US2918422A - Reforming-hydroforming system - Google Patents

Reforming-hydroforming system Download PDF

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Publication number
US2918422A
US2918422A US619547A US61954756A US2918422A US 2918422 A US2918422 A US 2918422A US 619547 A US619547 A US 619547A US 61954756 A US61954756 A US 61954756A US 2918422 A US2918422 A US 2918422A
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Prior art keywords
heavy
naphtha
fraction
light
reforming
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Expired - Lifetime
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US619547A
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English (en)
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Bernard L Evering
Alan K Roebuck
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Standard Oil Co
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Standard Oil Co
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Priority to NL104749D priority Critical patent/NL104749C/xx
Application filed by Standard Oil Co filed Critical Standard Oil Co
Priority to US619547A priority patent/US2918422A/en
Priority to GB32991/57A priority patent/GB818836A/en
Priority to FR1210653D priority patent/FR1210653A/fr
Priority to DEST13111A priority patent/DE1062859B/de
Application granted granted Critical
Publication of US2918422A publication Critical patent/US2918422A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • 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
    • C10G59/06—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 parallel stages only

Definitions

  • An object of this invention is to provide a combination reforming-hydroforming process which will produce from ordinary low octane number naphthas gasolines of 100 octane number or more in higher yields and/or at lower costs than has heretofore been possible.
  • a further object is to avoid the necessity of using expensive extraction and isomerization techniques in conjunction with reforming and/or hydroforming in order to achieve yield octane goals.
  • a further object is to obtain by-products of increased value, i.,e. larger yields of net hydrogen and normally gaseous oleiins.
  • a naphtha In practicing our invention we fractionate a naphtha to form a C5C7 fraction having an end point of about 200 F. (plus or minus 10 to 15 F.) and a heavy fraction boiling substantially in the range of about 200 to 400 F.
  • the light fraction is reformed by contact with an alkalized chromia alumina catalyst at about 975 to 1l25 F., preferably about 1050 F., under a pressure in the range of about atmospheric to 200 p.s.i., preferably about to 100, e.g. about 25 p.s.i.g., with a weight space velocity in the range of about .1 to l0 and preferably about 1 to 4 volumes of light naphtha per hour per volume of catalyst.
  • the reforming of the light naphtha may be in the presence of recycled hydrogen in a fixed bed, moving bed or fluid system but since the recycle of hydrogen is not as essential in this step as it is in the case of platinum-on-a1umina catalysts (particularly in a fluid system), the conversion of the light fraction under the defined conditions is herein termed reforming; it is chiefly dehydrogenation and aromatization with some isomerization.
  • the heavy naphtha fraction is hydroformed by contact in the presence of recycled hydrogen with a platinum-on-alumina catalyst, preferably by the Ultraforming technique (Ultraforming A New Catalytic Reforming Process by Forrester, Conn and Malloy, Petroleum Refiner, vol. 33, No. 4 (April 1954), pp.
  • the light naphtha reformate may be debutanized to render it suitable as a blending stock.
  • the hydroformed heavy naphtha is first debutanized and then fractionated to separate components boiling below about 200 F. which components are introduced as a part of the charge to the light naphtha reforming step.
  • the remaining hydroformed heavy naphtha when blended with the debutanized reformed light naphtha results in a full bodied gasoline of balanced volatility having a clear (unleaded) octane number of the order of 100 or higher.
  • the rercycle of the low boiling fractions of hydroformed heavy naphtha to the hy'droforming step or its treatment with platinum-on-alumina catalyst in a separate hydroforming step will, of course, lead to some improvement but will not give the remarkably enhanced yield octane number improvement attainable with alkalized chromia-on-alumina under the conditions defined for the reforming of the light naphtha fraction.
  • the alkalized chromia alumina catalyst is more susceptible to carbon formation and it should be employed only for low boiling charging stocks, i.e. heavy naphtha fractions should be excluded from charge thereto.
  • the reforming step produces about as much, if not more, net hydrogen than is produced from a like amount of charge in the hydroforming step, which is an important consideration since by-product hydrogen is valuable for up-grading other hydrocarbons and/or for the manufacture of ammonia or other chemicals.
  • Figure l is a schematic flow diagram of our improved reforming-hydroforming system and Figure 2 is a graph showing the remarkable improvement in yield-octane number relationship obtainable by employing alkalized chromia catalyst instead of platinum for the reforming of light naphtha.
  • n-pentane, n-hexane, etc. were technical grades, i.e about 95 mol percent pure; the light naphtha was a socalled plant-hexane haxing a sulfur content of about 41 p.p.m. and an ASTM boiling range of 117 to 167 F. and comprising about percent pentanes and 75 percent hexanes.
  • the alkalized chromia catalyst (as compared to platinum catalyst) produced approximately double the yield of Cs-igasoline of over 82 octane number, produced 30 percent olens and 3 percent aromatics where substantially none was produced by platinum and produced only 16 weight percent of gas Where platinum produced 60 weight percent.
  • the alkalized chromia catalyst gave a product octane number of 99.2 as compared toonly 63 when employing platinum catalyst; here again the product produced by the alkalized chromia catalyst is characterized by a large olefin content and a remarkably large aromatics content with much less weight percent gas than was produced with platinum catalyst.
  • the platinum catalyst provides a somewhat better yield-octane number relationship than alkalized chromia but since most light naphthas contain such a small amount of methylcyclopentane, its effect is usually negligible.
  • the isomate or aluminum chloride isomerization process is, of course, advantageous from the standpoint of yield but it produces no olens or aromatics and consumes a considerable amount of hydrogen instead of effecting net hydrogen production. Furthermore, the isomate process is not effective for C7 hydrocarbons and its investment and operating costs are relatively high ⁇ in the case of pentane, and hexane. Isomerized pentanes and hexanes have a better lead tetraethyl response than employed for producing naphthas having leaded octane numbers substantially above CFR-R while such products cannot be produced by the use of platinumon-alumina catalysts or by aluminum chloride isomerization without extensive and expensive recycle operations. A feature of our reformed light naphtha is itshigh olen content.
  • a naphtha charge from line 10 is introduced to fractionation system diagrammatically represented by tower 11 from which C4 and lighter hydrocarbons are removed through line 12, a C5-C7 fraction (having an end point of' about 200 F. plus or minus about 15 F.) is withdrawn through line 13 for charging to the alkalized chromia reforming system, a 200 F.-360 F. naphtha fraction is Withdrawn through line 14 as a charging stock for a platinum catalyst hydroforming (Ultraforming) system and higher boiling materials are withdrawn through line 15.
  • the platinum catalyst hydroforming charge Withdrawn through line 14 may require a desulfurization step (not shown) since it preferably should contain only about 5 to 30 p.p.m. of sulfur.
  • It may also contain about 1 to 6 p.p.m. (but not more than 10 p.p.m.) of chloride, about 2 to 20 p.p.m. of water and less than 5 p.p.m. of nitrogen.
  • the hydroformingrof the 20G-360 F; naphtha fraction may be effected with platinum-on-alumina catalyst as described in pending U.S. applications Serial Nos. 347,- 635, now ULS. 2,773,014, and 425,461, now U.S. 2,773,- 008, i.e. a regenerative, fixed-bed, swing reactor system is preferably employed with at least three heater-reactor stages each operating in the pressure range of about to 400 p.s.i.
  • the catalyst in the various reaction stages may be regenerated in any desired time sequence, the catalyst in each reactor preferably being on stream at least about 50 to 10() hours between periods of regeneration.
  • a hydroforming system 16 there is a production of net hydrogen which is removed through line 17.
  • the hydroformed product is introduced by line 18 to debutanizer 19, the C4 and lighter hydrocarbons being taken overhead through line 20 and the C41. hydrocarbons being introduced by line 21 to fractionator 22.
  • Portions of the charge boiling below about 200'F. are taken overhead through line 23 and condenser 24 to receiver 25 from which condensate is withdrawn by pump 26, a part of it being returnedl by line 27 asdrawn from the basel of' fractionator 22'through linef higher than 100.
  • the light naptha streams from lines 13 and 28 are charged to an alkalized chromia-on-alumina catalyst reforming system under conditions hereinabove set forth.
  • Such a catalyst may, for example, contain about 1'8 percent 110,03, 4 percent K2O, 4 percent Si02 and 74 percent A1203.
  • No novelty is claimed in the alkalized chromiaalumina catalyst. It is not even essential that hydrogen be recycled in such a system because large amounts of coke can be conveniently burned from s-uch catalysts in a uidized solids system and the heat thereby produced can be utilized for effecting the reforming operation.
  • a fluidized chromia reforming system is preferred, it should be understood that a xed bed chromia system may be employed with hydrogen recycle in the same manner as molybdena-onalumina fixed bed hydroforming operations have heretofore been carried out.
  • a net amount of hydrogen is produced in the reforming system and removed therefrom through line 31.
  • Reformate from the chromia-on-alumina system is withdrawn through line 32 to debutanizer 33 from which C4 and lighter hydrocarbons are removed through line 34 and withdrawn to a condensables recovery system through line 20.
  • the debutanized light naphtha product is Withdrawn through line 35 to line 36 wherein it is blended with high octane number Ultraformate from line 29 to give a totalproduct gasoline having a clear (unleaded) octane number of at least about 100.
  • the method of converting a naphtha charge into a superior motor fuel which comprises hydroforming with a platinum-alumina catalyst that portion of the naphtha boiling above about 200 F., splitting the hydroformed product to obtain a hydroformed heavy naphtha fraction boiling above about 200 F. and a debutanized light hydroformed naphtha fraction boiling below about 200 F., reforming the light debutanized hydroformed naphtha ⁇ fraction in admixture with that portion of the original naphtha boiling below about 200 F. by dehydrogenating and aromatizing said light, debutanized naphtha mixture with an alkalized chrominaon-alumina catalyst at a pressure in the range of atmospheric to 200 p.s.i.g.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US619547A 1956-10-31 1956-10-31 Reforming-hydroforming system Expired - Lifetime US2918422A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL104749D NL104749C (enrdf_load_stackoverflow) 1956-10-31
US619547A US2918422A (en) 1956-10-31 1956-10-31 Reforming-hydroforming system
GB32991/57A GB818836A (en) 1956-10-31 1957-10-22 Improvements in or relating to reforming naphtha
FR1210653D FR1210653A (fr) 1956-10-31 1957-10-29 Perfectionnements apportés au traitement des hydrocarbures en vue de l'obtention d'essence à haut indice d'octane
DEST13111A DE1062859B (de) 1956-10-31 1957-10-30 Verfahren zur Umwandlung eines Benzins in einen verbesserten Motortreibstoff

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US619547A US2918422A (en) 1956-10-31 1956-10-31 Reforming-hydroforming system

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US2918422A true US2918422A (en) 1959-12-22

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DE (1) DE1062859B (enrdf_load_stackoverflow)
FR (1) FR1210653A (enrdf_load_stackoverflow)
GB (1) GB818836A (enrdf_load_stackoverflow)
NL (1) NL104749C (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3016344A (en) * 1958-08-27 1962-01-09 Houdry Process Corp Upgrading natural gasoline
US3017344A (en) * 1958-05-05 1962-01-16 Texaco Inc Serial reforming of hydrocarbons
US4246094A (en) * 1979-06-11 1981-01-20 Standard Oil Company (Indiana) Process for upgrading naphtha hydrocarbons
US4347123A (en) * 1980-05-05 1982-08-31 Exxon Research & Engineering Co. Reforming with multimetallic catalysts
US9890335B2 (en) 2014-07-22 2018-02-13 Uop Llc Methods and systems for removing sulfur compounds from a hydrocarbon stream
EP3774700A4 (en) * 2018-03-27 2021-12-29 Phillips 66 Company Catalytic activation of isopentane-enriched mixtures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409695A (en) * 1943-01-30 1946-10-22 Standard Oil Dev Co Method for improving aviation fuels
US2653175A (en) * 1951-05-04 1953-09-22 Sun Oil Co Preparation of aromatic hydrocarbons
US2758062A (en) * 1951-09-04 1956-08-07 Exxon Research Engineering Co Two-stage hydroforming process
US2767124A (en) * 1952-04-29 1956-10-16 Phillips Petroleum Co Catalytic reforming process

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2349045A (en) * 1939-09-18 1944-05-16 Standard Oil Co Dehydro-aromatization
US2573149A (en) * 1948-11-20 1951-10-30 Universal Oil Prod Co Three-stage catalytic process for the reforming of gasoline
FR1067976A (fr) * 1951-09-04 1954-06-21 Standard Oil Dev Co Procédé d'hydroformation en deux stades
BE516505A (enrdf_load_stackoverflow) * 1951-12-28
NL92559C (enrdf_load_stackoverflow) * 1952-10-07

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409695A (en) * 1943-01-30 1946-10-22 Standard Oil Dev Co Method for improving aviation fuels
US2653175A (en) * 1951-05-04 1953-09-22 Sun Oil Co Preparation of aromatic hydrocarbons
US2758062A (en) * 1951-09-04 1956-08-07 Exxon Research Engineering Co Two-stage hydroforming process
US2767124A (en) * 1952-04-29 1956-10-16 Phillips Petroleum Co Catalytic reforming process

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3017344A (en) * 1958-05-05 1962-01-16 Texaco Inc Serial reforming of hydrocarbons
US3016344A (en) * 1958-08-27 1962-01-09 Houdry Process Corp Upgrading natural gasoline
US4246094A (en) * 1979-06-11 1981-01-20 Standard Oil Company (Indiana) Process for upgrading naphtha hydrocarbons
US4347123A (en) * 1980-05-05 1982-08-31 Exxon Research & Engineering Co. Reforming with multimetallic catalysts
US9890335B2 (en) 2014-07-22 2018-02-13 Uop Llc Methods and systems for removing sulfur compounds from a hydrocarbon stream
EP3774700A4 (en) * 2018-03-27 2021-12-29 Phillips 66 Company Catalytic activation of isopentane-enriched mixtures

Also Published As

Publication number Publication date
GB818836A (en) 1959-08-26
NL104749C (enrdf_load_stackoverflow)
DE1062859B (de) 1959-08-06
FR1210653A (fr) 1960-03-10

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