CA1084953A - Selective production of para-substituted benzenes - Google Patents
Selective production of para-substituted benzenesInfo
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- CA1084953A CA1084953A CA279,544A CA279544A CA1084953A CA 1084953 A CA1084953 A CA 1084953A CA 279544 A CA279544 A CA 279544A CA 1084953 A CA1084953 A CA 1084953A
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- toluene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/868—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains sulfur as hetero-atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
SELECTIVE PRODUCTION OF PARA-SUBSTITUTED
BENZENES
ABSTRACT OF THE DISCLOSURE
A process for the selective production of benzenes para-substituted by methyl and/or ethyl groups which comprises reacting toluene or ethylbenzene with a methylating or ethylating agent at a temperature of 300°C to 750°C in the presence of a catalyst comprising the crystalline alumino-silicate zeolite ZSM-23.
BENZENES
ABSTRACT OF THE DISCLOSURE
A process for the selective production of benzenes para-substituted by methyl and/or ethyl groups which comprises reacting toluene or ethylbenzene with a methylating or ethylating agent at a temperature of 300°C to 750°C in the presence of a catalyst comprising the crystalline alumino-silicate zeolite ZSM-23.
Description
~ 4'~3 S~T-'C~IVF PRODUC~IO~ C~ PA~-SUBSTITUTE3 ~ENZENES
~161(9~19) This invention relates to a process for the selectlve production of para-substituted benzenes by catalytic alkylatio~
of toluene or ethylbenzene ln the presence o~ a specified crystal-~ line aluminosilicate zeolite catalyst.
.
Alkylation of aromatlc hydrocarbons utilizing crystal-line aluminosillcate catalysts has heretofore been described.
U.s. 2,904,697 to Mattox refers to alkylation of aromatic hydro-carbons with an olefin in the presence Or a crystalline metallic aluminosilicate having uniform pore openings of about 6 to 15 Angstrom un~ts. U.S. 3,251,897 to Wise describes alkylation o~
aromatlc hydrocarbons in the presence of X- or Y-type crystalline aluminosilicate zeolites, speclf~cally such type zeolites wherein the cation i8 rare earth and/or hydrogen. U.S. 3,751,504 to Xeown et al. and U.S. 3,751,506 to Burress describe vapor phase alkylation of aromat~c hydrocarbons w~th olefins, e.g. benzene with ethylene, in the presence of a ZSM-5 type zeollte catalyst.
The alkylation of toluene with methanol in the presence . .
of a cation exchanged ~eolite Y has been described by Yashlma et al. in the Journal of Catalysis 16, 273-280 (1970). These workers reported selective production of para-xylene over the approxlmate temperature range of 200 to 275c., wlth the maximum yield o~ para-xylene in the mixture of xylenes, i.e. about 50 percent Or the xylene product mlxture, being observed at 225C.
- H~gher temperatures were reported to result in an lncrease ln the ~ield of meta-xylene and a dec~e~se ~n productlon o~ pæra and ortho-xylenes.
~ . :
10~4~S3 ~hile the above-noted prior art is considered of interest in connec~ion with the sub~ect matter of the present invention, the alkylation process described herein has been found to achieve unexpectedly highly selective production of para-substituted benzenes.
Of the xylene isomers, i.e. ortho-, meta- and para-xylene, the last mentioned is of particular value, being useful in the manufacture of terephthalic acid, an intermediate in the manufacture of synthetic fibers. Mixtures of xylene isomers either alone or in further admixture with ethylbenzene, generally containing an equilibrium concentration of about 24 weight percen~ para-xylene, have been previously separated by expensive superfraction and multistage refrigeration steps.
Such process, as will be realized, has involved high operation costs and has a limited yield.
Both ethyltoluene and diethylbenzene are valuable chemlcals. They may be dehydrogenated to produce the corresponding vinyltoluene and divinylbenzene. It has here-tofore been recognized that the presence of substantial quantities of the ortho isomers are highly undesirable in the charge undergoing dehydrogenation since they tend to lead to ring closure with formation of the corresponding indenes and indanes from ortho-ethyltoluene and naphthalene or its derivatives from ortho-diethylbenzene, which adversely affect the properties of the resultant polymer. The indenes, indanes and naphthalenes so formed are different to separate from the desired vinyl aromatic products. It has accordingly
~161(9~19) This invention relates to a process for the selectlve production of para-substituted benzenes by catalytic alkylatio~
of toluene or ethylbenzene ln the presence o~ a specified crystal-~ line aluminosilicate zeolite catalyst.
.
Alkylation of aromatlc hydrocarbons utilizing crystal-line aluminosillcate catalysts has heretofore been described.
U.s. 2,904,697 to Mattox refers to alkylation of aromatic hydro-carbons with an olefin in the presence Or a crystalline metallic aluminosilicate having uniform pore openings of about 6 to 15 Angstrom un~ts. U.S. 3,251,897 to Wise describes alkylation o~
aromatlc hydrocarbons in the presence of X- or Y-type crystalline aluminosilicate zeolites, speclf~cally such type zeolites wherein the cation i8 rare earth and/or hydrogen. U.S. 3,751,504 to Xeown et al. and U.S. 3,751,506 to Burress describe vapor phase alkylation of aromat~c hydrocarbons w~th olefins, e.g. benzene with ethylene, in the presence of a ZSM-5 type zeollte catalyst.
The alkylation of toluene with methanol in the presence . .
of a cation exchanged ~eolite Y has been described by Yashlma et al. in the Journal of Catalysis 16, 273-280 (1970). These workers reported selective production of para-xylene over the approxlmate temperature range of 200 to 275c., wlth the maximum yield o~ para-xylene in the mixture of xylenes, i.e. about 50 percent Or the xylene product mlxture, being observed at 225C.
- H~gher temperatures were reported to result in an lncrease ln the ~ield of meta-xylene and a dec~e~se ~n productlon o~ pæra and ortho-xylenes.
~ . :
10~4~S3 ~hile the above-noted prior art is considered of interest in connec~ion with the sub~ect matter of the present invention, the alkylation process described herein has been found to achieve unexpectedly highly selective production of para-substituted benzenes.
Of the xylene isomers, i.e. ortho-, meta- and para-xylene, the last mentioned is of particular value, being useful in the manufacture of terephthalic acid, an intermediate in the manufacture of synthetic fibers. Mixtures of xylene isomers either alone or in further admixture with ethylbenzene, generally containing an equilibrium concentration of about 24 weight percen~ para-xylene, have been previously separated by expensive superfraction and multistage refrigeration steps.
Such process, as will be realized, has involved high operation costs and has a limited yield.
Both ethyltoluene and diethylbenzene are valuable chemlcals. They may be dehydrogenated to produce the corresponding vinyltoluene and divinylbenzene. It has here-tofore been recognized that the presence of substantial quantities of the ortho isomers are highly undesirable in the charge undergoing dehydrogenation since they tend to lead to ring closure with formation of the corresponding indenes and indanes from ortho-ethyltoluene and naphthalene or its derivatives from ortho-diethylbenzene, which adversely affect the properties of the resultant polymer. The indenes, indanes and naphthalenes so formed are different to separate from the desired vinyl aromatic products. It has accordingly
- 2 -10~S3 heretofore been necessary to remove the ortho isomers from the ethyltoluene and diethylbenzene charge stocks by expensive distlllation techniques prior to dehydrogenation thereof.
It is evident that the availability of ethyltoluene or diethylbenzene in which the ortho isomer is initially absent or present only in trace amount would elim~nate the necessity for expensive prior removal of this isomer. Such products have, however, not heretofore been available.
According to the present lnvention a process for the selective production of benzenes para-substituted by methyl and/or ethyl groups comprises reacting toluene or ethylbenzene with a methylatlng or ethylating agent at a temperature of 300C to 750C in the presence of a catalyst comprising the crystalline aluminosilicate zeolite ZSM-23.
The reaction preferably takes place at a weight hourly space velocity of 5 to 1500: the preferred temperature range is 400 to 700C. The ZSM-23 is advantageously in the hydrogen form, and may constitute part of a composite with a porous matrix such as alumina. Toluene is very effectlvely methylated - 20 at a molar ratio of methylating agent to toluene between .O5 and 5, and between 0.1 and 2 when the preferred methylating agent, methanol, is employed. The preferred ethylating agent ~s ethylene.
~084~S3 It has been found that ZSM-23, particularly in the hydrogen or acid form, has the ability, without special treatments, to afford selectively high yields of the above-deslgnated para-substituted benzenes when employed as a catalyst in the alkylation of toluene or ethylbenzene.
Thus, compared to a conventional thermodynamic equ~librium xylene mixture in which the para:meta:ortho ratio is approximately 1:2:1, the process described herein affords a xylene product in which para-xylene predomlnates.
The improved yield of para-xylene of greater than 50 percent of the total xylene production, compared with approximately 24 percent equilibrium concentration, reduces the cost of production and most importantly the cost of separation of para-xylene from its isomers which is the most expensive step in the current method employed for produclng para-xylene.
Similarly with use of the ZSM-23 catalyst, pro-ductlon of ethyltoluene or diethylbenzene virtually free from the undeslred ortho isomer is realized. Thus, followlng the teachings of this invention, para ethyltoluene or para diethylbenzene may be selectively produced as the ma~or isomer in admixture with a minor amount of the meta isomer, together with trace amount or none of the ortho isomer. Such selecti~e production ls in sharp contrast to the equilibrium concentra-tions for ethyltoluene of 31.~ percent para, ~0.2 percent meta and 18.3 percent ortho and ~or diethylbenzene of 38 percent para, 55 percent meta and 7 percent ortho.
- 10~4~S3 ThG co~position of ZSM-23 usually satis~ie~, in terms of mole ratios of oxides and in the anhydrous state, the formula .
M20 A1203 : ~40-25G) SiO2 wherein M represents the cation complement of the zeolit~ consist-lng o~ metalllc and/or non-metallic cations, having valence n, which balances the negative charge on the alumlnum-containlng tetrahedra. It should be appreciated that chemlcal analysis of ZSM-23 (or, for that matter, many other zeolites) ra~ely manifests the perfect equi~alence between catlons and alumlnum demanded by structural considerations, since a good deal of the nitrogeneous base employed in synthesis remains in the crystalllzed material in non-catlonlc form. The apparent excess o~ cation is rather marked in the case of ZSM-23, chemical analysis somet~mes revealing 2.8 to 3 equ~valents of apparent nitrogenous cation per atom of framework aluminum in the as-synthesised zeolite. The actual cation content o~ the as-synthesi~ed material is from 8 to 40, more usually 8 to 25,percent sod~um, the balance being pyrrolidlne-derived cation.
The origlnal cations Or the as synthesized ZSM-23 can be replaced in accordance with techniques well known in the art, at leas~ ln part, by ion exchange with other cations. Preferred replacing cations include metal ions, ammonlum ions, hydrogen ions and mlxtures thereo~. Partlcularly preferred cations are -those which render the zeolite catalyt~cally active,especlally for hydrocarbon conversion. These include hydrogen,rare earth metals, aluminum metals of Groups IIA, IIIB, IVB, VIB, VIII, IB, IIB, IIIA, IVA.
The synthetic ZSM-23 zeolite possesses a definite distingulshing crystalline structure whose X-ray diffraction pattern shows substantially the slgnirlcant lines set forth in Table I.
- 10~49S3 ~AB~JE I
d (A ) I/T o 11.2 + 0.23 Medium 10.1 + 0.20 Weak 7.87 ~ 0.15 Weak 5.59 + 0.10 Weak 5.4~ + o.lo Weak 4.90 + 0.10 . Weak 4.53 + 0.10 Strong .. .
It is evident that the availability of ethyltoluene or diethylbenzene in which the ortho isomer is initially absent or present only in trace amount would elim~nate the necessity for expensive prior removal of this isomer. Such products have, however, not heretofore been available.
According to the present lnvention a process for the selective production of benzenes para-substituted by methyl and/or ethyl groups comprises reacting toluene or ethylbenzene with a methylatlng or ethylating agent at a temperature of 300C to 750C in the presence of a catalyst comprising the crystalline aluminosilicate zeolite ZSM-23.
The reaction preferably takes place at a weight hourly space velocity of 5 to 1500: the preferred temperature range is 400 to 700C. The ZSM-23 is advantageously in the hydrogen form, and may constitute part of a composite with a porous matrix such as alumina. Toluene is very effectlvely methylated - 20 at a molar ratio of methylating agent to toluene between .O5 and 5, and between 0.1 and 2 when the preferred methylating agent, methanol, is employed. The preferred ethylating agent ~s ethylene.
~084~S3 It has been found that ZSM-23, particularly in the hydrogen or acid form, has the ability, without special treatments, to afford selectively high yields of the above-deslgnated para-substituted benzenes when employed as a catalyst in the alkylation of toluene or ethylbenzene.
Thus, compared to a conventional thermodynamic equ~librium xylene mixture in which the para:meta:ortho ratio is approximately 1:2:1, the process described herein affords a xylene product in which para-xylene predomlnates.
The improved yield of para-xylene of greater than 50 percent of the total xylene production, compared with approximately 24 percent equilibrium concentration, reduces the cost of production and most importantly the cost of separation of para-xylene from its isomers which is the most expensive step in the current method employed for produclng para-xylene.
Similarly with use of the ZSM-23 catalyst, pro-ductlon of ethyltoluene or diethylbenzene virtually free from the undeslred ortho isomer is realized. Thus, followlng the teachings of this invention, para ethyltoluene or para diethylbenzene may be selectively produced as the ma~or isomer in admixture with a minor amount of the meta isomer, together with trace amount or none of the ortho isomer. Such selecti~e production ls in sharp contrast to the equilibrium concentra-tions for ethyltoluene of 31.~ percent para, ~0.2 percent meta and 18.3 percent ortho and ~or diethylbenzene of 38 percent para, 55 percent meta and 7 percent ortho.
- 10~4~S3 ThG co~position of ZSM-23 usually satis~ie~, in terms of mole ratios of oxides and in the anhydrous state, the formula .
M20 A1203 : ~40-25G) SiO2 wherein M represents the cation complement of the zeolit~ consist-lng o~ metalllc and/or non-metallic cations, having valence n, which balances the negative charge on the alumlnum-containlng tetrahedra. It should be appreciated that chemlcal analysis of ZSM-23 (or, for that matter, many other zeolites) ra~ely manifests the perfect equi~alence between catlons and alumlnum demanded by structural considerations, since a good deal of the nitrogeneous base employed in synthesis remains in the crystalllzed material in non-catlonlc form. The apparent excess o~ cation is rather marked in the case of ZSM-23, chemical analysis somet~mes revealing 2.8 to 3 equ~valents of apparent nitrogenous cation per atom of framework aluminum in the as-synthesised zeolite. The actual cation content o~ the as-synthesi~ed material is from 8 to 40, more usually 8 to 25,percent sod~um, the balance being pyrrolidlne-derived cation.
The origlnal cations Or the as synthesized ZSM-23 can be replaced in accordance with techniques well known in the art, at leas~ ln part, by ion exchange with other cations. Preferred replacing cations include metal ions, ammonlum ions, hydrogen ions and mlxtures thereo~. Partlcularly preferred cations are -those which render the zeolite catalyt~cally active,especlally for hydrocarbon conversion. These include hydrogen,rare earth metals, aluminum metals of Groups IIA, IIIB, IVB, VIB, VIII, IB, IIB, IIIA, IVA.
The synthetic ZSM-23 zeolite possesses a definite distingulshing crystalline structure whose X-ray diffraction pattern shows substantially the slgnirlcant lines set forth in Table I.
- 10~49S3 ~AB~JE I
d (A ) I/T o 11.2 + 0.23 Medium 10.1 + 0.20 Weak 7.87 ~ 0.15 Weak 5.59 + 0.10 Weak 5.4~ + o.lo Weak 4.90 + 0.10 . Weak 4.53 + 0.10 Strong .. .
3.90 + 0.08 Very Strong 3.72 + 0.08 Very Strong 3.6~ + 0.07 Very Strong 3.54 + 0.07 Medium 3.44 + 0.07 . Strong 3.36 1 0.~7 Weak 3.~ 1 0.07 Weak 3.05 + 0.06 Weak .2~99 + 0.06 Weak .2.85 1 0.06 Weak.
-. 2.54 ~ O.05 Medium 2.47 ~ 0.05 Weak 2.40 + 0.05 Weak 2.34 ~ 0.05 Weak .
. -. 0~.
_ 6 -- ~
10~4953 These values were determined by standard techniques. The radiation was the K-alph2 doublet of copper, and a scintil-latlon counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 t~mes theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d(obs.), the interplanar spacing in Angstrom units, corresponding to the recorded lines, were calculated. It should be understood that this X-ray diffraction pattern is characteristic of all the species of ZSM-23 compositions. Ion exchange of the sodium ion with cations reveals substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample, as well as if it has previously been sub~ected to thermal treat-ment.
The composition and preparation of ZSM-23 are fully described in Dutch Specification 76-06251. The zeolite may convenlently be con~erted to the hydrogen form by ammonium ion exchange of the as-synthesised zeolite and calcination of the ammonium form to yield the hydrogen form. Other forms of the zeolite whereln the original alkali metal has been reduced to less than about 1.5 percent by weight may ~e used.
Thus, the original alkali metal of the zeolite may be replaced by ion exchange with other suitable ions of ~roups B to VIII
' ~0849S3 of the Pe~iodic Table including, by way of example, nickel, zinc, calcium or rare earth metals. Generally, for the purpose of this invention, ZSM-23 will be used in the hydrogen form.
M in the above formula can be one or more of a variety of alkali metal cations, suitably defined as including all alkali metal ions derived from alkali metal oxide or hydroxide as well as alkali metal ions included in alkal~
metal silicates and aluminates (not including alkali metal salts such as sodium chloride or sodium sulfate which may be derived from neutralization of added inorganic acids such as HCI or H2SO4 or acid salts such as A12(SO4)3). Non-limiting examples of such suitable alkali metal ions include sodium and potassium.
In practicing the desired alkylation process it may be deslrable to incorporate the zeolite in another material resistant to the temperatures and other conditions employed in the alkylatlon process. Such matrlx materlals lnclude synthetic or naturally occurring substances as well as inorganic materlals such as clay, silica and/or metal oxides. The latter may be either naturally occurring or ln the form of gelatinous precipitates or gels includlng mixtures o~ silica and metal oxides. Naturally occurrlng clays which can be composited with the modlfied zeolite lnclude those of the montmorillonlte and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and lO~S3 Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially sub~ected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the modified zeolites employed herein may be composlted with a porous matrix material, such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylla, silica-titania as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zlrconia, sllica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form of a cogel.
The relative proportions of finely divided zeolite and inorganic oxide gel matrix may vary widely with the zeolite content ranging from between about 1 to about 90 persent by we~ght and more usually in the range of about 2 to about 70 percent by weight of the composite. Methylating agents other than methanol, such as methylchloride, methylbromide, dimethyl-ether or dimethylsulfide may be used, the molar ratio or methylating agent to mono al~yl benzene varying within the aforenoted range. Similarly, whilst ethylation is preferably effected utillzing an ethylating agent such as ethylene or a gaseous mixture high in this reactant, other suitable ethylating agents include ethyl alcohol, ethyl halides, e.g., ethyl chloride, diethyl ether, diethyl sulfide and ethylmercaptan.
The reaction product consisting predominantly o~ para-xylene, 108~S3 para-e~hyltoluene or para-diethylbenzene together with compara-tively smaller amounts, if any, of the corresponding meta and ortho derivat~ves may be separated by any suitable means, such 9~
10845~S3 passinF ~he organ c phase through a column in which c~romatographic separation of the isomers is accomplished.
The process of this invention may be carried out as a batch type, semi-continuous or continuous operation u~ zing a fixed or moving bed catalyst system. Multip'e injection of - the alkylating agent, e.g. methanol or ethylene, may suitably be employed. One embodiment entails use of a fluidized catalyst zone wherein the reactants, i.e. mono alkyl benzene and alkyl-ating agent are passed concurrently or countercurrently through a movlng fluidized bed of the catalyst. The catalyst after use is regenerated during which time accumulated coke is remo~ed by combustion.
The following examples will serve to illustrate the process of this invention without limiting the same:
ExamPle 1 ZSM-23 was prepared by forming a solution of 13.2 grams sodium aluminate (43.1% A12O3, 33.1% Na2O and 2~.7%
H20), 2.72 grams NaOH (50% solution with water) and 240 grams H2O. Then, 145.6 grams of pyrrolidine were added, followed by the addition of 1318 grams of colloidal silica (30% silica and 70% H2O). The resulting product was mixed until a homo-geneous gel was formed. The gel was composed of the following components in mole ratios:
R+ 0.92, where M is sodium and R+ is -+ ~ = the nitrogen-contain~ng cat~on derived R ~ M from pyrrolidine sioH~ = .0265 (not including any contribut~on 2 of OH- from pyrrolidine) ~2 ~ 371 (not including any contribution -30 OH of OH- from pyrrolidine) SiO2 = 118 -' 10~49~3 The mixture was s'irred at 3~0~. for 2 days, during which ti~.e crystallization t~as complete. mhe product crystals were filtered out ol solution and water washed continuously for approY.imately 16 hours and then dried at 230~.
X-ray analysis of the crystalline produc~ showed the crystals to have a diffraction pattern corresponding to Table I.
_12_ - 1084~S3 Additional lines showing the presence of trace amounts of un-identified crystalline material were also observed.
Chemical analysis of the crystalline product led to the following compositional figures:
Mole Ration on Composition Wt.% 23 asis C 4.96 N 1.11 Na 0.27 A123 1.65 1.0 SiO2 96.9 101 N20 2.68 Na20 0.36 Physical analysis of the crystalline product after calcination for 16 hours at 1000F. showed it to have a sur-face area of 215 m2/gram and adsorption tests (conducted as described hereinabove) provided the following results:
Adsorption Wt.
Cyclohexane 2.1 n-Hexane 6.1 Water 4.6 69.7 grams of the ZSM-23 so prepared were heat treated for 3 hours at 1000F. in nitrogen and then contacted four times at 180-200F. with a 10 weight percent solution of NH4Cl, each contact being for a period of 2 hours. The resulting product having a sodium content of 0.03 weight percent was calcined for 10 hours at 1000F. and thereafter steamed for 20 hours at 1100F.
Examples 2 - 4 A 2:1 mole ratio of toluene:methanol was passed over a 1 gram sample of the catalyst of Example 1. Reaction condi-tions and results are set forth in Table II below.
o a~
,1 ,i :~X
X ~ ~ U~
I~ In ~D
o E~
U~
~ o o n I~ C~ o~
~ ,.
a) o :~, o n _, o 1~
~1 H O O
H E~ O
~3 ~ o~
U~ ~ U~
3 ~` 1`
~1 o o ~o o 8 E~ ~ u~ u~
Q~
Q
X ~ ~ ~r P~
`` 1084~S3 Example 5 ZSM-23 in the hydrogen form was prepared by forming a solution of 52.8 grams of sodium aluminate, 10.88 grams of NaOH and 960 grams of water. Then, 582.4 grams of pyrrolidine were added, followed by the addition of 5537.6 grams of colloidal silica in 6872 grams of water. The resulting product was mixed until a homogenous gel was formed.
The mixture was stirred at 350F. for 3 days, during which time crystallization was complete. The product crystals were filtered out of solution and water washed.
X-ray analysis of the crystalline product showed the crystals to have a diffraction pattern corresponding to Table I.
305 grams of the ZSM-23 so prepared were calcined for 3 hours at 700F. in nitrogen and then contacted four times at 180-200F. with a 10 weight percent solution of NH4Cl utilizing 10 cc of solution per gram of zeolite, each contact being for a period of 2 hours. The ion exchanged product was then water washed free of chloride, dried at 230F. and calcined for lO
hours at 1000 F.
Examples_6-8 A 2;1 mole ratio of toluene:methanol was passed over a 0.3 gram sample of the catalyst of Example 5. Reaction con-ditions and results are shown in ~able III below.
~a~
~ a a~
x~ x ' ~ o~
,~
o E~
~, o ~ ~ ,~ ,~
_, o o ~'~ a~
H ~
H O O
~ E--~.) eOo o o o a~
X
10~49S3 Example 9 ZSM-23 was prepared by forming a solution of 52.8 grams of sodium aluminate, 10.88 grams of NaOH and 960 grams of water. Then, 582.4 grams of pyrrolidine were added, followed by the addition of 5537.6 grams of colloidal silica in 6872 grams of water. The resulting product was mixed until a homo-genous gel was formed.
The mixture was stirred at 350F. for 3 days, during which time crystallization was complete. The product crystals were filtered out of solution and water washed.
X-ray analysis of the crystalline product showed the crystals to have a diffraction pattern corresponding to Table I.
Examples lo-ll A 2:1 mole ratio of toluene:methanol was passed over lS a 1 gram sample of the catalyst of Example 9. Reaction condi-tions and results are set forth in Table IV below.
U~
aJ ~
aJ
,~ o~
x x U' o U ~ :- :
~o aJ
o S~ a P~
~D
a) ~ ,~ o~
_, o ,~, ~o ~ ,, ~ , _, H O O .-1 ~-1 ~ 0 .
r~ I~
~ ~) O O
aJO O O
E-l Q
~ O
X
r~
10t~49~3 It wil~ be evident from the above tabulated data that para-xylene was selectively produced in an amount greatly in excess of its equilibrium concentration.
Exar..ples 12-15 A 3.7:1 mole ratio of toluene:ethylene was passed over a 1 gram sample of the catalyst of Example 9. Reaction conditions and results are shown in Table V below.
~0~49S3 a) s C~ ~
~o ~ ~ ~ o O ~ ~ N IS~ C~
~
a~ ~ O
N N N C~.l C~ OC\ 3 N L
h C~ ~ ~ ~ o~
0~ t~
C
a OC) I~ J
:S ~4 ~_1 3 L~
O C) C~
~>
~O
r~ S
E~
o a) u~
h ~ t--~o ~1 ~
EO~ v .1 o o o o V U~ o o o E-~ o 3 l~ Lr~ U~
N ~ 3 IS~
~1 ~1 ~1 ~C
~0t~4~S3 It will ~e seen from the above ~abulate~ data that para ethyl~oluene was selectively produced in an amoun~ sub-stantially greater than its equilibrium concentra~ion.
Example 16 A 3.2:1 mole ratio of ethylbenzene:ethylene was passed over a 1 gram sample of the catalyst of Example 9 at 500C. utilizing a WHSV of about 6.3 hr 1.
Analysis of the product obtained gave the following results:
Wt. %
Benzene 15.91 Toluene .36 Ethylbenzene 78.32 Xylenes .27 Cg .60 Diethylbenzene Para 1.86 Meta 1.59 Ortho 0.17 Conversion 21.0 Diethylbenzene Selectivity 17.4 Diethylbenzene Isomer Mixture Para/Meta/Ortho 51.5/43.8/4.7 From the above results, it will be seen that the ZSM-23 catalyst afforded production of para-diethylbenzene in an amount substantially greater than its equilibrium concentra-tion and an amount of ortho-diethylbenzene substantially less than its equilibrium concentration. In addition, the formation of higher ethylated products was limited.
It is to be understood that the foregoing description is merely illustrative of preferred embodiments of the invention iO~45~S3 o~ t;hich ~.any variations may be made by those s~illed i n the ar'. within the scope of the following claims without departing from the spirit thereof.
-. 2.54 ~ O.05 Medium 2.47 ~ 0.05 Weak 2.40 + 0.05 Weak 2.34 ~ 0.05 Weak .
. -. 0~.
_ 6 -- ~
10~4953 These values were determined by standard techniques. The radiation was the K-alph2 doublet of copper, and a scintil-latlon counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 t~mes theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d(obs.), the interplanar spacing in Angstrom units, corresponding to the recorded lines, were calculated. It should be understood that this X-ray diffraction pattern is characteristic of all the species of ZSM-23 compositions. Ion exchange of the sodium ion with cations reveals substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample, as well as if it has previously been sub~ected to thermal treat-ment.
The composition and preparation of ZSM-23 are fully described in Dutch Specification 76-06251. The zeolite may convenlently be con~erted to the hydrogen form by ammonium ion exchange of the as-synthesised zeolite and calcination of the ammonium form to yield the hydrogen form. Other forms of the zeolite whereln the original alkali metal has been reduced to less than about 1.5 percent by weight may ~e used.
Thus, the original alkali metal of the zeolite may be replaced by ion exchange with other suitable ions of ~roups B to VIII
' ~0849S3 of the Pe~iodic Table including, by way of example, nickel, zinc, calcium or rare earth metals. Generally, for the purpose of this invention, ZSM-23 will be used in the hydrogen form.
M in the above formula can be one or more of a variety of alkali metal cations, suitably defined as including all alkali metal ions derived from alkali metal oxide or hydroxide as well as alkali metal ions included in alkal~
metal silicates and aluminates (not including alkali metal salts such as sodium chloride or sodium sulfate which may be derived from neutralization of added inorganic acids such as HCI or H2SO4 or acid salts such as A12(SO4)3). Non-limiting examples of such suitable alkali metal ions include sodium and potassium.
In practicing the desired alkylation process it may be deslrable to incorporate the zeolite in another material resistant to the temperatures and other conditions employed in the alkylatlon process. Such matrlx materlals lnclude synthetic or naturally occurring substances as well as inorganic materlals such as clay, silica and/or metal oxides. The latter may be either naturally occurring or ln the form of gelatinous precipitates or gels includlng mixtures o~ silica and metal oxides. Naturally occurrlng clays which can be composited with the modlfied zeolite lnclude those of the montmorillonlte and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and lO~S3 Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially sub~ected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the modified zeolites employed herein may be composlted with a porous matrix material, such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylla, silica-titania as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zlrconia, sllica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form of a cogel.
The relative proportions of finely divided zeolite and inorganic oxide gel matrix may vary widely with the zeolite content ranging from between about 1 to about 90 persent by we~ght and more usually in the range of about 2 to about 70 percent by weight of the composite. Methylating agents other than methanol, such as methylchloride, methylbromide, dimethyl-ether or dimethylsulfide may be used, the molar ratio or methylating agent to mono al~yl benzene varying within the aforenoted range. Similarly, whilst ethylation is preferably effected utillzing an ethylating agent such as ethylene or a gaseous mixture high in this reactant, other suitable ethylating agents include ethyl alcohol, ethyl halides, e.g., ethyl chloride, diethyl ether, diethyl sulfide and ethylmercaptan.
The reaction product consisting predominantly o~ para-xylene, 108~S3 para-e~hyltoluene or para-diethylbenzene together with compara-tively smaller amounts, if any, of the corresponding meta and ortho derivat~ves may be separated by any suitable means, such 9~
10845~S3 passinF ~he organ c phase through a column in which c~romatographic separation of the isomers is accomplished.
The process of this invention may be carried out as a batch type, semi-continuous or continuous operation u~ zing a fixed or moving bed catalyst system. Multip'e injection of - the alkylating agent, e.g. methanol or ethylene, may suitably be employed. One embodiment entails use of a fluidized catalyst zone wherein the reactants, i.e. mono alkyl benzene and alkyl-ating agent are passed concurrently or countercurrently through a movlng fluidized bed of the catalyst. The catalyst after use is regenerated during which time accumulated coke is remo~ed by combustion.
The following examples will serve to illustrate the process of this invention without limiting the same:
ExamPle 1 ZSM-23 was prepared by forming a solution of 13.2 grams sodium aluminate (43.1% A12O3, 33.1% Na2O and 2~.7%
H20), 2.72 grams NaOH (50% solution with water) and 240 grams H2O. Then, 145.6 grams of pyrrolidine were added, followed by the addition of 1318 grams of colloidal silica (30% silica and 70% H2O). The resulting product was mixed until a homo-geneous gel was formed. The gel was composed of the following components in mole ratios:
R+ 0.92, where M is sodium and R+ is -+ ~ = the nitrogen-contain~ng cat~on derived R ~ M from pyrrolidine sioH~ = .0265 (not including any contribut~on 2 of OH- from pyrrolidine) ~2 ~ 371 (not including any contribution -30 OH of OH- from pyrrolidine) SiO2 = 118 -' 10~49~3 The mixture was s'irred at 3~0~. for 2 days, during which ti~.e crystallization t~as complete. mhe product crystals were filtered out ol solution and water washed continuously for approY.imately 16 hours and then dried at 230~.
X-ray analysis of the crystalline produc~ showed the crystals to have a diffraction pattern corresponding to Table I.
_12_ - 1084~S3 Additional lines showing the presence of trace amounts of un-identified crystalline material were also observed.
Chemical analysis of the crystalline product led to the following compositional figures:
Mole Ration on Composition Wt.% 23 asis C 4.96 N 1.11 Na 0.27 A123 1.65 1.0 SiO2 96.9 101 N20 2.68 Na20 0.36 Physical analysis of the crystalline product after calcination for 16 hours at 1000F. showed it to have a sur-face area of 215 m2/gram and adsorption tests (conducted as described hereinabove) provided the following results:
Adsorption Wt.
Cyclohexane 2.1 n-Hexane 6.1 Water 4.6 69.7 grams of the ZSM-23 so prepared were heat treated for 3 hours at 1000F. in nitrogen and then contacted four times at 180-200F. with a 10 weight percent solution of NH4Cl, each contact being for a period of 2 hours. The resulting product having a sodium content of 0.03 weight percent was calcined for 10 hours at 1000F. and thereafter steamed for 20 hours at 1100F.
Examples 2 - 4 A 2:1 mole ratio of toluene:methanol was passed over a 1 gram sample of the catalyst of Example 1. Reaction condi-tions and results are set forth in Table II below.
o a~
,1 ,i :~X
X ~ ~ U~
I~ In ~D
o E~
U~
~ o o n I~ C~ o~
~ ,.
a) o :~, o n _, o 1~
~1 H O O
H E~ O
~3 ~ o~
U~ ~ U~
3 ~` 1`
~1 o o ~o o 8 E~ ~ u~ u~
Q~
Q
X ~ ~ ~r P~
`` 1084~S3 Example 5 ZSM-23 in the hydrogen form was prepared by forming a solution of 52.8 grams of sodium aluminate, 10.88 grams of NaOH and 960 grams of water. Then, 582.4 grams of pyrrolidine were added, followed by the addition of 5537.6 grams of colloidal silica in 6872 grams of water. The resulting product was mixed until a homogenous gel was formed.
The mixture was stirred at 350F. for 3 days, during which time crystallization was complete. The product crystals were filtered out of solution and water washed.
X-ray analysis of the crystalline product showed the crystals to have a diffraction pattern corresponding to Table I.
305 grams of the ZSM-23 so prepared were calcined for 3 hours at 700F. in nitrogen and then contacted four times at 180-200F. with a 10 weight percent solution of NH4Cl utilizing 10 cc of solution per gram of zeolite, each contact being for a period of 2 hours. The ion exchanged product was then water washed free of chloride, dried at 230F. and calcined for lO
hours at 1000 F.
Examples_6-8 A 2;1 mole ratio of toluene:methanol was passed over a 0.3 gram sample of the catalyst of Example 5. Reaction con-ditions and results are shown in ~able III below.
~a~
~ a a~
x~ x ' ~ o~
,~
o E~
~, o ~ ~ ,~ ,~
_, o o ~'~ a~
H ~
H O O
~ E--~.) eOo o o o a~
X
10~49S3 Example 9 ZSM-23 was prepared by forming a solution of 52.8 grams of sodium aluminate, 10.88 grams of NaOH and 960 grams of water. Then, 582.4 grams of pyrrolidine were added, followed by the addition of 5537.6 grams of colloidal silica in 6872 grams of water. The resulting product was mixed until a homo-genous gel was formed.
The mixture was stirred at 350F. for 3 days, during which time crystallization was complete. The product crystals were filtered out of solution and water washed.
X-ray analysis of the crystalline product showed the crystals to have a diffraction pattern corresponding to Table I.
Examples lo-ll A 2:1 mole ratio of toluene:methanol was passed over lS a 1 gram sample of the catalyst of Example 9. Reaction condi-tions and results are set forth in Table IV below.
U~
aJ ~
aJ
,~ o~
x x U' o U ~ :- :
~o aJ
o S~ a P~
~D
a) ~ ,~ o~
_, o ,~, ~o ~ ,, ~ , _, H O O .-1 ~-1 ~ 0 .
r~ I~
~ ~) O O
aJO O O
E-l Q
~ O
X
r~
10t~49~3 It wil~ be evident from the above tabulated data that para-xylene was selectively produced in an amount greatly in excess of its equilibrium concentration.
Exar..ples 12-15 A 3.7:1 mole ratio of toluene:ethylene was passed over a 1 gram sample of the catalyst of Example 9. Reaction conditions and results are shown in Table V below.
~0~49S3 a) s C~ ~
~o ~ ~ ~ o O ~ ~ N IS~ C~
~
a~ ~ O
N N N C~.l C~ OC\ 3 N L
h C~ ~ ~ ~ o~
0~ t~
C
a OC) I~ J
:S ~4 ~_1 3 L~
O C) C~
~>
~O
r~ S
E~
o a) u~
h ~ t--~o ~1 ~
EO~ v .1 o o o o V U~ o o o E-~ o 3 l~ Lr~ U~
N ~ 3 IS~
~1 ~1 ~1 ~C
~0t~4~S3 It will ~e seen from the above ~abulate~ data that para ethyl~oluene was selectively produced in an amoun~ sub-stantially greater than its equilibrium concentra~ion.
Example 16 A 3.2:1 mole ratio of ethylbenzene:ethylene was passed over a 1 gram sample of the catalyst of Example 9 at 500C. utilizing a WHSV of about 6.3 hr 1.
Analysis of the product obtained gave the following results:
Wt. %
Benzene 15.91 Toluene .36 Ethylbenzene 78.32 Xylenes .27 Cg .60 Diethylbenzene Para 1.86 Meta 1.59 Ortho 0.17 Conversion 21.0 Diethylbenzene Selectivity 17.4 Diethylbenzene Isomer Mixture Para/Meta/Ortho 51.5/43.8/4.7 From the above results, it will be seen that the ZSM-23 catalyst afforded production of para-diethylbenzene in an amount substantially greater than its equilibrium concentra-tion and an amount of ortho-diethylbenzene substantially less than its equilibrium concentration. In addition, the formation of higher ethylated products was limited.
It is to be understood that the foregoing description is merely illustrative of preferred embodiments of the invention iO~45~S3 o~ t;hich ~.any variations may be made by those s~illed i n the ar'. within the scope of the following claims without departing from the spirit thereof.
Claims (9)
1. A process for the selective production of benzenes para-substituted by methyl and/or ethyl groups which comprises reacting toluene or ethylbenzene with a methylating or ethylating agent at a temperature of 300°C
to 750°C in the presence of a catalyst comprising the crystalline aluminosilicate zeolite ZSM-23.
to 750°C in the presence of a catalyst comprising the crystalline aluminosilicate zeolite ZSM-23.
2. A process according to Claim 1 wherein said reacting takes place at a weight hourly space velocity of 5 to 1500.
3. A process according to Claim 1 wherein the ZSM-23 is in the hydrogen form.
4. A process according to Claim 1, 2 or 3 wherein the ZSM-23 is part of a composite with a porous matrix.
5. A process according to Claim 1, 2 or 3 wherein said temperature is between about 400°C and about 700°C.
6. A process according to Claim 1, 2 or 3 wherein the methylating agent is methanol.
7. A process according to Claim 1 wherein toluene is methylated at a molar ratio of methylating agent to toluene between .05 and 5.
8. A process according to Claim 7 wherein the methylating agent is methanol and the molar ratio of methanol to toluene is between 0.1 and 2.
9. A process according to Claim 1, 2 or 3 wherein the ethylating agent is ethylene.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US704,194 | 1976-07-12 | ||
| US05/704,194 US4049738A (en) | 1976-07-12 | 1976-07-12 | Selective production of para-xylene |
| US05/793,469 US4100217A (en) | 1976-07-12 | 1977-05-03 | Selective production of para-substituted benzenes |
| US793,469 | 1977-05-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084953A true CA1084953A (en) | 1980-09-02 |
Family
ID=27107275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA279,544A Expired CA1084953A (en) | 1976-07-12 | 1977-05-31 | Selective production of para-substituted benzenes |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS607604B2 (en) |
| CA (1) | CA1084953A (en) |
| DE (1) | DE2730949A1 (en) |
| FR (1) | FR2358373A1 (en) |
| GB (1) | GB1536827A (en) |
| IT (1) | IT1082110B (en) |
| NL (1) | NL7707709A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0005315B1 (en) | 1978-05-08 | 1981-12-02 | Imperial Chemical Industries Plc | Production of xylene hydrocarbons |
| US4301316A (en) * | 1979-11-20 | 1981-11-17 | Mobil Oil Corporation | Preparing phenylalkanes |
| US4358628A (en) * | 1981-06-26 | 1982-11-09 | Shell Oil Company | Alkylation of benzene compounds with detergent range olefins |
| JPS601140A (en) * | 1983-06-17 | 1985-01-07 | Idemitsu Kosan Co Ltd | Production of p-ethyltoluene |
| US4547605A (en) * | 1983-09-28 | 1985-10-15 | Mobil Oil Corporation | Catalyst for alkylation of aromatic hydrocarbons |
| JPS62172208U (en) * | 1986-04-21 | 1987-10-31 | ||
| JPH0510487Y2 (en) * | 1986-06-17 | 1993-03-15 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962346A (en) * | 1975-03-07 | 1976-06-08 | Minnesota Mining And Manufacturing Company | 1,1-Bis(perfluoroalkylsulfonyl)ethenes |
-
1977
- 1977-05-31 CA CA279,544A patent/CA1084953A/en not_active Expired
- 1977-06-23 IT IT25009/77A patent/IT1082110B/en active
- 1977-06-27 JP JP52075657A patent/JPS607604B2/en not_active Expired
- 1977-06-28 FR FR7719781A patent/FR2358373A1/en active Granted
- 1977-06-29 GB GB27225/77A patent/GB1536827A/en not_active Expired
- 1977-07-08 DE DE19772730949 patent/DE2730949A1/en active Granted
- 1977-07-11 NL NL7707709A patent/NL7707709A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| GB1536827A (en) | 1978-12-20 |
| FR2358373A1 (en) | 1978-02-10 |
| IT1082110B (en) | 1985-05-21 |
| JPS607604B2 (en) | 1985-02-26 |
| DE2730949C2 (en) | 1988-02-04 |
| NL7707709A (en) | 1978-01-16 |
| JPS539722A (en) | 1978-01-28 |
| FR2358373B1 (en) | 1983-10-14 |
| DE2730949A1 (en) | 1978-01-19 |
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