EP0020053A1 - Désulfurisation d'huile - Google Patents

Désulfurisation d'huile Download PDF

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Publication number
EP0020053A1
EP0020053A1 EP80301580A EP80301580A EP0020053A1 EP 0020053 A1 EP0020053 A1 EP 0020053A1 EP 80301580 A EP80301580 A EP 80301580A EP 80301580 A EP80301580 A EP 80301580A EP 0020053 A1 EP0020053 A1 EP 0020053A1
Authority
EP
European Patent Office
Prior art keywords
oil
sulphur
hydrogen fluoride
fluoride
reaction
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.)
Withdrawn
Application number
EP80301580A
Other languages
German (de)
English (en)
Inventor
Robert Lloyd
Maxwell James Turner
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.)
Kinneret Enterprises Ltd
Original Assignee
Kinneret Enterprises 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 Kinneret Enterprises Ltd filed Critical Kinneret Enterprises Ltd
Publication of EP0020053A1 publication Critical patent/EP0020053A1/fr
Withdrawn legal-status Critical Current

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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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • C10G17/04—Liquid-liquid treatment forming two immiscible phases
    • C10G17/07—Liquid-liquid treatment forming two immiscible phases using halogen acids or oxyacids of halogen

Definitions

  • This invention relates to a method of desulphurizing oil, particularly crude oil.
  • the invention provides a process of treating petroleum oil to reduce the sulphur content thereof, comprising treating said oil with hydrogen fluoride at an effective concentration level such that available sulphur in the oil is converted to a sulphur fluoride compound, and separating the oil from the sulphur fluoride produced by the reaction.
  • the oil is substantially dehydrated before treatment with the hydrogen fluoride.
  • some oils may be advantageously treated with an oxidizing agent, such as sulphur trioxide gas, to oxidize certain forms of sulphur present to a form more readily reactable with HF.
  • the hydrogen fluoride may be utilized in liquid or gas state.
  • the gas state is preferred as the conversion of the sulphur to a gas is not hindered by water present as in a liquid HF reaction. Water tends to cause any sulphur fluorides formed to precipitate and thus complicate its separation from the oil.
  • the sulphur forms mainly sulphur tetrafluoride in gaseous form and is readily separated from the liquid oil along with excess HF.
  • the sulphur fluoride and the excess hydrogen fluoride eminating from the hydrogen fluoride contact with oil be reclaimed, particularly to reuse the fluoride.
  • the hydrogen fluoride and sulphur fluorides removed from one gas-liquid reaction are passed to a gas separation tower wherein due to their significantly different specific gravities, they may be easily separated.
  • the hydrogen fluoride being the lighter gas separating out of the top of the gas separation tower and being recycled to the hydrogen fluoride gas storage
  • the sulphur fluorides being the heavier of the gases being removed from the bottom of the gas separation tower from where they can be passed to a hydrolyzation unit to convert the sulphur gas to sulphur crystals and the fluorides to hydrogen fluoride.
  • the hydrogen fluoride eminating from the gas-water contact unit can then also be fed back to the hydrogen fluoride storage.
  • Oil usually crude oil which has been extracted from the ground, generally contains a certain percentage of water.
  • the primary reaction of this invention it is necessary to substantially dehydrate the oil before reacting the oil with the hydrogen fluoride gas.
  • oil 18 is fed to a dehydration unit 10.
  • temperature drying at 240 F or temperatures thereabove is suitable.
  • a selective oil-water separator may be used to dehydrate the oil.
  • the dehydrated oil is then fed 20 to an oxidizing chamber 11 such as a counter-current flow gas-liquid contact unit.
  • an oxidizing agent such as gaseous So 3 is contacted with the oil by, say, being bubbled 21 through the oil. This oxidizes some of the free and bound sulphurs to an oxide form thus making it more available for reaction with the HF.
  • the liquid oil is then fed 22 to the main reactor 12.
  • the reactor is preferably a counter-current flow gas-liquid contacting unit. This unit may be a distillation tower, packed column, spray tower or other suitable unit.
  • the oil descends down the tower whilst hydrogen fluoride gas 23 is fed from storage unit 15 into the unit 12 from the bottom of the tower and passes up the tower.
  • the hydrogen fluoride gas contacts the descending oil and converts the sulphur that will react which may be in a free form or in compound with other substances in the oil to sulphur fluorides, generally sulphur tetrafluoride.
  • the sulphur fluorides which are gaseous along with the remaining hydrogen fluoride gas leave the top of the gas-liquid contact unit and are preferably then passed 24 to a gas separation tower 13 wherein as above described, the lighter hydrogen fluoride is removed 25 at the top, whilst the heavier sulphur fluorides are removed from the bottom 26.
  • the gas separation tower 13 is not essential, but very desirable.
  • the sulphur fluorides are then heated to from 220 0p to 240 0 F and compressed to from 60 to 100 psig before being passed to a gas-water contact unit 14 at similar temperatures and pressures, where on contact with water sprays 27 sulphur precipitates out and may be removed 35 for further use.
  • the fluoride from the sulphur fluorides is converted to hydrogen fluoride gas, removed 28 from the unit 14 and this is combined with the hydrogen fluoride gas leaving the gas separation tower to be passed back to the hydrogen fluoride gas storage 15.
  • Oil leaving the main reactor 12 has thus had its sulphur content reduced to from 0.1 to 0.05% providing the reaction in the reactor 12 has been carried out with sufficient residence time, concentrations and at a reasonable temperature, about 50°C.
  • the oil 34 leaving the reactor 12 contains a small amount of entrained HF which can be removed by treating the oil with an ammonia solution 33 to farm salts with the fluoride compounds in the aqueous phase.
  • the oil phase 31 may then be extracted from the aqueous phase 32 by say phase separation apparatus 30.
  • the oil leaving the gas-liquid contact unit is substantially desulphurized and of course the degree of desulphurization is dependant upon the efficiency of the gas-liquid contacting unit and the residence time therein. Obviously, to increase the level of desulphurization further contacting may be desirable.
  • the temperature of the HF gas passing into the gas-liquid contact unit is preferably around 80 o F, although this temperature may be varied according to the conditions desirable with particular oils. The desulphurized oil leaving the gas-liquid contact unit may then be passed for further processing in normal refinery practice.
  • the separation of the oil from the resulting reactiton mixture would comprise a solids separation stage as well as a liquid phase separation stage, thus allowing the oil to be extracted and passed to, say, an ammonia treatment stage 30 for stripping the oil of non-hydrocarbon components.

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)
EP80301580A 1979-05-25 1980-05-14 Désulfurisation d'huile Withdrawn EP0020053A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPD894679 1979-05-25
AU8946/79 1979-05-25

Publications (1)

Publication Number Publication Date
EP0020053A1 true EP0020053A1 (fr) 1980-12-10

Family

ID=3768125

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80301580A Withdrawn EP0020053A1 (fr) 1979-05-25 1980-05-14 Désulfurisation d'huile

Country Status (4)

Country Link
EP (1) EP0020053A1 (fr)
JP (1) JPS55157680A (fr)
AU (1) AU5824080A (fr)
ZA (1) ZA802983B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1876221A1 (fr) * 2006-07-07 2008-01-09 Abb Research Ltd. Procédé de traitement d'une huile isolante électrique
CN102144268B (zh) * 2008-09-26 2013-07-10 三菱电机株式会社 油浸电气设备

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174805A (ja) * 1983-03-24 1984-10-03 Reiko Co Ltd 光線調整フイルム

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2343841A (en) * 1943-06-08 1944-03-07 Standard Oil Co Removal of aromatics, sulphur, or unsaturates from hydrocarbons
US2581064A (en) * 1948-06-05 1952-01-01 Standard Oil Dev Co Treating oil with sulfur trioxide
US2643971A (en) * 1950-06-14 1953-06-30 Standard Oil Co Combination hf treating catalytic cracking process
GB732068A (en) * 1952-09-11 1955-06-15 Standard Oil Co Improvements in or relating to process and system for treating hydrocarbon oil with liquid hydrogen fluoride
FR1138769A (fr) * 1954-08-20 1957-06-19 Bataafsche Petroleum Procédé pour enlever les mercaptans et tous autres dérivés sulfurés d'une huile hydrocarbonée par traitement à l'acide fluorhydrique
US2971905A (en) * 1957-07-31 1961-02-14 Exxon Research Engineering Co Process for removing metallic contaminants from oils
GB1547664A (en) * 1974-12-30 1979-06-27 Exxon Research Engineering Co Removal of organic sulphur compounds from hydrocarbon feedstocks

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2343841A (en) * 1943-06-08 1944-03-07 Standard Oil Co Removal of aromatics, sulphur, or unsaturates from hydrocarbons
US2581064A (en) * 1948-06-05 1952-01-01 Standard Oil Dev Co Treating oil with sulfur trioxide
US2643971A (en) * 1950-06-14 1953-06-30 Standard Oil Co Combination hf treating catalytic cracking process
GB732068A (en) * 1952-09-11 1955-06-15 Standard Oil Co Improvements in or relating to process and system for treating hydrocarbon oil with liquid hydrogen fluoride
FR1138769A (fr) * 1954-08-20 1957-06-19 Bataafsche Petroleum Procédé pour enlever les mercaptans et tous autres dérivés sulfurés d'une huile hydrocarbonée par traitement à l'acide fluorhydrique
US2971905A (en) * 1957-07-31 1961-02-14 Exxon Research Engineering Co Process for removing metallic contaminants from oils
GB1547664A (en) * 1974-12-30 1979-06-27 Exxon Research Engineering Co Removal of organic sulphur compounds from hydrocarbon feedstocks

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 68, Nr. 12, March 11, 1968, ref. 51529r page 5506, column 1 Columbus Ohio (US) D.F. VARFOLOMEEV et al.: "Refining of highly unsaturated sulfurous distillates of thermal origin" * The whole doument * *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1876221A1 (fr) * 2006-07-07 2008-01-09 Abb Research Ltd. Procédé de traitement d'une huile isolante électrique
WO2008003790A1 (fr) * 2006-07-07 2008-01-10 Abb Research Ltd Procédé de traitement d'une huile électriquement isolante
CN102144268B (zh) * 2008-09-26 2013-07-10 三菱电机株式会社 油浸电气设备

Also Published As

Publication number Publication date
JPS55157680A (en) 1980-12-08
AU5824080A (en) 1980-11-27
ZA802983B (en) 1981-05-27

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Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LU NL SE

17P Request for examination filed

Effective date: 19810130

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19820421

ITCP It: supplementary protection certificate

Spc suppl protection certif: CCP 368

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TURNER, MAXWELL JAMES

Inventor name: LLOYD, ROBERT