US2606141A - Catalytic desulfurization of petroleum hydrocarbons - Google Patents

Catalytic desulfurization of petroleum hydrocarbons Download PDF

Info

Publication number
US2606141A
US2606141A US87068A US8706849A US2606141A US 2606141 A US2606141 A US 2606141A US 87068 A US87068 A US 87068A US 8706849 A US8706849 A US 8706849A US 2606141 A US2606141 A US 2606141A
Authority
US
United States
Prior art keywords
hydrogen
overhead product
column
fraction
proportion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US87068A
Other languages
English (en)
Inventor
Meyer Percy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anglo Iranian Oil Co Ltd
Original Assignee
Anglo Iranian Oil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anglo Iranian Oil Co Ltd filed Critical Anglo Iranian Oil Co Ltd
Application granted granted Critical
Publication of US2606141A publication Critical patent/US2606141A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
    • C10G45/28—Organic compounds; Autofining
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • 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
    • C10G7/00—Distillation of hydrocarbon oils

Definitions

  • the deficiency of naphthenes'inl a speciiic fraction may be remedied by,blending the fraction lWith another fraction .which is richer in naphthenes, but the scope of this expedient is limited by thev characteristics of the available fractions.
  • the autoning process can only be effectively applied to fractionsavhich are capable ofbeing recovered from the crude oil Without deleterious effect on their desirable properties.
  • it is diicult to separate the waxand lubricating'oil. fractions from the crude oill by .distillation Without thermal decomposition or cracking, but it'is, nevertheless, ⁇ highly desirable to provide a method of desulphurising such fractions.
  • a process forthe catalytic desulphurisation of petroleum fractions comprises passinga crude oilorya mixture of crude oil distillatesor residues Atira. primary distillation column, passingv the overhead'product from said column to an auton'in'gfzo'ne, passing vthe products from I*the autoiining 'zone to a distillation column for the separation'of the hydrogen and hydrogen sulphide as overhead product, and' the vrecovery of 'one or 4more desulphurised fractions, and passing some Aor all of said hydrogen-containing gaseous'- fraction and, if desiredyany Vor all of'said desulphurised fractions to the base ⁇ of the primary distillation column to control the degree of'vapcrisation achieved in said column and thereby-to'control the boiling range'of thejiraction'submitted'to autoining.
  • the 'crude oil is; 'rst debutanised vin va conventional distillation "column, and the debutanised 4crudevaporised-arid passed to the primary ydistillation vcolumn Vforv the separation overhead of the fraction to VVMbe autoned, the degree of distillation in therprimary column being kcontrolled by the admission of hydrogen to the base of the -column ⁇ anti/or by means of reflux returned to the top of the column.
  • reux. i 1 i varied according to the nature of the crude oiland the desired boiling range of the fraction to be autoned.
  • asphaltic residue recovered from the deasphalting process may be distilled for the recovery of paraflinic precipitant and the asphalt blended with hydrocarbon fractions recovered from the products of the autofining process for the production of fuel oils.
  • Paraflinic asphaltprecipitant may also be recovered from the products of the autoning reaction and after being separated from the asphalt may be returned to the de-asphalting stage. If desired, some of the paraninic. asphalt-precipitant may be recovered from vthe'liquid vcle-asphalted mixture prior to the entry of the mixture into the autofiningr zone.
  • the de-asphalted mixture maybe treated, as by cooling, by varying the content ofhydrogen, of paraflinic or of recycle hydrocarbons, or by varying the temperatureand pressure to separate the mixture into a'solid phase, comprising mainly Wax, and a liquid phase, comprising non-crystallisable liq uid fractions. Either the recovered Wax, or the residual liquid, may then be passed to thev autoflning zone.
  • hydrogen arisingfrom the process may be injected into the oil at 6; and there may at the same time be injected at this point a recycle stream of light distillate such as will yield sucient' free hydrogen to maintain a more than adequate supply of self-generated hydrogen ⁇ Water, if present in the crude oil, may be distilled voff in column 2, but Water or water vapour ifv found advantageous to catalyst performance may be injected at 6 and/or at 9. Leaving the furnace '1, the partially vaporised mixture passes to a fiash vessel 8, from which vapours are separated overhead at I 3, and tar or asphaltic residue is separated at I2.
  • the flash vessel 8 is tted With a perforated pipe II,vv into Which hydrogen, light hydrocarbons, and/or'steam, lmay be passed, these being preheated if necessary, to a suitable temperature by heater -IIJ. Y 'y The vapours leaving the flash vessel 8, are
  • the total vapours at I3 consist of a mixture of (a) Hydrocarbons freshly produced from the in-put crude oil.
  • v(b) A carrier such as hydrogen and/or recycle hydrogen-donating hydrocarbons.
  • the mixed vapours pass to a furnace I4, in which the temperature vis adjusted to suit the desired performance of the catalyst I5.
  • the drawing illustrates a 'batcliwise operation, the catalyst beingregenerated at intervals, but it is to be understood that a moving-bed or uidised catalytic process could lbe employed.
  • vapour After leaving the catalyst chambers, the vapour is cooled at I6 and passes to a vapourliquid separator at I1, from which non-condensed gas consisting mainly of hydrogen is recycled via line I8 and compressor I9 tol feed points 6, 9. In the course of operation the process generates excess hydrogen which mayrconveniently be withdrawn for storage or other disposal,' at point 20.
  • rIhe condensed liquid products from I1 are now subjected to conventional distillationat 2
  • Figure 2 illustrates a' process wherein a liquid-phase precipitation of'non-vola'tile asphaltic components is iirst'elected.
  • the crude oil or topped residuum enters at Iand'is contacted in vessel 2 with asphalt precipitants such as dissolved hydrogen, methane, ethane, propane, butane or similar light hydrocarbons entering at 3.
  • asphalt precipitants such as dissolved hydrogen, methane, ethane, propane, butane or similar light hydrocarbons entering at 3.
  • hydrogen Prior to entry to the heating system, hydrogen may be introduced Vinto the light hydrocarbon-oil mixture at 6, to assist vaporisation, or'alterna tively, the de-asphalted mixture of oilV and asphalt precipitant may rst be treated for WaX recovery by conventional methods, and either the oily components of the crude oil; or the waxy solid-phase-components of the crude oil, mixed oil blending, or otherwise removed from the system.
  • a continuous process for the hydrocatalytic desulphurization of petroleum hydrocarbons which comprises the steps of: passing a naphthene-containing feedstock selected from the class consisting of crude oil, and mixtures of crude oildistillates and residues to a primarydistillation column; recovering as an overhead product of said column a vapor mixture of normally gaseous and normally liquid components including a content of hydrogen-donating naphthenes recovered in a later step of the process and recycled to said column; passing said overhead product to an autoning zone wherein said overhead product is contacted with a sulphurresistant hydrogenation-dehydrogenation catalyst at a selected temperature within the range S50-800 F. and at a selected pressure within the range 25-500 lb./sq.
  • each said proportion is recycled 4.
  • the process of claim 1 including the steps of steps of: separating a number of desulphurized fractions from the products of the autoflning zone; recycling the lighter of said fractions to the top of said primary distillation column as reilux and recycling a proportion of the other desu1.

Landscapes

  • 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)
US87068A 1948-04-19 1949-04-12 Catalytic desulfurization of petroleum hydrocarbons Expired - Lifetime US2606141A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB10817/48A GB669551A (en) 1948-04-19 1948-04-19 Improvements relating to catalytic desulphurisation of petroleum hydrocarbons

Publications (1)

Publication Number Publication Date
US2606141A true US2606141A (en) 1952-08-05

Family

ID=9974838

Family Applications (1)

Application Number Title Priority Date Filing Date
US87068A Expired - Lifetime US2606141A (en) 1948-04-19 1949-04-12 Catalytic desulfurization of petroleum hydrocarbons

Country Status (6)

Country Link
US (1) US2606141A (en(2012))
BE (1) BE488538A (en(2012))
DE (1) DE907104C (en(2012))
FR (1) FR984640A (en(2012))
GB (1) GB669551A (en(2012))
NL (1) NL70360C (en(2012))

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2697682A (en) * 1949-05-23 1954-12-21 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
US2703780A (en) * 1950-07-22 1955-03-08 Esso Res And Engleering Compan Desulfurization by hydrogen transfer reaction
US2746907A (en) * 1952-01-11 1956-05-22 Union Oil Co Process for hydro-desulfurization of light hydrocarbons using a nickel oxide catalyst
US2749282A (en) * 1951-01-24 1956-06-05 British Petroleum Co Catalytic desulphurisation of petroleum hydrocarbons
US2749283A (en) * 1951-12-07 1956-06-05 British Petroleum Co Hydro-desulphurisation of cracked petroleum naphtha and straight run naphtha
US2752287A (en) * 1952-03-20 1956-06-26 British Petroleum Co Treatment of petroleum residues to obtain increased yield of gas oil improved dieselindex
US2766179A (en) * 1954-05-03 1956-10-09 Universal Oil Prod Co Hydrocarbon conversion process
US2771400A (en) * 1952-06-05 1956-11-20 British Petroleum Co Catalytic desulphurisation of motor fuels containing benzole
US2773007A (en) * 1952-07-24 1956-12-04 Universal Oil Prod Co Process for hydrofining and reforming feed stocks
US2844517A (en) * 1954-07-26 1958-07-22 Union Oil Co Hydrocarbon desulfurization process
US2889272A (en) * 1955-03-22 1959-06-02 British Petroleum Co Catalytic desulfurization of petroleum hydrocarbons in a two stage autofining process
US2889274A (en) * 1955-03-22 1959-06-02 British Petroleum Co Catalytic desulphurization of petroleum hydrocarbons and production of hydrogen therefrom
US2898292A (en) * 1957-11-05 1959-08-04 Socony Mobil Oil Co Inc Method for distributing a vapor-liquid feed and apparatus therefor
US2910432A (en) * 1953-04-16 1959-10-27 British Petroleum Co Desulfurization with fluorine-containing catalyst and regeneration of catalyst
US2943047A (en) * 1958-01-27 1960-06-28 Union Oil Co Hydrorefining of heavy mineral oils
US2956001A (en) * 1958-12-03 1960-10-11 Exxon Research Engineering Co Refining of microcrystalline wax
US2959538A (en) * 1956-11-27 1960-11-08 Exxon Research Engineering Co Hydrodesulfurization of whole crudes
US2988501A (en) * 1958-08-18 1961-06-13 Union Oil Co Hydrorefining of crude oils
US3008897A (en) * 1959-08-07 1961-11-14 Sinclair Refining Co Hydrocarbon demetallization process
US3027317A (en) * 1958-01-27 1962-03-27 Union Oil Co Hydrorefining of heavy mineral oils
US3052620A (en) * 1958-12-31 1962-09-04 Union Oil Co Refining of residual shale oils
US3183181A (en) * 1963-04-09 1965-05-11 Metallgesellschaft Ag Vaporization of hydrocarbons
US3184401A (en) * 1962-01-19 1965-05-18 Consolidation Coal Co Process for producing hydrogenenriched hydrocarbonaceous products from coal
US3238119A (en) * 1962-12-19 1966-03-01 Exxon Research Engineering Co Nitrogen removal from hydrocracking feeds
US3271302A (en) * 1964-06-17 1966-09-06 Universal Oil Prod Co Multiple-stage hydrorefining of petroleum crude oil
US3362901A (en) * 1966-01-11 1968-01-09 Sinclair Research Inc Two stage hydrogenation of reduced crude
US3530066A (en) * 1967-07-29 1970-09-22 Nippon Oil Co Ltd Catalytic hydrotreating process of petroleum hydrocarbons containing asphaltenes
US3775292A (en) * 1972-08-01 1973-11-27 Universal Oil Prod Co Combination process for the conversion of hydrocarbonaceous black oil
US4560466A (en) * 1984-10-29 1985-12-24 Phillips Petroleum Company Hydrodemetallization of heavy oils in the presence of water

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2740747A (en) * 1952-11-20 1956-04-03 Exxon Research Engineering Co Catalytically sweetening of naphtha
DE1026903B (de) * 1954-02-04 1958-03-27 Gulf Research Development Co Verfahren zur Behandlung von schwefelhaltigen Roherdoelen
DE1264657B (de) * 1954-12-30 1968-03-28 California Research Corp Verfahren zur Erhoehung der Octanzahl von Erdoeldestillaten, deren Siedebereiche zwischen 80 und 260 liegen
DE1008849B (de) * 1955-08-09 1957-05-23 Still Fa Carl Verfahren zur Verdampfung von Kohlenwasserstoffen und zur weiteren Aufheizung der Kohlenwasserstoffdaempfe zwecks katalytischer Raffination
DE1094904B (de) * 1957-04-20 1960-12-15 Metallgesellschaft Ag Verfahren zur katalytischen hydrierenden Raffination von Schmieroelen oder Schmieroelfraktionen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2174510A (en) * 1937-03-08 1939-10-03 Marion H Gwynn Method of continuously hydrofining carbonaceous vapors with solid sulphur sensitive catalytic surfaces
US2180372A (en) * 1936-12-11 1939-11-21 Standard Oil Co Process of making gasoline
US2282451A (en) * 1938-12-29 1942-05-12 Standard Alcohol Co Desulphurizing and cracking process
US2340922A (en) * 1941-04-15 1944-02-08 Atlantic Refining Co Desulphurization of hydrocarbon oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2180372A (en) * 1936-12-11 1939-11-21 Standard Oil Co Process of making gasoline
US2174510A (en) * 1937-03-08 1939-10-03 Marion H Gwynn Method of continuously hydrofining carbonaceous vapors with solid sulphur sensitive catalytic surfaces
US2282451A (en) * 1938-12-29 1942-05-12 Standard Alcohol Co Desulphurizing and cracking process
US2340922A (en) * 1941-04-15 1944-02-08 Atlantic Refining Co Desulphurization of hydrocarbon oils

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2697682A (en) * 1949-05-23 1954-12-21 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
US2703780A (en) * 1950-07-22 1955-03-08 Esso Res And Engleering Compan Desulfurization by hydrogen transfer reaction
US2749282A (en) * 1951-01-24 1956-06-05 British Petroleum Co Catalytic desulphurisation of petroleum hydrocarbons
US2749283A (en) * 1951-12-07 1956-06-05 British Petroleum Co Hydro-desulphurisation of cracked petroleum naphtha and straight run naphtha
US2746907A (en) * 1952-01-11 1956-05-22 Union Oil Co Process for hydro-desulfurization of light hydrocarbons using a nickel oxide catalyst
US2752287A (en) * 1952-03-20 1956-06-26 British Petroleum Co Treatment of petroleum residues to obtain increased yield of gas oil improved dieselindex
US2771400A (en) * 1952-06-05 1956-11-20 British Petroleum Co Catalytic desulphurisation of motor fuels containing benzole
US2773007A (en) * 1952-07-24 1956-12-04 Universal Oil Prod Co Process for hydrofining and reforming feed stocks
US2910432A (en) * 1953-04-16 1959-10-27 British Petroleum Co Desulfurization with fluorine-containing catalyst and regeneration of catalyst
US2766179A (en) * 1954-05-03 1956-10-09 Universal Oil Prod Co Hydrocarbon conversion process
US2844517A (en) * 1954-07-26 1958-07-22 Union Oil Co Hydrocarbon desulfurization process
US2889272A (en) * 1955-03-22 1959-06-02 British Petroleum Co Catalytic desulfurization of petroleum hydrocarbons in a two stage autofining process
US2889274A (en) * 1955-03-22 1959-06-02 British Petroleum Co Catalytic desulphurization of petroleum hydrocarbons and production of hydrogen therefrom
US2959538A (en) * 1956-11-27 1960-11-08 Exxon Research Engineering Co Hydrodesulfurization of whole crudes
US2898292A (en) * 1957-11-05 1959-08-04 Socony Mobil Oil Co Inc Method for distributing a vapor-liquid feed and apparatus therefor
US2943047A (en) * 1958-01-27 1960-06-28 Union Oil Co Hydrorefining of heavy mineral oils
US3027317A (en) * 1958-01-27 1962-03-27 Union Oil Co Hydrorefining of heavy mineral oils
US2988501A (en) * 1958-08-18 1961-06-13 Union Oil Co Hydrorefining of crude oils
US2956001A (en) * 1958-12-03 1960-10-11 Exxon Research Engineering Co Refining of microcrystalline wax
US3052620A (en) * 1958-12-31 1962-09-04 Union Oil Co Refining of residual shale oils
US3008897A (en) * 1959-08-07 1961-11-14 Sinclair Refining Co Hydrocarbon demetallization process
US3184401A (en) * 1962-01-19 1965-05-18 Consolidation Coal Co Process for producing hydrogenenriched hydrocarbonaceous products from coal
US3238119A (en) * 1962-12-19 1966-03-01 Exxon Research Engineering Co Nitrogen removal from hydrocracking feeds
US3183181A (en) * 1963-04-09 1965-05-11 Metallgesellschaft Ag Vaporization of hydrocarbons
US3271302A (en) * 1964-06-17 1966-09-06 Universal Oil Prod Co Multiple-stage hydrorefining of petroleum crude oil
US3362901A (en) * 1966-01-11 1968-01-09 Sinclair Research Inc Two stage hydrogenation of reduced crude
US3530066A (en) * 1967-07-29 1970-09-22 Nippon Oil Co Ltd Catalytic hydrotreating process of petroleum hydrocarbons containing asphaltenes
US3775292A (en) * 1972-08-01 1973-11-27 Universal Oil Prod Co Combination process for the conversion of hydrocarbonaceous black oil
US4560466A (en) * 1984-10-29 1985-12-24 Phillips Petroleum Company Hydrodemetallization of heavy oils in the presence of water

Also Published As

Publication number Publication date
GB669551A (en) 1952-04-02
NL70360C (en(2012))
DE907104C (de) 1954-03-22
BE488538A (en(2012))
FR984640A (fr) 1951-07-09

Similar Documents

Publication Publication Date Title
US2606141A (en) Catalytic desulfurization of petroleum hydrocarbons
KR102375080B1 (ko) 나프타 종류의 공급원료를 처리하는 방향족 컴플렉스 및 촉매 개질 유닛과 결합하여, 고도로 수소처리된 vgo 종류의 중질 공급원료를 처리하는 fcc 유닛을 사용하여 경질 올레핀들 및 btx 를 제조하는 방법
JP2020007321A (ja) 原油を石油化学製品に転化する、エチレン収率の改善された方法および装置
US20080149534A1 (en) Method of conversion of residues comprising 2 deasphaltings in series
US4395330A (en) Process for solvent deasphalting of residual hydrocarbon oils
US2769753A (en) Combination process for catalytic hydrodesulfurization and reforming of high sulfur hydrocarbon mixtures
US2337448A (en) Process for treating oils
US3238118A (en) Conversion of hydrocarbons in the presence of a hydrogenated donor diluent
US4938862A (en) Process for the thermal cracking of residual hydrocarbon oils
US3494859A (en) Two-stage hydrogenation of an aromatic hydrocarbon feedstock containing diolefins,monoolefins and sulfur compounds
US3380912A (en) Combination extraction-demetalation process for heavy oils
GB730562A (en) Improvements relating to the refining of crude petroleum
US2736685A (en) Process of petrolatum cracking in liquid and vapor phase
CA1243979A (en) Process for increasing deasphalted oil production from upgraded oil residua
US2983669A (en) Hydrodesulfurization of selected gasoline fractions
US4179355A (en) Combination residual oil hydrodesulfurization and thermal cracking process
US2002004A (en) Process for treating oil
US2853439A (en) Combination distillation and hydrocarbon conversion process
US3006843A (en) Preparing hydrocarbon fuels by solvent extraction, hydrodesulfurization and hydrogenation of cracked gas oils
US2770576A (en) Preparation of catalytic cracking feed
US2385325A (en) Catalytic cracking of petroleum oils
US4347120A (en) Upgrading of heavy hydrocarbons
JPS6249917B2 (en(2012))
US2749282A (en) Catalytic desulphurisation of petroleum hydrocarbons
JPS5869290A (ja) 炭化水素油を用いたガソリンの製造方法