US2672433A - Catalytic desulfurization of petroleum hydrocarbons - Google Patents

Catalytic desulfurization of petroleum hydrocarbons Download PDF

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Publication number
US2672433A
US2672433A US213176A US21317651A US2672433A US 2672433 A US2672433 A US 2672433A US 213176 A US213176 A US 213176A US 21317651 A US21317651 A US 21317651A US 2672433 A US2672433 A US 2672433A
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Prior art keywords
hydrogen
sulphur
zone
desulphurisation
residue
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US213176A
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English (en)
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Porter Frederick Willi Bertram
Rowland John
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Anglo Iranian Oil Co Ltd
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Anglo Iranian Oil Co Ltd
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps

Definitions

  • This invention relates to the hydrocatalytic desulphurisation of petroleum hydrocarbons.
  • Desulphurisation processes are also known in which a substance capable of supplying hydrogen under the conditions of the desulphurisation reaction is added to the feedstock to be desulpnurised, but this is only a special case of hydrofining and suffers from the disadvantage of the cost of supplying the hydrogen donor and from the additional disadvantage that the through-put of the feedstock is reduced .by the addition of the considerable quantity of hydrogen donor necessary to supply suflicient hydrogen.
  • the preferred catalyst for use in the autofining process is of the so-called cobalt molybdate type which comprises mixtures of the oxides of cobalt and molybdenum, or chemical compounds of cobalt, molybdenum and oxygen, or mixtures of one or both of said oxides with said compounds either alone or incorporated with a support. It has been found that there is a period at the commencement of each-run during which the gas make is negligible or non-existent and the desulphurisation is not at its maximum.
  • the regeneration of the used catalyst may be carried out by burning off the carbon and sulphur deposits with either a nitrogen/air or steam/air mixture.
  • the following conditions may be employed for regeneration.
  • the autofining process may be carried out in a static bed reactor or by the use of the moving bed or fluid catalyst techniques.
  • an autofin n process is meant a process m whi h Pe oleum, e d o i passed in v ncur, Q m.-;. n.
  • the 'autofin'i'ng zone may fibz-jtestisieient,ts sdppiy all the'hydrogen 'resuites tithe mal easanc zone admin in any case represent a'considerable saving in hydrogen.
  • he independent-hydrogenation zone may 'coniiis't'of a-hyd'rofining-zone for the treatment of Heavier petroleum -feedstocks such as wa x -dis'- r tillate, crude on 'and reducederude, that cannot be satisfactorily autofined.
  • tliehydrogenation zone may b'efor carrying out a well known hydrogenation process; such as the conversion of 'dii's'dbutylene to 'is'ooetane.
  • --a-crude -oil is fractionated for the recovery of a -light fraction, which isfautofined and a. residue, the excess gas make trom the autofining stage being used to hydrofinethe residueor a heavy fraction thereof.
  • the naphtha-kerosine blend is fed by a pump l to the preheater 2 after admixture with the recycle gas.
  • the hot vapours pass downwards through the autofining reactor 4 and after passing through the cooler or heat exchanger 5 are separated into two phases in the vessel 6.
  • the liquid phase which contains the desulphurised kerosine-naphtha blend is passed via line I to a stabiliser and distillation unit for separation of the fractions as desired.
  • the gas phase which contains upwards of per cent mol. hydrogen is split into two streams, one being recycled through line 3 and the booster 3 to maintain the conditions in the reactor 4 while the other, the excess gas, passes through a control valve 9.
  • the wax-distillate fraction is fed by a pump to into admixture with the excess gas from the autofining system and passes to the preheater H via line it.
  • the preheated products pass downward over the catalyst bed 12 through a pressure control valve 13 and cooler id to the separator IS.
  • the liquid phase is run ofi via line I! for stabilisation for removal of hydrogen sulphide and the gases vented via line 18.
  • the reactor 4 and its accompanying system are operated at a, pressure of 220 pounds per square inch pressure and the excess gas fed into the wax-distillate stream at +200 pounds per square inch.
  • the wax distillate section therefore operates as a once through hydrofining process i. 6. with no recycle, and pressure is supplied from the first section so that an economic hydrogen partial pressureis maintained in the second section. If necessary, the relative proportion of hydrogen in the excess gas can be increased by scrubbing out the hydrocarbons but this is not essential, neither is it essential to remove hydro gen sulphide from the recycle or excess gas.
  • This method of operation is a'specific example of this method of operation:
  • War-distillate desulphurisatiqn The method illustrated in Figure 2 is essentially the same as that illustrated in Figure l, the only difierence being the provision of a compressor l9 between the two sections to enable the wax-distillate desulphurisation to be carried out at a higher pressure and thereby increase the sulphur removal.
  • the amount of excess gas from the autofining section can be controlled, within limits, by adjustment of the space velocity. The following is a specific example of this method of operation:
  • Wax-distillate desulphurz'sation Korean wax-distil- Feedstock late cut 72%- 82% v o l o n crude.
  • Catalyst Mixed cobalt and molybdenum oxides on alumina Catalyst Mixed cobalt and molybdenum oxides on alumina.
  • crude petroleum stabilised to C. is fed via preheater 20 to the fractionating tower -2 I where a naphtha-kerosine cut boiling between 20 and 250 C. is taken overhead through condenser 22 to the reflux drum 23.
  • Some of'the naphtha-kerosine is returned to the tower as reflux by the reflux pump 24, the remainder being fed by the feed pump 25 to the preheater 26.
  • the naphtha-kerosine, together with the recycle gas, is brought up to reaction temperature and passes into the reactor 21.
  • the autofined product from the reactor passes out through a waste heat boiler 28 to a knock-out tower 29.
  • the pressure on the waste heat boiler is controlled to give an inlettemperature into the knock-out tower such that the kerosine is condensed whilst the naphtha and recycle gas pass off the top of the knock-out tower through a cooler 30 to a separator 3
  • the recycle gas separates from the liquid naphtha and is recycled by means of the gas booster 32 to the preheater inlet. Further control of the knock-out. tower is effected by returning some of the cold. naphtha from the separator as reflux by the.- pump 33.
  • the kerosine passes from the base of the knock-out tower through a cooler 34 to stor-- age.
  • the naphtha passes from the separator to a conventional stabiliser (not shown) where thedissolved hydrogen sulphide is removed.
  • The.- excess gas over and above that required to main-- tain the system under pressure, is released through the pressure control valve 35 to the compressor 36. Here, it is compressed to the required operating pressure and passes via the flow controller 3'! into the preheater inlet line, where it meets the residue from the fractionator 2
  • the gas-residue mixture is brought up to the reaction temperature in the preheater 38 and passes into the reactor 39.
  • the desulphurised product and the gas pass out via a pressure control valve 40, which can be used to control the preheater and reactor pressure or which can, if required, be bypassed.
  • the hydrocarbon-hydrogen stream passes through a cooler 4
  • the gas can either be vented via the pressure controller 43 or be recycled by the recycle booster 44 to the preheater inlet.
  • the desulphurised residue is' passed from the separator 42 via a stabiliser not shown) to remove dissolved hydrogen sulphide to storage. If required, fresh hydrogen from an external source ma beinjected into the suction of, the compressor 36 through line 45.
  • control valves 40, 43 and 31 and the gas recycle booster 44 depends on whether it is desired to operate with or without a gas recycle system and/or hydrogen added from an external source. This may be summarised as follows:
  • a process for the recovery of sulphur free products from naphthene-containing crude petroleum by the hydrocatalytic.desulphurisation process without the need for an extraneous source of hydrogen which comprises fractionating the crude petroleum for therecovery of a selected naphthene-containing low-boiling fraction and a.
  • said temperature and pressure being correlated so that organically combined sulphur in said fraction is converted into hydrogen sulphide and hydrogen is produced by dehydrogenation of naphthenes contained in said low-boiling fraction in an amount in excess or that required to convert organically combined sulphur contained in said low-boiling fraction into hydrogen sulphide and maintain the necessary partial pressure of hydrogen in said zone, separating hydrogen sulphide and a lwdrogen-rich gas mixture from the products of said first desulphurisation zone, recycling a portion of said hydrogen-rich gas mixture to said first desulphurisation zone to constitute the Whole of the hydrogen supplied to said zone, the hydrogen recycle rate being sufiicient to maintain the necessary partial pressure of hydrogen in said zone therein, passing another portion of said hydrogen-rich gas mixture in admixture with said residue to a second desulphurisation zone wherein said residue is contacted with a sulphur-resistant hydrogenation catalyst and hydrogen of the mixture at a temperature and pressure suitable for hydrofining of said residue whereby organic
  • a process in accordance with claim 1 wherein the recovered low-boiling fraction comprises the naphtha and kerosene fractions.
  • the low-boiling fraction comprises the naphtha and kerosene fractions and the dehydrogenationhydrogenation catalyst is a cobalt molybdate type.

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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)
US213176A 1950-03-15 1951-02-28 Catalytic desulfurization of petroleum hydrocarbons Expired - Lifetime US2672433A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB6499/50A GB712033A (en) 1950-03-15 1950-03-15 Improvements relating to the catalytic desulphurisation of petroleum hydrocarbons

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US213176A Expired - Lifetime US2672433A (en) 1950-03-15 1951-02-28 Catalytic desulfurization of petroleum hydrocarbons

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US (1) US2672433A (en, 2012)
BE (1) BE501920A (en, 2012)
FR (1) FR1040630A (en, 2012)
GB (1) GB712033A (en, 2012)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2833697A (en) * 1953-10-23 1958-05-06 Basf Ag Desulfurization of crude oils by catalytic high-pressure hydrogenation
US2880166A (en) * 1955-10-19 1959-03-31 Phillips Petroleum Co Improving color and color stability of kerosene by combined autofining and hydrofining
US2883337A (en) * 1954-06-21 1959-04-21 Union Oil Co Process for hydrodesulfurizing hydrocarbons employing an impure hydrogen stream
US2901417A (en) * 1954-05-17 1959-08-25 Exxon Research Engineering Co Hydrodesulfurization of a coked hydrocarbon stream comprising gasoline constituents and gas oil constituents
US2951032A (en) * 1956-02-16 1960-08-30 Union Oil Co Hydrocarbon desulfurization process
US2983669A (en) * 1958-12-30 1961-05-09 Houdry Process Corp Hydrodesulfurization of selected gasoline fractions
US3250698A (en) * 1962-10-02 1966-05-10 British Petroleum Co Autofining of petroleum hydrocarbons

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1025547B (de) * 1954-09-14 1958-03-06 Metallgesellschaft Ag Verfahren zur katalytischen Raffination von Benzol oder anderen Kohlenwasserstoffen, die aus der Verkokung, Schwelung oder Vergasung von Steinkohlen herruehren
DE1140918B (de) * 1957-03-23 1962-12-13 Metallgesellschaft Ag Verfahren zur Gewinnung von reinstem Benzol und Toluol durch hydrierende Raffinationund azeotrope Destillation
US3429803A (en) * 1966-08-01 1969-02-25 Universal Oil Prod Co Method for converting hydrocarbons

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417308A (en) * 1943-04-12 1947-03-11 Union Oil Co Desulphurization and hydroforming
US2486361A (en) * 1944-10-20 1949-10-25 Union Oil Co Catalytic conversion of hydrocarbons
US2567252A (en) * 1949-07-20 1951-09-11 Anglo Iranian Oil Co Ltd Refining of hydrocarbons
US2573726A (en) * 1947-06-30 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulphurisation of naphthas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417308A (en) * 1943-04-12 1947-03-11 Union Oil Co Desulphurization and hydroforming
US2486361A (en) * 1944-10-20 1949-10-25 Union Oil Co Catalytic conversion of hydrocarbons
US2573726A (en) * 1947-06-30 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulphurisation of naphthas
US2567252A (en) * 1949-07-20 1951-09-11 Anglo Iranian Oil Co Ltd Refining of hydrocarbons

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2833697A (en) * 1953-10-23 1958-05-06 Basf Ag Desulfurization of crude oils by catalytic high-pressure hydrogenation
US2901417A (en) * 1954-05-17 1959-08-25 Exxon Research Engineering Co Hydrodesulfurization of a coked hydrocarbon stream comprising gasoline constituents and gas oil constituents
US2883337A (en) * 1954-06-21 1959-04-21 Union Oil Co Process for hydrodesulfurizing hydrocarbons employing an impure hydrogen stream
US2880166A (en) * 1955-10-19 1959-03-31 Phillips Petroleum Co Improving color and color stability of kerosene by combined autofining and hydrofining
US2951032A (en) * 1956-02-16 1960-08-30 Union Oil Co Hydrocarbon desulfurization process
US2983669A (en) * 1958-12-30 1961-05-09 Houdry Process Corp Hydrodesulfurization of selected gasoline fractions
US3250698A (en) * 1962-10-02 1966-05-10 British Petroleum Co Autofining of petroleum hydrocarbons

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Publication number Publication date
GB712033A (en) 1954-07-14
BE501920A (en, 2012)
FR1040630A (fr) 1953-10-16

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