US2036973A - Method of preparing valuable hydrocarbon products from acid sludge - Google Patents
Method of preparing valuable hydrocarbon products from acid sludge Download PDFInfo
- Publication number
- US2036973A US2036973A US457672A US45767230A US2036973A US 2036973 A US2036973 A US 2036973A US 457672 A US457672 A US 457672A US 45767230 A US45767230 A US 45767230A US 2036973 A US2036973 A US 2036973A
- Authority
- US
- United States
- Prior art keywords
- sludge
- oil
- acid
- treatment
- hydrocarbon products
- 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
- 239000010802 sludge Substances 0.000 title description 21
- 239000002253 acid Substances 0.000 title description 13
- 238000000034 method Methods 0.000 title description 8
- 229930195733 hydrocarbon Natural products 0.000 title description 3
- 150000002430 hydrocarbons Chemical class 0.000 title description 3
- 239000004215 Carbon black (E152) Substances 0.000 title description 2
- 239000003921 oil Substances 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000011282 treatment Methods 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229940015607 hydro 40 Drugs 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000011345 viscous material Substances 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
- C10G17/10—Recovery of used refining agents
Definitions
- This invention relates to a method of refining under whichPennsylvania oils have a coefiicient petroleum hydrocarbons and it pertains particof 100). lilarly to the production of high viscosity oil and he hydrogenation of acid sludge residue. NPA color Many petroleum oils (mixed base oils) contain 1 t 2? %1 ggl c l lg g gfb visttiify llx asphaltic, naphthenic, and/or unsaturated compounds which may be hydrogenated to increase their value.
- the oil layer from the above treatment is finwhereby the sludge may be hydrogenated with a ished in the conventional manner; mahogany minimum amount of hydrogen and without inacids are extracted, and the oil is separated from jury to the catalyst. wax and preferably contacted with adsorbent clay
- I treat a mixed base petroleum at high temperatures to yield a high viscosity luwith sulfuric acid and I separate the resulting bricating oil.
- the sludge from the above treatment is heated from the oil layer and obtain therefrom a high in an open vessel, pipe still, and/or any other 35 viscosity lubricating oil.
- lVlid-Continent crude oil may be heated in cosity together with lighter oil products.
- the hydrogenation may be carried out in any cordance with conventional practice, and/ or it conventional apparatus by the use of any convenmay be reduced with steam so that cracking is tional catalyst. It should be noted that the comprevented.
- the residue, which may be replete removal of sulfur and sulfuric acid by heat quizd crude, is then treated with strong sulfuric treatment prevents the sulfuric acid or acid comacid.
- This treatment comprises agitating the oil pounds from injuring the catalyst in the hydro- 40 with acid (about 93%), using about one-half genation step and it should also be noted that I pound of acid per gallon of reduced crude.
- the remove a large amount of sulfur in oxide form oil is then allowed to settle, the sludge is withwhich would otherwise require hydrogen for condrawn, and the oil is given another treatment, verting it into hydrogen-sulfide.
- By removing the number of treatments or dumps of acid sulfur in oxidized formI effect a marked economy used depending upon the nature of the reduced in the consumption of hydrogen. 7 crude and the desired characteristics of the fin- Wherever herein reference is made to the use ished oil.
- the method of preparing valuable hydrocarbon products from acid sludges formed in the treatment of petroleum with sulphuric acid which comprises heating the sludge to a temperature between 400 and 500 F. whereby sulphur and sulphuric acid compounds are largely removed from the sludge without substantial formation of coke, and then subjecting the heated sludge to treatment with hydrogen in the presence of catalytic,
- the method of obtaining large yields of valuable lubricating oil from mixed base petroleums which comprises treating the petroleum with about one-half pound of concentrated sulfuric acid per gallon of petroleum whereby an oil layer and sludge are produced, recovering the oil layer from the sludge, heating the sludge to'a temperature between 400 F. and 500 F. whereby sulfur and sulfuric acid compounds are removed therefrom without substantial formation of coke, and then subjecting the heated sludge to treatment with hydrogen in the presence of catalytic materials to hydrogenate asphaltic, naphthenic and unsatarately withdrawing and recovering the oil layers after each treatment and finishing them to a high quality lubricating oil, heating the sludge to a temperature between 400 F. and 500 F.
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. 7, 1936 UNITED STATES- PATENT OFFICE:
METHOD OF PREPARING VALUABLE HY- DROCARBON PRODUCT FROM ACID SLUDGE 1 Frederick W. Sullivan, Jr flammond, Ind., as-
signor' to Standard Oil Company (Indiana), Chicago, 111., a corporation of Indiana No Drawing. Application May30, 1930,
Serial No. 457,672
3 Claims. ,(o1.196-14s) This invention relates to a method of refining under whichPennsylvania oils have a coefiicient petroleum hydrocarbons and it pertains particof 100). lilarly to the production of high viscosity oil and he hydrogenation of acid sludge residue. NPA color Many petroleum oils (mixed base oils) contain 1 t 2? %1 ggl c l lg g gfb visttiify llx asphaltic, naphthenic, and/or unsaturated compounds which may be hydrogenated to increase their value. However, high viscosity lubricating $1 2 2 +3% oils cannot be satisfactorily produced by hydro- 82 genation because heavy oils tend to crack at hydrogenation temperatures. The object of my in- A great improvement in the final quality with vention is to obtain high viscosity oils from peheavy acid treatment will be noted, but due to troleum and at the same time to hydrogenate at excessive sludge loss such treatment has not preleastaportion of the asphaltic,naphthenic and/or viously been economically feasible. The present unsaturated hydrocarbons. process, by the recovery of valuable products from A further object is to provide a simple process the sludge, makes such heavy acid treatment posfor removing sulfur, sulfuric acid and related comsible. pounds, such as sulfonic acids, sulfuric esters, etc. The oil layer from the above treatment is finwhereby the sludge may be hydrogenated with a ished in the conventional manner; mahogany minimum amount of hydrogen and without inacids are extracted, and the oil is separated from jury to the catalyst. wax and preferably contacted with adsorbent clay In my process I treat a mixed base petroleum at high temperatures to yield a high viscosity luwith sulfuric acid and I separate the resulting bricating oil. oil layer from the acid sludge. I finish the oil The sludge from the above treatment is heated from the oil layer and obtain therefrom a high in an open vessel, pipe still, and/or any other 35 viscosity lubricating oil. I heat the acid sludge means to a temperature of about 400 or 500 F. to remove the water, sulfur, sulfuric acid and This heat treatment decomposes sulfonic acid, sulfuric acid compounds, the sulfur being removed sulfuric acid and sulfuric esters. The sulfur is in oxidized form. Finally, I hydrogenate the visremoved in the form of sulfur dioxide, and the cous material which has been produced from the water is removed as steam. The resulting prodacid sludge. The invention will be more clearly net is a viscous substance of complex molecular understood from the following description of a structure. By hydrogenatingthis substance I preferred embodiment. may obtain lubricating oils of relatively high vis- A lVlid-Continent crude oil may be heated in cosity together with lighter oil products. a conventional pipe still and fractionated in 2.0- The hydrogenation may be carried out in any cordance with conventional practice, and/ or it conventional apparatus by the use of any convenmay be reduced with steam so that cracking is tional catalyst. It should be noted that the comprevented. The residue, which may be replete removal of sulfur and sulfuric acid by heat duced crude, is then treated with strong sulfuric treatment prevents the sulfuric acid or acid comacid. This treatment comprises agitating the oil pounds from injuring the catalyst in the hydro- 40 with acid (about 93%), using about one-half genation step and it should also be noted that I pound of acid per gallon of reduced crude. The remove a large amount of sulfur in oxide form oil is then allowed to settle, the sludge is withwhich would otherwise require hydrogen for condrawn, and the oil is given another treatment, verting it into hydrogen-sulfide. By removing the number of treatments or dumps of acid sulfur in oxidized formI effect a marked economy used depending upon the nature of the reduced in the consumption of hydrogen. 7 crude and the desired characteristics of the fin- Wherever herein reference is made to the use ished oil. of some given amount of 100% acid, it is un- The effect of such successive treatments on the derstood to be not specifically limited to the use properties of the final lubricant made from a low of acid of that particular concentration, but to grade lubricating stock is shown in the following refer to the use of an amount of acid of some table. (This refers to a stock corresponding apconvenient concentration equivalent in amount proximately with S. A. E. grade 20. The figures to the stated amount of 100% sulfuric acid. given under Temperature Viscosity Index are Iclaim: the viscosity index according to Dean and Davis, 1. The method of preparing valuable hydrocarbon products from acid sludges formed in the treatment of petroleum with sulphuric acid, which comprises heating the sludge to a temperature between 400 and 500 F. whereby sulphur and sulphuric acid compounds are largely removed from the sludge without substantial formation of coke, and then subjecting the heated sludge to treatment with hydrogen in the presence of catalytic,
materials to produce viscous lubricating oil and lighter oil products therefrom.
2. The method of obtaining large yields of valuable lubricating oil from mixed base petroleums which comprises treating the petroleum with about one-half pound of concentrated sulfuric acid per gallon of petroleum whereby an oil layer and sludge are produced, recovering the oil layer from the sludge, heating the sludge to'a temperature between 400 F. and 500 F. whereby sulfur and sulfuric acid compounds are removed therefrom without substantial formation of coke, and then subjecting the heated sludge to treatment with hydrogen in the presence of catalytic materials to hydrogenate asphaltic, naphthenic and unsatarately withdrawing and recovering the oil layers after each treatment and finishing them to a high quality lubricating oil, heating the sludge to a temperature between 400 F. and 500 F. whereby sulfur and sulfuric acid compounds are removed therefrom as oxygen compounds of sulfur without substantial formation of coke, then subjecting the heated sludge to treatment with hydrogen in the presence of catalytic materials to produce a hydrogenated viscous lubricating oil and blending the oil initially separated from the sludge with the hydrogenated oil;
FREDERICK W. SULLIVAN, JR.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US457672A US2036973A (en) | 1930-05-30 | 1930-05-30 | Method of preparing valuable hydrocarbon products from acid sludge |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US457672A US2036973A (en) | 1930-05-30 | 1930-05-30 | Method of preparing valuable hydrocarbon products from acid sludge |
Publications (1)
Publication Number | Publication Date |
---|---|
US2036973A true US2036973A (en) | 1936-04-07 |
Family
ID=23817681
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US457672A Expired - Lifetime US2036973A (en) | 1930-05-30 | 1930-05-30 | Method of preparing valuable hydrocarbon products from acid sludge |
Country Status (1)
Country | Link |
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US (1) | US2036973A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4110196A (en) * | 1976-12-10 | 1978-08-29 | Exxon Research & Engineering Co. | Conversion of sulfonic acids into a hydrocarbon oil of superior oxidation stability |
US4188500A (en) * | 1976-12-10 | 1980-02-12 | Exxon Research & Engineering Co. | Conversion of sulfonic acids into a hydrocarbon oil of superior oxidation stability |
US4618735A (en) * | 1983-09-13 | 1986-10-21 | Canadian Patents And Development Limited | Process and apparatus for the conversion of sludges |
-
1930
- 1930-05-30 US US457672A patent/US2036973A/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4110196A (en) * | 1976-12-10 | 1978-08-29 | Exxon Research & Engineering Co. | Conversion of sulfonic acids into a hydrocarbon oil of superior oxidation stability |
US4188500A (en) * | 1976-12-10 | 1980-02-12 | Exxon Research & Engineering Co. | Conversion of sulfonic acids into a hydrocarbon oil of superior oxidation stability |
US4618735A (en) * | 1983-09-13 | 1986-10-21 | Canadian Patents And Development Limited | Process and apparatus for the conversion of sludges |
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