EP2296836A1 - Catalysts comprising methane sulfonic acid for the acid hardening method - Google Patents
Catalysts comprising methane sulfonic acid for the acid hardening methodInfo
- Publication number
- EP2296836A1 EP2296836A1 EP09749648A EP09749648A EP2296836A1 EP 2296836 A1 EP2296836 A1 EP 2296836A1 EP 09749648 A EP09749648 A EP 09749648A EP 09749648 A EP09749648 A EP 09749648A EP 2296836 A1 EP2296836 A1 EP 2296836A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- binder
- molding material
- refractory
- mold
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 91
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229940098779 methanesulfonic acid Drugs 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title description 41
- 239000000203 mixture Substances 0.000 claims abstract description 95
- 239000011230 binding agent Substances 0.000 claims abstract description 88
- 239000012778 molding material Substances 0.000 claims abstract description 83
- 238000005266 casting Methods 0.000 claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 39
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000000465 moulding Methods 0.000 claims description 25
- 150000007524 organic acids Chemical class 0.000 claims description 20
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 239000004848 polyfunctional curative Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000011820 acidic refractory Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 230000009970 fire resistant effect Effects 0.000 abstract 6
- 230000009969 flowable effect Effects 0.000 abstract 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 81
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 239000004576 sand Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 20
- 150000001299 aldehydes Chemical class 0.000 description 19
- 239000007849 furan resin Substances 0.000 description 19
- 150000002989 phenols Chemical class 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 17
- -1 aromatic sulfonic acids Chemical class 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000005011 phenolic resin Substances 0.000 description 15
- 238000012545 processing Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 150000002576 ketones Chemical class 0.000 description 12
- 229920001568 phenolic resin Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 235000005985 organic acids Nutrition 0.000 description 11
- 229920003987 resole Polymers 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000002028 premature Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- LPCJHUPMQKSPDC-UHFFFAOYSA-N 3,5-diethylphenol Chemical compound CCC1=CC(O)=CC(CC)=C1 LPCJHUPMQKSPDC-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- RCNCKKACINZDOI-UHFFFAOYSA-N 4,5-dimethylbenzene-1,3-diol Chemical compound CC1=CC(O)=CC(O)=C1C RCNCKKACINZDOI-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- AJRRUHVEWQXOLO-UHFFFAOYSA-N 2-(fluoroamino)acetic acid Chemical compound OC(=O)CNF AJRRUHVEWQXOLO-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- HRUHVKFKXJGKBQ-UHFFFAOYSA-N 3,5-dibutylphenol Chemical compound CCCCC1=CC(O)=CC(CCCC)=C1 HRUHVKFKXJGKBQ-UHFFFAOYSA-N 0.000 description 1
- PEZSSBYAUDZEMO-UHFFFAOYSA-N 3,5-dicyclohexylphenol Chemical compound C=1C(O)=CC(C2CCCCC2)=CC=1C1CCCCC1 PEZSSBYAUDZEMO-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- CHQPRDVSUIJJNP-NSCUHMNNSA-N 4-[(e)-but-2-enyl]phenol Chemical compound C\C=C\CC1=CC=C(O)C=C1 CHQPRDVSUIJJNP-NSCUHMNNSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical class OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical class NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/224—Furan polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
Definitions
- the invention relates to a method for the production of cores and molds for the foundry industry and a molding material mixture, as used in the process.
- Molds for the production of metal bodies are composed of so-called cores and molds.
- the casting mold essentially represents a negative mold of the casting to be produced, wherein cores serve to form cavities in the interior of the casting, while the molds form the outer boundary.
- Different requirements are placed on the cores and molds.
- a relatively large surface area is available to dissipate gases generated by the action of the hot metal during casting.
- cores usually only a very small area is available, through which the gases can be derived. If there is too much gas, there is a risk that gas will pass from the core into the liquid metal and cause the formation of casting defects. leads.
- the internal cavities are therefore imaged by cores solidified by cold-box binders, a polyurethane-based binder, while the outer contour of the cast is represented by less expensive molds, such as a green sand mold, a furan resin mold. or a phenol resin bound form or by a steel mold.
- Casting molds are made of a refractory material, such as quartz sand, the Korner be connected after molding of the mold by a suitable binder to ensure sufficient mechanical strength of the mold.
- a refractory molding material which is mixed with a suitable binder.
- the molding material mixture obtained from molding material and binder is preferably present in a ⁇ eselfahigen form, so that it can be filled into a suitable mold and compacted there.
- the binder produces a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
- both organic and inorganic binders can be used, the curing of which can be effected by cold or hot processes.
- cold processes is used to refer to processes which are essentially at room temperature without heating the molding mixture Runaway ⁇ leads.
- Curing is usually carried out by a chemical reaction, which can be triggered, for example, by passing a gaseous catalyst through the molding mixture to be hardened or by adding a liquid catalyst to the molding material mixture.
- hot processes the molding material mixture is heated after molding to a sufficiently high temperature, for example, in the Extract binder contained solvents or to initiate a chemical reaction by which the binder is cured by crosslinking.
- organic binders such as e.g. Polyurethane, furan resin or epoxy-Acrylatbmdeffen used where the curing of the binder is carried out by adding a catalyst.
- binder depends on the shape and size of the cast piece to be produced, the conditions of production and the material used for the casting. For example, when producing small castings that are produced in large numbers, polyurethane binders are often used because they enable fast cycle times and therefore also series production.
- Processes in which the curing of the molding material mixture by heat or by subsequent addition of a catalyst have the advantage that the processing of the molding material mixture is not subject to any special time restrictions.
- the molding material mixture can first be produced in larger quantities, which are then processed within a longer period of time, usually several hours.
- the curing of the Formst offmischung takes place only after the molding, with a rapid reaction is sought.
- the casting mold can be removed immediately after curing from the mold, so that short cycle times can be realized. However, in order to obtain a good strength of the mold, the curing of the molding material mixture must be uniform within the mold.
- the mold is gassed after molding with the catalyst. For this purpose, the gaseous catalyst is passed through the casting mold.
- the molding material mixture hardens immediately after contact with the catalyst - A -
- no-bake binder In the production of molds for large castings, such as engine blocks of marine diesel or large machine parts, such as hubs of rotors for wind power plants, therefore, no-bake binder are used mostly.
- the refractory base molding material In the no-bake process, the refractory base molding material is first coated with a catalyst. Subsequently, the binder is added and distributed evenly by mixing on the already coated with the catalyst grains of the refractory base molding material. The molding material mixture can then be formed into a shaped body. Since binder and catalyst are gleichschreibig distributed in the molding material mixture, the curing is largely uniform even with large moldings.
- the curing of the molding material mixture begins. immediately after their manufacture.
- the components of the molding material mixture must be very closely matched.
- the reaction rate for a given amount of the binder and the refractory mold base for example, by the nature and amount of the catalyst or by the addition of retarding components influence.
- the processing of the molding material mixture under very controlled conditions Bedin ⁇ must be made because the rate of hardening for example by the temperature of the molding material mixture is enced beem-.
- the classic no-bake binders are based on furan resins and phenolic resins. They are offered as two-component systems, one component comprising a reactive furan resin and the other component an acid acting as a catalyst for curing the reactive resin component.
- Furan and phenolic resins show very good decay properties during casting. Under the action of heat of the liquid metal, the furan or phenolic resin decomposes and the strength of the mold is lost. After casting, therefore, cores, possibly after previous shaking of the cast, can pour out very well from cavities.
- furfuryl alcohol as an essential component.
- Furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol generally not pure furfuryl alcohol is used, but further compounds added to the furfuryl alcohol are added, which are polymerized into the resin. Examples of such compounds are aldehydes de, such as formaldehyde or diformal, ketones, such as acetone, phenols, urea or polyols, such as sugar alcohols or ethylene glycol.
- the resins may be added with other components that affect the properties of the resin, such as its elasticity. Melamm may be added, for example, to bind free formaldehyde.
- Furan no-bake binders are most often prepared by first producing furfuryl-containing precondensates from, for example, urea, formaldehyde and furfuryl alcohol under acidic conditions. The reaction conditions are chosen so that only a slight polymerization of furfuryl alcohol occurs. These precondensates are then diluted with furfuryl alcohol.
- Resoles can also be used to prepare furan no-bake agents. Resoles are prepared by polymerization of mixtures of phenol and formaldehyde. These resoles are then diluted with furfuryl alcohol.
- the second component of the furan no-bake agent forms an acid.
- this acid neutralizes alkaline components contained in the refractory molding material and, on the other hand, catalyzes the crosslinking of the reactive furan resin.
- acids mostly aromatic sulfonic acids and in some special cases also phosphoric acid or sulfuric acid are used.
- Phosphoric acid is used in concentrated form, ie at concentrations greater than 75%.
- Sulfuric acid can be added as a relatively strong acid as a starter for the curing of furan resins of weaker acids.
- a smell typical of sulfur compounds develops.
- there is a risk that the casting material sulfur is absorbed, which affects its properties.
- aromatic sulfonic acids are used as catalysts. Owing to their good availability and their high acidity, especially toluenesulphonic acid, xylyol sulphonic acid and benzenesulphonic acid are used.
- the choice of catalyst has a great influence on the properties of the binder.
- the rate of curing can be influenced by the amount of acid and by the strength of the acid. Higher amounts of acid or stronger acids lead to an increase in hardening speed.
- the furan resin becomes brittle upon curing, which adversely affects the strength of the casting mold.
- the resin is not completely cured or the curing takes a long time, which leads to a lower strength of the mold.
- Phenolic resins the second large group of acid-catalyzed, hard-to-bake no-bake binders, contain resoles as reactive resin components, ie phenolic resins which have been prepared with an excess of formaldehyde. Phenol resins show a significantly lower reactivity compared to fumarran resins and require strong sulfonic acids as catalysts. Phenol resins show a rela ⁇ tively high viscosity, the longer storage of the resin still increases. Especially at temperatures below 20 0 C, the viscosity increases sharply, so that the sand must be heated in order to apply the binder gleichschreibig on the surface of the sand grains can.
- the molding material mixture After the phenol no-bake binder has been applied to the refractory base molding material, the molding material mixture should be processed as promptly as possible so as not to suffer deterioration of the molding compound mixture by premature curing, resulting in deterioration of the strength of the molding compound mixture produced molds can lead.
- the flowability of the molding material mixture is usually poor. In the production of the mold, the molding material mixture must therefore be carefully compacted in order to achieve a high strength of the mold can.
- the preparation and processing of the molding material mixture should be carried out at temperatures in the range of 15 to 35 0 C. If the temperature is too low, the molding material mixture is difficult to process because of the high viscosity of the phenol no-bake resin. At temperatures of more than 35 ° C., the processing time is shortened by premature curing of the binder.
- molding mixtures based on phenol no-bake binders can also be worked up again, in which case mechanical or thermal or combined mechanical / thermal processes can also be used.
- the acid used as a catalyst in the case of furan or phenol no-bake processes has a very great influence on the properties of the casting mold.
- the acid must have sufficient strength to ensure a sufficient reaction rate during the curing of the mold.
- the curing must be well controllable, so that also sufficiently long processing times can be set. This is especially for the production of molds for very large Castings important, whose construction requires a longer period.
- the acid must not accumulate in the regeneration of the regeneration of old sands. If acid is introduced into the molding material mixture via the regenerated material, this shortens the processing time and leads to a deterioration in the strength of the casting mold produced from the regenerated material.
- the hardened binder should decompose, so that the mold loses its strength.
- the aromatic sulfonic acids used as a catalyst particularly p-toluenesulfonic acid, benzenesulfonic acid and Xylxolsulfonsaure, disintegrate under the influence of heat and during casting he testified ⁇ reducing atmosphere and set alongside sulfur dioxide aromatic pollutants such as benzene, toluene or xylene (BTX) free.
- BTX xylene
- WO 97/31732 describes a self-hardening furan-no-bake molding material mixture for the production of casting fores, which, in addition to a furan-containing resin, contains methanesulfonic acid as a catalytically active acid.
- the methanesulfonic acid can also be used in admixture with an organic sulfonic acid or an inorganic acid.
- organic sulfonic acids p-toluenesulfonic acid, benzenesulfonic acid and xylenesulfonic acid are mentioned.
- An example of an inorganic acid is called sulfuric acid.
- Methanesulfonic acid has a higher acidity than, for example, p-toluenesulfonic acid. When using this acid, therefore, a faster curing of the furan no-bake binder is achieved or the curing can be achieved even at low temperatures, ie at temperatures below 25 0 C within acceptable periods.
- methanesulfonic acid is very problematic because of its high reactivity, especially in the production of very large molds, since it acts as a fast curing, so only relatively short processing periods allowed.
- Another disadvantage is the use of methanesulfonic acid or methanesulfonic acid mixed with organic sulfonic acids for the emission of sulfur dioxide during casting.
- MAK maximum workplace concentration
- the emission of pollutants in particular the emission of sulfur dioxide and aromatic pollutants, such as benzene, toluene or xylene, can be drastically reduced during casting. As a result, the burden of used sand with these pollutants can be reduced.
- a free-flowing refractory molding base is provided;
- an acid is applied to the free-flowing refractory base stock to obtain an acid-coated refractory base stock;
- an acid-curable binder is applied to the acid-coated refractory molding base to obtain a molding material mixture;
- the mold is cured.
- the acid used as a catalyst for the curing of the resin is a mixture of methanesulfonic acid and at least one further sulfur-free acid.
- refractory molding base material for example, all refractory materials which are customary for the production of molded articles for the foundry industry can be used as the refractory molding base material per se.
- suitable refractory mold bases are quartz sand, zircon sand, olivine sand, aluminum silicate sand and chrome ore sand or mixtures thereof.
- quartz sand is used.
- the refractory base molding material should have a sufficient particle size so that the molded article produced from the molding material mixture has a sufficiently high porosity to allow the escape of volatile compounds during the casting process.
- At least 70 wt .-%, particularly preferably at least 80 wt .-% of the refractory molding base material has a particle size ⁇ 290 microns.
- the average particle size of the refractory base molding material should preferably be between 100 and 350 ⁇ m.
- the particle size can be determined, for example, by sieve analysis.
- the refractory base molding material should be present in ⁇ eselfahiger form, so that the catalyst or acid-curable binder, for example, in a mixer can be well applied to the grains of the refractory molding base material.
- Regenerated used sands are preferably used as refractory mold bases. From the used sand larger aggregates are removed and the used sand is separated into individual grains. After a mechanical or thermal treatment, the old sands are dedusted and can then be reused. Before being used again the acid balance of the regenerated Old ⁇ , sand is preferred checked. In particular, during a thermal Regene ⁇ turing can by-products contained in the sand, such as carbonates, can be converted into the corresponding oxides which then react alka ⁇ lisch and neutralize the binder as a catalyst added acid. Likewise, for example, in a mechanical regeneration, acid remain in the used sand, which should be taken into account in the preparation of the binder so as not to shorten the processing time of the molding material mixture.
- the refractory molding base should preferably be dry because the hardening reaction is slowed by water.
- the refractory molding base contains less than 1% by weight of water.
- the refractory base molding material should not be too warm.
- the refractory molding base should have a temperature in the range of 20 to 35 0 C. Possibly. the refractory molding material can be cooled or heated
- An acid is then applied to the free-flowing refractory to yield an acid-coated refractory base stock.
- the acid is applied by conventional methods to the refractory base molding material, for example, by the acid is sprayed onto the refractory base molding material.
- the Amount of acid is preferably selected in the range of 5 to 45 wt .-%, particularly preferably in the range of 20 to 30 wt .-%, based on the weight of the binder and calculated as the pure acid, ie without consideration of any solvent used , Unless the acid is already in liquid form and has a sufficiently low viscosity to be distributed in the form of a thin film on the grains of the refractory base molding material, the acid is dissolved in a suitable solvent.
- Exemplary solvents are water or alcohols or mixtures of water and alcohol.
- the solution when using water, the solution is, however, made as concentrated as possible in order to keep the introduced into the binder or the molding material amount of water as low as possible.
- the mixture of refractory base molding material and acid is well homogenized.
- An acid-curable binder is then applied to the acid-coated refractory base stock.
- the amount of the binder is preferably selected in the range of 0.25 to 5 wt .-%, particularly preferably in the range of 1 to 3 wt .-%, based on the refractory molding base material and calculated as the resin component.
- the acid-curable binder there may be used per se all binders which are ageable by acid, especially those acid-curable binders which are already customary for the production of molding compounds for the foundry industry.
- the binder may also contain other customary components, for example solvents for adjusting the viscosity or extenders which replace part of the crosslinkable resin.
- the binder is applied to the acid-coated refractory base stock and agitated by agitating the mixture Grains of refractory Formgr ⁇ ndstoffs distributed in the form of a thin film.
- the amounts of binder and acid are on the one hand a sufficient strength of the mold and on the other hand, ⁇ a sufficient processing time of the molding material mixture is achieved so selected. For example, a processing time in the range of 5 to 45 minutes is suitable.
- the binder-coated refractory molding base stock is then formed into a shaped article by conventional methods.
- the molding material mixture can be introduced into a suitable mold and compacted there.
- the resulting molded article is then allowed to cure.
- the catalyst used is a mixture of methanesulphonic acid and at least one further sulfur-free acid.
- the mixture both the resulting emissions during pouring of aromatic contaminants in particular BTX, and the emissions can be ver ⁇ Ringert of sulfur dioxide.
- the proportion of methanesulfonic acid having a high acid value is reduced, sufficient reactivity is achieved to cure the binder within a time suitable for industrial applications.
- any acid can be used per se, as long as it does not comprise sulfur-containing groups.
- Both inorganic and organic acids can be used, in which case a good reactivity of the binder system is achieved even in the case of organic acids, although such organic acids usually have a relatively low acid strength.
- the proportion of methanesulfuric acid in the acid used as a catalyst is dependent on the reactivity of the resin used in the binder, the at least one sulfur-free acid used in addition to the methanesulfonic acid and the amount of the acid used.
- the proportion of methanesulfonic acid in the acid used as catalyst is preferably less than 70% by weight, preferably less than 65% by weight, particularly preferably less chosen as 60% by weight and particularly preferably less than 55% by weight.
- the proportion of methanesulfonic acid in the acid used as the catalyst is preferably greater than 20 wt .-%, preferably greater than 30 wt .-%, more preferably greater than 35 wt .-% and particularly preferred greater than 40% by weight.
- the proportion of the sulfur-free acid is preferably selected to be greater than 30% by weight, preferably greater than 35% by weight, more preferably greater than 40% by weight, and particularly preferably greater than 45% by weight.
- an aromatic sulfonic acid may also be present in a small proportion in the acid used as the catalyst. This proportion is preferably less than 20% by weight, preferably less than 10% by weight and more preferably less than 5% by weight .-% chosen. Most preferably, no aromatic sulfonic acid is present in the acid used as a catalyst.
- Exemplary aromatic sulfonic acids are toluenesulfonic acid, benzenesulfonic acid and xylene sulfonic acid.
- the data relate to the anhydrous acids.
- any binder which can be cured by acid catalysis can be used per se in the process according to the invention.
- a furan no-bake binder or a phenol no-bake binder is preferably used as the acid-curable binder ,
- furan no-bake agent all furan resins can be used per se, as they are already used in furan-no-bake binder systems.
- the furan resins used in technical furan no-bake agents are usually precondensates or mixtures of furfuryl alcohol with other monomers or precondensates.
- the precondensates contained in Franan no-bake binders are prepared in a manner known per se.
- furfuryl alcohol is used in combination with urea and / or formaldehyde or urea / formaldehyde precondensates.
- Formaldehyde can be used both in monomeric form, for example in the form of a formal formula, and in the form of its polymers, such as trioxane or paraformaldehyde.
- formaldehyde other aldehydes or ketones can be used.
- Suitable aldehydes are, for example, acetaldehyde, propionaldehyde, butyraldehyde, acrolem, crotonaldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde, glyoxal and mixtures of these aldehydes.
- Formaldehyde is preferred, this being preferably used in the form of paraformaldehyde.
- ketones As ketone component, all ketones can be used which have a sufficiently high reactivity. Exemplary ketones are methyl ethyl ketone, methyl propyl ketone and acetone, with acetone being preferred.
- the said aldehydes and ketones can be used as a single compound but also in admixture with each other.
- the molar ratio of aldehyde, in particular formaldehyde, or ketone to furfuryl alcohol can be selected within wide ranges.
- 0.4 to 4 moles of furfuryl alcohol, preferably 0.5 to 2 moles of furfuryl alcohol, may be used per mole of aldehyde.
- furfuryl alcohol, formaldehyde and urea can be heated to boiling, for example, after adjusting the pH to more than 4.5, with water being continuously distilled off from the reaction mixture.
- the reaction time can be several hours, for example 2 hours. Under these reaction conditions occurs almost no polymerization of furfuryl alcohol. However, the furfuryl alcohol is condensed into a resin together with the formaldehyde and the urea.
- furfuryl alcohol, formaldehyde and urea are reacted at a pH of well below 4.5, for example at a pH of 2.0, in the heat, wherein the water formed in the condensation are distilled off under reduced pressure can.
- the reaction product has a relatively high viscosity and is diluted with furfuryl alcohol to produce the binder until the desired viscosity is achieved.
- phenol can be reacted under alkaline conditions, first with formaldehyde to a resole resin.
- This resol can then be treated with furfuryl alcohol or a furan group containing Resin reacted or mixed.
- furan phenomenonhalti- gen resins can be obtained for example moving to the above described Ver ⁇ .
- phenols for example resorcinol, cresols or bisphenol A.
- the proportion of phenol or higher phenols to the binder is preferably in the range of up to 45 wt .-%, preferably up to 20 wt .-%, more preferably selected up to 10 wt .-%. According to one embodiment, the proportion of phenol or higher phenols may be greater than 2 wt .-%, according to a further embodiment greater than 4 wt .-% can be selected.
- condensates of aldehydes and ketones which are then mixed with furfuryl alcohol to produce the binder.
- Such condensates can be prepared by reacting aldehydes and ketones under alkaline conditions.
- the aldehyde used is preferably formaldehyde, in particular in the form of paraformaldehyde.
- the ketone used is preferably acetone.
- the relative molar ratio of aldehyde to ketone is preferably selected in the range of 7: 1 to 1: 1, preferably 1.2: 1 to 3.0: 1.
- the condensation is preferably carried out under alkaline conditions at pH values in the range of 8 to 11.5, preferably 9 to 11.
- a suitable base is, for example, sodium carbonate.
- the amount of furfuryl alcohol contained in the furan-no-bake binder is determined by the endeavor to keep the proportion as low as possible for reasons of cost.
- an improvement in the strength of the casting mold is achieved by a high proportion of furfuryl alcohol.
- the proportion of furfuryl alcohol on Binder in the range of 30 to 95 wt .-%, preferably 50 to 90 wt .-%, particularly preferably 60 to 85 wt .-% selected.
- the proportion of urea and / or formaldehyde in the binder is preferably selected in the range of 2 to 70 wt .-%, preferably 5 to 45 wt .-%, particularly preferably 15 to 30 wt .-%.
- the proportions include both the unbound portions of these compounds contained in the binder and those bound in the resin.
- additives can be added to the furan resins, such as ethylene glycol or similar aliphatic polyols, for example, sugar alcohols, such as sorbitol, which serve as an extender and replace part of the furfuryl alcohol. Too high an addition of such extenders can lead to a reduction in the strength of the casting mold and lowering the reactivity in the unfavorable case.
- the proportion of these extenders in the binder is therefore preferably less than 25% by weight, preferably less than 15% by weight and more preferably less than 10% by weight.
- the proportion of diluents according to one embodiment is chosen to be greater than 5% by weight.
- the furan no-bake binders may further contain water.
- the proportion of water is preferably chosen as low as possible.
- the proportion of water in the binder is preferably less than 20% by weight, preferably less than 15% by weight. From an economic point of view, an amount of water of more than 5% by weight in the binder can be tolerated.
- Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and by Reaction of aldehydes and phenols in the molar ratio of 1: ⁇ 1, optionally in the presence of a catalyst, such as a basic catalyst, are available. They have a molecular weight M w of ⁇ 10,000 g / mol.
- phenolic resins For the preparation of phenolic resins, all conventionally used phenols are suitable. In addition to unsubstituted phenol, substituted phenols or mixtures thereof can be used. The phenolic compounds are unsubstituted either in both ortho positions or in an ortho and in the para position to allow polymerization. The remaining ring carbonators may be substituted. The choice of the substituent is not particularly limited, as long as the substituent does not adversely affect the polymerization of the phenol or aldehyde. Examples of substituted phenols are alkyl-substituted phenols, alkoxy-substituted phenols and aryl oxysubstituêt phenols.
- the abovementioned substituents have, for example, 1 to 26, preferably 1 to 15, carbon atoms.
- suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylene, 3,4-xylene, 3, 4, 5-trimethylphenol, 3-ethylphenol, 3, 5-diethylphenol, p-butylphenol, 3, 5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, 3, 5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3, 5-dimethoxyphenol and p-phenoxyphenol.
- phenol itself.
- high condensed phenols such as bisphenol A
- polyhydric phenols having more than one phenolic hydroxyl group are also suitable.
- Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups.
- suitable polyhydric phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, fluoroglycine, 2, 5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcm or 5-ethylresorcm.
- Mixtures of various mono- and polyhydric and / or substituted and / or condensed phenolic components can also be used for the preparation of the polyol component.
- phenols of the general formula I are phenols of the general formula I:
- A, B and C independently of one another from a hydrogen atom, a branched or unbranched alkyl radical, which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms, an aryl or alkylaryl radical, such as, for example, bisphenyls.
- a branched or unbranched alkyl radical which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms, an aryl or alkylaryl radical, such as, for example, bispheny
- Suitable aldehydes for the preparation of the phenolic resin component are the same aldehydes as are used in the preparation of the furan resin component in furan no-bake agents. According to one embodiment, aldehydes of the formula:
- R-CHO wherein R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
- R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
- Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde.
- formaldehyde either in its aqueous form, as para-formaldehyde or as a tnoxane.
- the molar ratio of aldehyde to phenol is preferably 1: 1.0 to 2.5: 1, more preferably 1.1: 1 to 2.2: 1, particularly preferably 1.2: 1 to 2.0: 1.
- sodium hydroxide, ammonia, sodium carbonate, calcium, magnesium and barium hydroxide or also tertiary amines can be used in the preparation of the resoles.
- the resoles can also be modified by further compounds, for example nitrogen-containing compounds, such as urea.
- the resoles are preferably mixed with furfuryl alcohol in the preparation of the binder.
- the binders may contain other customary additives, for example silanes as adhesion promoters.
- Suitable silanes are, for example, ammosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as ⁇ -hydroxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) -trimethoxysilane, N-ß- (ammoethyl) - ⁇ -arninopropyltnmethoxysilane.
- the binders may also contain activators which accelerate the curing of the binder.
- activators are, for example, resorcinol, bisphenol A. It is also possible to use mixtures which remain in the bottom during the distillation of resorcinol or bisphenol A. These mixtures contain oligomers of resorcinol or bisphenol A, for example dimers, trimers or polymers.
- polyols may also be added to the binder, such as polyether polyols or polyester polyols.
- Polyester polyols can be prepared, for example, by reaction of a dicarboxylic acid or a dicarboxylic acid anhydride with a glycol. Suitable dicarboxylic acids are, for example, adipic acid or oxalic acid.
- Suitable glycols are, for example, ethylene glycol, propylene glycol or diethylene glycol. The molecular weight of these compounds is preferably in the range of 300 to 800.
- Polyether polyols are commercially available. They can be prepared by reaction of an alkylene oxide with a glycol. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide or butylene oxide. Examples of suitable glycols are ethylene glycol, diethylene glycol and propylene glycol.
- solvents can also be present in the binder.
- a suitable solvent is, for example, water or alcohols, such as methanol or ethanol.
- the binder may also contain plasticizers, for example monoethylene glycol or diisobutyl phthalate.
- the molding material mixture may contain other customary constituents.
- exemplary further constituents are iron oxide, ground fibrous fibers, wood flour granules, ground coal or clay.
- Organic acids are preferably used as sulfur-free acids. Organic acids can easily be removed during the regeneration of old sand, so that they do not accumulate in the regenerated used sand. In a thermal regeneration, the organic acids decompose to harmless compounds, ultimately water and carbon dioxide, so that when using organic acids no special measures must be taken to clean, for example, the exhaust air during regeneration.
- Organic acids are compounds based on hydrocarbons which comprise at least one carboxyl group.
- the organic acids may also comprise further functional groups, for example hydroxyl groups, aldehyde groups or double bonds.
- the organic acids preferably comprise 1 to 10 carbon atoms, more preferably 2 to E carbon atoms.
- Saturated carboxylic acids are preferably used because they are readily accessible and have high stability, so that they can be stored for a long time without Qualitatsembu app.
- Sulfur-free acid used are preferably those organic acids which have a high acid strength.
- the organic acid preferably comprises at least one further electron-withdrawing group in addition to the at least one carboxyl group.
- the at least one further electron-withdrawing group is selected from the group of carboxyl group, hydroxy group, aldehyde group. Particular preference is given to using dicarboxylic acids, tricarboxylic acids or hydroxycarboxylic acids.
- the organic acid is selected from the group of citric acid, lactic acid, glycolic acid, glyoxylic acid, malic acid, oxalic acid. The acids can be used both individually and in admixture.
- the at least one further acid, in particular organic acid has a pK s value of less than 4.5, preferably less than 4.0.
- the at least one further acid, in particular organic acid has a pK s value of more than 1.0, according to a further embodiment a pK s value of more than 2.
- the acid is preferably added in the form of a solution.
- a solution As the solvent, water is preferably used. Since water, as already explained, slows down the curing of the molding material mixture, a concentrated solution of the acid is preferably used, the concentration of the acid in the solution preferably being chosen to be greater than 30% by weight.
- the temperature during the production and processing of the molding material mixture is preferably not too high.
- the curing of the shaped body produced from the molding material mixture should be as uniform as possible in order to achieve high strength.
- the hardening of the molded article at a temperature of less than 40 0 C preferably carried out in a temperature range of 15 to 30 0 C.
- a molding material mixture used which is particularly suitable for the production of large molds, these casting molds during casting a ver ⁇ reduced emission of defective compounds, especially BTX and sulfur compounds show.
- the invention therefore also relates to a molding material mixture for the production of casting molds, wherein the molding material mixture comprises at least
- a harder comprising a mixture of methanesulfonic acid and at least one further sulfur-free acid
- the invention relates to molds and cores, as obtained with the erfmdungsgespecializeden method, and their use for metal casting, in particular iron and steel casting.
- the mold was filled with 4.3 kg of liquid iron (casting temperature: 1400 ° C.), so that the weight ratio of the casting mold and liquid iron was about 1: 1.
- a defined partial flow was drawn off via a sampling probe and the substances contained in the partial flow were adsorbed on active carbon in accordance with the process according to DIN EN 14662-2.
- the qualitative and quantitative analysis of the adsorbed substances was carried out by gas chromatography.
- a partial flow was discharged from the exhaust gas and with a vacuum device m a Aspirated PE bag.
- the concentration of sulfur dioxide was determined by mass spectrometry.
- silica sand H32 (Quarzwerke Frechen) were to 3 kg per ⁇ first wells 0.4% of the curing agent shown in Table 5 and subsequent ⁇ hitd 1.0 wt .-% furfuryl alcohol Urea resin (Askuran EP 3576, Ashland-Südchemie-Kernfest GmbH, Hilden, DE).
- the mixture was prepared at room temperature (22 ° C.).
- the sand temperature was 21 0 C.
- the sand mixture was mixed for 1 minute each time intensive. Subsequently ⁇ ozod the molding mixture by hand was placed in the Prufriegelform and compacted with a hand drive.
- the molding material mixture in a mold 100 mm high and 100 mm diameter, compacted with a hand plate.
- the surface is checked at certain intervals with the surface hardener GF. If the test ball does not penetrate into the core surface, the demoulding time is given.
- the remaining remainder of the sand mixture after the bending core production is visually assessed for its flowability and its rolling behavior. If unrolling takes place in the same way, the sand processing time is over.
- test specimens were cuboidal test bars measuring 220 mm x 22.36 mm x 22.36 mm, known as Georg Fischer test bars.
- test bars were placed in a Georg Fischer Strength Tester equipped with a three-point bender (DISA-Industrie AG, Schaffhausen, CH) and the force was measured which resulted in the breakage of the test bars.
- the flexural strengths were measured according to the following scheme:
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- Mold Materials And Core Materials (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL09749648T PL2296836T3 (en) | 2008-05-23 | 2009-05-22 | Catalysts comprising methane sulfonic acid for the acid hardening method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008024727A DE102008024727A1 (en) | 2008-05-23 | 2008-05-23 | Methanesulfonic acid containing catalysts for the acid cure process |
PCT/EP2009/003643 WO2009141158A1 (en) | 2008-05-23 | 2009-05-22 | Catalysts comprising methane sulfonic acid for the acid hardening method |
Publications (2)
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EP2296836A1 true EP2296836A1 (en) | 2011-03-23 |
EP2296836B1 EP2296836B1 (en) | 2013-12-04 |
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EP09749648.3A Active EP2296836B1 (en) | 2008-05-23 | 2009-05-22 | Catalysts comprising methane sulfonic acid for the acid hardening method |
Country Status (13)
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US (1) | US8919421B2 (en) |
EP (1) | EP2296836B1 (en) |
JP (1) | JP5557293B2 (en) |
KR (1) | KR101643703B1 (en) |
CN (1) | CN102076440A (en) |
BR (1) | BRPI0912685B1 (en) |
DE (1) | DE102008024727A1 (en) |
EA (1) | EA021549B1 (en) |
MX (1) | MX2010012742A (en) |
PL (1) | PL2296836T3 (en) |
UA (1) | UA101502C2 (en) |
WO (1) | WO2009141158A1 (en) |
ZA (1) | ZA201008061B (en) |
Families Citing this family (15)
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JP5486293B2 (en) * | 2009-12-24 | 2014-05-07 | 花王株式会社 | Binder composition for mold making |
JP5913359B2 (en) * | 2010-12-16 | 2016-04-27 | ヒユツテネス−アルベルトス ヘーミッシエ ヴエルケ ゲーエムベーハー | Low-release cold-cure binder for foundry industry |
JP5986457B2 (en) | 2011-08-31 | 2016-09-06 | 花王株式会社 | Self-hardening binder composition for mold making |
DE202012013467U1 (en) * | 2012-02-09 | 2017-01-30 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Cold box binder systems and blends for use as additives to such binder systems |
JP6069047B2 (en) | 2012-04-27 | 2017-01-25 | 花王株式会社 | Hardener composition for mold making |
JP5355805B1 (en) | 2013-02-19 | 2013-11-27 | 伊藤忠セラテック株式会社 | Method for modifying refractory particles for mold, refractory particles for mold obtained thereby, and method for producing mold |
JP6277545B2 (en) * | 2014-02-13 | 2018-02-14 | 群栄化学工業株式会社 | Curing agent composition for acid curable resin |
CN103822803A (en) * | 2014-02-28 | 2014-05-28 | 湖北工业大学 | Sand casting tail gas acquisition device and method |
US10174183B2 (en) | 2015-03-09 | 2019-01-08 | Technology Research Association For Future Additive Manufacturing | Organic binder, granular material, three-dimensional lamination-shaped mold manufacturing apparatus, and three-dimensional lamination-shaped mold manufacturing method |
EP3260217A4 (en) | 2016-04-20 | 2018-08-29 | Technology Research Association for Future Additive Manufacturing | Granular material, method for manufacturing granular material, device for manufacturing mold by additive manufacturing, and method for manufacturing mold by additive manufacturing |
DE102017107658A1 (en) * | 2017-01-04 | 2018-07-05 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | A sizing composition for the foundry industry containing particulate amorphous silica and acid |
JP6892284B2 (en) * | 2017-02-28 | 2021-06-23 | ダイハツ工業株式会社 | Sand mold manufacturing method and casting sand |
DE102018100694A1 (en) * | 2018-01-12 | 2019-07-18 | Ask Chemicals Gmbh | Formaldehyde-reduced phenolic resin binder |
JP7168337B2 (en) * | 2018-03-29 | 2022-11-09 | 群栄化学工業株式会社 | Binder composition for mold making, sand composition for mold making, and method for producing mold |
JP7329388B2 (en) * | 2018-09-11 | 2023-08-18 | 花王株式会社 | Binder composition for mold making |
Family Cites Families (10)
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JPS5586642A (en) * | 1978-12-26 | 1980-06-30 | Dainippon Ink & Chem Inc | Composition for organic self-hardening mold |
JPS5772750A (en) * | 1980-10-27 | 1982-05-07 | Aisin Chem Co Ltd | Binder composition for mold |
US4478962A (en) | 1982-02-25 | 1984-10-23 | Cl Industries, Inc. | Binder compositions comprising furfuryl ester and furfuryl ester-furuyl alcohol combinations |
US5248707A (en) * | 1990-08-02 | 1993-09-28 | Borden, Inc. | Accelerators for refractory magnesia |
US5491180A (en) * | 1994-08-17 | 1996-02-13 | Kao Corporation | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
JPH09234540A (en) * | 1996-02-29 | 1997-09-09 | Elf Atochem Japan Kk | Binder coated sand grain for mold |
CN1251824C (en) * | 2001-05-14 | 2006-04-19 | 山东莱芜润达化工有限公司 | Casting film-covered sandy clay/phenolic resin nano compound, productive method nad use thereof |
DE10352796A1 (en) | 2003-11-12 | 2005-06-23 | Backers Maschinenbau Gmbh | Siebaggregat and Siebstern |
ITMI20032217A1 (en) | 2003-11-14 | 2005-05-15 | Cavenaghi Spa | BINDER SYSTEM FOR LOW DEVELOPMENTAL OF AROMATIC HYDROCARBONS |
US7211137B2 (en) * | 2004-10-15 | 2007-05-01 | Ashland Licensing And Intellectual Property Llc | Binder composition comprising condensed tannin and furfuryl alcohol and its uses |
-
2008
- 2008-05-23 DE DE102008024727A patent/DE102008024727A1/en not_active Withdrawn
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2009
- 2009-05-22 UA UAA201015488A patent/UA101502C2/en unknown
- 2009-05-22 EA EA201071344A patent/EA021549B1/en not_active IP Right Cessation
- 2009-05-22 KR KR1020107028541A patent/KR101643703B1/en active IP Right Grant
- 2009-05-22 MX MX2010012742A patent/MX2010012742A/en active IP Right Grant
- 2009-05-22 US US12/993,994 patent/US8919421B2/en not_active Expired - Fee Related
- 2009-05-22 JP JP2011509899A patent/JP5557293B2/en not_active Expired - Fee Related
- 2009-05-22 EP EP09749648.3A patent/EP2296836B1/en active Active
- 2009-05-22 CN CN2009801246237A patent/CN102076440A/en active Pending
- 2009-05-22 WO PCT/EP2009/003643 patent/WO2009141158A1/en active Application Filing
- 2009-05-22 PL PL09749648T patent/PL2296836T3/en unknown
- 2009-05-22 BR BRPI0912685-6A patent/BRPI0912685B1/en not_active IP Right Cessation
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US20110073269A1 (en) | 2011-03-31 |
DE102008024727A1 (en) | 2009-11-26 |
EA021549B1 (en) | 2015-07-30 |
BRPI0912685B1 (en) | 2018-01-16 |
KR20110010795A (en) | 2011-02-07 |
PL2296836T3 (en) | 2014-05-30 |
JP5557293B2 (en) | 2014-07-23 |
MX2010012742A (en) | 2010-12-21 |
UA101502C2 (en) | 2013-04-10 |
BRPI0912685A2 (en) | 2016-01-26 |
EA201071344A1 (en) | 2011-06-30 |
CN102076440A (en) | 2011-05-25 |
WO2009141158A1 (en) | 2009-11-26 |
US8919421B2 (en) | 2014-12-30 |
KR101643703B1 (en) | 2016-07-29 |
JP2011520615A (en) | 2011-07-21 |
EP2296836B1 (en) | 2013-12-04 |
ZA201008061B (en) | 2011-09-28 |
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