~ EMBODI~ENTS
In accordance with this invention, toluene and toluene deri~atives are dehydrocoupled by a process ~hich comprises contacting the toluene (and toluene derivatives) in the vapor phase at a temperature between about 450 CO and about 650 C. with an inorganic metalJ-oxygen composition represented by t~e empirical formula:
3i Pb Ma Mb x ~13~
-3a-where Ml is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups la, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is O to 10, and x is a number taken to satisfy the average valences of lead, Ml and M2 in the oxidation states in which they ex-ist in the compositior. to yield the toluene dehydrocoupled toluene product, with the proviso that when M2 is bismuth, Ml cannot be gallium or thallium; and when M2 is antimony, Ml cannot be indium, thallium, germanium, phosphorus, or thorium.
ii3~321 The inorganic metal/oxygen composition functions in a catalytic mode, a stoichiometric mode as an oxidant -or oxygen carrier, or a combined catalytic/stoichiometric mode for the dehydrocoupling of tolueneO
In the catalytic mode of operation, oxygen or an oxygen-containing gas such as air or oxygen-enriched 15 air is reacted with toluene in the presence of the in-organic metal/oxygen composition in an amount sufficient for the dehydrocoupling reaction. In the stoichiometric mode of operation, the inorganic metal/oxygen composition is the sole source o oxygenc That is, in the latter 20 instance the dehydrocoupling of toluene is conducted in the substantial absence of added free oxygen such as would be obtained from air. In the combined catalytic/stoichio-metric mode of operation, oxygen or an oxygen-containing gas is added as a reactant in a manner similar to that 25 noted hereinabove for the catalytic mode of operation.
Ho~e~er, the amount of added oxygen is not sufficient for the dehydrocoupling reaction and the required additional oxygen must be supplied by the inorganic metal/oxygen composition~
Of these three modes of operation, the stoichio-metric mode is generally preferred in that undesirable side reactions -- oxidati~e dealkylation, for example, to produce benzene and carbon dioxide -- are substantially reduced. It will, of course, be recognized that in spite 35 of the undesirability of producing benzene during the course of the reaction of the present process, benzene is 1~3~Zl a valuable article of commerceO It is therefore highly desirable to recover the benzene values when substantial production thereof occurs. The recovery and purification of such benzene values may be accomplished by any standard 5 method and means known to the artO
The term "dehydrocoupling" and related terms are -employ~ed herein to mean that the toluene molecules are coupled or dimerized -- with carbon-carbon bond formation occurring between the methyl group carbons -- and the coupled molecules have lost either one or two hydrogen atoms from the methyl group of each toluene moleculeO
~hen two hydrogen atoms per molecule of toluene are lost, the carbon-carbon bond at the coupling or dimer-ization site is unsaturated as by dehydrogeneration, that is, stilbene is the product. On the other hand, bibenzyl, having a saturated carbon~carbon bond at the coupling site, is the product when only one hydrogen atom per molecule of toluene is lost.
In general, the production o~ stilbene as the deh~drocoupled toluene product is preferred over the pro-duction o~ bibenzylO This stated preference is due to the unsaturated character of stilbene as op~osed to the sat-urated character of bibenzyl~- And, as is well known in the art, the presence of the unsaturated olefinic carbon-carbon double bond causes the stilbene to exhibit high reactivity, thereb~ facilitating its direct use as an organic inter-mediate in numerous organic synthesesO
The process of this invention is conveniently carr~ed out in an apparatus of the type suitable for carrring out chemical reactions in the vapor phaseO It can be conducted in a single reactor or in multiple reactors using either a fixed bed, a moving bed, or a fluidized bed s~stem to ef~ect contacting of the reactant or re-actants and inorganic metal/oxygen compositionO The reactant toluene or toluene derivative will generally be heated and introduced into the reactor as a vaporO However, ~39;~Z~
the reactant may be introduced to the reactor as a liquid and then vaporized.
The oxidative dehydrocoupling reaction is carried out in the vapor phase and under the influence of heatO
5 The temperature range under which the reaction can be -carried out ranges from about 450 CO to about 650 C. and preferably is conducted at from about 500 CO to about 600 C.
Pressure is not critical in the process of this inventionO The reaction may be carried out at subatmos-pheric, atmospheric, or superatmospheric pressures as -desired. It ~ill be generally preferred, however, to con- -duct the reaction at or near atmospheric pressureO Gen-erally, pressures from about 2O53 x 104 pascals or Pa tOo25 atmosphere or atm) to about 4~05 x 105 Pa (4.0 atm) may be conveniently employedO
The reaction time for the contact of the re-actant ~ith the inorganic metal/oxygen composition in this invention may be selected from a broad operable range which may vary from about Ool to about 60 secondsO The reaction time ma~ be defined as the length of time in seconds which the reactant gases measured under reaction conditions are in contact with the inorganic metal/oxygen composition in the reactor, The reaction time may var~ depending upon the reaction temperature and the desired toluene conversion level. At higher temperatures and lower toluene conversion le~els, shorter contact times are requiredO Generally, the contact time will var~ from about 0.5 second to about 20 seconds. Preferably, for optimum conversion and selectiv-ity in the preferred temperature range,-a contast time from about 1 second to about 12 seconds is employed.
In addition to the toluene and/or toluene deriv-atives, other inert substances such as nitrogen, helium, and the like may be present in the reactor~ Such inert materials may be introduced to the process alone or may be combined with the other materials as feedO l~ater or steam l i39~
may be added to the reaction zone, preferably being intro-duced with the feed in order to improve the selectivity to the desired products and parlicularly to suppress com-plete oxidation of C02. Steam-to-hydrocarbon ratios in the range from 0.1 to 10-or more are suitable, the upper limit being determined by practical cost considerationsO Ratios in the range from 0.~ to 3 are preferred~
The inorganic metal/oxygen composition suitable for use in this invention contains oxygen in such a manner that it is capable of releasing stoichiometric quantities of oxygen under the oxidative reaction conditions employedO
The oxygen in the composition is associated with the metals as oxides, as oxygen complexes of at least two of the metals present, or as mixtures of oxides and complexesO
The ~norganic metal/oxygen composition can be represented by the empirical formula:
_ _ Pb Ma ~ x where Ml is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups la, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is 0 to 10, and x is a num-ber taken to satisfy the average valences of lead, Ml and M in the oxidation states in which they exist in the com-position to yield the toluene dehydrocoupled toluene pro-duct with the proviso that when M2 is bismuth, Ml cannot be gallium or thallium; and when M2 is antimony, Ml cannot be indium, thallium, germanium, or thorium. Preferred com-positions are those represented by the above-noted empiri-cal formula wherein a is 0.5 to 5, b is 0.5 to 5, and x is a number taken to satisfy the average valences of Ml to M2 in the oxidation states in which they exist in the compo-sition.
Of the Ml elements listed, silver, zinc, indium, arsenic, lithium, sodium, potassium, rubidium, cesium, and ii39~i mixtures thereof, are preferred with barium, calcium, strontium, silver, zinc, potassium, zirconium, cobalt, and 3b and m xtures thereof, being most preferred. The pre-ferred M element is bismu~h.
The term "Periodic Table of the Elements" as employed herein re~ers to the Periodic Table of the Elements published in CRC Hand~ook of Chemistry and Physics, 59th ed., ~east, Ed., CRC P~ess, Inc., ~est Palm Beach, PL, 1978, Inside Pront Cover, The inorganic metal/oxygen composition may be employed in this invention alone or in association with a support or carrier. The use of a support may ~e partic-ularly advantageous where the composition is too soft or attrition-prone to retain its structural integrity during 15 reactor charging and~or under reaction conditions encount~
ered during the course of the reaction process. Suita~le supports $or the compositions are, for example, silica, alumina, silica-alumina, metal aluminates such as mag~
nesium~aluminate, calcium aluminate, and the like, As noted hereinabove, the dehydrocoupling reaction may ~e conducted in the presence or absence of added free oxygen. ~hen oxygen is not added to the system?
that is, t~e reactIon is conducted in the stoichiometric mode of operation, t~e oxygen required for the reaction is 25 provided by the inorganic metal/oxygen composition ~hich enters into the reaction and is consequently reduced Cor, ~13~;~. Zl g in actual practice , partially reduced) during the course of the reaction. This necessitates regeneration or re-oxidation which can be easily effected by heating the material in air or oxygen at temperatures from about 500 C. to about 650 CO for a period of time ranging from about 5 seconds to about one hour. In a semi-continuous operation, regeneration can be effected by periodic interruption of the reaction for re-oxidation of t~e reduced composition, that is, periods of reaction are cycled with periods of regeneration. Operation, ho~ever, can be on a continuous basis whereby a portion of the inorganic metal/oxygen composition can be con-tinuousl~ or intermittently removed, re-oxidized and the re-oxidized material can thereafter be continuously or intermittently returned to the reaction~ The latter method is particularly adapted to operations in which the inorganic metal/oxygen composition is fed in the form of a fluidized bed or a moving bed system.
When oxygen is employed as a reactant, the reaction may be conducted in either a catalytic mode of operation or a combined catalytic/stoichio~etric mode of operation, depending on the amount of oxygen supplied.
In the catalytic mode of operation, oxygen is supplied in an amount sufficient for the dehydrocoupling reaction.
The actual amount of oxygen supplied may be specified as a function of the amount of the toluene or other suitable hydrocarbon component. On this basis the amount of oxygen supplied is ordinarily selected to provide a hydrocarbon-to-oxygen mole ratio from about 1 to about 8 and prefer-3~ ably from about 2 to about 6~
In the combined catalytic/stoichiometric mode ofoperation, the amount of oxygen supplied as a reactant is not sufficient for the dehydrocoupling reaction, thereby requiring an additional source of oxygen~ The required additional oxygen will be supplied by the inorganic metal/-oxygen composition, that is, the composition will ser~e ~139~Z~
as the additional source of oxygen. As a result, the inorganic metal/oxygen composition enters into the reaction and is consequently reduced during the course of the re-action. This necessitates regeneration or re-oxidation of the reduced composition which can be easily effected as-described hereinabove~for the stoichiometric mode of operationO
In either mode of operation employing added oxygen as a reactant, whether catalytic or combined cata-lytic/stoichiometric, the added free oxygen may be sup-plied either as oxygen or an oxygen-containing gas such as air or oxygen-enriched airO
The inorganic metal/oxygen compositions can be prepared in several waysO The simplest method involves intimately mixing the po~dered metal oxides in the dry state and calciningO Another method involves adding the metal oxides to water with stirring, filtering to remove excess water or, alternatively, heating to evaporate the water, drying, and calcining. In another method of prep-aration, the powdered metal oxides can be intimatelymixed before forming a paste of them with water and further mixing the pasteO The paste can be spread and dried in air, after which it can be calcined in airO The calcined product can then be crushed and sieved to the desired mesh sizeO In still another method of preparation, the powdered metal oxides can be mixed in the dry state together with a material which facilitates forming the mixture into pellets and then pressed to form pellets which are calcined prior to useO A further method of preparation involves intimately mixing the powdered metal oxides in water and spray drying the resulting slurry or solution to produce relatively dust-free and free-flo~ing spherical particles which are also calcined prior to useO
In an alternative method of preparation, suitable inorganic metal/oxygen composition precursor.salts such as nitrates, carbonates, and acetates are intimately mixed or ~13~Zl .
dissolved in water or nitric acid and heated to thermally decompose the precursor salts to form the corresponding oxides and/or oxygen complexes. The oxides and/or oxygen complexes can then be treated as described hereinabove prior to use.
Temperatures employed for calcination of the inorganic metal/oxygen composition may vary from about 400 CO to about 1200 C. The higher temperatures from about 900 C. to~about 1100 C. result in higher selectiv-ity with some loss in activityO Preferred calcinationtemperatures, therefore, lie in the range from about 7noo C. to a~out 1000 CO Calcination times may vary from about 1 hour to about 12 hours or more and prefer-ably from about 2 hours to about 10 hours at the higher temperatures. The surface area of the composition is not critical. In general, however, a surface area less than about 10 m2/g is preferred, with values between about 0.1 m2/g and about 5 m2/g being most preferredO
As previously indicated, the process of this invention is preferably carried out in the absence of added free oxygen, that is, in the stoichiometric mode of operation, and utilizes only that oxygen supplied by the inorganic metal/oxygen compositionO Also, with few excep-tions, at substantially comparable conditions, the lower 25 the toluene conversion level, the higher will be the -selectivity to the dehydrocoupled productsO That is, under similar conditions, the selectivity to the dehydro-coupled toluene products is in general inversely propor-tional to the toluene conversion level~ However, for practical reasons, the dehydrocoupling reaction will generally be conducted at a toluene conversion level of about 20 to about 55 percentO
The dehydrocoupled toluene products, stilbene and bibenzyl, may be recovered and purified by any appro-3s priate method and means known to the art and further --elucidation here will be unnecessary duplication of the art~ As noted previously, stilbene, of course, is the preferred product~
113~Zl The following specific examples illustrating the best presently-known methods of practicing this invention are described in detail in order to facilitate a clear understanding of the invention. It should be understood, however, that the detailed expositions of the application of the invention, while indicating preferred embodiments, are given by way of illustration only and are not to be construed as limiting the invention cince various changes and difications within the spirit of the invention will become apparent to those skilled in the art from this de-tailed description.
.
Procedure A - A series of inorganic metal/-oxygen compositions having varied Pb/Ml atomic ratios were prepared by intimately mixing the appropriate amount in grams of lead (II) oxide (P W) and at least lS one Ml oxide (or hydroxide) in water, filtering to remove excess water or, alternatively, heating to evaporate the water. The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. The parameters for such compositions, conveniently designated as l-A-, are set forth in Table lo ~A
Z~
STARTING MATERIALS
GRAMS (MOLES) SAMPLE NO. PbMal x 1- _ 5 l-A-l- - Pb ZraOx PbO Zr2 .
(a) PbZr0.33x90 0 ( ) 16.6 (0.13) ~b) PbZrO 5x 80.0 (0.363 22.1 (0.18) (c~ PbZrOx 70.0 ~0.31) 38.7 ~0.31) Cd3 PbZr2Ox 50.0 (0.22) 55.2 (0.45) (e2 PbZr3Ox 40.0 ~0.18) 66.3 (0.54) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ l-A-2- Pb K O PbO 85% KOH
ta) PbK2OX 55.0 (0.25) 33.0 C0-503 _ _ _ _ _ 15 l-B-l- Pb YaOX PbO Y2O3 ~a) bY0.33x 38.0 Co.17) 6.4 C0.0283 (b~ PbYo.5x 36.0 ~0.163 9.0 C0.0402 (c~ PbYOx 30 0 Co.13) 15.0 C0.066 td2 PbY6OX 11.2 (Q,050~ 33.q Co~l52 Ce) P~Ylox 9 ~0 Q40) 45.4 C0.203 _ _ _ l-B-2- Pb Ho x PbO H2O3 (a) PbHoOx 11.8 C0.053) 10.0 C0-0262 ~;A .
_.
TABLE 1 CCont'd) CALCINATION CONDITIONS
` ATOMIC RATIO TEMPERATURE, C./TIME, HOURS
S~PLE NO. Pb~M INITIAL FINAL
S l-A-l- Pb/Zr ~a~ 3 400/2 700~12 (b) 2 400/2 700/12 ~cl 1 40Q/2 700fl2 ~dl 0.5 40012 700/12 ~el 0.33 400~2 7Q0~12 _ _ _ _ _ .
l-A-2- Pb~X
~al 0.S 350/2 700/6 _ 15 l-B-l- Pb~
Ca~ 3 400!12 700/12 Cb) 2 400/12 7Q0~12 ~cl 1 4Q0/12 700~12 (d~ 0.17 400/12 700/12 Cel 0.1 400~12 700/12 l-B-2- PbtHo (al 1 450~1 800./8 ..~ .. -~
Procedure B - The procedure described in Procedure A above was enployed except that following the final calcination, the calcined material was rem~ved from the oven, cooled, crushed, and mixed with a calcium aluminate cement (such as the product marketed under the trade mark "Alcoa-CA-25") in an amount corresponding to 25% by weight of the dry weight of the calcined material. The resulting solid mixture was slurried with water to form a thick paste and allowed to air dry. me air-dried paste was calcined in air in an open casserole dish for 2 hours at 400C. and then at a final temperature of 700 & . for an additional 2 hours. The supported inorganic metal/oxygen composition was rem~ved from the oven, cooled, crushed in a m~rtar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. The parameters for such compositions, conveniently designated as l-B-, are set forth in Table 1.
EX~MPLE 2 Procedure A - A series of inorganic metal/oxygen compositions having varied Pb/ ~ atomic ratios were prepared by dissolving the appropriate am~unt in grams of lead (II) acetate trihydrate [Pb(NO3)2~, or lead (II) oxide (PbO) and at least one ~ nitrate in approxLmately 100 milliliters of concentrated nitric acid (HNO3) and heating to evaporate and decompose the nitric acid and the salts. The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was remDved frcm the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 belcw. m e parameters for such compositions, conveniently designated as 2-A-, are set forth in Table 2.
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.
1~3~Zl Procedure B - The procedure described in Procedure A above was employed except that following the final calcination, the calcined material was .-supported on a calcium aluminate cement ("Alcoa-CA-25 s as described in Example 1, Procedure B hereinabove.
The parameters for such compositions, conveniently designated as 2-B-, are set forth in Table 20 113~f'~1 o ,_ o ,_ . ~ ~
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EX~PLE 3 -Procedure A - A solution containing an appropriate amount in grams of lead (II) carbonate (PbC03) dissolved in 300 milliliters of water and acidified to pH 6 with concentrated nitric acid was m xed with a solution containing an appropriate amount in grams of sodium hydrogen phosphate heptahydrate (NaHP04.7 H2O; ~11 = phosphorus, P) dissolved in 300 milliliters of water. The solutions were stirred at high speed for 2 hours. The precipitate was col-lected by suction filtration, dried, and calcined in air for an initial period at an initial temperature and then at a final temperature for an additonal period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to i4/30 mesh particles for evaluation in the toluene conver-sion reactor described in Example 6 below. The para-meters for such compositions, conveniently designated as 3-A-, are set forth in Table 3.
Procedure B - The procedure described in PTocedure A above was employed except that sodium hydrogen arsenate heptahydrate (NaHAsO4 .7H20; ~
arsenic, As) was employed and following the final calcination, the calcined material was supported on a calcium aluminate cement ('~lcoa-CA-25") as described in Example 1, Procedure B hereinabove. The parameters for such compositions, conveniently designated as 3-B-, are set forth in Table 3.
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E~A~IPLE 4 ProceduIe A - A series of inorganic metal/-oxygen compositions having ~aried Pb/M atomic ratios can be prepared by the following described procedure.
Dissolve the appropriate amount in grams of lead ~II) nitrate IPb(NO3)2] and at least one (water soluble) nitTate in water and heat to evaporate the water and decompose the nitrates. Place the resulting solid in an open casserole dish and calcine in air for an initial period at an initial temperature and then at a final temperature for an additional period (usually 1 hour at 4~0 C. and 800 C. for lO hours, respec-tively). Remove the calcined material from the oven, cool, crush in a mortar, and sieve to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. Following these steps should result in compositions, conveniently designated as 4-A-, having properties beneficial for use in the-process of this invention.
Procedure B - The procedure described in - Procedure A above was employed except that following the final calcination, the calcined material was supported on a calcium aluminate cement ('Alcoa-CA-25n~ as described in Example 1, Procedure B herein-above. The parameters for such compositions, con-veniently designated as 4-B-, are set forth in Table 4.
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STARTING MATERIALS
1 ' ` '` ` GRAMS` (MOLES) 'SAMPLE NO. PbMa ~ x '`' Pb ' 5 4'-'B-l- Pb-A~ax - Pb(NO3)2 AgNO3 (a) PbAgo 1x 140.0 (0.42) 7.2 (0.042) (b) PbAgo 125x 14000 (0042) 9.0 (0.053) (c) PbAgo 17x 80.0 (0.24) 6.8 (0.040) (d) PbAgo 25x 133.0 (0.40) 17.0 ~0.10) ~e) PbAgo 5x 121.0 (0.37) 31.0 (0.18) CALCINATION CONDITIONS
ATOMIC RATIO ''TEMPERATURE, C.'/TI~IÉ, HOURS
SAMPLE NOo' Pb/M `' INITI'AL FINAL
15 4-B-l- P~'/Ag (a) 10 450/1 800~10 (b) 8 450/1 800~10 (c) 6 450/1 800~10 (d) 4 450/1 800/10 (e) 2 450/1 800/10 ~A.
Procedure A - A series of inorganic metal/-oxygen compositions containing two or more M elements -were prepared by intimately mixing the appropriate amount of lead (II) oxide (PbO), lead (II) carbonate (PbC03), or lead (II) nitrate /Pb(NO3)2_7 with at least two M carbonates, nitrates, or oxides (or, alternatively, mixing an appropriate amount of a suitable lead-containing binary metal/oxygen com-position with at least one additional Ml carbonate,nitrate, or oxide) in water and heating to evaporate the water and/or decompose the carbonates and/or nitrates.
The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. The parameters for such compositions, con-veniently designated as 5-A-, are set forth in Table 5.
Procedure B - The procedure described in Procedure A above was employed except that following the final calcination, the calcined material was-supported on a calcium aluminate cement ("Alcoa-Ca-25~
as described in Example 1, Procedure B hereinabove.
The parameters for such compositions, conveniently designated as 5-B-, are set forth in Table 5.
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Zl E.~MPLE 6 .~0 Toluene Conversion Reactor - A stainless steel tube 20.32 centimeters (8 inches) in length and O.9S centi-meter (0.375 inch) in internal diameter having a usable capacity of 11 milliliters was employed as a reactor for the toluene conversion reactionO The reactor was arranged vertically and equipped at the upper end with reactant inlet means having calibrated flow controllers and vapor-izers, and at the lower end with reaction effluent outlet means for collecting the reaction effluent or, alternatively, for direct introduction thereof via a gas sampling valve into a gas-liquid chromatograph for analysis. The outlet means was also equipped with means for introducing an inert gas diluent -- nitrogen or helium, for example -- into the reaction effluent for analysis purposesO A radiant furnace was used to maintain a constant temperature during the reaction periodO The temperature was measured with a thermocouple in a temperature well located on the lower outside wall of the reactorO
B. Toluene Conversion - The reaction was con-ducted in the stoichiometric mode of operation unless other-wise noted~ The reactor was charged with approximately 11 milliliters of the inorganic metal/oxygell composition prepared as described in Examples 1-5 above. Glass wool plugs were used as supports for the compositionO The charged reactor was placed in a radiant furnace and heated to maintain a constant temperature through~ut the reaction periodO Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pressure of 10013 x 105 pascal (1 atmosphere) at a rate sufficient to provide a reactor residence ~contact) time of 4 seconds (unless otherwise noted) for the toluene (assuming a 50% void space in the reactor)O After the reaction had proceeded for 1 minute, the reaction effluent, diluted with helium, was analy7ed by gas-liquid chromatography~ The results are tabulated in Table 60 -- ` 113~;~`21 TEMPE~TURE, C./
CONTACT TIME, SAMPLE NO. SECONDSl COl~YERSION, %
1-A-l-~a~ 630 82.7 570 41.6 450 3.2 l-A-l-C~) 630 94.2 570 4S.3 540 28.6 l-A-l-Cc~ 630 86.0 570 47.6 480 8.0 l-~-l-Cd~ 630 4q.3 lS 540 450 3.3 l-A-1-Ce) 630 90.3 570 35.3 480 12.3 1-A-2-Ca~ 630 24.4 570 18,0 450 ` 4.8 l-B-l ~a~ 630 93,6 540 31.
450 9.9 l-B-l~C~l 630 96.0 540 57,6 SlQ 19,3 450 12.0 l-B-l-Cc~ 630 89,0 540 21.7 450 4.5 l-B-l^~d~ 630 72.6 540 17,;
4S0 ~.2 113~;'`Z~
TABLE 6 ~Cont'd) SELECTIVITY, ~
STILBENE +
SA~PLE NO. STILBENE BIBENZYL BENZENE BIBEN6YL
l-A-l-(a) 45.7 0.3 33.0 46.0 62.1 3.4 22.0 65.5 15.6 27.7 31.6 4~.3 l-A-l-~b) 11.8 0.0 60.4 11.8 52.3 0.1 33.6 52.4 56.2 1.6 32.3 57.8 l-A-l-(c~ ~ 33.0 0.0 43.0 33.0 62.2 0.4 27.0 62.6 50.0 15.3 22.0 65.3 l-A-l-~ 20.7 1.9 53.8 22.6 61.1 4.0 25.3 65.1 15.1 25.2 41.0 40.3 l-A-l-(e) 13.5 0.0 60.7 13.5 43.0 0.0 41.1 43.0 48.1 5.3 37.0 53.4 1-A-2-(a) 65.9 8.5 12.7 74,4 77.2 6.2 0.3 83.5 34.2 35.2 7.6 69.4 l-B-l-Ca) 6.7 0.0 67.8 6.7 - 60.2 0.3 30.0 60.5 30.9 7.2 39.3 38.1 l-B-l-Cb~ 4.8 0.0 70.4 4.8 55.7 0.0 25.7 55.7 63.0 0.6 25.5 63.6 57.1 1.0 25.9 58.1 l-B-l-(c) 6.2 0.0 72.9 6.2 53.1 0.0 39.0 53.1 31.5 6.3 42.3 37.8 l-B-l-~d~ 20.7 0.0 60.6 20.7 61.7 0.1 30.8 61.8 29.6 15.9 ~2.~ ~S.5 113~2~
~ 9 TABLE 6 (Cont ' d) TEMPERATURE, C~/
CONTACT TIME, SAMPLE NOo SECONDSl CONVERSION~
l-B-1- (e) 630 5307 540 9ol l-B-2- (a) 630 72~8 450 6~9
BA~KGROUND'OF THE INVENTION
Field of't~e Invent on ' This invention relates to the production of S dehydrocoupled toluene productsO It is particularly related to the oxidative synthesis of 1,2-diphenylethylene (stilbene) from toluene and to'ir.organic metal/oxygen compositions effective ~or oxidatively coupling toluene to produce stilbene.
Stilbene, because of its unsaturated character, is very reactive and may be employed in various organic syntheses. Derivatives of stilbene are useful in the production of products which may be used in the manu-facture of dyes, paints, and resinsO It is also useful in optical brighteners, in pharmaceuticals, and as an organic intermediateO
DescrIption'of th'e_P'rior Art Dehydrocoupling of ~oluene by the reaction with lead oxide to form stilbene has been reported by Behr and Van Dorp,' Che~.'B'er., 6~ 753 (1873) and Lorenz, ChemO Ber., 7 ~ 1996 Cl874) o In this reported work, stilbene is obtain-ed by~ conveying toluene over lead oxide maintained at or about at a dark red glo~O T~e coupling of toluene using elemental sulfur as the coupling agent has been reported by Renard, Bul'l'. S'o'cO Ch'im.''France, 3~ 958 ~1889); 5~ 278 (1891~ and t~e types of products produced by such coupling reactions ha~e been discussed by Horton,'3, Org. Chem., 14, 761 C1949~o ~ore recently, UOS. Patent No. 3~476~747 discloses arsenic pentoxide, antimony tetroxide, antimony pentoxide, bismuth trioxide, and manganese arsenate as oxidants for the oxidative dehydrocoupling of toluene to form 1,2-bis(aryl)ethylenes. Similarly, U.SO Patent No.
3,494,956 discloses lead oxide, cadmium oxide, and thallium oxide as suitable oxidants, and in Example 9 a mixture of toluene and oxygen passed over heated lead oxide produced bibenzylO In UOS. Patent NoO 3,557,235 the stoichiometric toluene coupling reaction is taught using an oxide of bismuth, lead, tellurium, barium, thallium, cadmium, or mixtures thereof which serves as the source of oxygen in the reactionO UOSO Patent No. 3,963,7g3 teaches the use of bismuth trioxide and thallium trioxide or mixtures thereof supported on basic carrier materials selected from the oxides of Group 2a elements and having a minimum surface area of 20 m /g as suitable for toluene coupling to produce bibenzylO The addition to the supported catalyst of small amounts of silver as a promoter is also disclosedO In UOSO Patent NoO 3,965,206 oxides of lead, cadmium, bismuth, and mixtures thereof are taught as suit-able oxidants for toluene coupling. This patent alsoteaches the disproportionation of the stilbene with ethylene to produce styrene~ U.SO Patent No. 3,980,580 discloses an oxygen composition of lead, magnesium, and aluminum as an oxidant for toluene couplingO Also, U.S.
Patent NoO 4,091,044 discloses oxygen compositions of lead and antimony and optionally with bismuth as oxidants for toluene coupling to form stilbene.
SUMMARY OF THE INVENTION
This invention is directed to a pTocess for the oxidative dehydrocoupling of toluene and toluene deriv-atives to stil~ene and stilbene derivativesO In another aspect, this invention is directed to inorganic metal/-oxygen compositions which are useful as the oxygen source for the oxidative dehydrocoupling of toluene to produce stilbene, or alternatively as catalysts or combination catalysts/oxygen source for the dehydrocoupling reaction ~3~
,, when oxygen or an oxygen-containing gas is heated with the toluene.
Accordingly, typical objects of this invention are to provide (1) inorganic metal/oxygen compositions useful as the oxygen source in oxidative dehydrocoupling of toluene and toluene derivatives, (2) inorganic metal/- -oxygen compositions useful as catalysts in the oxidative dehydrocoupling of toluene and toluene derivatives, (3) -inorganic metal/,oxygen compositions useful as combination catal~sts/oxygen source in the oxidative dehydrocoupling .of toluene and toluene derivatives, ~4) a one-step vapor phase process for the production of stilbene and stilbene derivatives and bibenzyl and bibenzyl derivatives, and (5) a one-step, Yapor phase dehydrocoupling process for converting toluene and toluene derivatives to stilbene and stilbene derivatives characterized by high toluene conversions and high. stilbene selectivities.
These and other objects and advantages of this invention are achieved by the process disclosed herein for deh~drocoupling toluene and toluene derivativesO
Toluene deh~drocoupled products are produced by heating toluene Cand toluene derivatives) in the presence of an --inorganic metal/oxygen composition which functions in a catal~tic mode, a stoichiometric mode as an oxidant or oxygen carrier, or a combined catalytic/stoichiometTic mode for the dehydrocoupling reaction.
DESCRIP~ION UF THE PREFERRE~ EMBODI~ENTS
In accordance with this invention, toluene and toluene deri~atives are dehydrocoupled by a process ~hich comprises contacting the toluene (and toluene derivatives) in the vapor phase at a temperature between about 450 CO and about 650 C. with an inorganic metalJ-oxygen composition represented by t~e empirical formula:
3i Pb Ma Mb x ~13~
-3a-where Ml is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups la, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is O to 10, and x is a number taken to satisfy the average valences of lead, Ml and M2 in the oxidation states in which they ex-ist in the compositior. to yield the toluene dehydrocoupled toluene product, with the proviso that when M2 is bismuth, Ml cannot be gallium or thallium; and when M2 is antimony, Ml cannot be indium, thallium, germanium, phosphorus, or thorium.
ii3~321 The inorganic metal/oxygen composition functions in a catalytic mode, a stoichiometric mode as an oxidant -or oxygen carrier, or a combined catalytic/stoichiometric mode for the dehydrocoupling of tolueneO
In the catalytic mode of operation, oxygen or an oxygen-containing gas such as air or oxygen-enriched 15 air is reacted with toluene in the presence of the in-organic metal/oxygen composition in an amount sufficient for the dehydrocoupling reaction. In the stoichiometric mode of operation, the inorganic metal/oxygen composition is the sole source o oxygenc That is, in the latter 20 instance the dehydrocoupling of toluene is conducted in the substantial absence of added free oxygen such as would be obtained from air. In the combined catalytic/stoichio-metric mode of operation, oxygen or an oxygen-containing gas is added as a reactant in a manner similar to that 25 noted hereinabove for the catalytic mode of operation.
Ho~e~er, the amount of added oxygen is not sufficient for the dehydrocoupling reaction and the required additional oxygen must be supplied by the inorganic metal/oxygen composition~
Of these three modes of operation, the stoichio-metric mode is generally preferred in that undesirable side reactions -- oxidati~e dealkylation, for example, to produce benzene and carbon dioxide -- are substantially reduced. It will, of course, be recognized that in spite 35 of the undesirability of producing benzene during the course of the reaction of the present process, benzene is 1~3~Zl a valuable article of commerceO It is therefore highly desirable to recover the benzene values when substantial production thereof occurs. The recovery and purification of such benzene values may be accomplished by any standard 5 method and means known to the artO
The term "dehydrocoupling" and related terms are -employ~ed herein to mean that the toluene molecules are coupled or dimerized -- with carbon-carbon bond formation occurring between the methyl group carbons -- and the coupled molecules have lost either one or two hydrogen atoms from the methyl group of each toluene moleculeO
~hen two hydrogen atoms per molecule of toluene are lost, the carbon-carbon bond at the coupling or dimer-ization site is unsaturated as by dehydrogeneration, that is, stilbene is the product. On the other hand, bibenzyl, having a saturated carbon~carbon bond at the coupling site, is the product when only one hydrogen atom per molecule of toluene is lost.
In general, the production o~ stilbene as the deh~drocoupled toluene product is preferred over the pro-duction o~ bibenzylO This stated preference is due to the unsaturated character of stilbene as op~osed to the sat-urated character of bibenzyl~- And, as is well known in the art, the presence of the unsaturated olefinic carbon-carbon double bond causes the stilbene to exhibit high reactivity, thereb~ facilitating its direct use as an organic inter-mediate in numerous organic synthesesO
The process of this invention is conveniently carr~ed out in an apparatus of the type suitable for carrring out chemical reactions in the vapor phaseO It can be conducted in a single reactor or in multiple reactors using either a fixed bed, a moving bed, or a fluidized bed s~stem to ef~ect contacting of the reactant or re-actants and inorganic metal/oxygen compositionO The reactant toluene or toluene derivative will generally be heated and introduced into the reactor as a vaporO However, ~39;~Z~
the reactant may be introduced to the reactor as a liquid and then vaporized.
The oxidative dehydrocoupling reaction is carried out in the vapor phase and under the influence of heatO
5 The temperature range under which the reaction can be -carried out ranges from about 450 CO to about 650 C. and preferably is conducted at from about 500 CO to about 600 C.
Pressure is not critical in the process of this inventionO The reaction may be carried out at subatmos-pheric, atmospheric, or superatmospheric pressures as -desired. It ~ill be generally preferred, however, to con- -duct the reaction at or near atmospheric pressureO Gen-erally, pressures from about 2O53 x 104 pascals or Pa tOo25 atmosphere or atm) to about 4~05 x 105 Pa (4.0 atm) may be conveniently employedO
The reaction time for the contact of the re-actant ~ith the inorganic metal/oxygen composition in this invention may be selected from a broad operable range which may vary from about Ool to about 60 secondsO The reaction time ma~ be defined as the length of time in seconds which the reactant gases measured under reaction conditions are in contact with the inorganic metal/oxygen composition in the reactor, The reaction time may var~ depending upon the reaction temperature and the desired toluene conversion level. At higher temperatures and lower toluene conversion le~els, shorter contact times are requiredO Generally, the contact time will var~ from about 0.5 second to about 20 seconds. Preferably, for optimum conversion and selectiv-ity in the preferred temperature range,-a contast time from about 1 second to about 12 seconds is employed.
In addition to the toluene and/or toluene deriv-atives, other inert substances such as nitrogen, helium, and the like may be present in the reactor~ Such inert materials may be introduced to the process alone or may be combined with the other materials as feedO l~ater or steam l i39~
may be added to the reaction zone, preferably being intro-duced with the feed in order to improve the selectivity to the desired products and parlicularly to suppress com-plete oxidation of C02. Steam-to-hydrocarbon ratios in the range from 0.1 to 10-or more are suitable, the upper limit being determined by practical cost considerationsO Ratios in the range from 0.~ to 3 are preferred~
The inorganic metal/oxygen composition suitable for use in this invention contains oxygen in such a manner that it is capable of releasing stoichiometric quantities of oxygen under the oxidative reaction conditions employedO
The oxygen in the composition is associated with the metals as oxides, as oxygen complexes of at least two of the metals present, or as mixtures of oxides and complexesO
The ~norganic metal/oxygen composition can be represented by the empirical formula:
_ _ Pb Ma ~ x where Ml is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups la, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is 0 to 10, and x is a num-ber taken to satisfy the average valences of lead, Ml and M in the oxidation states in which they exist in the com-position to yield the toluene dehydrocoupled toluene pro-duct with the proviso that when M2 is bismuth, Ml cannot be gallium or thallium; and when M2 is antimony, Ml cannot be indium, thallium, germanium, or thorium. Preferred com-positions are those represented by the above-noted empiri-cal formula wherein a is 0.5 to 5, b is 0.5 to 5, and x is a number taken to satisfy the average valences of Ml to M2 in the oxidation states in which they exist in the compo-sition.
Of the Ml elements listed, silver, zinc, indium, arsenic, lithium, sodium, potassium, rubidium, cesium, and ii39~i mixtures thereof, are preferred with barium, calcium, strontium, silver, zinc, potassium, zirconium, cobalt, and 3b and m xtures thereof, being most preferred. The pre-ferred M element is bismu~h.
The term "Periodic Table of the Elements" as employed herein re~ers to the Periodic Table of the Elements published in CRC Hand~ook of Chemistry and Physics, 59th ed., ~east, Ed., CRC P~ess, Inc., ~est Palm Beach, PL, 1978, Inside Pront Cover, The inorganic metal/oxygen composition may be employed in this invention alone or in association with a support or carrier. The use of a support may ~e partic-ularly advantageous where the composition is too soft or attrition-prone to retain its structural integrity during 15 reactor charging and~or under reaction conditions encount~
ered during the course of the reaction process. Suita~le supports $or the compositions are, for example, silica, alumina, silica-alumina, metal aluminates such as mag~
nesium~aluminate, calcium aluminate, and the like, As noted hereinabove, the dehydrocoupling reaction may ~e conducted in the presence or absence of added free oxygen. ~hen oxygen is not added to the system?
that is, t~e reactIon is conducted in the stoichiometric mode of operation, t~e oxygen required for the reaction is 25 provided by the inorganic metal/oxygen composition ~hich enters into the reaction and is consequently reduced Cor, ~13~;~. Zl g in actual practice , partially reduced) during the course of the reaction. This necessitates regeneration or re-oxidation which can be easily effected by heating the material in air or oxygen at temperatures from about 500 C. to about 650 CO for a period of time ranging from about 5 seconds to about one hour. In a semi-continuous operation, regeneration can be effected by periodic interruption of the reaction for re-oxidation of t~e reduced composition, that is, periods of reaction are cycled with periods of regeneration. Operation, ho~ever, can be on a continuous basis whereby a portion of the inorganic metal/oxygen composition can be con-tinuousl~ or intermittently removed, re-oxidized and the re-oxidized material can thereafter be continuously or intermittently returned to the reaction~ The latter method is particularly adapted to operations in which the inorganic metal/oxygen composition is fed in the form of a fluidized bed or a moving bed system.
When oxygen is employed as a reactant, the reaction may be conducted in either a catalytic mode of operation or a combined catalytic/stoichio~etric mode of operation, depending on the amount of oxygen supplied.
In the catalytic mode of operation, oxygen is supplied in an amount sufficient for the dehydrocoupling reaction.
The actual amount of oxygen supplied may be specified as a function of the amount of the toluene or other suitable hydrocarbon component. On this basis the amount of oxygen supplied is ordinarily selected to provide a hydrocarbon-to-oxygen mole ratio from about 1 to about 8 and prefer-3~ ably from about 2 to about 6~
In the combined catalytic/stoichiometric mode ofoperation, the amount of oxygen supplied as a reactant is not sufficient for the dehydrocoupling reaction, thereby requiring an additional source of oxygen~ The required additional oxygen will be supplied by the inorganic metal/-oxygen composition, that is, the composition will ser~e ~139~Z~
as the additional source of oxygen. As a result, the inorganic metal/oxygen composition enters into the reaction and is consequently reduced during the course of the re-action. This necessitates regeneration or re-oxidation of the reduced composition which can be easily effected as-described hereinabove~for the stoichiometric mode of operationO
In either mode of operation employing added oxygen as a reactant, whether catalytic or combined cata-lytic/stoichiometric, the added free oxygen may be sup-plied either as oxygen or an oxygen-containing gas such as air or oxygen-enriched airO
The inorganic metal/oxygen compositions can be prepared in several waysO The simplest method involves intimately mixing the po~dered metal oxides in the dry state and calciningO Another method involves adding the metal oxides to water with stirring, filtering to remove excess water or, alternatively, heating to evaporate the water, drying, and calcining. In another method of prep-aration, the powdered metal oxides can be intimatelymixed before forming a paste of them with water and further mixing the pasteO The paste can be spread and dried in air, after which it can be calcined in airO The calcined product can then be crushed and sieved to the desired mesh sizeO In still another method of preparation, the powdered metal oxides can be mixed in the dry state together with a material which facilitates forming the mixture into pellets and then pressed to form pellets which are calcined prior to useO A further method of preparation involves intimately mixing the powdered metal oxides in water and spray drying the resulting slurry or solution to produce relatively dust-free and free-flo~ing spherical particles which are also calcined prior to useO
In an alternative method of preparation, suitable inorganic metal/oxygen composition precursor.salts such as nitrates, carbonates, and acetates are intimately mixed or ~13~Zl .
dissolved in water or nitric acid and heated to thermally decompose the precursor salts to form the corresponding oxides and/or oxygen complexes. The oxides and/or oxygen complexes can then be treated as described hereinabove prior to use.
Temperatures employed for calcination of the inorganic metal/oxygen composition may vary from about 400 CO to about 1200 C. The higher temperatures from about 900 C. to~about 1100 C. result in higher selectiv-ity with some loss in activityO Preferred calcinationtemperatures, therefore, lie in the range from about 7noo C. to a~out 1000 CO Calcination times may vary from about 1 hour to about 12 hours or more and prefer-ably from about 2 hours to about 10 hours at the higher temperatures. The surface area of the composition is not critical. In general, however, a surface area less than about 10 m2/g is preferred, with values between about 0.1 m2/g and about 5 m2/g being most preferredO
As previously indicated, the process of this invention is preferably carried out in the absence of added free oxygen, that is, in the stoichiometric mode of operation, and utilizes only that oxygen supplied by the inorganic metal/oxygen compositionO Also, with few excep-tions, at substantially comparable conditions, the lower 25 the toluene conversion level, the higher will be the -selectivity to the dehydrocoupled productsO That is, under similar conditions, the selectivity to the dehydro-coupled toluene products is in general inversely propor-tional to the toluene conversion level~ However, for practical reasons, the dehydrocoupling reaction will generally be conducted at a toluene conversion level of about 20 to about 55 percentO
The dehydrocoupled toluene products, stilbene and bibenzyl, may be recovered and purified by any appro-3s priate method and means known to the art and further --elucidation here will be unnecessary duplication of the art~ As noted previously, stilbene, of course, is the preferred product~
113~Zl The following specific examples illustrating the best presently-known methods of practicing this invention are described in detail in order to facilitate a clear understanding of the invention. It should be understood, however, that the detailed expositions of the application of the invention, while indicating preferred embodiments, are given by way of illustration only and are not to be construed as limiting the invention cince various changes and difications within the spirit of the invention will become apparent to those skilled in the art from this de-tailed description.
.
Procedure A - A series of inorganic metal/-oxygen compositions having varied Pb/Ml atomic ratios were prepared by intimately mixing the appropriate amount in grams of lead (II) oxide (P W) and at least lS one Ml oxide (or hydroxide) in water, filtering to remove excess water or, alternatively, heating to evaporate the water. The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. The parameters for such compositions, conveniently designated as l-A-, are set forth in Table lo ~A
Z~
STARTING MATERIALS
GRAMS (MOLES) SAMPLE NO. PbMal x 1- _ 5 l-A-l- - Pb ZraOx PbO Zr2 .
(a) PbZr0.33x90 0 ( ) 16.6 (0.13) ~b) PbZrO 5x 80.0 (0.363 22.1 (0.18) (c~ PbZrOx 70.0 ~0.31) 38.7 ~0.31) Cd3 PbZr2Ox 50.0 (0.22) 55.2 (0.45) (e2 PbZr3Ox 40.0 ~0.18) 66.3 (0.54) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ l-A-2- Pb K O PbO 85% KOH
ta) PbK2OX 55.0 (0.25) 33.0 C0-503 _ _ _ _ _ 15 l-B-l- Pb YaOX PbO Y2O3 ~a) bY0.33x 38.0 Co.17) 6.4 C0.0283 (b~ PbYo.5x 36.0 ~0.163 9.0 C0.0402 (c~ PbYOx 30 0 Co.13) 15.0 C0.066 td2 PbY6OX 11.2 (Q,050~ 33.q Co~l52 Ce) P~Ylox 9 ~0 Q40) 45.4 C0.203 _ _ _ l-B-2- Pb Ho x PbO H2O3 (a) PbHoOx 11.8 C0.053) 10.0 C0-0262 ~;A .
_.
TABLE 1 CCont'd) CALCINATION CONDITIONS
` ATOMIC RATIO TEMPERATURE, C./TIME, HOURS
S~PLE NO. Pb~M INITIAL FINAL
S l-A-l- Pb/Zr ~a~ 3 400/2 700~12 (b) 2 400/2 700/12 ~cl 1 40Q/2 700fl2 ~dl 0.5 40012 700/12 ~el 0.33 400~2 7Q0~12 _ _ _ _ _ .
l-A-2- Pb~X
~al 0.S 350/2 700/6 _ 15 l-B-l- Pb~
Ca~ 3 400!12 700/12 Cb) 2 400/12 7Q0~12 ~cl 1 4Q0/12 700~12 (d~ 0.17 400/12 700/12 Cel 0.1 400~12 700/12 l-B-2- PbtHo (al 1 450~1 800./8 ..~ .. -~
Procedure B - The procedure described in Procedure A above was enployed except that following the final calcination, the calcined material was rem~ved from the oven, cooled, crushed, and mixed with a calcium aluminate cement (such as the product marketed under the trade mark "Alcoa-CA-25") in an amount corresponding to 25% by weight of the dry weight of the calcined material. The resulting solid mixture was slurried with water to form a thick paste and allowed to air dry. me air-dried paste was calcined in air in an open casserole dish for 2 hours at 400C. and then at a final temperature of 700 & . for an additional 2 hours. The supported inorganic metal/oxygen composition was rem~ved from the oven, cooled, crushed in a m~rtar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. The parameters for such compositions, conveniently designated as l-B-, are set forth in Table 1.
EX~MPLE 2 Procedure A - A series of inorganic metal/oxygen compositions having varied Pb/ ~ atomic ratios were prepared by dissolving the appropriate am~unt in grams of lead (II) acetate trihydrate [Pb(NO3)2~, or lead (II) oxide (PbO) and at least one ~ nitrate in approxLmately 100 milliliters of concentrated nitric acid (HNO3) and heating to evaporate and decompose the nitric acid and the salts. The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was remDved frcm the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 belcw. m e parameters for such compositions, conveniently designated as 2-A-, are set forth in Table 2.
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1~3~Zl Procedure B - The procedure described in Procedure A above was employed except that following the final calcination, the calcined material was .-supported on a calcium aluminate cement ("Alcoa-CA-25 s as described in Example 1, Procedure B hereinabove.
The parameters for such compositions, conveniently designated as 2-B-, are set forth in Table 20 113~f'~1 o ,_ o ,_ . ~ ~
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EX~PLE 3 -Procedure A - A solution containing an appropriate amount in grams of lead (II) carbonate (PbC03) dissolved in 300 milliliters of water and acidified to pH 6 with concentrated nitric acid was m xed with a solution containing an appropriate amount in grams of sodium hydrogen phosphate heptahydrate (NaHP04.7 H2O; ~11 = phosphorus, P) dissolved in 300 milliliters of water. The solutions were stirred at high speed for 2 hours. The precipitate was col-lected by suction filtration, dried, and calcined in air for an initial period at an initial temperature and then at a final temperature for an additonal period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to i4/30 mesh particles for evaluation in the toluene conver-sion reactor described in Example 6 below. The para-meters for such compositions, conveniently designated as 3-A-, are set forth in Table 3.
Procedure B - The procedure described in PTocedure A above was employed except that sodium hydrogen arsenate heptahydrate (NaHAsO4 .7H20; ~
arsenic, As) was employed and following the final calcination, the calcined material was supported on a calcium aluminate cement ('~lcoa-CA-25") as described in Example 1, Procedure B hereinabove. The parameters for such compositions, conveniently designated as 3-B-, are set forth in Table 3.
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E~A~IPLE 4 ProceduIe A - A series of inorganic metal/-oxygen compositions having ~aried Pb/M atomic ratios can be prepared by the following described procedure.
Dissolve the appropriate amount in grams of lead ~II) nitrate IPb(NO3)2] and at least one (water soluble) nitTate in water and heat to evaporate the water and decompose the nitrates. Place the resulting solid in an open casserole dish and calcine in air for an initial period at an initial temperature and then at a final temperature for an additional period (usually 1 hour at 4~0 C. and 800 C. for lO hours, respec-tively). Remove the calcined material from the oven, cool, crush in a mortar, and sieve to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. Following these steps should result in compositions, conveniently designated as 4-A-, having properties beneficial for use in the-process of this invention.
Procedure B - The procedure described in - Procedure A above was employed except that following the final calcination, the calcined material was supported on a calcium aluminate cement ('Alcoa-CA-25n~ as described in Example 1, Procedure B herein-above. The parameters for such compositions, con-veniently designated as 4-B-, are set forth in Table 4.
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STARTING MATERIALS
1 ' ` '` ` GRAMS` (MOLES) 'SAMPLE NO. PbMa ~ x '`' Pb ' 5 4'-'B-l- Pb-A~ax - Pb(NO3)2 AgNO3 (a) PbAgo 1x 140.0 (0.42) 7.2 (0.042) (b) PbAgo 125x 14000 (0042) 9.0 (0.053) (c) PbAgo 17x 80.0 (0.24) 6.8 (0.040) (d) PbAgo 25x 133.0 (0.40) 17.0 ~0.10) ~e) PbAgo 5x 121.0 (0.37) 31.0 (0.18) CALCINATION CONDITIONS
ATOMIC RATIO ''TEMPERATURE, C.'/TI~IÉ, HOURS
SAMPLE NOo' Pb/M `' INITI'AL FINAL
15 4-B-l- P~'/Ag (a) 10 450/1 800~10 (b) 8 450/1 800~10 (c) 6 450/1 800~10 (d) 4 450/1 800/10 (e) 2 450/1 800/10 ~A.
Procedure A - A series of inorganic metal/-oxygen compositions containing two or more M elements -were prepared by intimately mixing the appropriate amount of lead (II) oxide (PbO), lead (II) carbonate (PbC03), or lead (II) nitrate /Pb(NO3)2_7 with at least two M carbonates, nitrates, or oxides (or, alternatively, mixing an appropriate amount of a suitable lead-containing binary metal/oxygen com-position with at least one additional Ml carbonate,nitrate, or oxide) in water and heating to evaporate the water and/or decompose the carbonates and/or nitrates.
The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 6 below. The parameters for such compositions, con-veniently designated as 5-A-, are set forth in Table 5.
Procedure B - The procedure described in Procedure A above was employed except that following the final calcination, the calcined material was-supported on a calcium aluminate cement ("Alcoa-Ca-25~
as described in Example 1, Procedure B hereinabove.
The parameters for such compositions, conveniently designated as 5-B-, are set forth in Table 5.
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Zl E.~MPLE 6 .~0 Toluene Conversion Reactor - A stainless steel tube 20.32 centimeters (8 inches) in length and O.9S centi-meter (0.375 inch) in internal diameter having a usable capacity of 11 milliliters was employed as a reactor for the toluene conversion reactionO The reactor was arranged vertically and equipped at the upper end with reactant inlet means having calibrated flow controllers and vapor-izers, and at the lower end with reaction effluent outlet means for collecting the reaction effluent or, alternatively, for direct introduction thereof via a gas sampling valve into a gas-liquid chromatograph for analysis. The outlet means was also equipped with means for introducing an inert gas diluent -- nitrogen or helium, for example -- into the reaction effluent for analysis purposesO A radiant furnace was used to maintain a constant temperature during the reaction periodO The temperature was measured with a thermocouple in a temperature well located on the lower outside wall of the reactorO
B. Toluene Conversion - The reaction was con-ducted in the stoichiometric mode of operation unless other-wise noted~ The reactor was charged with approximately 11 milliliters of the inorganic metal/oxygell composition prepared as described in Examples 1-5 above. Glass wool plugs were used as supports for the compositionO The charged reactor was placed in a radiant furnace and heated to maintain a constant temperature through~ut the reaction periodO Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pressure of 10013 x 105 pascal (1 atmosphere) at a rate sufficient to provide a reactor residence ~contact) time of 4 seconds (unless otherwise noted) for the toluene (assuming a 50% void space in the reactor)O After the reaction had proceeded for 1 minute, the reaction effluent, diluted with helium, was analy7ed by gas-liquid chromatography~ The results are tabulated in Table 60 -- ` 113~;~`21 TEMPE~TURE, C./
CONTACT TIME, SAMPLE NO. SECONDSl COl~YERSION, %
1-A-l-~a~ 630 82.7 570 41.6 450 3.2 l-A-l-C~) 630 94.2 570 4S.3 540 28.6 l-A-l-Cc~ 630 86.0 570 47.6 480 8.0 l-~-l-Cd~ 630 4q.3 lS 540 450 3.3 l-A-1-Ce) 630 90.3 570 35.3 480 12.3 1-A-2-Ca~ 630 24.4 570 18,0 450 ` 4.8 l-B-l ~a~ 630 93,6 540 31.
450 9.9 l-B-l~C~l 630 96.0 540 57,6 SlQ 19,3 450 12.0 l-B-l-Cc~ 630 89,0 540 21.7 450 4.5 l-B-l^~d~ 630 72.6 540 17,;
4S0 ~.2 113~;'`Z~
TABLE 6 ~Cont'd) SELECTIVITY, ~
STILBENE +
SA~PLE NO. STILBENE BIBENZYL BENZENE BIBEN6YL
l-A-l-(a) 45.7 0.3 33.0 46.0 62.1 3.4 22.0 65.5 15.6 27.7 31.6 4~.3 l-A-l-~b) 11.8 0.0 60.4 11.8 52.3 0.1 33.6 52.4 56.2 1.6 32.3 57.8 l-A-l-(c~ ~ 33.0 0.0 43.0 33.0 62.2 0.4 27.0 62.6 50.0 15.3 22.0 65.3 l-A-l-~ 20.7 1.9 53.8 22.6 61.1 4.0 25.3 65.1 15.1 25.2 41.0 40.3 l-A-l-(e) 13.5 0.0 60.7 13.5 43.0 0.0 41.1 43.0 48.1 5.3 37.0 53.4 1-A-2-(a) 65.9 8.5 12.7 74,4 77.2 6.2 0.3 83.5 34.2 35.2 7.6 69.4 l-B-l-Ca) 6.7 0.0 67.8 6.7 - 60.2 0.3 30.0 60.5 30.9 7.2 39.3 38.1 l-B-l-Cb~ 4.8 0.0 70.4 4.8 55.7 0.0 25.7 55.7 63.0 0.6 25.5 63.6 57.1 1.0 25.9 58.1 l-B-l-(c) 6.2 0.0 72.9 6.2 53.1 0.0 39.0 53.1 31.5 6.3 42.3 37.8 l-B-l-~d~ 20.7 0.0 60.6 20.7 61.7 0.1 30.8 61.8 29.6 15.9 ~2.~ ~S.5 113~2~
~ 9 TABLE 6 (Cont ' d) TEMPERATURE, C~/
CONTACT TIME, SAMPLE NOo SECONDSl CONVERSION~
l-B-1- (e) 630 5307 540 9ol l-B-2- (a) 630 72~8 450 6~9
2-A-l- (a) 630 9006 540 l9oO
2-A-2- (a) 600 85~5 2-B-l- (a) 630 9200 540 20~2 2-B-l- (b) 630 7000 480 1~9 2-B-l-(c) 630 85oO
2-B-l- (d) 630 8201 480 lol 2-B-l- ~e) 630 5800 480 lo5 2-B-l- (f) 630 69~1 540 lloO
2-B-l-(g) 630 .6804 540 15.3 480 3~7 il3~
-io-TABLE 6 (Cont'd) SELECTIVITY, %
STILBENE
SAMPLE N0. STILBENE BIBENZYL BENZENE BIBENZYL
l-B-l-(e) 301 000 74.2 301 OoO(?) 1508 3603 1508 l-B-2-(a) 19.3 ncO 5609 19.3 5305 loO 42.3 54.5 5007 902 25o6 59.9 2-A-l-~a) 1003 003 59.3 10.6 5605 3c5 3003 60.0 6500 80n 1201 7300 2-A-2-(a) 2.6 000 89.1 206 1906 Ool 70.3 1907 2-B-l-(a) 1200 000 8105 1200 5909 -0.0 41.4 5909 5703 lol 2908 58~4 2-B-l-~b) 5206 004 3409 5300 80.0 loO 1709 8100 54c6 1204 2305 6700 2-B-l-~c) 2203 000 7005 2203 54.2 204 3300 5606 2-B-l-(d) 4104 000 2603 4104 lOo9 2203 3807 3302 2-B-l-(e) 5602 004 2805 5606 3803 1809 2803 57.2 2-B-l-(f) 4900 000 370 4900 7505 402 l9o9 7907 2-B-l-(g) 4704 000 ;909 47~4 45o8 1104 3005 570' i3~;~Zl TABLE 6 (Cont'd) TEMPERATURE, CO/
CONTACT TIME, SAMPLE NO SECONDSl CON~-ERSION %
.. _
2-A-2- (a) 600 85~5 2-B-l- (a) 630 9200 540 20~2 2-B-l- (b) 630 7000 480 1~9 2-B-l-(c) 630 85oO
2-B-l- (d) 630 8201 480 lol 2-B-l- ~e) 630 5800 480 lo5 2-B-l- (f) 630 69~1 540 lloO
2-B-l-(g) 630 .6804 540 15.3 480 3~7 il3~
-io-TABLE 6 (Cont'd) SELECTIVITY, %
STILBENE
SAMPLE N0. STILBENE BIBENZYL BENZENE BIBENZYL
l-B-l-(e) 301 000 74.2 301 OoO(?) 1508 3603 1508 l-B-2-(a) 19.3 ncO 5609 19.3 5305 loO 42.3 54.5 5007 902 25o6 59.9 2-A-l-~a) 1003 003 59.3 10.6 5605 3c5 3003 60.0 6500 80n 1201 7300 2-A-2-(a) 2.6 000 89.1 206 1906 Ool 70.3 1907 2-B-l-(a) 1200 000 8105 1200 5909 -0.0 41.4 5909 5703 lol 2908 58~4 2-B-l-~b) 5206 004 3409 5300 80.0 loO 1709 8100 54c6 1204 2305 6700 2-B-l-~c) 2203 000 7005 2203 54.2 204 3300 5606 2-B-l-(d) 4104 000 2603 4104 lOo9 2203 3807 3302 2-B-l-(e) 5602 004 2805 5606 3803 1809 2803 57.2 2-B-l-(f) 4900 000 370 4900 7505 402 l9o9 7907 2-B-l-(g) 4704 000 ;909 47~4 45o8 1104 3005 570' i3~;~Zl TABLE 6 (Cont'd) TEMPERATURE, CO/
CONTACT TIME, SAMPLE NO SECONDSl CON~-ERSION %
.. _
3-A-l-(a) 570 39.1 3-B-l-(a) 570 35-3
4-B-l-(a) 630 60.0 450 0.7 4-B-l-~b) 630 47O7 570 19.5 450 0.6 4-B-l-(c) 630 51.2 4-B-l-(d) 630 43.6 570 14.1 4-B-l-(e) 630 57O5 570 29.6 450 1.3
5-A-l-(a) 630 71O8 570 29.2 450 1.1 5-A-2-(a) 630 6509 5-A-3-(a) 630 90O0 450 lo9 5-A-4-(a) 630 91.1 5-B-l-(a) 630 90.0 570 45.7 450 lo9 li3~Zl -i2 TABLE 6 (Cont'd) _ SELECTIVITY, SA~IPLE ~0. STILBENE BIBENZYL BENZENE BIBENZYL
3-A-l-(a) 3805 4.3 39014Z.8 3-B-l-(a) 640-3 3.1 80567.4 4-B-l-(a) 5602 306 24045908 7~.ol 16.0 lloO8801 1008 36.5 38064703 4-B-l-(b) 53.7 7.3 22.06~ol 605 3205 40.939.0 4-B-l-(c) 3603 705 26.543.8 9ol 2904 330038.5 4-B-l-(d) 5302 9.5 210262.7 5002 30.8 11088100 0.0 2302 45002302 4-B-l-~e) 52.1 2.7 29045408 5-A-l-(a) 5706 205 20086001 58.9 16.3 1~o57502 304 31.7 41043501 5-A-2-(a) 3206 0.0 49073206 7806 0.0 1806?806 1305 29.3 11044209 5-A-3-Ca) 1409 000 73061409 5405 0.0 360554.5 l9o9 801 56002800 5-A-4-(a) lloO O~O 810311.0 5907 0.0 310159.7 1902 204 45,12106 5-B-l-Ca) 14~9 000 73061409 `` 113~Zl TABLE 6 (Cont'd) TEMPERATURE, C./
CONTACT TIME
SAMPLE NO. SECONDSl CONVERSION, %
5-B-2-(a) 630 80.5 570 53.7 450 3.5 5-B-3-~a) 630 979 450 16.1 ~i3~;~Z~
TABLE 6 (Cont'd) SELECTIVITY, ~
~~ ~~~ ` ~ ` STILBENE +
SAMPLE N0. STILBENE BIBENZYL BENZENE BIBENZYL
5-B-2-~a) 3302 0.0 56.2 3302 6409 205 25.8 67.4 5-B-3-(a) 303 000 6509 303 4705 0.1 35.8 4706 A contact time of 4 seconds was employed unless other-wise notedO
3~
Procedure A - A series of inorganic metal/-oxygen compositions were prepared by intimately mixing the appropriate amount of lead(II) oxide (PbO), lead (II) carbonate (PbCO3), or lead(II) nitrate LPb(NO3)2~ with at least two M carbonates, nitrates, or oxides (or, alter-natively, mixing an appropriate amount of a suitable lead-containing binary metal/oxygen composition with at least one additional Ml carbonate, nitrate, or oxide, depending on the element other than lead contained in the binary com-position) in water and heating to evaporate the water (and decompose the carbonates and/or nitrates, when em-ployed). The resulting solid was placed in an open cas-serole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conver-sion reactor described in Example 8 below. The parameters for such compositions, conveniently designated as 7-A-, are set forth in Table 7.
Procedure B - A series of inorganic metal/-oxygen compositions supported on a calcium aluminate ce-ment can be prepared according to the procedure described in Procedure A above except as follows: Following iA
~i 3 the final calcination, remove the calcined material from the oven, cool, crush, and mix with a calcium aluminate cement ('~lcoa-CA-25`'~ in an amount corresponding to 25 by weight of the calcined material. Slurry the solid mixture with water to form a thick paste and allow to air dry. Calcine the air dried paste in air in an open cas-serole dish for 2 hours at 400 C. and then at a final temperature of 700 C. for an additional 2 hours. Remove the supported inorganic metalloxygen composition from the oven, cool, crush in a mortar, and sieve to 14/30 mesh particles for evaluation in the toluene conversion re-actor described in Example 8 below. Following these steps should result in compositions, conveniently designated as 7-B-, having properties beneficial for use in the process of this invention.
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A. Toluene Conversion Reactor - A stainless steel tube 20.32 centimeters (8 inches) in length and 0.95 centimeter (0.375 inch) in internal diameter having a usable capacity of 11 milliliters was employed as a reactor for the toluene conversion reaction. The reactor was arranged vertically and equipped at the upper end with reactant inlet means having calibrated flow con-trollers and ~aporizers, and at the lower end with re-lQ action effluent outlet means for collecting the reactioneffluent or, alternatively, for direct introduction thereof via a gas sampling valve into a gas-liquid chromatograph for analysis. The outlet means was also equipped with means for introducing an inert gas diluent -- nitrogen or helium, for example -- into the reaction effluent for analysis purposes. A radi-ant furnace was used to maintain a constant temperature during.the reacton period. The temperature was measured with a thermocouple in a temperature well located on the lower outside w-all of the reactor.
B. Toluene Conversion - The reaction was con-.
ducted in the stoichiometric mode of operation unlessotherwise noted. The reactor was charged with approx-imatel~ 11 milliliters of the inorganic metal/oxygen composition prepared as described in Example 7 above.
Glass wool plugs were used as supports for the composition.
The charged reactor was placed in a radiant furnace and heated to maintain a constant temperature throughout the reaction period. Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pressure of 1.013 x 105 pascal ~1 atmosphere) at a rate sufficIent to p~ovide a reactor residence (contact~ time of 4 seconds (unless otherwise noted~ for the toluene (assuming a 50% yoid space in the reactor) After the reaction had proceeded for 1 minute, the reaction effluent, diluted ~ith helium, ~as analyzed by gas-liquid chromatography. The results are ta~ulated in Ta~le 8.
A i ~.~ .
- ` ~i 3~
TEMPERATURE, C./
CONTACT TIME, SAMPLE NO. SECONDSl CONVERSION, %
5~A-l-(a) 630 68.8 575 33.8 500 15.1 ~A-2-(a) 630 4406 575 43.5 500 2.5 ~A-3-(a) 630 55.5 575 40.0 500 9.7 ~A
.`~ "
1;13'~.Zi TABLE 8 (Cont ' d) - SELECTIVITY, %
STILBENE +
SAMPLE N0. STILBENE BIBENZYL BENZENE BIBENZYL
7-A-l-(a) 45.9 O.o 55.2 45.9 65.7 1.1 33.8 66.8 48.2 6.0 49.6 54.2 7-A-2-(a) 23.2 5.3 66.5 28.5 66.0 6.6 21.6 72.6 13.0 39.7 26.1 5?.. 7 7-A-3-(a) 65.2 1.3 31.7 66.5 73.6 1.6 24.7 75.2 35.4 11.4 13.1 4608 15 lA contact time of 4 seconds was employed unless other-wise noted.
y.. .
3~ ~ 2 A series of inorganic metal/oxygen composi-tions were prepared by intimately mixing the appropriate amount in grams of lead (II) oxide (PbO), bismuth (III) oxide (Bi2O3), (as M2) and at least one M oxide (or hy-droxide) in water, filtering to remove excess water or, alternatively, heating to evaporate the water, and then drying. The resulting solid was placed in an open cas-serole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was re-moved from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the tolu-ene conversion reactor described in Example 11 below. The parameters for such compositions, conveniently designated as 9-A-, are set forth in Table 9.
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EXA~PLE 10 Procedure ~ - The appropriate amounts in grams of lead CII~ nitrate IPb(NO3)2], bismuth CIII~
nitrate pentahydrate IBitNO3)3.5 H2O], and at least one M nitrate were dissolved in approximately 100 milliliters of concentrated nitric acid (HNO3) and heated to evapo-rate and decompose the nitric acid and nitrates. The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and t~en at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in E-xample 11 below. The parameters for one such composition, conveniently desig-nated as 2-A-, are set forth in Ta~le 10.
Procedure B - The procedure described in Procedure A a~ove was employed except that following the final calcination, the calcined material was re-moved from the oven, cooled, crushed, and mixed with acalcium aluminate cement (nAlcoa-CA-25") in an a-mount corresponding to 25~ by weight of the dry weight.of the calcined material. The resulting solid mixture was slurried with water to form a thick paste and allowed_ to air dry. The air-dried paste was calcined in air in an open casserole dish for 2 hours at 40Q~ C, and then at a final t~mperature of 700 C. for an additional 2 hours. The supported inorganic metal/oxygen composi.-tion was re~oved from the oyen, cooled, crushed in a mortar, and sie~ed to 14/30 mesh particles for evalu-ation in the toluene conversion reactor descri~ed in Example 11 below. T~e parameters for one such composi-tion, conveniently designated as 2-B, are set forth in Table 10.
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A. Toluene Conversion Reactor - A stain-less steel tube 20.32 centimeters ~8 inches) in length and 0.95 centi~eter (0.375 inch) in internal diameter ha~ing a usable capacity of 11 milliliters was employed as a reactor for the toluene conversion reaction. The reactor was arranged vertically and equipped at the upper end with reactant inlet means having calibrated flow controllers and ~aporizers, and at the lower end with reaction effluent outlet means for collecting the reaction effluent or, alternatively, for direct intro-duction thereof ~ia a gas samplin~ val~e into a gas-liquid chromatograph for analysis. T~e outlet means was also equipped with means for introducing an inert gas diluent -- nitrogen or helium, for example -- into the reaction ef~luent for analysis purposes. A radiant fur-nace ~as used to maintain a constant temperature durin~
the reaction period. The temperature was measured ~ith .a ther~ocouple in a temperature well located on the zo lower outside ~all of the reactor.
B. Tol-uene Con~ersion - The reaction was conducted in the stoichiometric mode of operation unless other~ise noted. The reactor was charged with approxi-mately 11 milliliters of the inorganic metal/oxygen co~position prepared as described in Examples 9 and 10 aBo~e. ~lass wool plugs were used as supports for the composition. The charged reactor was placed in a radiant furnace and heated to maintain a constant tem~er-ature throu~out the reaction period. Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pres-sure of 1.013 x 10 pascal Cl at~osphere~ at a rate sufficient to pro~ide a reactor residence Ccontact~ time of 4 seconds Cunless otherwise noted~ for the toluene Cass-umin~ a Sa% ~oid space in the reactorl. After the reaction had proceeded for 1 minute, the reaction effluent, diluted with helium, was analyzed ~y gas-liquid chroma-tography The results are ta~ulated in Ta~lell.
'A
. . .
. .
TEMPERATURE, C,/
CONTACT TIME, SAMPLE NO. ``SECONDSl CONVERSION, g ~-A-l-Ca~ 630 19.9 450 0.4 9-A-2-Ca) 630 35.7 540 5.6 450 0.7 9-A-3-Ca~ 630 17.4 570 5.3 450 0.6 9-A-4-Ca~ 630 35.8 570 16.1 450 0.6 9-A-5-~a~ 630 87.6 570 41.7 450 ~7.1 9-A-6-Ca~ 63012 95.4 575/2 68,1 500/2 3.8 9-A-7-Cal 575/2 13.9 500/2 3.4 9,-A~8-Ca~ 630 27.2 575 23.9 500 4.3 9-A-9-Ca~ 630t2 40.7 575/2 28,6 500!2 4.5 ~A ` `
.
... . .. . ... . ..
2~
TABLE 11 (Cont'd) SELECTIVITY, ~
STILBENE +
SAMPLE NO. STILBENE BIBENZ`YL BENZENE BIBENZYL
5 ~A~ a) 18.0 34.4 14.5 52.4 36.4 - 41.9 10.3 78.3 0.0 16.0 18.5 16.0 ~A-2-(a~ 39.4 16.5 21.3 55.9 22.4 46.0 15.0 68.4 0.0 17.1 11.4 17.1 ~A-3-ta~ 16.6 35.1 12.3 51.7 15.0 58.9 10.1 73.9 0.0 16.1 25.5 16.1 ~A-4-Ca~ 22.0 18.5 15.4 40.5 19.6 31.2 4.6 50.8 0.0 15.1 4Q,1 15.1 ~A-5-Ca2 43.4 0.0 40.9 43.4 65.3 5.4 19.2 70.7 5.2 7.5 4.4 12.7 ~A-6-Ca) 35.6 0.0 30,3 35.6 69.Q 9.6 5.3 78.6 20.8 ~7.4 7.4 78.2 ~A-7 Ca2 31.3 48.1 6.8 79,4 12.6 60.9 2.0 73.5 ~A-8-Ca~ 30.4 27.2 15.5 57,6 4~.7 24.9 9.1 74.6 15.3 55.7 4.3 71.0 QA-9 Ca~ 26.1 14.6 17.8 40.7 52.2 21~1 8,6 73.3 21.1 55.3 9.2 76,4 ?~
. . .
~50 TABLE 11 CCont'd2 TEMPERATURE, ~C./
CONTACT TIME, SA~PLE NO. SECONDSl CONyERS~ON, %
5 10-A-1 Ca2 63Q 9:7.0 530 48.3 _ 500 31.8 10-B-l-Ca2 63Q 43.1 575 22.8 45Q 2.1 ` SELECTIVITY, %
_ STILBENE +
SA~PLE NO. STILBENE BIBENZYL BENZENE BIBENZYL
10-A-l-(a) 7.0 0 0 71.0 7.0 71.7 2.3 11.8 74.0 57.9 8.0 8.0 65.9 lO-B-l-Ca2 27.9 14.4 21.1 42.3 38.3 30.3 10.8 68.6
3-A-l-(a) 3805 4.3 39014Z.8 3-B-l-(a) 640-3 3.1 80567.4 4-B-l-(a) 5602 306 24045908 7~.ol 16.0 lloO8801 1008 36.5 38064703 4-B-l-(b) 53.7 7.3 22.06~ol 605 3205 40.939.0 4-B-l-(c) 3603 705 26.543.8 9ol 2904 330038.5 4-B-l-(d) 5302 9.5 210262.7 5002 30.8 11088100 0.0 2302 45002302 4-B-l-~e) 52.1 2.7 29045408 5-A-l-(a) 5706 205 20086001 58.9 16.3 1~o57502 304 31.7 41043501 5-A-2-(a) 3206 0.0 49073206 7806 0.0 1806?806 1305 29.3 11044209 5-A-3-Ca) 1409 000 73061409 5405 0.0 360554.5 l9o9 801 56002800 5-A-4-(a) lloO O~O 810311.0 5907 0.0 310159.7 1902 204 45,12106 5-B-l-Ca) 14~9 000 73061409 `` 113~Zl TABLE 6 (Cont'd) TEMPERATURE, C./
CONTACT TIME
SAMPLE NO. SECONDSl CONVERSION, %
5-B-2-(a) 630 80.5 570 53.7 450 3.5 5-B-3-~a) 630 979 450 16.1 ~i3~;~Z~
TABLE 6 (Cont'd) SELECTIVITY, ~
~~ ~~~ ` ~ ` STILBENE +
SAMPLE N0. STILBENE BIBENZYL BENZENE BIBENZYL
5-B-2-~a) 3302 0.0 56.2 3302 6409 205 25.8 67.4 5-B-3-(a) 303 000 6509 303 4705 0.1 35.8 4706 A contact time of 4 seconds was employed unless other-wise notedO
3~
Procedure A - A series of inorganic metal/-oxygen compositions were prepared by intimately mixing the appropriate amount of lead(II) oxide (PbO), lead (II) carbonate (PbCO3), or lead(II) nitrate LPb(NO3)2~ with at least two M carbonates, nitrates, or oxides (or, alter-natively, mixing an appropriate amount of a suitable lead-containing binary metal/oxygen composition with at least one additional Ml carbonate, nitrate, or oxide, depending on the element other than lead contained in the binary com-position) in water and heating to evaporate the water (and decompose the carbonates and/or nitrates, when em-ployed). The resulting solid was placed in an open cas-serole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conver-sion reactor described in Example 8 below. The parameters for such compositions, conveniently designated as 7-A-, are set forth in Table 7.
Procedure B - A series of inorganic metal/-oxygen compositions supported on a calcium aluminate ce-ment can be prepared according to the procedure described in Procedure A above except as follows: Following iA
~i 3 the final calcination, remove the calcined material from the oven, cool, crush, and mix with a calcium aluminate cement ('~lcoa-CA-25`'~ in an amount corresponding to 25 by weight of the calcined material. Slurry the solid mixture with water to form a thick paste and allow to air dry. Calcine the air dried paste in air in an open cas-serole dish for 2 hours at 400 C. and then at a final temperature of 700 C. for an additional 2 hours. Remove the supported inorganic metalloxygen composition from the oven, cool, crush in a mortar, and sieve to 14/30 mesh particles for evaluation in the toluene conversion re-actor described in Example 8 below. Following these steps should result in compositions, conveniently designated as 7-B-, having properties beneficial for use in the process of this invention.
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A. Toluene Conversion Reactor - A stainless steel tube 20.32 centimeters (8 inches) in length and 0.95 centimeter (0.375 inch) in internal diameter having a usable capacity of 11 milliliters was employed as a reactor for the toluene conversion reaction. The reactor was arranged vertically and equipped at the upper end with reactant inlet means having calibrated flow con-trollers and ~aporizers, and at the lower end with re-lQ action effluent outlet means for collecting the reactioneffluent or, alternatively, for direct introduction thereof via a gas sampling valve into a gas-liquid chromatograph for analysis. The outlet means was also equipped with means for introducing an inert gas diluent -- nitrogen or helium, for example -- into the reaction effluent for analysis purposes. A radi-ant furnace was used to maintain a constant temperature during.the reacton period. The temperature was measured with a thermocouple in a temperature well located on the lower outside w-all of the reactor.
B. Toluene Conversion - The reaction was con-.
ducted in the stoichiometric mode of operation unlessotherwise noted. The reactor was charged with approx-imatel~ 11 milliliters of the inorganic metal/oxygen composition prepared as described in Example 7 above.
Glass wool plugs were used as supports for the composition.
The charged reactor was placed in a radiant furnace and heated to maintain a constant temperature throughout the reaction period. Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pressure of 1.013 x 105 pascal ~1 atmosphere) at a rate sufficIent to p~ovide a reactor residence (contact~ time of 4 seconds (unless otherwise noted~ for the toluene (assuming a 50% yoid space in the reactor) After the reaction had proceeded for 1 minute, the reaction effluent, diluted ~ith helium, ~as analyzed by gas-liquid chromatography. The results are ta~ulated in Ta~le 8.
A i ~.~ .
- ` ~i 3~
TEMPERATURE, C./
CONTACT TIME, SAMPLE NO. SECONDSl CONVERSION, %
5~A-l-(a) 630 68.8 575 33.8 500 15.1 ~A-2-(a) 630 4406 575 43.5 500 2.5 ~A-3-(a) 630 55.5 575 40.0 500 9.7 ~A
.`~ "
1;13'~.Zi TABLE 8 (Cont ' d) - SELECTIVITY, %
STILBENE +
SAMPLE N0. STILBENE BIBENZYL BENZENE BIBENZYL
7-A-l-(a) 45.9 O.o 55.2 45.9 65.7 1.1 33.8 66.8 48.2 6.0 49.6 54.2 7-A-2-(a) 23.2 5.3 66.5 28.5 66.0 6.6 21.6 72.6 13.0 39.7 26.1 5?.. 7 7-A-3-(a) 65.2 1.3 31.7 66.5 73.6 1.6 24.7 75.2 35.4 11.4 13.1 4608 15 lA contact time of 4 seconds was employed unless other-wise noted.
y.. .
3~ ~ 2 A series of inorganic metal/oxygen composi-tions were prepared by intimately mixing the appropriate amount in grams of lead (II) oxide (PbO), bismuth (III) oxide (Bi2O3), (as M2) and at least one M oxide (or hy-droxide) in water, filtering to remove excess water or, alternatively, heating to evaporate the water, and then drying. The resulting solid was placed in an open cas-serole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was re-moved from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the tolu-ene conversion reactor described in Example 11 below. The parameters for such compositions, conveniently designated as 9-A-, are set forth in Table 9.
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EXA~PLE 10 Procedure ~ - The appropriate amounts in grams of lead CII~ nitrate IPb(NO3)2], bismuth CIII~
nitrate pentahydrate IBitNO3)3.5 H2O], and at least one M nitrate were dissolved in approximately 100 milliliters of concentrated nitric acid (HNO3) and heated to evapo-rate and decompose the nitric acid and nitrates. The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and t~en at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in E-xample 11 below. The parameters for one such composition, conveniently desig-nated as 2-A-, are set forth in Ta~le 10.
Procedure B - The procedure described in Procedure A a~ove was employed except that following the final calcination, the calcined material was re-moved from the oven, cooled, crushed, and mixed with acalcium aluminate cement (nAlcoa-CA-25") in an a-mount corresponding to 25~ by weight of the dry weight.of the calcined material. The resulting solid mixture was slurried with water to form a thick paste and allowed_ to air dry. The air-dried paste was calcined in air in an open casserole dish for 2 hours at 40Q~ C, and then at a final t~mperature of 700 C. for an additional 2 hours. The supported inorganic metal/oxygen composi.-tion was re~oved from the oyen, cooled, crushed in a mortar, and sie~ed to 14/30 mesh particles for evalu-ation in the toluene conversion reactor descri~ed in Example 11 below. T~e parameters for one such composi-tion, conveniently designated as 2-B, are set forth in Table 10.
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.
A. Toluene Conversion Reactor - A stain-less steel tube 20.32 centimeters ~8 inches) in length and 0.95 centi~eter (0.375 inch) in internal diameter ha~ing a usable capacity of 11 milliliters was employed as a reactor for the toluene conversion reaction. The reactor was arranged vertically and equipped at the upper end with reactant inlet means having calibrated flow controllers and ~aporizers, and at the lower end with reaction effluent outlet means for collecting the reaction effluent or, alternatively, for direct intro-duction thereof ~ia a gas samplin~ val~e into a gas-liquid chromatograph for analysis. T~e outlet means was also equipped with means for introducing an inert gas diluent -- nitrogen or helium, for example -- into the reaction ef~luent for analysis purposes. A radiant fur-nace ~as used to maintain a constant temperature durin~
the reaction period. The temperature was measured ~ith .a ther~ocouple in a temperature well located on the zo lower outside ~all of the reactor.
B. Tol-uene Con~ersion - The reaction was conducted in the stoichiometric mode of operation unless other~ise noted. The reactor was charged with approxi-mately 11 milliliters of the inorganic metal/oxygen co~position prepared as described in Examples 9 and 10 aBo~e. ~lass wool plugs were used as supports for the composition. The charged reactor was placed in a radiant furnace and heated to maintain a constant tem~er-ature throu~out the reaction period. Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pres-sure of 1.013 x 10 pascal Cl at~osphere~ at a rate sufficient to pro~ide a reactor residence Ccontact~ time of 4 seconds Cunless otherwise noted~ for the toluene Cass-umin~ a Sa% ~oid space in the reactorl. After the reaction had proceeded for 1 minute, the reaction effluent, diluted with helium, was analyzed ~y gas-liquid chroma-tography The results are ta~ulated in Ta~lell.
'A
. . .
. .
TEMPERATURE, C,/
CONTACT TIME, SAMPLE NO. ``SECONDSl CONVERSION, g ~-A-l-Ca~ 630 19.9 450 0.4 9-A-2-Ca) 630 35.7 540 5.6 450 0.7 9-A-3-Ca~ 630 17.4 570 5.3 450 0.6 9-A-4-Ca~ 630 35.8 570 16.1 450 0.6 9-A-5-~a~ 630 87.6 570 41.7 450 ~7.1 9-A-6-Ca~ 63012 95.4 575/2 68,1 500/2 3.8 9-A-7-Cal 575/2 13.9 500/2 3.4 9,-A~8-Ca~ 630 27.2 575 23.9 500 4.3 9-A-9-Ca~ 630t2 40.7 575/2 28,6 500!2 4.5 ~A ` `
.
... . .. . ... . ..
2~
TABLE 11 (Cont'd) SELECTIVITY, ~
STILBENE +
SAMPLE NO. STILBENE BIBENZ`YL BENZENE BIBENZYL
5 ~A~ a) 18.0 34.4 14.5 52.4 36.4 - 41.9 10.3 78.3 0.0 16.0 18.5 16.0 ~A-2-(a~ 39.4 16.5 21.3 55.9 22.4 46.0 15.0 68.4 0.0 17.1 11.4 17.1 ~A-3-ta~ 16.6 35.1 12.3 51.7 15.0 58.9 10.1 73.9 0.0 16.1 25.5 16.1 ~A-4-Ca~ 22.0 18.5 15.4 40.5 19.6 31.2 4.6 50.8 0.0 15.1 4Q,1 15.1 ~A-5-Ca2 43.4 0.0 40.9 43.4 65.3 5.4 19.2 70.7 5.2 7.5 4.4 12.7 ~A-6-Ca) 35.6 0.0 30,3 35.6 69.Q 9.6 5.3 78.6 20.8 ~7.4 7.4 78.2 ~A-7 Ca2 31.3 48.1 6.8 79,4 12.6 60.9 2.0 73.5 ~A-8-Ca~ 30.4 27.2 15.5 57,6 4~.7 24.9 9.1 74.6 15.3 55.7 4.3 71.0 QA-9 Ca~ 26.1 14.6 17.8 40.7 52.2 21~1 8,6 73.3 21.1 55.3 9.2 76,4 ?~
. . .
~50 TABLE 11 CCont'd2 TEMPERATURE, ~C./
CONTACT TIME, SA~PLE NO. SECONDSl CONyERS~ON, %
5 10-A-1 Ca2 63Q 9:7.0 530 48.3 _ 500 31.8 10-B-l-Ca2 63Q 43.1 575 22.8 45Q 2.1 ` SELECTIVITY, %
_ STILBENE +
SA~PLE NO. STILBENE BIBENZYL BENZENE BIBENZYL
10-A-l-(a) 7.0 0 0 71.0 7.0 71.7 2.3 11.8 74.0 57.9 8.0 8.0 65.9 lO-B-l-Ca2 27.9 14.4 21.1 42.3 38.3 30.3 10.8 68.6
6.3 33.9 7.4 40.2 .
lA contact time of 4 seconds was employed unless otherwise noted.
.
tA~
. ` ~, .3 Procedure A - A series of inorganic metal/-oxygen compositions were prepared by intimately mixing the appropriate amount of lead (II) oxide (PbO), lead (II) carbonate (PbCO3), or lead (II) nitrate /Pb(NO3)2_~ with an antimony (M2) carbonate, nitrate, or oxide and an M car-bonate, nitrate or oxide (or, alternatively, mixing an appropriate amount of a suitable lead-containing binary metal/oxygen composition with an antimony (M2) carbonate, nitrate, or oxide or at least one Ml carbonate, nitrate, or oxide, depending on the element other than lead con-tained in the binary composition) in water and heating to evaporate the water (and decompose the carbonates and/
or nitrates, when employed). The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 13 below. The parameters for such compositions, conveniently designated as 12-A-, are set forth in Table 12.
- Procedure B - A series of inorganic metal/oxy-gen compositions supported on a calcium aluminate cement can be prepared according to the procedure ,iL~
~, . . .
2~
described in Procedure A above except as follows.
Following the final calcination, remove the calcined material from the oven, cool, crush, and mix with a calcium aluminate cement (nAlcoa-CA-2~) in an amount corresponding to 25% by weight of the calcined mater-ial. Slu,Ty the solid mixture with water to form a thick paste and allow to air dry. Calcine the air-dried paste in air in an open casserole dish for 2 hours at 400 C. and then at a final temperature of 700 C. for an additional 2 hours. Remove the sup-ported inorganic metal/oxygen composition from the oven, cool, crush in a mortar, and sieve to 14/30 mesh paricles for evaluation in the tcluene conversion reactor described in Example 13belo~-. Following these steps should result in compositions having properites ~eneficial for use in the process of this invention.
r~
"` ~'t 3'~
o o U~ o o o ~ o ~ o ~ _, ~ o o o o o o . o o o o t~ o ~ o ~ o Z o ~ o ~ o o V~
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3~`2i EX~PLE ~
A. Toluene Conversion Reactor - A stain-less steel tube 20~32 centimeters ~8 inches) in length and 0.95 centimeter ~0.375 inch) in internal diameter having a usable capacity of 11 milliliters was employed as a reactor-for the toluene conversion reaction. The reactor was arranged vertically and equipped at the upper end with reactant inlet means having cali~rated flow controllers and vaporizers, and at the lower end with reaction effluent outlet means for collecting the reaction effluent or, alter-natively, for direct introduction thereof via a gas sampling valve into a gas-liquid chromatograph for analysis. The outlet means was also equipped with means for introducting an inert gas diluent -- nitrogen or helium, for example -- into the reaction effluent for analysis purposes. A radiant furnace was used to maintain a constant temperature during the reaction period. The temperature was measured with a thermo-couple in a temperature well located on the loweroutside wall of the reactor.
B. Tol`uene Conversion - The reaction was conducted in the stoichiometric mode of operation unless otherwise noted. The reactor was charged with approximately ll milliliters of the inorganic metal/-oxygen composition prepared as descri~ed in Example l above. Glass wool plugs were used as supports for the composition. The charged reactor was placed in a radi~nt furnace and heated to maintain a constant temperature throughout the reaction period. Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pressure of 1.013 x 105 pascal ~1 atmosphere~ at a rate sufficient to proYide a reactor residence (contact) time of 4 seconds ~unless otherwise noted) for the toluene (assuming a 50~ void space in the reactor).
After the reaction had proceeded for 1 minute, the reaction effluent, diluted with helium, was analy~ed by gas-liquid chromatography. The results are tabulated in Table 13.
1 ~l 3qa ~ Z3L
TEMPERATURE, C./
CONTACT TIME, SAMPLE NO. ` SECONDSl CONVERSION, %
S 12-A-l-~a) 630/2 14.7 575/2 12.2 500/2 2.3 12-A-2-(a) 630/2 54.5 575/2 13.5 500/2 5.3 12-A-3-~a) 630 44.4 540 15.6 450 1.6 12-A-4-(a) 630 17.7 540 6.4 450 0.7 12-A-5-Ca~ 630/2 94.0 575/2 65.8 500f2 29.9 12-A-6-Ca) 630 50.9 540 16.2 A50 2.1 12-A 7-Ca~ 630/2 83,4 575/2 47.7 500~2 13.3 12-A-8-(a) 630/2 -35.9 575/2 10.3 500/2 5.4 ~A
,-` li3~32 TABLE 13 tCont'd) SELECTIVITy, %
STILBENE
SAMPLE NO. STILBENE BIBENZYL BENZENE BIBENZYL
5 12-A-1-(a) 13.2 31.1 21.7 44.3 17.4 32.9 24.0 50.3 9.1 48.2 24.7 57.3 12-A-2-(a) 37.4 8.4 22.0 45.8 29.2 34.4 21.2 63.6 24.2 46.4 ~ 16.8 70.6 12-A-3-Ca2 42.0 11.7 24.0 53.7 32.5 27.0 20.7 59.5 3.2 16.1 15.5 19.3 12-A-4-~a~ 26.6 24.8 27.6 51.4 30.1 33.0 25.4 63.1 0.0 11.6 55.7 11.6 1~A-5-Ca2 17.0 0.2 73.0 17.2 48.1 0.8 46.8 48.9 50.7 2.1 36.9 52.8 1~A-6-Cal 13,2 6.3 35.0 1~.5 30.6 29.3 13.2 59.9 8.8 41.2 17.9 50.0 1~A-7-(a2 9-5 0.0 83.9 ~.5 34.9 Q.0 53.8 34.9 52.3 0.0 38.8 52.3 12A-8-Cal 36.5 6.8 30.6 43.3 31.6 27.7 20.8 59.3 41.7 29.3 12.~ 71.0 1 A contact time of 4 seconds was e~ployed unless other-wise noted.
~3~Zl Thus, it is apparent that there has been provided, in accordance with the present invention, a process ttlat fully satisfies the objects and advan-tages set forth hereinabove. l~hile the invention has been described with respect to various specific examples and embodiments Ihereo`f, it is understood that the invention is not limited thereto and that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the invention.
lA contact time of 4 seconds was employed unless otherwise noted.
.
tA~
. ` ~, .3 Procedure A - A series of inorganic metal/-oxygen compositions were prepared by intimately mixing the appropriate amount of lead (II) oxide (PbO), lead (II) carbonate (PbCO3), or lead (II) nitrate /Pb(NO3)2_~ with an antimony (M2) carbonate, nitrate, or oxide and an M car-bonate, nitrate or oxide (or, alternatively, mixing an appropriate amount of a suitable lead-containing binary metal/oxygen composition with an antimony (M2) carbonate, nitrate, or oxide or at least one Ml carbonate, nitrate, or oxide, depending on the element other than lead con-tained in the binary composition) in water and heating to evaporate the water (and decompose the carbonates and/
or nitrates, when employed). The resulting solid was placed in an open casserole dish and calcined in air for an initial period at an initial temperature and then at a final temperature for an additional period. The calcined material was removed from the oven, cooled, crushed in a mortar, and sieved to 14/30 mesh particles for evaluation in the toluene conversion reactor described in Example 13 below. The parameters for such compositions, conveniently designated as 12-A-, are set forth in Table 12.
- Procedure B - A series of inorganic metal/oxy-gen compositions supported on a calcium aluminate cement can be prepared according to the procedure ,iL~
~, . . .
2~
described in Procedure A above except as follows.
Following the final calcination, remove the calcined material from the oven, cool, crush, and mix with a calcium aluminate cement (nAlcoa-CA-2~) in an amount corresponding to 25% by weight of the calcined mater-ial. Slu,Ty the solid mixture with water to form a thick paste and allow to air dry. Calcine the air-dried paste in air in an open casserole dish for 2 hours at 400 C. and then at a final temperature of 700 C. for an additional 2 hours. Remove the sup-ported inorganic metal/oxygen composition from the oven, cool, crush in a mortar, and sieve to 14/30 mesh paricles for evaluation in the tcluene conversion reactor described in Example 13belo~-. Following these steps should result in compositions having properites ~eneficial for use in the process of this invention.
r~
"` ~'t 3'~
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.~_ . ~ .r .. . . _ . . . _ ~ . _ .. .. , ... . .. _ .
3~`2i EX~PLE ~
A. Toluene Conversion Reactor - A stain-less steel tube 20~32 centimeters ~8 inches) in length and 0.95 centimeter ~0.375 inch) in internal diameter having a usable capacity of 11 milliliters was employed as a reactor-for the toluene conversion reaction. The reactor was arranged vertically and equipped at the upper end with reactant inlet means having cali~rated flow controllers and vaporizers, and at the lower end with reaction effluent outlet means for collecting the reaction effluent or, alter-natively, for direct introduction thereof via a gas sampling valve into a gas-liquid chromatograph for analysis. The outlet means was also equipped with means for introducting an inert gas diluent -- nitrogen or helium, for example -- into the reaction effluent for analysis purposes. A radiant furnace was used to maintain a constant temperature during the reaction period. The temperature was measured with a thermo-couple in a temperature well located on the loweroutside wall of the reactor.
B. Tol`uene Conversion - The reaction was conducted in the stoichiometric mode of operation unless otherwise noted. The reactor was charged with approximately ll milliliters of the inorganic metal/-oxygen composition prepared as descri~ed in Example l above. Glass wool plugs were used as supports for the composition. The charged reactor was placed in a radi~nt furnace and heated to maintain a constant temperature throughout the reaction period. Steam and toluene in a 2:1 mole ratio were fed to the reactor at a pressure of 1.013 x 105 pascal ~1 atmosphere~ at a rate sufficient to proYide a reactor residence (contact) time of 4 seconds ~unless otherwise noted) for the toluene (assuming a 50~ void space in the reactor).
After the reaction had proceeded for 1 minute, the reaction effluent, diluted with helium, was analy~ed by gas-liquid chromatography. The results are tabulated in Table 13.
1 ~l 3qa ~ Z3L
TEMPERATURE, C./
CONTACT TIME, SAMPLE NO. ` SECONDSl CONVERSION, %
S 12-A-l-~a) 630/2 14.7 575/2 12.2 500/2 2.3 12-A-2-(a) 630/2 54.5 575/2 13.5 500/2 5.3 12-A-3-~a) 630 44.4 540 15.6 450 1.6 12-A-4-(a) 630 17.7 540 6.4 450 0.7 12-A-5-Ca~ 630/2 94.0 575/2 65.8 500f2 29.9 12-A-6-Ca) 630 50.9 540 16.2 A50 2.1 12-A 7-Ca~ 630/2 83,4 575/2 47.7 500~2 13.3 12-A-8-(a) 630/2 -35.9 575/2 10.3 500/2 5.4 ~A
,-` li3~32 TABLE 13 tCont'd) SELECTIVITy, %
STILBENE
SAMPLE NO. STILBENE BIBENZYL BENZENE BIBENZYL
5 12-A-1-(a) 13.2 31.1 21.7 44.3 17.4 32.9 24.0 50.3 9.1 48.2 24.7 57.3 12-A-2-(a) 37.4 8.4 22.0 45.8 29.2 34.4 21.2 63.6 24.2 46.4 ~ 16.8 70.6 12-A-3-Ca2 42.0 11.7 24.0 53.7 32.5 27.0 20.7 59.5 3.2 16.1 15.5 19.3 12-A-4-~a~ 26.6 24.8 27.6 51.4 30.1 33.0 25.4 63.1 0.0 11.6 55.7 11.6 1~A-5-Ca2 17.0 0.2 73.0 17.2 48.1 0.8 46.8 48.9 50.7 2.1 36.9 52.8 1~A-6-Cal 13,2 6.3 35.0 1~.5 30.6 29.3 13.2 59.9 8.8 41.2 17.9 50.0 1~A-7-(a2 9-5 0.0 83.9 ~.5 34.9 Q.0 53.8 34.9 52.3 0.0 38.8 52.3 12A-8-Cal 36.5 6.8 30.6 43.3 31.6 27.7 20.8 59.3 41.7 29.3 12.~ 71.0 1 A contact time of 4 seconds was e~ployed unless other-wise noted.
~3~Zl Thus, it is apparent that there has been provided, in accordance with the present invention, a process ttlat fully satisfies the objects and advan-tages set forth hereinabove. l~hile the invention has been described with respect to various specific examples and embodiments Ihereo`f, it is understood that the invention is not limited thereto and that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the invention.
Claims (18)
1. A process for dehydrocoupling toluene which comprises contacting the toluene in the vapor phase at a temperature between about 450°C. and about 650°C. with an inorganic metal/oxygen composition characterized by the empirical formula:
where M1 is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups 1a, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is 0 to 10, and x is a number taken to satisfy the average valences of lead, M1 and M2 in the oxidation states in which they ex-ist in the composition to yield the toluene dehydrocoupled toluene product, with the proviso that when M2 is bismuth, M1 cannot be gallium or thallium; and when M2 is antimony, M1 cannot be indium, thallium, germanium, phosphorus, or thorium.
where M1 is at least one element selected from silver, zinc, gallium, indium, thallium, germanium, phosphorus, arsenic, thorium, the lanthanides, Groups 1a, 2a, 3b, 4b, and 8 of the Periodic Table of the Elements, and mixtures thereof, and M2 is an element selected from bismuth and antimony, and wherein a is 0.01 to 10, b is 0 to 10, and x is a number taken to satisfy the average valences of lead, M1 and M2 in the oxidation states in which they ex-ist in the composition to yield the toluene dehydrocoupled toluene product, with the proviso that when M2 is bismuth, M1 cannot be gallium or thallium; and when M2 is antimony, M1 cannot be indium, thallium, germanium, phosphorus, or thorium.
2. The process of Claim 1 characterized in that M1 is selected from silver, arsenic, zinc, cerium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, the lanthanides and Groups 3b, 4b and 8 of the Periodic Table of the Elements, and mixtures thereof.
3. The process of Claim 2 characterized in that M1 is selected from barium, calcium, strontium, zinc, sil-ver, cerium, potassium, zirconium, cobalt, and Group 3b, and mixtures thereof.
4. The process of Claim 1 characterized in that M2 is bismuth.
5. The process of Claim 1 characterized in that steam is introduced with the toluene in an amount suffi-cient to provide a steam-to-toluene mole ratio between about 0.1 and about 10.
6. The process of Claim 1 characterized in that b in the empirical formula representing the inorganic metal/oxygen composition is 0.5 to 5.
7. The process of Claim 6 characterized in that the contacting between the toluene and the inorganic metal/
oxygen composition is effected for a period between about 1 second and about 12 seconds.
oxygen composition is effected for a period between about 1 second and about 12 seconds.
8. The process of Claim 1 characterized in that the temperature is between about 500°C. and about 600°C.
9. The process of Claim 1 characterized in that the dehydrocoupling reaction is conducted in a stoi-chiometric mode of operation in the absence of added free oxygen.
10. The process of Claim 1 characterized in that a reactant selected from the group consisting of oxy-gen and an oxygen-containing gas is introduced with the toluene.
11. The process of Claim 10 characterized in that the oxygen and oxygen-containing gas is introduced in an amount sufficient to conduct the dehydrocoupling reac-tion in a catalytic mode of operation.
12. The process of Claim 11 characterized in that the oxygen and oxygen-containing gas is introduced in an amount sufficient to provide a toluene-to-oxygen mole ratio between about 1 and 8.
13. The process of Claim 10 characterized in that the oxygen and oxygen-containing gas is introduced in an amount sufficient to conduct the dehydrocoupling re-action in a combined catalytic/stoichiometric mode of operation.
14. The process of Claim 1 characterized in that the inorganic metalloxygen composition is admixed with a support material.
15. The process of Claim 14 characterized in that the support material is a metal aluminate.
16. The process of Claim 15 characterized in that the metal aluminate is calcium aluminate.
17. The process of Claim 1 characterized in that the dehydrocoupling reaction is conducted at a tolu-eneconversion level of about 20 to about 55 percent.
18. The process of Claim 1 characterized in that the dehydrocoupled toluene product is stilbene.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/101,941 US4255604A (en) | 1979-12-10 | 1979-12-10 | Dehydrocoupling of toluene |
| US101,941 | 1979-12-10 | ||
| US101,921 | 1979-12-10 | ||
| US101,944 | 1979-12-10 | ||
| US06/101,944 US4278826A (en) | 1979-12-10 | 1979-12-10 | Dehydrocoupling of toluene |
| US06/101,921 US4278824A (en) | 1979-12-10 | 1979-12-10 | Dehydrocoupling of toluene |
| US06/101,945 US4268704A (en) | 1979-12-10 | 1979-12-10 | Dehydrocoupling of toluene |
| US101,945 | 1993-08-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139321A true CA1139321A (en) | 1983-01-11 |
Family
ID=27493232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000366376A Expired CA1139321A (en) | 1979-12-10 | 1980-12-09 | Dehydrocoupling of toluene |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1139321A (en) |
-
1980
- 1980-12-09 CA CA000366376A patent/CA1139321A/en not_active Expired
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20000111 |