US1854866A - Purifying petroleum oils - Google Patents
Purifying petroleum oils Download PDFInfo
- Publication number
- US1854866A US1854866A US268369A US26836928A US1854866A US 1854866 A US1854866 A US 1854866A US 268369 A US268369 A US 268369A US 26836928 A US26836928 A US 26836928A US 1854866 A US1854866 A US 1854866A
- Authority
- US
- United States
- Prior art keywords
- acid
- sulfuric acid
- oil
- alkyl
- sulfuric
- 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
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- 239000003921 oil Substances 0.000 title description 32
- 239000003208 petroleum Substances 0.000 title description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 52
- 239000002253 acid Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 12
- -1 alkyl sulfuric acids Chemical class 0.000 description 9
- 150000008051 alkyl sulfates Chemical class 0.000 description 7
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- TYRGSDXYMNTMML-UHFFFAOYSA-N propyl hydrogen sulfate Chemical compound CCCOS(O)(=O)=O TYRGSDXYMNTMML-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- ZTHQBROSBNNGPU-UHFFFAOYSA-N Butyl hydrogen sulfate Chemical compound CCCCOS(O)(=O)=O ZTHQBROSBNNGPU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 241000669326 Selenaspidus articulatus Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- JYCKNDWZDXGNBW-UHFFFAOYSA-N dipropyl sulfate Chemical class CCCOS(=O)(=O)OCCC JYCKNDWZDXGNBW-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- JKLNYGDWYRKFKR-UHFFFAOYSA-N ethyl methyl sulfate Chemical compound CCOS(=O)(=O)OC JKLNYGDWYRKFKR-UHFFFAOYSA-N 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 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
- C10G17/06—Liquid-liquid treatment forming two immiscible phases using acids derived from sulfur or acid sludge thereof
Definitions
- This invention relates to purifying petroleum products; and it comprises a method of acid treating petroleum oils and petroleum products wherein certain acid alkyl sulfates are used in lieu of, or in addition to, sulfuric acid, said acid alkyl sulfates being advantageously materials made by absorbing ethylene and other gaseous olefins from still gases with sulfuric acid; all as more fully hereinafter set forth and as claimed.
- the action of the acid is beneficial but it is accompanied with some loss of oil; and the greater the amount of acid used for a given degree of decoloriza-
- the action of the sulfuric acid causes too great a loss of oil to permit thorough treatment.
- Alkyl sulfuric acids carrying methyl, ethyl or propyl groups, exercise a specificand advantageous action in decolorizing oils; and we have fur ther found that this action can be usefully employed in connection with the ordinary sulfuric acid treatment.
- Alkyl sulfates suitable for our purposes may be obtained by causing ordinary still gases containing gaseous olefins to react with sulfuric acid; either Application filed April 7, 1928. Serial No. 268,369.
- Still gases coming from stills 1 in which cracking is going forward contain ethylene and propylene as well as smaller quantities of higher olefins, such as propylene and butylene.
- Sulfuric acid of 1.84 speclfic gravity reacts readily with propylene (and butylene) but not with ethylene; and 1f there is any object in so doing, there may be a two-stage acid treatment of the still gas with acid; first with 1.84 acid which will form propyl sulfuric acid and then with fuming acid which will form ethyl sulfuric acid. But we ordinarily use a single treatment with fuming acid forming amixture of ethyl sulfuric and propyl sulfuric acids as the mixture is adapted to our purposes.
- Butyl sulfuric acid while not as desirable for our purposes as the other two, may still be used. However the amount of butylene in still gases going through condensers in contact with cool oily distillate is commonly quite small and its presence and the formation of butyl sulfuric acid may be disregarded. Still higher olefins, such as the amylenes, are substantially completely removed by the scrubbing action occurring 1n the condensers. In gases If the gas is not scrubbed, it may carry considerable proportions ofthe higher olefins.
- the gas and acid may be brought into reaction in any ordinary type of scrubbing apparatus.
- any high degree of conversion of the acid into alkyl compounds since we ordinarily use an excess of sulfuric acid in our treating process.
- Ethyl sulfuric acid can also the reaction of ordinary ethyl alcohol with sulfuric acid.
- Methyl sulfuric acid can be made by the reaction of methyl alcohol (methanol) with sulfuric acid.
- the lower layer consists of the reagent carrying with it most. of the color-bearing constituents of. the oil',. while the upper layer is oil.
- This oil may: cmry a little of the alkyl' sulfuric acid in solution; the amount being the greater the higher the alkyl. This is one of the reasons for preferring methyl, ethyl and. propyl sulfuric acids to their higher homologs. Methyl sulfate and ethyl sulfate do not dissolve to any substantial extent. In the event, that any substantial amount of alkyl sulfuric acid remainswiththe, oil, the oil, may be steamed to cause hydrolysis. The upper layer of oil can finally be washed with soda as. usual.
- the oil was better decelorized than by the action of an equivalent amount of sulfuric acid.
- the color given was approxlmately No. 2 on the N. P. A. scale. Still better results were obtained with a mixture consistingof 80per. cent sulfuric acid and QO-per cent of ethyl hydrogen sulfate (ethyl sulfuric furic acid al'one.
- Alkyl sulfuric acids, alone or in admixture with sulfuric acid will; produce lighter colored oils than will the same amount of sul Good results are also obtained by treating the oil' first with allryl sulfuric acid, alone or in admixture with sulfuric acid, and; then following with a treat-- mentwith a sulfuric acid alone.
- the oilobtained'by this double treatment is unusually light in color andthelossof oil. is not, great.
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
--'-tion, the greater the cost of treatment.
1 ably different with The result is that the Patented Apr. 19, 1932 UNITED STATES PATENT OFFICE BENJAMIN I1. SOUTHER, 0F PITTSBURGH, AND JOHN W. GREENE, OF WILKINSBURG,
PENNSYLVANIA, ASSIGNORS SYLVANIA, A CORPORATION OF TEXAS T0 GULF REFINING COMPANY, OF PITTSBURGH; PENN- PURIFYING PETROLEUM OILS No Drawing.
This invention relates to purifying petroleum products; and it comprises a method of acid treating petroleum oils and petroleum products wherein certain acid alkyl sulfates are used in lieu of, or in addition to, sulfuric acid, said acid alkyl sulfates being advantageously materials made by absorbing ethylene and other gaseous olefins from still gases with sulfuric acid; all as more fully hereinafter set forth and as claimed.
All petroleum oils and products, such as parafiin, are treated at one stage of manufacture or another with sulfuric acid. Sometimes fuming acid isused and sometimes weaker acid. Thesulfuric acid treatment is followed by a washing treatment with alkali. The exact nature of the actions exerted by the sulfuric acid in this treatment are still a. controversial matter and are probdifferent oils. The acid however decolorizcs the oil, removes sulfur and withdraws some components of the oil; these being the most reactive portions and hence the portions most subject to change. oil is stabilized against the action of air, light, etc. To some extent, the action of the acid causes polymerization. Some acid products in the nature of sulfonic acids go into the oil, whence they are withdrawn by the subsequent alkali treatment. All in all, the action of the acid is beneficial but it is accompanied with some loss of oil; and the greater the amount of acid used for a given degree of decoloriza- Sometimes, as in the case of cracked products containing considerable proportions of unsaturated compounds, the action of the sulfuric acid causes too great a loss of oil to permit thorough treatment.
We have found that certain alkyl sulfuric acids, carrying methyl, ethyl or propyl groups, exercise a specificand advantageous action in decolorizing oils; and we have fur ther found that this action can be usefully employed in connection with the ordinary sulfuric acid treatment. Alkyl sulfates suitable for our purposes may be obtained by causing ordinary still gases containing gaseous olefins to react with sulfuric acid; either Application filed April 7, 1928. Serial No. 268,369.
with the ordinary concentrated acid or with fuming acid. Still gases coming from stills 1 in which cracking is going forward contain ethylene and propylene as well as smaller quantities of higher olefins, such as propylene and butylene. Sulfuric acid of 1.84 speclfic gravity reacts readily with propylene (and butylene) but not with ethylene; and 1f there is any object in so doing, there may be a two-stage acid treatment of the still gas with acid; first with 1.84 acid which will form propyl sulfuric acid and then with fuming acid which will form ethyl sulfuric acid. But we ordinarily use a single treatment with fuming acid forming amixture of ethyl sulfuric and propyl sulfuric acids as the mixture is adapted to our purposes. Butyl sulfuric acid while not as desirable for our purposes as the other two, may still be used. However the amount of butylene in still gases going through condensers in contact with cool oily distillate is commonly quite small and its presence and the formation of butyl sulfuric acid may be disregarded. Still higher olefins, such as the amylenes, are substantially completely removed by the scrubbing action occurring 1n the condensers. In gases If the gas is not scrubbed, it may carry considerable proportions ofthe higher olefins.
In producing alkyl sulfuric acids from still gases, the gas and acid may be brought into reaction in any ordinary type of scrubbing apparatus. In general it is not worth while seeking any high degree of conversion of the acid into alkyl compounds since we ordinarily use an excess of sulfuric acid in our treating process.
Ethyl sulfuric acid can also the reaction of ordinary ethyl alcohol with sulfuric acid. Methyl sulfuric acid can be made by the reaction of methyl alcohol (methanol) with sulfuric acid.
In using still gases and sulfuric acid to form alkyl sulfates with an incomplete conversion of the sulfuric acid, as is done in the most advantageous embodiment of our inbe made by Q treatedwith 8, poundsofa mixture consisting Both have been found efficient for our puroses. Dialkylsulfates containing two alky-ls, such as methyl ethyl sulfate-,, may beused. But where we use the alkyl sulfate in conjunction with sulfuric acid as we on dinarily do, the use of the di-alkyl sulfates is equivalent to the use of the mono-alkyl sulfates.
On adding a small proportion of, any alkyl sulfate to petroleum oil and agitating, two layers are formed; The lower layer consists of the reagent carrying with it most. of the color-bearing constituents of. the oil',. while the upper layer is oil. This oil may: cmry a little of the alkyl' sulfuric acid in solution; the amount being the greater the higher the alkyl. This is one of the reasons for preferring methyl, ethyl and. propyl sulfuric acids to their higher homologs. Methyl sulfate and ethyl sulfate do not dissolve to any substantial extent. In the event, that any substantial amount of alkyl sulfuric acid remainswiththe, oil, the oil, may be steamed to cause hydrolysis. The upper layer of oil can finally be washed with soda as. usual.
Di-methyl sulfate and i but little soluble in petroleum oils, and the sol'ubi'lities of the mono-methyl sulfate and mono-ethyl sulfates are still less. On the other handythe di-butyl and, di-propyl sulfates are considerably more soluble,
a typical. embodiment of our invention,
a sample, of colored oil was, treated with a mixture of 90 per cent. dil-ethyl. sulfate and 10 per cent ofconcentrated', sulfuric acid, 10 per cent of the volume ofjthe oil-being used.
The oil was better decelorized than by the action of an equivalent amount of sulfuric acid. The color given was approxlmately No. 2 on the N. P. A. scale. Still better results were obtained with a mixture consistingof 80per. cent sulfuric acid and QO-per cent of ethyl hydrogen sulfate (ethyl sulfuric furic acid al'one.
acid).
Alkyl sulfuric acids, alone or in admixture with sulfuric acid, will; produce lighter colored oils than will the same amount of sul Good results are also obtained by treating the oil' first with allryl sulfuric acid, alone or in admixture with sulfuric acid, and; then following with a treat-- mentwith a sulfuric acid alone. The oilobtained'by this double treatment is unusually light in color andthelossof oil. is not, great.
A Venezuela; lubricating distillate treated? with.10. poundsof sulfuric; acid per barrel, gave. a darker productthan the same oil direthyl sulfate aredecole-rization and purification the process which comprises subjecting such an oil to the action of allryl hydrogen sulfates the said alkyl hydrogen sulfates being selected from the lower members of the alkyl series.
2. In the treatment of petroleum oil for de colori'zation and purification, the process which comprises subjecting such an oil to. the action of alkyl hydrogen sulfates in admirture with sulfuric acid; the said alkyl hydrogen sulfates being selected from the lower members of the alkyl series.
3. In the treatment of petroleum, oils for decolorization and purification the process which comprises subjecting such an oil tothc action of alkyl sulfates and subsequently treating with sulfuric acid; the said alkyl hydrogen sulfates being selected from the lower members of the alkyl. series.
In the purification of petroleum oils,.thc process which comprises treating such. an oil with; concentrated sulfuric acid contain.- ing alkyl sulfuric acids corresponding to the gaseous olefins ofstill gas resulting; from the cracking of hydrocarbon. oils.
5. In the purification of petroleum oils, the process which comprises subjecting said oils produced during a cracking step'to the action of mixed alkyl hydrogen sulfates resulting from the reaction of still gases and sulfuric acid, the said still gasesv being produced during said cracking step.
In testimony whereof,.we have hereunto affixed our signatures at Pittsburgh, Pennsylvania, this 5th day of April, 1928..
BENJAMIN L. SOUTHER- JOHN GREENE..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US268369A US1854866A (en) | 1928-04-07 | 1928-04-07 | Purifying petroleum oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US268369A US1854866A (en) | 1928-04-07 | 1928-04-07 | Purifying petroleum oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1854866A true US1854866A (en) | 1932-04-19 |
Family
ID=23022686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US268369A Expired - Lifetime US1854866A (en) | 1928-04-07 | 1928-04-07 | Purifying petroleum oils |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1854866A (en) |
-
1928
- 1928-04-07 US US268369A patent/US1854866A/en not_active Expired - Lifetime
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