CA1166434A - Process and composition for scavenging hydrogen sulfide in aqueous drilling fluids - Google Patents
Process and composition for scavenging hydrogen sulfide in aqueous drilling fluidsInfo
- Publication number
- CA1166434A CA1166434A CA000387423A CA387423A CA1166434A CA 1166434 A CA1166434 A CA 1166434A CA 000387423 A CA000387423 A CA 000387423A CA 387423 A CA387423 A CA 387423A CA 1166434 A CA1166434 A CA 1166434A
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- salt
- lignosulfonate
- wellbore
- soluble
- 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
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
PROCESS AND COMPOSITION FOR
SCAVENGING HYDROGEN SULFIDE
IN AQUEOUS DRILLING FLUIDS
ABSTRACT OF THE DISCLOSURE
An aqueous solution of 8-15 wt.% zinc chelate made by reacting an aqueous solution of zinc salt and lignosulfonate salt, which is added to a wellbore fluid contaminated with H2S provides a highly efficient H2S scavenger at about one pound of the zinc chelate solution per barrel of wellbore fluid.
SCAVENGING HYDROGEN SULFIDE
IN AQUEOUS DRILLING FLUIDS
ABSTRACT OF THE DISCLOSURE
An aqueous solution of 8-15 wt.% zinc chelate made by reacting an aqueous solution of zinc salt and lignosulfonate salt, which is added to a wellbore fluid contaminated with H2S provides a highly efficient H2S scavenger at about one pound of the zinc chelate solution per barrel of wellbore fluid.
Description
~66~3J
PROCESS AND COMPOSITIO~T FOR
SCAVENGI~TG HYDROGEN SULFIDE
IN AQUEOUS ~RILLING FLUIDS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a compositlon and process for scavenging hydrogen sulfide in aqueous drilling fluids. The scavenging of hydrogen sulfide prevents hydrogen sulfide corrosion of metallic surfaces of the apparatus employed in drilling, completion and workover of subterranean we`lls.
Re'ated Art - 3uring drilling in subterranean ~~orma~ior.s a fluid, usually at least in part aqueous is presen.
1~ in the wellbore. The fluids are circulated as in ro-tary drilling or placed in the bottom of the bore hole as in cable tool drilling~ In the circulating syst~ms the fluid is circulated down through the hollow drill string to pick up cutting ~ormed by the drill bit, ~5 carry them to the surface in the annulus surrounding the bit, and pass them through a series of mechanical devices and set-ling tanks tO remove the drilled scii~s and return the drilling fluid to the drill s~ring f~r recirculation. The fluid-also serves to cool the rotar~
2C bit. Other functions of the drilling fluids are tO
1166~3~
PROCESS AND COMPOSITIO~T FOR
SCAVENGI~TG HYDROGEN SULFIDE
IN AQUEOUS ~RILLING FLUIDS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a compositlon and process for scavenging hydrogen sulfide in aqueous drilling fluids. The scavenging of hydrogen sulfide prevents hydrogen sulfide corrosion of metallic surfaces of the apparatus employed in drilling, completion and workover of subterranean we`lls.
Re'ated Art - 3uring drilling in subterranean ~~orma~ior.s a fluid, usually at least in part aqueous is presen.
1~ in the wellbore. The fluids are circulated as in ro-tary drilling or placed in the bottom of the bore hole as in cable tool drilling~ In the circulating syst~ms the fluid is circulated down through the hollow drill string to pick up cutting ~ormed by the drill bit, ~5 carry them to the surface in the annulus surrounding the bit, and pass them through a series of mechanical devices and set-ling tanks tO remove the drilled scii~s and return the drilling fluid to the drill s~ring f~r recirculation. The fluid-also serves to cool the rotar~
2C bit. Other functions of the drilling fluids are tO
1166~3~
-2^
serve as weighting asents, e~erting pressure on the surrounding formations, thus preventing caving of the formation or blow out of pressurized oil or gas in the formation. In addition, the fluid also serves as a lubricating agent for the bearings of the drill bit and the surface of the cutting teeth.
The aqueous fluids may employ fresh water or brines, and may include emulsions of water and oil.
Generally various additives are included in the systems to control fluid loss, weight the fluid, increase par-ticle carrying capacity, inhibit corrosion and bacteria and the like. Some aqueous systems contain colloidal clays while others are relatively clay-free.
Hydrogen sulfide gas is often found in for-mations and may contaminate the drilling fluid. Insome instances, underground waters will contain dis-solved hydrogen sulfide. In addition sulfate-reducing bacteria will conYert sulfates into hydrogen sulfIde.
Hydrogen sulfide may readily dissolve in fluids having 2G a pH of less than about 11 which further reduces the pH and makes the fluid more corrosive. Hydrogen sul-fide gas will sometimes affect the viscosity, fluid l`oss and other properties of the fluid~ Thus, hydrogen sulfide may be the most harmful corrosive compound found in drilling fluid systems.
In the presence of moisture, hydrogen sul-fide gas will attack steel to form ferrous sulfide and free hydrogen. The ~ree hydrogen may penetrate into the metal components of the drilling system, causing hydrogen embrittlement. Hydrogen sulfide attacks metal surfaces and may cause pitting.
In addition to the corrosiYe problems, hy-drogen sulfide is extremely hazardous to the health of personnel working near a drilling rig~ The gas entrapped in the fluid in the bore under pressure, ' 1 ~66434 ,, ~ay escape in the open settling or holdi..g pits for the fluid on the surface. Since H2S is denser than aLir~ it is held in low spots or near the grQund. The readily de~actable "rotten egg" smell of the H2S at low concentration is not possible with higher lethal concentrations which paralyze olfactory nerves.
Various methods have been porposed for sca-venging hydrogen sulfide from wellbore fluids, e.g., US Pat. 2,429,593, the addition of alkali (~'aOH); US
Pat. 3,506,572 discloses the use of copper carbonate and/or hydrogen peroxide; US Pat. 3,301,323 discloses zinc acetate, cadmium chloride and ferrous sul~ate;
and US Pat. 3,928,211 discloses zinc carbonate, basic zinc carbonate and zinc hydroxide.
1 l66~3~
SU~RY OF THE I~i~'TION
-Briefly, the invention in one aspect is a liquid wellbore additive composition comprising 8 to 1~ preferably 10 to 13 weight percent of a zinc che-la~e prepared by the process of reacting a solublezinc salt and a lignosulfonate salt in an aqueous solution.
A further aspect of the present invention is the method of preventing corrosion of subterranean well apparatus exposed to an alkaline wellbore fluid contaminated by hydrogen sulfide by having present in said wellbore fluid a hydrogen sulfide scavenging amount of a zinc chelate of li~nosulfate. Generally at least 1 pound per barrel of wellbore fluid of an aqueous solution containing 8 to 15 weight percent zinc chelate of lignosulfonate compound is employed.
The term "hydrogen sulfide scavenging amount"
as that term is used herein means that amount of the zinc chelate of lignosulfon`ate which will effectively remove the hydrogen sulfide present in the wellbore fluid.
The amount of zinc chelate used in a parti-cular wellbore fluid, is primarily determined by the H2S present therein. ~or example, the basis for deter-mining the amount of a 12% solution of the presentzinc chelate is at le`ast one pound of said solution per barrel of wellbore fluid for each 250 ppm of H2S
present in the wellbore fluid. If less than 250 ppm of H2S present is detected, usually one pound of the 12~ solution is employed. It ~an be readily determined for other concentrations, i.e., 8-15% zinc chelate, the amount to be employed on this basis. Generally, however at least one pound and preferably at least 2 pounds of the 8-15 wt.~ zinc lignosulfonate chelate solution is employed per barrel of the wellbore fluid.
The reason for using this minimum amount, is because of the extreme dilution of the zinc chelate if less than one pound were used. In effect even though S theoretically a lesser amount could be employed based on H2S present, the dilution would reduce the likeli-hood of the zinc chelate molecules contacting the H2S.
In other words there is no* enough of the scavenger present to contact the few parts per million of H2S
present.
The present zinc chelate solution is a hy-drogen sulfide scavenger. In addition to inhibiting hydrogen sulfide corrosion, the zinc chelate also pro-vides some degree of protection against corrosion re-sulting from oxygen. The liquid zinc chelate is watersoluble.
Since the present additive composition is a liquid, (i.e., aqueous solution) it is'an advantage that it can be injected directly into the mud-pump section line with a chemical pump, thus avoiding costly and messy mixing of powders.
DETAILED DESCRIPTIO~ O~ THE I~ENTIO~
-The zinc chelate of li~nosulfonate is pre-pared by contacting a soluble salt of zinc and a soluble salt of lignosulfonate in an aqueous solution at ambient temperature, i.e., 20-30C. The reaction goes to com-pletion rapidly to produce a brown solution containing chelate. It is this entire reaction product which is the additive composition.
Preferably, highly soluble inorganic zinc salts such as zinc chloride, zinc bromide~ zinc iodide or mixtures thereof are employed however~ the less soluble salts such as zinc chlorate, zinc nitrate (tri-hydrate or hexahydrate) or zinc sulfate (heptahydrate and hexahydrate) may be either alone or in admixture with each other or with the more soluble zinc compounds.
The sulfate for example may be maae more soluble by using a higher reaction medium temperature than ambient.
The lignosulfate salt solution employed in the present invention is a crude product deri~ed fIom the processing of paper pulp and is employed the solu-tion neutralized with the appTopriate base, e.g., sodium hydroxide, calcium hydroxide or the like. Hence, nor-- mally sodium or calcium lignosu~fonate will be employed but other lignosulfonate solutions such as the ammoniu~
salt, iron salt, ma~nesium salt, chromium salt or mixtures thereof can be used. The sodium lignosulfonate is pre-ferred because of cost. This solution should haYe a pH
of less than 9, preferably a pH of 5-~ for the reaction with the zinc salt. The reaction product will have an acid pH, i.e., from about 3 to 6.
The lignosulfonate salt is highly complex mixture of materials and a molar type reaction is im-possible to determine. It has been found that complete chelation is obtained with from 2 to 3 pounds of ligno-sulfonate ~dry basis) per pound zinc in solution, preferably 2 5 pounds of lignosulfonate per pound of zinc.
Thus, in the aqueous reaction system therewi.ll be from 8 to 15 wt, ~ zinc present and 16 to 45 weight % lignosulfonate salt~ e.g., at 8 wt.% the range of lignosulfonate will be 16 to 30 weight % and at 15 wt.% Zn the range of lignosulfonate will be 24 to 45 wt.% (1:2-3 weight ratio Zn:lignosulfonate).
The crude lignosulfonate solutions employed may contain sugar, since they are unprocessed. The sugar, however, may cause a precipitate. Hence, the sugar should be as low as possible, and preferably not present, in order to avoid solids in the reaction product. It should also be appreciated that at a 15%
zinc chelate concentration the reaction product is a very viscous liquid which may be difficult to pump.
Thus, about a 12% zinc chelate which provides a high concentration of H2S scavenger in a form pumpable over a wide temperatuTe range is preferred.
The following examples are presented to il-lustrate the invnetion and are not intended to limit thescope thereof.
Examples 1 and 2 A 12 wt.% zinc lignosulfonate chelate solu-tion was prepared by contacting 40 wt.% of a zinc chlo-ride solution containing 30 wt.% zinc chloride dissolvedtherein and 60 wt.% of a solution of 50 wt.~ sodium lignosulfonate (pH 6.4) in a mixing vessel equipped with a stirrer. The solutions are mixed together for about 15 minutes to complete the reaction. The tem-perature of the solutions were ambient (about 25C)and no increase in the temperature of the reaction mixture was observed. The final pH of the reaction mixture was about 3.8. The product was a dark brown liquid having an increased viscosity from the starting materials.
1 l66~3~
- S-A 10 wt.% æinc lignosulfonate c~elate solu-tion was prepared in the sa~e manner except 33.3 wt.
solution containing a 30 wt.% zinc chloride; 50 Wt. ~
of 50 wt.% sodium lignosulfonate solution and 17 wt.%
water were employed. A similar dark brown viscous liquid was produced. The pH was also about 3.8 Examples 3-6 In the following runs the compositions pre-pared according to examples 1 and 2 were compared to two (2) commercial zinc containing H2S scavengers.
The compounds were tested in at the same pounds per barrel of wellbore fluid.
The evaluation was conducted in an unweighted fresh water lignosulfonate mud of the following composition:
22 lb/bbl Wyoming bentonite 25 lb/bbl Martin No. 5 Ball Clay 1.5 lb/bbl ~errochrome lignosulfonate 0.1 lb/bbl Sodium hydroxide Sulfide ion was added as^~sodium sulfide (Na2S.9H2O). Calculations are based on sulfide ion as measured in the mud filtrate using the Garrett Gas Train (GGT).
- The results of the tests are set out in the TABLE.
l l66~34 9, TABLE
Example 3 4 5 6 Blank IMC0 Sulf-X II(l), (solid) lb/bbl 2 0 S Mil-Gard(2), (solid) lb/bbl 2 0 10% Zinc Chelate (solution), lb/bbl 2 0 12S Zinc Chelate (solution) lb/bbl 2 0 Stirred 10 minutes at ll,Q00 rpm on the Multimixer pH 10.30 10.7S 10.809.55 10.30 API Filter Loss, ml 11.0 12.0 11.0 12.0 11.0 GGT/Sulfide,ppm 0.5 0.5 0 7 0,5 400 ; 15 Hot Rolled 16 hours at 150F. (Added 500 ppm sulfide after hot rol1in~
Apparent Viscosity, cpQ80F 16 16 17 18 13 Plastic Viscosity, cp13 13 13 13 11 Yield Point,lb/100 ft2S S 4 S 4 20~ Gel Stren~ths,lb/100 ft2 10 sec/10 min 0/4 0/0 0/S 0/8 0/0 pH 9.85 9.70 lO.S59.00 9.20 API Filter Loss, ml 9.3 9,3 9.4 8.9 S.9 Cake Thickness, 32nd inch 2 2 2 2 2 GGT/Sulfide,ppm 30 24 250 60 S00 Total Available Zinc,ppm 1328 2979 S71 686 0 Actual Sulfides removed,ppm 870 876 6S0 840 ---Efficiency ppm S /ppm zinc0.655 0.2941.135 1.225 ---~1~ Product of IMC0 Services, believed to be solid zinc cholato (2) Product of Milchem Incorporated, believed to be 3 mixture of zinc carbonato and zinc hydroxide (desi~nated DS "b3sic zinc cDrbonatc") ~ ' , .
_ 9 , .
:
The results show that there is a greater H2S removal efficiency for ~he present compositions (based on a~ailable zinc) than for higher zinc ion concentrations available from the other two mateTials.
.
! : :
.
. .
~ .
serve as weighting asents, e~erting pressure on the surrounding formations, thus preventing caving of the formation or blow out of pressurized oil or gas in the formation. In addition, the fluid also serves as a lubricating agent for the bearings of the drill bit and the surface of the cutting teeth.
The aqueous fluids may employ fresh water or brines, and may include emulsions of water and oil.
Generally various additives are included in the systems to control fluid loss, weight the fluid, increase par-ticle carrying capacity, inhibit corrosion and bacteria and the like. Some aqueous systems contain colloidal clays while others are relatively clay-free.
Hydrogen sulfide gas is often found in for-mations and may contaminate the drilling fluid. Insome instances, underground waters will contain dis-solved hydrogen sulfide. In addition sulfate-reducing bacteria will conYert sulfates into hydrogen sulfIde.
Hydrogen sulfide may readily dissolve in fluids having 2G a pH of less than about 11 which further reduces the pH and makes the fluid more corrosive. Hydrogen sul-fide gas will sometimes affect the viscosity, fluid l`oss and other properties of the fluid~ Thus, hydrogen sulfide may be the most harmful corrosive compound found in drilling fluid systems.
In the presence of moisture, hydrogen sul-fide gas will attack steel to form ferrous sulfide and free hydrogen. The ~ree hydrogen may penetrate into the metal components of the drilling system, causing hydrogen embrittlement. Hydrogen sulfide attacks metal surfaces and may cause pitting.
In addition to the corrosiYe problems, hy-drogen sulfide is extremely hazardous to the health of personnel working near a drilling rig~ The gas entrapped in the fluid in the bore under pressure, ' 1 ~66434 ,, ~ay escape in the open settling or holdi..g pits for the fluid on the surface. Since H2S is denser than aLir~ it is held in low spots or near the grQund. The readily de~actable "rotten egg" smell of the H2S at low concentration is not possible with higher lethal concentrations which paralyze olfactory nerves.
Various methods have been porposed for sca-venging hydrogen sulfide from wellbore fluids, e.g., US Pat. 2,429,593, the addition of alkali (~'aOH); US
Pat. 3,506,572 discloses the use of copper carbonate and/or hydrogen peroxide; US Pat. 3,301,323 discloses zinc acetate, cadmium chloride and ferrous sul~ate;
and US Pat. 3,928,211 discloses zinc carbonate, basic zinc carbonate and zinc hydroxide.
1 l66~3~
SU~RY OF THE I~i~'TION
-Briefly, the invention in one aspect is a liquid wellbore additive composition comprising 8 to 1~ preferably 10 to 13 weight percent of a zinc che-la~e prepared by the process of reacting a solublezinc salt and a lignosulfonate salt in an aqueous solution.
A further aspect of the present invention is the method of preventing corrosion of subterranean well apparatus exposed to an alkaline wellbore fluid contaminated by hydrogen sulfide by having present in said wellbore fluid a hydrogen sulfide scavenging amount of a zinc chelate of li~nosulfate. Generally at least 1 pound per barrel of wellbore fluid of an aqueous solution containing 8 to 15 weight percent zinc chelate of lignosulfonate compound is employed.
The term "hydrogen sulfide scavenging amount"
as that term is used herein means that amount of the zinc chelate of lignosulfon`ate which will effectively remove the hydrogen sulfide present in the wellbore fluid.
The amount of zinc chelate used in a parti-cular wellbore fluid, is primarily determined by the H2S present therein. ~or example, the basis for deter-mining the amount of a 12% solution of the presentzinc chelate is at le`ast one pound of said solution per barrel of wellbore fluid for each 250 ppm of H2S
present in the wellbore fluid. If less than 250 ppm of H2S present is detected, usually one pound of the 12~ solution is employed. It ~an be readily determined for other concentrations, i.e., 8-15% zinc chelate, the amount to be employed on this basis. Generally, however at least one pound and preferably at least 2 pounds of the 8-15 wt.~ zinc lignosulfonate chelate solution is employed per barrel of the wellbore fluid.
The reason for using this minimum amount, is because of the extreme dilution of the zinc chelate if less than one pound were used. In effect even though S theoretically a lesser amount could be employed based on H2S present, the dilution would reduce the likeli-hood of the zinc chelate molecules contacting the H2S.
In other words there is no* enough of the scavenger present to contact the few parts per million of H2S
present.
The present zinc chelate solution is a hy-drogen sulfide scavenger. In addition to inhibiting hydrogen sulfide corrosion, the zinc chelate also pro-vides some degree of protection against corrosion re-sulting from oxygen. The liquid zinc chelate is watersoluble.
Since the present additive composition is a liquid, (i.e., aqueous solution) it is'an advantage that it can be injected directly into the mud-pump section line with a chemical pump, thus avoiding costly and messy mixing of powders.
DETAILED DESCRIPTIO~ O~ THE I~ENTIO~
-The zinc chelate of li~nosulfonate is pre-pared by contacting a soluble salt of zinc and a soluble salt of lignosulfonate in an aqueous solution at ambient temperature, i.e., 20-30C. The reaction goes to com-pletion rapidly to produce a brown solution containing chelate. It is this entire reaction product which is the additive composition.
Preferably, highly soluble inorganic zinc salts such as zinc chloride, zinc bromide~ zinc iodide or mixtures thereof are employed however~ the less soluble salts such as zinc chlorate, zinc nitrate (tri-hydrate or hexahydrate) or zinc sulfate (heptahydrate and hexahydrate) may be either alone or in admixture with each other or with the more soluble zinc compounds.
The sulfate for example may be maae more soluble by using a higher reaction medium temperature than ambient.
The lignosulfate salt solution employed in the present invention is a crude product deri~ed fIom the processing of paper pulp and is employed the solu-tion neutralized with the appTopriate base, e.g., sodium hydroxide, calcium hydroxide or the like. Hence, nor-- mally sodium or calcium lignosu~fonate will be employed but other lignosulfonate solutions such as the ammoniu~
salt, iron salt, ma~nesium salt, chromium salt or mixtures thereof can be used. The sodium lignosulfonate is pre-ferred because of cost. This solution should haYe a pH
of less than 9, preferably a pH of 5-~ for the reaction with the zinc salt. The reaction product will have an acid pH, i.e., from about 3 to 6.
The lignosulfonate salt is highly complex mixture of materials and a molar type reaction is im-possible to determine. It has been found that complete chelation is obtained with from 2 to 3 pounds of ligno-sulfonate ~dry basis) per pound zinc in solution, preferably 2 5 pounds of lignosulfonate per pound of zinc.
Thus, in the aqueous reaction system therewi.ll be from 8 to 15 wt, ~ zinc present and 16 to 45 weight % lignosulfonate salt~ e.g., at 8 wt.% the range of lignosulfonate will be 16 to 30 weight % and at 15 wt.% Zn the range of lignosulfonate will be 24 to 45 wt.% (1:2-3 weight ratio Zn:lignosulfonate).
The crude lignosulfonate solutions employed may contain sugar, since they are unprocessed. The sugar, however, may cause a precipitate. Hence, the sugar should be as low as possible, and preferably not present, in order to avoid solids in the reaction product. It should also be appreciated that at a 15%
zinc chelate concentration the reaction product is a very viscous liquid which may be difficult to pump.
Thus, about a 12% zinc chelate which provides a high concentration of H2S scavenger in a form pumpable over a wide temperatuTe range is preferred.
The following examples are presented to il-lustrate the invnetion and are not intended to limit thescope thereof.
Examples 1 and 2 A 12 wt.% zinc lignosulfonate chelate solu-tion was prepared by contacting 40 wt.% of a zinc chlo-ride solution containing 30 wt.% zinc chloride dissolvedtherein and 60 wt.% of a solution of 50 wt.~ sodium lignosulfonate (pH 6.4) in a mixing vessel equipped with a stirrer. The solutions are mixed together for about 15 minutes to complete the reaction. The tem-perature of the solutions were ambient (about 25C)and no increase in the temperature of the reaction mixture was observed. The final pH of the reaction mixture was about 3.8. The product was a dark brown liquid having an increased viscosity from the starting materials.
1 l66~3~
- S-A 10 wt.% æinc lignosulfonate c~elate solu-tion was prepared in the sa~e manner except 33.3 wt.
solution containing a 30 wt.% zinc chloride; 50 Wt. ~
of 50 wt.% sodium lignosulfonate solution and 17 wt.%
water were employed. A similar dark brown viscous liquid was produced. The pH was also about 3.8 Examples 3-6 In the following runs the compositions pre-pared according to examples 1 and 2 were compared to two (2) commercial zinc containing H2S scavengers.
The compounds were tested in at the same pounds per barrel of wellbore fluid.
The evaluation was conducted in an unweighted fresh water lignosulfonate mud of the following composition:
22 lb/bbl Wyoming bentonite 25 lb/bbl Martin No. 5 Ball Clay 1.5 lb/bbl ~errochrome lignosulfonate 0.1 lb/bbl Sodium hydroxide Sulfide ion was added as^~sodium sulfide (Na2S.9H2O). Calculations are based on sulfide ion as measured in the mud filtrate using the Garrett Gas Train (GGT).
- The results of the tests are set out in the TABLE.
l l66~34 9, TABLE
Example 3 4 5 6 Blank IMC0 Sulf-X II(l), (solid) lb/bbl 2 0 S Mil-Gard(2), (solid) lb/bbl 2 0 10% Zinc Chelate (solution), lb/bbl 2 0 12S Zinc Chelate (solution) lb/bbl 2 0 Stirred 10 minutes at ll,Q00 rpm on the Multimixer pH 10.30 10.7S 10.809.55 10.30 API Filter Loss, ml 11.0 12.0 11.0 12.0 11.0 GGT/Sulfide,ppm 0.5 0.5 0 7 0,5 400 ; 15 Hot Rolled 16 hours at 150F. (Added 500 ppm sulfide after hot rol1in~
Apparent Viscosity, cpQ80F 16 16 17 18 13 Plastic Viscosity, cp13 13 13 13 11 Yield Point,lb/100 ft2S S 4 S 4 20~ Gel Stren~ths,lb/100 ft2 10 sec/10 min 0/4 0/0 0/S 0/8 0/0 pH 9.85 9.70 lO.S59.00 9.20 API Filter Loss, ml 9.3 9,3 9.4 8.9 S.9 Cake Thickness, 32nd inch 2 2 2 2 2 GGT/Sulfide,ppm 30 24 250 60 S00 Total Available Zinc,ppm 1328 2979 S71 686 0 Actual Sulfides removed,ppm 870 876 6S0 840 ---Efficiency ppm S /ppm zinc0.655 0.2941.135 1.225 ---~1~ Product of IMC0 Services, believed to be solid zinc cholato (2) Product of Milchem Incorporated, believed to be 3 mixture of zinc carbonato and zinc hydroxide (desi~nated DS "b3sic zinc cDrbonatc") ~ ' , .
_ 9 , .
:
The results show that there is a greater H2S removal efficiency for ~he present compositions (based on a~ailable zinc) than for higher zinc ion concentrations available from the other two mateTials.
.
! : :
.
. .
~ .
Claims (18)
1. A liquid wellbore additive composition for scavenging hydrogen sulfide prepared by the process of reacting in aqueous solution 8 to 15 weight percent zinc as a soluble salt and a soluble salt of lignosulfonate in a weight ratio of Zn:lignosulfonate of 1:2-3.
2. The wellbore additive composition according to claim 1, wherein the aqueous solution is at a temperature in the range of 20 to 30°C.
3. The wellbore additive composition according to claim 1, wherein the soluble zinc salt is zinc chloride, zinc iodide, zinc bromide or mixtures thereof.
4. The wellbore additive composition according to claim 1, wherein the soluble zinc salt is zinc chlorate, zinc nitrate, zinc sulfate, mixtures thereof or mixtures thereof with zinc chloride, zinc iodide or zinc bromide.
5. The wellbore additive composition according to claim 1, wherein said zinc salt is zinc chloride.
6. The wellbore additive-composition according to claim 1, wherein said lignosulfonate salt is the sodium or calcium salt.
7. The wellbore additive composition according to claim 3, 4 or 5, wherein said lignosulfonate salt is the sodium or calcium salt.
8. The wellbore additive composition according to claim 1, wherein the lignosulfonate salt is the sodium salt.
9. The wellbore additive composition according to claim 3, 4 or 5, wherein said lignosulfonate salt is the sodium salt.
10. The method of preventing corrosion of sub-terranean well apparatus exposed to an alkaline well-bore fluid contaminated by hydrogen sulfide comprising adding to said wellbore fluid at least one pound of a liquid solution containing a zinc lignosulfonate chelate for each barrel of wellbore fluid, said liquid solution being derived by reacting in aqueous solution 8 to 15 weight percent zinc as a soluble salt and a soluble salt of lignosulfonate in a weight ratio of Zn:lignosulfonate of 1:2-3.
11. The method according to claim 10, wherein at least two pounds of said aqueous solution containing 8 to 15 weight % zinc lignosulfonate chelate is added for each barrel of wellbore fluid.
12. The method according to claim 11, wherein said aqueous solution contains 10 to 13 weight % zinc lignosulfonate chelate.
13. The method according to claim 10, wherein at least an amount of said aqueous solution of 8 to 15 weight % zinc lignosulfonate chelate, equivalent to one pound of a 12 weight % zinc lignosulfonate chelate solution is added to said wellbore fluid per barrel of wellbore fluid for each 250 ppm hydrogen sulfide pre-sent in said wellbore fluid.
14. The method according to claim 10, wherein the soluble zinc salt is zinc chloride, zinc iodide, zinc bromide or mixtures thereof.
15. The method according to claim 10, wherein the soluble zinc salt is zinc chlorate, zinc nitrate, zinc sulfate, mixtures thereof or mixtures thereof with zinc chloride, zinc iodide or zinc bromide.
16. The method according to claim 10, wherein said zinc salt is zinc chloride.
17. The method according to claim 10, 11 or 12, wherein said lignosulfonate salt is the sodium or calcium salt.
18. The method according to claim 10, 11 or 12, wherein said lignosulfonate salt is the sodium salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28736181A | 1981-07-27 | 1981-07-27 | |
| US287,361 | 1981-07-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1166434A true CA1166434A (en) | 1984-05-01 |
Family
ID=23102563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000387423A Expired CA1166434A (en) | 1981-07-27 | 1981-10-06 | Process and composition for scavenging hydrogen sulfide in aqueous drilling fluids |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1166434A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8080225B2 (en) | 2005-11-07 | 2011-12-20 | Specialist Process Technologies Limited | Functional fluid and a process for the preparation of the functional fluid |
| CN111500266A (en) * | 2019-01-30 | 2020-08-07 | 中国石油化工股份有限公司 | Completion fluid composition and application thereof |
| CN115678038A (en) * | 2022-11-07 | 2023-02-03 | 中策橡胶集团股份有限公司 | Lignin zinc salt compound, preparation method and application thereof, rubber composition and tire |
-
1981
- 1981-10-06 CA CA000387423A patent/CA1166434A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8080225B2 (en) | 2005-11-07 | 2011-12-20 | Specialist Process Technologies Limited | Functional fluid and a process for the preparation of the functional fluid |
| US8591767B2 (en) | 2005-11-07 | 2013-11-26 | Specialist Process Technologies Limited | Functional fluid and a process for the preparation of the functional fluid |
| CN111500266A (en) * | 2019-01-30 | 2020-08-07 | 中国石油化工股份有限公司 | Completion fluid composition and application thereof |
| CN115678038A (en) * | 2022-11-07 | 2023-02-03 | 中策橡胶集团股份有限公司 | Lignin zinc salt compound, preparation method and application thereof, rubber composition and tire |
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