US2729591A - Sweetening of petroleum oils containing mercaptans with alkali and oxygen and then with alkali, a solutizer and oxygen - Google Patents
Sweetening of petroleum oils containing mercaptans with alkali and oxygen and then with alkali, a solutizer and oxygen Download PDFInfo
- Publication number
- US2729591A US2729591A US294722A US29472252A US2729591A US 2729591 A US2729591 A US 2729591A US 294722 A US294722 A US 294722A US 29472252 A US29472252 A US 29472252A US 2729591 A US2729591 A US 2729591A
- Authority
- US
- United States
- Prior art keywords
- mercaptans
- oxygen
- alkali solution
- oil
- disulphides
- 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
Links
- 239000003513 alkali Substances 0.000 title claims description 38
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims description 28
- 239000001301 oxygen Substances 0.000 title claims description 28
- 239000003208 petroleum Substances 0.000 title claims description 9
- 239000003921 oil Substances 0.000 title description 25
- 239000003518 caustics Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000005864 Sulphur Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 6
- 229930003836 cresol Natural products 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 1
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal phenolate Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229960003903 oxygen Drugs 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
Definitions
- solutiser process wherein the oils are contacted with an aqueouscaustic alkali solution containing a substance, such as an alkali metal phenolate or isobutyrate, capable of'increasing the solubility of the mercaptans in
- This invention relates to the sweetening of petroleum the caustic solution.
- the caustic solution is regenerated According to the invention therefore, a process for the sweetening of petroleum oils containing mercaptans, con sists in treating the oils with an aqueous caustic alkali solution containing a substance which is capable of increasing thesolubilityof the inercaptans in the alkali,
- the aqueous caustic alkali solution containing the solubility promoter will heerinafter be referred to as the solutiser solution.
- the mechanism of the sweetening operation appears to be that the mercaptans first go from the oil phase to the aqueous phase, at which stage both the mercaptan and total sulphur content of the oil are reduced.
- the mercaptans are oxidised in the aqueous phase, presumably to the insoluble disulphides which then return to the oil phase, thus increasing the sulphur content which gradually returns to its original value while the mercaptan content drops to zero.
- the caustic solution is thus continuously regenerated so that no separate regeneration process is needed. It is to be understood that the scope of the invention is in no way limited by the above explanation of the mechanism of the reaction.
- the treatment of the oil with the solutiser solution may advantageously be carried out in two or more stages, all in the presence of oxygen or an oxygen-containing gas.
- the process of the invention is capable of sweeteninga sour naphtha containing 0.05% by weight mercaptan sulphur.
- the contact time required is of the order of 20-30 minutes in a two-stage process when giving the naphtha a 50/50 Wash with the solutiser solution.
- Commercial cresol may conveniently be used as the solubility promoter.
- a process. of sweetening a petroleum oil containing mercaptans, which comprises mixing the oil with an aqueous caustic alkali solution in the presence of, free oxygen so as to convert part of said mercaptans into disulphides, separating the oil from, the caustic alkali solution, mixing the separated oil in the presence of free oxy gen but in the absence of a catalyst for the oxidation of mercaptans to disulphides with an aqueous caustic alkali solution containing a commercial cresol capable of increasing the solubility of the mercaptans in the alkali solution, so as to client a turther conversion of mercaptans into disulphides, and separating a sweetened oil from the caustic alkali s lu ion.
- a process of sweetening a petroleum oil containing mercaptans which comprises mixing the oil with an aqueous caustic alkali solution in the presence of free oxygen so as to convert part; of said mercaptans into disulphides, separating the oil from the caustic alkali sohu tion, mixing the separated oil in the. presence of free oxygen but in the absence of a. catalyst for the oxidation of mercaptans to disulphides with an aqueous solution consisting of N NaQH+1.5 N commercial cresol so as to effect a further conversion of mercaptans into disulphides, and separating a sweetened oil from the caustic alkali solution.
- alkali solution a naphtha containing not more than 0.05% weight mercaptan sulphur, mixing the separated naphtha in the presence of free oxygen but in the absence of a catalyst for the oxidation of mercaptans to disulphides with an aqueous caustic alkali solution containing a substance which is capable of increasing the solubility of the mercaptans in the alkali solution, so as to effect a further conversion of mercaptans into disulphides, and separating a sweetened oil from the caustic alkali solution.
- a process of sweetening a sour naphtha containing more than 0.05% weight of mercaptan sulphur which comprises mixing the naphtha with an aqueous caustic alkali solution in the presence of free oxygen so as to convert part of said mercaptans into disulphides, separating from the caustic alkali solution a naphtha containing not more than 0.05 weight mercaptan sulphur, mixing the separatednaphtha in the presence of free oxygen but in the absence of a catalyst for the oxidation of necrcaptans to disulphides with an aqueous caustic alkali solution containing a commercial cresol capable of increasing the solubility of the mercaptans in the alkali solution, so as to effect a further conversion of mercaptans into disulphides, and separating a sweetened 'oil from the caustic alkali solution.
- a process of sweetening a sour naphtha containing more than 0.05% weight of mercaptan sulphur which comprises mixing the napht a with an aqueous caustic alkali solution in the presence of free oxygen so as to convert part of said mercaptans into disulphides, separating from the caustic alkali solution a naphtha containing not more than 0.05% weight mercaptan sulphur, mixing the separated naphtha in the presence of free oxygen but in the absence of a catalyst for the oxidation of mercaptans to disulphides with an aqueous, solution consisting of '5 N NaOH+1.5 N commercial cresol so as to efiect a further conversion of mercaptans into disulphides, and separating a sweetened oil from the caustic alkali solution.
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)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB15827/51A GB728586A (en) | 1951-07-04 | 1951-07-04 | Improvements relating to the sweetening of petroleum oils containing mercaptans |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2729591A true US2729591A (en) | 1956-01-03 |
Family
ID=10066248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US294722A Expired - Lifetime US2729591A (en) | 1951-07-04 | 1952-06-20 | Sweetening of petroleum oils containing mercaptans with alkali and oxygen and then with alkali, a solutizer and oxygen |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2729591A (he) |
| BE (1) | BE512549A (he) |
| DE (1) | DE940005C (he) |
| FR (1) | FR1059231A (he) |
| GB (1) | GB728586A (he) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063935A (en) * | 1959-09-08 | 1962-11-13 | Shell Oil Co | Hydrocarbon sweetening process |
| US4428828A (en) | 1981-01-02 | 1984-01-31 | Chevron Research Company | Upgrading hydrocarbonaceous oils with an aqueous liquid |
| US4481106A (en) * | 1983-12-05 | 1984-11-06 | Uop Inc. | Hydrocarbon treating process |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2413945A (en) * | 1944-03-09 | 1947-01-07 | Standard Oil Co | Treating petroleum distillates |
| US2427212A (en) * | 1944-12-02 | 1947-09-09 | Pure Oil Co | Removal of peroxides from hydrocarbon oils |
| US2474028A (en) * | 1946-04-06 | 1949-06-21 | Inventors Guild | Recovery of phenol salts from aqueous solutions |
| GB629914A (en) * | 1944-12-06 | 1949-09-30 | Pure Oil Co | A method for sweetening hydrocarbon liquids containing mercaptans |
| CA471373A (en) * | 1951-02-06 | C. Bond Donald | Removal of acidic sulfur compounds from hydrocarbon oils | |
| US2552399A (en) * | 1949-02-19 | 1951-05-08 | Standard Oil Dev Co | Treating petroleum distillates |
| CA475538A (en) * | 1951-07-24 | C. Bond Donald | Sweetening of hydrocarbon liquids | |
| US2638439A (en) * | 1951-04-18 | 1953-05-12 | Standard Oil Dev Co | Treatment of petroleum distillates |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2015038A (en) * | 1932-07-23 | 1935-09-17 | Texas Co | Process of sweetening petroleum hydrocarbons |
| US2346497A (en) * | 1941-09-02 | 1944-04-11 | Shell Dev | Solutizer process |
| US2329616A (en) * | 1942-04-27 | 1943-09-14 | Air Reduction | Treatment of hydrocarbon oils |
-
0
- BE BE512549D patent/BE512549A/xx unknown
-
1951
- 1951-07-04 GB GB15827/51A patent/GB728586A/en not_active Expired
-
1952
- 1952-06-20 US US294722A patent/US2729591A/en not_active Expired - Lifetime
- 1952-06-22 DE DEA16031A patent/DE940005C/de not_active Expired
- 1952-06-26 FR FR1059231D patent/FR1059231A/fr not_active Expired
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA471373A (en) * | 1951-02-06 | C. Bond Donald | Removal of acidic sulfur compounds from hydrocarbon oils | |
| CA475538A (en) * | 1951-07-24 | C. Bond Donald | Sweetening of hydrocarbon liquids | |
| US2413945A (en) * | 1944-03-09 | 1947-01-07 | Standard Oil Co | Treating petroleum distillates |
| US2427212A (en) * | 1944-12-02 | 1947-09-09 | Pure Oil Co | Removal of peroxides from hydrocarbon oils |
| GB629914A (en) * | 1944-12-06 | 1949-09-30 | Pure Oil Co | A method for sweetening hydrocarbon liquids containing mercaptans |
| US2474028A (en) * | 1946-04-06 | 1949-06-21 | Inventors Guild | Recovery of phenol salts from aqueous solutions |
| US2552399A (en) * | 1949-02-19 | 1951-05-08 | Standard Oil Dev Co | Treating petroleum distillates |
| US2638439A (en) * | 1951-04-18 | 1953-05-12 | Standard Oil Dev Co | Treatment of petroleum distillates |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063935A (en) * | 1959-09-08 | 1962-11-13 | Shell Oil Co | Hydrocarbon sweetening process |
| US4428828A (en) | 1981-01-02 | 1984-01-31 | Chevron Research Company | Upgrading hydrocarbonaceous oils with an aqueous liquid |
| US4481106A (en) * | 1983-12-05 | 1984-11-06 | Uop Inc. | Hydrocarbon treating process |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1059231A (fr) | 1954-03-23 |
| BE512549A (he) | |
| DE940005C (de) | 1956-03-08 |
| GB728586A (en) | 1955-04-20 |
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