CN100487073C - Hydrolysiable high elastic well remending liquid temperary blocking agent - Google Patents
Hydrolysiable high elastic well remending liquid temperary blocking agent Download PDFInfo
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- CN100487073C CN100487073C CNB2005100721186A CN200510072118A CN100487073C CN 100487073 C CN100487073 C CN 100487073C CN B2005100721186 A CNB2005100721186 A CN B2005100721186A CN 200510072118 A CN200510072118 A CN 200510072118A CN 100487073 C CN100487073 C CN 100487073C
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- remending
- temperary
- blocking agent
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- 239000007788 liquid Substances 0.000 title claims abstract description 24
- 239000002981 blocking agent Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 239000008107 starch Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000001788 irregular Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 14
- 239000012530 fluid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000004159 Potassium persulphate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013013 elastic material Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to hydrolysable high elasticity well workover liquid temporary blocking agent used in oil field workover treatment. It is made up of 40-80% de-ionized water, 10-30% acrylic acid, 8-30% starch, 0.1-1.5% sodium per-sulfate, and 0.1-1.0% N,N-methylene-bisacrylamide. The water-bearing of the product is 40%-80%. It can be degraded easily in water, and can lose full strength in 24 hours below 60 centigrade degree. The degraded residue is little and has low system viscosity.
Description
Technical field
The present invention relates to oil well repairing operation, specifically, is a kind of Hydrolysiable high elastic well remending liquid temperary blocking agent.
Background technology
The most of onshore oil field of China has entered development phase intermediary and later stages at present, and the oil gas well pressure reduces year by year, and the workover fluid leakage phenomena often takes place.Workover fluid leakage in the workover treatment process has not only increased the workover fluid consumption, causes workover treatment normally to carry out, and also may cause the pollution on oil reservoir (stratum), influences output after the workover treatment.
Solution to this problem mainly contains following several at present:
(1) in workover fluid, adds oil-soluble resin.The principle of this method is to utilize oil-soluble resin shutoff stratum to reach the effect that reduces leakage.By in-place oil oil-soluble resin is dissolved after the workover treatment, thereby recover zone permeability.Obviously this method can only be used for moisture lower oil well, is the situation of oil-in-water type for moisture height or output liquid, and the dissolving of oil-soluble resin needs for a long time.Oil-soluble resin intensity matching problem low and formation pore also is the inconvenience in using in addition.
(2) in workover fluid, add viscid bitumen, thickness resin etc.The principle of this method and to add oil-soluble resin basic identical.The matching problem that does not just have particle diameter and formation pore.Shortcoming is can't block up effectively temporarily for the stratum of macropore.
(3) in workover fluid, add solubility in acid temporary plugging agent such as lime carbonate etc.Shield-temporary plugging in the similar drilling fluid of its principle.Its sufficient part is not only to exist the matching problem of particle diameter and formation pore, and needs to carry out acidification to dispel block after the workover treatment.
(4) snubbing serving technology.Its advantage is the preceding production capacity of well workover that it could protect and keep the stratum to greatest extent, makes measure almost nil to the injury on stratum, can remove the required well control fluid of routine work from simultaneously.This technology only is suitable for pressure height, stratum that rate of permeation is low.Can't be applied in the very low stratum of reservoir pressure, and leakage often occurs in this class stratum.Snubbing serving needs expensive not kill-job equipment in addition.
(5) foam workover fluid.This technology is specially adapted to low pressure, misses and has operations such as the low permeability formation sand washing, induced flow, well-flushing, the row of helping, bottom hole flushing of gas lock effect.Inapplicable for unconspicuous this technology of high permeability formation of gas lock effect.This technology needs pressure fan when construction, cost is higher.
(6) the salt solution saturated solution that contains inorganic salt particle is cooked workover fluid.Its principle is to utilize the temporary transient shutoff of inorganic salt particle stratum, and during the sand washing operation and after the sand washing operation, saturated brine is constantly diluted, and the inorganic salt particle dissolving on shutoff stratum is stopped up thereby remove.This technology is fit to highly aqueous well operations very much.Its deficiency is that inorganic salt solution density is bigger, the easier leakage.And it is sticking stifled also difficult to want to improve brinish.
Summary of the invention
The object of the present invention is to provide a kind of rubber like, the highly elastic material of tensile strength more than 0.01MPa, i.e. hydrolyzable high elastic well remending liquid temperary blocking agent.
The present invention is achieved in that
(1) chemical ingredients of the present invention is appropriately crosslinked starch-acrylate graft copolymer, and there is not molecular formula accurately in this material.Manufacture method, proportioning raw materials, visible " super strength water absorbent " open source literatures such as (Zou Xinxi write, Chemical Industry Press, Beijing) of complete processing like this type of material type.Proportioning of the present invention is as follows:
The key of this project invention is with " appropriately crosslinked starch-acrylate graft copolymer " this material that has existed, and it is in the suitable moisture scope, gives its new purposes.
1. deionized water 40～80%; Its effect is other raw material of dissolving, and the polymerization solvent for use is provided.
2. vinylformic acid 10～30%; Normal temperature and pressure is down for being liquid state; The polymeric principal monomer; Dosage is difficult to polymerization very little; Dosage is too many sudden and violent easily poly-.Unavailable other the similar raw material substitution of this component.
3. W-Gum 8～30%; Normal temperature and pressure is white solid powder down; Suitably adding can reduce product cost and improve product suction back gel-strength, and the too many back of dosage increases product density.This component can substitute with other starch (as potato starch).
4. Sodium Persulfate 0.05～0.2%; Normal temperature and pressure is white solid powder down; Initiator of polyreaction, dosage are difficult to polymerization very little; Dosage is too many sudden and violent easily poly-.Can replace with Potassium Persulphate.It is not obvious to the product performance influence to replace the back.
5. N,N methylene bis acrylamide 0.05～0.2%; Normal temperature and pressure is white solid powder down; The linking agent of product; The crosslinked body of the difficult very little formation of dosage; The intensity that becomes fragile the too many product of dosage reduces.Unavailable other the similar raw material substitution of this component.
Deionized water prepares (being easy to buy on this type of Equipment Market) with the high purity water device in the above raw material, and all the other can buy on market.Common reference books such as the visible chemical industry dictionary of details such as the concrete molecular formula of each raw material.
(2) preparation method
The course of processing is followed successively by:
1. material mixing arrives all material mixings together common uncovered puddling in the jar; After adding all raw materials, the time of puddling should not be less than 30 minutes and puddle evenly guaranteeing.Temperature should be lower than 35 ℃ when puddling, unexpected polymerization when preventing to puddle.
2. polymerization is carried out in polymerization reaction kettle, and polymerization reaction kettle is a stainless steel polymerization reaction kettle common on the market.After being pumped into the raw mix of puddling in the polymerization reaction kettle, be warmed to 70～80 ℃, vacuumized simultaneously 20 minutes, logical then nitrogen 1 hour; Material begins to be incubated 12 to 18 hours down at 70～80 ℃ after the polymerization.
3. pulverize, with air compressor from reactor top injecting compressed air, the bulk product extrusion reaction still that polymerization is good, available commercially available single-screw extruder, product is processed into irregular strip and sheet, and particle diameter or overall dimension are between 0.5～20mm.
4. screening packing need be with the granule sieving packing of pulverizing according to the user, finished product.
More than the used all devices of processing all can be buied on market.
When producing, product can not be dried, should control the moisture between 40～80% of product, obtain elastomeric product.
Effect of the present invention is: efficiently solve existing well remending liquid temperary blocking agent and be not easy effectively temporarily stifled stratum, need dissolve the problem of de-plugging with crude oil, the invention provides a kind of rubber like, the highly elastic material of tensile strength more than 0.01MPa, this material is duct, shutoff stratum rapidly, prevents the workover fluid leakage.This material can very fast (2～3 days) in water degraded, so after workover treatment finished to go into operation again, this material degradation product was taken out of by water, zone permeability can recover very soon.
This material has following characteristics:
(1) outward appearance is irregular 1 to 20 millimeter uneven elastic granule of size.
(2) can fast shutoff most permeable zone, dissolving degraded back zone permeability can very fast recovery.
(3) duct, stratum size is not required.Material itself is the duct, stratum that soft particle can adapt to different sizes.
(4) be applicable to high aqueous oil and water well operation.Degraded easily in water.Under 60 ℃ of temperature, can in water, lose whole intensity in 24 hours, dissolving degraded back residue is few, and system viscosity is low.
Cooperate guanidine sol solution and HPAM solution to use together during hydrolysis high elastic well remending liquid temperary blocking agent rig-site utilization.Form (in every side's workover fluid): water 1.0m
3, 2～6Kg guanidine glue is mixed evenly earlier adding Hydrolysiable high elastic well remending liquid temperary blocking agent 10～20Kg/m at make-up station
3Inject weak zone with the highest discharge capacity from oil pipe or oil jacket annular space with cementing truck.
Amount to year July in the test in place to 2004 of Dagang Oilfield and to have carried out 14 mouthfuls of wells, wherein 1 mouthful of well test stops because of other reason midway, the stifled temporarily effect of all the other 13 mouthfuls of wells is fairly obvious, wherein some well had once been attempted a lot of temporary blocking methods and medicament all effect was bad, can not carry out the sand washing operation, and behind the application Hydrolysiable high elastic well remending liquid temperary blocking agent, stifled temporarily effect is fairly obvious, can carry out the sand washing operation smoothly;
Embodiment
Embodiment 1
Raw material (being commercially available industrial goods): deionized water 40%, vinylformic acid 30%, W-Gum 29.9%, Sodium Persulfate 0.05%, N,N methylene bis acrylamide 0.05%.With above mixing of materials evenly in polymerization reaction kettle polymerization obtain the snappiness gel of rubber like after 14～18 hours, with polymerisate extruding polymerization reactor, be processed into irregular strip and sheet with single-screw extruder, both obtained Hydrolysiable high elastic well remending liquid temperary blocking agent, during application Hydrolysiable high elastic well remending liquid temperary blocking agent is mixed in 0.2% the guanidine glue solution, be injected into together in the well with cementing truck then, every meter weak zone consumption is 20-100Kg.
Embodiment 2
Raw material (being commercially available industrial goods): deionized water 50%, vinylformic acid 30%, potato starch 19.9%, Potassium Persulphate 0.05%, N,N methylene bis acrylamide 0.05%.Above mixing of materials is evenly obtained the snappiness gel of rubber like after polymerization 10-18 hour in polymerization reaction kettle, with polymerisate extruding polymerization reactor, be processed into irregular strip and sheet with single-screw extruder, both obtained Hydrolysiable high elastic well remending liquid temperary blocking agent, during application Hydrolysiable high elastic well remending liquid temperary blocking agent is mixed in 0.2% the guanidine glue solution, be injected into together in the well with cementing truck then, every meter of Hydrolysiable high elastic well remending liquid temperary blocking agent misses layer by layer that consumption is 20～50Kg.
Embodiment 3
Raw material (being commercially available industrial goods): deionized water 60%, vinylformic acid 20%, W-Gum 19.8%, Sodium Persulfate 0.1%, N,N methylene bis acrylamide 0.1%.With above mixing of materials evenly in polymerization reaction kettle polymerization obtain the snappiness gel of rubber like after 14～18 hours, with polymerisate extruding polymerization reactor, be processed into irregular strip and sheet with single-screw extruder, both obtained Hydrolysiable high elastic well remending liquid temperary blocking agent, during application Hydrolysiable high elastic well remending liquid temperary blocking agent is mixed in 0.2% the guanidine glue solution, be injected into together in the well with cementing truck then, every meter weak zone consumption is 20-80Kg.
Embodiment 4
Raw material (being commercially available industrial goods): deionized water 70%, vinylformic acid 20%, potato starch 9.7%, Potassium Persulphate 0.15%, N,N methylene bis acrylamide 0.15%.With above mixing of materials evenly in polymerization reaction kettle polymerization obtain the snappiness gel of rubber like after 14～18 hours, with polymerisate extruding polymerization reactor, be processed into irregular strip and sheet with single-screw extruder, both obtained Hydrolysiable high elastic well remending liquid temperary blocking agent, during application Hydrolysiable high elastic well remending liquid temperary blocking agent is mixed in 0.2% the guanidine glue solution, be injected into together in the well with cementing truck then, every meter weak zone consumption is 20-100Kg.
Embodiment 5
Raw material (being commercially available industrial goods): deionized water 80%, vinylformic acid 10%, W-Gum 9.6%, Sodium Persulfate 0.2%, N,N methylene bis acrylamide 0.2%.With above mixing of materials evenly in polymerization reaction kettle polymerization obtain the snappiness gel of rubber like after 14～18 hours, with polymerisate extruding polymerization reactor, be processed into irregular strip and sheet with single-screw extruder, both obtained Hydrolysiable high elastic well remending liquid temperary blocking agent, during application Hydrolysiable high elastic well remending liquid temperary blocking agent is mixed in 0.2% the guanidine glue solution, be injected into together in the well with cementing truck then, every meter weak zone consumption is 20-100Kg.
Claims (2)
1. Hydrolysiable high elastic well remending liquid temperary blocking agent, its preparation method is:
1. material mixing arrives all material mixings together common uncovered puddling in the jar; After adding all raw materials, the time of puddling, temperature was lower than 35 ℃ when puddling greater than more than 30 minutes;
2. polymerization is carried out in polymerization reaction kettle, be pumped into the raw mix of puddling in the polymerization reaction kettle after, be warmed to 70～80 ℃, vacuumized logical then nitrogen 1 hour simultaneously 20 minutes; Material begins to be incubated 12 to 18 hours down at 70～80 ℃ after the polymerization;
3. pulverize, with air compressor from reactor top injecting compressed air, the bulk product extrusion reaction still that polymerization is good, available commercially available single-screw extruder, product is processed into irregular strip and sheet, and particle diameter or overall dimension are between 0.5～20mm;
4. screening packing need be with the granule sieving packing of pulverizing according to the user, finished product;
It is characterized in that: raw material weight per-cent is:
Deionized water 40～80%, vinylformic acid 10～30%, starch 8～30%, initiator are Sodium Persulfate 0.05～0.2%, linking agent is a N,N methylene bis acrylamide 0.05～0.2%, product moisture between 40～80%.
2. Hydrolysiable high elastic well remending liquid temperary blocking agent according to claim 1 is characterized in that: starch or W-Gum, or potato starch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100721186A CN100487073C (en) | 2005-05-25 | 2005-05-25 | Hydrolysiable high elastic well remending liquid temperary blocking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100721186A CN100487073C (en) | 2005-05-25 | 2005-05-25 | Hydrolysiable high elastic well remending liquid temperary blocking agent |
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| Publication Number | Publication Date |
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| CN1869147A CN1869147A (en) | 2006-11-29 |
| CN100487073C true CN100487073C (en) | 2009-05-13 |
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| CNB2005100721186A Expired - Fee Related CN100487073C (en) | 2005-05-25 | 2005-05-25 | Hydrolysiable high elastic well remending liquid temperary blocking agent |
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2005
- 2005-05-25 CN CNB2005100721186A patent/CN100487073C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1869147A (en) | 2006-11-29 |
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