EP0020053A1 - Désulfurisation d'huile - Google Patents
Désulfurisation d'huile Download PDFInfo
- 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- Withdrawn
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005864 Sulphur Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- QTJXVIKNLHZIKL-UHFFFAOYSA-N sulfur difluoride Chemical compound FSF QTJXVIKNLHZIKL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003208 petroleum Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- -1 sulphur fluoride compound Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 41
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 9
- 239000010779 crude oil Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- 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)
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)
| 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)
| 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)
| 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 |
-
1979
- 1979-05-25 AU AU58240/80A patent/AU5824080A/en not_active Abandoned
-
1980
- 1980-05-14 EP EP80301580A patent/EP0020053A1/fr not_active Withdrawn
- 1980-05-19 JP JP6632280A patent/JPS55157680A/ja active Pending
- 1980-05-20 ZA ZA00802983A patent/ZA802983B/xx unknown
Patent Citations (7)
| 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)
| 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)
| 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 |
| ZA802983B (en) | 1981-05-27 |
| AU5824080A (en) | 1980-11-27 |
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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 |