WO2014024827A1 - 炭化水素資源回収用ボールシーラーならびにその製造方法及びそれを用いる坑井の処理方法 - Google Patents
炭化水素資源回収用ボールシーラーならびにその製造方法及びそれを用いる坑井の処理方法 Download PDFInfo
- Publication number
- WO2014024827A1 WO2014024827A1 PCT/JP2013/071121 JP2013071121W WO2014024827A1 WO 2014024827 A1 WO2014024827 A1 WO 2014024827A1 JP 2013071121 W JP2013071121 W JP 2013071121W WO 2014024827 A1 WO2014024827 A1 WO 2014024827A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ball
- resin
- ball sealer
- surface layer
- polyglycolic acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920005989 resin Polymers 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 93
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 89
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 89
- 239000002344 surface layer Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000002347 injection Methods 0.000 claims abstract description 11
- 239000007924 injection Substances 0.000 claims abstract description 11
- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims abstract description 4
- 239000012779 reinforcing material Substances 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 26
- 230000004907 flux Effects 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 abstract 1
- 239000003209 petroleum derivative Substances 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 239000011162 core material Substances 0.000 description 26
- 238000000465 moulding Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000009467 reduction Effects 0.000 description 14
- 238000005755 formation reaction Methods 0.000 description 11
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229920001432 poly(L-lactide) Polymers 0.000 description 6
- 229920000747 poly(lactic acid) Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
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- 230000015556 catabolic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- -1 tin halide Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000021120 animal protein Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001308 poly(aminoacid) Polymers 0.000 description 2
- 229920000111 poly(butyric acid) Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
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- 230000008439 repair process Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B34/00—Valve arrangements for boreholes or wells
- E21B34/06—Valve arrangements for boreholes or wells in wells
- E21B34/14—Valve arrangements for boreholes or wells in wells operated by movement of tools, e.g. sleeve valves operated by pistons or wire line tools
- E21B34/142—Valve arrangements for boreholes or wells in wells operated by movement of tools, e.g. sleeve valves operated by pistons or wire line tools unsupported or free-falling elements, e.g. balls, plugs, darts or pistons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14065—Positioning or centering articles in the mould
- B29C45/14073—Positioning or centering articles in the mould using means being retractable during injection
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/261—Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/043—PGA, i.e. polyglycolic acid or polyglycolide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
- B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/26—Sealing devices, e.g. packaging for pistons or pipe joints
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/772—Articles characterised by their shape and not otherwise provided for
- B29L2031/7734—Spherical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a ball sealer as a kind of tool for forming or repairing downholes (wells) for the recovery of hydrocarbon resources including oil and gas, and in particular, a flack plug or flack as such a tool.
- the present invention relates to a ball sealer (so-called flack ball) suitable for forming a sleeve (hydraulic crushing plug or tube), a manufacturing method thereof, and a well treatment method using the same.
- downhole tools For the recovery of hydrocarbon resources from formations containing hydrocarbon resources including oil and gas (hereinafter sometimes referred to as “petroleum”), downholes (underground pits or Wells are provided, but tools such as flack plugs, bridge plugs, ball sealers, seal plugs, packers, etc. (hereinafter collectively referred to as “downhole tools”) for the formation, repair or promotion of resource recovery. Is often disposed of in the downhole as it is without being collected on the ground after use, or disposed of by dropping it down (examples of such downhole tools or modes of use thereof are, for example, patent documents) 1 to 7).
- a member (downhole tool member) constituting the whole or a joint for promoting disintegration is formed of a degradable polymer.
- degradable polymers include polysaccharides such as starch or dextrin; animal protein polymers such as chitin and chitosan; polylactic acid (PLA, typically poly L-lactic acid (PLLA)), polyglycolic acid (PGA), aliphatic polyesters such as polybutyric acid and polyvaleric acid; and polyamino acids, polyethylene oxide and the like (Patent Documents 1 and 2).
- the ball sealer as an example of the downhole tool as described above is excessive in the perforations for recovering the oil formed in the formation using a perforating gun in the hydraulic fracturing method.
- a sealing material for suppressing the inflow of working water there have been many uses for directly sealing perforations (for example, Patent Document 6).
- a ball sealer used for such applications a non-degradable material such as nylon or phenolic resin or a non-degradable material such as aluminum, which is coated with a rubbery surface layer to improve the sealing performance as necessary. Therefore, a comparatively small one having a diameter of 16 to 32 mm (5/8 inch to 1.25 inch, Patent Document 62, column 46 to 48) has been used.
- a ball sealer having a larger diameter as a part of a member constituting a flack plug or a flux leave (hydraulic crushing plug or tube) used in the hydraulic crushing method. More specifically, a direction in which a high pressure water flow is introduced to a partitioned work area by placing a ball plug (incorporation) and a ball plug with a built-in ball sealer at a predetermined position of the formed down hole, and going straight to the down hole.
- a perforation (perforations) for recovering oil is formed by crushing the formation by applying a water stream (for example, Patent Documents 1 and 2).
- Such a ball sealer constituting a part of a flack plug or a flux leave generally has the above-described perforation, for example, about 25 to 100 mm (1 to 4 inches) in diameter.
- a larger diameter is often required.
- a large-diameter ball sealer is manufactured by hot compression molding or injection molding using a biodegradable resin, which is not crystalline, but is crystalline, heat shrinkage or crystallization Since shrinkage and voids are generated due to shrinkage, it is difficult to produce a large-diameter ball with good dimensional accuracy required for a flack ball as a sealing (liquid leakage preventing) member. For this reason, in the past, in order to manufacture such a relatively large diameter flack ball with a biodegradable resin material, a very complicated and costly method of solidification extrusion ⁇ cutting has been employed. Is the actual situation.
- the main object of the present invention is to use a relatively large diameter ball sealer by a relatively simple process using a polyglycolic acid resin, which is a biodegradable resin with good mechanical strength.
- Another object of the present invention is to provide a production method that can be formed with good dimensional accuracy, and a ball sealer for hydrocarbon resource recovery thus formed.
- a further object of the present invention is to provide a well treatment method using the above ball sealer for hydrocarbon resource recovery.
- the ball sealer for hydrocarbon resource recovery of the present invention has at least a two-layer structure of a spherical core body and a surface layer resin material covering the spherical core body, and is composed of a generally spherical structure as a whole. It is made of polyglycolic acid resin and has a diameter of about 25 mm (1 inch) or more.
- the ball sealer manufacturing method of the present invention is a method for manufacturing the above-described hydrocarbon resource recovery ball sealer, in which a spherical core body is disposed with a support pin in a mold cavity, and in this state, the core A surface layer resin made of polyglycolic acid resin is injection-molded around the body, and the support pin is retracted to the wall surface of the mold cavity in synchronization with the completion of injection of the surface layer resin, and then the surface layer resin is cured. Is.
- polyglycolic acid (PGA) resin exhibits excellent mechanical strength including particularly high compressive strength. It can be said that it has extremely excellent characteristics as a ball sealer (that is, a flack ball) that is built in together with a seat and functions as a bearing seal member that receives high-pressure water flow in fracturing.
- PGA resin has a characteristic that is significantly different from other aliphatic polyester resins such as polylactic acid (PLLA), and its thickness reduction rate in water is constant over time due to its water vapor barrier property (in other words, This shows a linear thickness reduction rate (the details are disclosed in the PCT / JP2013 / 061075 specification), and when an inorganic or organic short fiber reinforcing material is blended, the initial thickness reduction rate is remarkably suppressed.
- the control period can be controlled by the aspect ratio (L / D) of the short fiber reinforcing material to be blended, and the final thickness reduction rate after the thickness reduction of a certain ratio (for example, 50%) becomes the initial thickness reduction rate.
- the characteristics are significantly increased as compared with those disclosed in Japanese Patent Application No. 2012-154947. These characteristics are used for temporary use including ball sealers. It shows that PGA resin has very good suitability in dimensional design according to usage conditions of unhall tool members.
- this PGA resin when this PGA resin is formed into a large sphere having a diameter of about 25 mm or more suitable as a flack ball by hot compression molding or injection molding, in addition to thermal shrinkage after molding, linear thickness reduction rate characteristics in water The shrinkage at the time of crystallization (solidification) due to the extremely large crystallinity corresponding to the water vapor barrier property to be given was extremely large, and it was difficult to form a flack ball that required high dimensional accuracy.
- the present inventors have noted that the characteristics of the PGA resin such as the high rigidity or compressive strength expected of the flack ball can be sufficiently achieved even by forming only the surface layer of the flack ball from the PGA resin.
- the shrinkage at the time of crystallization of PGA resin does not lead to a decrease in dimensional accuracy that is inconvenient for the formation of the outer shell of the flack ball product, if it is not the collective solidification molding of the entire flack ball but the solid molding of the surface layer alone. I thought it would be.
- the present invention has been achieved by confirming that at least the surface layer is made of PGA resin and a large-diameter flack ball can be formed with good dimensional accuracy.
- the well treatment method of the present invention supplies a flack ball together with a working fluid to a ball seat having an opening provided inside a long flux leave inserted in a well formed in the formation,
- the opening of the ball seat arranged at a predetermined position is sealed to form a seal portion to shut off the working fluid, and the working fluid is ejected from the opening provided in the flux leave wall immediately above the seal portion, thereby opening the opening.
- the method includes a fracturing cycle in which an inner wall of a well is drilled to form a perforation, and then the flack ball is disassembled on the spot, and the ball sealer of the present invention is used as the flack ball. is there.
- a plurality of ball seats whose opening diameters gradually increase are provided at predetermined intervals from the downstream side toward the upstream side in the extension direction in the long flux leave, and the plurality of ball seats having a gradually increasing diameter together with the working fluid.
- a method of sequentially supplying flack balls and sequentially performing a fracturing cycle including formation of a seal portion and formation of a perforation from a downstream side to an upstream side, and at least a part of the plurality of flack balls as a part of the present invention.
- the surface layer of the ball sealer (flak ball) for hydrocarbon resource recovery of the present invention is formed of a polyglycolic acid resin.
- Polyglycolic acid resin is excellent in initial mechanical strength including the highest level of compressive strength among thermoplastic resins, and has a great effect of suppressing the rate of thickness reduction in water by using a material containing a short fiber reinforcement. In this respect, it is particularly preferably used.
- polyglycolic acid resin in addition to a glycolic acid homopolymer consisting of only glycolic acid units (—OCH 2 —CO—) as repeating units (ie, polyglycolic acid (PGA)), other single monomers are used.
- the hydrolysis rate, crystallinity, etc. of the polyglycolic acid resin can be adjusted to some extent.
- a polyglycolic acid resin having a weight average molecular weight of 70,000 or more, preferably 100,000 to 500,000 is used.
- the weight average molecular weight is less than 70,000, the initial mechanical strength characteristics required for the flack ball are impaired.
- the weight average molecular weight exceeds 500,000, molding processability is deteriorated, which is not preferable.
- the melt viscosity (JIS K7199) measured at a melting point plus 50 ° C. (270 ° C. in the case of polyglycolic acid alone) and a shear rate of 120 seconds ⁇ 1 is 20 to Those in the range of 2000 Pa ⁇ s, particularly 200 to 1500 Pa ⁇ s are preferably used.
- glycolide which is a dimer of glycolic acid
- a small amount of catalyst for example, organic carboxylate tin, tin halide.
- a ring-opening polymerization method by heating to a temperature of about 120 to 250 ° C. in the presence of a cation catalyst such as antimony halide) and substantially in the absence of a solvent (ie, bulk polymerization conditions). It is preferable.
- lactide typified by lactide which is a dimer of lactic acid
- lactones for example, caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone 1 It is preferable to use more than one species.
- the melting point (Tm) of polyglycolic acid resin is generally 200 ° C. or higher.
- polyglycolic acid (PGA) has a melting point of about 220 ° C., a glass transition temperature of about 38 ° C., and a crystallization temperature of about 90 ° C.
- the specific gravity is about 1.32 in the molten state (220 ° C.), but rises to about 1.55 at the time of solidification and crystallization (room temperature). Causes the generation of voids.
- the characteristics of these polyglycolic acid resins vary depending on the molecular weight of the polyglycolic acid resin and the type of comonomer used.
- a polyglycolic acid resin is usually used alone, but for the purpose of controlling its decomposability and the like, other aliphatic polyesters, aromatic polyesters, elastomers, etc.
- Other thermoplastic resins can also be blended.
- the amount added should not be limited to an amount that does not prevent the polyglycolic acid resin from being present as a matrix resin necessary for exhibiting linear thickness reduction rate characteristics, more specifically, should be suppressed to less than 30% by weight, Preferably it is less than 20% by weight, more preferably less than 10% by weight.
- Short fiber reinforcement It is also preferable to mix a short fiber reinforcing material with the PGA resin constituting the surface layer of the flack ball of the present invention. Thereby, as mentioned above, in addition to the reinforcing effect, the effect of suppressing the initial thickness reduction rate compared to the PGA resin alone can be obtained.
- a short fiber reinforcing material a composition suitable for melt molding is given among inorganic or organic fiber reinforcing materials such as glass fiber, carbon fiber, boron fiber, aramid fiber, liquid crystal polymer fiber, and cellulosic fiber (kenaf fiber).
- the minor axis (D) is 0.1 ⁇ m to 1 mm, more preferably 1 to 100 ⁇ m, particularly preferably 5 to 20 ⁇ m, and the aspect ratio (L / D) is 2 to 1000, more preferably 3 to 300, Particularly preferred are those usually referred to as milled fiber or chopped fiber of 3 to 150. If the minor axis (D) is less than 0.1 ⁇ m, sufficient strength for delaying the collapse cannot be expressed, and if it exceeds 1000 ⁇ m, the uniformity of the collapse behavior of the molded product is lost. When the aspect ratio (L / D) is less than 2, the effect of delaying disintegration cannot be obtained.
- the aspect ratio (L / D) exceeds 1000, it is difficult to uniformly disperse the short fiber reinforcing material by melt kneading. Further, when the aspect ratio (L / D) is increased within the above range, the initial suppression period of the thickness reduction rate tends to increase, and thereby, the increase / decrease control of the initial suppression period of the thickness reduction rate is possible to some extent. Become.
- the short fiber reinforcing material When the short fiber reinforcing material is blended, it is blended at a ratio of 1 to 50 parts by weight, more preferably 5 to 45 parts by weight, particularly preferably 10 to 40 parts by weight, per 100 parts by weight of the polyglycolic acid resin. preferable. If it is less than 1 part by weight, the blending effect is poor, and if it exceeds 50 parts by weight, it may be difficult to uniformly disperse the short fiber reinforcing material by melt kneading. Within the above range, when the amount of the short fiber reinforcement is increased, the initial suppression period of the thickness reduction rate tends to increase. By combining the above aspect ratios, the increase / decrease control of the initial suppression period of the thickness reduction rate is achieved. Is possible.
- Powder reinforcement It is also preferable to use a powdered (including granular) reinforcing material instead of or in addition to the short fiber reinforcing material.
- Powdery reinforcing materials include mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, ferrite, clay, glass powder, zinc oxide, nickel carbonate, iron oxide, lime powder, magnesium carbonate, barium sulfate
- the median average particle diameter is about 0.1 ⁇ m to 1 mm, In particular, those having a size of 1 to 100 ⁇ m are preferably used.
- these powdery reinforcements have the same improvement effect on compressive strength as the properties of the resulting molded product, and have the characteristics of giving better dimensional stability, although the degradation delay effect is poor. is there.
- powdery reinforcing materials can be used in combination of two or more thereof, and can also be used in combination with a short fiber reinforcing material.
- the amount added (as a total amount when used together with the short fiber reinforcing material) is 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 15 to 15% by weight based on the total amount of the molding material including the resin material. It is 50% by weight, more preferably 20 to 40% by weight.
- the short fiber reinforcing material or the powdered reinforcing material is mixed with the resin material after being treated with a sizing agent or a surface treatment agent.
- the sizing agent or surface treatment agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanium compounds. These compounds may be preliminarily subjected to focusing treatment and surface treatment on the reinforcing material, or may be added simultaneously with the preparation of the resin composition.
- the reinforcing material can be directly melt-kneaded with the total amount of the polyglycolic acid resin constituting the molded body, but if desired, a polyglycolic acid resin composition (masterbatch) having a high concentration of the reinforcing material is prepared.
- the masterbatch can be diluted with an additional amount of polyglycolic acid resin to prepare a resin material having a desired reinforcing material concentration. From the viewpoint of uniform dispersibility of the reinforcing material, it is preferable to use a resin material in which a polyglycolic acid resin and a reinforcing material (other fillers) are previously melt-kneaded and pelletized. *
- FIG. 1 is a schematic cross-sectional view of a mold 10 in an intermediate stage of the method of the present invention.
- the spherical core body 12 disposed in the cavity 11 is a mold in which the upper mold 10a and the lower mold 10b are joined via the boundary surface 10c.
- the mold In a closed state of the mold, the mold is held by a plurality of support pins 13 protruding from the vertical direction as shown.
- the molten PGA resin is injected into the cavity 11 through the mold runner 14 and the gate 15, and in synchronization with the completion of the injection (that is, immediately before or almost simultaneously with the completion of the injection),
- the tips of the support pins 13 are retracted from the illustrated core support positions in the directions indicated by the arrows, and when the injection is completed, the retract to the position of the inner surface 10s of the mold is almost completed.
- the compact is cooled and crystallized in the mold.
- the mold temperature any temperature lower than the melting point can be used, but it is preferably 50 to 150 ° C. from the viewpoint of the cooling rate and the crystallization rate.
- the temperature is less than 50 ° C., the cooling becomes too fast, the resin does not spread uniformly at the time of injection, and the crystallinity on the outside with respect to the inside of the molded body becomes small and the uniformity of physical properties is impaired.
- the temperature is 150 ° C. or higher, the crystallization rate is slow, so that a long time is required for cooling.
- the mold is opened and the formed laminated molded body is taken out.
- the molded body may be water-cooled to obtain heat. Further, if necessary, heat treatment is performed at 100 to 200 ° C. for several minutes to several hours, so that residual strain can be removed and the crystallinity can be made uniform. Furthermore, if necessary, some unevenness corresponding to the gate 15, some unevenness remaining in the support pin 13 corresponding part, and unevenness of the dividing line corresponding to the boundary surface 10 c are removed by polishing or the like to finish a smooth surface. It is preferable.
- the number of support pins 13 is preferably 3 to 20, particularly 3 to 12, with respect to each of the upper mold 10a and the lower mold 10b.
- Each of the support pins is preferably arranged so that the tip thereof is in contact with the center of the spherical core from above and below, preferably within a range of 90 ° as the center angle ⁇ .
- a rod-like body having a circular or weak elliptical shape with a cross section of about 0.5 to 15 mm 2 is preferably used as the support pin.
- the flack ball of the present invention forms a surface layer made of the above-mentioned PGA resin on a spherical core and has a total diameter of about 25 mm (1 inch) or more, preferably about 32 mm (1.25 inches). ), Particularly preferably about 38 mm (1.5 inches) or more, as a generally spherical shaped body.
- the upper diameter limit is generally about 127 mm (5 inches) or less, preferably about 102 mm (4 inches) or less.
- substantially spherical is preferably substantially spherical, but does not exclude ellipsoids having a minor axis / major axis ratio of 0.5 or more, preferably 0.8 or more, particularly 0.9 or more. It means that.
- the material of the spherical core may be PGA resin, but only the surface layer that controls the characteristics of the flack ball is formed of PGA resin, and the core is made of another biodegradable resin such as polylactic acid (PLA, Aliphatic polyesters other than PGA resins such as L-lactic acid (PLLA)), polybutyric acid and polyvaleric acid; polysaccharides such as starch and dextrin; animal protein polymers such as chitin and chitosan; and further polyamino acids and polyethylene oxide May be formed.
- PLA polylactic acid
- PLLA Aliphatic polyesters other than PGA resins
- polysaccharides such as starch and dextrin
- animal protein polymers such as chitin and chitosan
- further polyamino acids and polyethylene oxide May be formed.
- a hollow spherical core may be used in consideration of maintaining the mechanical strength represented by the compressive strength of the entire fla
- the surface layer PGA resin and the biodegradable resin constituting the spherical core include a heat stabilizer and a light as necessary within the scope of the object of the present invention.
- Various additives such as a curable resin, an antioxidant, a UV absorber, a nucleating agent such as boron nitride, a flame retardant, and a colorant composed of a pigment or dye may be added as appropriate.
- the thickness of the surface PGA resin layer is about 2.5 to 44 mm (0.1 to 1.75 inches), more preferably about 3.8 to 38 mm (0.15 to 1.5 inches), particularly about 5 It is preferably in the range of 1 to 32 mm (0.2 to 1.25 inches). If it is less than about 2.5 mm (0.1 inches), the compression strength expected when only the surface layer is formed of PGA resin may not be obtained, and the molding efficiency by insert molding will deteriorate. On the other hand, when the thickness exceeds about 44 mm (1.75 inches), the effect of preventing the occurrence of sink marks and voids due to thermal shrinkage due to the thickness suppression of the PGA resin surface layer by insert molding, which is the object of the present invention, and shrinkage during crystallization becomes poor.
- the diameter of the spherical core body is the above value (typically about 25 mm (1 inch)). ) May be exceeded.
- the spherical core itself may have a laminated structure by insert molding according to the present invention (in this case, the surface layer resin may not be a PGA resin).
- the laminated core to be formed is scheduled to be covered with the PGA resin surface layer, it is not necessary to consider that the surface accuracy is excessively fine.
- FIG. 2 is a partial cross-sectional view of the flux leave 10 inserted in the downhole D formed in the formation F.
- the ball seat Bsm arranged at the position is shown.
- the flack balls ... 1n, ... 1m, ... left in positions such as ... Bsn, ... Bsm, ... are decomposed after a predetermined period according to the decomposition characteristics of the constituent resin in the work environment. -Expected to disappear.
- the flux leave used in such an embodiment may be required to have a length as long as several hundred meters formed by adding an intermediate tube.
- a small diameter is about 12.7 mm (0.5 inch) and a large is about 127 mm (5 inch) in diameter.
- a large number of flackball sets may be required.
- one preferred application of the present invention is a set of a plurality of flack balls having different diameters within the range of about 12.7 mm (0.5 inch) to about 12.7 mm (5 inch) mm.
- One or more, preferably half or more, of a part (not all) of them includes the flack ball of the present invention having a diameter of about 25 mm (1 inch) or more and having a laminated structure.
- the remaining small-diameter side flack balls are preferably single-layer molded balls made of polyglycolic acid resin.
- HFIP hexafluoroisopropanol
- melt viscosity of polyglycolic acid was measured as follows in accordance with JIS K7199. An orifice having a diameter of 1 mm and a length of 10 mm was set in a semi-automatic capillary rheometer manufactured by Yasuda Seiki Seisakusho, and after raising the temperature to 270 ° C., a sufficiently pre-dried resin was charged into the cylinder. After 300 seconds of preheating, the viscosity at 120 seconds -1 was measured.
- Example 1 Polyglycolic acid (PGA) (melt viscosity: 600 Pa ⁇ s @ 270 ° C., 120 seconds ⁇ 1 , manufactured by Kureha Co., Ltd.) is supplied to an injection molding machine (“SAV-100-75” manufactured by Yamashiro Seiki Seisakusho), and cylinder PGA balls having a diameter of 0.5 inch (about 13 mm) were prepared by a mold (a split mold for injection molding having a normal horizontal joining surface) set at 100 ° C. by melt-kneading at a temperature of 250 ° C.
- SAV-100-75 injection molding machine
- cylinder PGA balls having a diameter of 0.5 inch (about 13 mm) were prepared by a mold (a split mold for injection molding having a normal horizontal joining surface) set at 100 ° C. by melt-kneading at a temperature of 250 ° C.
- the 0.5 inch produced above is formed on three cylindrical support pins 13 having a cross-sectional area of 1.5 mm 2 in the lower mold 10b of the vertical insert mold 10 shown in FIG.
- the PGA ball core 12 was placed as a core, closed by lowering the upper mold 10 a having three similar support pins 13, and the PGA ball core 12 was held in the approximate center of the cavity 11 to be formed. In this state as shown in FIG.
- the mold temperature is set to 100 ° C.
- the same PGA as described above is supplied to the vertical injection molding machine, melt-kneaded at a cylinder temperature of 250 ° C., and the mold diameter 1 Injecting into the 5-inch cavity 11, the upper and lower mold support pins 13 were retracted to the inner surface position of the mold almost simultaneously with the completion.
- the mold After the completion of injection, after cooling for 35 seconds while being held in a mold at 100 ° C., the mold was opened, and the appearance of a 1.5 inch diameter laminated ball obtained by insert molding was observed. There was no deformation due to sink marks. Moreover, when several of the plurality of laminated balls thus obtained were cut in half and the inside was observed, no void was observed. Unevenness corresponding to the gate portion, the dividing line, and the support pin of the obtained laminated ball was smoothed by removing it with a cutter and polishing it.
- Example 2 A ball having a diameter of 1.5 inches was produced by insert molding in the same manner as in Example 1, and this was used as the spherical core body 12 and again using the insert molding die 10 having a cavity diameter of 2.5 inches. In the same manner as in Example 1, insert molding was performed.
- Example 3 Instead of using PGA alone as the surface layer material, a mixture of 70/30 in weight ratio between the same PGA and glass fiber (GF) (“GL-HF” manufactured by Owens Corning, minor axis 10 ⁇ m, fiber length 3 mm) is used. Then, insert molding was carried out in the same manner as in Example 1 to obtain a laminated ball having a diameter of 1.5 inches made of PGA having a core body composed of PGA alone and a surface layer containing glass fiber (GF).
- GF glass fiber
- Example 4 Insert molding was performed in the same manner as in Example 1 except that polylactic acid (PLLA, Nature Works 4032D, weight average molecular weight 260,000, melting point 170 ° C.) was used instead of PGA as the core constituting resin. Obtained a laminated ball having a diameter of 1.5 inches, which is made of PLLA alone and the surface layer is made of PGA.
- polylactic acid PLLA, Nature Works 4032D, weight average molecular weight 260,000, melting point 170 ° C.
- Example 5 Instead of PGA alone as the surface layer material, the same procedure as in Example 1 was used, except that a 70/30 mixture in weight ratio of the same PGA and glass powder ("ASF-1340" manufactured by Asahi Glass, average particle size: 2 ⁇ m) was used. Insert molding was performed to obtain a laminated ball having a diameter of 1.5 inches, the core being made of PGA alone and the surface layer being made of PGA blended with glass powder (GP).
- ASF-1340 manufactured by Asahi Glass, average particle size: 2 ⁇ m
- Example 6 70/30 by weight ratio of the same PGA and milled glass fiber (MF) (“EHF50-3” manufactured by Central Glass, short diameter 11 ⁇ m, average length 50 ⁇ m) instead of PGA alone as the core material and surface layer material Except that, insert molding was performed in the same manner as in Example 1 to obtain a laminated ball having a diameter of 1.5 inches made of PGA in which the core body and the surface layer were blended with milled glass fiber (MF).
- EHF50-3 milled glass fiber manufactured by Central Glass, short diameter 11 ⁇ m, average length 50 ⁇ m
- Example 1 The diameter is the same as in the preparation of the core PGA ball of Example 1 except that only the PGA used in Example 1 is used as a molding material and the injection mold having a cavity diameter increased to 1.5 inches is used. A 1.5 inch PGA single layer ball was formed. The cooling time was 35 seconds as in Example 1. However, since the temperature of the ball when taken out from the mold was high, it was further cooled by being immersed in water. The obtained ball was deformed by sink marks, and when cut in half, a void of about 1 cc was observed.
- a large-diameter ball sealer suitable for use in a hydraulic fracturing method which is widely used for hydrocarbon resource recovery, has good mechanical strength and good dimensional design.
- a technique for manufacturing a polyglycolic acid resin which is a biodegradable resin, at least as a surface-constituting resin with a relatively simple process and good dimensional accuracy.
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Abstract
Description
(ポリグリコール酸樹脂)
本発明の炭化水素資源回収用ボールシーラー(フラックボール)の表層は、ポリグリコール酸樹脂により形成される。ポリグリコール酸樹脂は、熱可塑性樹脂では最高レベルの圧縮強度をはじめとする初期力学強度が優れ、また短繊維補強材を配合した材料にすることにより、水中での厚み減少速度の抑制効果が大きいという点でも、特に好ましく用いられる。ポリグリコール酸樹脂(PGA樹脂)としては、繰り返し単位としてグリコール酸単位(-OCH2-CO-)のみからなるグリコール酸単独重合体(すなわちポリグリコ-ル酸(PGA))に加えて、他の単量体(コモノマー)単位、好ましくは乳酸等のヒドロキシルカルボン酸単位、を50重量%以下、好ましくは30重量%以下、更に好ましくは10重量%以下、の割合で含むグリコール酸共重合体を含む。他の単量体単位を含む共重合体とすることにより、ポリグリコ-ル酸樹脂の加水分解速度、結晶性等をある程度調整することができる。
本発明のフラックボールの表層を構成するPGA樹脂には、短繊維補強材を配合することも好ましい。これにより、前述したように、補強効果に加えて、PGA樹脂単独に比べた初期厚み減少速度の抑制効果が得られる。短繊維補強材としては、ガラスファイバー、カーボンファイバー、ボロンファイバー、アラミド繊維、液晶ポリマー繊維、セルロース系繊維(ケナフ繊維)等の無機または有機繊維補強材のうち、溶融成型に適した組成物を与えるように、短径(D)が0.1μm~1mm、より好ましくは1~100μm、特に好ましくは5~20μm、アスペクト比(L/D)が、2~1000、より好ましくは、3~300、特に好ましくは3~150である、通常ミルドファイバーあるいはチョップドファイバーと称されるものが好ましく用いられる。短径(D)が、0.1μm未満では、崩壊を遅延させるための十分な強度が発現できず、1000μmを超えると、成型品の崩壊挙動の均一性が失われる。アスペクト比(L/D)が、2未満であると、崩壊遅延の効果が得られず、1000を超えると溶融混練により繊短繊維補強材を均一に分散させることが困難となる。また、上記範囲内でアスペクト比(L/D)が増大すると、厚み減少速度の初期抑制期間が、増大する傾向が認められ、これにより、厚み減少速度の初期抑制期間の増減制御がある程度可能となる。
短繊維補強材に代えて、あるいはこれに加えて粉末状(粒状を含む)補強材を用いることも好ましい。粉末状補強材としては、マイカ、シリカ、タルク、アルミナ、カオリン、硫酸カルシウム、炭酸カルシウム、酸化チタン、フェライト、クレー、ガラス粉、酸化亜鉛、炭酸ニッケル、酸化鉄、石灰粉末、炭酸マグネシウム、硫酸バリウム等の無機粉末であって、メディアン平均粒径(粒径分布に基づいて、小粒径側あるいは大粒径側からの累積重量が50%に達する粒径)が、0.1μm~1mm程度、特に1~100μmのものが好ましく用いられる。これら粉末状補強材は、短繊維補強材と比べて、得られる成形体の特性として、圧縮強度に関し同等の向上効果を示し、分解遅延効果は乏しいものの、より良好な寸法安定性を与える特徴がある。
ポリグリコ-ル酸(PGA)およびポリ乳酸(PLA)の重量平均分子量(Mw)は、各10mgの試料を、トリフルオロ酢酸ナトリウムを5mMの濃度で溶解させたヘキサフルオロイソプロパノール(HFIP)に、溶解させて10mLとした後、メンブレンフィルタ―で濾過して試料溶液を得た。この試料溶液の10μlをゲルパーミエーションクロマトグラフィー(GPC)装置に注入して、下記条件で分子量を測定した。なお、試料溶液は、溶解後、30分以内にGPC装置に注入した。
<GPC測定条件>
装置:Shimazu LC-9A
カラム:昭和電工(株)製 HFIP-806M 2本(直列接続)+プレカラム:HFIP-LG 1本
カラム温度:40℃
溶離液:トリフルオロ酢酸ナトリウムを5mMの濃度で溶解させたHFIP溶液
流速:1mL/分
検出器:示差屈折率計
分子量校正:分子量の異なる標準分子量のポリメタクリル酸メチル5種(POLYMER LABORATORIES Ltd.製)を用いて作成した分子量の検量線データを使用。
ポリグリコール酸の溶融粘度は、JIS・K7199に準拠して、以下のようにして測定した。安田精機製作所製のセミオートマチックキャピラリーレオメーターに径1mm・長さ10mmのオリフィスをセットし、270℃に昇温したのち十分に事前乾燥した樹脂をシリンダーに投入した。300秒間の予熱の後、120秒-1における粘度を測定した。
ポリグリコール酸(PGA)(溶融粘度:600Pa・s@270℃、120秒-1、(株)クレハ製)を射出成型機(山城精機製作所製「SAV-100-75」)に供給し、シリンダー温度250℃で溶融混練し、100℃に設定した金型(通常の水平接合面を有する射出成型用割型)により直径0.5インチ(約13mm)のPGAボールを作製した。次いで、図1に示すような竪型インサート射出成型用金型10の下型10bの断面積1.5mm2の円柱状の支持ピン13の3本の上に、上記で作製した0.5インチのPGAボール12を芯体として配置し、同様な支持ピン13の3本を備えた上型10aの降下により閉型し、形成されるキャビティ11のほぼ中央にPGAボール芯体12を保持した。図2に示すようなこの状態で、金型温度を100℃に設定し、上記と同じPGAを竪型射出成型機に供給し、シリンダー温度250℃で溶融混練して、上記金型の直径1.5インチのキャビティ11中に射出し、その完了とほぼ同時に、上下型の支持ピン13を、金型の内面位置まで後退させた。射出完了後、100℃の金型中に保持したままでの35秒間の冷却の後、金型を開いて、得られたインサート成形による直径1.5インチの積層ボールの外観を観察したところ、ヒケによる変形は見られなかった。またこのようにして得られた複数の積層ボールのうち数個を半分に切断し内部を観察したところ、ボイドはみられなかった。得られた積層ボールのゲート部や分割線、および支持ピンに対応する凹凸はカッターを用いて除去したのち研磨することで平滑とした。
実施例1と同様にしてインサート成形で直径1.5インチのボールを作製後、これを球状芯体12として用い、再度、キャビティ直径が2.5インチとなるインサート成型用金型10を用いる以外は実施例1と同様に、インサート成形を行った。
表層材料としてPGA単独の代わりに、同じPGAとガラスファイバー(GF)(オーウェンスコーニング製「GL-HF」、短径10μm、繊維長3mm)との重量比で70/30の混合物を用いる以外は、実施例1と同様にしてインサート成形を行ない、芯体がPGA単独で、表層がガラスファイバー(GF)を配合したPGAからなる直径1.5インチの積層ボールを得た。
芯体構成樹脂としてPGAの代わりに、ポリ乳酸(PLLA、ネイチャーワークス製4032D、重量平均分子量26万、融点170℃)を使用した以外は、実施例1と同様にしてインサート成形を行ない、芯体がPLLA単独で、表層がPGAからなる直径1.5インチの積層ボールを得た。
表層材料としてPGA単独の代わりに、同じPGAとガラス粉末(旭硝子製「ASF-1340」、平均粒径:2μm)との重量比で70/30の混合物を用いる以外は、実施例1と同様にしてインサート成形を行ない、芯体がPGA単独で、表層がガラス粉末(GP)を配合したPGAからなる直径1.5インチの積層ボールを得た。
芯体材料および表層材料としてPGA単独の代わりに、同じPGAとミルドガラスファイバー(MF)(セントラル硝子製「EHF50-3」、短径11μm、平均長50μm)との重量比で70/30の混合物を用いる以外は、実施例1と同様にしてインサート成形を行ない、芯体および表層がミルドガラスファイバー(MF)を配合したPGAからなる直径1.5インチの積層ボールを得た。
成形原料として実施例1で用いたPGAのみを用い、キャビティ直径を1.5インチまで増大した射出成型用金型を用いる以外は、実施例1の芯体PGAボールの作成と同様にして、直径1.5インチのPGA単層ボールを形成した。冷却時間は実施例1と同様に35秒間としたが、金型から取り出した際のボールの温度が高かったため、水に漬けることでさらに冷却した。得られたボールはヒケにより変形しており、半分に切断したところ1cc程度のボイドがみられた。
Claims (11)
- 球形の芯体と、これを覆う表層樹脂材との少なくとも2層構造を有し、全体として概ね球状の構造体からなり、その少なくとも表層樹脂材がポリグリコール酸樹脂からなり、直径が約25mm(1インチ)以上である炭化水素資源回収用ボールシーラー。
- 表層樹脂材が、短径(D)が0.1μm~1mm、アスペクト比(L/D)が2~1000である無機あるいは有機の短繊維補強材を配合したポリグリコール酸樹脂からなる請求項1に記載のボールシーラー。
- 表層樹脂材中にポリグリコール酸樹脂100重量部あたり、1~50重量部の短繊維補強材が含まれる請求項2に記載のボールシーラー。
- 表層樹脂材が、平均粒径が0.1μm~1mmの粉末状補強材を配合したポリグリコール酸樹脂からなる請求項1~3のいずれかに記載のボールシーラー。
- 表層樹脂材の全量中に5~70重量%の割合で粉末状補強材が含まれる請求項4に記載のボールシーラー。
- 芯体が生分解性樹脂からなる請求項1~5のいずれかに記載のボールシーラー。
- 芯体がポリグリコール酸樹脂からなる請求項6に記載のボールシーラー。
- 金型キャビティ内のほぼ中央に、球形の芯体を支持ピンで配設し、この状態で上記芯体の周囲にポリグリコール酸樹脂からなる表層樹脂を射出成型し、該表層樹脂の射出完了と同期して支持ピンを金型キャビティの壁面まで後退させてから表層樹脂を硬化させる請求項1~7のいずれかに記載の炭化水素資源回収用ボールシーラーの製造方法。
- 約12.7mm(0.5インチ)~約127mm(5インチ)の範囲内で、異なる直径を有する複数のボールシーラーを含み、そのうちの一部且つ一以上は請求項1~7のいずれかに記載のボールシーラーである、炭化水素資源回収用ボールシーラーの組。
- 地層中に形成した坑井に内挿された長尺フラックスリーブの内部に設けた開口を有するボール座に、作業流体とともにフラックボールを供給して、所定位置に配置されたボール座の開口を封ずることによりシール部を形成して作業流体を遮断し、シール部の直上のフラックスリーブ壁に設けた開口より作業流体を噴出させることにより、開口に隣接する坑井内壁を掘削して穿孔を形成するフラクチャリングサイクルを含み、その後フラックボールをその場で分解させる方法であり、フラックボールとして請求項1~7のいずれかに記載のボールシーラーを用いることを特徴とする坑井の処理方法。
- 長尺フラックスリーブ内の延長方向下流側から上流側に向かう所定間隔に、開口径が次第に増大する複数のボール座を設け、作業流体とともに、次第に増大する直径を有するフラックボールを順次供給し、シール部の形成および穿孔の形成を含むフラクチャリングサイクルを、下流側から順次行う方法であり、前記複数のフラックボールの少なくとも一部として請求項1~7のいずれかに記載のボールシーラーを用いることを特徴とする坑井の処理方法。
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Also Published As
Publication number | Publication date |
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JP6151255B2 (ja) | 2017-06-21 |
EP2884041A1 (en) | 2015-06-17 |
CN104395550A (zh) | 2015-03-04 |
US9644453B2 (en) | 2017-05-09 |
JPWO2014024827A1 (ja) | 2016-07-25 |
EP2884041B1 (en) | 2018-11-14 |
CN104395550B (zh) | 2017-10-03 |
US20150144348A1 (en) | 2015-05-28 |
EP2884041A4 (en) | 2016-04-06 |
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