CA1135493A - Aluminum hydroxide gel system - Google Patents
Aluminum hydroxide gel systemInfo
- Publication number
- CA1135493A CA1135493A CA000341031A CA341031A CA1135493A CA 1135493 A CA1135493 A CA 1135493A CA 000341031 A CA000341031 A CA 000341031A CA 341031 A CA341031 A CA 341031A CA 1135493 A CA1135493 A CA 1135493A
- Authority
- CA
- Canada
- Prior art keywords
- fluid
- aluminum hydroxide
- drilling fluid
- drilling
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/16—Clay-containing compositions characterised by the inorganic compounds other than clay
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
ALUMINUM HYDROXIDE GEL SYSTEM
ABSTRACT OF THE DISCLOSURE
A1(OH)3 is added to a drilling fluid system together with other optional additives such as carboxymethyl cellulose, bentonite, polymer, potash, barite, etc., and acts as a primary viscoxifier. The principal advantage is due to the fact that it is an amphoteric material, i.e. it is soluble in both acid and alkaline conditions, but is insoluble in neutral or moderate pH conditions. This means that the entire mud system and its filter cake are completely acid or strong alkali soluble so that the entire colloidal suspension can be changed to a clear fluid and the filter cake completely dissolved by simply lowering or raising the pH of the system, a characteristic that is particularly desirable if formation damage is to be avoided and when the drill string is differ-entially stuck.
ABSTRACT OF THE DISCLOSURE
A1(OH)3 is added to a drilling fluid system together with other optional additives such as carboxymethyl cellulose, bentonite, polymer, potash, barite, etc., and acts as a primary viscoxifier. The principal advantage is due to the fact that it is an amphoteric material, i.e. it is soluble in both acid and alkaline conditions, but is insoluble in neutral or moderate pH conditions. This means that the entire mud system and its filter cake are completely acid or strong alkali soluble so that the entire colloidal suspension can be changed to a clear fluid and the filter cake completely dissolved by simply lowering or raising the pH of the system, a characteristic that is particularly desirable if formation damage is to be avoided and when the drill string is differ-entially stuck.
Description
~13~4~3~
"ALUMINUM HYDROXIDE GEL SYSTEM"
BACKGROUND OF THE INVENTION
This invention relates to new and useful improve-ments in drilling fluid systems.
A drilling fluid is normally pumped downwardly through the drill string, outwardly through the bit and then upwardly through the annulus existing between the bore-hole and the drill string. It is used for cooling and lu-brication purposes, to carry the drilling chips, grits, etc., from the drill bit to the surface wnereupon it may be separated in mud ponds and the like, and~ with certain addi-tives, to act as a control for the formation through which the drill is passing. For example, in well drilling oper-ations, shale containing formations are sometimes encount-ered in which conventional aqueous drilling muds are diffi-cult or impossible to use because the a~ueous portion of the drilling mud reacts with the clays in the shale to cause shale erosion, caving and extrusion into the well bore. Under extreme occurrences, the shale sometimes ex--trudes into the drill borehole and bears against the drill string, making drilling difficult or impossible.
In other words, it is to be appreciated that the drilling fluid or mud is tailor-made to suit specific pur-poses and specific conditions. The drilling fluid is thus one of the tools used when drilling wells.
One of the desirable features of a drilling mud ';: : .
'~
~L~3S~3~
"ALUMINUM HYDROXIDE GEL SYSTEM"
BACKGROUND OF THE INVENTION
This invention relates to new and useful improve-ments in drilling fluid systems.
A drilling fluid is normally pumped downwardly through the drill string, outwardly through the bit and then upwardly through the annulus existing between the bore-hole and the drill string. It is used for cooling and lu-brication purposes, to carry the drilling chips, grits, etc., from the drill bit to the surface wnereupon it may be separated in mud ponds and the like, and~ with certain addi-tives, to act as a control for the formation through which the drill is passing. For example, in well drilling oper-ations, shale containing formations are sometimes encount-ered in which conventional aqueous drilling muds are diffi-cult or impossible to use because the a~ueous portion of the drilling mud reacts with the clays in the shale to cause shale erosion, caving and extrusion into the well bore. Under extreme occurrences, the shale sometimes ex--trudes into the drill borehole and bears against the drill string, making drilling difficult or impossible.
In other words, it is to be appreciated that the drilling fluid or mud is tailor-made to suit specific pur-poses and specific conditions. The drilling fluid is thus one of the tools used when drilling wells.
One of the desirable features of a drilling mud ';: : .
'~
~L~3S~3~
-2-is to provide a fluid having desirable rheological proper-ties yet at the same time provide the desired characteris-tics.
For example, if the viscosifier used, is used in sufficient quantities in order to obtain the desired re-sults, an undesirable filter or mud cake is often formed in the bore which restricts the passage of the mud and some-times stops circulation altogether.
SUMMARY OF THE INVENTION
-The present invention overcomes disadvantages in-herent with conventional mud or drilling fluid systems by the addition of an amphoteric material. This produces a compound which is partially insoluble in a neutral or moderate pH, it being understood that the mud system is normally operating in neutral or moderate pH conditions.
This means that the entire colloidal suspension of the drilling fluid can be changed to a clear fluid and and filter cake which may have formed can be dissolved com-pletely by simply lowering or raising the pH of the sys-tem and this is tne principal advantage o~ the present in-vention.
In accordance with the invention there is provid-ed a drilling fluid which includes a viscosifier, said vis-cosifier taking the form of an amphoteric material, consist-ing of aluminum hydroxide colloidal gel having a pH of be-tween 7.5 - 11.0, said gel being substantially insoluble at 9~
a pH in the same range o-f 7.5 - 11Ø
Another aspect of the invention in accordance with the foregoing, is to provide an acid soluble work-over or completion fluid for well drilling which includes an acid soluble material selected from the group consisting of calcium carbonate, sodium chloride, calcium chloride and calcium bromide.
Another advantage of the present invention is to use a viscosifier comprising aluminum hydroxide which, when mixed with a drillin~ mud system, is temperature stable up to approximately 300 - 900F thereby overcoming disadvantages of most of all organic polymers which are thermally degradable at between 300- 400F.
A still further advantage of the invention is to provide an aluminum hydroxide gel system usable in a drilling fluid system which is simple in manufacture and otherwise well suited to the purpose for which it is de-signed.
With the foregoing in view, and other ad-vantages as will become apparent to those skilled in the art to which this invention relates as this speciLication proceeds, which includes a description of the preferred embodiment of the principles of the present invention.
DETAILED DESCRIPTION
Proceeding therefore to describe the invention in detail, an aluminum hydroxide gel is prepared by one of i~3~ 3 severa] methods.
Aluminum hydroxide [Al(OH)3] is an amphoteric material partially insoluble in or near neutral or moderate pH. Amphoteric materials are, however, reactant with or soluble in strongly alkaline or acidic pH. When the aluminum hydroxide is precipitated, it Eorms a stable colloidal sus-pension in the form of a gel which has desirable rheologi-cal properties and is suitable for drilling fluid usage.
This colloidal suspension is made up of both soluble and in-10soluble aluminum hydroxide.
It is used as the primary viscosifier to buildthe drilling fluid system, which together with other option-al additives such as carboxymethyl cellulose (CMC), ben-tonite, polymer~ potash and barite, etc., forms a diversi-fied mud systern which can give excellent rheological proper-ties, good water loss control and desired mud weight.
One method utilized to generate the aluminum hydroxide gel is by treating sodium aluminate with an acid such as hydrochloric acid:
20NaAl(OH)~ + HCl~ Al(OH)3 + NaCl + H20 i~.,J
;~`
:,' ' ': :
., ' ~354~
Sodium aluminate is readily available in powder or liquid form and when an aqueous solution of this material (about 60 to 65 kg/m gives a pH 12 - 14) is treated with . , :~lLi35~3 acid to bring the pH down to preferably 8.5 - 9.0 (although it is still effective within the range of 7.5 - 11.0), a white gelatinous colloidal suspension is formed and this is the basis of the mud system and acts as the viscosifier.
The fluid thus formed is a highly shear-thinning pseudo-plastic fluid with an n-value equal 0.2 - 0.3. It will be appreciated that the properties of the base fluid can be adjusted by conventional mud additivies as desired.
Other methods can be used to generate the aluminum hydroxide gel with only a slight variation in the resultant properties:
(1) Aluminum chlorohydrate (AlC13 6H20) and sodium hydroxide.
(2) Solub]e alumina (A1203 6H20) reacting with sodium hydroxide. This reaction may be too slow to have any practical use.
For example, if the viscosifier used, is used in sufficient quantities in order to obtain the desired re-sults, an undesirable filter or mud cake is often formed in the bore which restricts the passage of the mud and some-times stops circulation altogether.
SUMMARY OF THE INVENTION
-The present invention overcomes disadvantages in-herent with conventional mud or drilling fluid systems by the addition of an amphoteric material. This produces a compound which is partially insoluble in a neutral or moderate pH, it being understood that the mud system is normally operating in neutral or moderate pH conditions.
This means that the entire colloidal suspension of the drilling fluid can be changed to a clear fluid and and filter cake which may have formed can be dissolved com-pletely by simply lowering or raising the pH of the sys-tem and this is tne principal advantage o~ the present in-vention.
In accordance with the invention there is provid-ed a drilling fluid which includes a viscosifier, said vis-cosifier taking the form of an amphoteric material, consist-ing of aluminum hydroxide colloidal gel having a pH of be-tween 7.5 - 11.0, said gel being substantially insoluble at 9~
a pH in the same range o-f 7.5 - 11Ø
Another aspect of the invention in accordance with the foregoing, is to provide an acid soluble work-over or completion fluid for well drilling which includes an acid soluble material selected from the group consisting of calcium carbonate, sodium chloride, calcium chloride and calcium bromide.
Another advantage of the present invention is to use a viscosifier comprising aluminum hydroxide which, when mixed with a drillin~ mud system, is temperature stable up to approximately 300 - 900F thereby overcoming disadvantages of most of all organic polymers which are thermally degradable at between 300- 400F.
A still further advantage of the invention is to provide an aluminum hydroxide gel system usable in a drilling fluid system which is simple in manufacture and otherwise well suited to the purpose for which it is de-signed.
With the foregoing in view, and other ad-vantages as will become apparent to those skilled in the art to which this invention relates as this speciLication proceeds, which includes a description of the preferred embodiment of the principles of the present invention.
DETAILED DESCRIPTION
Proceeding therefore to describe the invention in detail, an aluminum hydroxide gel is prepared by one of i~3~ 3 severa] methods.
Aluminum hydroxide [Al(OH)3] is an amphoteric material partially insoluble in or near neutral or moderate pH. Amphoteric materials are, however, reactant with or soluble in strongly alkaline or acidic pH. When the aluminum hydroxide is precipitated, it Eorms a stable colloidal sus-pension in the form of a gel which has desirable rheologi-cal properties and is suitable for drilling fluid usage.
This colloidal suspension is made up of both soluble and in-10soluble aluminum hydroxide.
It is used as the primary viscosifier to buildthe drilling fluid system, which together with other option-al additives such as carboxymethyl cellulose (CMC), ben-tonite, polymer~ potash and barite, etc., forms a diversi-fied mud systern which can give excellent rheological proper-ties, good water loss control and desired mud weight.
One method utilized to generate the aluminum hydroxide gel is by treating sodium aluminate with an acid such as hydrochloric acid:
20NaAl(OH)~ + HCl~ Al(OH)3 + NaCl + H20 i~.,J
;~`
:,' ' ': :
., ' ~354~
Sodium aluminate is readily available in powder or liquid form and when an aqueous solution of this material (about 60 to 65 kg/m gives a pH 12 - 14) is treated with . , :~lLi35~3 acid to bring the pH down to preferably 8.5 - 9.0 (although it is still effective within the range of 7.5 - 11.0), a white gelatinous colloidal suspension is formed and this is the basis of the mud system and acts as the viscosifier.
The fluid thus formed is a highly shear-thinning pseudo-plastic fluid with an n-value equal 0.2 - 0.3. It will be appreciated that the properties of the base fluid can be adjusted by conventional mud additivies as desired.
Other methods can be used to generate the aluminum hydroxide gel with only a slight variation in the resultant properties:
(1) Aluminum chlorohydrate (AlC13 6H20) and sodium hydroxide.
(2) Solub]e alumina (A1203 6H20) reacting with sodium hydroxide. This reaction may be too slow to have any practical use.
(3) other aluminum salts such as aluminum sulfate, potassium aluminum sulfate, and the like reacting with sodium hydroxide.
Method (2) (soluble alumina) may be too slow in reaction time to have any practical use and the most econo-mical way known to the applicant to generate the aluminum hydroxide gel, is with sodium aluminate and hydrochloric acid.
Because of the fact that aluminum hydroxide gel is totally soluble at very low pH (acidic) or very high pH
(alkaline), it can be used to form the basis of a temperature-1~L3S~3 stable, non-damaging work-over and/or completion fluid.
Using acid-soluble material such as calcium car-bonate and/or water-soluble salts such as sodium chloride, calcium chloride, calcium bromide, and the like, a totally acid-soluble work-over fluid or completion fluid system can be designed.
As mentioned previously, the entire mud system can be changed to a clear fluid and any filtercake which may have formed, can be completely dissolved by lowering or raising the pH of the system by conventional means. This, of course, is particularly desirable if formation damage is to be avoided and when the drill string is differentially stuck.
Given below are experimental results of the aluminum hydroxide gel system.
Aluminum hydroxide gel (Al(OE)3) is prepared by adding sodium aluminate (NaAl(OE)4) in the quantities spec-ified below, to water pre-treated with acid.
Virtually anystrong acid can be used to treat the water. In this instance, 12N HCl at the rate of 50 to 100 m3 HCl per 1000 m3s H20 is used.
After addition of sodium aluminate to the acidified water the pH is checked and adjusted to the desired range of between 8.5 - 9.5 if necessary.
Table 1 is a list of the mud properties of the aluminum hydroxide gel system. The theta (0) values are ~135~93 conventional Fann 35 (6-speed V G meter) dial readings.
I ~Q
=~~ n ~ u~
C _~ 0~ , O 1~ N O
O O O O ~ ;
C~i . _ E
2 *
3 ~ ~ ~ 3 In order to control water loss hydroxyethylcellu-lose (HEC) along with some inert solids (drilled solids) is added to the system. This choice of water loss control agent is not unique and any of a variety of polymers can be used.
For example, the biopolymers xanthan gum (XC - polymer) and carboxmethylcellulose (CMC) have also been found to control water loss in this system. The drilled solids ( D.S.) were added only to provide a particulate solids matrix. These solids aid the water loss control polymer in forming a tight filter cake and thus a lower A.P.I. fluid loss. In an actual drilling mud this role would be filled by solids generated at the bit and by weight material (if any) added to the system.
g eE3 o o v~
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E ~ E E
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' ~: d . ~ C~i O n~ .-- 1_ LLI ~ LLI
CO 2 + ¢ ~- '5 .
,, :: ::, -:
', ' ' ' ~ ' .
IL~3~33 In use it is desirable that the amount of aluminum hydroxide be between 6% and 12% by weight of the total dril-ling mud under normal conditions. However, when an acid soluble material is used selected from the group consisting of calcium carbonate, sodium chloride, calcium chloride or calcium bromide~ to provide an acid soluble work-over fluid, then the percentage by weight of the aluminum hydroxide may be between 2% and 10% of the total weight of the drilling fluid.
Since various modifications can be made in my in-vention as hereinabove described, and many apparently widely different embodiments of same made within the spirit and scope of the claims without departing from such spirit and scope, it is intended that all matter contained in the accom-panying specification shall be interpreted as illustrative only and not in a limiting sense.
Method (2) (soluble alumina) may be too slow in reaction time to have any practical use and the most econo-mical way known to the applicant to generate the aluminum hydroxide gel, is with sodium aluminate and hydrochloric acid.
Because of the fact that aluminum hydroxide gel is totally soluble at very low pH (acidic) or very high pH
(alkaline), it can be used to form the basis of a temperature-1~L3S~3 stable, non-damaging work-over and/or completion fluid.
Using acid-soluble material such as calcium car-bonate and/or water-soluble salts such as sodium chloride, calcium chloride, calcium bromide, and the like, a totally acid-soluble work-over fluid or completion fluid system can be designed.
As mentioned previously, the entire mud system can be changed to a clear fluid and any filtercake which may have formed, can be completely dissolved by lowering or raising the pH of the system by conventional means. This, of course, is particularly desirable if formation damage is to be avoided and when the drill string is differentially stuck.
Given below are experimental results of the aluminum hydroxide gel system.
Aluminum hydroxide gel (Al(OE)3) is prepared by adding sodium aluminate (NaAl(OE)4) in the quantities spec-ified below, to water pre-treated with acid.
Virtually anystrong acid can be used to treat the water. In this instance, 12N HCl at the rate of 50 to 100 m3 HCl per 1000 m3s H20 is used.
After addition of sodium aluminate to the acidified water the pH is checked and adjusted to the desired range of between 8.5 - 9.5 if necessary.
Table 1 is a list of the mud properties of the aluminum hydroxide gel system. The theta (0) values are ~135~93 conventional Fann 35 (6-speed V G meter) dial readings.
I ~Q
=~~ n ~ u~
C _~ 0~ , O 1~ N O
O O O O ~ ;
C~i . _ E
2 *
3 ~ ~ ~ 3 In order to control water loss hydroxyethylcellu-lose (HEC) along with some inert solids (drilled solids) is added to the system. This choice of water loss control agent is not unique and any of a variety of polymers can be used.
For example, the biopolymers xanthan gum (XC - polymer) and carboxmethylcellulose (CMC) have also been found to control water loss in this system. The drilled solids ( D.S.) were added only to provide a particulate solids matrix. These solids aid the water loss control polymer in forming a tight filter cake and thus a lower A.P.I. fluid loss. In an actual drilling mud this role would be filled by solids generated at the bit and by weight material (if any) added to the system.
g eE3 o o v~
,,~, Z o o ~----L~
~ ~ ~ o _ _ ___ _~
~ . ~ ~ ~
U~ ~ _ _ _ _ ._ o~
I ~:: __. _ .. _... ... ~ ._._.. ____ ~ 00 U~
IJJ r~ u~ co .. . ~ -- L
~ a _~ __ o ~~ 1~
cc q7 00 ~ ~
~ O O ___ _ ~
LL~ CD C~ I~ I_ ~
_ E
lY 00 O Lt~ O t~
~ C~J
O ~D O N O
N a~ CO CO
_ o . o o E
C~ ~ ~ L~ ~ -a~ 1~) _I_ ~__ C~ C~
E ~ E E
^ cn v ~
C~ l_ O ~ U~
' ~: d . ~ C~i O n~ .-- 1_ LLI ~ LLI
CO 2 + ¢ ~- '5 .
,, :: ::, -:
', ' ' ' ~ ' .
IL~3~33 In use it is desirable that the amount of aluminum hydroxide be between 6% and 12% by weight of the total dril-ling mud under normal conditions. However, when an acid soluble material is used selected from the group consisting of calcium carbonate, sodium chloride, calcium chloride or calcium bromide~ to provide an acid soluble work-over fluid, then the percentage by weight of the aluminum hydroxide may be between 2% and 10% of the total weight of the drilling fluid.
Since various modifications can be made in my in-vention as hereinabove described, and many apparently widely different embodiments of same made within the spirit and scope of the claims without departing from such spirit and scope, it is intended that all matter contained in the accom-panying specification shall be interpreted as illustrative only and not in a limiting sense.
Claims
WHAT I CLAIM AS MY INVENTION IS:
(1) A drilling fluid which includes a viscosi-fier, said viscosifier taking the form of an amphoteric material, consisting of aluminum hydroxide colloidal gel having a pH of between 7.5 - 11.0, said gel being substan-tially insoluble at a pH in the same range of 7.5 - 11Ø
(2) The fluid according to Claim 1 in which the viscosifier comprises a highly shear-thinning pseudo-plastic fluid with n-value equal to 0.2 - 0.3.
(3) The fluid according to Claim 1 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 6.0% and 12.0% by weight of the total drilling fluid.
(4) The fluid according to Claim 2 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 6.0% and 12.0% by weight of the total drilling fluid.
(5) An acid soluble work-over or completion fluid for well drilling according to Claim 1 which in-cludes an acid soluble material selected from the group consisting of calcium carbonate, sodium chloride, calcium chloride and calcium bromide.
(6) The fluid according to Claim 5 in which the aluminum hydroxide consists of a highly shear-thinning pseudo-plastic fluid with n-value equal to 0.2 - 0.3.
(7) The fluid according to Claim 5 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 2.0% and 10.0% by weight of the total drilling fluid.
(8) The fluid according to Claim 6 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 2.0% and 10.0% by weight of the total drilling fluid.
(1) A drilling fluid which includes a viscosi-fier, said viscosifier taking the form of an amphoteric material, consisting of aluminum hydroxide colloidal gel having a pH of between 7.5 - 11.0, said gel being substan-tially insoluble at a pH in the same range of 7.5 - 11Ø
(2) The fluid according to Claim 1 in which the viscosifier comprises a highly shear-thinning pseudo-plastic fluid with n-value equal to 0.2 - 0.3.
(3) The fluid according to Claim 1 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 6.0% and 12.0% by weight of the total drilling fluid.
(4) The fluid according to Claim 2 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 6.0% and 12.0% by weight of the total drilling fluid.
(5) An acid soluble work-over or completion fluid for well drilling according to Claim 1 which in-cludes an acid soluble material selected from the group consisting of calcium carbonate, sodium chloride, calcium chloride and calcium bromide.
(6) The fluid according to Claim 5 in which the aluminum hydroxide consists of a highly shear-thinning pseudo-plastic fluid with n-value equal to 0.2 - 0.3.
(7) The fluid according to Claim 5 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 2.0% and 10.0% by weight of the total drilling fluid.
(8) The fluid according to Claim 6 in which the aluminum hydroxide in the drilling fluid is present in the amounts of between 2.0% and 10.0% by weight of the total drilling fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000341031A CA1135493A (en) | 1979-11-30 | 1979-11-30 | Aluminum hydroxide gel system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000341031A CA1135493A (en) | 1979-11-30 | 1979-11-30 | Aluminum hydroxide gel system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1135493A true CA1135493A (en) | 1982-11-16 |
Family
ID=4115730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000341031A Expired CA1135493A (en) | 1979-11-30 | 1979-11-30 | Aluminum hydroxide gel system |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1135493A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541485A (en) * | 1983-06-24 | 1985-09-17 | W. R. Grace & Co. | Completion and workover fluid |
| US4719021A (en) * | 1984-11-28 | 1988-01-12 | Sun Drilling Products Corporation | Shale-stabilizing drilling fluids and method for producing same |
-
1979
- 1979-11-30 CA CA000341031A patent/CA1135493A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541485A (en) * | 1983-06-24 | 1985-09-17 | W. R. Grace & Co. | Completion and workover fluid |
| US4719021A (en) * | 1984-11-28 | 1988-01-12 | Sun Drilling Products Corporation | Shale-stabilizing drilling fluids and method for producing same |
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