US3806443A - Selective hydrocracking before and after reforming - Google Patents

Selective hydrocracking before and after reforming Download PDF

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US3806443A
US3806443A US00257119A US25711972A US3806443A US 3806443 A US3806443 A US 3806443A US 00257119 A US00257119 A US 00257119A US 25711972 A US25711972 A US 25711972A US 3806443 A US3806443 A US 3806443A
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catalyst
reforming
selective
normal
product
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J Maziuk
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Priority to US00257119A priority Critical patent/US3806443A/en
Priority to GB2407473A priority patent/GB1417508A/en
Priority to NL7307290A priority patent/NL7307290A/xx
Priority to BE131498A priority patent/BE800001A/xx
Priority to FR7319207A priority patent/FR2189499B1/fr
Priority to JP5793473A priority patent/JPS5521796B2/ja
Priority to DE2326834A priority patent/DE2326834A1/de
Priority to IT24674/73A priority patent/IT998118B/it
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
    • B01J29/56—Iron group metals or copper
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S208/00—Mineral oils: processes and products
    • Y10S208/02—Molecular sieve

Definitions

  • Reforming of hydrocarbons is a widely used process in petroleum technology for upgrading hydrocarbon fractions such as naphthas, gasolines and kerosines to improve the anti-knock characteristics thereof.
  • Hydrocarbon fractions suitable for upgrading by reforming are composed of normal and branched parafiins, naphthenic hydrocarbons and even some aromatic hydrocarbons.
  • During reforming a multitude of reactions take place including dehydrogenation, isomerization, dehydrocyclization, hydrocracking, and combinations thereof to yield a product of increased aromatics content and branched chain hydrocarbons.
  • Normal and slightly branched paraflin hydrocarbons found in the above hydrocarbon fractions are generally of low octane rating. Highly branched-chain parafiin hydrocarbons, on the other hand, are characteristic of higher octane ratings. Therefore, one object of reforming is to effect isomerization of the normal and slightly branched chain parafiins to higher octane products by any one of the aforementioned reactions.
  • the production of aromatics during reforming is accomplished by one or more of the above identified reactions leading to the production of naphthenes which are then dehydrogenated to aromatics such as benzene, toluene and xylene.
  • One method for producing aromatics involves the isomerization of alkyl cyclopentanes to form cyclohexanes which thereafter are dehydrogenated to aromatics.
  • This invention relates to a method and combination of processing steps for effecting a selective conversion and a rearrangement of petroleum hydrocarbon constituents to form aromatic enriched products and improve yields of LPG materials.
  • the present invention is concerned with one or more methods for selectively conducting chemical reactions with an arrangement of catalytic compositions possessing selective reaction properties with respect to different hydrocarbon components existing in the naphtha boiling range material.
  • the present invention relates to effecting a selective catalytic conversion of hydrocarbon components comprising ring, normal and isoparafiin hydrocarbon components in a sequence of hydrogenating conversion steps maintained under operating conditions selected to obtain products rich in aromatics and LPG material.
  • the invention is concerned with an arrangement and sequence of catalytic reactions designed to manipulate the reaction of hydrocracking, dehydrogenation, isomerization and dehydrocyclization in an amount selected to improve upon the yields of LPG products and relatively high octane aromatic components.
  • the present invention is concerned with contacting a relatively wide boiling range naphtha hydrocarbon material boiling in the range of C hydrocarbons up to about 380 or 400 F. under selective hydrocracking conditions suitable for particularly removing the relatively low boiling C and C normal parafiins and not more than a minor amount of C parafiins by a selective cracking thereof to LPG (propane and butane) products.
  • LPG propane and butane
  • the naphtha charge remaining after the selective removal particularly of low boiling normal parafiin constituents and comprising C and higher boiling naphtha boiling range materials is subjected to reforming conditions in the presence of a platinum type reforming catalyst maintained under conditions selected to reestablish the presence of normal paraflins and thus a relationship approaching equilibrium between normal and branched compounds existing in the hydrocarbon charge encountering the reforming reactions comprising dehydrogenation of naphthenes, isomerization of isomerizable hydrocarbons and dehydrocyclization of non-aromatic hydrocarbon constituents.
  • the reforming catalyst may be relied upon to hydrocrack these low octane compounds formed during the reforming operation by pushing the severity of the reforming operation but it is preferred that the reformate product comprising any C and higher boiling normal paraffin constituents be subjected to a selective hydrocracking operation designed to convert particularly the low boiling normal paraflins formed during the operation.
  • the present invention includes the selective cracking of low and high boiling normal paraflin components comprising the naphtha boiling material processed in the combination of catalytic contact steps comprising this invention.
  • This established relationship between normal and branched chain hydrocarbon components brought about by the rearrangement of branched components provides additional normal paraffiu constituents suitable for conversion to LPG material.
  • crystalline aluminosilicates of an average pore size generally less than about 6 angstroms pore diameter but greater than about 4.5 angstroms, that is, about angstroms and comprising, for example, erionite are particularly selective for cracking of C normal parafiins to the substantial exclusion of cracking branched and ring constituents.
  • a nickel erionite crystalline aluminosilicate such as hereinafter described will have a preference for cracking normal C hydrocarbons to that of C C and higher boiling normal paraffin.
  • a platinum type reforming catalyst including bimetallic and non-bimetallic reforming catalysts and those comprising platinum or palladium in combination with another Group VIII metal component such as rhenium, iridium, ruthenium and osmium promoted with a halogen will indiscriminately effect hydrocrac'king under elevated temperature reforming conditions of the normal and branched parafiin components comprising the hydrocarbon material in the reforming operation.
  • a platinum type reforming catalyst under controlled isomerizing and hydrocracking severity conditions may be relied upon to produce LPG type products or products more easily converted to LPG products with a small pore nickel erionite selective hydrocracking catalyst in another reaction zone or contact step.
  • hydrocracking reactions performed with platinum reforming catalysts are more usually rate controlled reactions wherein, for example, a normal C hydrocarbon will crack more easily than a C hydrocarbon or a lower carbon number paraffin and thus a high severity reforming operation would be required to crack, for example, a C paraflin.
  • a high severity non-selective hydrocracking operation with the platinum reforming catalyst is undesirable since cracking of branched C and C hydrocarbons will be accomplished before cracking of normal hexane. This will result in cracking desired high octane branched chain hydrocarbons.
  • such an operation produces an undesired mixture of light gases particularly comprising C and C hydrocarbons rather than C and C hydrocarbons.
  • Crystalline aluminosilicate conversion catalysts identified with the prior art which are not selective within the limits defined herein or those particularly known as methane producers rather than producers of propane and butane are of little interest in pursuing the concepts of this invention.
  • high methane producing crystalline aluminosilicate catalysts generally small pore crystalline zeolites promoted with Zn, Cd and Hg or other hydrocracking catalyst compositions which non-selectively produce gaseous streams rich in methane are of little interest for practicing the concept of this invention unless they can be controlled by operating conditions to exclude the undesirable production of light gaseous hydrocarbon constituents particularly methane and ethane.
  • catalyst A platinum type of reforming catalyst used
  • catalyst B selective crystalline aluminosilicate hydrocrackin'g catalyst relied upon particularly for the production of LPG gases
  • the platinum type reforming catalyst, catalyst A, selected for use in the sequence of process steps of this invention may be selected from any one of a number of known prior art reforming catalysts suitable for accomplishing the results desired.
  • These catalysts include generally, for example, alumina as the carrier material for one or more hydrogenation-dehydrogenation components distributed thereon with the alumina being in either the eta, chi, gamma or mixed forms thereof.
  • the alumina carrier is promoted with, for example, one or more Group VIII metal components either with or without an acidic promoter such as silica, boron or a 'halogen.
  • the platinum type of reforming catalyst is intended to include platinum, palladium, osmium, iridium, ruthenium, rhenium and mixtures thereof deposited on an alumina containing carrier or support with the alumina components generally being in an amount up to about by weight. Other components such as magnesium, zirconium, thorium, vanadium and titanium may also be combined or distributed in the alumina carrier.
  • the platinum type catalyst may also include various amounts of halogen such as chlorine or fluorine in amounts ranging from about 0.1% up to about 10%; usually not more than 5 or 6%.
  • the platinum reforming catalysts described may be one of those described in the prior art as homogeneous mixtures of metal components, alloys, and metal halide complexes thereof.
  • a bimetal catalyst composition suitable for the reforming operation of this invention may be platinum combined with either rhenium, ruthenium, osmium or iridium and an alumina carrier promoted with chlorine to provide desired acid activity.
  • the selective conversion catalyst or hydrocracking catalyst herein referred to as a type B catalyst is a porous solid particle material having a majority of its pores of substantially uniform small dimension which are large enough to allow uptake and egress of normal paraflin molecules such as, for example, normal hexane and smaller carbon atoms, but too small to allow a similar uptake of either branched or ring compounds such as, for example, methylpentane, cyclohexane or benzene.
  • those hydrocarbons comprising C and longer chain normal parafiin hydrocarbons up to about C hydrocarbons encounter ditfusion limitations which increase with length of chain and thus are slower to crack when employing the small pore crystalline aluminosilicate catalyst intended for use by this invention.
  • the selective hydrocracking catalytic material, type B is a porous crystalline material wherein a substantial majority of its pores are of an average uniform dimension of about 5 angstroms and in the range of from about 4.5 up to about 6.0 angstrom units effective diameter.
  • This is essentially a selective crystalline aluminosilicate of the erionite variety provided with inpore acid activity cracking sites and catalytically effective bydrogenationdehydrogenation sites.
  • the hydrogenation-dehydrogenation functions may be associated with the small pore shape selective crystalline material but externally located to the pore and in some cases located both within and externally to the pore.
  • the hydrogenation-dehydrogenation component provided during manufacture of the catalyst involves one or more of the elements such as a transition metal.
  • the elements such as a transition metal.
  • one or more of the elements of nickel, cobalt, molybdenum, iron or of the platinum or palladium family are employed.
  • One or more of the elements employed may involve an element selected from a higher molecular weight transition metal which have hydrogenation-dehydrogenation activity, such as tungsten.
  • a crystalline aluminosilicate of desired porosity such as erionite may be modified to produce useful catalysts for this invention by effecting the introduction of one or more of the above identified transition elements in such a way that the final quantity of the element may be located in either the internal, external or mixed internalexternal pore structure of the crystalline aluminosilicate.
  • Introduction of one or more of such metallic elements or components may be achieved by processes allowing the metal to penetrate the existing or preformed pore solid and be fixed therein or by formation on the pore solid itself in a compositional environment which contains the desired metal component in a form suitable to be incorporated into the porous structure in the formation thereof, or in the course of its modification to a desired pore structure.
  • the type B catalyst is preferred with certain limited magnitudes of acid catalytic activity.
  • the preferred acid activity will have an alpha value in excess of 10.
  • a more preferred acidity level is between 5 and 300 alpha; for operations more nearly at 800 F., above about 500 alpha; for operations near 700 F., above about 200 alpha.
  • a very practical method of assaying the alpha acidity of the type B catalyst is that of testing its n-hexane cracking activity under conditions of cracking, in the absence of hydrogen. Such a procedure is identified in Journal of Catalysis, volume 4, No. 4, August 1965.
  • the operating conditions employed in the proces combination of this invention and particularly that of the reforming operation with type A catalyst are those conditions which promote dehydrogenation of naphthenes along with reactions associated with isomerization which reestablish a relationship between normal paralfins to branched paraffins and include operating temperatures selected from within the range of from about 800 F. to about 1000 F. and preferably from about 850 F. up to about 980 F., liquid hourly space velocity in the range of from about 0.1 to about 10, preferably from about 0.5 to about 5; a pressure in the range of from about atmospheric up to about 600 p.s.i.g. and preferably from about 100 to about 400 p.s.i.g.; and a hydrogen to hydrocarbon ratio selected from within the range of from about 0.5 to about 20 and preferably from about 1 to 10.
  • type B catalyst or the selective normal parafl'in conversion catalyst may be operated at conditions similar to reforming operating conditions depending on the catalyst employed therein. However, it is important that the operating conditions be selected which will particularly promote the formation of LPG gaseous material from the hydrocarbon charge material brought in contact with type B catalyst. Therefore, catalyst type B Type B, catalyst example A natural crystalline aluminosilicate identified as erionite obtained from Nevada was analyzed with the following results:
  • a sample of the above identified erionite was crushed to provide a powder.
  • the powder was exchanged twice with 6 ml. of 5 M ammonium chloride solution per gram (bone dry baiss) of the erionite powder for 4 hours at F. with filtering after each exchange. Thereafter the exchanged erionite is washed with 10 ml. of water per gram of erionite and filtered. Then the erionite zeolite is exchanged with 4.4 ml. of 0.5 M nickel acetate solution (adjusted to 6 pH with acetic acid) per gram of the zeolite for 4 hours at 210 F. and filtered.
  • the nickel exchanged zeolite is then washed with 10 ml. of water per gram of zeolite and filtered.
  • the exchanged zeolite prepared as above identified is then dried for at least 16 hours or to a constant weight at a temperature in the range of 225 to 250 F.
  • the dried erionite zeolite promoted with nickel is then pelleted and crushed to a 10/14 mesh.
  • the 10/14 mesh refers to passing through U.S. Standard Sieve No. 10 (Tyler equivalent 9 mesh) and retained on U.S. Standard Sieve No. 14 (Tyler equivalent 12 mesh).
  • Hydrofining of the charge naphtha may be accomplished in the presence of any one of a number of different hydrofining catalysts known and available in the prior art.
  • Suitable hydrofining catalysts include the metals and/or sulfides of Group VIII and Group VI metals of the Periodic Table employed alone or in combination with one another such as cobalt or nickel and molybdenum or tungsten.
  • Such catalyst may be employed alone or in combination with a support or carrier material such as alumina, silica, zirconia, titania and clays or mixtures thereof.
  • the hydrofining catalyst is an amorphous base catalyst but it may also contain a small amount of a crystalline aluminosilicate in combination with the amorphous carrier component.
  • Suitable hydrofining catalysts include cobalt-molybdenum dispersed on alumina, nickel-tungsten sulfide alone or dispersed on a carrier or support such as alumina or silica-alumina.
  • temperature, pressure and space velocity conditions are selected from those well known in the prior art which will be effective in reducing the level of nitrogen and sulfur in the charge to that suitable for initial contact with the selective crystalline aluminosilicate conversion catalyst.
  • the selective crystalline aluminosilicate hydrocracking catalyst is fairly tolerant of nitrogen and sulfur compounds and thus will assist with the removal of these contaminants during conversion of n-paraffin components in the naphtha charge.
  • the selective hydrocracking catalyst B may form a down-stream portion of the desulfurizing catalyst bed.
  • the amount of nitrogen in the naphtha reforming feed should be reduced not to exceed about 2 p.p.m.
  • a naphtha charge such as identified in Table 1 was passed sequentially through the combination of catalyst contact steps comprising a selective crystalline aluminosilicate hydrocracking catalyst (SCI) for normal paraffin conversion to LPG, a platinum-aluminum reform-ing catalyst and then a final contact with a selective crystalline aluminosilicate hydrocracking catalyst (8C2).
  • SCI selective crystalline aluminosilicate hydrocracking catalyst
  • Table 2 below identifies the operating conditions employed in one particular combination and provides the results obtained with the combination of conditions recited for improving product selectivity to LPG.
  • the SCI and SCZ catalyst steps used the nickel erionite catalyst prepared as described above in combination with 0.6 Wt. percent platinum dispersed on alumina and promoted with chlorine.
  • Table 2 provides characteristics of the product obtained after each of the contacting steps as well as the cumulative yields obtained after traverse of the combination of processing steps. From these data it will be observed that product selectivity to LPG product comprising C and C hydrocarbons was vastly improved by the combination of selective hydrocracking before and i c r vit .72 2 :23 5 y 0 60 after reforming. It W111 also be observed that the aromatic R 41 rich high octane product of the combination process of M+ O 40 this invention has a much lower benzene content than a similar octane product of the processes compared.
  • Pona andlysls P the combination of this invention is also unexpectedly Paraflins eifective in reducing the concentration of benzene in a Naphthenes &5 high octane product suitable for use in preparing motor Aromatics 9.5 fuels.
  • Table 2 the data of Table 2 have been separated and rearranged to provide Tables 3 and 4 below.
  • Table 3 below emphasizes the yield improvement in LPG material (C and C hydrocarbons) and particularly that of propane obtained by the processing combination of this invention.
  • Table 4 differences in the product slate obtained from the three dilferent identified operations are compared.
  • Table 4 particularly emphasizes the changes in the product slate from the different processing steps of the combination (SC1-l-PtR+SC2) particularly with respect to octane rating, C and C hydrocarbons yield and the decrease yield of normal paraffins.
  • the combination of processing steps comprising this invention and the product slate obtained therefrom can be varied by varying, for example, the reforming operating conditions and/or the catalyst employed therein.
  • reforming catalysts of different composition are known to influence the various reforming reactions.
  • Catalyst acidity may be employed to influence the various reactions of isomerization in the direction desired. That is, acidic reforming catalyst may be relied upon to enhance isomen'zing reactions which change the balance between normal and branched parafiins and/or the cracking reactions encountered depending upon the temperature and space velocity employed.
  • a silica promoted reforming catalyst may be selected to enhance dehydrocylization reactions for example at temperatures less suitable for isomerizing reactions.
  • a catalyst of very low acidity may be employed in the first reaction zone with subsequent reaction zones provided with catalyst compositions of the same or diiferent acid activity to promote desired reactions.
  • the processing combination of this invention contemplates the use of the selective crystalline aluminosilicate conversion catalyst (SCl) to effect a part of the desulfurizing of the naphtha charged to the process. It also contempltes use of the crystalline selective hydrocracking catalyst as a down stream portion of the hydrofining catalyst bed of a different composition such as CoMo on alumina or the selective hydrocracking catalyst (SCI) may be in admixture with the desulfurizing catalyst. Under some circumstances it may be desirable to maintain the hydrofining, catalyst and the selective nickel erionite conversion catalyst in separate reactor beds with means between beds for removing undesired gaseous constituent with or without means for altering the temperature between catalyst beds as required.
  • SCl selective crystalline aluminosilicate conversion catalyst
  • means are provided between the initial selective nickel erionite hydrocracking catalyst conversion step and the reforming step to separate, for example, sulfur and nitrogen before passing the naphtha charge depleted of sulfur to a heating zone wherein it is heated either alone or in the presence of hydrogen to a temperature sufiiciently elevated to effect primarily dehydrogenation of naphthenes therein upon contact with the chlorine promoted platinum alumina reforming catalyst.
  • the total product of the reforming operation may be passed in contact with a selective crystalline aluminosilicate (CAS) conversion catalyst such as nickel promoted erionite for the purpose of selectively cracking to LPG products only the n-parafiins found in the reformate product.
  • CAS selective crystalline aluminosilicate
  • the reformate product may be first, separated to recover C and h1gher boiling material from gaseous material lowei' boilmg than C hydrocarbons. Thereafter the C and higher boiling material and comprising normal paraifin components therein formed during the reforming operation is passed in contact with the selective nickel erionite hydrocracking catalyst defined herein under desired temperature and pressure hydrocracking conditions selected toachieve the further production of LPG products comprising C and C hydrocarbons as described herein.
  • the selective hydrocracking catalyst SC2 relied upon to convert normal paraffins in the C reformate may be the same catalyst relied upon initially to remove nparafiins and sulfur from the naphtha charge.
  • catalyst suitable for accomplishing this purpose may also be relied upon provided the catalyst does not hydrogenate or otherwise destroy aromatics existing therein.
  • a crystalline aluminosilicate hydrocracking catalyst of larger pore diameter than the particular selective catalyst herein defined may be used provided it will convert normal and some branched parafiin to form LPG products without destroying aromatics formed in the combmation.
  • a naphtha boiling range material such as used in the above examples and boiling from about C hydrocarbons up to about 340 F. is introduced to the process by conduit 2.
  • Hydrogen such as hydrogen rich gaseous product of reforming is introduced by conduit 4 for admixture with the naphtha charge being passed to a preheat furnace 6.
  • furnace 6 the mixture is preheated to an elevated temperature in the range of 600 F. up to about 800 F., or higher and sufiicient to effect desulfurization of the naphtha upon contact with the desulfurizing catalyst or the combination of catalysts provided in reactor 10 in this specific embodiment.
  • the preheated naphtha boiling charge is passed by conduit 8 to reactor 10 wherein is housed, in this specific embodi ment, an amorphous base desulfurization catalyst 12 such as cobalt-molybdenum on alumina in an upper portion of the reactor and a selective crystalline aluminosilicate (CAS) hydrocracking catalyst (SCI or nickel erionite) 14 in the lower portion of the reactor.
  • an amorphous base desulfurization catalyst 12 such as cobalt-molybdenum on alumina in an upper portion of the reactor and a selective crystalline aluminosilicate (CAS) hydrocracking catalyst (SCI or nickel erionite) 14 in the lower portion of the reactor.
  • CAS selective crystalline aluminosilicate
  • the sole fill of reactor 10 for example, may be the selective catalyst (SCI) defined hereinbefore and having a pore size of about 5 A.
  • gaseous products comprising LPG material such as C and C hydrocarbons along with lower boiling hydrocarbons, hydrogen sulfide and ammonia as well as unconsumed hydrogen is removed from the upper portion thereof 'by conduit 20.
  • This gaseous product is passed through equipment not shown to obtain a separation and recovery of LPG materials from the remaining gaseous product.
  • Higher boiling hydrocarbon material and more usually comprising and higher boiling hydrocarbons are removed from separation step 18 by conduit 22 for passage through a platinum catalyst reforming operation.
  • the platinum catalyst reforming operation depicted comprises a plurality of sequentially arranged catalytic reactors pro vided with furnace means for preheating the hydrocarbon charge passed to each reactor to provide an inlet temperature of about 900 F.
  • the reforming reactors may be maintained at a pressure selected from within the range of 100 p.s.i.g. up to about 600 p.s.i.g. relying upon temperatures selected from within the range of from about 800 R, up to about 1000 F.
  • the hydrocarbon material in conduit 22 is passed to furnace 24 in admixture with hydrogen containing gas admitted by conduit 23, wherein the mixture is preheated to an elevated temperature particularly suitable for effecting dehydrogenation of naphthenes in the mixture upon contact with a suitable platinum reforming catalyst in Pt. R1 or reactor 28.
  • the effiuent of reactor 28 is then passed by conduit 30 to furnace 32 wherein its temperature is elevated to that suitable for passage to PtRZ by conduit 34.
  • reactor 36 dehydrogenation, isomerization and even some dehydrocyclization reactions may occur.
  • the eflluent from reactor 36 may be passed, if desired, by conduit 38 to furnace 40 for reheating thereof as required and before passage by conduit 42 to PtR3 or reactor 44.
  • PtR3 (44) reactions of dehydrocyclization and hydrocracking are promoted and controlled by the reaction conditions and catalyst composition employed therein. Under some circumstances it may be desirable to replace all or a portion of the platinum reforming catalyst in reactor 44 with the shape selective conversion catalyst. In this arrangement the recovery of product could be effected similarly to that disclosed in US. Pats. 3,395,094 or 3,432,- 425.
  • the reformate product is then passed by conduit 46 to one or more separator vessels represented by vessl 48.
  • separator 48 gaseous products of reforming and comprising hydrogen are separated from higher boiling reformate material comprising C and higher boiling hydrocarbons including aromatic enriched product of the process.
  • the gaseous product of reforming boiling below C hydrocarbons is removed by conduit 50 and passed to suitable recovery equipment not shown wherein hydrogen rich gases are recovered from higher boiling hydrocarbons such as those forming LPG products.
  • the higher boiling portion of the reformer effluent separated in separator 48 is removed by conduit 52 and sentto furnace 54 in admixture with hydrogen containing gas introduced by conduit 56.
  • furnace 54 the reformer effluent higher boiling than LPG material is reheated to an elevated temperature before it is passed by conduit 58 to reactor 60 containing a selective conversion catalyst represented as 5C2.
  • reactor 60 the reformer effluent boiling above LPG material and containing some formed normal paraffins during the platinum catalyst reforming operation is subjected to a further selective cracking operation for the conversion of normal paraffin components to additional LPG material.
  • the selective cracking of normal parafi'ins may be effected at temperatures below the reforming temperatures relying upon pressures below, equal to or above the reforming pressure.
  • gaseous products comprising LPG material such as propane and butane are separated and removed by conduit 66 from a higher boiling aromatic enriched product removed by conduit 68.
  • LPG material produced by the process combination of this invention is combined for further use as desired.
  • the aromatic enriched product formed by the combination and being of a high octane rating and relatively low benzene content is thereafter used, for example, in gasoline blending operations.
  • a method for upgrading naphtha boiling in the range of to 400 F. to produce propane and a liquid product of high aromatic content which comprises,
  • hydrocracking catalyst comprises acid nickel erionite.

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US00257119A 1972-05-26 1972-05-26 Selective hydrocracking before and after reforming Expired - Lifetime US3806443A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US00257119A US3806443A (en) 1972-05-26 1972-05-26 Selective hydrocracking before and after reforming
GB2407473A GB1417508A (en) 1972-05-26 1973-05-21 Selective processing of naphtha before and after catalytic reforming for the production of lpg and aromatic-rich concentrates
BE131498A BE800001A (fr) 1972-05-26 1973-05-24 Traitement selectif d'un naphta pour la production de gaz de petrole liquefie et de concentres riches en comoposes aromatiques,
NL7307290A NL7307290A (xx) 1972-05-26 1973-05-24
FR7319207A FR2189499B1 (xx) 1972-05-26 1973-05-25
JP5793473A JPS5521796B2 (xx) 1972-05-26 1973-05-25
DE2326834A DE2326834A1 (de) 1972-05-26 1973-05-25 Verfahren zur verarbeitung von kohlenwasserstoffnaphtha zu einem fluessigen produkt mit einem hohen aromatengehalt
IT24674/73A IT998118B (it) 1972-05-26 1973-05-25 Procedimento per migliorare le caratteristiche di una nafta idrocarburica

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GB (1) GB1417508A (xx)
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Cited By (14)

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US3867276A (en) * 1972-03-24 1975-02-18 Universal Oil Prod Co High octane motor fuel production
US3899411A (en) * 1974-01-08 1975-08-12 Mobil Oil Corp Octane cracking
US3928174A (en) * 1975-01-02 1975-12-23 Mobil Oil Corp Combination process for producing LPG and aromatic rich material from naphtha
US4831208A (en) * 1987-03-05 1989-05-16 Uop Chemical processing with an operational step sensitive to a feedstream component
US4906353A (en) * 1987-11-27 1990-03-06 Mobil Oil Corp. Dual mode hydrocarbon conversion process
US5409595A (en) * 1993-08-16 1995-04-25 Mobil Oil Corporation Heavy naphtha conversion
US5439583A (en) * 1984-10-31 1995-08-08 Chevron Research And Technology Company Sulfur removal systems for protection of reforming crystals
US8471083B2 (en) * 2010-07-28 2013-06-25 Chevron U.S.A. Inc. Process for the production of para-xylene
CN103597060A (zh) * 2011-03-25 2014-02-19 吉坤日矿日石能源株式会社 单环芳香族烃的制造方法
US8846995B2 (en) 2010-03-26 2014-09-30 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US9233892B2 (en) 2011-03-25 2016-01-12 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US9382174B2 (en) 2011-03-25 2016-07-05 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US9862897B2 (en) 2013-02-21 2018-01-09 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbon
US10087376B2 (en) 2010-01-20 2018-10-02 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons

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JP4837114B2 (ja) 2010-03-26 2011-12-14 千代田化工建設株式会社 芳香族炭化水素の製造方法および芳香族炭化水素の製造プラント
JP5646381B2 (ja) * 2011-03-25 2014-12-24 Ｊｘ日鉱日石エネルギー株式会社 単環芳香族炭化水素の製造方法
JP5690623B2 (ja) * 2011-03-25 2015-03-25 Ｊｘ日鉱日石エネルギー株式会社 単環芳香族炭化水素の製造方法

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US3575846A (en) * 1967-09-14 1971-04-20 Exxon Research Engineering Co Catalysts for the selective conversion of straight-chain hydrocarbons

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867276A (en) * 1972-03-24 1975-02-18 Universal Oil Prod Co High octane motor fuel production
US3899411A (en) * 1974-01-08 1975-08-12 Mobil Oil Corp Octane cracking
US3928174A (en) * 1975-01-02 1975-12-23 Mobil Oil Corp Combination process for producing LPG and aromatic rich material from naphtha
US5439583A (en) * 1984-10-31 1995-08-08 Chevron Research And Technology Company Sulfur removal systems for protection of reforming crystals
US5518607A (en) * 1984-10-31 1996-05-21 Field; Leslie A. Sulfur removal systems for protection of reforming catalysts
US4831208A (en) * 1987-03-05 1989-05-16 Uop Chemical processing with an operational step sensitive to a feedstream component
US4906353A (en) * 1987-11-27 1990-03-06 Mobil Oil Corp. Dual mode hydrocarbon conversion process
US5409595A (en) * 1993-08-16 1995-04-25 Mobil Oil Corporation Heavy naphtha conversion
US10087376B2 (en) 2010-01-20 2018-10-02 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US8846995B2 (en) 2010-03-26 2014-09-30 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US8471083B2 (en) * 2010-07-28 2013-06-25 Chevron U.S.A. Inc. Process for the production of para-xylene
US20140114106A1 (en) * 2010-07-28 2014-04-24 Chevron U.S.A. Inc. Process for the production of para-xylene
US9115041B2 (en) * 2010-07-28 2015-08-25 Chevron U.S.A. Inc. Process for the production of para-xylene
CN103597060B (zh) * 2011-03-25 2015-12-02 吉坤日矿日石能源株式会社 单环芳香族烃的制造方法
US9233892B2 (en) 2011-03-25 2016-01-12 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
US9382173B2 (en) 2011-03-25 2016-07-05 Jx Nippon Oil & Energy Corporation Method of producing single-ring aromatic hydrocarbons
US9382174B2 (en) 2011-03-25 2016-07-05 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbons
CN103597060A (zh) * 2011-03-25 2014-02-19 吉坤日矿日石能源株式会社 单环芳香族烃的制造方法
US9862897B2 (en) 2013-02-21 2018-01-09 Jx Nippon Oil & Energy Corporation Method for producing monocyclic aromatic hydrocarbon

Also Published As

Publication number Publication date
JPS4941323A (xx) 1974-04-18
FR2189499B1 (xx) 1976-09-17
NL7307290A (xx) 1973-11-28
FR2189499A1 (xx) 1974-01-25
JPS5521796B2 (xx) 1980-06-12
BE800001A (fr) 1973-11-26
DE2326834A1 (de) 1973-12-06
GB1417508A (en) 1975-12-10
IT998118B (it) 1976-01-20

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