EP3947504A1 - Polyurethan/polyisocyanurat-schaumstoffblock einer thermischen isolationsmasse eines behälters und herstellungsverfahren dafür - Google Patents
Polyurethan/polyisocyanurat-schaumstoffblock einer thermischen isolationsmasse eines behälters und herstellungsverfahren dafürInfo
- Publication number
- EP3947504A1 EP3947504A1 EP20723452.7A EP20723452A EP3947504A1 EP 3947504 A1 EP3947504 A1 EP 3947504A1 EP 20723452 A EP20723452 A EP 20723452A EP 3947504 A1 EP3947504 A1 EP 3947504A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- foam
- block
- polyurethane
- polyisocyanurate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 224
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 122
- 239000004814 polyurethane Substances 0.000 title claims abstract description 122
- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 112
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 112
- 238000009413 insulation Methods 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title description 21
- 239000000835 fiber Substances 0.000 claims abstract description 206
- 239000000203 mixture Substances 0.000 claims description 73
- 230000002787 reinforcement Effects 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 34
- 239000004604 Blowing Agent Substances 0.000 claims description 20
- 230000004888 barrier function Effects 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- 238000007667 floating Methods 0.000 claims description 9
- 239000012263 liquid product Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 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 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 3
- 229960002594 arsenic trioxide Drugs 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 150000007973 cyanuric acids Chemical class 0.000 claims description 3
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 claims description 3
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 239000012796 inorganic flame retardant Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 239000001175 calcium sulphate Substances 0.000 claims 1
- 235000011132 calcium sulphate Nutrition 0.000 claims 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 27
- 239000003949 liquefied natural gas Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229920005862 polyol Polymers 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 12
- 239000006071 cream Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 229920005830 Polyurethane Foam Polymers 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 239000011496 polyurethane foam Substances 0.000 description 7
- 230000006870 function Effects 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000008602 contraction Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic isocyanates Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 2
- NLOLSXYRJFEOTA-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C=CC(F)(F)F NLOLSXYRJFEOTA-UHFFFAOYSA-N 0.000 description 2
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- XFZJGFIKQCCLGK-UHFFFAOYSA-M 1,1-dimethyl-4-phenylpiperazinium iodide Chemical compound [I-].C1C[N+](C)(C)CCN1C1=CC=CC=C1 XFZJGFIKQCCLGK-UHFFFAOYSA-M 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000009422 external insulation Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
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Definitions
- the invention relates to blocks of polyurethane (PUR) and / or polyisocyanurate (PIR) foams mounted in a thermal insulation block which must have, given their specific applications,
- said blocks of foam being used within a tank, integrated in a membrane structure (also called an integrated tank) or self-supporting / semi-supporting type A, B or C, used to accommodate extremely cold fluids, called cryogenic, such as in particular Liquefied Natural Gas (LNG) or Liquefied Petroleum Gas (LPG).
- cryogenic such as in particular Liquefied Natural Gas (LNG) or Liquefied Petroleum Gas (LPG).
- the present invention also relates to a process for preparing these foam blocks from at least one polyisocyanate and at least one polyol.
- the present invention relates more particularly to a sealed and thermally insulating tank using such foams, a vessel equipped with at least one such tank, a method of loading / unloading such a vessel and a transfer system for a liquid product contained in such a vessel.
- PUR polyurethane foam is a cellular insulator, composed of fine cells which store a gas which may have low thermal conductivity. PUR foam is used in a large number of applications such as the automotive industry as flexible PUR foam or in thermal insulation as rigid PUR foam.
- the formation of polyurethane type foams is well known to those skilled in the art. Its formation involves a multi-component reaction between a polyol (compound carrying at least two hydroxy groups), a polyisocyanate (compound carrying at least two isocyanate — NCO functions) and an expanding agent, also designated by expression "blowing agent”.
- This condensation reaction is in particular catalyzed by compounds with basic and / or nucleophilic characters such as tertiary amines or metal-carboxylate coordination complexes such as tin or bismuth salts.
- compounds with basic and / or nucleophilic characters such as tertiary amines or metal-carboxylate coordination complexes such as tin or bismuth salts.
- PUR foams are polyether polyols or polyester polyols. Thus, a large number of compounds are necessary for the formation of PUR foam.
- Polyisocyanurate (PIR) and polyurethane / polyisocyanurate (PUR-PIR) foams are also used in the building industry (construction / renovation) and have the advantage of providing better fire-resistant properties as well as a higher compressive strength than PUR.
- the process for forming these foams is similar to the process for forming PUR foams. In fact, obtaining PUR, PIR and PUR-PIR foams depends on the ratio
- PUR, PIR and PUR-PIR foams are well known to those skilled in the art, nevertheless the addition of fibers involves specific technical problems, such as the need for good impregnation of the fibers, so that at the present time, there are no such foams exhibiting at least locally a relatively substantial amount of fibers.
- thermal insulation of such a tank undergoes, during the loading of the extremely cold fluid, said cryogenic, a very significant temperature gradient in its thickness which causes heterogeneous contraction phenomena of the foam block.
- This heterogeneous contraction of the foam block induces a bimetal effect which leads to a flexing of the block along its longitudinal axis - the two ends having a tendency to rise significantly - due to the non-uniform contraction of the latter in the thickness.
- the foam block being conventionally fixed mechanically or by gluing, this deflection critically lowers the exploitable mechanical properties of the PUR, PIR and PUR-PIR foam block, or even locally the thermal properties of the thermal insulation block (integrating the foam block according to l 'invention).
- the thickness E of the secondary thermal insulation layer has been reduced from 170 mm (millimeter) in a MARK III structure, to 300 mm in a MARK III Flex structure and then to 380 mm in a MARK III Flex + structure.
- PIR polyisocyanurate
- the present invention thus intends to remedy the shortcomings of the state of
- the present invention relates to a block of foam
- polyurethane / polyisocyanurate fiber from a thermal insulation block from a sealed and thermally insulating tank, the density of the block of fiber foam is between 30 and 300 kg / m 3 , the block of foam is
- fiber-reinforced polyurethane / polyisocyanurate having an average fiber density Tf of between 1% and 60% by mass of fibers, preferably between 2% and 30%, and having a width L of at least ten centimeters, advantageously between 10 and 500 centimeters, and a thickness E, from the lower face of said block to its upper face, of at least ten centimeters, advantageously between 10 and 100 centimeters, the block of fibered polyurethane / polyisocyanurate foam being composed of cells storing a gas, advantageously of low thermal conductivity.
- the block of fibered polyurethane / polyisocyanurate foam consists, at least 95% by mass of said block, of cells storing a gas, advantageously of low thermal conductivity, of the foam
- the foam block according to the invention consists (only) of polyurethane (PUR) and / or polyisocyanurate (PIR) foam, fibers, which are preferably of a single nature such as glass fibers , and gas trapped in the cells, and optionally a minimal portion, for example, of fillers or other functional adjuvants, or for the latter a maximum of 5% by mass, or even preferably a maximum of 2% or of 1% by mass of the foam block according to the invention (the foam block of
- PUR polyurethane
- PIR polyisocyanurate
- the foam block according to the invention is obtained:
- reaction ingredients optionally fillers / adjuvants, with the fibers), preferably in a double strip laminator (DBL);
- the aforesaid foam is characterized in that the fiber density increases according to the thickness E, from the lower face of said block to its upper face, by a lower density range of between 1% and 9.99 % by mass of fibers at a higher density range of between 10% and 35% by mass of fibers.
- the present invention is intended to apply in particular, but not
- the foam block is installed at the level of the secondary layer, conventionally referred to as the “secondary”.
- the foam block has a thickness of at least twenty-five (25) centimeters (cm), even more preferably at least 30 or 35 cm.
- the terms “upper” and “lower” are understood to mean a meaning or a direction given to the foam block once the latter is in position in the thermal insulation block of a tank.
- the part or the upper face of the foam block is that located near or on the side of the container of the tank, when the thermal insulation block is placed in the tank, while the lower part or face of the block of foam is that located towards or on the side of the outside of the tank, that is to say in particular towards the hull of a ship in the case where the tank is integrated or mounted in a cryogenic liquid transport and / or storage vessel.
- cells storing a gas is understood to mean the fact that the polyurethane / polyisocyanurate foam has closed cells enclosing a gas, preferably exhibiting low thermal conductivity, originating from a gas injected during a step of nucleation of the reaction mixture or originating, directly or indirectly, from the chemical or physical blowing agent.
- fiber (s) or the expression “fiber reinforcement” is understood to mean the fact that the fibers can be in two distinct forms:
- fiber fabric in the form of at least one fabric of fibers, in which the fibers are perfectly aligned in at least one direction, in other words the fibers have at least one preferred direction of fibers.
- fiber mat per se refers to a clear technical definition known to those skilled in the art.
- hydrocarbons chlorofluorocarbons, hydrochlorocarbons,
- hydrofluorocarbons hydrochlorofluorocarbons, and mixtures thereof, as well as the corresponding alkyl ethers.
- Physical blowing agents such as molecular nitrogen N2, oxygen O2 or CO2 are found in gas form. These gases are dispersed or dissolved in the liquid mass of copolymer, for example under high pressure, using a static mixer. By depressurizing the system, nucleation and growth of bubbles generates cellular structure.
- average density Tf in fibers is understood to mean the fiber density expressed as mass of fibers relative to the total mass of the block of fiber-reinforced foam, without considering the local percentages (within the block) which vary from these fibers.
- the fiber-reinforced foam block is compatible with use in tanks integrated into a supporting structure but also self-supporting / semi-supporting tanks of type A, B or C according to regulations (IMO)
- IGC that is to say as an external insulation associated with self-supporting tanks for the storage and / or transport of very cold liquids such as LNG or LPG.
- the thermal properties of the block of fiber foam are at least one of the thermal properties of the block of fiber foam.
- the block of foam has, in the thickness E, a thermal conductivity of less than 30 mW / mK (milliwatt per meter per Kelvin), i.e. 0 , 03 W / mK, preferably less than 25 mW / mK, even more preferably less than 23 mW / mK, measured at 20 ° C, and a thermal conductivity of less than 20 mW / mK when the top face of the block is found at -160 ° C, the foam block then being in operating condition, the tank in which it is housed containing LNG.
- mW / mK milliwatt per meter per Kelvin
- the density of the block of fiber-reinforced foam is between 50 and 250 kg / m 3 , preferably between 90 and 210 kg / m 3 .
- the density range of the fiber foam block is preferably between 30 and 90 kg / m 3 while in the case of a membrane, the even preferred density range is between 90 and 210 kg / m 3 .
- the increase in fiber density related to the
- total mass of the polyurethane / polyisocyanurate fiber foam corresponds to an increase gradient of between 0.05% and 1.5% by mass of fibers per centimeter, preferably between 0.2% and 1.2% by mass fiber per centimeter. These density values are averaged over the entire block.
- At least 60%, preferably at least 80%, of the aforesaid cells storing a gas, advantageously of low thermal conductivity, have an elongated or stretched shape along an axis parallel to the axis of a thickness E of the block of fiber-reinforced polyurethane / polyisocyanurate foam.
- the fibers consist of glass fiber or of hemp fiber, preferably of glass fiber.
- the fibers are long to continuous fibers.
- the average density of Tf fibers is between 2% and
- the foam block according to the invention is in a
- parallelepipedal or cubic may have one or more protuberances local, for example in the form of the anchors presented below, or else conversely empty or hollow portions, while still being able to be qualified as parallelepiped or cubic.
- the fiber density in the lower region is between 2% and 6% by weight of fibers and the fiber density in the upper region is between 12% and 25. % by mass of fiber.
- the lower face and / or the upper face, preferably the upper face, of said block has (s) anchors able to engage with a means for engaging the thermal insulation block (not shown in the figures). appended figures) in order to fix or anchor the foam block to said solid, preferably said anchors being made of a material other than the foam or fibers.
- anchors can also be made of plastic / polymers or composites combining one or more polymers with ceramic and / or metallic materials), for example having a hooking tab, in the form of an L, so as to engage with an element or part of the thermal insulation block enclosing or housing the block of fiber foam.
- This part of the thermal insulation block may consist of a metallic membrane sealing the container, for example of stainless steel or manganese-based, in the case of a membrane tank or of a vapor barrier (having the function of technique of ensuring a seal to the surrounding environment outside the tank) in the case of self-supporting or semi-supporting tanks of type A, B or C.
- this element or this part of the mass of thermal insulation in a membrane tank
- these anchors can also have the function of anchoring the foam block to the hull, in the case of a membrane tank, to the self-supporting structure in the case of a self-supporting tank. of type A, B or C, it being understood that these anchors are then those present on the underside of the foam block.
- these anchors are inserted at least in part in the fiber reinforcements, those constituting the lower or upper layer of the fiber reinforcement stack, so as to allow their location on the faces once the block of foam has been prepared / finished, without however protruding from said face.
- these anchors are present only on the face
- the block of fiber-reinforced foam according to the invention comprises a flame retardant in a proportion of between 0.1% and 5% by mass, of the organophosphorus type, advantageously triethylphosphate (TEP), tris (2- chloroiso-propyl) phosphate (TCPP), tris (1, 3-dichloroisopropyl) phosphate (TDCP), tris (2-chloroethyl) phosphate or tris (2,3-dibromopropyl) phosphate, or a mixture of these , or of the inorganic flame retardant type, advantageously red phosphorus, expandable graphite, an aluminum oxide hydrate, an antimony trioxide, an arsenic oxide, an ammonium polyphosphate, a calcium sulfate or cyanuric acid derivatives, a mixture thereof.
- the organophosphorus type advantageously triethylphosphate (TEP), tris (2- chloroiso-propyl) phosphate (TCPP
- the invention also relates to a sealed and thermally insulating tank integrated into a supporting structure, said tank consisting of:
- a tank integrated into a supporting structure comprising a sealed and thermally insulating tank comprising at least one sealed metal membrane composed of a plurality of metal strakes or metal plates which may include corrugations and a thermally insulating mass comprising at least one adjacent thermally insulating barrier to said membrane, or
- thermoly insulating solid comprises a plurality of blocks of foam
- IRC code is understood to mean the "international collection of rules relating to the construction and equipment of ships transporting liquefied gases in bulk", well known to those skilled in the art, at l 'like the types B and C of tanks cited, or in English “International Code for the Construction and Equipment of Ships Carrying Liquefied Gases in Bulk”.
- membrane tank or tank
- integrated tank to designate the same category of tanks, fitted in particular to tankers transporting and / or storing at least partly liquefied gas.
- the “membrane tanks” are integrated in a supporting structure while the tanks of type A, B or C are said to be self-supporting or semi-supporting (type A specifically).
- This tank comprises a plurality of blocks of foam
- the invention also relates to a vessel for transporting a cold liquid product, the vessel comprising at least one hull and a sealed and thermally insulating tank as described briefly above, arranged in the hull or mounted on said vessel when said tank is of type A, B or C according to the definition given by the IGC code.
- such a vessel comprises at least one sealed and insulating tank as described above, said tank comprising two barriers of 'successive sealing, one primary in contact with a product contained in the tank and the other secondary disposed between the primary barrier and a supporting structure, preferably constituted by at least part of the walls of the vessel, these two barriers of sealing being alternated with two thermally insulating barriers or a single thermally insulating barrier arranged between the primary barrier and the supporting structure.
- Such tanks are classically designated as integrated tanks according to the code of the International Maritime Organization (IMO), such as for example tanks of the NO type, including types NO 96 ® , NO 96L03 ® , NO
- IMO International Maritime Organization
- the tank called membrane type or type A, B or C,
- LNG Liquefied Natural Gas
- GL Liquefied Gas
- the invention also relates to a transfer system for a cold liquid product, the system comprising a vessel as defined above, insulated pipes arranged so as to connect the tank installed in the hull of the vessel to a control unit. floating or terrestrial storage and a pump for driving a flow of cold liquid product through insulated pipelines from or to the floating or terrestrial storage unit to or from the ship.
- the invention also relates to a method for loading or unloading a ship as defined above, in which a cold liquid product is conveyed through isolated pipes from or to a floating or terrestrial storage unit towards or from the ship.
- the present invention also relates to the process for preparing a block of polyurethane / polyisocyanurate foam fiberized from a thermal insulation block of a sealed and thermally insulating tank as defined briefly above, said process characterized in that it comprises the stages:
- expansion of the fibered polyurethane / polyisocyanurate foam is said to be free, either without the constraint exerted by a volume of closed section, or in which the expansion of the fibered polyurethane / polyisocyanurate foam is physically constrained by walls of 'A double strip laminator, preferably is physically constrained by the walls of a double strip laminator forming a tunnel of rectangular section with a distance between the walls disposed laterally equal to L and a distance between the walls disposed horizontally equal to E, enclosing thus the expanding fiber foam so as to obtain the aforesaid block of foam
- cream time is understood to mean the time required, to
- the cream time is well known to those skilled in the art.
- the cream time is the time elapsed until the mixture turns white under the action of the nucleation of the bubbles (cells storing a gas) and the expansion of the foam after mixing the chemical components. at room temperature.
- the cream time can be determined visually or with the aid of an ultrasonic sensor detecting a variation in thickness indicating the formation of foam.
- the fiber reinforcements extend essentially in a direction perpendicular to the direction of the gravitational flow of the mixture of chemical components
- (a) is meant the fact that these fiber reinforcements are present in the form of a thin layer spreading, during impregnation step (b), along a plane perpendicular to the direction of flow of said mixture of components.
- the plurality of fiber reinforcements having a width L and arranged in superimposed layers, are driven in a longitudinal direction I while the mixture of chemical components is deposited on the fiber reinforcements. from a distributor allowing / allowing the gravitational flow of the mixture of chemical components.
- the mixture of chemical components possibly exiting under pressure from the dispenser, falls under the effect of at least its own weight on the stacked fiber layers, thus impregnating these fiber reinforcements from the upper layer to the lower layer. .
- the foam block according to the invention is prepared by a so-called free expansion
- the physical blowing agent is preferably mixed in liquid or supercritical form with the foamable (co) polymer composition and then converted to the gas phase during the PUR / PIR foam expansion step.
- polyols is meant any carbon structure bearing at least two
- Polyisocyanates suitable for the formation of PUR, PIR and PUR-PIR foam are known to those skilled in the art and include, for example, aromatic, aliphatic, cycloaliphatic, arylaliphatic polyisocyanates and their mixtures, advantageously aromatic polyisocyanates.
- polyisocyanates suitable in the context of the present invention include aromatic isocyanates such as the 4,4'-, 2,4'- and 2,2'- isomers of diphenylmethane diisocyanate (MDI), any compound resulting from of the MDI
- TDI toluene 2,4- and 2,6-diisocyanate
- m- and p-phenylene diisocyanate naphthalene-1, 5-diisocyanate
- IPDI isophorone diisocyanate
- H12MDI 4,4'-dicyclohexylmethane diisocyanate
- CHDI 4-cyclohexane diisocyanate
- the polyisocyanates are the 4,4'-, 2,4'- and 2,2'- isomers of diphenylmethane diisocyanate (MDI).
- reaction catalyst which may for example be chosen from tertiary amines, such as N, Ndimethylcyclohexylamine or N, N-dimethylbenzylamine or from organometallic compounds based on bismuth, potassium or tin.
- fiber-reinforced polyurethane / polyisocyanurate leads to a foam volume of polyurethane / polyisocyanurate fiber, at the outlet of the double-strip laminator, representing between 85 and 99%, preferably between 90% and 99%, of the expansion volume of this same polyurethane / polyisocyanurate fiber foam in the case of an expansion free, without the stress of the walls of such a double strip laminator.
- a foam is obtained, the cells of which, of ovoid shape, are preferably oriented along the axis E, leading to advantageous properties of resistance to crushing in this direction E (measured according to the ISO 844 standard), combined with properties already described in the plane normal to this axis E. Tests and experiments were carried out by the Applicant to determine the broad and preferred domains mentioned above but are not presented here for the sake of clarity and conciseness.
- a block of fiber-reinforced PUR / PIR foam is obtained in which at least 60%, generally more than 80% or even more than 90%, cells storing a gas with low thermal conductivity extend longitudinally along an axis parallel to the axis of the thickness E of the foam block and we contribute, in addition to the specific choices related to characteristics of the fiber reinforcements and the viscosity of the mixture of chemical components, perfect homogeneity of the block of fiber foam.
- the elongated or stretched shape can be defined by an extended shape in
- length that is to say it has one dimension: its length, greater than its other dimensions (width and thickness).
- Polyurethane / polyisocyanurate fiber foam is free, ie without the stress exerted by a closed section volume.
- the preparation of the polyurethane / polyisocyanurate foam is said to be "free expansion" insofar as the expansion of the fiber-reinforced foam is not constrained on at least one side or on at least one expansion face so that the swelling of the fiber-reinforced foam is free on this side or this face, unlike a mold defining a volume finished.
- polyurethane / fiber-reinforced polyisocyanurate said fiber-reinforced foam is cut to obtain the aforementioned block of polyurethane / fiber-based polyisocyanurate foam.
- the mixture of components and at least the blowing agent impregnating them is applied to the mixture.
- fibers a pressure application system (which may for example be a roller system, of the type designated "nip roll” in English) intended to apply pressure to the upper face of the assembly consisting of the aforesaid mixture and of the fibers.
- This pressure system makes it possible, on the one hand, to level the upper face of this assembly and, by the pressure exerted on the assembly, helps to promote the impregnation of the fibers in the aforesaid mixture.
- This pressure system may consist of a single or a double roller, the relative positions of which, above the liquid assembly, and possibly below the foam support, are adjusted in such a way that the liquid assembly is forced to spread out in a perfectly uniform manner.
- an equivalent quantity of the liquid assembly is obtained at any point of the section defined by the spacing between the two rollers or of the upper roller and of the conveyor belt.
- the main object of this pressure system is to complete the liquid dispensing device in that it contributes to uniformity, in the thickness / width, the liquid assembly before most of its expansion.
- the dynamic viscosity h of the aforesaid mixture of components is between 30 mPa.s and 3000 mPa.s, preferably between 50 mPa.s and 1500 mPa.s;
- At least 60% of the aforesaid cells storing a gas advantageously of low thermal conductivity, have an elongated or stretched shape along an axis parallel to the axis of a thickness E of the block of polyurethane foam / fibered polyisocyanurate ;
- At least 80%, preferably at least 90%, of the aforesaid cells storing a gas, advantageously of low thermal conductivity, have an elongated or stretched shape along an axis parallel to the axis of a thickness E of the foam block of
- this characteristic linked to the elongated shape of the cells storing a gas, advantageously of low thermal conductivity, and their rate / proportion in the block according to the invention is more particularly directed in the context of the setting.
- implementation of the preparation process with a DBL but it is absolutely not limited to this case. Indeed, in the case of free expansion, more specifically when there is no
- the (reinforcements of) fibers are arranged over an entire width L and step b) of impregnation of the fibers with the mixture of components, to obtain a polyurethane / polyisocyanurate foam, and a blowing agent operates via a controlled liquid distributor, simultaneously over the entire width L;
- the blowing agent consists of an expanding agent
- the physical expansion agent is chosen from alkanes and cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes, fluoroolefins having between 1 and 8 carbon atoms and tetraalkylsilanes having between 1 and 3 carbon atoms in the alkyl chain, in particular tetramethylsilane, or a mixture thereof.
- fluoroalkanes propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone and fluoroalkanes; the fluoroalkanes being chosen are those which do not degrade the ozone layer, for example
- fluoroolefins examples include 1 -chloro-3,3,3-trifluoropropene, 1, 1, 1, 4,4,4-hexafluorobutene (for example HFO FEA1100 sold by the company Dupont).
- the blowing agent is ethylene glycol dimethacrylate copolymer
- FIFC-227ea also internationally referred to as FIFC-227ea, e.g.
- the chemical expansion agent consists of water.
- nucleation gas is incorporated into at least one polyol compound, preferably using a static / dynamic mixer at a pressure between 20 and 250 bars, the nucleation gas representing between 0 and 50% by volume of polyol, preferably between 0.05 and 20% by volume of the volume of polyol;
- step a) of mixing the chemical components the temperature of each of the reagents for obtaining
- polyurethane / polyisocyanurate is between 10 ° C and 40 ° C, preferably between 15 ° C and 30 ° C;
- an organophosphorus flame retardant advantageously triethylphosphate (TEP), tris (2-chloroiso-propyl) phosphate (TCPP), tris (1, 3- dichloroisopropyl) phosphate (TDCP), tris (2-chloroethyl) phosphate or tris (2,3-dibromopropyl) phosphate, or a mixture thereof, or a flame retardant inorganic, preferably red phosphorus, expandable graphite, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate, calcium sulfate or cyanuric acid derivatives, a mixture of these.
- DEEP diethyl ethane phosphonate
- TEP triethyl phosphate
- DMPP propyl phosphonate dimethyl
- DPC cresyl diphenyl phosphate
- This flame retardant when it is present in the composition according to the invention, is found in an amount of between 0.01% and 25% by weight of the PUR / PIR foam.
- FIG.1 is a schematic view illustrating the different steps of the process for preparing a block of fiber-reinforced PUR / PIR foam according to the invention.
- FIG.2 is a schematic representation of one embodiment of a controlled liquid dispenser according to the invention.
- FIG.3 is a schematic view of two sets of thermal insulation panels, fixed one on the other, respectively forming a primary space and a secondary insulation space for a tank, these panels being constituted by a plurality of blocks of polyurethane / polyisocyanurate foam according to the invention.
- FIG.4 is a partial view of a block of foam according to the invention in which a plurality of anchors have been placed during its preparation so as to allow the fixing or anchoring of said block of foam .
- FIG.5 illustrates an embodiment of an anchor, visible in a schematic section (cut away), capable of being inserted into a block of foam according to the invention.
- FIG.6 is a cutaway schematic representation of an LNG tanker, in which are installed the two sets of thermal insulation panels of the type of those shown in Figure 3, and a terminal loading / unloading of this tank.
- the preparation of the fiber-reinforced PUR / PIR according to the invention is carried out in the presence of catalysts making it possible to promote the isocyanate-polyol reaction.
- catalysts making it possible to promote the isocyanate-polyol reaction.
- Such compounds are described, for example, in the prior art document entitled “Kunststoffhandbuch, volume 7, Polyurethane", Imprimerie Cari Flanser, 3rd edition 1993, chapter 3.4.1. These compounds include amine based catalysts and organic compound catalysts.
- the invention is carried out in the presence of one or more stabilizers intended to promote the formation of regular cellular structures during the formation of the foam.
- stabilizers intended to promote the formation of regular cellular structures during the formation of the foam.
- foam stabilizers comprising silicones such as siloxane-oxyalkylene copolymers and other organopolysiloxanes.
- Those skilled in the art know the amounts of stabilizers, between 0.5% and 4% by weight of the PUR / PIR foam, to be used depending on the reagents envisaged.
- the mixture of chemical components can include plasticizers, for example polybasic esters, preferably dibasic, carboxylic acids with monohydric alcohols. , or consist of polymeric plasticizers such as polyesters of adipic, sebacic and / or phthalic acids.
- plasticizers for example polybasic esters, preferably dibasic, carboxylic acids with monohydric alcohols. , or consist of polymeric plasticizers such as polyesters of adipic, sebacic and / or phthalic acids.
- Organic and / or inorganic fillers in particular reinforcing fillers, can also be considered in the mixture of chemical components such as siliceous minerals, metal oxides (for example kaolin, oxides of titanium or of iron) and / or metal salts.
- characteristics of the fiber reinforcements in particular the density of fibers in the fiber reinforcement, and an equally specific choice of the foam for the impregnation of said reinforcements.
- the present invention is not primarily aimed at a new chemical preparation of fiber-reinforced PUR / PIR foam but rather a new block of fiber-reinforced PUR / PIR foam in which, thanks to a Specific fiber gradient depending on the thickness or height of the block, this fiber-reinforced foam block does not undergo any sag (or minimal sag) or deformation of its general parallelepipedal shape / structure other than a slight contraction of its dimensions.
- a plurality of fiber reinforcements 10 is unwound and brought in parallel alignment with one another on or above a conveyor belt 11 intended to lead these reinforcements 10.
- the impregnation of the fiber reinforcements 10 is carried out, within the framework of the present invention, by gravity, that is to say that one flows from a liquid distributor located above the reinforcements of fiber 10, the mixture 12 of chemical components, blowing agent (s) and any other functional agents used to obtain the PUR / PIR foam, directly on the fibers 10.
- the aforesaid mixture 12 must impregnate all of the fiber reinforcements 10, whether they are for the latter several mats or several fabrics, in a very homogeneous manner, over the time of cream t c so that the start of the expansion of the PUR / PIR foam takes place after or at the earliest just when the fiber reinforcements 10 are all impregnated with the mixture 12.
- the expansion of the PUR / PIR foam is carried out by maintaining a perfect specific distribution of the fibers 10 in the volume of the PUR / PIR foam block, so as to obtain the desired fiber density gradient.
- the object of the present invention is achieved by arranging fiber reinforcements parallel to each other, or in superimposed layers, each of these reinforcements making it possible to achieve a fiber density - weight of fibers relative to the weight of the fiber foam considering a given volume - more or less important compared to the others.
- the upper fiber reinforcements achieve a higher fiber density than those of the lower layers. More precisely, if we consider all of the fiber reinforcements, the upper fiber reinforcement has a fiber density at least equal to that of the lower fiber reinforcement and, if we consider all the fiber reinforcements , the upper fiber reinforcement - the one at the top of the layers
- the superimposed - has a fiber density at least twice as high, and preferably at least three times as high, than that of the lower fiber reinforcement (that at the very bottom of the superimposed layers).
- the local density of fibers in which the local density of fibers is expressed in the block of fiber-reinforced foam, this also amounts to defining that the density of fibers in the upper half of the block is between 10 % and 35% by mass of fibers, preferably between 10.01% and 25% by mass of fibers, and from 1% to 9.99% by mass of fibers, preferably between 6% and 9.9% by mass of fibers, in the lower half of the PUR / PIR foam block.
- the positive gradient in fiber density (by mass of the foam block) in the block, from its lower face to its upper face is established in the range of ( +) 0.1% to (+) 2% by mass of fibers per centimeter, preferably from 0.05% to 1.5% by mass of fibers per centimeter and more preferably between 0.2% and 1, 2% by mass of fibers per centimeter.
- this is an average gradient calculated on the height or thickness of the block of fiber foam.
- the cream time of the components of the mixture 12 to form the PUR / PIR foam is known to those skilled in the art and chosen in such a way that the transport belt 11 brings the assembly together. formed from the mixture 12 of components, the blowing agent and the fibers 10 for example up to a double strip laminator, not shown in the accompanying figures, while the expansion of the foam has just started, in other words the PUR / PIR foam expansion then ends in the dual belt laminator.
- a pressure system using one or two rollers, is optionally arranged before the double strip laminator, or between the zone of impregnation of the mixture on the fibers and the double strip laminator.
- the expansion of the volume of the foam is carried out in the laminator when the expansion volume of this foam reaches between 30% and 60% of the expansion volume of this same foam when the expansion is left free, or without any constraint.
- the double belt laminator will be able to constrain the expansion of the PUR / PIR foam in its second expansion phase, when this is close or relatively close to its maximum expansion, that is to say when its expansion brings the foam close to all the walls, forming a tunnel of rectangular or square section, of the double strip laminator.
- the freezing point of the mixture of components that is to say the moment when at least 60% of the polymerization of the mixture of components is reached, in other words 70% to 80% of the maximum volume expansion of the mixture, imperatively takes place in the double strip laminator, possibly in the second half of the length of the double strip laminator (i.e. closer to the exit of the laminator than to the entry of the latter).
- a controlled liquid distributor 15 comprises a supply channel 16 of the assembly formed of the mixture 12 of chemical components and at least of the swelling agent from the tank forming a reagent mixer, not shown in the appended figures, in which on the one hand all the chemical components and the swelling agent are mixed and d on the other hand, the nucleation, or even the heating, of such a mixture is carried out.
- This liquid assembly formed of the mixture 12 of chemical components and of the blowing agent is then distributed, under pressure, in two channels 17 extending transversely to respectively end in two identical distribution plates 18, extending along the width L ( each having a length substantially equal to L / 2), comprising a plurality of nozzles 19 for the flow of said mixture 12 over the fiber reinforcements 10.
- These flow nozzles 19 consist of orifices of calibrated section having a determined length. The length of these flow nozzles 19 is thus determined so that the liquid leaves with an identical flow rate between all the nozzles 19 so that the impregnation of the fiber reinforcements 10 takes place at the same time, or simultaneously, on the section of width L of the fiber reinforcements 10, and that the surface mass of liquid deposited in line with each nozzle is equal. In doing so, if we consider a section of width L of fibers 10, the latter are impregnated
- the controlled liquid distributor 15 shown in this FIG. 2 is a
- fiber reinforcements 10 just before the cream time t c of the PUR / PIR foam lies in the choice of a specific viscosity of the liquid (consisting of the mixture 12 of chemical components and the blowing agent) to be bonded with the specific characteristics of the different fiber reinforcements, variable depending on the fiber density.
- the permeability characteristics of the fiber reinforcements must allow good penetration of the liquid into the first layers of fibers 10, to reach the following ones up to the last layer (the lower layer of fibers 10, that is to say the one located lowest in the stack fiber reinforcements), so that the impregnation time ti of the fibers 10 is achieved within the time period given by the chemical components corresponding substantially, but always less, to the cream time t c.
- the viscosity of the mixture 12 of components is chosen, for example by heating, adding plasticizers and / or by a greater or lesser nucleation, such that the impregnation of all the fibers 10 by the mixture 12 of chemicals and of the swelling agent, over a section of width L, is obtained just before the cream time, that is to say before or just before the beginning of the expansion of the foam of
- the block of fiber-reinforced foam is intended for use in a very specific environment, and must therefore guarantee specific mechanical and thermal properties.
- the fiber-reinforced foam block obtained by the preparation according to the present invention thus conventionally forms part of a thermal insulation block 30, either in the example used in FIG. 3, in a top or primary panel 31 and / or a panel lower or secondary 32 of such an insulation block 30 of a tank 71 intended to receive an extremely cold liquid, such as LNG or LPG.
- Such a tank 71 can for example equip a ground tank, a floating barge or the like (such as an FSRU “Floating Storage Regasification Unit” or a FLNG “Floating Liquefied Natural Gas”) or even a ship, such as an LNG carrier. , transporting this energetic liquid between two ports.
- a floating barge or the like such as an FSRU “Floating Storage Regasification Unit” or a FLNG “Floating Liquefied Natural Gas”
- a ship such as an LNG carrier.
- the foam block according to the invention shown in FIG. 4 comprises a plurality of anchors 40, distributed over its various faces, upper 41, and lateral 42, 43. These anchors 40 are placed so as to be flush with the surface of said faces 41, 42, 43 of the foam block, without having a foam thickness (or not significant) covering it and / or protecting it from the outside.
- FIG. 5 shows, in cut-away view, an embodiment of such an insert 40.
- This insert 40 has a plate 44 extending in a plane.
- This plate 44 comprises a plurality of orifices 45 which consist of a mechanical anchoring means, in other words one of the two elements making it possible to fix, when engaged with an element of the thermal insulation block (not shown in the accompanying figures), the foam block in or in the thermal insulation block of the tank.
- the plate 44 also comprises a plurality of identical fixing studs 46 as well as a central fixing stud 47 having larger dimensions than that of the fixing studs 46. The function of these studs 46, 47 is to fix the best possible. 'insert 40 in the block of fiber foam according to the invention.
- the fixing studs 46 are ideally placed
- one of these orifices 45 of the anchor 40 can as such be used to form the female part of the anchor, but it is also possible to provide that the anchor requires the use of a plurality of orifices 45.
- these orifices 45 consist of an anchoring solution but the invention is in no way limited to this embodiment and one or more anchors 40 of shape and mechanical characteristics can be considered. different.
- a cutaway view of an LNG carrier 70 shows a sealed and insulating tank 71 of generally prismatic shape mounted in the double hull 72 of the vessel.
- the wall of the vessel 71 comprises a primary waterproof barrier intended to be in contact with the LNG contained in the vessel, a secondary waterproof barrier arranged between the primary waterproof barrier and the double hull 72 of the ship, and two insulating barriers arranged respectively between the vessel. primary watertight barrier and the secondary watertight barrier and between the secondary watertight barrier and the double shell 72.
- the loading / unloading pipes 73 arranged on the upper deck of the ship can be connected, by means of suitable connectors, to a maritime or port terminal for transferring an LNG cargo from or to the tank. 71.
- FIG. 6 represents an example of a maritime terminal comprising a loading and unloading station 75, an underwater pipe 76 and an onshore installation 77.
- the loading and unloading station 75 is a fixed off-shore installation. comprising a movable arm 74 and a tower 78 which supports the movable arm 74.
- the movable arm 74 carries a bundle of insulated flexible pipes 79 which can be connected to the pipes of
- the movable swivel arm 74 adapts to all sizes of LNG carriers.
- a connecting pipe, not shown, extends inside the tower 78.
- the loading and unloading station 75 allows the loading and unloading of the LNG carrier 70 from or to the onshore installation 77.
- the latter comprises liquefied gas storage tanks 80 and connecting pipes 81 connected by the underwater pipe 76 to the loading or unloading station 75.
- the underwater pipe 76 allows the transfer of the liquefied gas between the loading or unloading station 75 and the shore installation 77 over a great distance, for example 5 km, which makes it possible to keep the LNG carrier 70 at a great distance from the coast during loading and unloading operations.
- pumps on board the ship 70 and / or pumps fitted to the shore installation 77 and / or pumps fitted to the loading and unloading station are used. 75.
- the object of the present invention namely in this case the block of fiber-reinforced polyurethane / polyisocyanurate foam, is not intended to be reduced to a tank integrated into a supporting structure but it is also intended for tanks of type B and C of the IGC code in force on the date of filing of the present application, but also for future versions of this code except that these very substantial modifications apply to these tanks of type B and C, it being understood moreover that other types of tanks could, in this hypothesis of a modification of the IGC code, become applications
- a polyurethane foam composition integrating fibers in the form of mats, is used to demonstrate the invention, these fibers always appearing as long to continuous, more precisely the lengths of these fibers are exactly the same in the compositions according to the invention and those according to the state of the art.
- the Applicant has in particular tested the subject of the invention with so-called short fibers (as opposed to the definition given above for long to continuous fibers) or which are in the form of a fabric and the results obtained are equivalent or almost similar to those obtained with a mat of long to continuous fibers, as presented below.
- the characteristics of the fiber reinforcements and of the PUR foam are as follows:
- the characteristics of the fiber reinforcements and of the PUR foam are as follows:
- the first composition (with 8 layers of U809 or U801 for a block 180 mm thick) in Table 3 consists of a composition in accordance with document FR 2882756.
- the results for such a composition according to this document are very significantly lower than those obtained with a composition according to the present invention (last composition of Table 3).
- the fiber-reinforced PUR / PIR foams according to the invention do not exhibit any significant degradation of their property relating to (very low) thermal conductivity.
- a fiber-reinforced foam according to the invention having a fiber density gradient of 1% by mass per centimeter (from the lower face towards the upper face of the block of fiber-reinforced foam), the following are obtained. following values of thermal conductivity:
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1903123A FR3094451B1 (fr) | 2019-03-26 | 2019-03-26 | Bloc de mousse polyuréthane/polyisocyanurate d’un massif d’isolation thermique d’une cuve et son procédé de préparation |
PCT/FR2020/000059 WO2020193874A1 (fr) | 2019-03-26 | 2020-03-16 | Bloc de mousse polyuréthane/polyisocyanurate d'un massif d'isolation thermique d'une cuve et son procédé de préparation |
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EP3947504A1 true EP3947504A1 (de) | 2022-02-09 |
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EP20723452.7A Pending EP3947504A1 (de) | 2019-03-26 | 2020-03-16 | Polyurethan/polyisocyanurat-schaumstoffblock einer thermischen isolationsmasse eines behälters und herstellungsverfahren dafür |
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EP (1) | EP3947504A1 (de) |
JP (1) | JP7541996B2 (de) |
KR (1) | KR20210146953A (de) |
CN (1) | CN113631611B (de) |
FR (1) | FR3094451B1 (de) |
SG (1) | SG11202110316VA (de) |
WO (1) | WO2020193874A1 (de) |
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WO2021233765A1 (en) * | 2020-05-18 | 2021-11-25 | Basf Se | A polyurethane-forming system, a composite comprising the polyurethane-forming system and a fiber-reinforced material, a process for the production of the composite, and the use of the composite |
FR3130676B1 (fr) * | 2021-12-22 | 2024-03-08 | Gaztransport Et Technigaz | Méthode de production en continu d’un panneau isolant par une machine de production |
FR3130677B1 (fr) * | 2021-12-22 | 2024-03-08 | Gaztransport Et Technigaz | Méthode de production d’un panneau isolant par une machine de production. |
TW202348668A (zh) | 2022-06-10 | 2023-12-16 | 美商陶氏全球科技有限責任公司 | 剛性聚胺甲酸酯發泡體配方及製造適用於低溫應用之纖維強化聚胺甲酸酯發泡體之方法 |
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JPS5820352Y2 (ja) * | 1980-04-18 | 1983-04-27 | 株式会社アイジ−技術研究所 | 耐火断熱パネル |
US5024342A (en) * | 1988-11-07 | 1991-06-18 | Dallum Barry J | Corrosion resistant containers |
FR2724623B1 (fr) * | 1994-09-20 | 1997-01-10 | Gaztransport Et Technigaz | Cuve etanche et thermiquement isolante perfectionnee integree dans une structure porteuse |
JP2002021264A (ja) | 2000-07-11 | 2002-01-23 | Sowa Kagaku Sangyo Kk | 外断熱複合防水工法およびそれによって得られる構造体 |
JP4456376B2 (ja) * | 2004-02-12 | 2010-04-28 | ニチアス株式会社 | ポリオール組成物及びその組成物を用いるガラス繊維強化硬質ポリウレタンフォーム |
FR2882756B1 (fr) * | 2005-03-04 | 2007-04-27 | Gaz Transp Et Technigaz Soc Pa | Mousse de polyurethanne-polyisocyanurate renforcee de fibres de verre |
CA2534237A1 (fr) | 2005-03-04 | 2006-09-04 | Gaz Transport Et Technigaz | Mousse de polyurethanne/polyisocyanurate renforcee de fibres de verre |
CN101578312B (zh) * | 2007-01-09 | 2012-06-06 | 巴斯夫欧洲公司 | 用于液化天然气罐绝热的水发泡硬质泡沫 |
KR101225629B1 (ko) * | 2010-04-26 | 2013-01-24 | 한화엘앤씨 주식회사 | 독립형 액화가스 탱크의 단열구조 및 그 형성방법 |
CN104781315B (zh) * | 2012-09-07 | 2019-03-08 | 巴斯夫欧洲公司 | 减小收缩的硬质聚氨酯泡沫 |
FR3022971B1 (fr) | 2014-06-25 | 2017-03-31 | Gaztransport Et Technigaz | Cuve etanche et isolante et son procede de fabrication |
EP4151682A1 (de) | 2016-05-25 | 2023-03-22 | Basf Se | Faserverstärkung von reaktivschaumstoffen aus einem doppelbandschäum- oder einem blockschäumverfahren |
JP2018176996A (ja) | 2017-04-13 | 2018-11-15 | 三井E&S造船株式会社 | 船舶 |
FR3088571B1 (fr) * | 2018-11-19 | 2021-12-17 | Gaztransport Et Technigaz | Procede et systeme de preparation d’un bloc de mousse polyurethane/polyisocyanurate d’un massif d’isolation thermique d’une cuve |
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2019
- 2019-03-26 FR FR1903123A patent/FR3094451B1/fr active Active
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2020
- 2020-03-16 CN CN202080024116.2A patent/CN113631611B/zh active Active
- 2020-03-16 KR KR1020217033304A patent/KR20210146953A/ko active Search and Examination
- 2020-03-16 SG SG11202110316VA patent/SG11202110316VA/en unknown
- 2020-03-16 EP EP20723452.7A patent/EP3947504A1/de active Pending
- 2020-03-16 WO PCT/FR2020/000059 patent/WO2020193874A1/fr active Application Filing
- 2020-03-16 JP JP2021556765A patent/JP7541996B2/ja active Active
Also Published As
Publication number | Publication date |
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WO2020193874A1 (fr) | 2020-10-01 |
JP7541996B2 (ja) | 2024-08-29 |
CN113631611A (zh) | 2021-11-09 |
FR3094451A1 (fr) | 2020-10-02 |
KR20210146953A (ko) | 2021-12-06 |
JP2022528619A (ja) | 2022-06-15 |
CN113631611B (zh) | 2024-02-23 |
FR3094451B1 (fr) | 2022-12-23 |
SG11202110316VA (en) | 2021-10-28 |
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