CN105086969A - Degradable resin material for operation of oil and gas field and preparation method thereof - Google Patents
Degradable resin material for operation of oil and gas field and preparation method thereof Download PDFInfo
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- CN105086969A CN105086969A CN201510408908.0A CN201510408908A CN105086969A CN 105086969 A CN105086969 A CN 105086969A CN 201510408908 A CN201510408908 A CN 201510408908A CN 105086969 A CN105086969 A CN 105086969A
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- polyglycolic acid
- butylene succinate
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- hydroxybutyrate ester
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 229920005989 resin Polymers 0.000 title claims abstract description 82
- 239000011347 resin Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 84
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 84
- 239000000956 alloy Substances 0.000 claims abstract description 73
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 73
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims abstract description 59
- 239000004970 Chain extender Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000004631 polybutylene succinate Substances 0.000 claims description 82
- 229920002961 polybutylene succinate Polymers 0.000 claims description 82
- 229920006167 biodegradable resin Polymers 0.000 claims description 59
- 150000002148 esters Chemical class 0.000 claims description 57
- -1 poly butylene succinate Polymers 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 45
- 239000002086 nanomaterial Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 32
- 238000002203 pretreatment Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000002074 melt spinning Methods 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 14
- 238000005553 drilling Methods 0.000 abstract description 9
- 230000006378 damage Effects 0.000 abstract description 6
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 24
- 239000012530 fluid Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000010276 construction Methods 0.000 description 10
- 208000010392 Bone Fractures Diseases 0.000 description 9
- 206010017076 Fracture Diseases 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 208000014674 injury Diseases 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
Classifications
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- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
-
- 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
- C09K8/03—Specific additives for general use in well-drilling compositions
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a degradable resin material for operation of an oil and gas field and a preparation method thereof. The method comprises the step of performing a melt-mixing reaction on polymer of two or three of polyglycolic acid, butylene succinate and poly-3-hydroxybutyrate with a chain extender to prepare resin alloy, namely the degradable resin material for operation of the oil and gas field. The degradable resin material prepared by the method can be prepared into flakes, powder, particles, spheres and other shapes, or one of polyglycolic acid, butylene succinate and poly-3-hydroxybutyrate is prepared into flakes, powder, particles, spheres and other shapes. The degradable resin material can be used for temporarily plugging and reducing filtration to protect reservoirs, temporarily plugging blast-holes, constructed reservoirs and the like in various oil and gas field constructing operations, such as well drilling, completion and repairing and acid fracturing. The degradable resin material has the advantages of complete degradability and zero harm to stratum.
Description
Technical field
Biodegradable resin material that the present invention relates to oilfield operation and preparation method thereof, belongs to oil and gas exploitation technical field.
Background technology
In the various construction operation of oil-gas field, as in drilling well, completion, well workover or stimulation work process, widely use filtrate reducing material to reduce the intrusion of working fluid to reservoir, reduce its injury to reservoir.The fluid loss agent used blocks Reservoir Fracture, hole, thus reduces working fluid intrusion, and the pore constriction of shutoff reservoir, crack, after operation completes, these plugging materials have been blocked oil gas too and flowed into pit shaft from reservoir, bring injury to reservoir.
Bring injury in order to reduce fluid loss agent to reservoir, usually use stifled property material temporarily, after construction operation completes, the fluid loss agent of stifled property can dissolve voluntarily, degrades and disappear temporarily, and this is the target that oilfield engineering scientific and technical personnel pursue always.
The temporary plugging agent of frequent use mainly contains water-soluble, acid-soluble and oil soluble three class.Water-soluble have polymer class, and as polyacrylamide, polyvinyl alcohol etc., water-soluble inorganic salt is mainly used in saturated brine system, as the salt such as Repone K, sodium-chlor grain.Acid-soluble mainly calcium carbonate granule, after operation to be onstructed completes, uses hydrochloric acid to remove.Oil-soluble temporary plugging agent is some resin materials mainly, as the resin of C6-C10, and pitch etc.
But these block up property material temporarily and all there are some shortcoming and defect, water-soluble stifled material temporarily, its transport fluid needs to be organic hydrocarbon, and after operation completes, need the water having q.s in stratum, in follow-up discharge opeing process, the production water on stratum is dissolved, and removes it and blocks up temporarily, dredging gas channel, if stratum does not have enough water, or reservoir pressure is not enough, does not have enough aquatic products to go out, just need follow-uply in stratum, squeezing water, dissolve these water-soluble stifled materials temporarily, often cannot be dissolved releasing completely, bring certain infringement to stratum; Acid-soluble stifled material temporarily, after completing temporary stifled operation function, needing to inject acid solution carries out acid-soluble to its temporary stifled material, removes its blocking, is not suitable for for acid sensitivity reservoir, it is exactly non-acid sensitivity reservoir, also to increase one-stop operation, increase operating cost, owing to cannot ensure that acid solution is fully soaked all stifled temporarily materials, cause being dissolved completely, remove the blocking of its gas channel; For oil soluble stifled material temporarily, first inapplicable gas well, its two, be exactly oil well, because in-place oil is just to edge contact stifled temporarily, when dissolving reaches capacity, mainly by diffusion convection current, realize slow dissolving, this causes duration of contact long, and insufficient, and formation exists certain infringement.
There is above deficiency based on existing stifled material temporarily, need the material that invention can only lean on formation temperature just can degrade in the earth formation.Because hydrocarbon-bearing pool buried depth is different, therefore, the bottom temperature of Oil/gas Well is also different, as Daqing oil field main force reservoir buried depth only has 1000-1600 rice, bottom temperature only has 50-60 DEG C, as in Tarim Oilfield tower, the hydrocarbon-bearing pool such as in front of the mountains of Ta Bei, storehouse car, buried depth 5000-8000 rice, bottom temperature is 130-180 DEG C, and this just requires that degradation material can be degraded under condition of different temperatures.
Summary of the invention
For solving the problems of the technologies described above, biodegradable resin material that the object of the present invention is to provide oilfield operation and preparation method thereof.This biodegradable resin material is the type material just can degraded at the formation temperature, and can play in the various construction operation of oil-gas field and block up the effect of grade temporarily, formation zero injures.
For achieving the above object; the invention provides the preparation method of the biodegradable resin material of oilfield operation; it comprises the following steps: make polymkeric substance and chainextender carry out melting mixing reaction (preferably carrying out under nitrogen protection); prepare resin alloy; be the biodegradable resin material of described oilfield operation, wherein said polymkeric substance comprises in polyglycolic acid (PGA), poly butylene succinate (PBS) and poly-3-hydroxybutyrate ester (PHA) two or three.
In above-mentioned preparation method, preferably, with the total mass of described polymkeric substance for benchmark, described polymkeric substance is made up of (sum of the two is 100%) the polyglycolic acid of 5-95% and the poly butylene succinate of 5-95%; Or be made up of (sum of the two is 100%) the poly-3-hydroxybutyrate ester of 5-95% polyglycolic acid and 5-95%; Or be made up of (sum of the two is 100%) the poly butylene succinate of 5-95% and the poly-3-hydroxybutyrate ester of 5-95%; Or be made up of (three's sum is 100%) the poly-3-hydroxybutyrate ester of the poly butylene succinate of 5-80%, the polyglycolic acid of 5-50% and 5-80%.
In the present invention, carry out melting mixing by making in polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester two or three with chainextender and the resin alloy that formed has new structure, its mechanical property, chemical property all change.By adjusting the ratio of each polymkeric substance, the structure that certain proportion multistage is inlayed can be formed, to obtain the material of varying strength, differing temps degraded, meeting the requirement of the stifled temporarily material of the difference construction object of different depths oil-gas field.
In above-mentioned preparation method, preferably, the weight-average molecular weight (Mw) of described polyglycolic acid is 10,000-12 ten thousand (more preferably adopting polyglycolic acid section); The weight-average molecular weight of described poly butylene succinate is 10,000-25 ten thousand (more preferably adopting poly butylene succinate section); The weight-average molecular weight of described poly-3-hydroxybutyrate ester is 10,000-8 ten thousand (more preferably adopting poly-3-hydroxybutyrate ester to cut into slices).
In the present invention, the weight-average molecular weight of the polyglycolic acid adopted is 10,000-12 ten thousand, and it has-(O-CH in structural formula
2-CO) homopolymer of-shown oxyacetic acid repeating unit, its second-order transition temperature (Tg) is about 36 DEG C, and the ester group under reservoir temperature condition in its structure can be degradable, and degradation speed is fast, intermediates is oxyacetic acid, and final product is carbonic acid gas and water.The weight-average molecular weight of the poly butylene succinate adopted is 10,000-25 ten thousand, and it has-(CO (CH in structural formula
2)
2cOO (CH
2)
4the homopolymer of O)-repeating unit, its fusing point is 114 DEG C, second-order transition temperature is-32 DEG C, all containing hydroxyl and carboxyl in molecular structure, ester group in its molecular structure can be degradable under reservoir temperature, final product is carbonic acid gas and water, and especially degradation rate is higher in lower than the reservoir of 50 DEG C.The weight-average molecular weight of the poly-3-hydroxybutyrate ester adopted is 10,000-8 ten thousand, its second-order transition temperature is 50 DEG C, and fusing point is 140-220 DEG C, and the ester group under reservoir temperature condition in its structure can be degradable, intermediates is oxyacetic acid, and final product is carbonic acid gas and water.Visible, these three kinds of polymkeric substance of polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester all (formation temperature and local water) can be degraded under reservoir conditions, the final product of degraded is water and carbonic acid gas, environmentally friendly, does not pollute reservoir rock and local water.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: carry out the dry pre-treatment of vacuum stirring to described polymkeric substance, make the water content of polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester all lower than 0.1wt% (weight percentage), more preferably, lower than 0.01wt%; Particularly preferably, to the vacuum stirring drying of described polyglycolic acid be: 90-105 DEG C, under vacuum tightness 10-100 kPa, stir dry 2-8 hour; To the vacuum stirring drying of described poly butylene succinate be: 60-75 DEG C, under vacuum tightness 10-100 kPa, stir dry 3-14 hour; To the vacuum stirring drying of described poly-3-hydroxybutyrate ester be: 90-105 DEG C, under vacuum tightness 10-100 kPa, stir dry 2-8 hour.After described pre-treatment, make the water content of three kinds of polymkeric substance lower than 0.1%, be preferably lower than 0.01%, be conducive to the carrying out of follow-up melting mixing reaction like this.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: when carrying out the reaction of described melting mixing, add inorganic nano material, prepare resin nano alloy, be the biodegradable resin material of described oilfield operation; Wherein said inorganic nano material comprises nano silicon and/or nano titanium oxide, and its particle diameter is 5-20nm, and the addition of described inorganic nano material is the 0.01-3% of described total polymer mass.
In above-mentioned preparation method, preferably, described chainextender is the chainextender containing active group epoxy group(ing), is more preferably the combination of one or more of ADR-4300 (containing 5 active epoxy bases in each molecule), ADR-4370 (containing 9 active epoxy bases in each molecule), ADR-4368 (containing 9 active epoxy bases in each molecule) and the ADR-4380 (containing 3 active epoxy bases in each molecule) that BASF stock company (BASFSE) produces.
In above-mentioned preparation method, preferably, the addition of described chainextender is the 0.05%-5.0% of described total polymer mass, and more preferably, the addition of described chainextender is the 0.1-0.3% of described total polymer mass.
Raw material performed polymer molecule based on the polymkeric substance that the present invention selects polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester to degrade, its end group is hydroxyl and carboxyl, can react with the chainextender containing active group epoxy group(ing); Such as, active group epoxy group(ing) all containing different number in each molecule of ADR-4300, ADR-4370, ADR-4368 and ADR-4380 that BASF stock company produces, Ligature can be there is with the reactive group of PGA, PBS and PHA (terminal hydroxy group, end carboxyl), form more macromolecular polymer alloy, shown in example reaction equation described as follows:
In above-mentioned preparation method, preferably, the temperature of described melting mixing reaction is 180-280 DEG C, is more preferably 200-240 DEG C, is particularly preferably 205-220 DEG C, most preferably is 205-210 DEG C; If temperature does not reach above-mentioned lower limit, then polyreaction has the tendency that cannot fully carry out, and on the other hand, above-mentioned in limited time upper when exceeding, the resin of generation then has the tendency of thermolysis.The time of described melting mixing reaction is 3-20 minute, is preferably 5-8 minute.
In above-mentioned preparation method, preferably, with the temperature rise rate of 5-20 DEG C/min, temperature is risen to the temperature of melting mixing reaction.
According to the specific embodiment of the present invention, preferably, described melting mixing adopts reciprocating single-screw intermixing extruder to carry out.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: react to melting mixing the resin alloy for preparing with the use of wortle (such as the wortle of 3 millimeters) or resin nano alloy is cut into slices, then (such as wind cooling temperature lowering) is lowered the temperature, prepare the resin alloy after section or resin nano alloy, be the biodegradable resin material of described oilfield operation.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: make in polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester two or three first to mix in mixer, the temperature and time of mixing can carry out conventional adjustment by those skilled in the art, and can carry out under vacuum, and then join reciprocating single-screw intermixing extruder and chainextender (or further with inorganic nano material) hybrid reaction.
According to reservoir conditions, application target is different, the resin alloy prepared or resin nano alloy can be processed as required sheet, powder, particle, ball, the shapes such as fiber, the such as ball of Φ (diameter) 20-80 millimeter, the particle of Φ 0.8-5 millimeter different-grain diameter, the powder of 40 order-200 orders (74-420 μm), thickness is 0.1-0.3 millimeter, diameter or the length of side are the flap of 5-10 millimeter, Φ 10-150 micron, length is the fiber yarn etc. of 2-15 millimeter, be the biodegradable resin material of oilfield operation, concrete preparation process is as described below.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: adopt plastic grinder by described resin alloy or resin nano alloy or described polyglycolic acid, one in poly butylene succinate and poly-3-hydroxybutyrate ester (can be after the dry pre-treatment of vacuum stirring) or described polyglycolic acid, mixture that is a kind of and described inorganic nano material in poly butylene succinate and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) grinds, and by cooled with liquid nitrogen, controlling mill temperature is-10 to 0 DEG C, the screening of the sieve of different meshes is used to obtain the powder of required order number, the such as powder of the different size of 40 order-200 orders (i.e. 74-420 μm), be the biodegradable resin material of described oilfield operation.This Powdered biodegradable resin material may be used for the operations such as drilling fluid, well finishing liquid, workover fluid, well control fluid, acid solution, fracturing liquid and shouts reservoir hole and microfracture temporarily stifled, to reduce leak-off, reduces process fluid to the injury of reservoir.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: adopt tablets press (can with the use of wortle) that the mixture that is a kind of and described inorganic nano material in the one in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) is heated to 160-200 DEG C and carry out granulation; Or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) be heated to 110-120 DEG C with the mixture of described inorganic nano material and carry out granulation; Then be cooled to 15-35 DEG C (preferably with the speed of 5-20 DEG C/min cooling), obtained particle diameter is the particle of Φ 0.8-1 millimeter, Φ 1-1.5 millimeter, Φ 1.5-2 millimeter, Φ 2-2.5 millimeter, Φ 2.5-3 millimeter or Φ 3-5 millimeter etc., is the biodegradable resin material of described oilfield operation.The crack that this particulate state biodegradable resin material may be used in drilling well, Completion Operations is blocked up temporarily, also may be used for the crack that shutoff in pressure break has pressed off, implements crack and turns to, or blocks up refracturing etc. temporarily for always stitching.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: the mixture that is a kind of and described inorganic nano material in the one in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) is rolled at 160-190 DEG C (can use rolling machine) and become thickness to be the thin slice of 0.1-0.3 millimeter; Or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) being rolled at 100-110 DEG C (can use rolling machine) with the mixture of described inorganic nano material becomes thickness to be the thin slice of 0.1-0.3 millimeter; Then be cooled to 20-30 DEG C (preferably with the speed of 5-20 DEG C/min cooling), pulverizing (can use flaker) is again that square and/or the similar square and/or leg-of-mutton flap of 5-10 millimeter is (if the flap of irregular polygon for diameter is the flap of the circular and/or similar circle of 5-10 millimeter and/or the length of side, the circular diameter that Ze Yiqi center is done for the center of circle is in the scope of 5-10 millimeter), be the biodegradable resin material of described oilfield operation.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: adopt melt spinning machine that the mixture that is a kind of and described inorganic nano material in the one in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) is heated to 200-210 DEG C, carry out drawing and setting at 65-90 DEG C; Or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) be heated to 110-120 DEG C with the mixture of described inorganic nano material, then carry out drawing and setting at 40-60 DEG C; Form the fiber yarn of Φ 10-150 micron, then cut into the short-fibre silk that length is 2-15 millimeter, be the biodegradable resin material of described oilfield operation.This fibrous biodegradable resin material may be used for blocking up natural fracture temporarily in drilling well, Completion Operations, carry propping agent in pressing crack construction, shutoff presses off crack, realize the hydraulic fracture that man-made fracture turns to formation new, improve hydraulic fracture impact scope, improve the transformation volume of waterfrac treatment.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: adopt injection moulding machine that the mixture that is a kind of and described inorganic nano material in the one in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) is heated to 160-200 DEG C, be 100-175 rev/min at balanced screw speed, back pressure is 300-700 kPa, spout temperature is 20-25 DEG C, feeding temperature is 150-160 DEG C, metering zone temperature is 190-210 DEG C, jet orifice temperature is 190-210 DEG C, die temperature is (injection speed suitably hurry up) under the condition of 20-25 DEG C, the mould of different size is used to obtain the ball of Φ 4-15 millimeter, or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) be heated to 110-120 DEG C with the mixture of described inorganic nano material, be 100-175 rev/min at balanced screw speed, back pressure is 300-700 kPa, spout temperature is 20-25 DEG C, feeding temperature is 100-110 DEG C, metering zone temperature is 110-120 DEG C, jet orifice temperature is 110-120 DEG C, die temperature is (injection speed suitably hurry up) under the condition of 20-25 DEG C, the mould of different size is used to obtain the ball of Φ 4-15 millimeter, be the biodegradable resin material of described oilfield operation.This spherical biodegradable resin material may be used for shutoff crack, perforation holes, screen casing, meets the stifled temporarily construction requirement of long well section or huge thick span reservoir.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: the mixture that is a kind of and described inorganic nano material in the one in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly-3-hydroxybutyrate ester (can for after the dry pre-treatment of vacuum stirring) is heated to 160-210 DEG C; Or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) or described poly butylene succinate (can for after the dry pre-treatment of vacuum stirring) be heated to 100-125 DEG C with the mixture of described inorganic nano material; Be cast in mould, obtained bar (can adopt the mould of different size, obtained sectional dimension is the bar of 100 × 100 millimeters), again by the ball that described bar processing (can adopt machining milling machine or lathe etc.) is Φ 20-80 millimeter, be the biodegradable resin material of described oilfield operation.This spherical biodegradable resin material may be used for pitching in staged fracturing.
In above-mentioned preparation method, the temperature that one of three kinds of polymkeric substance mix with inorganic nano material can be the temperature higher than this melting point polymer, such as can higher than fusing point 5-10 DEG C.Preferably, the mixing temperature of polyglycolic acid and described inorganic nano material is 220-235 DEG C, the mixing temperature of poly-3-hydroxybutyrate ester and described inorganic nano material is 140-230 DEG C, and the mixing temperature of poly butylene succinate and described inorganic nano material is 114-124 DEG C.The addition of described inorganic nano material is the 0.01-3% of this polymer quality.Above-mentioned a kind of polymkeric substance can adopt reciprocating single-screw intermixing extruder or mixer etc. with mixing of described inorganic nano material, as long as make the two form uniform mixture.Can also cut into slices with the use of wortle (such as the wortle of the 3 millimeters) mixture to the polymkeric substance prepared and inorganic nano material afterwards, then (such as wind cooling temperature lowering) is lowered the temperature, prepare mixture section, to be processed into above-mentioned different shape.
According to the specific embodiment of the present invention, preferably, in above-mentioned preparation method, for PGA/PBS/PHA tri-kinds of polymkeric substance and chainextender or the resin alloy be obtained by reacting with inorganic nano material and chainextender or resin nano alloy, or PGA/PBS, PGA/PHA, PBS/PHA two kinds of polymkeric substance and chainextender or the resin alloy be obtained by reacting with inorganic nano material and chainextender or resin nano alloy, and need to make fiber yarn or flaky material, chainextender is preferably the ADR-4300 that BASF stock company produces, its addition is the 0.1-5.0% of total polymer mass, preferred addition is the 0.5-1.0% of total polymer mass, for PGA/PBS/PHA tri-kinds of polymkeric substance and chainextender or the resin alloy be obtained by reacting with inorganic nano material and chainextender or resin nano alloy, or PGA/PBS/, PGA/PHA, PBS/PHA two kinds of polymkeric substance and chainextender or the resin alloy be obtained by reacting with inorganic nano material and chainextender or resin nano alloy, and need to make particle or spheroidal material, chainextender is preferably the ADR-4370 of BASF stock company, its addition is the 0.05%-5.0% of total polymer mass, and preferred addition is the 0.1-0.3% of total polymer mass.
The present invention selects polyglycolic acid, raw material based on the polymkeric substance that poly butylene succinate and poly-3-hydroxybutyrate ester can be degraded, it is all containing hydroxyl and carboxyl, can react with the chainextender containing active group epoxy group(ing), these prepolymers two kinds of (PGA/PBS are wherein chosen by certain proportioning, PGA/PHA, PBS/PHA), or three kinds (PGA/PBS/PHA), add the chainextender containing active group epoxy group(ing) again, as the ADR-4300 that BASF stock company produces, ADR-4370, the combination of one or more in ADR4368 and ADR-4380, carry out melting mixing reaction under certain conditions, prepare resin alloy, inorganic nano material can also be added further to prepare resin nano alloy.
According to reservoir conditions, application target difference, the shapes such as required sheet, powder, particle, ball, fiber can be processed as by the resin alloy prepared or resin nano alloy or by a kind of in a kind of or polyglycolic acid, poly butylene succinate and the poly-3-hydroxybutyrate ester in polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester with the mixture of inorganic nano material, be the biodegradable resin material of oilfield operation.Due in construction operation process be by there is surface temperature process fluid Injection Well at the bottom of, surface temperature is lower than formation temperature, stratum is lowered the temperature, the biodegradable resin material of this oilfield operation is lower than being stable under low temperature conditions, and do not degrade, formation realizes shutoff, stop process fluid invaded formation, reduce the infringement of process fluid formation, also reduce the consumption of process fluid simultaneously, saved operating cost; After operation completes, Formation heat is delivered to the biodegradable resin material of this oilfield operation, slowly reaches formation temperature, this biodegradable resin material is at the formation temperature, within the regular hour, slowly degradable, thus remove the blocking of formation gas channel, formation zero injures.
On the other hand, present invention also offers the biodegradable resin material of oilfield operation, it is prepared by the preparation method of the biodegradable resin material of above-mentioned oilfield operation.
The biodegradable resin material of this oilfield operation can according to reservoir conditions, application target difference, be processed to required shape, it mainly has the following advantages: (1) is in the various construction operation of oil-gas field, as in drilling well, completion, well workover or stimulation work process, this biodegradable resin material can be widely used to reduce the intrusion of operation liquid to reservoir, reduce its injury to reservoir; (2) formation pore throat realizes stifled temporarily, stops process fluid invaded formation, reduces the infringement of process fluid formation, also reduce the consumption of process fluid simultaneously, saved operating cost; (3) after operation completes, Formation heat is delivered to this biodegradable resin material, slowly reaches formation temperature, this material is at the formation temperature, within the regular hour, slowly degradable, thus remove the blocking of formation gas channel, formation zero injures.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the biodegradable resin material of embodiment.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of biodegradable resin material of oilfield operation, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 60,000 polyglycolic acid section 90-100 DEG C, under vacuum tightness 90 kPas, stir dry 4 hours; By weight-average molecular weight (Mw) be 100,000 poly butylene succinate section 70-75 DEG C, under vacuum tightness 90 kPas, stir dry 9 hours; By weight-average molecular weight (Mw) be 50,000 the section of poly-3-hydroxybutyrate ester 100-105 DEG C, under vacuum tightness 90 kPas, stir dry 4 hours, make its water ratio lower than 0.1wt%, best lower than 0.01wt%;
(2) polyglycolic acid section double centner, poly butylene succinate after getting above-mentioned dewatering are cut into slices during 500 kilograms and poly-3-hydroxybutyrate ester cut into slices 400 kilograms and be added to whipping appts stainless steel mixer, heat to 50 DEG C, under vacuum tightness 90 kPas, batch mixing 10 minutes;
(3) mixture of the polyglycolic acid in mixer, poly butylene succinate and poly-3-hydroxybutyrate ester is added in reciprocating single-screw intermixing extruder, adding 2 kilograms of particle diameters is the silicon-dioxide of 10-20nm, and add the chainextender ADR-4370 of 1.5 kilograms of BASF stock company productions, then under nitrogen protection, with the temperature rise rate of 8 DEG C/min, heat to 206 DEG C, then carry out melting mixing and react 7 minutes, obtained PGA/PBS/PHA resin nano alloy;
(4) with the use of the wortle of 3 millimeters, obtained PGA/PBS/PHA resin nano alloy is cut into slices, then wind cooling temperature lowering, obtained PGA/PBS/PHA resin nano alloy section;
(5) plastic grinder is used to grind the section of obtained PGA/PBS/PHA resin nano alloy, and by cooled with liquid nitrogen, controlling mill temperature is-10 to 0 DEG C, use 80 mesh sieves to carry out screening and obtain 80 object PGA/PBS/PHA resin nano powdered alloys, obtained Powdered biodegradable resin material.
Adopt the Powdered biodegradable resin material prepared at B1 horizontal well (this well vertical depth 4000m, bottom temperature 131 DEG C, extended horizontal depth 870m, acid stimulation measure need be implemented to lateral segment) block up uniform acid distribution acidizing treatment temporarily, use acid solution 150 side, Powdered biodegradable resin material 300 kilograms, acid formula: the Powdered biodegradable resin material of 15wt%HCL+1.5wt%HF+2wt%KMS-6 inhibiter+2wt%DXJ-3 acidifying multipurpose additive+0.2wt%, oil pipe injects, discharge capacity 1.2 side/minute, during acidizing treatment, under the condition of displacement constant, infusion pressure increase 1.5MPa, achieve stifled uniform acid distribution temporarily, after acidifying, output is increased to 39.6 sides/sky by 11.2 sides before measure/sky.Stifled uniform acid distribution is respond well temporarily to prove it.
Embodiment 2
PGA/PBS/PHA resin nano alloy obtained in embodiment 1 is cut into slices at 200 DEG C through screw pelletizer granulation; particle diameter is Φ 1-1.5 millimeter; with the rate of temperature fall of 10 DEG C/min; reduce the temperature to 20 DEG C; obtain shaping Φ 1-1.5 mm granules, obtained particulate state biodegradable resin material.
The particulate state biodegradable resin material of this Φ 1-1.5 millimeter is used for B2 well (in well depth 6417-6563m well section, this well section temperature 150 DEG C-153 DEG C, penetrate out 5 layers, 6417-6428m, 6461-6472m, 6493-6506m, 6522-6533m and 6549-6563m) the temporary stall of well is to frac job, melon jelly fracturing fluid is used to carry, divide three stifled turnaround fracture temporarily, use Φ 1-1.5 mm granules stifled material 128 kilograms respectively temporarily for 3 times, 150 kilograms and 280 kilograms, after turning to for 3 times under identical infusion discharge capacity, pressure raises 5.8MPa respectively, 7.2MPa and 13.5MPa, temporary stall is to successful, this particle temporarily at stifled material 150 DEG C 9 hours degradable.
Embodiment 3
Present embodiments provide a kind of biodegradable resin material of oilfield operation, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 2.5 ten thousand polyglycolic acid section 100-105 DEG C, under vacuum tightness 90 kPas, stir dry 3.5 hours; By weight-average molecular weight (Mw) be 20,000 poly butylene succinate section 70-75 DEG C, under vacuum tightness 90 kPas, stir dry 7.5 hours, make its water ratio lower than 0.1wt%, best lower than 0.01wt%;
(2) polyglycolic acid after getting above-mentioned dewatering is cut into slices during 800 kilograms and poly butylene succinate cut into slices 200 kilograms and be added to whipping appts stainless steel mixer, heats to 50 DEG C, under vacuum tightness 90 kPas, and batch mixing 10 minutes;
(3) mixture of the polyglycolic acid in mixer and poly butylene succinate is added in reciprocating single-screw intermixing extruder, adding 6 kilograms of particle diameters is the silicon-dioxide of 10-15nm, and add the chainextender ADR-4300 of 1.2 kilograms of BASF stock company productions, then under nitrogen protection, with the temperature rise rate of 8 DEG C/min, heat to 205 DEG C, then carry out melting mixing and react 8 minutes, obtained PGA/PBS resin nano alloy;
(4) at 190 DEG C, the PGA/PBS resin nano alloy of melting is extruded through reciprocating single-screw intermixing extruder, rolling machine is adopted to be rolled by PGA/PBS resin nano alloy as thickness is the thin slice of 0.3 millimeter, with the rate of temperature fall of 10 DEG C/min, reduce the temperature to 25 DEG C, pulverize the flap for the length of side (square flap) 5-10 millimeter again, obtained sheet biodegradable resin material.
This sheet biodegradable resin material is used for the drilling well of B3 well Reservoir Section, and (this well is serious in the leakage of 2251-2257m section, cannot continue to creep into, this section of bottom temperature is 85 DEG C, fast 30 sides of drilling fluid leakage/hour) plugging operations, well head pressure-bearing 10MPa after shutoff, within 30 minutes, pressure does not fall, continue enforcement and creep into operation, get into 2612m finishing drilling, without leakage, prove that its plugging effect is good, it is I class reservoir that well logging display 2251-2257m misses section, completion operation (leak stopping is gone into operation 23 days to completion) crude production rate 67 sides/sky afterwards, proves that degradation property is good.
Embodiment 4
Present embodiments provide a kind of biodegradable resin material of oilfield operation, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 6.0 ten thousand polyglycolic acid section 100-105 DEG C, under vacuum tightness 90 kPas, stir dry 4.5 hours; By weight-average molecular weight (Mw) be 7.0 ten thousand the section of poly-3-hydroxybutyrate ester 100-105 DEG C, under vacuum tightness 90 kPas, stir dry 4 hours, make its water ratio lower than 0.1wt%, best lower than 0.01wt%;
(2) polyglycolic acid after getting above-mentioned dewatering is cut into slices during 500 kilograms and poly-3-hydroxybutyrate ester cut into slices 500 kilograms and be added to whipping appts stainless steel mixer, heats to 50 DEG C, under vacuum tightness 90 kPas, and batch mixing 10 minutes;
(3) mixture of the polyglycolic acid in mixer and poly-3-hydroxybutyrate ester is added in reciprocating single-screw intermixing extruder, add the mixture titanium dioxide of 0.5 kilogram (silicon-dioxide of 1.5 kilograms and) of silicon-dioxide that 2 kilograms of particle diameters are 5-150nm and titanium dioxide, and add the chainextender ADR-4370 of 1.5 kilograms of BASF stock company productions, then under nitrogen protection, with the temperature rise rate of 10 DEG C/min, heat to 210 DEG C, then carry out melting mixing and react 7 minutes, obtained PGA/PHA resin nano alloy;
(4) with the use of the wortle of 3 millimeters, obtained PGA/PHA resin nano alloy is cut into slices, then wind cooling temperature lowering, obtained PGA/PHA resin nano alloy section;
(5) section of PGA/PHA resin nano alloy is got, injection moulding machine is used to carry out injection molding, during injection moulding, spout temperature is 25 DEG C, the section of PGA/PHA resin nano alloy is heated to 170 DEG C, balanced screw speed is 150 revs/min, back pressure is 500 kPas, feeding temperature is 160 DEG C, metering zone temperature is 200 DEG C, jet orifice temperature is 205 DEG C, die temperature is 25 DEG C, injection speed suitably hurry up, use the mould of Φ 8 millimeters, the spherical biodegradable resin material of obtained Φ 8 millimeters, can be used for perforation holes, screen casing, meet the stifled temporarily construction requirement of long well section or huge thick span reservoir.
The spherical biodegradable resin material of this Φ 8 millimeters is as perforation holes ball sealer, carry out fracturing fracture to turn to, use the ball of Φ 8 millimeters at B4 well (fracturing section 6735-6742m and 6789-6796m two sections, 60 DEG C, phasing degree spiral perforation, hole close 16 holes/m) implement without instrument layering turnaround fracture, use 40, the ball of Φ 8 millimeters altogether, 1 pitching turnaround fracture, after steering ball enters borehole, pressure raises 7.5MPa, proves that it has good interlayer steering qualities.The spherical biodegradable resin material of this Φ 8 millimeters at 150 DEG C 8 hours degradable.
Embodiment 5
Present embodiments provide a kind of biodegradable resin material of oilfield operation, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 1.5 ten thousand poly butylene succinate section 60-75 DEG C, under vacuum tightness 80 kPas, stir dry 6.0 hours; By weight-average molecular weight (Mw) be 1.0 ten thousand the section of poly-3-hydroxybutyrate ester 90-95 DEG C, under vacuum tightness 90 kPas, stir dry 5 hours, make its water ratio lower than 0.1wt%, best lower than 0.01wt%;
(2) poly butylene succinate after getting above-mentioned dewatering is cut into slices during 700 kilograms and poly-3-hydroxybutyrate ester cut into slices 300 kilograms and be added to whipping appts stainless steel mixer, heats to 50 DEG C, under vacuum tightness 90 kPas, and batch mixing 10 minutes;
(3) mixture of poly butylene succinate in mixer and poly-3-hydroxybutyrate ester is added in reciprocating single-screw intermixing extruder, and add the chainextender ADR-4370 of 1.5 kilograms of BASF stock company productions, then under nitrogen protection, with the temperature rise rate of 8 DEG C/min, heat to 205 DEG C, then carry out melting mixing and react 5 minutes, obtained PBS/PHA resin alloy;
(4) with the use of the wortle of 3 millimeters, obtained PBS/PHA resin alloy is cut into slices, then wind cooling temperature lowering, obtained PBS/PHA resin alloy section;
(5) obtained PBS/PHA resin alloy section is got, be added in vacuum resin liquid filling machine, Vacuum Pressure is 90 kPas, heat up with the temperature rise rate of 10 DEG C/min, temperature is elevated to 210 DEG C, molten state PBS/PHA resin alloy is cast in the mould of Φ 70 millimeters, under this negative pressure of vacuum, with the speed cooling down of 10 DEG C/min, the resin alloy cast of obtained Φ 70 millimeters, then machining lathe is used, by the foundry goods of this Φ 70 millimeters, be processed into Φ 25.40 millimeters, Φ 28.58 millimeters, Φ 31.75 millimeters, Φ 34.93 millimeters, Φ 38.10 millimeters, Φ 41.28 millimeters, Φ 44.45 millimeters, Φ 47.63 millimeters, Φ 50.80 millimeters, Φ 53.98 millimeters, Φ 57.15 millimeters, Φ 60.33 millimeters, Φ 63.50 millimeters, the spherical biodegradable resin material of Φ 66.68 millimeters and Φ 69.85 millimeters of equal-specifications, can be used for the sliding sleeve opening long well section segmentation tool, meet layering (section) the rebuilding construction requirement of long well section or huge thick span reservoir.
Adopt the Φ 25.40 millimeters prepared, Φ 28.58 millimeters, Φ 31.75 millimeters, Φ 34.93 millimeters, Φ 38.10 millimeters, Φ 41.28 millimeters, Φ 44.45 millimeters, Φ 47.63 millimeters, Φ 50.80 millimeters, Φ 53.98 millimeters and Φ 57.15 millimeters of spherical biodegradable resin materials are used for the sliding sleeve staged fracturing that B5 horizontal well (vertical depth 3160m) opens long well section (687m) 11 sections of instruments, when ball is to shaft bottom correspondence sliding sleeve, pressure break raises 15-20MPa, layering success, the row of returning after full well section pressure break completes, construct 74 hours apart from first paragraph, construct 5 hours apart from final stage, return and discharge degradation product chip, returning after 24 hours is drained through in journey ball chip of not degrading, proof has good layering and degradation effect.
Claims (15)
1. the preparation method of the biodegradable resin material of oilfield operation, it comprises the following steps: make polymkeric substance and chainextender carry out melting mixing reaction, prepare resin alloy, be the biodegradable resin material of described oilfield operation, wherein said polymkeric substance comprises in polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester two or three.
2. preparation method according to claim 1, wherein, with the total mass of described polymkeric substance for benchmark, described polymkeric substance is made up of the polyglycolic acid of 5-95% and the poly butylene succinate of 5-95%; Or be made up of the poly-3-hydroxybutyrate ester of 5-95% polyglycolic acid and 5-95%; Or be made up of the poly butylene succinate of 5-95% and the poly-3-hydroxybutyrate ester of 5-95%; Or be made up of the poly-3-hydroxybutyrate ester of the poly butylene succinate of 5-80%, the polyglycolic acid of 5-50% and 5-80%.
3. preparation method according to claim 1, wherein, the weight-average molecular weight of described polyglycolic acid is 10,000-12 ten thousand; The weight-average molecular weight of described poly butylene succinate is 10,000-25 ten thousand; The weight-average molecular weight of described poly-3-hydroxybutyrate ester is 10,000-8 ten thousand.
4. the preparation method according to claim 1 or 3, it is further comprising the steps of: carry out the dry pre-treatment of vacuum stirring to described polymkeric substance, make the water content of polyglycolic acid, poly butylene succinate and poly-3-hydroxybutyrate ester all lower than 0.1wt%, preferably, lower than 0.01wt%, and the molecular weight of the polymkeric substance after pre-treatment is not changed; More preferably, to the vacuum stirring drying of described polyglycolic acid be: 90-105 DEG C, under vacuum tightness 10-100 kPa, stir dry 2-8 hour; To the vacuum stirring drying of described poly butylene succinate be: 60-75 DEG C, under vacuum tightness 10-100 kPa, stir dry 3-14 hour; To the vacuum stirring drying of described poly-3-hydroxybutyrate ester be: 90-105 DEG C, under vacuum tightness 10-100 kPa, stir dry 2-8 hour.
5. preparation method according to claim 1, it is further comprising the steps of: when carrying out the reaction of described melting mixing, adding inorganic nano material, preparing resin nano alloy, being the biodegradable resin material of described oilfield operation; Wherein said inorganic nano material comprises nano silicon and/or nano titanium oxide, and its particle diameter is 5-20nm, and the addition of described inorganic nano material is the 0.01-3% of described total polymer mass.
6. preparation method according to claim 1, wherein, described chainextender is the chainextender containing active group epoxy group(ing), is preferably the combination of one or more of ADR-4300, ADR-4370, ADR-4368 and ADR-4380 that BASF stock company produces; The addition of described chainextender is the 0.05%-5.0% of described total polymer mass, and preferably, the addition of described chainextender is the 0.1-0.3% of described total polymer mass.
7. preparation method according to claim 1, wherein, the temperature of described melting mixing reaction is 200-240 DEG C, is preferably 205-220 DEG C, is more preferably 205-210 DEG C; The time of described melting mixing reaction is 3-20 minute, is preferably 5-8 minute.
8. preparation method according to claim 1 or 5, described melting mixing adopts reciprocating single-screw intermixing extruder to carry out; Preferably, described preparation method is further comprising the steps of: react to melting mixing the resin alloy for preparing with the use of wortle or resin nano alloy is cut into slices, then lower the temperature, prepare the resin alloy after section or resin nano alloy, be the biodegradable resin material of described oilfield operation.
9. according to claim 1, 4, preparation method described in 5 or 8, it is further comprising the steps of: adopt plastic grinder by described resin alloy or resin nano alloy or described polyglycolic acid, one in poly butylene succinate and poly-3-hydroxybutyrate ester or described polyglycolic acid, mixture that is a kind of and described inorganic nano material in poly butylene succinate and poly-3-hydroxybutyrate ester grinds, and by cooled with liquid nitrogen, controlling mill temperature is-10 to 0 DEG C, screening obtains 40 order-200 object powder, be the biodegradable resin material of described oilfield operation.
10. the preparation method according to claim 1,4,5 or 8, it is further comprising the steps of: adopt tablets press that a kind of or described polyglycolic acid in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester and the mixture that is a kind of and described inorganic nano material in poly-3-hydroxybutyrate ester are heated to 160-200 DEG C and carry out granulation; Or the mixture of described poly butylene succinate or described poly butylene succinate and described inorganic nano material is heated to 110-120 DEG C and carries out granulation; Then be cooled to 15-35 DEG C, obtained particle diameter is the particle of Φ 0.8-1 millimeter, Φ 1-1.5 millimeter, Φ 1.5-2 millimeter, Φ 2-2.5 millimeter, Φ 2.5-3 millimeter or Φ 3-5 millimeter, is the biodegradable resin material of described oilfield operation.
11. preparation methods according to claim 1,4,5 or 8, it is further comprising the steps of: a kind of or described polyglycolic acid in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester and the mixture that is a kind of and described inorganic nano material in poly-3-hydroxybutyrate ester are rolled into the thin slice that thickness is 0.1-0.3 millimeter at 160-190 DEG C; Or the mixture of described poly butylene succinate or described poly butylene succinate and described inorganic nano material is rolled into the thin slice that thickness is 0.1-0.3 millimeter at 100-110 DEG C; Then 20-30 DEG C is cooled to, pulverize again as diameter to be 5-10 millimeter circle and/or the flap of similar circle and/or the length of side be 5-10 millimeter is square and/or similar square and/or leg-of-mutton flap, be the biodegradable resin material of described oilfield operation.
12. preparation methods according to claim 1,4,5 or 8, it is further comprising the steps of: adopt melt spinning machine that a kind of or described polyglycolic acid in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester and the mixture that is a kind of and described inorganic nano material in poly-3-hydroxybutyrate ester are heated to 200-210 DEG C, then carry out drawing and setting at 65-90 DEG C; Or the mixture of described poly butylene succinate or described poly butylene succinate and described inorganic nano material is heated to 110-120 DEG C, then carries out drawing and setting at 40-60 DEG C; Form the fiber yarn of Φ 10-150 micron, then cut into the short-fibre silk that length is 2-15 millimeter, be the biodegradable resin material of described oilfield operation.
13. according to claim 1, 4, preparation method described in 5 or 8, it is further comprising the steps of: adopt injection moulding machine that a kind of or described polyglycolic acid in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester and the mixture that is a kind of and described inorganic nano material in poly-3-hydroxybutyrate ester are heated to 160-200 DEG C, be 100-175 rev/min at balanced screw speed, back pressure is 300-700 kPa, spout temperature is 20-25 DEG C, feeding temperature is 150-160 DEG C, metering zone temperature is 190-210 DEG C, jet orifice temperature is 190-210 DEG C, die temperature is under the condition of 20-25 DEG C, the ball of obtained Φ 4-15 millimeter, or the mixture of described poly butylene succinate or described poly butylene succinate and described inorganic nano material is heated to 110-120 DEG C, balanced screw speed be 100-175 rev/min, under back pressure is 300-700 kPa, spout temperature is 20-25 DEG C, feeding temperature is 100-110 DEG C, metering zone temperature is 110-120 DEG C, jet orifice temperature is 110-120 DEG C, die temperature is the condition of 20-25 DEG C, the ball of obtained Φ 4-15 millimeter, is the biodegradable resin material of described oilfield operation.
14. preparation methods according to claim 1,4,5 or 8, it is further comprising the steps of: a kind of or described polyglycolic acid in described resin alloy or resin nano alloy or described polyglycolic acid and poly-3-hydroxybutyrate ester and the mixture that is a kind of and described inorganic nano material in poly-3-hydroxybutyrate ester are heated to 160-210 DEG C; Or the mixture of described poly butylene succinate or described poly butylene succinate and described inorganic nano material is heated to 100-125 DEG C; Be cast in mould, obtained bar, more described bar be processed as the ball of Φ 20-80 millimeter, be the biodegradable resin material of described oilfield operation.
The biodegradable resin material of 15. oilfield operations, it is prepared by the preparation method of the biodegradable resin material of the oilfield operation according to any one of claim 1-14.
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| CN113403051A (en) * | 2021-06-23 | 2021-09-17 | 新疆中凌工程技术有限公司 | Self-adaptive temporary plugging ball and manufacturing method thereof |
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