CA1069845A - Double solvent extraction of organic constituents from tar sands - Google Patents
Double solvent extraction of organic constituents from tar sandsInfo
- Publication number
- CA1069845A CA1069845A CA262,845A CA262845A CA1069845A CA 1069845 A CA1069845 A CA 1069845A CA 262845 A CA262845 A CA 262845A CA 1069845 A CA1069845 A CA 1069845A
- Authority
- CA
- Canada
- Prior art keywords
- sand
- methanol
- fraction
- tar
- light naphtha
- 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
Links
- 239000000470 constituent Substances 0.000 title abstract description 14
- 238000000638 solvent extraction Methods 0.000 title abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011275 tar sand Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 40
- 239000004576 sand Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002032 methanolic fraction Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims 2
- 238000000605 extraction Methods 0.000 abstract description 21
- 239000011269 tar Substances 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 13
- 239000011368 organic material Substances 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 239000012071 phase Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000284 extract Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000543381 Cliftonia monophylla Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGYGBOORGRYDGQ-UHFFFAOYSA-N benzene;methanol Chemical compound OC.C1=CC=CC=C1 KGYGBOORGRYDGQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007790 solid phase 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
Abstract
DOUBLE SOLVENT EXTRACTION OF ORGANIC CONSTITUENTS FROM
TAR SANDS
ABSTRACT OF THE DISCLOSURE
Extraction of hydrocarbons from tar sands with a light naphtha/
methanol solvent system results in rapid decrepitation of the tar-sand aggregate and separation of organic matter into three phases. Distribution of the extracted and non-extracted organic material is among the phases. The most desirable, non-polar organic materials are recovered from the light naphtha phase; more polar soluble constituents are recovered from the methanol phase; and less desirable asphaltenes separate as a precipitate.
TAR SANDS
ABSTRACT OF THE DISCLOSURE
Extraction of hydrocarbons from tar sands with a light naphtha/
methanol solvent system results in rapid decrepitation of the tar-sand aggregate and separation of organic matter into three phases. Distribution of the extracted and non-extracted organic material is among the phases. The most desirable, non-polar organic materials are recovered from the light naphtha phase; more polar soluble constituents are recovered from the methanol phase; and less desirable asphaltenes separate as a precipitate.
Description
BACKCROUND OF ~IE INVEN ~ON
FIELD OF THE INVENTION
This invention relates to a process wherein a double-solvent treatment is used for the selectlve recovery of hydrocarbons and organic materials from tar sands. The process of this invention is particularly adapted to separate such hydrocarbons and organic constituents, hereinafter referred to as organlc constituents, from aggregates in which mineral parti-cles are discrete and comprise the major portion of the naturally-occurring aggregate9 in order to recover virtually solid-free materials which may be further treated in standard refinery operations. It is to be distinguished from those trea~ment of natural asphalt ln which only coarsest particles of sand or minerals are removed~ leaving finely divided clays or other minerals in the extract. The process is also to be distinguished from treatments for the recovery of oil from consolidated materials, such as shale. According to the process of this invention, hydrocarbons and organic materials are selectively extracted from tar sands by a mixture of light naphtha and methanol.The extraction results in rapid collapse of the aggregate and the simultaneous separation of the mixture into three phases, which separation is brought about by trace amounts of wa~er. The most desirable, non-polar comp~nents of the extract are recovered from the naphtha phase; more polar soluble components are recovered from the methanol phase; and the majority of the less desirable asphaltenes remain insoluble but are separated from the sand and are found at the interface of the two solvents. These asphaltenes may be recovered from the interface or may be removed by filtration of the lower methanol layer through the sand.
; DESCRIPTION OF THE PRIOR ART
`~ As sources of crude oil become less available, there is a greater need to develop known bùt less easily handled petroleum resources. One such resources is tar sand~ a sandy material having both water and tar within its interstices. Large deposits are found in v~rious parts of the world. For .
8~5 example, one of the largest known deposits of tar sands lies in the Athabasca district of Alberta Canada, and extends for many thousands of square miles.
These sands contain tremendous reserves of hydrcarbon const~tuents.
For example~ the oil in the sands may vary from about 5% to 21% by volume~
generally in the range of about 12% by volume. The gravity of the oil ranges from abollt 6 to 10 API~ generally about 8API. The tar sand beds may range from about 100 to 400 feet thick, covered by an overburden from about 200 to 300 feet~ A typical oil recovered fro~ the sands has an initial boiling point of about 300F.~ 1.0% distillation to 430F., 20% dis~illation to 650F.~ and ~ !
SO.O~/O distillation to 980F. Tar sands represent a significant petroleum re~
source which may ease the growing shortage of so~rces available to satisfy our ~ - -petroleum demand. ~owever~ before the petroleum material in the tar sand can be employed in ordinary oil refining operation~ it must be separated from the ; solid, sandy material.
1~ Thus~ tar sands suffer the disadvantage of ~equiring additional pro-cessing steps over conventional forms of oil recovery. The high cost of se- ;
parating tar from sand has been the greatest restriction on the use of tar sand as an economical source of crude petroleum. It is, therefor, essential to the commercial feasibility of any process for the recovery of hydrocarbons from tar sands that its cost be low while maintaining a high recovery of hydrocarbons.
The peculiar nature of the tar sand aggregate has heretofore irustra~ed attempts to attain these goals, though, some are relatively soft and free~flowing `~ while others are very hard and rocklike. ~or example, the tar sands of the ~ ~
- Athabasca district are composed of an almost pure silica sand, each grain of ~ ;
which is surrounded by a layer of water which~ in turn~ is surrounded by a film of oil. The oil film may also contain significan~ quantities of clay. The interstices between the grains are largely filled with oil. This construction of the ag8regate is believed to exist because the water content of the tar sands has a greater surface tension than the oil~ Although~ it is r¢cognized that the exact compositions of the tar sands vary, even in an im~ediate location, the .
- . ~
: ~ . . . . .
1Qti~38~5 foregoing construction Or the tar sand a~Kregate is apparently a general characteristlc of the sands.
~arious methods have been prepared for the recovery of hydrocarbons from tar sands, including direct fluid coking and retorting.
These thermal processes are uneconomical due to the fact that the heat i~parted to the sand cannot be effectively and efficienkly recovered therefrom. Accordingly, attention has more recently focused on solvent extraction as a general method which may provide a commercially feasible process for the treatment of tar sands.
U.S. Patent No. 2,825,677 disclosed a two-stage process whereln a hydrocarbon diluent, having a lesser speci~ic gravity than that of the ; tar-sand oil, is first added to the sand to dilute the oil phase and reduce its viscosity, thereby makin~ it more mobile and susceptible to the stopping forces of the aqueous phase. The specific gra~ity of the oil phase is reduced to a point below that of the aqueous phase to facility separation. In the first stage, a hydrocarbon diluent3 such as benzene, toluene, gasoline, coal tar naphtha, or petroleum naphtha is ` e~lployed. In the second stage, large qua~tities o~ water (2 volume of water ` per volume o~ oil) are added and the combined mass is sub~ected to a pressure separation, preferably centrifugation. This method is inadeq ~ e -because of the large quantitles of water required and the formation of oil-water em~lsions which are very difflcult to break. A similar ~ater./
hydrocarbon-diluent process is also disclosed in U.S. Patent 3,553,098.
A non-aqueous recovery process is disclosed in U.S. 3,131,141, which process may be also characterized as a two-stage method since the tar sand is subject to contact with a series of solvents. The initial solvent contacting stage employs a light gas oil boiling within the range from about 400F to 700F. to segregate a bitumen-gas oil phase and a sand-gas oil phase. The separated sand-gas oil phase is then contacted yl ~4~
- . .
.
~0i69~45 with a liquified, normally gaseous hydrocarbon, preferably propane or butane, to separate a sand-liquified, normally gaseous hy~rocarbon phase. F~rther separation steps produce sand, gas oil, and liquified, normally gaseous hydrocarbon. This process, while achieving good recovery of the two solvents employed for e~traction, has a relatively low rate of extraction and requlres heat 2nd pressure to effect the ~esired separations.
' .
. ' , .
.
, `',' '' ' .
.... .
38~5 Sands with solvent recovery by steam stripplng the separated sand is disclosed in U.S. 3,475,31~. Prior methods haa ~aught the c~mplete removal of tar from the sand, but it was recognized that complete removal may be dis-advantageous in that additional processing steps are required when refining the extracted tar to obtain the desired oil products~ Specifically, the extracted tar must 8 through a flash distillation step in which undesirable oil products could selectively be removed from the tar sands, leaving the undesirable asphal-tenes on the sand, by solvent extraction with a solvent consisting of a saturated hydrocarbon or mixture of saturated hydrocarbons having from 5 to 9 carbon atomsper molecule. Recognizing that it may be desirable to re~ove a certain portion of asphaltenes from the tar sand to use as fuel for the process, U.S. 3,4759318 ; further discloses the use of a controlled amount of an aromatic solvent having from 6 to 9 carbon atoms per molecule to extract the desired amount of asphaltenes.
` U.S. 3,079,326 discloses a double-sol~ent system (i.e., naphtha/methanol) for fractionating tar products obtained from low-temperatures pyrolysis of coal~
The methanol solvent employed is an aqueous solution containing from 20 to 60%
water which is used in a ratio ~arying from 0.5 to 2.0 volumes per volume of coal tar.
, S~RY OF THE INVENTION ~-An object of the present invention is to provide an economical proces~
for the selective extraction of desirable organic constituents from tar sand.
A further object is to provide such a process which minimizes energy, equipment,and water requirements and maximizes extraction yield, rate of extraction, and separation properties of the post-extraction system.
The extraction of organic constituents from tar sands according to the process of the present invention is acconplished by a double-sol~ent system of light naphtha and methanol. The addition of heat to the extraction zone is not normally required because the extraction temperature may be as low as about 50F.
Rapid decrepitation of the tar sand a8gregate occurs, follo~Jed by separation oftwo layers of solution. The heavy asphaltenes are partitioned between the inter-- face of the two solutions and on the fluid surface. Further product separation of the liquid layers following extraction of hydrocarbons and organlc ' ' ' ~984S
.
materials from the tar sand is a unique feature Or this process.
Depending on the water content of the tar sand, the separatlon may occur simultaneously ~th the extraction or may be accomplished by the addition of a small quantity of water, at least about 1% to the binary extract. After removal of the upper, light naphtha fraction by decantatlon, the ma~or portion of the methanol fraction is separately withdrawn. The remaining portion is filtered through the sand. This deposits all of the asphaltenes on the sand. The light naphtha fraction is separated to avoid filtration thereof through the sand. The methanol ~raction is much easier to filter than the whole binary mix.
While not wlshing to be bound by any specific theory of operability, it is believed that the effectiveness of the double-solvent system of the invention is based on the ability of methanol to penetrate the water layer surrounding the sand gralns of the tar sand ~ aggregate. By contrast, it is known that a solvent, such as hexane ~orks ;~ ineffectively in a water system and penetration of the aggregate water -- layers by such a solvent is difficult. The methanol penetration of ~;
the water layer is beneficial in reducing the interfacial tension between the double solvent/tar-sand oil phase and the solid phase so that the fine sand grains separate more readily from the hydrocarbon organic matter phase.
~oreover, the separation o~ the binary solvent~tar-sand oil mixture into a light naphtha phase and a methanol phase results in a favorable distribution of the extracted hydrocarbons organic ~tter between the phases, in addltion to improving the performance of the later filtration step. The most desirable, non-polar components of the extracted constituents are recovered frcn the light naphtha phase, the more polar, soluble constituents are recovered from the methanol phase and the less desirable asphaltenes are withdrawn with the sand.
. .
. .. .
The solid asphaltenes deposited on the surface of the sand may also be recovered. For example, the sand fraction ~Jith deposited asphaltenes may be combusted or burned with oxygen containing gas and thus used as source Or energy for the process.
Alternatively, the asphaltenes deposited on the sand surface may be further recovered as by extraction by an aromatic solvent. Aromatic compounds especially effective for such further extraction are aromatics benzene and pyridine. Alternatively, the n2~ority of the asphaltenes may be recovered by decantatlon or other method of with-drawal of oil llquids followed by filtration to remove entrained asphaltene particles.
An important aspect of the present inYention is the ease with which the particular duel solvents may be recovered due to the large differences in the boiling point between the solvents, the respective extracts and the good filtration properties of the methanol layer.
Thus, khe present invention has the advantage of providing deasphalting and extraction in one step, which eliminates or greatly simplifies a subsequent distillation step in which undesired asphaltenes are removed. m e process also has the advantage of not forming difficult to separate ~rater-oil emulsions as found in the recovery of tar-sand hydrocarbons by addition of large qu~ntlties of water. Additionally, some tar sands deposits occur in locations where , water resources are scarce. If such is the case, the double-solvent extraction method of this invention can be considered as a method of extracting organic constituents from tar-sand aggregate at the mine site. Finally, a light naphtha/methanol solvent system is much less expensive to operate than conventional aromatic solvent8 processes by ~0~8~
virtue of the lower initial cost of the solvents and khe eas~ th which t~e solvents may be recovered from their respective extracts.
DESCRIPTION OF PREFERRED ~30DIMEN~S
The light naphtha solvent employed in the process of this invention is a hydrocarbon or a mixture of hydrocarbons having ~rom 5 to 9 carbon atoms per molecule. Although the light naphtha will usually predorlnantly comprise straight-chain para~rins, the light naphtha may also comprlse naphthenes and branched paraffins. The boiling point o~ the light naphtha may vary from aboùt 20 to 200C However, the boiling point will preferably range from about 40 to 100C.
Preferable naphthas comprise straight run naphtha or petroleum ether, alkylates and raffinate product o~ Udex extraction.
A suitable amount of llght naphtha~methanol solvent for extracting hydrocarbons and organic constituents from tar sand may vary fron about 1 to lO volumes of solvent per volume of tar sand.
m e volu~e ratio of ligh~ naphtha to methanol in the solvent system may vary, depending on the characteri~tics of the particular tar sand to be processed. Speci~ically, the ratio should be roughly equal to the ratio of light naphtha extract to methanol extract which is ` 20 recovered from the tar sand. In a preferred embodiment of thisinvention, howe~erg the light naphthaimetnanol ratio ranges from 60/40 to 70/30. ~road range 50/50 to 80/20.
~` A comparison of the extraction rates of various solvent systems demonstrated the following relationships: MeOH ~ ht naphtha C 50/50 benzene MeOH C 70/30 light naphtha/methanol benzeneO
" ~hus, the extraction rate of the light naphtha/methanol solvent systen ~ .
' .
84~
is ~reater than either of the t~Jo components alone and co~a~able with benzene. However, the quality o~ extracts is considerably hi~her ~th the 70/30 light naphtha/metha~ol system than ~.~th the benzene system, as shown by the follo~Jing Examples.
An Oil Cree k Oklahoma tar sand (45 grams) ~as mixed with 150 cc of 70/30 light naphtha/methanol solvent. A solid, sand fraction immediately separated from the mixture, and, after the ~dditlon of about O.5 to 1% water to the solvent/tar-sand oil mixture, two liquid f`ractions form~d; a light naphtha fraction 2nd a methanol f`racvion. The light naphtha fraction was decanted l~rom the extraction vessel and distilled to separate the light naohtha from its extract. The methanol fraction ~ras then separated from the solids. Although the separation method of this example is filtration~ it should be understood that other methods which are well-known in the art, such as centrifugation, may zlso be employed to separate the methanol fraction frcm the solids. Fol-lowing this separation, the methanol fraction was distilled to separate the methanol from its extract. Both the distilled light o naphtha and methanol may be reused in the extraction step. The -8a-~ - ~, . . .
~0698~i total extracted organic materlal yield of this example was found to be 4.9% by weight of the tar sand treated. This value compares ~avorably with the 4.8% yield obtained by benzene extraction of the same tar sand.
Table 1 shows the elemental analysis of the various extracts of the example. Examination of Table 1 will reveal the favorable distribution of heteroatoms among the fractions obtained by the solvent extraction method of the invention.
:~ _9_ ~L~638~S
~d ~, ~1 I s r l L~
~o ~, (y t~
U~
l ~ ' ~ ' d ~o ~ -.
N L~ t ~ t~
~s I N N r-l N ,~
In 3 1~ r~ ,0 ~ ~1 '~ 'o ~ -~ X ~ N : ` ~
~Itl ~
C~ 1 3 L~ ~ O
~ ~ t~o t o t o ~
j ~ rr~ ' .
.
~ O
r~
C) C~
q `"' -: .
~1 , I
~il N
~1 , rl ~1 N 0~ O
.~
~ ~ ' ~ ~ .
$ ~ o v~ i N
`- --11--:, ;9~
From the foregoing description, it is evldent that the present invention provides a process for separating or~anlc constituents from tar sand that is efficlent and econo~ical, and one that does not entail high losses of valuable ~aterlals. Of particular importance is the fact that the relatively si~ple equipment3 energy and water requirements o~ the process of the invention make it feasible to separate organic constitu~r.ts from tar sand at the mine site. This is an important econo~ical factor in any process for recovering organic constituents fro~ tar sand.
Thus, by means of the present invention, tar sand can ke nined, organic constituents selectively removed therefrom, the sand returned to fill the mining site, and only the organic corstituents recovered from the process need be shipped for further processing.
FIELD OF THE INVENTION
This invention relates to a process wherein a double-solvent treatment is used for the selectlve recovery of hydrocarbons and organic materials from tar sands. The process of this invention is particularly adapted to separate such hydrocarbons and organic constituents, hereinafter referred to as organlc constituents, from aggregates in which mineral parti-cles are discrete and comprise the major portion of the naturally-occurring aggregate9 in order to recover virtually solid-free materials which may be further treated in standard refinery operations. It is to be distinguished from those trea~ment of natural asphalt ln which only coarsest particles of sand or minerals are removed~ leaving finely divided clays or other minerals in the extract. The process is also to be distinguished from treatments for the recovery of oil from consolidated materials, such as shale. According to the process of this invention, hydrocarbons and organic materials are selectively extracted from tar sands by a mixture of light naphtha and methanol.The extraction results in rapid collapse of the aggregate and the simultaneous separation of the mixture into three phases, which separation is brought about by trace amounts of wa~er. The most desirable, non-polar comp~nents of the extract are recovered from the naphtha phase; more polar soluble components are recovered from the methanol phase; and the majority of the less desirable asphaltenes remain insoluble but are separated from the sand and are found at the interface of the two solvents. These asphaltenes may be recovered from the interface or may be removed by filtration of the lower methanol layer through the sand.
; DESCRIPTION OF THE PRIOR ART
`~ As sources of crude oil become less available, there is a greater need to develop known bùt less easily handled petroleum resources. One such resources is tar sand~ a sandy material having both water and tar within its interstices. Large deposits are found in v~rious parts of the world. For .
8~5 example, one of the largest known deposits of tar sands lies in the Athabasca district of Alberta Canada, and extends for many thousands of square miles.
These sands contain tremendous reserves of hydrcarbon const~tuents.
For example~ the oil in the sands may vary from about 5% to 21% by volume~
generally in the range of about 12% by volume. The gravity of the oil ranges from abollt 6 to 10 API~ generally about 8API. The tar sand beds may range from about 100 to 400 feet thick, covered by an overburden from about 200 to 300 feet~ A typical oil recovered fro~ the sands has an initial boiling point of about 300F.~ 1.0% distillation to 430F., 20% dis~illation to 650F.~ and ~ !
SO.O~/O distillation to 980F. Tar sands represent a significant petroleum re~
source which may ease the growing shortage of so~rces available to satisfy our ~ - -petroleum demand. ~owever~ before the petroleum material in the tar sand can be employed in ordinary oil refining operation~ it must be separated from the ; solid, sandy material.
1~ Thus~ tar sands suffer the disadvantage of ~equiring additional pro-cessing steps over conventional forms of oil recovery. The high cost of se- ;
parating tar from sand has been the greatest restriction on the use of tar sand as an economical source of crude petroleum. It is, therefor, essential to the commercial feasibility of any process for the recovery of hydrocarbons from tar sands that its cost be low while maintaining a high recovery of hydrocarbons.
The peculiar nature of the tar sand aggregate has heretofore irustra~ed attempts to attain these goals, though, some are relatively soft and free~flowing `~ while others are very hard and rocklike. ~or example, the tar sands of the ~ ~
- Athabasca district are composed of an almost pure silica sand, each grain of ~ ;
which is surrounded by a layer of water which~ in turn~ is surrounded by a film of oil. The oil film may also contain significan~ quantities of clay. The interstices between the grains are largely filled with oil. This construction of the ag8regate is believed to exist because the water content of the tar sands has a greater surface tension than the oil~ Although~ it is r¢cognized that the exact compositions of the tar sands vary, even in an im~ediate location, the .
- . ~
: ~ . . . . .
1Qti~38~5 foregoing construction Or the tar sand a~Kregate is apparently a general characteristlc of the sands.
~arious methods have been prepared for the recovery of hydrocarbons from tar sands, including direct fluid coking and retorting.
These thermal processes are uneconomical due to the fact that the heat i~parted to the sand cannot be effectively and efficienkly recovered therefrom. Accordingly, attention has more recently focused on solvent extraction as a general method which may provide a commercially feasible process for the treatment of tar sands.
U.S. Patent No. 2,825,677 disclosed a two-stage process whereln a hydrocarbon diluent, having a lesser speci~ic gravity than that of the ; tar-sand oil, is first added to the sand to dilute the oil phase and reduce its viscosity, thereby makin~ it more mobile and susceptible to the stopping forces of the aqueous phase. The specific gra~ity of the oil phase is reduced to a point below that of the aqueous phase to facility separation. In the first stage, a hydrocarbon diluent3 such as benzene, toluene, gasoline, coal tar naphtha, or petroleum naphtha is ` e~lployed. In the second stage, large qua~tities o~ water (2 volume of water ` per volume o~ oil) are added and the combined mass is sub~ected to a pressure separation, preferably centrifugation. This method is inadeq ~ e -because of the large quantitles of water required and the formation of oil-water em~lsions which are very difflcult to break. A similar ~ater./
hydrocarbon-diluent process is also disclosed in U.S. Patent 3,553,098.
A non-aqueous recovery process is disclosed in U.S. 3,131,141, which process may be also characterized as a two-stage method since the tar sand is subject to contact with a series of solvents. The initial solvent contacting stage employs a light gas oil boiling within the range from about 400F to 700F. to segregate a bitumen-gas oil phase and a sand-gas oil phase. The separated sand-gas oil phase is then contacted yl ~4~
- . .
.
~0i69~45 with a liquified, normally gaseous hydrocarbon, preferably propane or butane, to separate a sand-liquified, normally gaseous hy~rocarbon phase. F~rther separation steps produce sand, gas oil, and liquified, normally gaseous hydrocarbon. This process, while achieving good recovery of the two solvents employed for e~traction, has a relatively low rate of extraction and requlres heat 2nd pressure to effect the ~esired separations.
' .
. ' , .
.
, `',' '' ' .
.... .
38~5 Sands with solvent recovery by steam stripplng the separated sand is disclosed in U.S. 3,475,31~. Prior methods haa ~aught the c~mplete removal of tar from the sand, but it was recognized that complete removal may be dis-advantageous in that additional processing steps are required when refining the extracted tar to obtain the desired oil products~ Specifically, the extracted tar must 8 through a flash distillation step in which undesirable oil products could selectively be removed from the tar sands, leaving the undesirable asphal-tenes on the sand, by solvent extraction with a solvent consisting of a saturated hydrocarbon or mixture of saturated hydrocarbons having from 5 to 9 carbon atomsper molecule. Recognizing that it may be desirable to re~ove a certain portion of asphaltenes from the tar sand to use as fuel for the process, U.S. 3,4759318 ; further discloses the use of a controlled amount of an aromatic solvent having from 6 to 9 carbon atoms per molecule to extract the desired amount of asphaltenes.
` U.S. 3,079,326 discloses a double-sol~ent system (i.e., naphtha/methanol) for fractionating tar products obtained from low-temperatures pyrolysis of coal~
The methanol solvent employed is an aqueous solution containing from 20 to 60%
water which is used in a ratio ~arying from 0.5 to 2.0 volumes per volume of coal tar.
, S~RY OF THE INVENTION ~-An object of the present invention is to provide an economical proces~
for the selective extraction of desirable organic constituents from tar sand.
A further object is to provide such a process which minimizes energy, equipment,and water requirements and maximizes extraction yield, rate of extraction, and separation properties of the post-extraction system.
The extraction of organic constituents from tar sands according to the process of the present invention is acconplished by a double-sol~ent system of light naphtha and methanol. The addition of heat to the extraction zone is not normally required because the extraction temperature may be as low as about 50F.
Rapid decrepitation of the tar sand a8gregate occurs, follo~Jed by separation oftwo layers of solution. The heavy asphaltenes are partitioned between the inter-- face of the two solutions and on the fluid surface. Further product separation of the liquid layers following extraction of hydrocarbons and organlc ' ' ' ~984S
.
materials from the tar sand is a unique feature Or this process.
Depending on the water content of the tar sand, the separatlon may occur simultaneously ~th the extraction or may be accomplished by the addition of a small quantity of water, at least about 1% to the binary extract. After removal of the upper, light naphtha fraction by decantatlon, the ma~or portion of the methanol fraction is separately withdrawn. The remaining portion is filtered through the sand. This deposits all of the asphaltenes on the sand. The light naphtha fraction is separated to avoid filtration thereof through the sand. The methanol ~raction is much easier to filter than the whole binary mix.
While not wlshing to be bound by any specific theory of operability, it is believed that the effectiveness of the double-solvent system of the invention is based on the ability of methanol to penetrate the water layer surrounding the sand gralns of the tar sand ~ aggregate. By contrast, it is known that a solvent, such as hexane ~orks ;~ ineffectively in a water system and penetration of the aggregate water -- layers by such a solvent is difficult. The methanol penetration of ~;
the water layer is beneficial in reducing the interfacial tension between the double solvent/tar-sand oil phase and the solid phase so that the fine sand grains separate more readily from the hydrocarbon organic matter phase.
~oreover, the separation o~ the binary solvent~tar-sand oil mixture into a light naphtha phase and a methanol phase results in a favorable distribution of the extracted hydrocarbons organic ~tter between the phases, in addltion to improving the performance of the later filtration step. The most desirable, non-polar components of the extracted constituents are recovered frcn the light naphtha phase, the more polar, soluble constituents are recovered from the methanol phase and the less desirable asphaltenes are withdrawn with the sand.
. .
. .. .
The solid asphaltenes deposited on the surface of the sand may also be recovered. For example, the sand fraction ~Jith deposited asphaltenes may be combusted or burned with oxygen containing gas and thus used as source Or energy for the process.
Alternatively, the asphaltenes deposited on the sand surface may be further recovered as by extraction by an aromatic solvent. Aromatic compounds especially effective for such further extraction are aromatics benzene and pyridine. Alternatively, the n2~ority of the asphaltenes may be recovered by decantatlon or other method of with-drawal of oil llquids followed by filtration to remove entrained asphaltene particles.
An important aspect of the present inYention is the ease with which the particular duel solvents may be recovered due to the large differences in the boiling point between the solvents, the respective extracts and the good filtration properties of the methanol layer.
Thus, khe present invention has the advantage of providing deasphalting and extraction in one step, which eliminates or greatly simplifies a subsequent distillation step in which undesired asphaltenes are removed. m e process also has the advantage of not forming difficult to separate ~rater-oil emulsions as found in the recovery of tar-sand hydrocarbons by addition of large qu~ntlties of water. Additionally, some tar sands deposits occur in locations where , water resources are scarce. If such is the case, the double-solvent extraction method of this invention can be considered as a method of extracting organic constituents from tar-sand aggregate at the mine site. Finally, a light naphtha/methanol solvent system is much less expensive to operate than conventional aromatic solvent8 processes by ~0~8~
virtue of the lower initial cost of the solvents and khe eas~ th which t~e solvents may be recovered from their respective extracts.
DESCRIPTION OF PREFERRED ~30DIMEN~S
The light naphtha solvent employed in the process of this invention is a hydrocarbon or a mixture of hydrocarbons having ~rom 5 to 9 carbon atoms per molecule. Although the light naphtha will usually predorlnantly comprise straight-chain para~rins, the light naphtha may also comprlse naphthenes and branched paraffins. The boiling point o~ the light naphtha may vary from aboùt 20 to 200C However, the boiling point will preferably range from about 40 to 100C.
Preferable naphthas comprise straight run naphtha or petroleum ether, alkylates and raffinate product o~ Udex extraction.
A suitable amount of llght naphtha~methanol solvent for extracting hydrocarbons and organic constituents from tar sand may vary fron about 1 to lO volumes of solvent per volume of tar sand.
m e volu~e ratio of ligh~ naphtha to methanol in the solvent system may vary, depending on the characteri~tics of the particular tar sand to be processed. Speci~ically, the ratio should be roughly equal to the ratio of light naphtha extract to methanol extract which is ` 20 recovered from the tar sand. In a preferred embodiment of thisinvention, howe~erg the light naphthaimetnanol ratio ranges from 60/40 to 70/30. ~road range 50/50 to 80/20.
~` A comparison of the extraction rates of various solvent systems demonstrated the following relationships: MeOH ~ ht naphtha C 50/50 benzene MeOH C 70/30 light naphtha/methanol benzeneO
" ~hus, the extraction rate of the light naphtha/methanol solvent systen ~ .
' .
84~
is ~reater than either of the t~Jo components alone and co~a~able with benzene. However, the quality o~ extracts is considerably hi~her ~th the 70/30 light naphtha/metha~ol system than ~.~th the benzene system, as shown by the follo~Jing Examples.
An Oil Cree k Oklahoma tar sand (45 grams) ~as mixed with 150 cc of 70/30 light naphtha/methanol solvent. A solid, sand fraction immediately separated from the mixture, and, after the ~dditlon of about O.5 to 1% water to the solvent/tar-sand oil mixture, two liquid f`ractions form~d; a light naphtha fraction 2nd a methanol f`racvion. The light naphtha fraction was decanted l~rom the extraction vessel and distilled to separate the light naohtha from its extract. The methanol fraction ~ras then separated from the solids. Although the separation method of this example is filtration~ it should be understood that other methods which are well-known in the art, such as centrifugation, may zlso be employed to separate the methanol fraction frcm the solids. Fol-lowing this separation, the methanol fraction was distilled to separate the methanol from its extract. Both the distilled light o naphtha and methanol may be reused in the extraction step. The -8a-~ - ~, . . .
~0698~i total extracted organic materlal yield of this example was found to be 4.9% by weight of the tar sand treated. This value compares ~avorably with the 4.8% yield obtained by benzene extraction of the same tar sand.
Table 1 shows the elemental analysis of the various extracts of the example. Examination of Table 1 will reveal the favorable distribution of heteroatoms among the fractions obtained by the solvent extraction method of the invention.
:~ _9_ ~L~638~S
~d ~, ~1 I s r l L~
~o ~, (y t~
U~
l ~ ' ~ ' d ~o ~ -.
N L~ t ~ t~
~s I N N r-l N ,~
In 3 1~ r~ ,0 ~ ~1 '~ 'o ~ -~ X ~ N : ` ~
~Itl ~
C~ 1 3 L~ ~ O
~ ~ t~o t o t o ~
j ~ rr~ ' .
.
~ O
r~
C) C~
q `"' -: .
~1 , I
~il N
~1 , rl ~1 N 0~ O
.~
~ ~ ' ~ ~ .
$ ~ o v~ i N
`- --11--:, ;9~
From the foregoing description, it is evldent that the present invention provides a process for separating or~anlc constituents from tar sand that is efficlent and econo~ical, and one that does not entail high losses of valuable ~aterlals. Of particular importance is the fact that the relatively si~ple equipment3 energy and water requirements o~ the process of the invention make it feasible to separate organic constitu~r.ts from tar sand at the mine site. This is an important econo~ical factor in any process for recovering organic constituents fro~ tar sand.
Thus, by means of the present invention, tar sand can ke nined, organic constituents selectively removed therefrom, the sand returned to fill the mining site, and only the organic corstituents recovered from the process need be shipped for further processing.
Claims (8)
1. A process for recovering hydrocarbons from tar sand which comprises:
(A) mixing tar sand with a suitable amount of light naphtha/methanol solvent to produce a light naphtha fraction, a methanol fraction, and a solid sand fraction having asphaltenes deposited on the sand surface;
(B) decanting said light naphtha fraction; and (C) separating said methanol fraction from said solid, sand fraction.
(A) mixing tar sand with a suitable amount of light naphtha/methanol solvent to produce a light naphtha fraction, a methanol fraction, and a solid sand fraction having asphaltenes deposited on the sand surface;
(B) decanting said light naphtha fraction; and (C) separating said methanol fraction from said solid, sand fraction.
2. The process of claim 1, wherein said light naphtha/
methanol solvent is composed of 70 vol. % of light naphtha and 30 vol. %
of methanol.
methanol solvent is composed of 70 vol. % of light naphtha and 30 vol. %
of methanol.
3. The process of claim 1 wherein said methanol fraction is separated from the solid sand fraction by filtration.
4. The process of claim 1 wherein the separated, sand fraction is combusted and used as a source of energy.
5. The process of claim 1 wherein said asphaltenes deposited on the separated sand fraction are further extracted by an aromatic solvent.
6. The process of claim 5 wherein said aromatic compound is pyridine.
7. The process of claim 5 wherein said aromatic compound is gamma-picoline.
8. A process for recovering hydrocarbons from tar sand which comprises:
(A) mixing tar sand with a suitable amount of light naphtha/methanol solvent to produce a light naphtha/methanol fraction and solid fractions comprising asphaltenes and sand;
(B) adding about 1 vol. % water to said light naphtha/
methanol fraction to produce a separated light naphtha fraction from a methanol fraction;
(C) decanting said light naphtha and methanol fractions;
and (D) separating asphaltenes from said methanol fraction.
(A) mixing tar sand with a suitable amount of light naphtha/methanol solvent to produce a light naphtha/methanol fraction and solid fractions comprising asphaltenes and sand;
(B) adding about 1 vol. % water to said light naphtha/
methanol fraction to produce a separated light naphtha fraction from a methanol fraction;
(C) decanting said light naphtha and methanol fractions;
and (D) separating asphaltenes from said methanol fraction.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/648,597 US4046668A (en) | 1976-01-12 | 1976-01-12 | Double solvent extraction of organic constituents from tar sands |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1069845A true CA1069845A (en) | 1980-01-15 |
Family
ID=24601448
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA262,845A Expired CA1069845A (en) | 1976-01-12 | 1976-10-06 | Double solvent extraction of organic constituents from tar sands |
Country Status (2)
Country | Link |
---|---|
US (1) | US4046668A (en) |
CA (1) | CA1069845A (en) |
Families Citing this family (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4217202A (en) * | 1977-10-21 | 1980-08-12 | Gulf Research & Development Company | Process for selective recovery of relatively metals-free bitumen from tar sand using a halogenated aliphatic solvent in combination with a second solvent |
US4293404A (en) * | 1980-07-21 | 1981-10-06 | Mobil Oil Corporation | Dehydroxylation and/or demercaptolation of heavy petroleum oils |
US4455216A (en) * | 1980-12-04 | 1984-06-19 | Mobil Oil Corporation | Polarity gradient extraction method |
US4464246A (en) * | 1980-12-30 | 1984-08-07 | Kohle Energy Research Consultants Inc. | Reagent and process for recovering oil and kerogens from oil shale |
US4374023A (en) * | 1981-10-26 | 1983-02-15 | Chevron Research Company | Process for recovering hydrocarbons from a diatomite-type ore |
US4495057A (en) * | 1982-05-07 | 1985-01-22 | Bahram Amirijafari | Combination thermal and solvent extraction oil recovery process and apparatus |
US4419217A (en) * | 1983-02-17 | 1983-12-06 | Mobil Oil Corporation | Process for improving the yield of shale oil |
US5756357A (en) * | 1993-04-27 | 1998-05-26 | Dexsil Corporation | Method for detecting hydrocarbons in soil |
US6117682A (en) * | 1993-04-27 | 2000-09-12 | Dexsil Corporation | Method for detecting hydrocarbons in water |
US5534136A (en) * | 1994-12-29 | 1996-07-09 | Rosenbloom; William J. | Method and apparatus for the solvent extraction of oil from bitumen containing tar sand |
AU4859200A (en) * | 1999-05-24 | 2000-12-12 | James W. Bunger And Associates, Inc. | Process for enhancing the value of hydrocarbonaceous natural resources |
US8257580B2 (en) | 2004-10-13 | 2012-09-04 | Marathon Oil Canada Corporation | Dry, stackable tailings and methods for producing the same |
US7909989B2 (en) * | 2004-10-13 | 2011-03-22 | Marathon Oil Canada Corporation | Method for obtaining bitumen from tar sands |
US8101067B2 (en) * | 2004-10-13 | 2012-01-24 | Marathon Oil Canada Corporation | Methods for obtaining bitumen from bituminous materials |
US7985333B2 (en) * | 2004-10-13 | 2011-07-26 | Marathon Oil Canada Corporation | System and method of separating bitumen from tar sands |
US7585407B2 (en) | 2006-03-07 | 2009-09-08 | Marathon Oil Canada Corporation | Processing asphaltene-containing tailings |
US7811444B2 (en) | 2006-06-08 | 2010-10-12 | Marathon Oil Canada Corporation | Oxidation of asphaltenes |
US7824453B2 (en) * | 2006-09-08 | 2010-11-02 | Marathon Oil Canada Corporation | Biodiesel production and use in oil sands processing |
US7749379B2 (en) | 2006-10-06 | 2010-07-06 | Vary Petrochem, Llc | Separating compositions and methods of use |
US8062512B2 (en) | 2006-10-06 | 2011-11-22 | Vary Petrochem, Llc | Processes for bitumen separation |
US7758746B2 (en) * | 2006-10-06 | 2010-07-20 | Vary Petrochem, Llc | Separating compositions and methods of use |
US20090145809A1 (en) * | 2007-12-10 | 2009-06-11 | Chevron Phillips Chemical Company Lp | Compositions for oil recovery and methods of using same |
US8449763B2 (en) * | 2009-04-15 | 2013-05-28 | Marathon Canadian Oil Sands Holding Limited | Nozzle reactor and method of use |
US20110017642A1 (en) * | 2009-07-24 | 2011-01-27 | Duyvesteyn Willem P C | System and method for converting material comprising bitumen into light hydrocarbon liquid product |
WO2011014725A1 (en) * | 2009-07-30 | 2011-02-03 | Marathon Oil Canada Corporation | Methods for obtaining bitumen from bituminous materials |
US8663462B2 (en) * | 2009-09-16 | 2014-03-04 | Shell Canada Energy Cheveron Canada Limited | Methods for obtaining bitumen from bituminous materials |
US8864982B2 (en) * | 2009-12-28 | 2014-10-21 | Shell Canada Energy Cheveron Canada Limited | Methods for obtaining bitumen from bituminous materials |
US8877044B2 (en) * | 2010-01-22 | 2014-11-04 | Shell Canada Energy Cheveron Canada Limited | Methods for extracting bitumen from bituminous material |
US20110180458A1 (en) * | 2010-01-22 | 2011-07-28 | Marathon Oil Canada Corporation | Methods for extracting bitumen from bituminous material |
US20110180454A1 (en) * | 2010-01-28 | 2011-07-28 | Marathon Oil Canada Corporation | Methods for preparing solid hydrocarbons for cracking |
US8435402B2 (en) * | 2010-03-29 | 2013-05-07 | Marathon Canadian Oil Sands Holding Limited | Nozzle reactor and method of use |
WO2011137378A2 (en) | 2010-04-30 | 2011-11-03 | University Of Utah Research Foundation | Ozonation conversion of heavy hydrocarbons for resource recovery |
US8586515B2 (en) | 2010-10-25 | 2013-11-19 | Marathon Oil Canada Corporation | Method for making biofuels and biolubricants |
US8968556B2 (en) | 2010-12-09 | 2015-03-03 | Shell Canada Energy Cheveron Canada Limited | Process for extracting bitumen and drying the tailings |
US8920636B2 (en) | 2011-06-28 | 2014-12-30 | Shell Canada Energy and Chervon Canada Limited | Methods of transporting various bitumen extraction products and compositions thereof |
CA2783773A1 (en) | 2011-07-26 | 2013-01-26 | Marathon Oil Canada Corporation | Methods for obtaining bitumen from bituminous materials |
US8636958B2 (en) | 2011-09-07 | 2014-01-28 | Marathon Oil Canada Corporation | Nozzle reactor and method of use |
CN103420548B (en) * | 2012-05-15 | 2016-01-20 | 中国石油天然气股份有限公司 | A kind of compound extracting solvent of oily sludge |
CN103693824B (en) * | 2012-09-28 | 2015-10-28 | 中国石油天然气股份有限公司 | A kind of degree of depth extraction coking treatment process of oily sludge |
US11053464B2 (en) | 2014-03-22 | 2021-07-06 | United Laboratories International, Llc | Solvent composition and process for removal of asphalt and other contaminant materials |
WO2016138005A1 (en) | 2015-02-27 | 2016-09-01 | Schlumberger Technology Corporation | Vertical drilling and fracturing methodology |
US10138427B2 (en) | 2016-06-22 | 2018-11-27 | Extrakt Process Solutions, Llc | Separation of hydrocarbons from particulate matter using salt and polymer |
CA3036529A1 (en) | 2016-09-12 | 2018-03-15 | Schlumberger Canada Limited | Attaining access to compromised fractured production regions at an oilfield |
AU2018205724B2 (en) | 2017-01-04 | 2023-08-10 | Schlumberger Technology B.V. | Reservoir stimulation comprising hydraulic fracturing through extended tunnels |
WO2019014160A1 (en) | 2017-07-10 | 2019-01-17 | Schlumberger Technology Corporation | Radial drilling link transmission and flex shaft protective cover |
WO2019014161A1 (en) | 2017-07-10 | 2019-01-17 | Schlumberger Technology Corporation | Controlled release of hose |
JP7167154B2 (en) | 2017-08-08 | 2022-11-08 | カルテヴァット,インク. | System and method for continuous stirred tank solvent extraction using feedstock |
MX2020001563A (en) | 2017-08-08 | 2022-02-01 | Kultevat Inc | Rubber and by-product extraction systems and methods. |
US11193332B2 (en) | 2018-09-13 | 2021-12-07 | Schlumberger Technology Corporation | Slider compensated flexible shaft drilling system |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1904521A (en) * | 1927-10-27 | 1933-04-18 | Standard Ig Co | Separation of oils from solid residues |
US2453060A (en) * | 1944-08-26 | 1948-11-02 | Union Oil Co | Process and apparatus for treating bituminous sands |
US3392105A (en) * | 1965-04-15 | 1968-07-09 | Marathon Oil Co | Use of a soluble oil in the extraction of hydrocarbons from oil sands |
US3475318A (en) * | 1966-03-28 | 1969-10-28 | Shell Oil Co | Selective solvent extraction plus filtration of tar sands |
US3459653A (en) * | 1966-07-18 | 1969-08-05 | Shell Oil Co | Filtration of solvent-water extracted tar sand |
-
1976
- 1976-01-12 US US05/648,597 patent/US4046668A/en not_active Expired - Lifetime
- 1976-10-06 CA CA262,845A patent/CA1069845A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
US4046668A (en) | 1977-09-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1069845A (en) | Double solvent extraction of organic constituents from tar sands | |
US4250016A (en) | Recovery of bitumen from tar sand | |
US4036732A (en) | Tar sands extraction process | |
EP0134088B1 (en) | Treatment of viscous crude oil | |
CA1143686A (en) | Solvent extraction method | |
US8101067B2 (en) | Methods for obtaining bitumen from bituminous materials | |
US4022277A (en) | In situ solvent fractionation of bitumens contained in tar sands | |
US20130045902A1 (en) | Composition and method for recovering heavy oil | |
US4906355A (en) | Tar sands extract fines removal process | |
US3993555A (en) | Method of separating bitumen from tar sand with cold solvent | |
US3509037A (en) | Tar sand separation process using solvent,hot water and correlated conditions | |
Idris et al. | A review on the effects of asphaltene on petroleum processing | |
US3594306A (en) | Separation cell and scavenger cell froths treatment | |
US4271009A (en) | Method for reducing the nitrogen content of shale oil | |
US9540569B2 (en) | Propane process for producing crude oil and bitumen products | |
US4134821A (en) | Maintenance of solvent balance in coal liquefaction process | |
US2772209A (en) | Recovery of oil from bituminous sands | |
CA2165865C (en) | Process for deasphalting bitumen | |
WO2015095131A1 (en) | Hydroprocessing oil sands-derived, bitumen compositions | |
CA2584003C (en) | Process for improving and recuperating waste, heavy and extra heavy hydrocarbons | |
US3070541A (en) | Recovery of oil from bituminous sands | |
CA2304972A1 (en) | A process for low temperature separation and isolation of crude heavy oil | |
WO2012051440A2 (en) | Hydrocarbon extraction of oil from oil sand | |
US4268378A (en) | Method for removing nitrogen from shale oil by hydrogenation and liquid sulfur dioxide extraction | |
US10160914B2 (en) | Process and system for above ground extraction of crude oil |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |