US1435824A - Refining liquid hydrocarbons - Google Patents
Refining liquid hydrocarbons Download PDFInfo
- Publication number
- US1435824A US1435824A US301359A US30135919A US1435824A US 1435824 A US1435824 A US 1435824A US 301359 A US301359 A US 301359A US 30135919 A US30135919 A US 30135919A US 1435824 A US1435824 A US 1435824A
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- US
- United States
- Prior art keywords
- hypochlorite
- liquid hydrocarbons
- hydrocarbons
- treatment
- liquid
- 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.)
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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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/02—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with halogen or compounds generating halogen; Hypochlorous acid or salts thereof
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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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/12—Halides
Definitions
- This invention relates to a process of refining benzine, kerosene or other distillates from petroleum, shale oil and the like by the removal therefrom of the sulphur compounds such as organic sulphides, polysulphides and hydro-sulphides they may contain.
- This invention particularly relates to the refining of oil for the removal of bad odors, to destroy any coloring matter originally present and to eliminate or prevent development of acid or corrosive products. So far as the causes of these objectionable pro-perties are known, organic compounds of The precise structure of all the sulfur compounds present in petroleum distillate and the like is not known, but I find that all the sulfur in these oils is amenable to treatment according to this invention. 7
- the liquid hydrocarbon is subjected to treatment with an alkaline solution of a hypochlorite, whereby the sulphur compounds contained in the liquid hydrocarbon are oxidized and bodies produced that readily pass into and are removed with the lye.
- the treatment is effected in the presence of an excess of alkali.
- the invention comprises the features which are hereinafter described.
- the invention may be carried into effect in any suitable form of electrolytic apparatus.
- an iron or steel vessel a of upstanding cylindrical form may be employed suitably earthed and carbon or graphite anodes cmay be used, and heat may be applied to the vessel in any suitable or convenient way.
- the liquid hydrocarbdn may be poured into the electrolyte and the electrolysis may proceed while the electrolyte is actively stirred by a stirrer 7). Heat may be applied to the vessel so that the treatment may take place at the optimum 1919.
- hypochlorite any suitable hypochlorite may be used such as sodium hypochlorite with the addition of free alkali.
- the presence of free alkali has'the effect of preventing corrosion of the vessel, of inhibiting chlorination of hydrocarbons, of stabilizing the hypochlorite and of assisting in the removal of the products of the treatment which result mainly from the oxidation of the organic sulphur compounds originally present in the liquid hydrocarbon treated.
- the alkaline solution of a hypochlorite may be produced in an apparatus external to the mixer in which the operation proceeds.
- the solution may be prepared by any of the known methods, such as electrolysis of a salt solution in special cells for the production of hypochlorite, by passing liquid chlorine into a solution of an alkali such as caustic soda or milk of lime, or by dissolving bleaching powder in sufficient water to produce a solution of-the proper hypochlorite content and alkalinity.
- Liquid hydrocarbons refined according to this invention are chlorine free for all practical purposes.
- the oil to be treated should be analyzed so as to discover its sulphur content.
- the amount of free alkali should at least be of the order of 0.1 per cent concentration.
- Th concentration of the hypochlorite should be at least 0.25 normal.
- the current density in the electrodes may be from .15 to .40 amperes per square centimeter.
- The' duration of treatment should be determined by test with each individual oil.
- the oxidized sulphur compounds are of high molecular weight and are relatively insoluble in'alkali, they may be removed from'solution in the refined oil by means of filtration through animal charcoal, dehydrated alumina, fullers earth or any suitable decolorizing agent.
- the hydrocarbon Before treating hydrocarbons containing hydro-sulphides or mercaptans, the hydrocarbon may be first treated with caustic soda so that it may be substantially deprived of these bodies before treatment according to the invention and thus the hypochlorite economized.
- a process for refining liquid hydrocarbons containing sulfur compounds comprising subjecting said hydrocarbons to treatment with a solution comprising a hypochlorite in concentration at least 0.25 normal and free alkali in concentration at least 0.1 per cent.
- a process for refining liquid h drocarbons containing sulfur compoun s comprising subjecting said hydrocarbons to treatment with a solution consisting of a hypochlorite and free alkali without introducin chlorine into the liquid hydrocarbons.
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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)
Description
A. E. DUNSTAN. REF |N|NG LIQUID HYDROCARBONS. APPLICATION FILED JUNE 2. 1919.
11.,4L35,82%, Patented Nov. M, 1922.
Inventor w. 2. Zia Attorney,
Patented Nov. Ml, 1922.;
warren srarss ALBERT ERNESTJDUNSTAN, 01E SUNBUBY, ENGLAND.
REFINING LIQUID HYDROCARBO'NS.
Application filed June 2,
T all whom it may concern Be it known that I, ALBERT ERNEST DUN- STAN, D. Sc, a subject of the Kin of Great Britain and Ireland, residing at fieadhurst, Cadbury Road, Sunbury-on-Thames, England, have invented certain new and useful Improvements Relatin to Refining Liquid Hydrocarbons, of whic the following is a I specification.
- sulfur are chiefly responsible.
This invention relates to a process of refining benzine, kerosene or other distillates from petroleum, shale oil and the like by the removal therefrom of the sulphur compounds such as organic sulphides, polysulphides and hydro-sulphides they may contain.
This invention particularly relates to the refining of oil for the removal of bad odors, to destroy any coloring matter originally present and to eliminate or prevent development of acid or corrosive products. So far as the causes of these objectionable pro-perties are known, organic compounds of The precise structure of all the sulfur compounds present in petroleum distillate and the like is not known, but I find that all the sulfur in these oils is amenable to treatment according to this invention. 7
According to the invention the liquid hydrocarbon is subjected to treatment with an alkaline solution of a hypochlorite, whereby the sulphur compounds contained in the liquid hydrocarbon are oxidized and bodies produced that readily pass into and are removed with the lye.
According to the invention, moreover, the treatment is effected in the presence of an excess of alkali. I
The invention comprises the features which are hereinafter described.
The invention is diagrammatically illustrated in the accompanylng drawing.
The invention may be carried into effect in any suitable form of electrolytic apparatus. For example an iron or steel vessel a of upstanding cylindrical form may be employed suitably earthed and carbon or graphite anodes cmay be used, and heat may be applied to the vessel in any suitable or convenient way. 'The liquid hydrocarbdn may be poured into the electrolyte and the electrolysis may proceed while the electrolyte is actively stirred by a stirrer 7). Heat may be applied to the vessel so that the treatment may take place at the optimum 1919. Serial N0. 301,359.
temperature. I have found a temperature of 120 F. efl'ective.
Any suitable hypochlorite may be used such as sodium hypochlorite with the addition of free alkali.
The presence of free alkali has'the effect of preventing corrosion of the vessel, of inhibiting chlorination of hydrocarbons, of stabilizing the hypochlorite and of assisting in the removal of the products of the treatment which result mainly from the oxidation of the organic sulphur compounds originally present in the liquid hydrocarbon treated.
The alkaline solution of a hypochlorite may be produced in an apparatus external to the mixer in which the operation proceeds. In fact, the solution may be prepared by any of the known methods, such as electrolysis of a salt solution in special cells for the production of hypochlorite, by passing liquid chlorine into a solution of an alkali such as caustic soda or milk of lime, or by dissolving bleaching powder in sufficient water to produce a solution of-the proper hypochlorite content and alkalinity.
s has been pointed out above the presence of freealkali renders the solution free from uncombined chlorine, and inhibits the chlorination of the hydrocarbon. Liquid hydrocarbons refined according to this invention are chlorine free for all practical purposes.
The oil to be treated should be analyzed so as to discover its sulphur content. For each unit amount of sulphur there should be provided at least one unit amount of oxygen resulting from the decomposition of hypochlorite. The amount of free alkali should at least be of the order of 0.1 per cent concentration. Th concentration of the hypochlorite should be at least 0.25 normal. The current density in the electrodes may be from .15 to .40 amperes per square centimeter. The' duration of treatment should be determined by test with each individual oil.
In cases where the oxidized sulphur compounds are of high molecular weight and are relatively insoluble in'alkali, they may be removed from'solution in the refined oil by means of filtration through animal charcoal, dehydrated alumina, fullers earth or any suitable decolorizing agent.
Before treating hydrocarbons containing hydro-sulphides or mercaptans,,the hydrocarbon may be first treated with caustic soda so that it may be substantially deprived of these bodies before treatment according to the invention and thus the hypochlorite economized.
Iclaim:" '1. A process for refining liquid hydrocarbons containing sulfur compounds, comprising subjecting said hydrocarbons to treatment with a solution comprising a hypochlorite in concentration at least 0.25 normal and free alkali in concentration at least 0.1 per cent.
2. A process for refining liquid h drocarbons containing sulfur compoun s, comprising subjecting said hydrocarbons to treatment with a solution consisting of a hypochlorite and free alkali without introducin chlorine into the liquid hydrocarbons.
3. 1% process for refining liqmd hydrocarbons containing sulfur compounds, comprising subjecting said hydrocarbons to treatment with an alkaline solution of a hypochlorite in proportion to provide about one unit of oxygen from decomposition of the hypochlorite .to each unit of sulfur in the liquid hydrocarbom I ALBERT ERNEST DUNSTAN.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US301359A US1435824A (en) | 1919-06-02 | 1919-06-02 | Refining liquid hydrocarbons |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US301359A US1435824A (en) | 1919-06-02 | 1919-06-02 | Refining liquid hydrocarbons |
Publications (1)
Publication Number | Publication Date |
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US1435824A true US1435824A (en) | 1922-11-14 |
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US301359A Expired - Lifetime US1435824A (en) | 1919-06-02 | 1919-06-02 | Refining liquid hydrocarbons |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2488855A (en) * | 1947-06-20 | 1949-11-22 | Jr Joseph O Denton | Sweetening and desulfurizing hydrocarbons |
US2581117A (en) * | 1949-12-16 | 1952-01-01 | Standard Oil Dev Co | Treatment of cracked naphthas with a hypochlorite followed by an alkali sulfide |
US2631121A (en) * | 1949-08-13 | 1953-03-10 | Standard Oil Dev Co | Hypochlorite sweetening process |
US2651594A (en) * | 1949-05-26 | 1953-09-08 | Standard Oil Dev Co | Kerosene finishing process |
US2662858A (en) * | 1949-11-10 | 1953-12-15 | Standard Oil Dev Co | Stabilizing hypochlorite solutions |
US2702237A (en) * | 1950-05-17 | 1955-02-15 | Standard Oil Co | Inhibited chlorine-containing petroleum oils and method of preparing same |
US3052625A (en) * | 1959-10-06 | 1962-09-04 | Exxon Research Engineering Co | Production of color-stable kerosene by hydrofining followed by hypochlorite treatment |
US3401101A (en) * | 1966-08-05 | 1968-09-10 | Howard F. Keller Jr. | Separation of hydrogen sulfide and mercaptans from fluid streams |
US7914669B2 (en) | 2003-12-24 | 2011-03-29 | Saudi Arabian Oil Company | Reactive extraction of sulfur compounds from hydrocarbon streams |
US9296956B2 (en) | 2010-10-28 | 2016-03-29 | Chevron U.S.A. Inc. | Method for reducing mercaptans in hydrocarbons |
-
1919
- 1919-06-02 US US301359A patent/US1435824A/en not_active Expired - Lifetime
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2488855A (en) * | 1947-06-20 | 1949-11-22 | Jr Joseph O Denton | Sweetening and desulfurizing hydrocarbons |
US2651594A (en) * | 1949-05-26 | 1953-09-08 | Standard Oil Dev Co | Kerosene finishing process |
US2631121A (en) * | 1949-08-13 | 1953-03-10 | Standard Oil Dev Co | Hypochlorite sweetening process |
US2662858A (en) * | 1949-11-10 | 1953-12-15 | Standard Oil Dev Co | Stabilizing hypochlorite solutions |
US2581117A (en) * | 1949-12-16 | 1952-01-01 | Standard Oil Dev Co | Treatment of cracked naphthas with a hypochlorite followed by an alkali sulfide |
US2702237A (en) * | 1950-05-17 | 1955-02-15 | Standard Oil Co | Inhibited chlorine-containing petroleum oils and method of preparing same |
US3052625A (en) * | 1959-10-06 | 1962-09-04 | Exxon Research Engineering Co | Production of color-stable kerosene by hydrofining followed by hypochlorite treatment |
US3401101A (en) * | 1966-08-05 | 1968-09-10 | Howard F. Keller Jr. | Separation of hydrogen sulfide and mercaptans from fluid streams |
US7914669B2 (en) | 2003-12-24 | 2011-03-29 | Saudi Arabian Oil Company | Reactive extraction of sulfur compounds from hydrocarbon streams |
US9296956B2 (en) | 2010-10-28 | 2016-03-29 | Chevron U.S.A. Inc. | Method for reducing mercaptans in hydrocarbons |
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