US1904173A - Method of removing corrosive sulphur from hydrocarbon oils - Google Patents
Method of removing corrosive sulphur from hydrocarbon oils Download PDFInfo
- Publication number
- US1904173A US1904173A US279620A US27962028A US1904173A US 1904173 A US1904173 A US 1904173A US 279620 A US279620 A US 279620A US 27962028 A US27962028 A US 27962028A US 1904173 A US1904173 A US 1904173A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbon oils
- oil
- sulphur
- lye
- treating
- 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
- 239000003921 oil Substances 0.000 title description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 16
- 239000005864 Sulphur Substances 0.000 title description 16
- 238000000034 method Methods 0.000 title description 15
- 239000004215 Carbon black (E152) Substances 0.000 title description 8
- 229930195733 hydrocarbon Natural products 0.000 title description 8
- 150000002430 hydrocarbons Chemical class 0.000 title description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 44
- 239000000344 soap Substances 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 6
- 239000003518 caustics Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002888 oleic acid derivatives Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011436 cob Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
Definitions
- substances are especially naphthenic acid soaps, sulphonic acid soaps, fatty acid soaps,
- contact-promoting bodies such as rosin, sulphonated oleic acid, Turkey red oil, or the like, may be used.
- Mid-Continent natural or first-run naphtha is agitated under pressure of about 100 lbs. per square inch at about 212 F. for 15 minutes with a 30 Baum spent absorption lye containing 1% by weight of naph- 1928.
- thenio acid soap preferably sodium naphthena-te.
- the naphtha was tested by shaking repeatedly with metallic mercury at room temperature. The mercury remained bright, showing that corrosive sulphur had been eliminated from the naphtha.
- naphthenic acid soap prepared from lye used in treating Colombian or Peruvian gasoline.
- This lye contains substantial amounts of naphthenic acid soaps, which may be separated and then dissolved in the proper amount in the spent lye to be used for treating. Alternatively, a portion of the lye containing the soapsmay be added di rectly to the spent lye treating solution.
- the naphthenic soap lye referred to does not contain enough sodium sulphid and caustic to be used satisfactorily alone.
- We have found that about 0.1 to 5.0% of the naphthenic soap is satisfactory; around 1% being best in many cases.
- the permissible upper limit is determined largely by the tendency of the oil to form objectionable emulsions with the oil. The amount of soap should not be large enough to induce this.
- alkali and ammonium salts of the higher fatty acids or mixtures of these soaps may be used; also other soaps, such as oleates and/or stearates of aluminum, iron andcalcium.
- the amount of these may be varied widely, but in general should be between 0.1 and 5.0%.
- the invention is not limited to any particular method of treating.
- a continuous mixer 0f the type shown in the 'United States patent to Charles Leaver, No. 1,635,718, granted July 12, 1927, and inthe copending United States application of Stratford, McIntyre, and Moor, Serial No. 239,656, filed December 13, 1927.
- the lye may be used in any suitable way, preferably at temperatures between 220 to 300 F. and pressure sufficient to prevent undesirable vaporization.
- a relatively large volume of lye is used, preferably about equal to the volume of oil.
- the inlet pressure in the treater may average about 100 to 150 pounds per square inch and the outlet pressure about 60 to 100 pounds.
- caustic soda lyes have been particularly referred to herein, it will be understood that the invention is equally applicable to other alkaline treating agents, such as caustic potashlyes.
- the invention may also be applied in connectionwith fresh orspent treating lyes containing lead or other heavy metals. 7
- soaps and the like also facilitate the action of fresh lye on corrosive sulphur present in oil.
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)
Description
Patented Apr. 18, 1933 UNITED STATES PATENT OFFICE REGINALD K. STRATFORD AND WILLIAM P. DOOHAN, OF SARNIA, ONTARIO, CANADA,
ASSIG-NORS 'IO STANDARD OIL DEVELOPMENT COMPANY, A CORPORATION OF DELA- I WARE METHOD OF REMOVING CORROSIVE SULPHUR FROM HYDROCARBON OILS N0 Drawing. Application filed May 21,
substances are especially naphthenic acid soaps, sulphonic acid soaps, fatty acid soaps,
or mixtures of any of the foregoing. Other contact-promoting bodies, such as rosin, sulphonated oleic acid, Turkey red oil, or the like, may be used.
It is well known that corrosive sulphur, when existing as elementary sulphur and in certain compounds, cannot be successfully removed from oil by treating with caustic alkali unless the oil is heated to a relatively high temperature. Alkali sulphids, however, under certain conditions are known to have the power of fixing elementary sulphur at lower temperature. In the U. S. patent to Cobb, No. 1,300,816, granted April 15, 1919, removal of corrosive sulphur by specially prepared solutions containing such sulphids is described and claimed.
By means of our invention, it is possible to use with advantage the so called spent caustic solutions which contain sulphids produced by contact with sulphur-containing oils. While the utility of this invention is chiefly in connection with such solutions, we have found that the action of even fresh caustic solutions is promoted by the presence of soaps and other compounds of the type mentioned.
The present invention will be fully understood from the following description:
Mid-Continent natural or first-run naphtha is agitated under pressure of about 100 lbs. per square inch at about 212 F. for 15 minutes with a 30 Baum spent absorption lye containing 1% by weight of naph- 1928. Serial N0. 279,620.
thenio acid soap, preferably sodium naphthena-te. About 35% of the sodium 'hydroxid originally present in the lye had been converted into salts, mostly sodium sulphid. About 65% of the sodium hydroxid remained as such. After the treatment, the naphtha was tested by shaking repeatedly with metallic mercury at room temperature. The mercury remained bright, showing that corrosive sulphur had been eliminated from the naphtha.
We prefer a naphthenic acid soap prepared from lye used in treating Colombian or Peruvian gasoline. This lye contains substantial amounts of naphthenic acid soaps, which may be separated and then dissolved in the proper amount in the spent lye to be used for treating. Alternatively, a portion of the lye containing the soapsmay be added di rectly to the spent lye treating solution. Ordinarily, the naphthenic soap lye referred to does not contain enough sodium sulphid and caustic to be used satisfactorily alone. We have found that about 0.1 to 5.0% of the naphthenic soap is satisfactory; around 1% being best in many cases. The permissible upper limit is determined largely by the tendency of the oil to form objectionable emulsions with the oil. The amount of soap should not be large enough to induce this.
Instead of naphthenic acid soaps, we may use alkali and ammonium salts of the higher fatty acids or mixtures of these soaps; also other soaps, such as oleates and/or stearates of aluminum, iron andcalcium. The amount of these may be varied widely, but in general should be between 0.1 and 5.0%.
The invention is not limited to any particular method of treating. We prefer to use a continuous mixer 0f the type shown in the 'United States patent to Charles Leaver, No. 1,635,718, granted July 12, 1927, and inthe copending United States application of Stratford, McIntyre, and Moor, Serial No. 239,656, filed December 13, 1927. The lye may be used in any suitable way, preferably at temperatures between 220 to 300 F. and pressure sufficient to prevent undesirable vaporization. A relatively large volume of lye is used, preferably about equal to the volume of oil. When treating gasoline, the inlet pressure in the treater may average about 100 to 150 pounds per square inch and the outlet pressure about 60 to 100 pounds. Although caustic soda lyes have been particularly referred to herein, it will be understood that the invention is equally applicable to other alkaline treating agents, such as caustic potashlyes. The invention may also be applied in connectionwith fresh orspent treating lyes containing lead or other heavy metals. 7
As stated above, soaps and the like also facilitate the action of fresh lye on corrosive sulphur present in oil. In working with fresh lye, we prefer to use the treating method described in Serial No. 239,656, just mentioned.
- Various changes and alternative procedures may be adopted-within the scope of the appendedclaims in which it is our intention to claim all novelty inherent in the invention as broadly as the prior art permits.
' We claim:
1. The method of removing corrosive sulphur from hydrocarbon oils, consisting of bringing the oil into intimate contact at a temperature between 212 and 300 F. with an alkaline solution containing a substance adapted to promote contact between the oil and treating solution.
2. The method of removing corrosive sulphur from hydrocarbon oils, comprising bringing the oil into intimate contact ata temperature between 212300 F. with a large volume of a solution of caustic'soda containing a small percentage of soap adapted to promote contact between the oil and the treating solution. 7
3. The method of removing-corrosive sulphur from hydrocarbon oils, comprising bringing the oil into intimate contact at a temperature between 212300 F. with a large volume of a caustic soda solution containing a small percentage of a naphthenic acid soap.
4:. The method of removing corrosive sulphur from hydrocarbon oils, comprising agitating the oil under pressure and'at a temperature between 212 and 300 F. with a caustic soda solution containing a small percentage of a soap adapted to promote contact between the oil and the treating solution.
5; Method according to claim- 4, in which the soap adapted to promote contact is derived from lye which has been used in treating Colombian or Peruvian gasoline.
6. Method according to claim 4, in which the contact-promoting substance is about 1% by weight of a'naphthenic acid soap.
7 -Method according to claim 4 in which the soap adapted to promote contact is introduced into the treating solution in the form oflye containing soaps produced by treatment of Colombian or Peruvian gasoline.
8. The method of removing corrosive sulphur from gasoline, consisting of agitating the gasoline under pressure and at elevated temperature with a spent lye containing residual caustic soda, together with a substance adapted to promote-contact between the caustic soda and the gasoline.
9. The method of removing corrosive sulphur from hydrocarbon oils, comprising bringing the oilinto intimate contact at a temperature between 212 F. and 300 F. with an alkaline solution containing rosin.
' 10. The. method of removing corrosive sulphur from hydrocarbon oils, comprising bringing-the oilinto intimate contactat a temperature between 212 F. and 300 F. with sulphonated oleic acid.
REGINALD K. STRATFORD. -WILLIAM P; 'DOQHAN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US279620A US1904173A (en) | 1928-05-21 | 1928-05-21 | Method of removing corrosive sulphur from hydrocarbon oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US279620A US1904173A (en) | 1928-05-21 | 1928-05-21 | Method of removing corrosive sulphur from hydrocarbon oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1904173A true US1904173A (en) | 1933-04-18 |
Family
ID=23069739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US279620A Expired - Lifetime US1904173A (en) | 1928-05-21 | 1928-05-21 | Method of removing corrosive sulphur from hydrocarbon oils |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1904173A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428695A (en) * | 1945-02-12 | 1947-10-07 | Pure Oil Co | Hydrocarbon extraction process |
| US2434868A (en) * | 1945-11-05 | 1948-01-20 | Shell Dev | Process for the removal of carbonyl sulfide from a hydrocarbon fluid |
| US2455679A (en) * | 1946-10-03 | 1948-12-07 | Standard Oil Dev Co | Distillation of acid-treated oils |
-
1928
- 1928-05-21 US US279620A patent/US1904173A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428695A (en) * | 1945-02-12 | 1947-10-07 | Pure Oil Co | Hydrocarbon extraction process |
| US2434868A (en) * | 1945-11-05 | 1948-01-20 | Shell Dev | Process for the removal of carbonyl sulfide from a hydrocarbon fluid |
| US2455679A (en) * | 1946-10-03 | 1948-12-07 | Standard Oil Dev Co | Distillation of acid-treated oils |
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