US2267458A - Treatment of hydrocarbons - Google Patents
Treatment of hydrocarbons Download PDFInfo
- Publication number
- US2267458A US2267458A US225555A US22555538A US2267458A US 2267458 A US2267458 A US 2267458A US 225555 A US225555 A US 225555A US 22555538 A US22555538 A US 22555538A US 2267458 A US2267458 A US 2267458A
- Authority
- US
- United States
- Prior art keywords
- acid
- treatment
- alkylation
- hydrocarbons
- sulfuric acid
- 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
- 229930195733 hydrocarbon Natural products 0.000 title description 17
- 150000002430 hydrocarbons Chemical class 0.000 title description 14
- 239000002253 acid Substances 0.000 description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 239000003921 oil Substances 0.000 description 16
- 230000029936 alkylation Effects 0.000 description 14
- 238000005804 alkylation reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000007670 refining Methods 0.000 description 9
- 239000010802 sludge Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- -1 olefin hydrocarbons Chemical class 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C10G17/06—Liquid-liquid treatment forming two immiscible phases using acids derived from sulfur or acid sludge thereof
Definitions
- This invention relates to the refining of hydrocarbon oils by acid treatment and-has to do particularly with the utilization of a used orspent acid, formed by previously alkylating isoparafiin hydrocarbons with olefin hydrocarbons in the presence of sulfuric acid, as the acid treating reagent.
- the spent acid comprises mainly sulfuric acid and organic carbon containing materials, prin cipally as hydrocarbon compoundsyand differs from ordinary Sludge'acid obtained from the acid treatment ofhydrocarbon oils in that the water content is ve'ry'l'ow.
- the organic carbon" containing materials may run from 1 to and usually about 4 to 10%; While the acid is no longer effective as an alkylation catalyst, has been found that the acid can'be usedadvantageously for the acid treatment of, hydrocarbon oils to refine the oil by removing undesir-- able constituents therefrom, such as gums, resins, sulfur compounds and the like.
- oils that may be treated according to the invention are any hydrocarbon oilsordinarily subjected to refining by acid treatment. It is intended that petroleum oils, such as distillates, including lubricating oil, kerosene and naphtha or gasoline may be used.
- the invention is particularly applicable to the treatment of cracked distillates or cracked gasoline wherein the distillate is ordinarily givenan acid dosage of about 3 to 5 pounds and the acid treated oil, after the separation of the acid sludge, neutralized and rerun by steam distillation.
- the amount of used acid required for acid treatment is ordinarily in the same proportion by weight as that used in the case of new acid.
- spent acid in an amount equivalent to new acid on a percentage acidity basis; or the spent acid may be fortified with a stronger acid, such as 98% acid, or fuming acid to bring the acidity up to the equivalent of new acid and then a dosage, equivalent by weight to that usedin the treatment with the new acid, used.
- a stronger acid such as 98% acid, or fuming acid
- a cracked naphtha having an initial boiling point of 113 F. and an end point of 402 F. was treated with the used acid.
- the results obtained, as compared with those fromtreating the same naphtha without any acid and with fresh acid are shown in the following table. The.
- oils in each case were neutralized, steam distilled and sweetened.
- the spent acid from the acid treating operation may be run to the acid recovery plant wherein it is restored to desired concentration and reused inthe alkylation operation.
- the use of the spent alkylation acid in the refining of oils by-acid treatment may produce a refined oil of improved properties, such as color. sulfur and gum content, and less sludge formation and acid treating loss, as compared to ventional methods of acid treatment employed. normal acid treatingoperations.
- a process for refining hydrocarbon oils containing objectionable sulfur, color and gumforming compounds which comprises subjecting the oil to treatment with used sulfuric acid, which has been obtained from the alkylation of isoparaffins with olefins in the presence of strong sulfuric acid, whereby such objectionable compounds are substantially removed.
- a process for the refining of hydrocarbon distillates containing undesirable sulfur, color and gum-forming compounds whichcomprises treating the distillate with used sulfuric acid, which has been obtained from an alkylation operation wherein isoparafflns are alkylated with olefin hydrocarbons in the presence of strong sulfuric acid as a catalyst, whereby such undesirable compounds are substantially removed.
- a process for the refining of light petroleum distillates to remove sulfur, color and gumforming compounds which comprises contacting the distillate with used sulfuric acid, which has been obtained by alkylating low boiling isoparaffins with olefins in the presence of strong sulfuric acid as the catalyst, said used acid containing about 1 to 20% of organic material soluble therein, and separating the acid sludge from the treated distillate.
- a process for the refining of cracked hydrocarbon distillates to remove sulfur, color and gum-forming compounds which comprises contacting the distillate with used sulfuric acid, which has been formed in the alkylation of low boiling isoparaflins with olefins in the presence of strong sulfuric acid as a catalyst, said used acid consisting essentially of sulfuric acid and organic material soluble therein, and separating the acid sludge from the treated'oil.
- a process which comprises subjecting an alkylation acid containing organic material soluble therein for the acid treatment of petroleum distillates to remove color and gum-forming compounds therefrom.
- a process which comprises alkylating low boiling isoparaflins with normally gaseous olefins and polymers thereof in the presence of strong sulfuric acid, whereby saturated high antiknock gasoline hydrocarbons are formed, separating the used acid containing organic material soluble therein from the reaction products, treating a petroleum distillate with said used acid containing said soluble organic material to refine the distillate by removing sulfur, color and gumforming compounds therefrom, separating a sludge acid from the last mentioned treating operation, recovering a strong sulfuric acid of alkylation strength from said sludge acid and returning the recovered acid to the alkylation operation.
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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
Dec. 23; 1941. A. R. GOLDSBY 2,267,458
TREATMENT OF HYDROCARBONS Filed Aug. 18, 1958 HY DROCARBON CHARGE ACID CHARGE.
ALKYLATION .USED
ACID
HYDROC'ARBON OIL v T l ACiD I TREAT-ED on. TREATMENT T ACID RECOVERY RECOVERED ACID ARTHUR R.GOLDSBY INV TOR g, T MM &,,
ATTORNEYS Patented Dec. 23,1941
TREATMENT or nrnnocannons Arthur R. Goldsby, Beacon,N. Y., assignor, by mesne assignments, to The Texas Company, New York, N. ,Y., a corporation of Delaware Application August 18,1938, Serial No. 225,555
. 8 Claims.
This invention relates to the refining of hydrocarbon oils by acid treatment and-has to do particularly with the utilization of a used orspent acid, formed by previously alkylating isoparafiin hydrocarbons with olefin hydrocarbons in the presence of sulfuric acid, as the acid treating reagent.
In the alkylation of low boiling isoparaflins, such as isobutane and isopentane with olefins, for example normally gaseous olefins or poly- The sludge acid separated from the treating operation is subjected to conventional acid recovery methods whereby a restored acid, suitable mers thereof, in the presence of sulfuric acid to I produce branch chain saturated gasoline hydrocfabout 93% sulfuric acid, by an unsaturated carbons of-high antiknock value, the acid gradually becomes spent and ineffective as a catalyst for suchpurpose.
The spent acid comprises mainly sulfuric acid and organic carbon containing materials, prin cipally as hydrocarbon compoundsyand differs from ordinary Sludge'acid obtained from the acid treatment ofhydrocarbon oils in that the water content is ve'ry'l'ow. The organic carbon" containing materials may run from 1 to and usually about 4 to 10%; While the acid is no longer effective as an alkylation catalyst, has been found that the acid can'be usedadvantageously for the acid treatment of, hydrocarbon oils to refine the oil by removing undesir-- able constituents therefrom, such as gums, resins, sulfur compounds and the like. i
The oils that may be treated according to the invention are any hydrocarbon oilsordinarily subjected to refining by acid treatment. It is intended that petroleum oils, such as distillates, including lubricating oil, kerosene and naphtha or gasoline may be used. The invention is particularly applicable to the treatment of cracked distillates or cracked gasoline wherein the distillate is ordinarily givenan acid dosage of about 3 to 5 pounds and the acid treated oil, after the separation of the acid sludge, neutralized and rerun by steam distillation. The amount of used acid required for acid treatment is ordinarily in the same proportion by weight as that used in the case of new acid. In some cases, however, it may be desirable to use spent acid in an amount equivalent to new acid on a percentage acidity basis; or the spent acid may be fortified with a stronger acid, such as 98% acid, or fuming acid to bring the acidity up to the equivalent of new acid and then a dosage, equivalent by weight to that usedin the treatment with the new acid, used.
Any well known or preferred type of acid treating equipment may be used and the confor reuse in the alkylation operation may be obtained. 1 1 i The accompanying drawing is a flow chart showing the operation of the process.
- An example will now be given of the process.
of the invention as applied to the use of spent acid derived from an alkylation operation in which isobutane was alkylated, in the presence hydrocarbon fraction of cracking still gases containing C3 and C4 hydrocarbons, using afresh feed ratio of isobutane to olefins of about' 3zl, a
ratio by weight of acid to olefins in the feed of about 0.6:1, and a temperatureof about 65 F. The used acid 'fromthe operation analyzed as follows: Percent HzSOrby titration; 86.6 Percent H2804 (CH2), free-.. 91.1
Percent organic calculated as carbon 0.48 Percent organic calculated as (CHzhh--- 5.04 Specific gravity at 60 F 1.702
A cracked naphtha having an initial boiling point of 113 F. and an end point of 402 F. was treated with the used acid. The results obtained, as compared with those fromtreating the same naphtha without any acid and with fresh acid are shown in the following table. The.
oils in each case were neutralized, steam distilled and sweetened.
Spent The spent acid from the acid treating operation may be run to the acid recovery plant wherein it is restored to desired concentration and reused inthe alkylation operation.
The use of the spent alkylation acid in the refining of oils by-acid treatment may produce a refined oil of improved properties, such as color. sulfur and gum content, and less sludge formation and acid treating loss, as compared to ventional methods of acid treatment employed. normal acid treatingoperations.
Obviously many modifications and variations of the invention as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
I claim:
1. A process for refining hydrocarbon oils containing objectionable sulfur, color and gumforming compounds, which comprises subjecting the oil to treatment with used sulfuric acid, which has been obtained from the alkylation of isoparaffins with olefins in the presence of strong sulfuric acid, whereby such objectionable compounds are substantially removed.
2. A process for the refining of hydrocarbon distillates containing undesirable sulfur, color and gum-forming compounds, whichcomprises treating the distillate with used sulfuric acid, which has been obtained from an alkylation operation wherein isoparafflns are alkylated with olefin hydrocarbons in the presence of strong sulfuric acid as a catalyst, whereby such undesirable compounds are substantially removed.
3. A process for the refining of light petroleum distillates to remove sulfur, color and gumforming compounds which comprises contacting the distillate with used sulfuric acid, which has been obtained by alkylating low boiling isoparaffins with olefins in the presence of strong sulfuric acid as the catalyst, said used acid containing about 1 to 20% of organic material soluble therein, and separating the acid sludge from the treated distillate.
. 4. A process for the refining of cracked hydrocarbon distillates to remove sulfur, color and gum-forming compounds, which comprises contacting the distillate with used sulfuric acid, which has been formed in the alkylation of low boiling isoparaflins with olefins in the presence of strong sulfuric acid as a catalyst, said used acid consisting essentially of sulfuric acid and organic material soluble therein, and separating the acid sludge from the treated'oil.
5. A process which comprises subjecting an alkylation acid containing organic material soluble therein for the acid treatment of petroleum distillates to remove color and gum-forming compounds therefrom.
6. A process which comprises alkylating low boiling isoparaflins with normally gaseous olefins and polymers thereof in the presence of strong sulfuric acid, whereby saturated high antiknock gasoline hydrocarbons are formed, separating the used acid containing organic material soluble therein from the reaction products, treating a petroleum distillate with said used acid containing said soluble organic material to refine the distillate by removing sulfur, color and gumforming compounds therefrom, separating a sludge acid from the last mentioned treating operation, recovering a strong sulfuric acid of alkylation strength from said sludge acid and returning the recovered acid to the alkylation operation.
7. In the refining of hydrocarbon oil containing undesirable sulfur, color and gum forming compounds, the process which comprises treating the oil with preformed acid sludge, derived from an alkylation operation wherein an isoparafiin is alkylated with an olefin hydrocarbon in the presence of sulfuric acid as a catalyst, whereby such undesirable compounds are substantially removed from the oil. 1
8. In the refining of cracked naphtha containing undesirable sulfur, color and gum forming
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US225555A US2267458A (en) | 1938-08-18 | 1938-08-18 | Treatment of hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US225555A US2267458A (en) | 1938-08-18 | 1938-08-18 | Treatment of hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2267458A true US2267458A (en) | 1941-12-23 |
Family
ID=22845329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US225555A Expired - Lifetime US2267458A (en) | 1938-08-18 | 1938-08-18 | Treatment of hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2267458A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2418203A (en) * | 1946-11-14 | 1947-04-01 | Stauffer Chemical Co | Manufacture of superphosphate fertilizers |
| US2425584A (en) * | 1945-04-26 | 1947-08-12 | Standard Oil Dev Co | Conditioning sulphuric acid sludge |
| US2438445A (en) * | 1943-09-15 | 1948-03-23 | Standard Oil Dev Co | Process for the acid-treating of catalytically cracked naphtha |
| US2468329A (en) * | 1944-08-21 | 1949-04-26 | Union Oil Co | Method for treatment of soils for agricultural purposes |
| US2882225A (en) * | 1953-04-10 | 1959-04-14 | American Oil Co | Method for the production of colorstable furnace oil |
| US2906610A (en) * | 1956-01-05 | 1959-09-29 | Exxon Research Engineering Co | Recovery of alkylation acid |
| US4561969A (en) * | 1984-09-28 | 1985-12-31 | The United States Of America As Represented By The United States Department Of Energy | Method for removing chlorine compounds from hydrocarbon mixtures |
| WO2011068663A1 (en) | 2009-12-04 | 2011-06-09 | Exxonmobil Research And Engineering Company | Method for increasing color quality and stability of fuel field of the invention |
| WO2013006527A1 (en) | 2011-07-07 | 2013-01-10 | Exxonmobil Research And Engineering Company | Method for increasing thermal stability of a fuel composition using a solid phosphoric acid catalyst |
| WO2018204256A1 (en) | 2017-05-01 | 2018-11-08 | Exxonmobil Research And Engineering Company | Jet fuel treating for blending compatibility |
-
1938
- 1938-08-18 US US225555A patent/US2267458A/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2438445A (en) * | 1943-09-15 | 1948-03-23 | Standard Oil Dev Co | Process for the acid-treating of catalytically cracked naphtha |
| US2468329A (en) * | 1944-08-21 | 1949-04-26 | Union Oil Co | Method for treatment of soils for agricultural purposes |
| US2425584A (en) * | 1945-04-26 | 1947-08-12 | Standard Oil Dev Co | Conditioning sulphuric acid sludge |
| US2418203A (en) * | 1946-11-14 | 1947-04-01 | Stauffer Chemical Co | Manufacture of superphosphate fertilizers |
| US2882225A (en) * | 1953-04-10 | 1959-04-14 | American Oil Co | Method for the production of colorstable furnace oil |
| US2906610A (en) * | 1956-01-05 | 1959-09-29 | Exxon Research Engineering Co | Recovery of alkylation acid |
| US4561969A (en) * | 1984-09-28 | 1985-12-31 | The United States Of America As Represented By The United States Department Of Energy | Method for removing chlorine compounds from hydrocarbon mixtures |
| WO2011068663A1 (en) | 2009-12-04 | 2011-06-09 | Exxonmobil Research And Engineering Company | Method for increasing color quality and stability of fuel field of the invention |
| US20110131870A1 (en) * | 2009-12-04 | 2011-06-09 | Exxonmobil Research And Engineering Company | Method for increasing color quality and stability of fuel field of the invention |
| US8822742B2 (en) | 2009-12-04 | 2014-09-02 | Exxonmobil Research And Engineering Company | Method for increasing color quality and stability of fuel |
| WO2013006527A1 (en) | 2011-07-07 | 2013-01-10 | Exxonmobil Research And Engineering Company | Method for increasing thermal stability of a fuel composition using a solid phosphoric acid catalyst |
| US9028675B2 (en) | 2011-07-07 | 2015-05-12 | Exxonmobil Research And Engineering Company | Method for increasing thermal stability of a fuel composition using a solid phosphoric acid catalyst |
| WO2018204256A1 (en) | 2017-05-01 | 2018-11-08 | Exxonmobil Research And Engineering Company | Jet fuel treating for blending compatibility |
| US11118125B2 (en) | 2017-05-01 | 2021-09-14 | Exxonmobil Research And Engineering Company | Jet fuel treating for blending compatibility |
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