US2106234A - Process for solvent extraction of oils - Google Patents

Process for solvent extraction of oils Download PDF

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US2106234A
US2106234A US711963A US71196334A US2106234A US 2106234 A US2106234 A US 2106234A US 711963 A US711963 A US 711963A US 71196334 A US71196334 A US 71196334A US 2106234 A US2106234 A US 2106234A
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solvent
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extract phase
extract
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US711963A
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Ulric B Bray
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Union Oil Company of California
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Union Oil Company of California
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G21/00Refining of hydrocarbon oils in the absence of hydrogen, by extraction with selective solvents
    • C10G21/02Refining of hydrocarbon oils in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately

Description

Y Jan. 25, 1938.
U. B. BRAY PROCESS FOR SOLVENT EXTRACTIONl OF OILS Filed Feb. 19, 1954 -I INVENTOR Zinc B Br'ay ATTORNEY.
Patented Jan. 25,` i938 @its Prem# ortica PROCESS FOR SOLEEIT EXTRACTION 0F Unic' n. Bray, rains verses Estates, Calif., as-
slgnor to Union Oil Company of California, Los Angeles, Calif., a corporation of California Application February 19, 1934, semi No. 111,963
Claims.
' by the use of solvents which selectively dissolve the undesirable hydrocarbons but which exhibit only a very limited solvent power upon the desirable paraflinic hydrocarbons.
When I use the term paramnic hydrocarbons I mean those highly saturated compounds which are present in petroleum and are characterized bya low temperature viscosity susceptibility, i. e., they exhibit a minimum 'change in viscosity for a. given change in temperature. They also are characterized by relative stability to air and sunlight, exhibiting little tendency toward discoloration or sludge formation. This denition is not meant to include those compounds which are usuallysolid or semi-solid at ordinary temperatures and which are known as "wax or petrolatum; but, of course, it is obvious that my invention is meant to also include the selective extraction of waxy oils. As a matter of convenience hereafter, I will refer to the undesirable components, such as oleiinic, naphthenic and/or aromatic hydrocarbons, as the non-parafnic components of petroleum. These fractions are characterized by a relatively high temperature viscosity susceptibility and are relatively un-l vstable to air and sunlight,` exhibiting discoloration and sludge formation` 'A number of selective solvents for extraction have been found; for example, it has been shown that such materials as aniline, chloraniline, nitrobenzene, dichlorethyl ether, phenol, chlorophenol, cresol and cresol with a small proportion` of water, for instance 4%, are highly selective as solvents for the non-paraiiinic hydrocarbons. When these solvents are commingled with petroleum or petroleum fractions under the proper conditions of temperature, the-undesirable nonparainic hydrocarbons passinto solution to a greater or less extent but a substantial propor'- of the container and forms an extract phase when relatively heavy"solvents are employed. The` relatively light paraiiinic hydrocarbons rise to the top of the vessel and form a ramnate phase.
These phases are then readily separable by ordinary decantation means. The rainate phase isv usually found to contain a smallquantity of the selective solvent and the extract phase ordinarily contains a relatively large quantity of the sola vent. These fractions may be puried by distil- 5A lation whereby the solvent is distilled away from the hydrocarbon oils. A
In the usual solvent extraction of mineral oil with the above mentioned selective solvents, the separation is not complete. Particularly, all .of the parainic hydrocarbons, i. e. the more valuable lubricants, are not obtained inthe raflinate phase but instead,some of the high grade parafflnic oil fractions are found in the extract phase. Also, the extract phase may contain kcertain fractions of oil characterized by properties intermeldiate low and high grade. lThese fractions arel not desired in the nal rafllnate but are valuable as second grade oils when separated from. the fractions of low quality.
-It has been known in the solvent a 20 extraction art kthat after making a primary separationof rafli- 'natefromjextract, additional fractions can be made to separate from the extract phase by one or more'reductions of temperature which correspondingly reduce the solubility of these oils of relatively high parainicity in the extract phase. These oils `then form intermediate -rainates which can be separately recovered by decantation from the remaining extract phase. The solubility of oils of relatively high paralniclty in the extract phase can also be reduced by the addition of an anti-solvent thereto, the presence of which causes a phase-separation between anintermediate raiiin'ate and remaining extract phase. This intermediate rainate 'comprises second grade oil of quality'superior -to the oil remaining dissolved in the extract phase. V
An anti-solvent maybe Ydefined/.as a"`iate'rlalwhich tends to prevent the solution of a hydro- 40 carbon fraction which, except for the presence of the anti-solvent, would be dissolved in the extract phase upon extraction of the oilwith a selective solvent. A number vof substances are suitable for use as an anti-solvent; for instance liquid normally gaseous hydrocarbons such as liquid ethane, propane or butane, or methyl, ethyl or isopropyl -alco ols, methyl cellosolve (monomethyl ether o! ethylene glycol) and other oxygenated compounds such as acetone or methyl 50 acetate. Evenrwater Vmay-be used as an antisolvent .when the -selective solvent with which it is employed vis at least partly soluble therein. AOne vor more of these anti-solvents may be employed.
vlu
Some cases, the addition of an anti-solvent lil to the extract phase renders temperature reduction unnecessary to separate relatively high quality oil fractions therefrom. In other cases, refrigeration of the extract phase will be necessary but will be less than when no anti-solvent is present. In a solvent extraction process of this character, the expense of refrigeration is la substantial item in the cost of operation. My process lowers this cost. y
Under certain conditions, the anti-solvent which may be' employed may be a substance which is a selective solvent when employed alone. For instance, there may be mixed with the extract phase to function as an anti-solvent a; selective solvent having less solvent power for thehigher grade material present therein than the solvent power of the'selective solvent originally used to produce the extract. As an example, oil may be treated with chloraniline or a mixture of liquid sulphur dioxideand benzene to obtain an extract phase. These solvents are characterized by high solvent power for higher grade material. To the extract phase thus produced there may be added liquid sulphur dioxide or other solvent having relatively less solvent power for the higher grade material. For this reason and under these conditons, certain selective solvents may be employed as anti-solvents and by their presence in the extract phase the higher grade fractions therein are rejected to form an intermediate railinate.
I have found that when the anti-solvent employed is a liquid, normally gaseous substance such as liquid propane, butane, sulphur dioxide or the like, the rejection of desirable oils from the extract phase by the presence 'of said antisolvent is aidedewhen the pressure is sutliciently reduced in the rejection stage to cause evaporation of a portion. of the anti-solvent, thereby reducing the temperature of the mixture of the extract phase and anti-solvent remaining liquid. In this case the liquid, normally gaseous material, for instance ethane, propane, butane or similar substances, not'only functions as an antisolvent to remove the relatively high grade fractions from the extract phase but also operates as an internal refrigerant. After evaporation for internal refrigeration, sufficient amounts of said liquid, normally gaseous material should remain associated in the liquid phase with the extract to function as'an anti-solvent.
It is an object of my invention to separate anoil by means of a selective solvent into a raflinate phase and an extract'phase and to intermix saicl It is another object of my invention to recover an intermediate rafiinate from said extract by mixing the extract phase with a liquid, normally gaseous anti-solvent and employing said antisolvent as an internal refrigerant to aid in reducing the temperature of the extract phase to prcmote the separation of the intermediate raflina e.
The refrigeration of the extract phase for rc- Jection of intermediate raiiinate can also be omitted or reduced in degreeby removing a considerable portion of the selective solvent from the extract phase before treating the extract phase with a`n anti-solvent at the temperature appropriate for separation of the relatively paraflinic fractions. In addition to the effect of the antisolvent, the solubility of the relatively valuable parainic fractions in the extract is reduced by the lpresence of a lower proportion of selective solvent. In some cases; unless the proportion of solvent in the extract phase is reduced, excessively large amounts of anti-solvent must be added to cause phase separation of the extract phase `and rejection vof an intermediate rafllnate.
Therefore, it is another object of my invention to separate an oil by means of a. selective solvent into a raffinate and an extract, remove a portion of the selective solvent from the extract phase and then intermix said extract with an anti-solvent to separate an intermediate raftlnatefrom the extract phase.
The gure is a schematic arrangement of one form of apparatuswhich may be employed to carry out my process.
Referring to the figure, oil enters the system via line I0 controlled by valve II by action of pump I2 and passes into primary extractor I3, wherein it is countercurrently extracted with selective solvent introduced through line I4 controlled by valve I5 by action of pump I6. Raflinate phase from extractor I3 is removed via line I 1 and valve I8 and passes through coil 2,0 in heater 2l prior to entrance into secondary extractor 23 via line 23. Countercurrent extraction isagain accomplished in 23 by selective solvent introduced through line 25 controlled by valve 26 by action of pump 2l.
passes through coil 32 in heater 33 and line 34 connected with vapor separator 35. Its temperature is raised suiciently in 32 to vaporize in 35 the selective solvent associated therewith and these vapors are removed through line 36 controlled by valve 31. High grade rainate exits via line 38 and valve 39. Intermediate extract phase is removed from secondary extractor 23 through line 40 controlled by valve 4I by action of pump 42. 1
When the same solvent or a different solvent of substantially the same or lower solvent power is employed in both extractors I3 and 23, the raflinate from the primary extractor is preferably heated before extraction in the secondary extractor in order to increase the amount of intermediate extract produced yin the secondary extractor. When the solvent employed in 23 has greater. solvent power than the solvent used in I3, heater V2i may be omitted in some cases.
Extract phase from primary extractor I3 passes Rafiinate phase issues from` extractor23 through 30 controlled by valve 3| and.
through line 45 controlled by valve 46. When it is desired to lower the proportion of selective solvent in theextract phase prior to the addition of the anti-solvent thereto, valve 41 inline 45 may be entirely closed in order to by-pass the stream of extract phase via line 48 and valve 49.
In this event, the extract phase. flows through amount of selective solvent therefrom in 55.
These vapors pass from the system via line 56,
controlled by valve 51. The extract phase containing the desired proportion of selective sol-.
vent passes from vaporizer 55 through line 60 controlled by valve 6| by action of pump 62. It then passes through coil 63 in heat exchange relationship with coil 50. The material then iiows through line 64 and valve 65. The temperature f the extract phase may be further lowered by v the desired proportion of solvent. In some cases it may not be necessary to lower theiproportion of solvent to oil in the extract phase passing from extractor I3 via line 45 before the addition of the anti-solvena In that event valves 49 and 65 are closed and valve 41 remains open.
Anti-solvent is introduced into the stream 0f extract owing through line 45 by line 10 con.-
trolled by valve 1| by action of pump 12. The" combined vstream passes into oriice mixer 13` Where thorough agitation occurs, after which it passesinto cooler 15 via line 14. Cooling may be accomplished by any desired means such as by external refrigeration but when liquid, normally gaseous anti-solvent is employed I prefer to employ internal refrigeration. That is, the pressure is suiciently reduced in cooler 15 to vaporize a portion oi the anti-solvent with consequent cooling of the remaining liquid. The vaporized portion of the -anti-solventexits from cooler 15 through line 16 controlled by valve 11. The extract phase and anti-solvent are sufciently cooled in 15 to cause phase separation in separator 80 to which the chilled mixture passes by -solvent and the selective solvent.
action of pump 8| through line 82 controlled by valve 83. Extract phase from. passes through line-84 controlled by valve 85, through heater 86 and line 81 into vapor separator 88. The stream is suiciently heated in 86 to vaporize theanti- These vapors pass through exit line 89 controlled by valve 90. 'Ihe low grade extract oil is removed through line 9| controlled by valve 92.
Rafnate phase rejected in separatorv 80 passes through line 93controlled by valve 94 through heater 95 and line 96 into vapor separator 91. Suicient heat is imparted in 95 to vaporize the anti-solvent and any selective solvent associated with the intermediate grade rainate. These vavalve 99. In some cases it is desired to heat sufiiciently to remove only the anti-solvent from the oil and solvent in vapor separator 91. Th'e intermediate grade raiiinate exits from 91 through line |00 controlled by valve |0| by action of pump |02.
'Although theintermediate grade raffinate iowing through line V|00 and the intermediate grade extract produced in secondary extractor 23 may be separately recovered and separately distilled to obtain nal products within the desired boiling point range, I prefer to intermix these streams flowing through lines |00 and 40. This combined stream .is heated' in -heater |05 prior to passage into fractionating tower |06 via line |01. Fractionating tower |06 may be provided with the usual traysI |08 and other usual appurtenances.
Vapors exit from fractionating tower |06 via line |09 controlled by valve ||0. vResidual-oil passes from the tower through line controlled by valve ||2. Intermediate side cut distillates can be taken from tower |06 by lines ||3 and |4 controlled by valves ||5 and ||6 respectively. Fractionation in |06 may be accomplished under vacuum and/or with steam injection as desired.
As an example of the operation of the apparatus disclosed in the gure, a dewaxed Santa Fe Springs lubricating distillate characterized by' A. P. I. gravity at 60 F. of 19.8, carbon residue of 0.24%, acid number of'0.16 and viscosity gravity constant. of 0.874 was extracted in extractor |3 with 175 volume percent. Ichloraniline at n45 F. The raffinate thus produced was heated in.
, acid number of 0.04 and viscosity gravity constant Sucient extract phase passing from extractor I3 Wasbypassed via line 48 through heater 52 and vapor separator 55'so that upon re-uniting with the stream passing through valve 41 the combined stream comprised 70 volume percent.
chloraniline based on the original charge of oil. To this stream was added volume percent. liquid propane as an anti-solvent. Sufcient propane was vaporized in cooler 15 to reduce the temperature of the mixture to 40 F. at which phase separation occurred. Extract removed via line 9| had an A. P. I. gravity at 60 F. ofv'1.3. Rejected intermediate ranate freed of propane and chloraniline passing through line |00 had an A. P. I. gravity at 60 F. of 21.9 carbon residue of 0.16%, acid number of 0.04 and viscosity gravity constant of 0.857; In one modified operation, only the propane was vaporized from the intermediate rejected rainate in 91 and the unvafporized residue in line |00 was combinedwith the intermediate extract passing through line 90. The mixture was4 distilled under vacuum into separate cuts of desired boiling point range in heater |05 and fractionating tower |06.
As a further modification of my process, ex tractor 23 may be omitted in some cases, all ofthe extraction` taking place in I3. In -this event, heater 2| is employed to distill the selective solvent from 'the raflinate passing through line |1.-
It will be understood that the foregoing is merelyillustrative of certain embodiments of my invention and that many modifications may be. made therein without departing from the spirit of my invention. s
I claim:
fili4 1. A process for the separation of parafinic' and non-paralnic fractions from mineral oil containing thesame which'comprises extracting said oil with a selective solvent, separating the extract I phase soluble in said solvent from the rainate phase insoluble therein, reducing the selective solvent'content of said extract phase, then commingling said extract phase with an anti-solvent and separating from said extract phase an intermediate raiiinate` rendered insoluble in said extract phase by said anti-solvent said intermediate raffinate containing the bulk of said anti-solvent.
2. A process for the separation'of paraiinic and non-paraffinic' fractions from mineral oil containing thesame which comprises extracting said oil with a selective solvent, Aseparating vthe extract phase soluble in said solvent from the raiiinate phase insoluble therein, reducing the selective solvent content of said extract phase,then
commingling said extract phase with an anti-solvent, cooling said extract phase, and separating from said extract phase an intermediate raffinate n portion of said anti-solvent, cooling said extract .phase by internal refrigeration and separating from said extract phase an intermediate raiiinate rendered insoluble in said extractphase by said` anti-solvent said intermediate raflinate containing the bulk of said anti-solvent.
, 4. A process for the separation of paraiilnic and non-paraiiinic fractions from mineral oil containing the same which comprises extracting said` oil with a selective solvent,v separating the extract phase soluble in saidisolvent from the rafnnate phase insoluble therein, commingling said extract phase with a liquid, normally gaseous anti-solvent, vaporizing a portion of said antisolvent, cooling said extract phase by internal refrigeration and l separating from said extract phase an intermediate raiilnate Vrendered insoluble in sai'd extract phase by said anti-solvent said intermediate raiilnate containing the bulk of said anti-solvent.
5. A process for the separation of parafilnic and vnon-paraiiinic fractions from mineral oil containing the same which comprises extracting said oil with a selective solvent, separating the extract phase soluble in said solvent from the raillnate phase insoluble therein, heating a portion of said extract phase to 4vaporize solvent, removing said vapors frcm said heated portion, intermixing the unheated portion of said extract phase with the heated portion, commingling said extract phase with an anti-solvent and separating from said extract phase an intermediate raffinate rendered insoluble in said extract phase by said anti-solvent said intermediate ramnate containing the bulk of said anti-solvent.
marc B'. BRAY
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE747938C (en) * 1938-05-21 1944-10-20 Process for the production of deep stock diesel oils
US2550058A (en) * 1948-07-15 1951-04-24 Texaco Development Corp Production of oil-free wax and dewaxed oil from wax-bearing lubricating oil stock with a dewaxing solvent liquid
US2572583A (en) * 1948-12-21 1951-10-23 Phillips Petroleum Co Improved liquid-liquid contacting process using di(beta-cyanoethyl)-amine
US2587375A (en) * 1945-05-17 1952-02-26 William R Paulsen Atmospheric pressure regulator
US2667446A (en) * 1950-09-25 1954-01-26 Phillips Petroleum Co Manufacture of high octane gasoline
US2671753A (en) * 1950-10-19 1954-03-09 Standard Oil Dev Co Recovery of oxidation inhibitors
US2721164A (en) * 1950-12-22 1955-10-18 Exxon Research Engineering Co Ammonia extraction process
US2739925A (en) * 1951-10-24 1956-03-27 Standard Oil Co Refining of hydrocarbon distillates
US2754249A (en) * 1953-06-29 1956-07-10 Socony Mobil Oil Co Inc Solvent treatment of hydrocarbon mixtures
US3041268A (en) * 1959-12-23 1962-06-26 Shell Oil Co Solvent fractionation of wax containing mixtures
US4304660A (en) * 1980-04-14 1981-12-08 Texaco Inc. Manufacture of refrigeration oils
US4311583A (en) * 1980-02-27 1982-01-19 Texaco, Inc. Solvent extraction process

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE747938C (en) * 1938-05-21 1944-10-20 Process for the production of deep stock diesel oils
US2587375A (en) * 1945-05-17 1952-02-26 William R Paulsen Atmospheric pressure regulator
US2550058A (en) * 1948-07-15 1951-04-24 Texaco Development Corp Production of oil-free wax and dewaxed oil from wax-bearing lubricating oil stock with a dewaxing solvent liquid
US2572583A (en) * 1948-12-21 1951-10-23 Phillips Petroleum Co Improved liquid-liquid contacting process using di(beta-cyanoethyl)-amine
US2667446A (en) * 1950-09-25 1954-01-26 Phillips Petroleum Co Manufacture of high octane gasoline
US2671753A (en) * 1950-10-19 1954-03-09 Standard Oil Dev Co Recovery of oxidation inhibitors
US2721164A (en) * 1950-12-22 1955-10-18 Exxon Research Engineering Co Ammonia extraction process
US2739925A (en) * 1951-10-24 1956-03-27 Standard Oil Co Refining of hydrocarbon distillates
US2754249A (en) * 1953-06-29 1956-07-10 Socony Mobil Oil Co Inc Solvent treatment of hydrocarbon mixtures
US3041268A (en) * 1959-12-23 1962-06-26 Shell Oil Co Solvent fractionation of wax containing mixtures
US4311583A (en) * 1980-02-27 1982-01-19 Texaco, Inc. Solvent extraction process
US4304660A (en) * 1980-04-14 1981-12-08 Texaco Inc. Manufacture of refrigeration oils
DE3107363A1 (en) * 1980-04-14 1982-01-07 Texaco Development Corp., 10650 White Plains, N.Y. "METHOD FOR PRODUCING REFRIGERATING MACHINE OILS"

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