CN104987682A - Biodegradable resin material applied to oil and gas fields and preparation method for biodegradable resin material - Google Patents
Biodegradable resin material applied to oil and gas fields and preparation method for biodegradable resin material Download PDFInfo
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- CN104987682A CN104987682A CN201510408970.XA CN201510408970A CN104987682A CN 104987682 A CN104987682 A CN 104987682A CN 201510408970 A CN201510408970 A CN 201510408970A CN 104987682 A CN104987682 A CN 104987682A
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- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 93
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 91
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 76
- 239000000956 alloy Substances 0.000 claims abstract description 73
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- 229920000642 polymer Polymers 0.000 claims abstract description 16
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- 238000003756 stirring Methods 0.000 claims description 45
- 239000002086 nanomaterial Substances 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 36
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- 238000002844 melting Methods 0.000 claims description 28
- 230000008018 melting Effects 0.000 claims description 28
- 238000002203 pretreatment Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
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- 238000012216 screening Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 abstract description 13
- 238000010276 construction Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 9
- 238000005553 drilling Methods 0.000 abstract description 9
- 239000004626 polylactic acid Substances 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
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- 239000003921 oil Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
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- 208000010392 Bone Fractures Diseases 0.000 description 9
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
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- 238000001816 cooling Methods 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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Abstract
The invention provides a biodegradable resin material applied to oil and gas fields and a preparation method for the biodegradable resin material. According to the preparation method for the biodegradable resin material applied to the oil and gas fields, two or three polymers of polyglycolic-colactic acid, polycaprolactone and polylactic acid and a chain extender are subject to melt mixing reaction to obtain a resin alloy, namely the biodegradable resin material applied to the oil and gas fields. The biodegradable resin material applied to the oil and gas fields is prepared from the method, can be prepared into the shapes of sheets, powder, granules, spheres and the like, or can be prepared into the shapes of the sheets, the powder, the granules, the spheres and the like by one of the polyglycolic-colactic acid, the polycaprolactone and the polylactic acid, is used for temporarily blocking filtrate to protect a reservoir, temporarily blocking a blast hole, a constructed layer section and the like in various construction (well drilling, well completing, well repairing, and acidizing and fracturing) operations of the oil and gas fields, and has the advantages of complete degradation and zero damage to stratum.
Description
Technical field
The present invention relates to biodegradable resin material being applied to oil-gas field and preparation method thereof, belong to oil and gas exploitation technical field.
Background technology
In the various construction operation of Oil/gas Well, 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, the object of the present invention is to provide biodegradable resin material being applied to oil-gas field 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 Well 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 being applied to oil-gas field; 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 described biodegradable resin material being applied to oil-gas field, wherein said polymkeric substance comprises in polyglycolic acid (PGA), polycaprolactone (PCL) and poly(lactic acid) (PLA) two or three.
In the present invention, there is in the structural formula of the polycaprolactone adopted H-(O-(CH
2)
5-CO)
n-OH, its second-order transition temperature is-60 DEG C, and fusing point is 60 DEG C, and the temporary plugging agent difficulty be therefore used for this polymkeric substance higher than the Oil/gas Well construction operation of 60 DEG C is large.The polyglycolic acid adopted has-(O-CH
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.Poly(lactic acid) (poly(lactic acid) of the crystalline forming) fusing point adopted is 180-210 DEG C, and the ester group in its molecular structure can be degradable under reservoir temperature, and final product is carbonic acid gas and water.Visible, these three kinds of polymkeric substance of polyglycolic acid (PGA), polycaprolactone (PCL) and poly(lactic acid) (PLA) 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, do not pollute reservoir rock and local water.
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 10-90% and the polycaprolactone of 10-90%; Or be made up of (sum of the two is 100%) the polyglycolic acid of 10-90% and the poly(lactic acid) of 10-90%; Or be made up of (sum of the two is 100%) the polycaprolactone of 10-90% and the poly(lactic acid) of 10-90%; Or be made up of (three's sum is 100%) the poly(lactic acid) of the polyglycolic acid of 10-80%, the polycaprolactone of 10-60% and 10-70%.
In the present invention, carry out melting mixing by making in polyglycolic acid, polycaprolactone and poly(lactic acid) 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 Well.Specifically, polycaprolactone can resolve into carbonic acid gas and water at the formation temperature completely, crystalline melt point is low, only have 60 DEG C, the temporary plugging agent difficulty being used for this polymkeric substance higher than the Oil/gas Well construction operation of 60 DEG C is large, but by carrying out mixing with one or both and chainextender in other two kinds of polymkeric substance, obtained resin alloy just can have new mechanics, chemical property.
In above-mentioned preparation method, preferably, the weight-average molecular weight of described polyglycolic acid is 10,000-12 ten thousand (more preferably adopting polyglycolic acid section); The weight-average molecular weight of described polycaprolactone is 10,000-15 ten thousand (more preferably adopting polycaprolactone section); The weight-average molecular weight of described poly(lactic acid) is 10,000-15 ten thousand (more preferably adopting polylactic acid slice).
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, polycaprolactone and poly(lactic acid) all lower than 0.1wt% (weight percentage), more preferably, lower than 0.01wt%; Particularly preferably, stirring drying to the initial vacuum of described polyglycolic acid is: 90-105 DEG C, under low vacuum 10-100 kPa, stir dry 2-8 hour (being more preferably 4-6 hour); To the vacuum stirring drying of described polycaprolactone be: 50-55 DEG C, under vacuum tightness 10-100 kPa, stir dry 5-16 hour; To the vacuum stirring drying of described poly(lactic acid) be: 80-95 DEG C, under vacuum tightness 10-100 kPa, stir dry 2-12 hour (being more preferably 6-8 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 preferably the combination of one or more of ADR-4300, ADR-4370 and ADR-4380 that BASF stock company (BASF SE) produces.More preferably, described chainextender is ADR-4370, all containing 9 active group epoxy group(ing) in its each molecule.
In above-mentioned preparation method, preferably, 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.
Raw material performed polymer molecule based on the polymkeric substance that the present invention selects polyglycolic acid, polycaprolactone and poly(lactic acid) 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) (3-9) all containing different number in each molecule of ADR-4300, ADR-4370 and ADR-4380 that BASF stock company produces, Ligature can be there is with the reactive group of PGA, PCL and PLA (terminal hydroxy group, end carboxyl), form more macromolecular polymer alloy, shown in example reaction equation described as follows:
In above-mentioned preparation method, preferably, for the polymkeric substance be made up of polycaprolactone, polyglycolic acid and poly(lactic acid), the temperature of described melting mixing reaction is 200-230 DEG C, is more preferably 205-220 DEG C, most preferably is 205-210 DEG C; For the polymkeric substance be made up of polycaprolactone and poly(lactic acid), the temperature of described melting mixing reaction is 180-230 DEG C, is more preferably 205-220 DEG C, most preferably is 205-210 DEG C; For the polymkeric substance be made up of polycaprolactone and polyglycolic acid, the temperature of described melting mixing reaction is 180-220 DEG C, is more preferably 190-210 DEG C, most preferably is 200-205 DEG C; For the polymkeric substance be made up of polyglycolic acid and poly(lactic acid), the temperature of described melting mixing reaction is 205-240 DEG C, is more preferably 205-220 DEG C, most preferably is 205-210 DEG C.Temperature does not reach above-mentioned in limited time lower, and polymerization 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.
In above-mentioned preparation method, preferably, the time of described melting mixing reaction is 3-20 minute, is more preferably 5-8 minute.If the reaction times does not reach above-mentioned lower limit, then reaction is carried out insufficient, and on the other hand, if exceed the above-mentioned upper limit, then the color of resin generated can deepen.
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 described biodegradable resin material being applied to oil-gas field.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: make in polyglycolic acid, polycaprolactone and poly(lactic acid) 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 difference, the resin alloy prepared or resin nano alloy can be processed as the shapes such as required sheet, powder, particle, ball, fiber, the such as ball of Φ (diameter) 20-80 millimeter, the particle of Φ 0.8-5 millimeter different-grain diameter, 40 order-200 object powder, the flap of thickness to be 0.1-0.3 millimeter, diameter or the length of side be 5-10 millimeter, Φ 10-150 micron, length are the fiber yarn etc. of 2-15 millimeter, be the biodegradable resin material being applied to oil-gas field, 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 polycaprolactone and poly(lactic acid) (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 polycaprolactone and poly(lactic acid) (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 described biodegradable resin material being applied to oil-gas field.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(lactic acid) (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly(lactic acid) (can for after the dry pre-treatment of vacuum stirring) is heated to 160-200 DEG C and carry out granulation; Or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) be heated to 50-60 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 described biodegradable resin material being applied to oil-gas field.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(lactic acid) (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly(lactic acid) (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 polycaprolactone (can for after the dry pre-treatment of vacuum stirring) or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) being rolled at 50-55 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 described biodegradable resin material being applied to oil-gas field.
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(lactic acid) (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly(lactic acid) (can for after the dry pre-treatment of vacuum stirring) is heated to 200-210 DEG C, then carry out drawing and setting at 65-90 DEG C; Or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) be heated to 60-65 DEG C with the mixture of described inorganic nano material, then carry out drawing and setting at 30-40 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 described biodegradable resin material being applied to oil-gas field.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(lactic acid) (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly(lactic acid) (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 polycaprolactone (can for after the dry pre-treatment of vacuum stirring) or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) be heated to 60-65 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 55-60 DEG C, metering zone temperature is 60-65 DEG C, jet orifice temperature is 58-62 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 described biodegradable resin material being applied to oil-gas field.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(lactic acid) (can for after the dry pre-treatment of vacuum stirring) or described polyglycolic acid and poly(lactic acid) (can for after the dry pre-treatment of vacuum stirring) is heated to 160-200 DEG C; Or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) or described polycaprolactone (can for after the dry pre-treatment of vacuum stirring) be heated to 60-75 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 described biodegradable resin material being applied to oil-gas field.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, and the mixing temperature of poly(lactic acid) and described inorganic nano material is 180-220 DEG C, and the mixing temperature of polycaprolactone and described inorganic nano material is 60-70 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/PCL/PLA 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/PCL, PGA/PLA, PCL/PLA 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, active group epoxy group(ing) all containing 3 in its each molecule, 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/PCL/PLA 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/PCL, PGA/PLA, PCL/PLA 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, active group epoxy group(ing) all containing 9 in its each molecule, its addition is the 0.05%-5.0% of total polymer mass, preferred addition is the 0.1-0.3% of total polymer mass.
The present invention selects polyglycolic acid (PGA), raw material based on the polymkeric substance that polycaprolactone (PCL) and poly(lactic acid) (PLA) 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/PCL are wherein chosen by certain proportioning, PGA/PLA, PCL/PLA), or three kinds (PGA/PCL/PLA), add the chainextender containing active group epoxy group(ing) again, as the ADR-4300 that BASF stock company produces, the combination of one or more in ADR-4370 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, polycaprolactone and the poly(lactic acid) in polyglycolic acid, polycaprolactone and poly(lactic acid) with the mixture of inorganic nano material, be the biodegradable resin material being applied to oil-gas field.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, this biodegradable resin material being applied to oil-gas field 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 that this is applied to oil-gas field, 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 being applied to oil-gas field, it is prepared by the above-mentioned preparation method being applied to the biodegradable resin material of oil-gas field.
This biodegradable resin material being applied to oil-gas field 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 Well, 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 being applied to oil-gas field, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 80,000 polycaprolactone section 50-55 DEG C, under vacuum tightness 90 kPas, stir dry 12 hours; By weight-average molecular weight (Mw) be 80,000 polyglycolic acid section 100-105 DEG C, under vacuum tightness 90 kPas, stir dry 4 hours; By weight-average molecular weight (Mw) be 40,000 polylactic acid slice 90-95 DEG C, under vacuum tightness 90 kPas, stir dry 6 hours, make its water ratio lower than 0.1wt%, best lower than 0.01wt%;
(2) cut into slices 750 kilograms and polylactic acid slice 150 kilograms of polycaprolactone section double centner, polyglycolic acid after getting above-mentioned dewatering is added in the stainless steel mixer with whipping appts, heat to 50 DEG C, under vacuum tightness 90 kPas, batch mixing 10 minutes;
(3) mixture of the polyglycolic acid in mixer, polycaprolactone and poly(lactic acid) is added in reciprocating single-screw intermixing extruder, adding 3.5 kilograms of particle diameters is the silicon-dioxide of 15-20nm, and add the chainextender ADR-4370 of 1 kilogram of BASF stock company production, then under nitrogen protection, with the temperature rise rate of 8 DEG C/min, heat to 202 DEG C, then carry out melting mixing and react 7 minutes, obtained PGA/PCL/PLA resin nano alloy;
(4) with the use of the wortle of 3 millimeters, obtained PGA/PCL/PLA resin nano alloy is cut into slices, then wind cooling temperature lowering, obtained PGA/PCL/PLA resin nano alloy section;
(5) plastic grinder is used to grind the section of obtained PGA/PCL/PLA resin nano alloy, and by cooled with liquid nitrogen, controlling mill temperature is-10 to 0 DEG C, use 200 orders (74 μm) to sieve and carry out the PGA/PCL/PLA resin nano powdered alloy that screening obtains 200 orders (74 μm), obtained Powdered biodegradable resin material.
Adopt 200 orders (74 μm) the Powdered biodegradable resin material stifled experiment temporarily prepared: rock core basic data: rock core length: 5.01 centimetres, core diameter φ 2.51, under 150 DEG C of temperature condition, with normal saline solution (NaCl:7wt%, CaCl
2: 0.6wt%, MgCl
26H
2o:0.4wt%) the saline water permeates rate recording rock core is 40.18 × 10-3 μm 2, under room temperature condition, the PGA/PCL/PLA resin nano powdered alloy temporary plugging agent of 2cm thickness 200 order (74 μm) is contained in die, be placed in rock core injection side, bearing capacity at 150 DEG C in 2cm thickness temporary plugging agent situation, pressure is measured with normal saline solution constant flow 5mL/min when being warming up to 150 DEG C, infusion pressure increase transfers Isobarically Control to during 40MPa, and rate of permeation reduces to 0.09 × 10
-3μm
2, under permeability plugging 99.77%, 40MPa pressure reduction, plugging effect is better; Core holding unit injection side and outlet end valve are closed, put into 150 DEG C of baking ovens 20 hours, take out and load rock core flow system, 150 DEG C time, normal saline solution measures its rate of permeation is again 39.12 × 10-3 μm 2, core permeability recovery value 97.36%, illustrates this Powdered biodegradable resin material degraded thoroughly.
Embodiment 2
PGA/PCL/PLA 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 C1 well (in well depth 6513-6572m well section, this well section temperature 152 DEG C-153 DEG C, penetrate out 2 layers, 6513-6524m and 6561-6572m) the temporary stall of well is to frac job, melon jelly fracturing fluid is used to carry, divide 1 stifled turnaround fracture temporarily, use this Φ 1-1.5 mm granules stifled material 268 kilograms temporarily, after turning under identical infusion discharge capacity, pressure raises 15.2MPa, temporary stall to successful, this particle temporarily at stifled material 150 DEG C 12 hours degradable.
Embodiment 3
Present embodiments provide a kind of biodegradable resin material being applied to oil-gas field, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 20,000 polycaprolactone section 50-55 DEG C, under vacuum tightness 90 kPas, stir dry 11 hours; By weight-average molecular weight (Mw) be 1.5 ten thousand polyglycolic acid section 95-100 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) polycaprolactone after getting above-mentioned dewatering is cut into slices during 500 kilograms and polyglycolic acid cut into slices 500 kilograms and be added to whipping appts stainless steel mixer, heats to 45 DEG C, under vacuum tightness 90 kPas, and batch mixing 10 minutes;
(3) mixture of the polyglycolic acid in mixer and polycaprolactone is added in reciprocating single-screw intermixing extruder, adding 5 kilograms of particle diameters is the silicon-dioxide of 10-20nm, and add the chainextender ADR-4300 of 1.3 kilograms of BASF stock company productions, then under nitrogen protection, with the temperature rise rate of 10 DEG C/min, heat to 205 DEG C, then carry out melting mixing and react 8 minutes, obtained PGA/PCL resin nano alloy;
(4) at 190 DEG C, the PGA/PCL resin nano alloy of melting is extruded through reciprocating single-screw intermixing extruder, rolling machine is adopted to be rolled by PGA/PCL 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 C2 well Reservoir Section, and (this well is serious in the leakage of 4167-4171m section, cannot continue to creep into, this section of bottom temperature is 130 DEG C, fast 20 sides of drilling fluid leakage/hour) plugging operations, well head pressure-bearing 12MPa after shutoff, within 30 minutes, pressure does not fall, continue enforcement and creep into operation, get into 4190m finishing drilling, without leakage, prove that its plugging effect is good, directly going into operation after completion, (leak stopping is gone into operation 12 days to completion,) crude production rate 53 sides/sky afterwards, prove that degradation property is good.
Embodiment 4
Present embodiments provide a kind of biodegradable resin material being applied to oil-gas field, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 1.5 ten thousand polyglycolic acid section 100-105 DEG C, under vacuum tightness 90 kPas, stir dry 4 hours; By weight-average molecular weight (Mw) be 10,000 polylactic acid slice 90-95 DEG C, under vacuum tightness 90 kPas, stir dry 6 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 700 kilograms and is added in the stainless steel mixer with whipping appts with polylactic acid slice 300 kilograms, 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(lactic acid) is added in reciprocating single-screw intermixing extruder, and add the chainextender ADR-4370 of 2 kilograms of BASF stock company productions, then under nitrogen protection, with the temperature rise rate of 8 DEG C/min, heat to 200 DEG C, then carry out melting mixing and react 7 minutes, obtained PGA/PLA resin alloy;
(4) with the use of the wortle of 3 millimeters, obtained PGA/PLA resin alloy is cut into slices, then wind cooling temperature lowering, obtained PGA/PLA resin alloy section;
(5) injection moulding machine is used to carry out injection molding, during injection moulding, spout temperature is 25 DEG C, the section of PGA/PLA resin 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, and metering zone temperature is 200 DEG C, and jet orifice temperature is 200 DEG C, die temperature is 25 DEG C, injection speed suitably hurry up, uses the mould of Φ 6 millimeters, the spherical biodegradable resin material of obtained Φ 6 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 6 millimeters is as perforation holes ball sealer, carry out fracturing fracture to turn to, use the ball of Φ 6 millimeters at C3 well (fracturing section 4235-6243m and 4277-6789m two sections, 60 DEG C, phasing degree spiral perforation, hole close 16 holes/m) implement without instrument layering turnaround fracture, use 50, the ball of Φ 6 millimeters altogether, 1 pitching turnaround fracture, after steering ball enters borehole, pressure raises 11.3MPa, proves that it has good interlayer steering qualities.Spherical biodegradable resin material 24 hours degradation rates at 130 DEG C of this Φ 6 millimeters are greater than 95%.
Embodiment 5
Present embodiments provide a kind of biodegradable resin material being applied to oil-gas field, as shown in Figure 1, it is prepared by following steps:
(1) by weight-average molecular weight (Mw) be 30,000 polycaprolactone section 50-55 DEG C, under vacuum tightness 90 kPas, stir dry 12 hours; By weight-average molecular weight (Mw) be 20,000 polylactic acid slice 90-95 DEG C, under vacuum tightness 90 kPas, stir dry 6 hours, make its water ratio lower than 0.1wt%, best lower than 0.01wt%;
(2) polycaprolactone after getting above-mentioned dewatering is cut into slices 350 kilograms and is added in the stainless steel mixer with whipping appts with polylactic acid slice 650 kilograms, heats to 50 DEG C, under vacuum tightness 90 kPas, and batch mixing 10 minutes;
(3) mixture of the polycaprolactone in mixer and poly(lactic acid) is added in reciprocating single-screw intermixing extruder, adding 1 kilogram of particle diameter is the silicon-dioxide of 10-20nm, and add the chainextender ADR-4300 of 1 kilogram of BASF stock company production, then under nitrogen protection, with the temperature rise rate of 8 DEG C/min, heat to 202 DEG C, then carry out melting mixing and react 7 minutes, obtained PCL/PLA resin nano alloy;
(4) with the use of the wortle of 3 millimeters, obtained PCL/PLA resin nano alloy is cut into slices, then wind cooling temperature lowering, obtained PCL/PLA resin nano alloy section;
(5) adopt melt spinning machine that described resin nano alloy section is heated to 200-210 DEG C and carry out melt-spinning, then drawing and setting is carried out at 80 DEG C, form the fiber yarn of Φ 20-30 micron, cut into the short-fibre silk that length is 8 millimeters again, obtain resin nano alloy short-fibre silk, be the described biodegradable resin material being applied to oil-gas field.
The obtained short-fibre silk of 1.5 grams 8 millimeters is inserted (long 5.08 centimetres of aluminum rock core in the key joint of aluminum rock core, core diameter 2.5 centimetres, long 2 centimetres of key joint seam, wide end seam is wide 2 millimeters, and narrow end seam is wide 0.5 millimeter), with short-fibre silk, crack is tamped, rock core is connected in flowing experiment, under 130 DEG C of temperature condition, with normal saline solution (NaCl:7wt%, CaCl
2: 0.6wt%, MgCl
26H
2o:0.4wt%) constant voltage 20MPa injects, and infusion pressure-stabilisation stops infusion in 20 minutes, and under short-fibre silk 20MPa pressure reduction, plugging effect is better; Core holding unit injection side and outlet end valve are closed, put into 130 DEG C of baking ovens 40 hours, take out aluminum core observation, short-fibre silk is degradable, the degraded of short-fibre silk biodegradable resin material is described thoroughly.
Claims (16)
1. be applied to the preparation method of the biodegradable resin material of oil-gas field, it comprises the following steps: make polymkeric substance and chainextender carry out melting mixing reaction, prepare resin alloy, be the described biodegradable resin material being applied to oil-gas field, wherein said polymkeric substance comprises in polyglycolic acid, polycaprolactone and poly(lactic acid) 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 10-90% and the polycaprolactone of 10-90%; Or be made up of the polyglycolic acid of 10-90% and the poly(lactic acid) of 10-90%; Or be made up of the polycaprolactone of 10-90% and the poly(lactic acid) of 10-90%; Or be made up of the poly(lactic acid) of the polyglycolic acid of 10-80%, the polycaprolactone of 10-60% and 10-70%.
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 polycaprolactone is 10,000-15 ten thousand; The weight-average molecular weight of described poly(lactic acid) is 10,000-15 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, polycaprolactone and poly(lactic acid) 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 4-8 hour; To the vacuum stirring drying of described polycaprolactone be: 50-55 DEG C, under vacuum tightness 10-100 kPa, stir dry 5-16 hour; To the vacuum stirring drying of described poly(lactic acid) be: 80-95 DEG C, under vacuum tightness 10-100 kPa, stir dry 2-12 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 described biodegradable resin material being applied to oil-gas field; 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 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, for the polymkeric substance be made up of polycaprolactone, polyglycolic acid and poly(lactic acid), the temperature of described melting mixing reaction is 200-230 DEG C, is preferably 205-220 DEG C, is more preferably 205-210 DEG C; For the polymkeric substance be made up of polycaprolactone and poly(lactic acid), the temperature of described melting mixing reaction is 180-230 DEG C, is preferably 205-220 DEG C, is more preferably 205-210 DEG C; For the polymkeric substance be made up of polycaprolactone and polyglycolic acid, the temperature of described melting mixing reaction is 180-220 DEG C, is preferably 190-210 DEG C, is more preferably 200-205 DEG C; For the polymkeric substance be made up of polyglycolic acid and poly(lactic acid), the temperature of described melting mixing reaction is 205-240 DEG C, is preferably 205-220 DEG C, is more preferably 205-210 DEG C.
8. preparation method according to claim 1, wherein, the time of described melting mixing reaction is 3-20 minute, is more preferably 5-8 minute.
9. 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 described biodegradable resin material being applied to oil-gas field.
10. the preparation method according to claim 1,4,5 or 9, it is further comprising the steps of: adopt plastic grinder to be ground by the mixture that is a kind of and described inorganic nano material in a kind of or described polyglycolic acid, polycaprolactone and the poly(lactic acid) in described resin alloy or resin nano alloy or described polyglycolic acid, polycaprolactone and poly(lactic acid), and by cooled with liquid nitrogen, controlling mill temperature is-10 to 0 DEG C, screening obtains 40 order-200 object powder, is the described biodegradable resin material being applied to oil-gas field.
11. preparation methods according to claim 1,4,5 or 9, 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(lactic acid) and the mixture that is a kind of and described inorganic nano material in poly(lactic acid) are heated to 160-200 DEG C and carry out granulation; Or the mixture of described polycaprolactone or described polycaprolactone and described inorganic nano material is heated to 50-60 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 described biodegradable resin material being applied to oil-gas field.
12. preparation methods according to claim 1,4,5 or 9, 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(lactic acid) and the mixture that is a kind of and described inorganic nano material in poly(lactic acid) are rolled into the thin slice that thickness is 0.1-0.3 millimeter at 160-190 DEG C; Or the mixture of described polycaprolactone or described polycaprolactone and described inorganic nano material is rolled into the thin slice that thickness is 0.1-0.3 millimeter at 50-55 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 described biodegradable resin material being applied to oil-gas field.
13. preparation methods according to claim 1,4,5 or 9, 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(lactic acid) and the mixture that is a kind of and described inorganic nano material in poly(lactic acid) are heated to 200-210 DEG C, then carry out drawing and setting at 65-90 DEG C; Or the mixture of described polycaprolactone or described polycaprolactone and described inorganic nano material is heated to 60-65 DEG C, then carries out drawing and setting at 30-40 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 described biodegradable resin material being applied to oil-gas field.
14. according to claim 1, 4, preparation method described in 5 or 9, 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(lactic acid) and the mixture that is a kind of and described inorganic nano material in poly(lactic acid) 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 polycaprolactone or described polycaprolactone and described inorganic nano material is heated to 60-65 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 55-60 DEG C, metering zone temperature is 60-65 DEG C, jet orifice temperature is 58-62 DEG C, die temperature is the condition of 20-25 DEG C, the ball of obtained Φ 4-15 millimeter, is the described biodegradable resin material being applied to oil-gas field.
15. the preparation method according to claim 1,4,5 or 9, 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(lactic acid) and the mixture that is a kind of and described inorganic nano material in poly(lactic acid) are heated to 160-200 DEG C; Or described polycaprolactone is heated to 60-75 DEG C; Be cast in mould, obtained bar, more described bar be processed as the ball of Φ 20-80 millimeter, be the described biodegradable resin material being applied to oil-gas field.
16. biodegradable resin materials being applied to oil-gas field, it is prepared by the preparation method being applied to the biodegradable resin material of oil-gas field according to any one of claim 1-15.
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Application publication date: 20151021 |