CA2208046A1 - Method for recovering and concurrently partly upgrading heavy oils, bitumens and oil shale organic matter, and for extracting certain wastes - Google Patents
Method for recovering and concurrently partly upgrading heavy oils, bitumens and oil shale organic matter, and for extracting certain wastesInfo
- Publication number
- CA2208046A1 CA2208046A1 CA 2208046 CA2208046A CA2208046A1 CA 2208046 A1 CA2208046 A1 CA 2208046A1 CA 2208046 CA2208046 CA 2208046 CA 2208046 A CA2208046 A CA 2208046A CA 2208046 A1 CA2208046 A1 CA 2208046A1
- Authority
- CA
- Canada
- Prior art keywords
- water
- oil
- bitumens
- organic matter
- recovering
- 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.)
- Abandoned
Links
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
An exploratory study of bitumen extraction from samples of oilsands from Alberta's Athabasca oil sands with supercritical water at 400dC
and 14-24.5MPa was conducted by the Applicants.
Extract yields, which typically ran betwen 80-90% depended mainly on how efficiently the sands were swept by the supercritical water, but were substantially insensitive to sweep rates; and despite the high temperature surprisingly little toluene-insoluble preasphaltic and heavier material was generated. Analyses of the extracts showed significant composition shifts to lower molecular weight moieties, it is concluded that near-critical water can promote a variety of thermally-driven homolytic and/or hydrolytic bond scissons.
In the above investigations we observed that conjoint use of such water and carbon monoxide can lead to significant upgrading of the precursor material during recovery. We also found that the addition of a catalyst, such as iron oxide, accelerated the upgrading action.
and 14-24.5MPa was conducted by the Applicants.
Extract yields, which typically ran betwen 80-90% depended mainly on how efficiently the sands were swept by the supercritical water, but were substantially insensitive to sweep rates; and despite the high temperature surprisingly little toluene-insoluble preasphaltic and heavier material was generated. Analyses of the extracts showed significant composition shifts to lower molecular weight moieties, it is concluded that near-critical water can promote a variety of thermally-driven homolytic and/or hydrolytic bond scissons.
In the above investigations we observed that conjoint use of such water and carbon monoxide can lead to significant upgrading of the precursor material during recovery. We also found that the addition of a catalyst, such as iron oxide, accelerated the upgrading action.
Description
, CA 02208046 1997-08-26 Amended - June 25 1997 Disclosure to Canadian (and US) Patent Offices Detailed labo, ~ )~y studies [1 2] make it evident that substantial gains can accrue from eAl,~ n of organic matter -such as heavy fossil hyd,Jcan ons and oertain toxic wastes - with (~IO".' -'Iy) sL~r~,,itic,al water.
For example eAtlactivn of bitumen from (Athabasca) oil sands with water at 400~C under pressures between 14 and 21.5 MPa yielded up to 90% of the organic material in the feed sand; and despite the see"~' ~gly severe opel " ,9 cor~i~vns the p.Jporibn of tetrahydrofuran (THF)-soluble pr~a5~ "' matter in the residual solid was no greater than measured after eAbd t;ng the bitumen under much milder corl' 9~ ~s - e.g. with toluene at its normal boiling point. It was also found that the presenoe of carbon ll~noAide - when l ' l; ' ' with steam and under reaction corl~litia ls thereby yt r,er_ lg e~.,~"hl hydrogen by an intemal shift reaction - promoted si~l '" ll hydr~
of the bitumen during o~b~ this was: pr~ssed in app._cidLly higher p,opol'ions of aromatic and aliphatic h)~d,vca,l,ons (and corl~apon'' Ig!y reduoed concent~ ' ~s of aspl~ es and resins) as well as in the substantial elimination of organic sulfur as hydrogen sulfide' .
Much the same was observed when coarsely crushed oil shale was eAtl ~ ' with water at 400~C and pressures between 14 and 21.5 MPa. Recovery of organic matter - in this case material directly derived from kerogen - ranged to 70~~ tor almost 75% more than r~lte~i:J . t: ' l~l~ by retorting the oil shale at 350-500~C; and although the extract co, ' ' ,ed si~l!ticallUy greater p,oportbns of a~p~P'~ ~es and resins than unrefined py,ulyt' 'Iy ~nel. ' ' shale oil, and consequently tended to possess an app ac;ably higher (ap~ar_ It) molecular weighf aromatic carbon contents ran to no more than 3540% and atomic H/C ratbs ranged to 1.57.
Praeecet' lg from these observations - which are echoed by several other laboratory studies - we have formulated The relevant reaction sequences can be fommally l~ ~l ,' ' by shift reaction H20 + CO =, H2 + COz h~d~ dtiull R - R' + H2 ~ R.H + R'.H
and desulfurization R.SH + H2 =~ R.H + H2S
For example eAtlactivn of bitumen from (Athabasca) oil sands with water at 400~C under pressures between 14 and 21.5 MPa yielded up to 90% of the organic material in the feed sand; and despite the see"~' ~gly severe opel " ,9 cor~i~vns the p.Jporibn of tetrahydrofuran (THF)-soluble pr~a5~ "' matter in the residual solid was no greater than measured after eAbd t;ng the bitumen under much milder corl' 9~ ~s - e.g. with toluene at its normal boiling point. It was also found that the presenoe of carbon ll~noAide - when l ' l; ' ' with steam and under reaction corl~litia ls thereby yt r,er_ lg e~.,~"hl hydrogen by an intemal shift reaction - promoted si~l '" ll hydr~
of the bitumen during o~b~ this was: pr~ssed in app._cidLly higher p,opol'ions of aromatic and aliphatic h)~d,vca,l,ons (and corl~apon'' Ig!y reduoed concent~ ' ~s of aspl~ es and resins) as well as in the substantial elimination of organic sulfur as hydrogen sulfide' .
Much the same was observed when coarsely crushed oil shale was eAtl ~ ' with water at 400~C and pressures between 14 and 21.5 MPa. Recovery of organic matter - in this case material directly derived from kerogen - ranged to 70~~ tor almost 75% more than r~lte~i:J . t: ' l~l~ by retorting the oil shale at 350-500~C; and although the extract co, ' ' ,ed si~l!ticallUy greater p,oportbns of a~p~P'~ ~es and resins than unrefined py,ulyt' 'Iy ~nel. ' ' shale oil, and consequently tended to possess an app ac;ably higher (ap~ar_ It) molecular weighf aromatic carbon contents ran to no more than 3540% and atomic H/C ratbs ranged to 1.57.
Praeecet' lg from these observations - which are echoed by several other laboratory studies - we have formulated The relevant reaction sequences can be fommally l~ ~l ,' ' by shift reaction H20 + CO =, H2 + COz h~d~ dtiull R - R' + H2 ~ R.H + R'.H
and desulfurization R.SH + H2 =~ R.H + H2S
2 Neither of these ~:hal d ~l i " ~ constitutes a serbus in,~ - N le, ll to sl lhsequent Up91 ~ y. both can be readily countered by conventional hyd~vprvcessing.
and here discbse a procedure that gives practical ~ ~,bn to eAbavliun of organic carbon, in whatever form, with nc,~ 'Iy su,ucrv, iIical~ water. Its a\ ,~ is a prhri of particular benefit for efficient in-situ recovery of heavy oil, bitumen and kerogen-derived matter from their l- ,ec'ivnv inorganic envelopes, but is not limited to such ope, " ~s.
The folbwing ~- Il, '-s will serve to illustrate n" , ' tU.~!v forms of o b_ 9~.1.
1. One example, s"e ~ ~ -'Iy, but not exclusively, designed for in-situ recovery of heavy oiis, entaiis (a) v~vlll,!~ ~9 two suitably spaced small diameter bc~,vl)cvlvs (I and ll) vertically into the payzone;
(b) where necessary, en~l~,vi"g communicatbn between these hoies by hydraulically or ele~vt,i -11y fracturing the ~O~ n, or using of ~ " _vt~vna~ induding hori~ol)ldl, drilling to establish suitable communication;
(c) through one hoie (I) injecting steam - and, where wn~vl~ti ben6" 'al, carbon nlonoA;v~ - into the fommation at bmperatures in the range of 40v~450~C (~750 0~F) and pressures between14 and 21.5 MPa (~ 2~rv0~v psi);
(d) through the other hole (Il) producing the steam with its bad of eAI,dv~vJ oil; and (e~ at the surface passing the produced stream through a pressure iet-down vessel in which bwer pres-sures andhr b~wer temperatures wiU cause the oil (and any coproduced inorganic saits) to fail out -i.e., to ~ntaneovsly separate from the steam.
Before p,v~essing the sep~dt~d crude btdown oil - e.g., by secondary hyd.Jgend~vn or coking - it can then, where nec~sary, be freed of i,,o,~,;v matter by filtration or use of an allIi~vi~nt. The recovered steam is reheated, re-pressurized, and recycled to the inj;ection hob.
BHumens and related asphr" ~, from a productbn ~ . ,t only dr~fering from heavy oiis in specific gravities, can be recovereci from oil sands~ (or their equivabnts) and prv~essed by sulJsldl." 'Iy the same steps.
1,A. Where the enciosing lor", " ) is suffldently tight - i.e. where the porosity and pe"ll ~ - of the effective roof or fbor of the p~vspevti~c payzone are sl~ ) iJ low - the ,rb;3c'i~cs of the procedure ~ Il, "'ic ~ in #1 can also be attained by 3 This v~vsiy, lation implies near-critical as well as as SvpO.vli" ~ ' H20 in sensu stric~D. It refbcts observations [1,2]
that whereas optimum ope, ' ,g t~vlll~,eralures will generaiiy be ciose ~v the cfitical temperature of water, optimum pressures may sor"vt;.,les prove to lie well beiow the critical pressure of water.
and here discbse a procedure that gives practical ~ ~,bn to eAbavliun of organic carbon, in whatever form, with nc,~ 'Iy su,ucrv, iIical~ water. Its a\ ,~ is a prhri of particular benefit for efficient in-situ recovery of heavy oil, bitumen and kerogen-derived matter from their l- ,ec'ivnv inorganic envelopes, but is not limited to such ope, " ~s.
The folbwing ~- Il, '-s will serve to illustrate n" , ' tU.~!v forms of o b_ 9~.1.
1. One example, s"e ~ ~ -'Iy, but not exclusively, designed for in-situ recovery of heavy oiis, entaiis (a) v~vlll,!~ ~9 two suitably spaced small diameter bc~,vl)cvlvs (I and ll) vertically into the payzone;
(b) where necessary, en~l~,vi"g communicatbn between these hoies by hydraulically or ele~vt,i -11y fracturing the ~O~ n, or using of ~ " _vt~vna~ induding hori~ol)ldl, drilling to establish suitable communication;
(c) through one hoie (I) injecting steam - and, where wn~vl~ti ben6" 'al, carbon nlonoA;v~ - into the fommation at bmperatures in the range of 40v~450~C (~750 0~F) and pressures between14 and 21.5 MPa (~ 2~rv0~v psi);
(d) through the other hole (Il) producing the steam with its bad of eAI,dv~vJ oil; and (e~ at the surface passing the produced stream through a pressure iet-down vessel in which bwer pres-sures andhr b~wer temperatures wiU cause the oil (and any coproduced inorganic saits) to fail out -i.e., to ~ntaneovsly separate from the steam.
Before p,v~essing the sep~dt~d crude btdown oil - e.g., by secondary hyd.Jgend~vn or coking - it can then, where nec~sary, be freed of i,,o,~,;v matter by filtration or use of an allIi~vi~nt. The recovered steam is reheated, re-pressurized, and recycled to the inj;ection hob.
BHumens and related asphr" ~, from a productbn ~ . ,t only dr~fering from heavy oiis in specific gravities, can be recovereci from oil sands~ (or their equivabnts) and prv~essed by sulJsldl." 'Iy the same steps.
1,A. Where the enciosing lor", " ) is suffldently tight - i.e. where the porosity and pe"ll ~ - of the effective roof or fbor of the p~vspevti~c payzone are sl~ ) iJ low - the ,rb;3c'i~cs of the procedure ~ Il, "'ic ~ in #1 can also be attained by 3 This v~vsiy, lation implies near-critical as well as as SvpO.vli" ~ ' H20 in sensu stric~D. It refbcts observations [1,2]
that whereas optimum ope, ' ,g t~vlll~,eralures will generaiiy be ciose ~v the cfitical temperature of water, optimum pressures may sor"vt;.,les prove to lie well beiow the critical pressure of water.
4 Except in Alberta, these are more co, - ll l vn'J referred to as tar sands or bituminous sands . CA 02208046 1997-08-26 i (a) cc",pbti"g two bGr~holcs hGri~or, 11y over an appropr.at~, distance;
(b) where the strata make this desirable, inserting a suitably perh:rdt~d casing into each; and (c) injecting stearn at 400450~C and 14 - 21 MPa through either hole while producing through the other.
2. Another example of i" ,, ' e l l~ g our procedure - this version partkularly suitable for in-situ oAb ~ of organic matter from very dense envelopes such as oil shales, but not confined to such strata - involves (a) creating an underground retort by COIII~ ,9 a borehole of suitable diameter vertically into the payzone;
(b) ~Idyll~ll ' ,9 the f~"",atbn near the bottom of the hole, e.g. by lateral eA~ ;iv~ charges;
(c) as in example 1, injecting steam and, H desired, carbon m~ oAide at t~"~,dIures in the range of 400450~C (750 840~F) and pressures between 14 and 21.5 MPa (~2000-3000 psi);
~d) producing the steam with its load of extracted organk matter through an off-take pipe conce"l-ically ,a ~ ~'-' ed within the borehob, so that the annulus between them serves as the injectbn hole; and (d) P~i"g as in exampb 1.
Suhsequent coking then albws u~,y, ' ,9 of the organk material and will simultaneously separate it from er,3 ' ,ed ino,yanics In tAd""~l~ 1, 1,A and 2 - and, indeed, a cl~af~t~r s; featvre of the recovery t~,~ e - is (i) the use of near-su~e,~;rilbal steam as a 'solvent' - and hence, the ,~cogn' ' ~ that loss of solvent to the io" " ' n, whkh has precluded depbyment of conventional organk solvents, is in N I -~.~, id, and (ii) continuous injection of steam and, consequently, uninterrupted 'sweeping' of the payzone during the entire production cycle (which beginswith steam injection).
However, also fu"d&"e"ldl to ~ ' ry ope, ation of the schemes e,~_" ,, "'' ~ ~ in 1, 1 A and 2 is the ~ ~de~I0- " ,9 that optimum injection I~",,~-dI~Ires and pressures are site- specific and depend on the thermal ulld-d,t~ ' s of the pay zone as well as those of its i"""ediat~ly over- and underlying strata. Our eAperbnoe to date suggestc that optimum I~,-,,ue,~lures in the pay zone will in most, but not all, cases, lie between 375 and 400~C and optimum pressures will range from 14 to 17.5 MPa.
3. In a third example of our procedure, an app~pri ~ !y constructed and sized pressure vessel is depbyed for pro-cessing m~ed oil sand, oil shaie or coalS In such an ope,. " ~, the feed is coarseiy crushed before being trans-ferred to the pressure vessei, but ali other steps co"tlspond to those outlined above.
4. The procedure indkated in example #3 can also be used to facilitate pe-",~,e"l disposal of sub~,' 'Iy water-insoluble toxic organic wastes ~c: '-d with i"o,ydnn, matter. For that purpose, eAb ' ~ with S~ ; ' water at b""~,dl-lres in the range 450~00~C and pressures above 17 MPa serves to separate and conce"hale the toxic material and thereby assist its efficient final destruction, e.g., by high-t~",~,e.uture combustion.
rer .~.~c~s.
1. N. ~rku..ik and J. Caideron; Fuel Process. Technol. 25, 3344, 1990 2. O. Ogunsola and N. 8erkowitz; ibid. ~i, 95-107, 1995 ~.~
NorbertBerkowitz, CM PhD PEng 105, 11660 - 79 Avenue Cdl"on~n, AB T6(~ OP7 Stephen Rae Dunn 1144 Cd~ ~ ~t Road NW
Calgary, AB T3A 2J8 S In this case, cAll_ ~ with nominally su,ue,~;,;~al H20 and CO would facilitate optimal 'skimming', i.e. ~:,t~ 1iun of a high p,upo, i' l as crude oils or oil precursors. The residual, partialiy devolatilized char can then be deployed as ciean fuel for, e.g.,. gene,~tiun of ole~,tli(,ity.
(b) where the strata make this desirable, inserting a suitably perh:rdt~d casing into each; and (c) injecting stearn at 400450~C and 14 - 21 MPa through either hole while producing through the other.
2. Another example of i" ,, ' e l l~ g our procedure - this version partkularly suitable for in-situ oAb ~ of organic matter from very dense envelopes such as oil shales, but not confined to such strata - involves (a) creating an underground retort by COIII~ ,9 a borehole of suitable diameter vertically into the payzone;
(b) ~Idyll~ll ' ,9 the f~"",atbn near the bottom of the hole, e.g. by lateral eA~ ;iv~ charges;
(c) as in example 1, injecting steam and, H desired, carbon m~ oAide at t~"~,dIures in the range of 400450~C (750 840~F) and pressures between 14 and 21.5 MPa (~2000-3000 psi);
~d) producing the steam with its load of extracted organk matter through an off-take pipe conce"l-ically ,a ~ ~'-' ed within the borehob, so that the annulus between them serves as the injectbn hole; and (d) P~i"g as in exampb 1.
Suhsequent coking then albws u~,y, ' ,9 of the organk material and will simultaneously separate it from er,3 ' ,ed ino,yanics In tAd""~l~ 1, 1,A and 2 - and, indeed, a cl~af~t~r s; featvre of the recovery t~,~ e - is (i) the use of near-su~e,~;rilbal steam as a 'solvent' - and hence, the ,~cogn' ' ~ that loss of solvent to the io" " ' n, whkh has precluded depbyment of conventional organk solvents, is in N I -~.~, id, and (ii) continuous injection of steam and, consequently, uninterrupted 'sweeping' of the payzone during the entire production cycle (which beginswith steam injection).
However, also fu"d&"e"ldl to ~ ' ry ope, ation of the schemes e,~_" ,, "'' ~ ~ in 1, 1 A and 2 is the ~ ~de~I0- " ,9 that optimum injection I~",,~-dI~Ires and pressures are site- specific and depend on the thermal ulld-d,t~ ' s of the pay zone as well as those of its i"""ediat~ly over- and underlying strata. Our eAperbnoe to date suggestc that optimum I~,-,,ue,~lures in the pay zone will in most, but not all, cases, lie between 375 and 400~C and optimum pressures will range from 14 to 17.5 MPa.
3. In a third example of our procedure, an app~pri ~ !y constructed and sized pressure vessel is depbyed for pro-cessing m~ed oil sand, oil shaie or coalS In such an ope,. " ~, the feed is coarseiy crushed before being trans-ferred to the pressure vessei, but ali other steps co"tlspond to those outlined above.
4. The procedure indkated in example #3 can also be used to facilitate pe-",~,e"l disposal of sub~,' 'Iy water-insoluble toxic organic wastes ~c: '-d with i"o,ydnn, matter. For that purpose, eAb ' ~ with S~ ; ' water at b""~,dl-lres in the range 450~00~C and pressures above 17 MPa serves to separate and conce"hale the toxic material and thereby assist its efficient final destruction, e.g., by high-t~",~,e.uture combustion.
rer .~.~c~s.
1. N. ~rku..ik and J. Caideron; Fuel Process. Technol. 25, 3344, 1990 2. O. Ogunsola and N. 8erkowitz; ibid. ~i, 95-107, 1995 ~.~
NorbertBerkowitz, CM PhD PEng 105, 11660 - 79 Avenue Cdl"on~n, AB T6(~ OP7 Stephen Rae Dunn 1144 Cd~ ~ ~t Road NW
Calgary, AB T3A 2J8 S In this case, cAll_ ~ with nominally su,ue,~;,;~al H20 and CO would facilitate optimal 'skimming', i.e. ~:,t~ 1iun of a high p,upo, i' l as crude oils or oil precursors. The residual, partialiy devolatilized char can then be deployed as ciean fuel for, e.g.,. gene,~tiun of ole~,tli(,ity.
Claims (6)
1. A method for producing heavy/semi-heavy oils in situ.
2. A method for extracting bitumen from oilsands.
3. A method for extracting oil from oil shales.
4. A method for upgrading heavy/semi-heavy oil, bitumen, oil shale in a surface plant
5. A method for upgrading heavy/semi-heavy oil in si situ.
6. A method for extracting toxics from contaminated material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2208046 CA2208046A1 (en) | 1997-07-03 | 1997-07-03 | Method for recovering and concurrently partly upgrading heavy oils, bitumens and oil shale organic matter, and for extracting certain wastes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2208046 CA2208046A1 (en) | 1997-07-03 | 1997-07-03 | Method for recovering and concurrently partly upgrading heavy oils, bitumens and oil shale organic matter, and for extracting certain wastes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2208046A1 true CA2208046A1 (en) | 1999-01-03 |
Family
ID=4160903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2208046 Abandoned CA2208046A1 (en) | 1997-07-03 | 1997-07-03 | Method for recovering and concurrently partly upgrading heavy oils, bitumens and oil shale organic matter, and for extracting certain wastes |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2208046A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006029112A1 (en) * | 2004-09-08 | 2006-03-16 | Sovani Meksvanh | Solar augmented geothermal energy |
| US7947165B2 (en) | 2005-09-14 | 2011-05-24 | Yeda Research And Development Co.Ltd | Method for extracting and upgrading of heavy and semi-heavy oils and bitumens |
-
1997
- 1997-07-03 CA CA 2208046 patent/CA2208046A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006029112A1 (en) * | 2004-09-08 | 2006-03-16 | Sovani Meksvanh | Solar augmented geothermal energy |
| US7472548B2 (en) | 2004-09-08 | 2009-01-06 | Sovani Meksvanh | Solar augmented geothermal energy |
| US7947165B2 (en) | 2005-09-14 | 2011-05-24 | Yeda Research And Development Co.Ltd | Method for extracting and upgrading of heavy and semi-heavy oils and bitumens |
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