US2378209A - Process for the production of aromatic hydrocarbons - Google Patents
Process for the production of aromatic hydrocarbons Download PDFInfo
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- US2378209A US2378209A US465923A US46592342A US2378209A US 2378209 A US2378209 A US 2378209A US 465923 A US465923 A US 465923A US 46592342 A US46592342 A US 46592342A US 2378209 A US2378209 A US 2378209A
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- hydrocarbons
- aromatic hydrocarbons
- dehydrogenation
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- aromatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
Definitions
- the presentinvention relates to a process for the production of aromatic hydrocarbons from naphthenic hydrocarbon fractions of the nature of gasoline.
- naphthenic hydrocarbon fractions of the nature of gasoline is meant hydrocarbon fractions from various sources boiling predominantly within the gasoline boiling range and containing appreciable concentrations, such as or more, of naphthenic hydrocarbons in admixture with paramn hydrocarbons and also frequently containing appreciable concentrations volve contacting the naphthenic fraction in the vapor phase with a dehydrogenating contact mass.
- the aromatichydrocarbons formed by the treatment are removed or concentrated by one of the various well-known methods such as fractional distillation, solvent extraction, extractive distillation, or by a combination of treatments such as alkylation, followed by fractionation, extraction, etc.
- the invention relates to a process for the production of aromatic hydrocarbons from such petroleum fractions wherein maximum yields of aromatic hydrocarbons ma be the most economically produced by a combination of three separate catalytic treatments.
- the invention also relates to the production of arcmatic hydrocarbons from such fractions by two sub-combination treatments involving the use of two catalysts which may advantageously be employed in certain cases.
- hydrocarbon fractions of the nature of gasoline derived from naphthenic basepetroleums and from certain conversion processes and bydrocarbon syntheses contain appreciable concentrations of naphthenic hydrocarbons. These various fractions usually contain appreciable concen trations of paraiiln hydrocarbons and many of them also contain in addition appreciable concentrations of oleflnic hydrocarbons and/or aromatic hydrocarbons.
- the paraflin hydrocarbons generally are predominantly the normal isomers, the monomethyl isomers being next in frequency of occurrence.
- the naphthenic hydrocarbons in such distlllates consist, in general, of complex mixtures of naphthenic hydrocarbons haxing sixmembered rings and naphthenic hydrocarbons having ilve-membered rings.
- the naphthenic hydrocarbons having six-membered rings may be easily converted by dehydrogenation to benzene and the 7 corresponding alkyl benzenes.
- the process of the present invention is applicafractions to be treated are the so-called Cs and/or C1 and/or 0: fractions from naphthenic straight run, cracked and/or reformed stocks consisting essentially of the hydrocarbons having six and/or seven and/or eight carbon atoms, respectively.
- the material to be treated is, according to the present process, treated with two or three separate dehydrogenation catalysts under suitable conditions.
- the material is treated-first under dehydrogenation conditions (with respect to hydroaromatic hydrocarbons) with a dehydrogenating' metal sulfide.
- any of the known metal sulfide dehydrogenation catalysts may be employed.
- catalysts consisting largely of one or more sulfides of Fe, Co, Ni, M0 or W.
- Particularly suitable catalysts for example, comprise substantial proportions of tungsten sulfide, preferably in,
- the aromatic hydrocarbons may be removed from the product by extraction with one ofthemanysolvents, forexampleSOaaniline, etc., having a selective solvent action for aromatic hydrocarbonaoritmayinsomecasesbesimply fractionally distilled to recover a pureor relatively concentrated aromatic fraction, or the aromatic hydrocarbon may be conveniently separated by an extractive distillation in a known manner.
- one ofthemanysolvents forexampleSOaaniline, etc.
- a molybdenum oxide catalyst Any of the molybdenum oxide hydrotorming catalysts may be employed.
- Very suitable catalysts for example, comprise 4% to 30% molybdenum oxide on a suitable adsorptive support such as absorptive alumina, adsorptive magnesia, activated clay, or the like. Molybdenum oxide supported (15%) on adsor'ptive alumina is an especially good catalyst for this purpose.
- Suitable dehydrogenation conditions with respect to temperature, Pressure, partial pressure of hydrogen and space velocity are chosen within the following approximate limits:
- chromium oxide dehydrogeuation catalysts Any of the chromium oxide dehydrogeuation catalysts may be employed. Thus, for example, one may use precipitated and pllled catalysts consisting of CtaOs, CnOe-AlzOa,
- chromium Temperature C' About425-550 Pressure g atmospheres About 0.1-7 Partial pressure of hydrogen I atmospheres-.. 0.5 Liquid hourly space
- the product from the treatment with the chromium oxide catalyst may, if desired, be used per se or may be treated to recover aromatic hydrocarbons in -a pure or more concentrated form. The aromatic content of this product depends upon whether or notaromatic hydrocarbons have been removed after the first or second of the above-described delwdrogenation treatments. I!
- aromatic hydrocarbons have beenremoved from the product after the first and/or second dehydrogenation treatment, this product usually contains about 50% aromatic hydrocarbons. If aromatic hydrocarbons have been removed only after the first dehydrogenation step, aromatic contents oi about 70% are usually present. It aromatic the first or second of the above-described dehydrogenation steps, the aromatic content of this product is much higher, for example 80%. It the aromatic hydrocarbons formed are removed from hydrocarbons have not been removed after either a the product after the chromium oxide treatment,
- the non-aromatic fraction may, if desired, be recycled back to the chromium oxide treatment. In this way substantially complete conversion of the naphthenic fraction to aromatic hydrocarbons may be obtained.
- the process has been described as comprising three separate dehydrogenation treatmerits under three definite dehydrogenation conditions with three separate types of dehydrogenation catalyst.
- This three-step process gives optimum results. It is not necessary, however, that the complete efilciency of the above-described three-step process be utilized.
- the invention also contemplates two sub-combinations oi! this three-step process which, while not as efilcient as the three-step process, are nevertheless superior to any of the single-step processes heretofore proposed and may be profitably employed, for e ample, where it is desired to avoid the cost of providing three separate dehydrogenation units.
- the first of these alternative two-step processes involves contacting the naphthenic hydrocarbon fraction first with a metal sulfide dehydrogenation catalyst as above described in the first step of the three-step process and then contacting the product, either with or without subsequent removal or concentration of aromatic hydrocar- 1 bons, with a molybdenum oxide catalyst as described in the second step 01 the three-step proccycled to the first dehydrogenation treatment with the metal sulfide, no appreciable further amounts of aromatic hydrocarbons are formed.
- chromium oxide catalyst is round to be very poor.
- the naphthenic petroleum traction preterably a straight run gasoline fraction
- a molybdenum oxide catalyst as described in the second step of the three-step process
- the product either with or without subsequent removal or concentration of aromatic hydrocarbons
- a chromium oxide catalyst as described in the third step of the three-step process.
- the product contained about 26% by weight of aromatic hydrocarbons.
- the aromatic hydrocarbons were extracted trom'the product.
- the remaining non-aromatic portion was exceptionally suited for treatment with a chromium oxidematic hydrocarbons are obtained.
- the product from the dehydrogenation treatment with the metal sulfide catalyst is contacted under dehydrogenation conditions with the mo- Lvbdenum oxide catalyst as described, the product contains considerable additional aromatic hydrocarbons, for example 20%-40%.
- the aromatic hydrocarbons are removed from this product and the aromatic-free product realumina (11% Cr) catalyst under the following conditions:
- a process for the production of aromatic hydrocarbons from naphthenic fractions of the nature of gasoline which comprises contacting the naphthenic gasoline fraction under dehydrogenaflmconditicnsflrstwltha' oxidecatalyst ing metal sulfide catalyst. thenwithamolybchosen'withinthetollowinglimih.
- chromium oxide catalyst consists essentially of chromium oxide and alumina.
- a process for the production oi aromatic hydrocarbons from naphthenic fractions of the nature of gasoline which comprises contacting the naphthenic fraction with a metal sulfide dehydrogenation catalyst under conditions chosen within the following limits:
- the metal sulfide dehydrogenation catalyst comprisestlmsstensuliide.
Description
Patented June I PROCESS FOR THE PRODUCTION OF AROMATIC HYDROCABBONS Donald L. Fuller and Bernard S. Greensfelder, Oakland, Calif., assignors to Shell Development Company, San Francisco,
of Delaware No Drawing.
Calif., a corporation Application November 1'1, 1942, Serial No. 465,923
13 Claims. (o1. 260-673.5l a
The presentinvention relates to a process for the production of aromatic hydrocarbons from naphthenic hydrocarbon fractions of the nature of gasoline. By "naphthenic hydrocarbon fractions of the nature of gasoline" is meant hydrocarbon fractions from various sources boiling predominantly within the gasoline boiling range and containing appreciable concentrations, such as or more, of naphthenic hydrocarbons in admixture with paramn hydrocarbons and also frequently containing appreciable concentrations volve contacting the naphthenic fraction in the vapor phase with a dehydrogenating contact mass. In such cases where it is desired, the aromatichydrocarbons formed by the treatment are removed or concentrated by one of the various well-known methods such as fractional distillation, solvent extraction, extractive distillation, or by a combination of treatments such as alkylation, followed by fractionation, extraction, etc.
Since the primary reaction involved in the proposed processes is the dehydrogenation of cerof oleflnic hydrocarbons and/or aromatic hydrocarbons. More particularly, the invention relates to a process for the production of aromatic hydrocarbons from such petroleum fractions wherein maximum yields of aromatic hydrocarbons ma be the most economically produced by a combination of three separate catalytic treatments. The invention also relates to the production of arcmatic hydrocarbons from such fractions by two sub-combination treatments involving the use of two catalysts which may advantageously be employed in certain cases.
Many hydrocarbon fractions of the nature of gasoline derived from naphthenic basepetroleums and from certain conversion processes and bydrocarbon syntheses contain appreciable concentrations of naphthenic hydrocarbons. These various fractions usually contain appreciable concen trations of paraiiln hydrocarbons and many of them also contain in addition appreciable concentrations of oleflnic hydrocarbons and/or aromatic hydrocarbons. The paraflin hydrocarbons generally are predominantly the normal isomers, the monomethyl isomers being next in frequency of occurrence. The naphthenic hydrocarbons in such distlllates consist, in general, of complex mixtures of naphthenic hydrocarbons haxing sixmembered rings and naphthenic hydrocarbons having ilve-membered rings. The naphthenic hydrocarbons having six-membered rings (that is, cyclohexane and its homologues) may be easily converted by dehydrogenation to benzene and the 7 corresponding alkyl benzenes. I
In view of the relative ease with which hydroaromatic naphthenic hydrocarbons may be dehydrogenated to corresponding aromatic hydrocarbons, numerous processes have been developed for the catalytic treatment of such distillates under dehydrogenation conditions to produce distillates of more aromatic character. In certain instances where the catalytic dehydrogenation treatment is sufliciently eilicient, it "has proved practical to pro- Y duce substantially pure aromatic hydrocarbons by such treatment. These various all intain of the naphthenie hydrocarbons into the corresponding aromatic hydrocarbons, it is not surprising that nearly all of the many known dehydrogenation catalysts have been found to be effective for this treatment. Thus, it has been proposed to effect such treatment with various compounds such as the oxides, halides, sulfides, chromates, tungstates, molybdates, phosphates, borates, phosphites, chromites, manganates, etc., of such metals as Cu, Mg, Ca, Zn, Cd, Ba, B, Al, La, Tl, Si, Ti, Zr, Sn, Pb, Pt, Th, V, Nb, Sb, Ta, Bi, Cr, Se, Mo, Te, W, U, Mn, Re, Fe, Co, Ni, Ru, Pd, Rh, Ce, Pr and others. Also, many special catalystscontaining one or more of these dehydrogenating compounds usually in combination with one or more other materials have been developed for this purpose and the relative merits of these various catalysts have been studied. The appraisal of these various proposed catalysts has been based upon such factors as the increase in octane number of the distillate, the increase in the aromaticity of the distillate, the reaction conditions required to eflect these improvements in octane number and aromaticity, the thermal stability of the catalyst, the case with which the catalyst can be prepared, the ease with which the catalyst can be regenerated when spent, the car- =hon-forming tendency under the reaction conditions, the susceptibility of the catalyst to be poisoned by sulfur compounds, nitrogen bases, etc., found in such distlllates, and similar practical aspects of their use. It has not been generally appreciated, however, that many oi these catalysts, although they give substantially equivalent Liquid hourly space have now found that by the application of combinations oi two or three types of dehydrogenation catalysts in series much greater conversionstoaromatlchydrocarbonsmaybeobtained thanbytheuseofanyonetypeofdehydrogenation catalyst alone. In fact, by the process oi the present invention, it i possible to convert mphthenic fractions of the class described and consisting of hydrocarbons having six or'seven carbon atoms entirely into benzene or toluene. respectively. Furthermore, the desirable result may be obtained while realizing much better catalystlifeandprocessefiiciencythanhasbeen possible in most of the hitherto-proposed processes The process of the present inventionis applicafractions to be treated are the so-called Cs and/or C1 and/or 0: fractions from naphthenic straight run, cracked and/or reformed stocks consisting essentially of the hydrocarbons having six and/or seven and/or eight carbon atoms, respectively.
The material to be treated is, according to the present process, treated with two or three separate dehydrogenation catalysts under suitable conditions. According to the one aspect of the invention, the material is treated-first under dehydrogenation conditions (with respect to hydroaromatic hydrocarbons) with a dehydrogenating' metal sulfide.
For this treatment any of the known metal sulfide dehydrogenation catalysts may be employed. Thus, for example, onemay apply catalysts consisting largely of one or more sulfides of Fe, Co, Ni, M0 or W. Particularly suitable catalysts, for example, comprise substantial proportions of tungsten sulfide, preferably in,
combination with a sulfide of a metal selected from group VIII, for example Fe, Co or Ni. These catalysts are employed in the present process under dehydrogenation conditions. Dehydrogenation conditions most suitable for catalysts of this type are different from the conditions used in destructive hydrogenation and are usually diilerent from the conditions most suitable for dehydrogenation with catalysts of the oxide type. Suitable dehydrogenation conditions with respect to temperature, pressure, partial pressure of hydrogen and space velocity depend somewhat upon the particular catalyst but are, in general, within the following limits:
Temperature -..C About 425-550 Pressure ..atmospheres About 10-70 Partial pressure of hydrogen atmospheres About 8-60 velocity About 0.5-4.0
-Naphthenic gasoline fractions when treated under these conditions with these catalysts are considerably aromatized. Thus, for example, in the case of the treatment of straight run fractions the products from this treatment are found to contain between about 20% and 40% aromatic hydrocarbons. Unsaturated hydrocarbons such asolefins, if present in the feed, are substantially completely hydrogenated. The aromatic hydrocarbons formed in this step of the asvaaoo V I processmayberemovediromtheproductii desired,byany-oneoftlmseveralknownmethods.
For example, the aromatic hydrocarbons may be removed from the product by extraction with one ofthemanysolvents, forexampleSOaaniline, etc., having a selective solvent action for aromatic hydrocarbonaoritmayinsomecasesbesimply fractionally distilled to recover a pureor relatively concentrated aromatic fraction, or the aromatic hydrocarbon may be conveniently separated by an extractive distillation in a known manner.
The product from the above-described first ste of the process. either with or without subsequent removal of the aromatic hydrocarbons formed, is contacted under dehydrogenation conditions with a molybdenum oxide catalyst. Any of the molybdenum oxide hydrotorming catalysts may be employed. Very suitable catalysts, for example, comprise 4% to 30% molybdenum oxide on a suitable adsorptive support such as absorptive alumina, adsorptive magnesia, activated clay, or the like. Molybdenum oxide supported (15%) on adsor'ptive alumina is an especially good catalyst for this purpose. Suitable dehydrogenation conditions with respect to temperature, Pressure, partial pressure of hydrogen and space velocity are chosen within the following approximate limits:
Temperature C About 425-550 Pressure atmospheres About 2-50 Partial pressure of hydrogen atmospheres. About 1-40 Liquid hourly space velocity About 0.1-4.0
lyst. Any of the chromium oxide dehydrogeuation catalysts may be employed. Thus, for example, one may use precipitated and pllled catalysts consisting of CtaOs, CnOe-AlzOa,
ClaOa-AhOs-KrO, CraO's-SlOz, CraOs-Zi'O: C1'2O:M'8O, etc. Also, one may use chromium Temperature C'. About425-550 Pressure g atmospheres About 0.1-7 Partial pressure of hydrogen I atmospheres-.. 0.5 Liquid hourly space The product from the treatment with the chromium oxide catalyst may, if desired, be used per se or may be treated to recover aromatic hydrocarbons in -a pure or more concentrated form. The aromatic content of this product depends upon whether or notaromatic hydrocarbons have been removed after the first or second of the above-described delwdrogenation treatments. I!
aromatic hydrocarbons have beenremoved from the product after the first and/or second dehydrogenation treatment, this product usually contains about 50% aromatic hydrocarbons. If aromatic hydrocarbons have been removed only after the first dehydrogenation step, aromatic contents oi about 70% are usually present. It aromatic the first or second of the above-described dehydrogenation steps, the aromatic content of this product is much higher, for example 80%. It the aromatic hydrocarbons formed are removed from hydrocarbons have not been removed after either a the product after the chromium oxide treatment,
the non-aromatic fraction may, if desired, be recycled back to the chromium oxide treatment. In this way substantially complete conversion of the naphthenic fraction to aromatic hydrocarbons may be obtained.
In the above, the process has been described as comprising three separate dehydrogenation treatmerits under three definite dehydrogenation conditions with three separate types of dehydrogenation catalyst. This three-step process gives optimum results. It is not necessary, however, that the complete efilciency of the above-described three-step process be utilized. The invention also contemplates two sub-combinations oi! this three-step process which, while not as efilcient as the three-step process, are nevertheless superior to any of the single-step processes heretofore proposed and may be profitably employed, for e ample, where it is desired to avoid the cost of providing three separate dehydrogenation units.
The first of these alternative two-step processes involves contacting the naphthenic hydrocarbon fraction first with a metal sulfide dehydrogenation catalyst as above described in the first step of the three-step process and then contacting the product, either with or without subsequent removal or concentration of aromatic hydrocar- 1 bons, with a molybdenum oxide catalyst as described in the second step 01 the three-step proccycled to the first dehydrogenation treatment with the metal sulfide, no appreciable further amounts of aromatic hydrocarbons are formed.
By contacting this product, however, under dehydrogenation conditions with the chromium oxide catalyst as described, additional amounts (for example, 10%-70%) of aromatic hydrocarbons are formed. 'It is also to be noted that ii the material is contacted with the various dehydrogenation catalysts in any other way, appreciable increase in yield of aromatic hydrocarbons over that obtained by the conventional one-step process is not obtained. Thus, if the naphthenic i'raction is contacted with the molybdenum oxide or chromium oxide catalyst first, only very small amounts of aromatic hydrocarbons are Iormed by subsequent contacting 01' this material under dehydrogenation conditions with the metal sulfide catalyst, or it the material is contacted with the chromium oxide catalyst prior to contacting it with the molybdenum oxide catalyst, the dehydrogenation with the molybdenum oxide catalyst gives much lower yields of aromatic hydrocarbons than those obtained with the chromium-oxide catalyst in. the last step 0! the described process, and the catalytic Me of the ess. It will be observed that this alternative processis the same as the above-described threestep process except that the dehydrogenation treatment with a chromium oxide catalyst is omitted.
chromium oxide catalyst is round to be very poor.
A suitable application of the process is illustrated by the iolowing example:
A hydrocarbon traction consisting essentially 01 a mixture of normal paramn and cycloparaifin hydrocarbons of both hydroaromatic and nonhydroaromatic character was treated with a tungsten sulfide-nickel sulfide catalyst under the folowing conditions: Temperature C 4'75 Pressure atmospheres 25 M01 ratio of hydrogen to'hydrocarbon 8 Liquid hourly space velocity 1.0
According to the second alternative two-step I process, the naphthenic petroleum traction, preterably a straight run gasoline fraction, is first contacted with a molybdenum oxide catalyst as described in the second step of the three-step process and the product, either with or without subsequent removal or concentration of aromatic hydrocarbons, is treated with a chromium oxide catalyst as described in the third step of the three-step process. It will be observed that this alternative process is the same as the recycled, no appreciable additional yields of aro- The product contained about 27% by weight of aromatic hydrocarbons, chiefly toluene. The aromatic hydrocarbons were extracted from the product and the non-aromatic portion treated with a molybdenum oxide-alumina catalyst (14% Mo) under the following conditions:
Temperature C 490 Pressure atmospheres 10 Mel ratio of. hydrogen to hydrocarbon 3 Liquid hourly space velocity 0.6
The product contained about 26% by weight of aromatic hydrocarbons. The aromatic hydrocarbons were extracted trom'the product. The remaining non-aromatic portion was exceptionally suited for treatment with a chromium oxidematic hydrocarbons are obtained. when, however, the product from the dehydrogenation treatment with the metal sulfide catalyst is contacted under dehydrogenation conditions with the mo- Lvbdenum oxide catalyst as described, the product contains considerable additional aromatic hydrocarbons, for example 20%-40%. Again. ii the aromatic hydrocarbons are removed from this product and the aromatic-free product realumina (11% Cr) catalyst under the following conditions:
Temperature C 4'75 Pressure atmospheres 1 Mol ratio of hydrogen to hydrocarbon 0 Liquid hourly space velocity, 0.4
The ultimate yield 0! aromatic hydrocarbons obtained by the above combination of steps is higher than could be obtained with the said hydrocarbon fraction by the same number of passes with any one of the three catalysts separately or by any other order 0! the three treatments.
we claim as our invention:
1. A process for the production of aromatic hydrocarbons from naphthenic fractions of the nature of gasoline which comprises contacting the naphthenic gasoline fraction under dehydrogenaflmconditicnsflrstwltha' oxidecatalyst ing metal sulfide catalyst. thenwithamolybchosen'withinthetollowinglimih.
denum odds and then Q m o c Pressure .a AboutHn 2.111emlordhgtoclflml1lnrdn the metal dehydrogenation catalyst com- 3. W140- Pm mm Liquid hourly space velocity.--" About 0.1-4.0
a r The process according to claim. 6 wherein the me s e one on c comprises tun sten sulfide and nickel sulfide. 10 the m i'lheproceasaccordingtoclaimlwherein the molybdenum oxide catalyst consists essentialiy oi molybdenum oxide supported upon alumine. I
5.111epr0cessaccordingtoclaim1wherein the chromium oxide catalyst consists essentially of chromium oxide and alumina.
6. A process for the production oi aromatic hydrocarbons from naphthenic fractions of the nature of gasoline which comprises contacting the naphthenic fraction with a metal sulfide dehydrogenation catalyst under conditions chosen within the following limits:
Temperature 0-- About 425-550 Pressure -atmospheres About 10-70 Partial pressure of hydrogen atmospheres" About s-oo Liquid hourly space velocity About 0.5-4.0
P118123 tungsten sulfide.
8.'lheprocessaccordingioclaimflwher-ein the metal sulfide dehydrosenation catalyst com prises tungsten sulfide and nickel sulfide.
'9.The process accordingtoclaim6wherein the molybdenum oxide catalyst consists essentially or molybdenum oxide supported upon alumina. l0.'l'heprocessaccordingtoclaim1wherein the naphthenic traction consists predominantly of hydrocarbons having seven carbon atoms.
1i."lhe process according to claim 8 wherein the naphthenictraction consists predominantly of hydrocarbons having seven carbon atoms.
12. The process according to claim 1 wherein aromatic hydrocarbons produced are removed from the product after each or said catalytic treatments. v
13. The process according to claim 8 wherein aromatic hydrocarbons produced are removed from the product prior to the treatment with the molybdenum oxide catalyst.
csnnrrclrs or conmsclzton.
NA L, FULLER, ET s.
It is hereby certified 0nd column, line 36, for -"case" June 12,. 1914.5.
I -thai; error appears flue printed speeiiicatidn;
or the above numbered 'patent requiring correction asidllows:
Page 1, sec-1 read- --ease page 2, second column,
61, for "6.5" read o-5-'-; and that, the said Letters -Patent should be ism with this correction therein that the the case in the Patent'ofrice.
same may conform to iiie record off (Seall Leslie Frazer First Assistant; Commissioner of Patents.
senaibn conditions first with a Willameting metal sulfide catalyst, thenwith a denumoaidecatalystandtbenwlthachromlmn onidecl-talyat.
2.'1he procea according to claim 1 wherein the metal sulfide dehydrogenation catalyst comprisestlmsstensuliide.
a'l'heprocesaccordingtoclaimiwherein the metal sulfide dehydrogenation catalyst oomhydrogenation catalyst under conditions chosen within the following limits:
Temperature 0-- About 425-550 Pressure -atmospheres About 10-70 Partial pressure of hydrosen atmospheres" About s-so Liquid hourly space velocity About 0.5-4.0
to selectively dehvdrogenate naphthenes and hydrogenate any olefins present, and then contacting the thus-treated fraction with a molybdenum asnsos oxidecataiystlmdsr cmditim atmospheres Ami-4o- Liquid hourly space velocity.--" Amos-4.0
'L'l'heprocesaucording-toclaimflwherein themetalsuifidedehydrogenationcatalystcomprise tungstensulfide.
8.'lheprocessaccordingtoclainrflwher-ein the metal sulfide dehydrasenation catalyst com prises tungsten sulfide and nickel sulfide.
'9.The process accordingtoclaim6wherein the molybdenum oxide catalyst consists essentially or molybdenum oxide supported upon alumina. l0.'1'heprocessaccordingtoclaim1wherein the naphthenic traction consists predominantly of hydrocarbons havins seven carbon atoms.
IL'The process according to claim 8 wherein the naphthenictraction consists predominantly of hydrocarbons having seven carbon atoms.
12. The process according to claim 1 wherein aromatic hydrocarbons produced are removed from the product after each or said catalytic treatments. v
13. The process according to claim 8 wherein aromatic hydrocarbons produced are removed from the product prior to the treatment with the molybdenum oxide catalyst.
DONALD L. FULLER. BERNARD S. GREENBFELDm.
csnnrrcirs or conmscizton.
It is hereby certified 0nd column, line 36, for -"case" DONAL]? L, FULLER, ET at.
June 12,. 1914.5.
I -that error appears the printed speeiiicatidri;
oi the above numbered 'patent requiring correction esfdllows:
Page 1, see-1 read- --ease page 2, second column,
61, roi- "6.5" read o-5-'-; and that, the said Letters Patent should be item with this correction therein that the the case in the Patent'ofrice.
same mayv conform to the record off Signed a sealed t i 2n d y or October, A. p. 1 9s Leslie Frazer
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| US465923A US2378209A (en) | 1942-11-17 | 1942-11-17 | Process for the production of aromatic hydrocarbons |
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| US465923A US2378209A (en) | 1942-11-17 | 1942-11-17 | Process for the production of aromatic hydrocarbons |
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Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2446547A (en) * | 1946-03-01 | 1948-08-10 | Houdry Process Corp | Catalytic conversion of hydrocarbons with a thorium phosphate catalyst |
| US2449050A (en) * | 1946-03-01 | 1948-09-14 | Houdry Process Corp | Catalytic conversion of hydrocarbons with a cerium phosphate catalyst |
| US2632739A (en) * | 1949-10-12 | 1953-03-24 | Standard Oil Dev Co | Catalyst for producing aromatic hydrocarbons |
| US2645604A (en) * | 1949-09-07 | 1953-07-14 | Phillips Petroleum Co | Tandem-bed hydroforming process |
| US2661380A (en) * | 1951-02-20 | 1953-12-01 | Socony Vacuum Oil Co Inc | Oxidative dehydrogenation of cyclic hydrocarbons |
| US2689265A (en) * | 1949-10-12 | 1954-09-14 | Standard Oil Dev Co | Method for preparing aromatic hydrocarbons |
| US2865842A (en) * | 1954-12-29 | 1958-12-23 | Sun Oil Co | Cracking of a hydrocarbon oil with a silica-alumina-tungsten phosphate catalyst composite |
| US2958717A (en) * | 1958-10-29 | 1960-11-01 | Petro Tex Chem Corp | Catalytic dehydrogenation of hydrocarbons |
| US3009871A (en) * | 1956-05-16 | 1961-11-21 | Vitro Corp Of America | Catalytic process for dehydrogenation of hydrocarbons |
| US3039954A (en) * | 1956-12-27 | 1962-06-19 | Texaco Inc | Method of treating hydrocarbons |
| US3207801A (en) * | 1961-08-07 | 1965-09-21 | Socony Mobil Oil Co Inc | Catalytic dehydrocyclization |
| US3226421A (en) * | 1961-07-14 | 1965-12-28 | Edison Soc | Catalytic process for the preparation of nitriles |
| US3247271A (en) * | 1963-09-13 | 1966-04-19 | Socony Mobil Oil Co Inc | Method of producing dienes and aromatics |
| US3254128A (en) * | 1961-11-09 | 1966-05-31 | Eastman Kodak Co | Catalytic dehydrogenation of primary alcohols to aldehydes |
| US3370083A (en) * | 1962-08-23 | 1968-02-20 | Montedison Spa | Catalytic process for the preparation of nitriles |
| US3370087A (en) * | 1966-05-18 | 1968-02-20 | Eastman Kodak Co | Oxidative dehydrogenation process |
| US3449461A (en) * | 1966-11-23 | 1969-06-10 | Shell Oil Co | Dehydrocyclization of paraffins |
| US3490067A (en) * | 1965-05-25 | 1970-01-13 | Commissariat Energie Atomique | Ceramic part for electrodes |
| US3532740A (en) * | 1966-05-18 | 1970-10-06 | Eastman Kodak Co | Oxidative dehydrogenation process |
| US3770616A (en) * | 1970-05-15 | 1973-11-06 | Asahi Chemical Ind | Method of reforming hydrocarbons |
| US3879486A (en) * | 1973-01-18 | 1975-04-22 | Atlantic Richfield Co | Conversion of non-cyclic C{HD 3{B -C{HD 5 {B alkanes and alkenes to aromatic hydrocarbons |
| US3886224A (en) * | 1973-01-18 | 1975-05-27 | Atlantic Richfield Co | Conversion of non-cyclic C{HD 3{B {14 C{HD 5 {B alkanes to aromatic hydrocarbons |
| US3909393A (en) * | 1972-08-16 | 1975-09-30 | Catalyse Soc Prod Francais | Trimetallic reforming catalyst and use thereof |
| US4048099A (en) * | 1972-01-10 | 1977-09-13 | Uop Inc. | Hydrocarbon conversion with an acidic trimetallic catalytic composite |
| US4093536A (en) * | 1974-04-15 | 1978-06-06 | Phillips Petroleum Company | Catalytic cracking and dehydrocyclizing of alkanes using alkaline earth oxides promoted with manganese oxide and/or rhenium oxide |
| US4215017A (en) * | 1978-12-28 | 1980-07-29 | Phillips Petroleum Company | Catalyst for disproportionation/double-bond isomerization of olefins |
-
1942
- 1942-11-17 US US465923A patent/US2378209A/en not_active Expired - Lifetime
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2446547A (en) * | 1946-03-01 | 1948-08-10 | Houdry Process Corp | Catalytic conversion of hydrocarbons with a thorium phosphate catalyst |
| US2449050A (en) * | 1946-03-01 | 1948-09-14 | Houdry Process Corp | Catalytic conversion of hydrocarbons with a cerium phosphate catalyst |
| US2645604A (en) * | 1949-09-07 | 1953-07-14 | Phillips Petroleum Co | Tandem-bed hydroforming process |
| US2632739A (en) * | 1949-10-12 | 1953-03-24 | Standard Oil Dev Co | Catalyst for producing aromatic hydrocarbons |
| US2689265A (en) * | 1949-10-12 | 1954-09-14 | Standard Oil Dev Co | Method for preparing aromatic hydrocarbons |
| US2661380A (en) * | 1951-02-20 | 1953-12-01 | Socony Vacuum Oil Co Inc | Oxidative dehydrogenation of cyclic hydrocarbons |
| US2865842A (en) * | 1954-12-29 | 1958-12-23 | Sun Oil Co | Cracking of a hydrocarbon oil with a silica-alumina-tungsten phosphate catalyst composite |
| US3009871A (en) * | 1956-05-16 | 1961-11-21 | Vitro Corp Of America | Catalytic process for dehydrogenation of hydrocarbons |
| US3039954A (en) * | 1956-12-27 | 1962-06-19 | Texaco Inc | Method of treating hydrocarbons |
| US2958717A (en) * | 1958-10-29 | 1960-11-01 | Petro Tex Chem Corp | Catalytic dehydrogenation of hydrocarbons |
| US3226421A (en) * | 1961-07-14 | 1965-12-28 | Edison Soc | Catalytic process for the preparation of nitriles |
| US3207801A (en) * | 1961-08-07 | 1965-09-21 | Socony Mobil Oil Co Inc | Catalytic dehydrocyclization |
| US3254128A (en) * | 1961-11-09 | 1966-05-31 | Eastman Kodak Co | Catalytic dehydrogenation of primary alcohols to aldehydes |
| US3370083A (en) * | 1962-08-23 | 1968-02-20 | Montedison Spa | Catalytic process for the preparation of nitriles |
| US3247271A (en) * | 1963-09-13 | 1966-04-19 | Socony Mobil Oil Co Inc | Method of producing dienes and aromatics |
| US3490067A (en) * | 1965-05-25 | 1970-01-13 | Commissariat Energie Atomique | Ceramic part for electrodes |
| US3370087A (en) * | 1966-05-18 | 1968-02-20 | Eastman Kodak Co | Oxidative dehydrogenation process |
| US3532740A (en) * | 1966-05-18 | 1970-10-06 | Eastman Kodak Co | Oxidative dehydrogenation process |
| US3449461A (en) * | 1966-11-23 | 1969-06-10 | Shell Oil Co | Dehydrocyclization of paraffins |
| US3770616A (en) * | 1970-05-15 | 1973-11-06 | Asahi Chemical Ind | Method of reforming hydrocarbons |
| US4048099A (en) * | 1972-01-10 | 1977-09-13 | Uop Inc. | Hydrocarbon conversion with an acidic trimetallic catalytic composite |
| US3909393A (en) * | 1972-08-16 | 1975-09-30 | Catalyse Soc Prod Francais | Trimetallic reforming catalyst and use thereof |
| US3879486A (en) * | 1973-01-18 | 1975-04-22 | Atlantic Richfield Co | Conversion of non-cyclic C{HD 3{B -C{HD 5 {B alkanes and alkenes to aromatic hydrocarbons |
| US3886224A (en) * | 1973-01-18 | 1975-05-27 | Atlantic Richfield Co | Conversion of non-cyclic C{HD 3{B {14 C{HD 5 {B alkanes to aromatic hydrocarbons |
| US4093536A (en) * | 1974-04-15 | 1978-06-06 | Phillips Petroleum Company | Catalytic cracking and dehydrocyclizing of alkanes using alkaline earth oxides promoted with manganese oxide and/or rhenium oxide |
| US4215017A (en) * | 1978-12-28 | 1980-07-29 | Phillips Petroleum Company | Catalyst for disproportionation/double-bond isomerization of olefins |
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