CN105647496A - Expandable biopolymer temporary plug profile control agent and preparation method thereof - Google Patents
Expandable biopolymer temporary plug profile control agent and preparation method thereof Download PDFInfo
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- CN105647496A CN105647496A CN201610063078.7A CN201610063078A CN105647496A CN 105647496 A CN105647496 A CN 105647496A CN 201610063078 A CN201610063078 A CN 201610063078A CN 105647496 A CN105647496 A CN 105647496A
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- 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
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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- 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
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- C09K8/5045—Compositions based on water or polar solvents containing inorganic compounds
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Abstract
The invention discloses an expandable biopolymer temporary plug profile control agent and a preparation method thereof. The expandable biopolymer temporary plug profile control agent is mainly prepared from biodegradation polymer, a reinforcing agent, a toughening agent, a foaming agent, a crosslinking agent, a water blocking agent, a coupling agent, a functional auxiliary and a carrying agent, and can be prepared through a double-screw extruder mixing method and a mixer mixing method under certain process conditions. The prepared expandable biopolymer temporary plug profile control agent is low in carbon, environmentally friendly, expandable, resistant to high temperature, high in plugging ratio, large in plugging strength, capable of achieving the self-plug-removal function, free of toxicity and pollution to stratums, low in cost and convenient to construct, and has very high economic value and broad market prospects.
Description
Technical field
The present invention relates to a kind of oil production stifled amendment temporarily, it is characterised in that utilize biopolymer low-carbon environment-friendly, can degradation property has invented a kind of expandability completely, high temperature resistant, sealing ratiod height, plugging strength big, explain plugging function by oneself block up amendment and its preparation method temporarily.
Background technology
In the oil production middle and later periods, along with oil well is handled up the increase of round, vapour between well, water breakthrough are particularly thorny, seriously have impact on heavy oil development effect. Heavy crude reservoir has the features such as compacting is weak, loose cementation, macropore height ooze, stratum nonuniformity is serious, in exploitation via steam injection process, owing to the nonuniformity (comprise plane with longitudinal direction) of reservoir is serious, oil reservoir is caused to inhale vapour uneven, the high-temperature steam injected rises to reservoir top portion on trending towards, in addition the steam overlap phenomenon generally existed, under the alternating action of steam injection, oil recovery, rock stratum skeleton is destroyed. Owing to connection property is good, under pressure drop effect, well area far away particle, constantly to shaft bottom migration, forms stratum macropore gradually, causes vapour to be altered, the problems such as steam heat efficiency is low, seriously have impact on oil production rate, also become the principal contradiction affecting super-viscous oil and efficiently developing. Vapour alters harm mainly: cause energy excessive, and steam utilization reduces; Oil reservoir employs uneven aggravation of contradictions, affects oil well and normally produces, and reduces production time efficiency; Cause sand production, overlap bad; Offset well cannot drilling well or workover treatment; Meanwhile, vapour is altered and is also aggravated formation sand production, when steam enters in recovery well pressure cone of depression, reservoir sand will be promoted to migrate to shaft bottom, both interact aggravation vapour alter.
In order to effectively suppress vapour between well to alter interference, improve oil well longitudinal direction and are-al remaining oil development degree, can implement to block up profile control measures temporarily under oil reservoir understanding more clearly situation. Employ inequality for oil well at present, vapour alters interference problem and mainly takes to block up amendment temporarily; under reservoir condition; selectively; centering low permeability layer is protected; and at earth formation deep to high permeability formation shutoff; force injecting steam to turn to, reach and start that potentiality layer, containment steam are unidirectional advances by leaps and bounds and expand the swept volume of steam, thus reach and alleviate vapour and alter, eliminate inter-well interference, expand injecting steam swept volume, improve the object of cycle petroleum production.
Stifled amendment is mainly divided into 7 classes temporarily at present: frozen glue class, gel-like, microballoon class, particulate species, precipitation class, foam class and microbiology class.
1. gel-type stifled amendment temporarily: frozen glue class amendment is Ploymer Gel Plugging Agent, is use maximum, a most widely used class blocking agent at present both at home and abroad, forms the material with space net structure by polymers soln with suitable linking agent and become. Available polymkeric substance comprises synthetic polymer, Natural and Modified Natural Materials, biological degradation polyalcohol etc., their common feature is dissolved in water, water has excellent tackifying, linear macromolecule chain there is polar group, can react with polyvalent metal ion or organic group, generate build cross-linking products frozen glue, after forming frozen glue, viscosity increases considerably, lost flowability. The polynuclear hydroxy bridge complex ion that linking agent can be formed with high volence metal ion or low molecule aldehyde compound etc. A large amount of gel-type profile control system used is all taking partially hydrolyzed polyacrylamide (HPAM) as host at present, with Cr3+��Al3+, resol, phenol and Resorcinol etc. be the system of linking agent.
2. gel-type stifled amendment temporarily: gel is solid-state or the colloidal dispersion of semi-solid state, have by the interconnection space net structure formed of colloidal solid, polymer or surfactant molecule, structure is filled with liquid in space, liquid is enclosed in and wherein maintains static, making system lose mobility, its character is between solid and liquid. Gel is divided into the big class of rigid gel and elastogel two, and silicic acid gel is one of conventional gel in oil field. Adding people's ionogen in rare silicate solution or add acid in the silicate solutions of proper content, then generate silicic acid gel, this gelatinous transparent and flexible, its intensity is enough to stop the current by stratum.
3. polymer microballoon stifled amendment temporarily: polymer microballoon technology is a kind of novel profile control technique that development in recent years is got up, its advantage comprises by ectocine little, can direct waste water, resisting high temperature, high salt, and inject without viscosity, pollution-free, cost is lower. The Mechanism of profile control and displacement of polymer microballoon is cross-linked polymer microsphere is nano level/micron order microballoon, and to oil reservoir pore throat diameter, its initial particle meets the requirement of " entering to go "; Microballoon, after aquation is swelling, can reach the particle diameter requirement of the big pore throat of shutoff, and have certain intensity, meets the requirement of the big pore throat of formation " firmly stifled ", follow-up liquid stream is turned to; Microballoon has elasticity, is out of shape under a certain pressure and moves forward to earth formation deep, meets the requirement that adjusting driving agnet can enter earth formation deep and play a role.
4. particulate species stifled amendment temporarily: mainly comprise great soil group, such as soil, clay etc.; Non-volume expansion type granular, such as shell, milk of lime, bluestone powder etc.; The particle of volume expansion type, such as lightly crosslinked polyacrylamide, polyvinyl alcohol powder, and the pre-crosslinked gel particle etc. succeeded in developing recently. The tune of this kind of blocking agent blocks up the mechanism of action mainly physical clogging effect, comprises trapping effect, throwing out etc. Volume expansion type granular water-swellable, enhances its shut-off capacity, is more suitable for the shutoff of crack and macropore.
5. sedimentation type stifled amendment temporarily: being called sedimentation type amendment to precipitate the amendment as shutoff material, this kind of chemical agent injects to stratum, forms precipitation duct, tamper shutoff stratum on stratum. Owing to this kind of reactant is all the aqueous solution, and viscosity lower (near with aqueous phase), thus can optionally enter high water accepting layer, after reaction, most permeable zone is produced more effective blocking effect in the earth formation. Such as, aqueous sodium carbonate and ferric chloride aqueous solutions react in stratum, generate ferric hydroxide precipitate. This kind of amendment source is wide, and cost is low, and construction safety is convenient, and de-plugging easily (high pressure acidifying, alkali lye pressure break), but must take effective sfgd. when constructing, otherwise can block oil reservoir, pollutes stratum.
6. the stifled water of foam class stifled amendment temporarily: be divided into two-phase foam and three-phase froth according to the composition of foaming liquid. Three-phase froth is than two-phase foam stabilization. The profile control mechanism of three-phase froth is the gas-liquid inhibition effect Jamin effect relying on stable aerated fluid repeatedly to add in water filling layer, change the seepage direction in water accepting layer and intake profile, thus expand the pasta of sweeping injecting water and amass, slow down waterline fltting speed and the water regain in main water flow direction, it is to increase inject swept volume and the oil displacement efficiency of water.
7. microorganism stifled profile control technique temporarily: microorganism is used for water injection well profile control and starts from the U.S. the earliest. Its principle is that the bacterial classification and nutritive medium thereof that can produce biological degradation polyalcohol are injected stratum so that it is breeding in a large number, crack most permeable zone can be played good selectively blocking off effect by the biological degradation polyalcohol that somatic cells and metabolism thereof produce. The effect of microorganism formation is many-sided, reaches the object improved and inject profile control mainly through following two aspects:Microorganism mainly enters current macropore, growth and breeding in porous medium, forms the original permeability that hypha body bacterium colony reduces;Microorganism can produce a large amount of gas in growth and breeding process, change the environment of solution medium, form gas lock on the one hand, cause crystallization and the precipitation of the mineral substance such as salt on the other hand, blocking water exit, notes displacing agent and is forced to walk around bottleneck area after making, start low permeability layer, feed through to the region that water drive does not involve, it is to increase recovery percent of reserves.
Patent CN201510493724.9 discloses a kind of thermal recovery envelope and alters agent and its preparation method, belongs to chemical water shutoff in oilfield amendment field. This thermal recovery envelope alters agent, is that water is formed by flyash 35.00��41.00%, alum 0.90��1.10%, water glass 0.19��0.22%, Sodium sulfate anhydrous.min(99) 0.80��1.00%, unslaked lime 2.80��3.30%, sodium hydroxide 0��1.10%, wilkinite 1.60��3.10%, guar gum 0��0.03%, surplus. This thermal recovery envelope is altered agent and is applicable to the shutoff that steam-stimulated well vapour alters passage. The granule type of main component that to be a kind of taking flyash be is stifled amendment (that is: envelope alters agent) temporarily, and in 12 hours this invention presetting periods, after consolidation, ultimate compression strength reaches 2.9MPa, resistance to heating temperature 300 DEG C. But this kind of granule type stifled amendment temporarily, sealing ratiod is lower. Patent CN99113250.5 discloses the high-temperature temporary blocking agent and its preparation method that control steam entry profile in a kind of viscous crude field cyclic steam stimulation. This invention have employed the system that polyacrylamide, magnesium oxide, acrylamide, methylene-bisacrylamide, ammonium persulphate and water form, and is formed into colloid through cross-linking polymerization. Become colloid and solid phase particles shutoff most permeable zone in the earth formation, along with carrying out gradually of steam injection process, become colloid gradually to destroy, obtain layer steam injection, close the object of layer oil recovery. But still there is the low problem of sealing ratiod, although magnesium oxide heatproof can reach more than 300 DEG C, but the one-tenth colloid temperature tolerance formed with polyacrylamide is not good, just starts to decompose, thus have impact on overall plugging effect after temperature reaches 120. CN01134373.7 discloses a kind of high temp profile control agent and its production and use, and it is prepared from by formaldehyde, phenol, water glass, and wherein the mol ratio of formaldehyde and phenol is 2.5-3.5: 1, and water glass content is 5-15% (weight). Its preparation process comprises formaldehyde, phenol stirring reaction and reacts with sodium silicate aqueous solution and become. This high temp profile control agent is used for the stifled water of pyrochemistry of oil well and the high-temperature profile control of steamed well. This invention 7 days weight loss in heatproof 300 DEG C of situations is 25%, illustrates that temperature tolerance is better, but this temporary stifled amendment does not possess low-carbon environment-friendly, there is formation and pollutes, can not de-plugging problem voluntarily. Patent CN201310485276.9 discloses a kind of degradable elasticity temporary plugging agent and its preparation method; Material main composition be: 100 parts��150 parts, degradable polymer elastomerics, 1 part��3 parts, softening agent, 0.5 part��2 parts, tensio-active agent and lubricant 0.5 part��1.5 parts; Degradable polymer elastomerics is made primarily of vinyl starch 2 parts��5 parts, butyl acrylate 10 parts��15 parts, MALEIC ANHYDRIDE 1 part��3 parts, initiator 0.05 part��0.15 part, solvent 6 parts��12 parts and nitrogen 100 parts��150 parts. This invention has the advantage of soft elasticity, oil soluble and degradability, but plugging strength and temperature tolerance are not good. Patent CN00102576.7 discloses a kind of temporary plugging agent utilizing waste polyolefine to prepare, and this temporary plugging agent main composition is: polyolefine 5��96, hydrocarbon-fraction 0.1��83, tensio-active agent 0.1��15, water 0.1��68. This temporary plugging agent mainly utilizes waste polyolefine to be prepared from, and polyolefine mainly exists can not degrade voluntarily, the problem that high-temperature fusant intensity is little. Patent CN201510363546.8 discloses a kind of alkaline-resisting amendment of pre-crosslinked gel volume expansion grain and its production and use, and the preparation method of amendment comprises S1: preparation toughness strong elasticity particle;S2: the Oil treatment of toughness strong elasticity particle; S3: material mixes in advance; S4: carry out polyreaction, obtains the described alkaline-resisting amendment of pre-crosslinked gel volume expansion grain. Patent CN201510359647.8 discloses the preparation method of a kind of polysaccharide xanthan gum polymer gel profile control agent, polysaccharide xanthan gum is dissolved in distilled water configuration solution, in solution, adds monomer and linking agent, lead to into the isolated air of nitrogen, then adding initiator, isothermal reaction obtains amendment. Being applicable to formation temperature is 150 DEG C and following oil reservoir, but plugging strength and heat-resisting also do not reach steam injection well requirement.
In sum, it is applied to the stifled temporarily amendment of injecting-steam viscous crude oil well, when needing to bear high temperature, high wet, high pressure and different salinity simultaneously, reach high sealing ratiod, high strength, from de-plugging effect, and become instinct control lower, and above-mentioned single stifled amendment temporarily often exists the different contradictions of this respect, based on this problem, study and invented a kind of expandability biopolymer stifled amendment and its preparation method temporarily.
Summary of the invention
It is an object of the invention in conjunction with the feature of biological degradation polyalcohol own, by the modification to biological degradation polyalcohol, reach a kind of oil production stifled profile control effect temporarily, especially the melt strength of biological degradation polyalcohol, high temperature resistant, resistant to hydrolysis performance is improved, from the feature that the de-plugging cycle is adjustable, impart stifled amendment expandability temporarily simultaneously, improve sealing ratiod with this. Solve prior art defect further. Accordingly, the present invention discloses a kind of expandability biopolymer stifled amendment temporarily.
Another object of the present invention is to disclose the preparation method that a kind of expandability biopolymer blocks up amendment temporarily.
For solving the problems of the technologies described above, the technical solution used in the present invention as follows described in:
A kind of expandability biopolymer is stifled amendment temporarily, by biological degradation polyalcohol, toughener, toughner, whipping agent, linking agent, waterproofing agent, coupling agent, functional agent and carry agent and form. Each component weight percent is respectively: biological degradation polyalcohol 10 ~ 30%: toughener 65 ~ 88%, toughner 1 ~ 5%, whipping agent 0.1 ~ 0.5%, linking agent 0.05 ~ 0.3%, waterproofing agent 0.05 ~ 0.2%, coupling agent 0.01 ~ 0.1%, functional agent 0.05 ~ 0.3%, carries agent 0.01 ~ 0.05%.
Described biological degradation polyalcohol is one or more mixtures in polyhydroxyalkanoate (PHA), poly butylene succinate (PBS), poly-adipic acid terephthalic acid copolymerization fourth diester (PBAT), polylactide (PLA), PGA (PGA), polyoxyethylene (PEO), pla-pcl (PCL), poly (propylene carbonate) (PPC).
Described toughener is 800 ~ 3000 mesh inorganic powders and the mixture of 20 ~ 120 order vegetable fibres. .
Described toughner is Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), vinyl acetate copolymer (EVA), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), methyl methacrylate and multipolymer (ACR) thereof one or more mixtures wherein.
Described whipping agent is AC (Cellmic C 121), AIBN (Diisopropyl azodicarboxylate), azoformamide potassium formiate (AP) one wherein.
Described linking agent is isocyanic ester, diacrylate-1, one or more mixtures in the ADR4370S of 4-butanediol ester, Ethylene glycol dimethacrylate, quadrol (DA), N, N-dihydroxyl (di-isopropyl) aniline (HPA), BASF, vinyltriethoxysilane (A151), dicumyl peroxide (DCP).
Described waterproofing agent is the one in acrylamide, carbodiimide.
Described coupling agent is the one in silane coupling agent, aluminate, phthalate, aluminium titanium composite coupler.
Described agent of carrying is polyacrylamide (PAM).
Described functional agent is oxidation inhibitor, thermo-stabilizer and lubricant two or more mixture wherein, thermal oxidation stabilizer wherein is a kind of Hinered phenols, phosphorous acid esters, two or more mixture of calcium zinc stabilizer, and slipping agent wherein is one or more compounds in polyethylene wax, oxidized polyethlene wax, ethylene bis stearamide (EBS), Zinic stearas, calcium stearate, erucicamide, organic silicone.
Described biological degradation polyalcohol is the polylactide (PLA) of weight-average molecular weight 120000 ~ 200000.
Described toughener inorganic powder is calcium carbonate, talcum powder, the one in wollastonite, mica powder, kaolin, and in toughener, vegetable fibre is at least one in wood powder, powdered rice hulls, wheat shell powder, tangerine bar powder.
Described toughner is the mixture of ACR or ACR and LDPE or the mixture of ACR and EVA.
A kind of expandability biopolymer of the present invention is blocked up the useful effect of amendment temporarily and is:
(1) low-carbon environment-friendly, can biological degradation. The stifled temporarily amendment of the present invention utilizes biological degradation polyalcohol, toughener to reach low-carbon environment-friendly, and de-plugging object voluntarily under hot and humid environment, degradation cycle is adjustable within the specific limits by toughner and linking agent synergy.
(2) high temperature resistant. The stifled temporarily amendment thermolysis of the present invention starts temperature and reaches 260 DEG C, and complete degradation temperature reaches 350 DEG C. The stifled temporarily amendment of the present invention utilizes toughener, toughner, linking agent, coupling agent synergy to improve the heat resistance of stifled amendment temporarily, solves polymkeric substance non-refractory problem.
(3) plugging strength is big. The stifled temporarily amendment of the present invention utilizes toughener, toughner, linking agent and coupling agent synergy, it is that the compound containing polyfunctional group structure is to superpolymer macromole branching on the one hand, produce space steric effect, hinder the chain movement of macromole, it is that macromolecular chain lengthens and reunites on the other hand, increases mutual winding, another further aspect produces between macromole to be cross-linked, formation chemical bond and weighting agent all limit the motion of macromole so that melt strength raises, and plugging strength increases.
(4) sealing ratiod height. The stifled temporarily amendment of the present invention is directly implemented into whipping agent in polymer macromolecule, foams voluntarily along with steam injecting temperature raises, produces gas lock, form Jamin effect, it is to increase sealing ratiod after squeezing stratum; Polymkeric substance at high temperature softens on the other hand, can change with stratum throat size and shape, thus further increases the sealing ratiod of stifled amendment temporarily.
(5) there is particle migration effect between solid sand, preventing layer. the temporarily stifled amendment of the present invention is heated foaming and intumescing in down-hole formation throat, and produce crosslinked, form three-dimensional netted skeleton structure, in temperature, under water and microbial process, along with the prolongation of time is degraded gradually, form honeycomb, the bubble Kongzui of a large amount of degradeds becomes a three-dimensional netted honeycomb porous structure eventually, and between honeycomb, form duct, labyrinth, some particulate matter are so just made to be blocked in home position or honeycomb, thus play solid sand, particle migration between preventing layer, return the possibility told and bury recovery well section, and the flow direction pit shaft that this kind of honeycomb duct is enough to make in stratum.
(6) the stifled temporarily amendment product of the present invention is nontoxic, formation is pollution-free, cost is low, easy construction, has very high economic worth and wide market outlook.
A kind of expandability biopolymer blocks up the following described realization of preparation method of amendment temporarily:
The preparation method that a kind of expandability biopolymer blocks up amendment temporarily obtains by the mixing method of twin screw extruder, and preparation process is as follows:
Raw materials pretreatment: biological degradation polyalcohol in not higher than 105 DEG C of situations dry 2 ~ 6 hours, is then cooled to less than 60 DEG C for subsequent use; Toughener inorganic powder is in the high-speed mixer of 80 ~ 110 DEG C, and high-speed mixing added coupling agent after 3 ~ 5 minutes, then high-speed mixing 3 ~ 5 minutes, and then to be cooled to less than 60 DEG C for subsequent use in discharging;
Raw material mixes: put in high-speed mixer by said ratio by the toughener inorganic powder of biological degradation polyalcohol, coupling agent treatment, toughner, whipping agent, linking agent, waterproofing agent and functional agent, it is less than high-speed mixing in 60 DEG C of situations, mixes discharging in 1 ~ 3 minute;
Mixing: the material of above-mentioned mixing to be put into length-to-diameter ratio and is no more than in the twin screw extruder of 44:1 to carry out mixing, < extrude in 6MPa situation, screw speed be every minute 180 ~ 400 turns, temperature is 140 ~ 180 DEG C;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: by the pulvis made and toughener vegetable fibre with carry agent and fully mix, and the expandability biopolymer namely preparing the present invention blocks up amendment temporarily.
Above-mentioned preparation method's preferred process parameter is twin screw extruder length-to-diameter ratio 36:1, melting temperature 140 ~ 160 DEG C, screw speed every minute 200 ~ 300 turns, extrusion pressure 2MP.
A kind of expandability biopolymer of the present invention is blocked up the amendment twin screw extruder useful effect of mixing method temporarily and is:
The stifled temporarily amendment expansion ratio that can obtain under these processing condition is higher, can effectively improve the sealing ratiod to macropore.
Extrude at a lower temperature ensure that linking agent and whipping agent can not premature reaction, ensure that the later stage of material uses crosslinked foaming effect.
Twin screw extruder screw speed should control within the specific limits, and when screw speed is too low, material is excessively long in the twin screw extruder machine cylinder residence time, and linking agent and whipping agent can be made the possibility of decomposition reaction occur, produces crosslinked too early and foaming.
Low pressure is extruded, and avoids the crosslinked too early and foaming that temperature raises and cause, ensure that the later stage result of use of the present invention.
Toughener plant does not need drying treatment, need to not add in mixing preparation process yet, only needs later stage mixing can reach service requirements, so the stifled temporarily amendment cost adopting the mixing method of twin screw extruder to prepare is lower.
The preparation method that a kind of expandability biopolymer blocks up amendment temporarily obtains by Banbury mixer banburying method, and preparation process is as follows:
Raw materials pretreatment: biological degradation polyalcohol, not higher than 105 DEG C, toughener vegetable fibre in not higher than 110 DEG C of situations dry 2 ~ 6 hours, is then cooled to less than 60 DEG C for subsequent use;
Banburying: biological degradation polyalcohol, toughener, toughner, whipping agent, linking agent, waterproofing agent, coupling agent and functional agent are put in Banbury mixer in <banburying of pressurizeing in 6MPa situation by said ratio, banburying temperature 130 ~ 170 DEG C, being vented more than 2 times, banburying put material after 8 ~ 18 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: by the pulvis made, agent fully mixes with carrying, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Above-mentioned preparation method's preferred process parameter is banburying temperature 140 ~ 160 DEG C, 8 ~ 12 minutes banburying time, banburying pressure 5MPa.
A kind of expandability biopolymer of the present invention is blocked up the amendment Banbury mixer useful effect of banburying method temporarily and is:
(1), without the need to raw material mixing, directly banburying can prepare, decrease manufacture link, thus reduction preparation cost.
(2) linking agent and whipping agent temperature of reaction are easy to control, not easily produce crosslinked too early and foamed phenomenon.
Toughener can be biodegradable completely polymkeric substance institute coated, plugging strength and sealing ratiod effect is better.
(4) can realizing toughener high-content compound, this is that twin screw extruder is not accomplished.
(5) performance stable homogeneous, convenient construction.
Embodiment
Stifled amendment and its preparation method specifically illustrate a kind of expandability biopolymer the present invention proposed below with reference to better embodiment temporarily.
Embodiment 1:
By weight percentage, formula (units/kg)
PLA(weight-average molecular weight 120000) 16%, wood powder (80 order) 30%, powdered rice hulls (80 order) 45%, calcium carbonate (3000 order) 2%, LDPE4.5%, ACR1.5%, AC0.45%, ADR4370S0.05%, DCP0.05%, vinyltriethoxysilane 0.15%, carbodiimide 0.1%, silane coupling agent (KH550) 0.02%, EBS0.04%, oxidized polyethlene wax 0.05%, calcium stearate 0.05%, hindered phenol (1010) 0.02%, phosphorous acid ester (168) 0.04%, polyacrylamide 0.03%.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 1, and concrete steps are as follows:
Raw materials pretreatment: PLA is drying 4 hours in 100 DEG C of situations, then being cooled to less than 50 DEG C for subsequent use, calcium carbonate is in the high-speed mixer of 110 DEG C, and high-speed mixing adds silane coupling agent (KH550) after 3 minutes, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 50 DEG C for subsequent use in discharging;
Raw material mix: by said ratio by the calcium carbonate of PLA, coupling agent treatment, LDPE, ACR, ADR4370S, DCP, vinyltriethoxysilane, carbodiimide, EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168), metering after put in the lump in high-speed mixer, high-speed mixing, mixing temperature 50 DEG C, mixes discharging in 2 minutes;
Mixing: the material of above-mentioned mixing to be put into the twin screw extruder of length-to-diameter ratio 36:1 carries out mixing extrusion, extrusion pressure 2MPa, screw speed be every minute 220 turns, temperature is followed successively by (unit: DEG C) from feeding section to extruding zone: 140-140-145-145-150-150-155-160-155;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with wood powder, powdered rice hulls and polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 1, and concrete steps are as follows:
Raw materials pretreatment: by PLA, wood powder, powdered rice hulls drying 4 hours in 100 DEG C of situations, be then cooled to less than 50 DEG C for subsequent use;
Banburying: PLA, wood powder, powdered rice hulls, calcium carbonate, LDPE, ACR, AC, ADR4370S, DCP, vinyltriethoxysilane, carbodiimide, silane coupling agent (KH550), EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in Banbury mixer by said ratio, pressurization 5MPa banburying, banburying temperature 150 DEG C, being vented 4 times, banburying put material after 12 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Embodiment 2:
By weight percentage, formula (units/kg)
PLA(weight-average molecular weight 120000) 8%, PBAT0.5%, wood powder (80 order) 85%, talcum powder (3000 order) 3%, EVA2%, ACR0.8%, AC0.2%, ADR4370S0.05%, DCP0.05%, diacrylate-1,4-butyleneglycol 0.15%, carbodiimide 0.1%, silane coupling agent (KH550) 0.02%, EBS0.02%, oxidized polyethlene wax 0.02%, calcium stearate 0.04%, hindered phenol (1010) 0.01%, phosphorous acid ester (168) 0.02%, polyacrylamide 0.02%.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 2, and concrete steps are as follows:
Raw materials pretreatment: by PLA, PBAT drying 4 hours in 100 DEG C, 70 DEG C situations respectively, then less than 50 DEG C it are cooled to for subsequent use, talcum powder is in the high-speed mixer of 110 DEG C, high-speed mixing adds silane coupling agent (KH550) after 3 minutes, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 50 DEG C for subsequent use in discharging;
Raw material mix: by said ratio by PLA, PBAT, the talcum powder of coupling agent treatment, EVA2, ACR, AC, ADR4370S, dicumyl peroxide, diacrylate-1,4-butyleneglycol, carbodiimide, EBS0.02, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in high-speed mixer after measuring in the lump, high-speed mixing, mixing temperature 50 DEG C, mixes discharging in 2 minutes;
Mixing: the material of above-mentioned mixing to be put into the twin screw extruder of length-to-diameter ratio 36:1 carries out mixing extrusion, extrusion pressure 2MPa, screw speed be every minute 220 turns, temperature is followed successively by (unit: DEG C) from feeding section to extruding zone: 145-145-150-150-150-155-155-160-155;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with wood powder and polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 2, and concrete steps are as follows:
Raw materials pretreatment: by PLA, PBAT, wood powder drying 4 hours in 100 DEG C, 70 DEG C, 105 DEG C situations respectively, be then cooled to less than 50 DEG C for subsequent use;
Banburying: by said ratio by PLA, PBAT, talcum powder, EVA, ACR, AC, ADR4370S, DCP, diacrylate-1,4-butyleneglycol, carbodiimide, silane coupling agent (KH550), EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in Banbury mixer after measuring in the lump, pressurization 4MPa banburying, banburying temperature 150 DEG C, being vented 4 times, banburying put material after 15 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Embodiment 3:
By weight percentage, formula (units/kg)
PLA(weight-average molecular weight 120000) 30%, powdered rice hulls (80 order) 60%, talcum powder (3000 order) 5%, EVA4%, ACR0.3%, AC0.3%, ADR4370S0.03%, DCP0.03%, vinyltriethoxysilane 0.1%, carbodiimide 0.05%, silane coupling agent (KH550) 0.05%, EBS0.02%, oxidized polyethlene wax 0.02%, calcium stearate 0.05%, hindered phenol (1010) 0.01%, phosphorous acid ester (168) 0.02%, polyacrylamide 0.02%.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 3, and concrete steps are as follows:
Raw materials pretreatment: PLA is drying 4 hours in 80 DEG C of situations, then being cooled to less than 50 DEG C for subsequent use, talcum powder is in the high-speed mixer of 110 DEG C, and high-speed mixing adds silane coupling agent (KH550) after 3 minutes, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 50 DEG C for subsequent use in discharging;
Raw material mixes: the talcum powder of PLA, coupling agent treatment, EVA, ACR, AC, ADR4370S, DCP, vinyltriethoxysilane, carbodiimide, EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in the lump in high-speed mixer by said ratio, high-speed mixing, mixing temperature 50 DEG C, mixes discharging in 2 minutes;
Mixing: the material of above-mentioned mixing to be put into the twin screw extruder of length-to-diameter ratio 40:1 carries out mixing extrusion, extrusion pressure 2MPa, screw speed be every minute 300 turns, temperature is followed successively by (unit: DEG C) from feeding section to extruding zone: 150-155-160-160-165-165-170-170-175;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with powdered rice hulls and polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 3, and concrete steps are as follows:
Raw materials pretreatment: by PLA, powdered rice hulls drying 4 hours in 100 DEG C of situations, be then cooled to less than 50 DEG C for subsequent use;
Banburying: PLA, powdered rice hulls, talcum powder, EVA, ACR, AC, ADR4370S, DCP, vinyltriethoxysilane, carbodiimide, silane coupling agent (KH550), EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in Banbury mixer in the lump by said ratio, pressurization 4MPa banburying, banburying temperature 170 DEG C, being vented 3 times, banburying put material after 15 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Embodiment 4:
By weight percentage, formula (units/kg)
PLA(weight-average molecular weight 120000) 25%, powdered rice hulls (80 order) 67%, talcum powder (3000 order) 3%, EVA3%, ACR1%, AC0.5%, ADR4370S0.02%, DCP0.03%, carbodiimide 0.2%, silane coupling agent (KH550) 0.1%, EBS0.02%, oxidized polyethlene wax 0.03%, calcium stearate 0.05%, hindered phenol (1010) 0.01%, phosphorous acid ester (168) 0.02%, polyacrylamide 0.02%.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 4, and concrete steps are as follows:
Raw materials pretreatment: PLA is drying 4 hours in 80 DEG C of situations, then being cooled to less than 50 DEG C for subsequent use, talcum powder is in the high-speed mixer of 110 DEG C, and high-speed mixing adds silane coupling agent (KH550) after 3 minutes, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 50 DEG C for subsequent use in discharging;
Raw material mixes: by said ratio by PLA, the talcum powder of coupling agent treatment, EVA, ACR, AC, ADR4370S, DCP, carbodiimide, EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) put in high-speed mixer in the lump, high-speed mixing, mixing temperature 50 DEG C, mixes discharging in 3 minutes;
Mixing: the material of above-mentioned mixing to be put into the twin screw extruder of length-to-diameter ratio 36:1 carries out mixing extrusion, extrusion pressure 2MPa, screw speed be every minute 250 turns, temperature is followed successively by (unit: DEG C) from feeding section to extruding zone: 145-145-150-150-155-155-155-160-160-155;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with powdered rice hulls and polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 4, and concrete steps are as follows:
Raw materials pretreatment: by PLA, powdered rice hulls drying 4 hours in 100 DEG C of situations, be then cooled to less than 50 DEG C for subsequent use;
Banburying: by said ratio by PLA, powdered rice hulls, talcum powder, EVA, ACR, AC, ADR4370S, DCP, carbodiimide, silane coupling agent (KH550), EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) put in Banbury mixer in the lump, pressurization 5MPa banburying, banburying temperature 155 DEG C, being vented 3 times, banburying put material after 10 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Embodiment 5:
By weight percentage, formula (units/kg)
PLA(weight-average molecular weight 120000) 20%, powdered rice hulls (80 order) 78%, talcum powder (3000 order) 0.5%, ACR1%, AC0.02%, ADR4370S0.05%, DCP0.2%, carbodiimide 0.1%, silane coupling agent (KH550) 0.01%, EBS0.02%, oxidized polyethlene wax 0.03%, calcium stearate 0.03%, hindered phenol (1010) 0.01%, phosphorous acid ester (168) 0.01%, polyacrylamide 0.02%.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 5, and concrete steps are as follows:
Raw materials pretreatment: PLA is drying 4 hours in 80 DEG C of situations, then being cooled to less than 50 DEG C for subsequent use, talcum powder is in the high-speed mixer of 110 DEG C, and high-speed mixing adds silane coupling agent (KH550) after 3 minutes, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 50 DEG C for subsequent use in discharging;
Raw material mixes: the talcum powder of PLA, coupling agent treatment, ACR, AC, ADR4370S, DCP, carbodiimide, EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in the lump in high-speed mixer by said ratio, high-speed mixing, mixing temperature 50 DEG C, mixes discharging in 3 minutes;
Mixing: the material of above-mentioned mixing to be put in the twin screw extruder that length-to-diameter ratio is 36:1 and carries out mixing extrusion, extrusion pressure 2MPa, screw speed be every minute 180 turns, temperature is followed successively by (unit: DEG C) from feeding section to extruding zone: 140-140-145-145-150-150-155-160-155;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with powdered rice hulls and polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 5, and concrete steps are as follows:
Raw materials pretreatment: by PLA, powdered rice hulls drying 4 hours in 100 DEG C of situations, be then cooled to less than 50 DEG C for subsequent use;
Banburying: PLA, powdered rice hulls, talcum powder, ACR, AC, ADR4370S, DCP, carbodiimide, silane coupling agent (KH550), EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in Banbury mixer in the lump by said ratio, pressurization 5MPa banburying, banburying temperature 155 DEG C, being vented 3 times, banburying put material after 8 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Embodiment 6:
By weight percentage, formula (units/kg)
PLA(weight-average molecular weight 120000) 13%, powdered rice hulls (80 order) 40%, wood powder 40%, talcum powder (3000 order) 3%, ACR3.6%, AC0.03%, ADR4370S0.05%, DCP0.02%, carbodiimide 0.1%, silane coupling agent (KH550) 0.02%, EBS0.03%, oxidized polyethlene wax 0.05%, calcium stearate 0.05%, hindered phenol (1010) 0.01%, phosphorous acid ester (168) 0.02%, polyacrylamide 0.02%.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 6, is described as follows:
Raw materials pretreatment: PLA is drying 4 hours in 80 DEG C of situations, then being cooled to less than 50 DEG C for subsequent use, talcum powder is in the high-speed mixer of 110 DEG C, and high-speed mixing adds silane coupling agent (KH550) after 3 minutes, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 50 DEG C for subsequent use in discharging;
Raw material mixes: the talcum powder of PLA, coupling agent treatment, ACR, AC, ADR4370S, DCP, carbodiimide, EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in the lump in high-speed mixer by said ratio, high-speed mixing, mixing temperature 50 DEG C, mixes discharging in 3 minutes;
Mixing: the material of above-mentioned mixing to be put into the twin screw extruder of length-to-diameter ratio 36:1 carries out mixing extrusion, extrusion pressure 2MPa, screw speed be every minute 400 turns, temperature is followed successively by from feeding section to extruding zone: 140-140-145-145-150-150-155-160-155 DEG C;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with wood powder, powdered rice hulls and polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 6, and concrete steps are as follows:
Raw materials pretreatment: by PLA, powdered rice hulls, wood powder drying 4 hours in 100 DEG C of situations, be then cooled to less than 50 DEG C for subsequent use;
Banburying: PLA, powdered rice hulls, wood powder, talcum powder, ACR, AC, ADR4370S, DCP, carbodiimide, silane coupling agent (KH550), EBS, oxidized polyethlene wax, calcium stearate, hindered phenol (1010), phosphorous acid ester (168) are put in Banbury mixer in the lump by said ratio, pressurization 5MPa banburying, banburying temperature 155 DEG C, being vented 3 times, banburying put material after 18 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: fully mixed with polyacrylamide by the pulvis made, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
Stifled amendment is obtained by the mixing method of twin screw extruder temporarily for the expandability biopolymer of embodiments of the invention 1-6, and stifled amendment is also obtained by Banbury mixer banburying method temporarily for the expandability biopolymer of embodiments of the invention 1-6.
In the specific implementation, before steam injection, after stifled amendment enters stratum temporarily, stifled amendment preferentially enters serious most permeable zone in debt, macropore temporarily in the present invention. Biological degradation polyalcohol wherein is heated to reach and starts softening change in vitreous state when 60 DEG C. Along with the rising gradually of steam injecting temperature, when reaching 140 DEG C, melting gradually, temperature raises further again, become pseudo-plasticity rheid, and very fast foaming and intumescing, produce gas lock and form Jamin effect, molten mass is by between toughener particle, and between toughener and stratum, it being bonded as the adherend of high strength, it is achieved that shutoff envelope is altered, macropore plugging, thus improve steam entry profile, the steam of injection is turned to. When temperature reaches 260 DEG C, after 7 days, degrade in beginning, and hydrolysis and biological degradation occur simultaneously, generating water and carbonic acid gas, the degraded of bubble hole produces three-dimensional netted honeycomb porous structure after breaking, serving solid sand, between preventing layer, particle migration, returns to tell and buries recovery well section effect.
(1) low-carbon environment-friendly, can biological degradation. The stifled temporarily amendment of the present invention utilizes biological degradation polyalcohol, toughener to reach low-carbon environment-friendly, and de-plugging object voluntarily under hot and humid environment, degradation cycle is adjustable within the specific limits by toughner and linking agent synergy.
(2) high temperature resistant. The stifled temporarily amendment thermolysis of the present invention starts temperature and reaches 260 DEG C, and complete degradation temperature reaches 350 DEG C. The stifled temporarily amendment of the present invention utilizes toughener, toughner, linking agent, coupling agent synergy to improve the heat resistance of stifled amendment temporarily, solves polymkeric substance non-refractory problem.
(3) plugging strength is big. The stifled temporarily amendment of the present invention utilizes toughener, toughner, linking agent and coupling agent synergy, it is that the compound containing polyfunctional group structure is to superpolymer macromole branching on the one hand, produce space steric effect, hinder the chain movement of macromole, it is that macromolecular chain lengthens and reunites on the other hand, increases mutual winding, another further aspect produces between macromole to be cross-linked, formation chemical bond and weighting agent all limit the motion of macromole so that melt strength raises, and plugging strength increases.
(4) sealing ratiod height. The stifled temporarily amendment of the present invention is directly implemented into whipping agent in polymer macromolecule, foams voluntarily along with steam injecting temperature raises, produces gas lock, form Jamin effect, it is to increase sealing ratiod after squeezing stratum; Polymkeric substance at high temperature softens on the other hand, can change with stratum throat size and shape, thus further increases the sealing ratiod of stifled amendment temporarily.
(5) there is particle migration effect between solid sand, preventing layer. the temporarily stifled amendment of the present invention is heated foaming and intumescing in down-hole formation throat, and produce crosslinked, form three-dimensional netted skeleton structure, in temperature, under water and microbial process, along with the prolongation of time is degraded gradually, form honeycomb, the bubble Kongzui of a large amount of degradeds becomes a three-dimensional netted honeycomb porous structure eventually, and between honeycomb, form duct, labyrinth, some particulate matter are so just made to be blocked in home position or honeycomb, thus play solid sand, particle migration between preventing layer, return the possibility told and bury recovery well section, and the flow direction pit shaft that this kind of honeycomb duct is enough to make in stratum.
(6) the stifled temporarily amendment product of the present invention is nontoxic, formation is pollution-free, cost is low, easy construction, has very high economic worth and wide market outlook.
(7) the mixing method of the twin screw extruder of the present invention and Banbury mixer banburying method can prepare the good expandability biopolymer of Performance comparision stifled amendment temporarily under the rational processing condition of control.
Described on comprehensive, the technical scheme of the present invention can fully effectively realize foregoing invention object, and the temporarily stifled performance of profile modification of the present invention and feature principle all verified in an embodiment fully, and effect and the object of expection can be reached, and embodiments of the invention can also convert according to these principles, above-described embodiment is only the description to the preferred embodiments of the present invention, but not limiting the scope of the invention, therefore, persons skilled in the art are in the technical scope disclosed by the present invention, the change that can expect easily, all belong within protection scope of the present invention.
Claims (10)
1. an expandability biopolymer stifled amendment temporarily, major ingredient is by biological degradation polyalcohol, toughener, toughner, whipping agent, linking agent, waterproofing agent, coupling agent, functional agent and carries agent and forms, it is characterized in that, described each composition weight percent is as follows: biological degradation polyalcohol 10 ~ 30%, toughener 65 ~ 88%, toughner 1 ~ 6%, whipping agent 0.1 ~ 0.5%, linking agent 0.05 ~ 0.3%, waterproofing agent 0.05 ~ 0.2%, coupling agent 0.01 ~ 0.1%, functional agent 0.05 ~ 0.3%, carries agent 0.01 ~ 0.05%.
2. a kind of expandability biopolymer as claimed in claim 1 stifled amendment temporarily, it is characterised in that: described biological degradation polyalcohol is one or more mixtures in polyhydroxyalkanoate (PHA), poly butylene succinate (PBS), poly-adipic acid terephthalic acid copolymerization fourth diester (PBAT), polylactide (PLA), PGA (PGA), polyoxyethylene (PEO), pla-pcl (PCL), poly (propylene carbonate) (PPC).
3. a kind of expandability biopolymer as claimed in claim 1 stifled amendment temporarily, it is characterised in that: described toughener is 800 ~ 3000 mesh inorganic powders and the mixture of 20 ~ 120 order vegetable fibres.
4. a kind of expandability biopolymer as claimed in claim 1 stifled amendment temporarily, it is characterised in that: described toughner is Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), vinyl acetate copolymer (EVA), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), methyl methacrylate and multipolymer (ACR) thereof one or more mixtures wherein.
5. a kind of expandability biopolymer as claimed in claim 1 stifled amendment temporarily, it is characterized in that: described functional agent is oxidation inhibitor, thermo-stabilizer and lubricant two or more mixture wherein, thermal oxidation stabilizer wherein is a kind of Hinered phenols, phosphorous acid esters, two or more mixture of calcium zinc stabilizer, and slipping agent wherein is one or more compounds in polyethylene wax, oxidized polyethlene wax, ethylene bis stearamide (EBS), Zinic stearas, calcium stearate, erucicamide, organic silicone.
6. a kind of expandability biopolymer as claimed in claim 1 stifled amendment temporarily, it is characterised in that: described biological degradation polyalcohol is the polylactide (PLA) of weight-average molecular weight 120000 ~ 200000; Described toughener inorganic powder is calcium carbonate, talcum powder, the one in wollastonite, mica powder, kaolin, and toughener vegetable fibre is at least one in wood powder, powdered rice hulls, wheat shell powder, tangerine bar powder; Described toughner is the mixture of ACR or ACR and LDPE or the mixture of ACR and EVA.
7. a kind of expandability biopolymer as claimed in claim 1 blocks up the preparation method of amendment temporarily, it is characterised in that, the mixing method of twin screw extruder, described preparation process is as follows:
Raw materials pretreatment: biological degradation polyalcohol in not higher than 105 DEG C of situations dry 2 ~ 6 hours, then less than 60 DEG C it are cooled to for subsequent use, toughener inorganic powder is in the high-speed mixer of 80 ~ 110 DEG C, high-speed mixing is after 3 ~ 5 minutes, add coupling agent in proportion, high-speed mixing 3 ~ 5 minutes again, then to be cooled to less than 60 DEG C for subsequent use in discharging;
Raw material mixes: put in high-speed mixer by said ratio by the toughener inorganic powder of biological degradation polyalcohol, coupling agent treatment, toughner, whipping agent, linking agent, waterproofing agent and functional agent, it is less than high-speed mixing in 60 DEG C of situations, mixes discharging in 1 ~ 3 minute;
Mixing: the material of above-mentioned mixing to be entered with throwing be no more than in the twin screw extruder of 44:1 to length-to-diameter ratio to carry out mixing, < extrude in 6MPa situation, screw speed be every minute 180 ~ 400 turns, temperature is 140 ~ 180 DEG C;
Cut: above-mentioned mixing molten materials is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: by the pulvis made and toughener vegetable fibre with carry agent and fully mix, and the expandability biopolymer namely preparing the present invention blocks up amendment temporarily.
8. the preparation method of a kind of expandability biopolymer as claimed in claim 7 stifled amendment temporarily, it is characterised in that: described twin screw extruder length-to-diameter ratio 36:1, melting temperature 140 ~ 160 DEG C, screw speed every minute 200 ~ 300 turns, extrusion pressure 2MP.
9. a kind of expandability biopolymer as claimed in claim 1 blocks up the preparation method of amendment temporarily, it is characterised in that, Banbury mixer banburying method, described preparation process is as follows:
Raw materials pretreatment: biological degradation polyalcohol, not higher than 105 DEG C, toughener vegetable fibre in not higher than 110 DEG C of situations dry 2 ~ 6 hours, is then cooled to less than 60 DEG C for subsequent use;
Banburying: biological degradation polyalcohol, toughener, toughner, whipping agent, linking agent, waterproofing agent, coupling agent and functional agent are put in Banbury mixer by said ratio, in <banburying of pressurizeing in 6MPa situation, banburying temperature 130 ~ 170 DEG C, is vented more than 2 times, and banburying put material after 8 ~ 18 minutes;
Cut: the molten materials of above-mentioned banburying is cut into while hot and is no more than 10cm �� 10cm block, be cooled to less than 40 DEG C;
Pulverize and grinding: the block crusher of cooling and shredder are made 20 ~ 120 object pulvis;
Finished product mixes: by the pulvis made, agent fully mixes with carrying, and namely prepares the expandability biopolymer stifled amendment temporarily of the present invention.
10. a kind of expandability biopolymer as claimed in claim 9 blocks up the preparation method of amendment temporarily, it is characterised in that: described banburying temperature is 140 ~ 160 DEG C, 8 ~ 12 minutes banburying time, banburying pressure 5MPa.
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| CN109777383B (en) * | 2019-03-18 | 2021-07-06 | 四川捷贝通能源科技有限公司 | Multi-core microsphere selective water shutoff agent and preparation method thereof |
| CN111849439A (en) * | 2019-04-26 | 2020-10-30 | 费尔蒙特山拓有限公司 | Compression-resistant buoyancy spherical plugging agent |
| CN111927387A (en) * | 2020-08-28 | 2020-11-13 | 西南石油大学 | Two-stage temporary plugging combined selective water plugging method |
| CN112552889A (en) * | 2020-11-16 | 2021-03-26 | 西安石油大油气科技有限公司 | Self-cleaning or self-degrading temporary plugging agent and preparation method thereof |
| CN112940697A (en) * | 2021-02-25 | 2021-06-11 | 成都泽赛普石油工程技术服务有限公司 | Acid-resistant temporary plugging agent and preparation method thereof |
| CN113025303A (en) * | 2021-03-18 | 2021-06-25 | 中国石油大学(华东) | Supramolecular elastomer-based self-polymerization fracturing sand modifier and preparation method thereof |
| CN116064013A (en) * | 2022-12-01 | 2023-05-05 | 重庆页岩气勘探开发有限责任公司 | Temporary plugging agent for shale gas exploitation fracturing and preparation method thereof |
| CN115926764A (en) * | 2023-03-13 | 2023-04-07 | 山东科兴化工有限责任公司 | Microgel suspending agent for water injection well and preparation method thereof |
| CN115926764B (en) * | 2023-03-13 | 2023-05-05 | 山东科兴化工有限责任公司 | Microgel suspending agent for water injection well and preparation method thereof |
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