NO120157B - - Google Patents
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- Publication number
- NO120157B NO120157B NO16201966A NO16201966A NO120157B NO 120157 B NO120157 B NO 120157B NO 16201966 A NO16201966 A NO 16201966A NO 16201966 A NO16201966 A NO 16201966A NO 120157 B NO120157 B NO 120157B
- Authority
- NO
- Norway
- Prior art keywords
- oxidation
- reaction
- acid
- propylbenzene
- aromatic
- Prior art date
Links
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000007254 oxidation reaction Methods 0.000 claims description 42
- 230000003647 oxidation Effects 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 10
- 235000010233 benzoic acid Nutrition 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical group Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 5
- 239000000543 intermediate Substances 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000001649 bromium compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 51
- -1 aromatic carboxylic acids Chemical class 0.000 description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- 235000002867 manganese chloride Nutrition 0.000 description 5
- 229940099607 manganese chloride Drugs 0.000 description 5
- 239000011565 manganese chloride Substances 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- SZAIENRDRCMPRX-UHFFFAOYSA-N 1,2,3-trimethyl-4-propylbenzene Chemical compound CCCC1=CC=C(C)C(C)=C1C SZAIENRDRCMPRX-UHFFFAOYSA-N 0.000 description 3
- KKIGDGWHHNXWNM-UHFFFAOYSA-N 1,2,3-tripropylbenzene Chemical compound CCCC1=CC=CC(CCC)=C1CCC KKIGDGWHHNXWNM-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000005425 toluyl group Chemical group 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 2
- NWACCXJCJNDIDK-UHFFFAOYSA-N 1,2,3-tributylbenzene Chemical compound CCCCC1=CC=CC(CCCC)=C1CCCC NWACCXJCJNDIDK-UHFFFAOYSA-N 0.000 description 2
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- IRUSTUOJENXLMN-UHFFFAOYSA-N 1,2-dimethyl-3-propylbenzene Chemical compound CCCC1=CC=CC(C)=C1C IRUSTUOJENXLMN-UHFFFAOYSA-N 0.000 description 2
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 2
- IPLGMFMLGWZEMC-UHFFFAOYSA-N 1-butan-2-yl-2-propylbenzene Chemical compound C(C)(CC)C1=C(C=CC=C1)CCC IPLGMFMLGWZEMC-UHFFFAOYSA-N 0.000 description 2
- WKIFVFNHYMPFRE-UHFFFAOYSA-N 1-butyl-2-propylbenzene Chemical compound CCCCC1=CC=CC=C1CCC WKIFVFNHYMPFRE-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 2
- UHBIKXOBLZWFKM-UHFFFAOYSA-N 8-hydroxy-2-quinolinecarboxylic acid Chemical compound C1=CC=C(O)C2=NC(C(=O)O)=CC=C21 UHBIKXOBLZWFKM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 2
- CNIHNBMHZVGVGT-UHFFFAOYSA-N CCCC1=CC=C(CC)C(CC)=C1CC Chemical compound CCCC1=CC=C(CC)C(CC)=C1CC CNIHNBMHZVGVGT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004153 Potassium bromate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229940094037 potassium bromate Drugs 0.000 description 2
- 235000019396 potassium bromate Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- BRSVRMKLQUOMAQ-UHFFFAOYSA-N (3-ethyl-4-methylhexan-3-yl)benzene Chemical compound C(C)C(C1=CC=CC=C1)(C(C)CC)CC BRSVRMKLQUOMAQ-UHFFFAOYSA-N 0.000 description 1
- RQIPUTBJZIXELR-UHFFFAOYSA-N 1,2,3-tri(butan-2-yl)benzene Chemical compound CCC(C)C1=CC=CC(C(C)CC)=C1C(C)CC RQIPUTBJZIXELR-UHFFFAOYSA-N 0.000 description 1
- YFRXVFLZCASGSM-UHFFFAOYSA-N 1,2,3-tributyl-4-ethylbenzene Chemical compound C(CCC)C1=C(C(=C(C=C1)CC)CCCC)CCCC YFRXVFLZCASGSM-UHFFFAOYSA-N 0.000 description 1
- WQTZITWJFJFJFY-UHFFFAOYSA-N 1,2-di(butan-2-yl)benzene Chemical compound CCC(C)C1=CC=CC=C1C(C)CC WQTZITWJFJFJFY-UHFFFAOYSA-N 0.000 description 1
- HOHBTGYFYZCTPQ-UHFFFAOYSA-N 1,2-dibutyl-3-ethylbenzene Chemical compound CCCCC1=CC=CC(CC)=C1CCCC HOHBTGYFYZCTPQ-UHFFFAOYSA-N 0.000 description 1
- BQEVAYYEEDQNGG-UHFFFAOYSA-N 1,2-dibutyl-3-propylbenzene Chemical compound C(CCC)C=1C(=C(C=CC1)CCC)CCCC BQEVAYYEEDQNGG-UHFFFAOYSA-N 0.000 description 1
- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical compound CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-UHFFFAOYSA-N 0.000 description 1
- AOUYSKOCGPYYCZ-UHFFFAOYSA-N 1,2-diethyl-3-propylbenzene Chemical compound CCCC1=CC=CC(CC)=C1CC AOUYSKOCGPYYCZ-UHFFFAOYSA-N 0.000 description 1
- VPHBYBUYWBZLEX-UHFFFAOYSA-N 1,2-dipropylbenzene Chemical compound CCCC1=CC=CC=C1CCC VPHBYBUYWBZLEX-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- UYIMUYWOACTPDI-UHFFFAOYSA-N 1-butan-2-yl-2,3,4-trimethylbenzene Chemical compound CC1=C(C(=C(C=C1)C(C)CC)C)C UYIMUYWOACTPDI-UHFFFAOYSA-N 0.000 description 1
- YLGWPZFNZWSPDF-UHFFFAOYSA-N 1-butan-2-yl-2,3-diethylbenzene Chemical compound CCC(C)C1=CC=CC(CC)=C1CC YLGWPZFNZWSPDF-UHFFFAOYSA-N 0.000 description 1
- VAUOSVQRIKZEJF-UHFFFAOYSA-N 1-butan-2-yl-2,3-dimethylbenzene Chemical compound CCC(C)C1=CC=CC(C)=C1C VAUOSVQRIKZEJF-UHFFFAOYSA-N 0.000 description 1
- MLXMBIUVXPMUPK-UHFFFAOYSA-N 1-butan-2-yl-2-ethylbenzene Chemical compound CCC(C)C1=CC=CC=C1CC MLXMBIUVXPMUPK-UHFFFAOYSA-N 0.000 description 1
- AGNYWDNEEQTSFJ-UHFFFAOYSA-N 1-butyl-2,3,4-trimethylbenzene Chemical compound CCCCC1=CC=C(C)C(C)=C1C AGNYWDNEEQTSFJ-UHFFFAOYSA-N 0.000 description 1
- GGEAMKUCMNORPH-UHFFFAOYSA-N 1-butyl-2,3-diethylbenzene Chemical compound CCCCC1=CC=CC(CC)=C1CC GGEAMKUCMNORPH-UHFFFAOYSA-N 0.000 description 1
- YFRGOBSBDSYRNN-UHFFFAOYSA-N 1-butyl-2,3-dimethylbenzene Chemical compound CCCCC1=CC=CC(C)=C1C YFRGOBSBDSYRNN-UHFFFAOYSA-N 0.000 description 1
- RLZIHYLPZDHHBO-UHFFFAOYSA-N 1-butyl-2,3-dipropylbenzene Chemical compound CCCCC1=CC=CC(CCC)=C1CCC RLZIHYLPZDHHBO-UHFFFAOYSA-N 0.000 description 1
- BAMWORSGQSUNSC-UHFFFAOYSA-N 1-ethyl-2,3,4-trimethylbenzene Chemical compound CCC1=CC=C(C)C(C)=C1C BAMWORSGQSUNSC-UHFFFAOYSA-N 0.000 description 1
- OULLMTKIVBMNRQ-UHFFFAOYSA-N 1-ethyl-2,3-dipropylbenzene Chemical compound CCCC1=CC=CC(CC)=C1CCC OULLMTKIVBMNRQ-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- DMUVQFCRCMDZPW-UHFFFAOYSA-N 1-ethyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1CC DMUVQFCRCMDZPW-UHFFFAOYSA-N 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- QFNABHBYVSJWLO-UHFFFAOYSA-N 3,4,4a,5-tetrahydro-2h-naphthalen-1-one Chemical compound C1C=CC=C2C(=O)CCCC21 QFNABHBYVSJWLO-UHFFFAOYSA-N 0.000 description 1
- NGBBRIOWGVZNKE-UHFFFAOYSA-N 3-ethylhexan-3-ylbenzene Chemical compound CCCC(CC)(CC)C1=CC=CC=C1 NGBBRIOWGVZNKE-UHFFFAOYSA-N 0.000 description 1
- WLVNEALRNQEPMS-UHFFFAOYSA-N 3-ethylpentan-3-ylbenzene Chemical compound CCC(CC)(CC)C1=CC=CC=C1 WLVNEALRNQEPMS-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000013178 Rhus coriaria Nutrition 0.000 description 1
- 244000264648 Rhus coriaria Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FSMKWMUIGNZOKH-UHFFFAOYSA-O [N+](=O)([O-])[O-].[NH4+].[Nd] Chemical compound [N+](=O)([O-])[O-].[NH4+].[Nd] FSMKWMUIGNZOKH-UHFFFAOYSA-O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- SLVCCWGFGQVDMN-UHFFFAOYSA-N hexan-3-ylbenzene Chemical compound CCCC(CC)C1=CC=CC=C1 SLVCCWGFGQVDMN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B39/00—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00
- F04B39/10—Adaptations or arrangements of distribution members
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Applications Or Details Of Rotary Compressors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compressors, Vaccum Pumps And Other Relevant Systems (AREA)
Description
Fremgangsmåte for fremstilling av aromatiske di- eller poly-karboksylsyrer. Process for the production of aromatic di- or polycarboxylic acids.
Nærværende oppfinnelse vedrører fremstillingen av aromatiske di- eller poly-karboksylsyrer, som f. eks. tereftalsyre, The present invention relates to the production of aromatic di- or polycarboxylic acids, such as e.g. terephthalic acid,
isoftalsyre og ftalsyre, som ikke kan frem-bringes på enkelt måte ved oksydasjon i isophthalic acid and phthalic acid, which cannot be produced in a simple way by oxidation i
dampfase, ved oksydasjon av alkylsubstituerte aromatiske kullvannstoffer med luft vapor phase, by oxidation of alkyl-substituted aromatic hydrocarbons with air
og surstoffholdige gasser. and oxygen-containing gases.
Det er allerede gjort tallrike forslag Numerous proposals have already been made
for å fremstille aromatiske karboksylsyrer to produce aromatic carboxylic acids
ved oksydasjon i flytende fase av alkylsubstituerte aromatiske kullvannstoffer. by liquid-phase oxidation of alkyl-substituted aromatic hydrocarbons.
Imidlertid kunne det fastslås at en stor However, it could be determined that a large
forskjell består i om man oksyderer en the difference consists in whether one oxidizes one
enkelt alkylsubstituent i en aromatisk ring single alkyl substituent in an aromatic ring
for å fremstille en aromatisk mono-karboksylsyre, eller om man derpå oksyrerer to produce an aromatic monocarboxylic acid, or if one subsequently oxidises
ytterligere en eller flere alkylsubstituenter further one or more alkyl substituents
for å utvinne en di- eller poly-karboksylsyre. to recover a di- or poly-carboxylic acid.
For fremstilling av di- eller polykarboksylsyrer var det hittil nødvendig enten For the production of di- or polycarboxylic acids, it has hitherto been necessary either
å anvende strengere oksydasjonsbetingel-ser med oksyderende virkende kjemikalier to use stricter oxidation conditions with oxidizing chemicals
eller foreta oksydasjonen trinnvis, hvorved or carry out the oxidation step by step, whereby
gjenvinning og tilbakeføring av mellom-produktene og det ikke omsatte materiale recycling and return of the intermediate products and the unconverted material
såvel som fremstilling av bestemte mel-lomprodukter var nødvendig. En luftoksy-dasjon i flytende fase førte ikke frem på as well as the production of certain intermediate products was necessary. An air oxidation in the liquid phase did not lead to
grunn av de sterkt selektive oksydasjons-betingelser for å oksydere en annen eller due to the highly selective oxidation conditions for oxidizing another or
ytterligere alkylsubstituent med teknisk further alkyl substituent with technical
aksepterbare utbytter til en karboksylgruppe, når allerede en karboksylgruppe acceptable yields to a carboxyl group, when already a carboxyl group
var oppstått ved oksydasjon. Ble nemlig had arisen by oxidation. Stay because
oksydasjonsbetingelsene forsterket i den the oxidation conditions reinforced in it
grad som var tilstrekkelig for å oksydere degree that was sufficient to oxidize
den ytterligere alkylsubstituent, ble for det meste en ringspaltning iakttatt. Derfor ble oksydasjonen med luft nesten utelukkende anvendt til fremstilling av o-ftalsyre ved oksydasjon i dampfasen, fordi i dette tilfelle kan sluttproduktet på grunn av sin flyktighet fjernes fra oksydasjonsgassen allerede ved sin dannelse ved hjelp av reaksjonsgassene fra oksydasjonskatalysa-toren. the additional alkyl substituent, mostly a ring cleavage was observed. Therefore, the oxidation with air was almost exclusively used for the production of ophthalic acid by oxidation in the vapor phase, because in this case the end product can, due to its volatility, be removed from the oxidation gas already during its formation with the help of the reaction gases from the oxidation catalyst.
Luftoksydasjonen i flytende fase for fremstilling av aromatiske mono-karboksylsyrer er allerede flere ganger beskrevet i litteraturen. I denne forbindelse skal det henvises til U.S. patent nr. 2 245 528, i hvilket anvendelsen av en tungmetallkata-lysator for oksydasjon av alkylsubstituerte aromatiske kullvannstoffer med moleky-lært surstoff i flytende fase er beskrevet, hvorved fortrinnsvis et oppløsningsmiddel som eddiksyre skal anvendes. I det nevnte patentskrift beskrives oksydasjonen av toluol, etylbenzol og kumol til benzoesyre og oksydasjonsmellomprodukter. Videre nevnes oksydasjonen av xyloler til toluyl- og ftalsyrer. Utbyttet av ftalsyrer angis med 2 %, utbyttet av toluylsyrer dog med omtrent 50 %, hvorved resten består av tallrike andre oksydasjonsprodukter. The air oxidation in the liquid phase for the production of aromatic monocarboxylic acids has already been described several times in the literature. In this connection, reference should be made to the U.S. patent no. 2 245 528, in which the use of a heavy metal catalyst for the oxidation of alkyl-substituted aromatic hydrocarbons with molecular oxygen in the liquid phase is described, whereby preferably a solvent such as acetic acid is to be used. In the aforementioned patent, the oxidation of toluene, ethylbenzene and cumene to benzoic acid and oxidation intermediates is described. The oxidation of xylenes to toluyl and phthalic acids is also mentioned. The yield of phthalic acids is stated at 2%, the yield of toluyl acids however at approximately 50%, whereby the rest consists of numerous other oxidation products.
U.S. patent nr. 2 276 774 vedrører en forbedring av fremgangsmåten i det først omtalte patent, idet man fant at ved anvendelse av et stålreaksjonskar som inneholder krom for unngåelse av en korrosjon forminskes såvel utbyttene som også oksy-dasjonshastigheten ved fremstilling av benzoesyre fra toluol under anvendelse av en koboltkatalysator. Forbedringen består nu i i tillegg til koboltkatalysatoren å anvende et i eddiksyre oppløselig salt av bly eller barium, fortrinnsvis bly- eller barium-acetat, for å motvirke den hemmende virk-ning av det kromholdige stål og derved øke utbyttet. På denne måte lykkedes det ved oksydasjon av toluol til benzoesyre å oppnå omdannelsesutbytter på ca. 35—50 %. Videre nevnes i U.S. patent nr. 2 276 774 oksydasjonen av etylbenzol til acetofenon og benzoesyre og oksydasjonen av en van-lig blanding av xyloler til toluylsyrer. U.S. patent no. 2 276 774 relates to an improvement of the method in the first mentioned patent, as it was found that when using a steel reaction vessel containing chromium to avoid corrosion, both the yields and the oxidation rate in the production of benzoic acid from toluene are reduced using of a cobalt catalyst. The improvement now consists in, in addition to the cobalt catalyst, using an acetic acid-soluble salt of lead or barium, preferably lead or barium acetate, to counteract the inhibiting effect of the chrome-containing steel and thereby increase the yield. In this way, by oxidizing toluene to benzoic acid, it was possible to achieve conversion yields of approx. 35-50%. Furthermore, mention is made in the U.S. patent no. 2 276 774 the oxidation of ethylbenzene to acetophenone and benzoic acid and the oxidation of a common mixture of xylenes to toluyl acids.
Endelig angir U.S. patent nr. 2 479 067 igjen en forbedring av den førstnevnte metode. I spalte 1 i dette patent beskrives manglene ved den tidligere fremgangsmåte med henblikk på dens lave utbytter av di-karboksylsyrer. Dette litteratursted anbe-faler anvendelsen av en blyacetatholdig katalysator i eddiksyre for oksydasjon av p-toluylsyre med luft for å øke utbyttet av tereftalsyre. Den ved eksempler beskrevne omdannelse er dog bare ca. 21,3 %. Finally, the U.S. states patent no. 2 479 067 again an improvement of the first-mentioned method. In column 1 of this patent, the shortcomings of the previous method are described with regard to its low yields of dicarboxylic acids. This reference recommends the use of a lead acetate-containing catalyst in acetic acid for the oxidation of p-toluic acid with air to increase the yield of terephthalic acid. The transformation described by examples is, however, only approx. 21.3%.
Samtlige hittil nevnte litteratursteder kan være egnet for utvinning av mono-karboksylsyrer. Men inntil nu er ingen for-skrift eller annen publikasjon kjent som angir betingelsene for fremstilling av di-eller poly-karboksylsyrer lette å gjennom-føre i praksis og med teknisk aksepterbare utbytter. Tross det større antall tidligere publikasjoner som beskriver fremgangsmåter for forbedring av utbyttene, f. eks. av tereftalsyre ved oksydasjon av alkylsubstituerte aromatiske kullvannstoffer mangler det brukbare metoder for å øke de hittil erholdte utbytter vesentlig. Ofte måtte ved de hittil beskrevne fremgangsmåter sær-lige betingelser opprettholdes ved gjen-nemføringen av oksydasjonsreaksjonen, eller det var nødveiidig med et ytterligere nærvær av fra 15 til 95 deler av en substituert benzoesyre. En ytterligere ulempe ved de hittil publiserte forslag besto i at angivelsene for gjennemføring av fremgangsmåten var holdt så generelt at fag-mannen først ved omstendelige egne un-dersøkelser måtte fastslå på hvilken måte de gunstigste resultater oppnås. All literature sources mentioned so far can be suitable for the extraction of monocarboxylic acids. But until now, no regulation or other publication is known which states the conditions for the production of di- or polycarboxylic acids that are easy to carry out in practice and with technically acceptable yields. Despite the greater number of previous publications describing methods for improving yields, e.g. of terephthalic acid by oxidation of alkyl-substituted aromatic hydrocarbons, there is a lack of usable methods to significantly increase the yields obtained so far. Often, in the methods described so far, special conditions had to be maintained when carrying out the oxidation reaction, or the additional presence of from 15 to 95 parts of a substituted benzoic acid was necessary. A further disadvantage of the proposals published so far consisted in the fact that the instructions for carrying out the method were kept so general that the person skilled in the art first had to determine by extensive own investigations in which way the most favorable results are achieved.
Foreliggende oppfinnelse fjerner disse mangler, og fremfor alt oppnås vesentlig høyere utbytter. Videre er det ikke nød-vendig å tilsette reaksjonsblandingen substituerte benzoesyrer, men ved forskriftene etter nærværende oppfinnelse kommer man på enkelt måte frem til en fullstendig oksydasjon av de innførte utgangsstoffer til de tilsvarende karboksylsyrer i høye utbytter. The present invention removes these shortcomings, and above all significantly higher yields are achieved. Furthermore, it is not necessary to add substituted benzoic acids to the reaction mixture, but with the regulations according to the present invention, a complete oxidation of the introduced starting materials to the corresponding carboxylic acids in high yields is achieved in a simple way.
Oppfinnelsen vedrører en fremgangsmåte for fremstilling av aromatiske di- eller The invention relates to a method for producing aromatic di- or
poly-karboksylsyrer ved oksydasjon av aromatiske kullvannstoffer, som kan være substituert med minst to alkylgrupper med 1—4 kullstoffatomer og som eventuelt kan være substituert med et halogenatom, såvel som deres oksydasjonsmellemproduk-ter med surstoff i flytende fase i nærvær av tungmetalloksydasjonskatalysatorer ved forhøyet temperatur og eventuelt under forhøyet trykk, såvel som i nærvær av et organisk oppløsningsmiddel, og karakter-istisk er at man som katalysator anvender ett eller flere tungmetallbromider eller en blanding av ett eller flere tungmetallsalter og en uorganisk eller organisk forbindelse som avgir et bromion. polycarboxylic acids by oxidation of aromatic hydrocarbons, which may be substituted with at least two alkyl groups with 1-4 carbon atoms and which may optionally be substituted with a halogen atom, as well as their oxidation intermediates with oxygen in the liquid phase in the presence of heavy metal oxidation catalysts at elevated temperature and optionally under elevated pressure, as well as in the presence of an organic solvent, and it is characteristic that one or more heavy metal bromides or a mixture of one or more heavy metal salts and an inorganic or organic compound which emits a bromine ion is used as a catalyst.
Metaller av gruppen tunge metaller vist i «Periodic Chart of Elements» på si-dene 56 og 57 i «Handbook of Chemistry», 8th Edition, utgitt av Handbook Publishers, Inc., Sandusky, Ohio, 1952, er blitt funnet spesielt anvendelige som metallet eller me-tallionet i metall-bromkatalysatoren. Av tungmetallgruppen er de metaller som har et atomnummer ikke høyere enn 84 blitt funnet å være mest egnet. Det er fastslått at utmerkede resultater oppnås ved bruk av et metall som har et atomnummer 23— 28 inkl. Særlig fremragende resultater oppnås spesielt ved fremstillingen av poly-basiske syrer med et metall fra gruppen bestående av mangan, kobolt, nikkel, krom, vanadium, molybden, gadolinium, wolfram, tinn og cerium. Metals of the heavy metal group shown in the "Periodic Chart of Elements" on pages 56 and 57 of the "Handbook of Chemistry", 8th Edition, published by Handbook Publishers, Inc., Sandusky, Ohio, 1952, have been found particularly useful as the metal or metal ion in the metal-bromine catalyst. Of the heavy metal group, those metals having an atomic number no higher than 84 have been found to be most suitable. It has been established that excellent results are obtained by using a metal having an atomic number of 23-28 inclusive. Particularly excellent results are obtained especially in the production of polybasic acids with a metal from the group consisting of manganese, cobalt, nickel, chromium, vanadium, molybdenum, gadolinium, tungsten, tin and cerium.
Det er også blitt funnet at katalysatoren kan være et enkelt metall eller en kombinasjon av metaller. Metallet kan tilsettes i elementær, bundet eller ionisk form og bromet kan tilsettes på lignende måte i elementær, bundet eller ionisk form. Som kilde for ionisk brom kan ammoniumbromid eller andre bromforbindelser som er oppløselige i reaksjonsmediet anvendes. Tilfredsstillende resultater er blitt oppnådd, f. eks. med kaliumbromat, tetrabrometan og benzylbromid. It has also been found that the catalyst can be a single metal or a combination of metals. The metal can be added in elemental, bound or ionic form and the bromine can be added similarly in elemental, bound or ionic form. As a source of ionic bromine, ammonium bromide or other bromine compounds which are soluble in the reaction medium can be used. Satisfactory results have been achieved, e.g. with potassium bromate, tetrabromoethane and benzyl bromide.
Metallet kan tilføres i form av metall-salter. F. eks. metallet mangan kan tilsettes som mangansaltet av en lavere alifatisk karboksylsyre, som manganacetat, i form av et organisk kompleks, av hvilke skal nevnes acetylacetonat, 8-hydroksy-kinolinat og etylendiamintetra-acetat, såvel som andre oppløselige mangansalter som boratene, halogenidene og nitratene som også er effektive. The metal can be supplied in the form of metal salts. For example the metal manganese can be added as the manganese salt of a lower aliphatic carboxylic acid, such as manganese acetate, in the form of an organic complex, of which mention should be made of acetylacetonate, 8-hydroxyquinolinate and ethylenediaminetetraacetate, as well as other soluble manganese salts such as the borates, halides and nitrates which are also effective.
Reaksjonstemperaturen skal være tilstrekkelig høy, slik at den ønskede oksyda-sjonsreaksjon inntrer, og dog ikke så høy at uønsket forkulling eller dannelse av tjære finner sted. Således kan temperatu-rene ligge i området 120 til 275° C, helst mellom 150 til 250° C, og fortrinnsvis mellom 170 og 225° C under bruk av luft. Lavere temperaturer fra ca. 50° C kan brukes når rent surstoff eller surstoffanriket luft anvendes. Reaksjonstiden skal være tilstrekkelig for å oppnå ønsket omdannelse av det substituerte aromatiske materiale til den ønskede aromatiske karboksyfor-bindelse, f. eks. innenfor området 0,5 til 25 eller mer ved satsvis behandling og fortrinnsvis mindre ved kontinuerlig behandling. The reaction temperature must be sufficiently high, so that the desired oxidation reaction occurs, but not so high that unwanted charring or formation of tar takes place. Thus, the temperatures can lie in the range 120 to 275° C, preferably between 150 to 250° C, and preferably between 170 and 225° C using air. Lower temperatures from approx. 50° C can be used when pure oxygen or oxygen-enriched air is used. The reaction time must be sufficient to achieve the desired conversion of the substituted aromatic material into the desired aromatic carboxy compound, e.g. within the range of 0.5 to 25 or more in case of batch treatment and preferably less in case of continuous treatment.
Det anvendte surstoff kan foreligge i form av i det vesentlige 100 % surstoffgass eller i form av gassformede blandinger inneholdende lavere konsentrasjoner av surstoff, som f. eks. luft. Mengden av totalt surstoff matet inn i reaksjonsblandingen i forhold til kullvannstoffet ligger i området ca. 2 til 500 mol surstoff pr. mol substituert, aromatisk materiale, og vanligvis i området fra 2 til 300 mol, og fortrinnsvis i området fra 2 til 75 mol. The oxygen used can be in the form of essentially 100% oxygen gas or in the form of gaseous mixtures containing lower concentrations of oxygen, such as e.g. air. The amount of total oxygen fed into the reaction mixture in relation to the coal hydrogen is in the range of approx. 2 to 500 mol of oxygen per moles of substituted, aromatic material, and usually in the range from 2 to 300 moles, and preferably in the range from 2 to 75 moles.
Fremgangsmåten etter nærværende oppfinnelse kan utføres i det vesentlige i flytende fase, idet en flytende fase opprettholdes i reaksjonssonen. På denne måte fordampes det innmatede ikke vesentlig. Forholdet mellom temperatur og trykk skal reguleres slik at en flytende fase frem-skaffes i reaksjonssonen. Vanligvis vil trykket være i området fra atmosfæretrykk opp til ca. 105 kg/cm-. Den flytende fase kan inneholde alt eller en del av den organiske reaksjonsdeltager, eller den kan omfatte et reaksjonsmedium, i hvilket den organiske reaksjonsdeltager er oppløselig eller sus-pendert. The method according to the present invention can be carried out essentially in liquid phase, a liquid phase being maintained in the reaction zone. In this way, the feed does not evaporate significantly. The relationship between temperature and pressure must be regulated so that a liquid phase is produced in the reaction zone. Usually the pressure will be in the range from atmospheric pressure up to approx. 105 kg/cm-. The liquid phase can contain all or part of the organic reaction participant, or it can comprise a reaction medium in which the organic reaction participant is soluble or suspended.
Når betingelsene er slike at det ønskede karboksyaromatiske produkt kan oppnås og lett skilles fra reaksjonsblandingen i fravær av ytterligere reaksjonsmedium, er slik tilsatt medium ikke nødvendig. Hvor alle slike betingelser imidlertid ikke kan oppnås eller hvor nærværet av et ytterligere reaksjonsmedium er ønsket for å lette utførelsen av den ønskede reaksjon eller utvinnelsen av det ønskede produkt eller produkter, kan et tilsatt medium inklude-res. Dette tilleggsmedium kan være, og er ofte, en mono-karboksylsyre som er relativt stabil eller inert overfor oksydasjon i reaksjonssystemet og inneholder fortrinnsvis ca. 1 til 8 kullstoffatomer i molekylet. Mettede, alifatiske syrer inneholdende 2 til 4 kullstoffatomer i molekylet og fritt for vannstoffatomer bundet til tertiære kullstoffatomer og benzoesyre er spesielt fore-trukne. Hvor alle fordeler ved et surt medium ikke er nødvendig, kan andre inerte media brukes. When the conditions are such that the desired carboxyaromatic product can be obtained and easily separated from the reaction mixture in the absence of additional reaction medium, such added medium is not necessary. However, where all such conditions cannot be achieved or where the presence of an additional reaction medium is desired to facilitate the performance of the desired reaction or the recovery of the desired product or products, an added medium may be included. This additional medium can be, and often is, a monocarboxylic acid which is relatively stable or inert to oxidation in the reaction system and preferably contains approx. 1 to 8 carbon atoms in the molecule. Saturated, aliphatic acids containing 2 to 4 carbon atoms in the molecule and free of hydrogen atoms bound to tertiary carbon atoms and benzoic acid are particularly preferred. Where all the advantages of an acidic medium are not required, other inert media can be used.
Hvor det lavere alifatiske mono-kar-boksylsyremedium brukes, er det vanligvis ikke nødvendig å bruke store mengder av det. Slike syrer i mengder på 0,1 til 10 vektdeler, særlig 0,5 til 4, og fortrinnsvis 1 til 2,5 pr. del aromatisk materiale, er blitt funnet å være tilstrekkelig. Where the lower aliphatic monocarboxylic acid medium is used, it is usually not necessary to use large amounts of it. Such acids in amounts of 0.1 to 10 parts by weight, especially 0.5 to 4, and preferably 1 to 2.5 per part aromatic material, has been found to be sufficient.
Katalysatoren kan f. eks. være manganbromid, og den kan tilsettes som sådan eller ved hjelp av materialer som gir en katalytisk mengde av mangan og av brom i reaksjonssystemet. Mangan kan tilsettes i form av metallet, oksydet eller acetatet eller analoge karboksylsalter, inkludert et salt av en karboksylsyre som kan dannes i reaksjonssystemet eller som et mangan-halogenid; og bromet kan, som foran angitt, tilsettes i form av elementært brom, som ammoniumbromid eller andre bromforbindelser oppløselige i systemet, f. eks. kaliumbromat. Hvis ønsket, kan bromet foreligge i form av et oppløselig, organisk bromid, nemlig tetrabrometan, benzylbromid o. 1. The catalyst can e.g. be manganese bromide, and it can be added as such or by means of materials which provide a catalytic amount of manganese and of bromine in the reaction system. Manganese may be added in the form of the metal, oxide or acetate or analogous carboxylic salts, including a salt of a carboxylic acid which may be formed in the reaction system or as a manganese halide; and the bromine can, as indicated above, be added in the form of elemental bromine, such as ammonium bromide or other bromine compounds soluble in the system, e.g. potassium bromate. If desired, the bromine can be present in the form of a soluble, organic bromide, namely tetrabromoethane, benzyl bromide, etc. 1.
Det er ønskelig at bromet ikke er sta-bilt bundet i den organiske forbindelse, f. eks. som brombenzol. Mengden av katalysatoren beregnet som MnBr, kan ligge i It is desirable that the bromine is not stably bound in the organic compound, e.g. such as bromobenzene. The amount of the catalyst, calculated as MnBr, can lie in
området ca. 0,1 til 10 vektprosent eller mer area approx. 0.1 to 10% by weight or more
av tilsatt aromatisk reaksjonsdeltager, of added aromatic reactant,
særlig 0,3 til 2, fortrinnsvis 0,5 til 1,7 %. in particular 0.3 to 2, preferably 0.5 to 1.7%.
Blandinger av materialer kan brukes, og Mixtures of materials can be used, and
mengdene av mangan og brom kan varie-res fra deres støkiometriske forhold beregnet som MnBr2, f. eks. i mengder fra 1 til 20 atomer mangan pr. atom brom, og ca. 1 til 10 atomer brom pr. atom mangan. Dessuten the amounts of manganese and bromine can be varied from their stoichiometric ratio calculated as MnBr2, e.g. in amounts from 1 to 20 atoms of manganese per bromine atom, and approx. 1 to 10 atoms of bromine per atom of manganese. Furthermore
kan mangan som angitt ovenfor brukes i form av et organisk kompleks f. eks. som acetylacetonat, 8-hydroksy-kinolinat og etylendiamintetre-acetat av mangan. can manganese as indicated above be used in the form of an organic complex, e.g. such as acetylacetonate, 8-hydroxyquinolinate and ethylene diamine triacetate of manganese.
For ytterligere å beskrive oppfinnelsen henvises til de i eksemplene spesielt beskrevne utførelsesf ormer: To further describe the invention, reference is made to the embodiments specifically described in the examples:
Eksempel 1: Example 1:
I et egnet reaksjonskar som har korrosjonsbestandig indre overflate (f. eks. glass, keramikk, korrosjonsbestandig metall eller legering), utstyrt med røremidler som en mekanisk omrøringsanordning og/eller midler for å påvirke gasstrømmen, og med midler for oppvarmning eller kjøling av innholdet som en slynge eller kappe (og fortrinnsvis en tilbakeløpskjøler utstyrt med en spesiell anordning for å skille fra vann og føre tilbake ikke-vandig konden-sat til reaksjonskaret, et gassinnlednings-rør og et utløp for å slippe ut lavt-kokende materialer), tilsattes: In a suitable reaction vessel having a corrosion-resistant inner surface (e.g. glass, ceramic, corrosion-resistant metal or alloy), equipped with stirring means such as a mechanical stirring device and/or means to affect the gas flow, and with means for heating or cooling the contents which a loop or jacket (and preferably a reflux condenser equipped with a special device to separate from water and return non-aqueous condensate to the reaction vessel, a gas inlet pipe and an outlet to discharge low-boiling materials), is added:
48,8 vektdeler xylol (95 % para) 48.8 parts by weight xylol (95% para)
125 » » eddiksyre (100 %) 125 » » acetic acid (100%)
0,6 » » manganacetat 0,5 » » ammoniumbromid Reaksjonskaret er omtrent halvfullt av den flytende blanding. 0.6 » » manganese acetate 0.5 » » ammonium bromide The reaction vessel is approximately half full of the liquid mixture.
Luft mates inn i reaksjonsblandingen i en mengde på 3000 volum/time/volum av reaksjonsblandingen '(målt ved reaksjons-karets utløp ved atmosfæretrykk og ca. 27° C), mens reaksjonsblandingen holdes ved 195° C under kraftig omrøring i to timer; og trykket holdes på ca. 14—30 kg/ cm<2>. Dette trykk er slik at reaksjonsblandingen inneholder en flytende fase inneholdende eddiksyre. Air is fed into the reaction mixture in an amount of 3000 volumes/hour/volume of the reaction mixture (measured at the outlet of the reaction vessel at atmospheric pressure and about 27° C), while the reaction mixture is kept at 195° C under vigorous stirring for two hours; and the pressure is kept at approx. 14-30 kg/cm<2>. This pressure is such that the reaction mixture contains a liquid phase containing acetic acid.
Den rå, faste tereftalsyre i blandingen kan skilles fra ved filtrering, vaskes tre. ganger med ca. 100 % eddiksyre, og hver vasking utføres med ca. 100 vektdeler ed-: diksyre pr. 40 deler bunnfelling og vaskes; derpå tre ganger med vann under bruk av tilnærmet samme mengder. Eddigsyrevæs-kene destilleres, og residuet kan føres tilbake til reaksjonskaret eller kan behandles for å utvinne en blanding av aromatiske syrer fra det. Utløpsgassene fra reaksjonskaret føres gjennom to tørriskjølere i serie, og væsken som blir oppsamlet i disse under reaksjonen vaskes med ca. 2 volumdeler vann for å fjerne vannoppløselige materialer, og en liten mengde ureagert xylol gjen- i vinnes. i The crude, solid terephthalic acid in the mixture can be separated by filtration, washed three. times by approx. 100% acetic acid, and each wash is carried out with approx. 100 parts by weight of acetic acid per 40 parts sediment and wash; then three times with water using approximately the same quantities. The acetic acid liquids are distilled, and the residue can be returned to the reaction vessel or can be treated to extract a mixture of aromatic acids from it. The outlet gases from the reaction vessel are passed through two dry ice coolers in series, and the liquid that is collected in these during the reaction is washed with approx. 2 parts by volume of water to remove water-soluble materials, and a small amount of unreacted xylol is recovered. in
Et lysfarvet tereftalsyreprodukt oppnås med et vektutbytte på ca. 1.18 % i(75 % av teoretisk utbytte).. Lignende xesultater oppnås med mangan eller koboltbromid som katalysator. Med manganklorid malene oppnås imidlertid bare ca..25—30 vektprosent utbytte (en fire til fem gangers differanse) under sammenlignbare betingelser. Resultatene oppnådd med mangan-fluorid, acetat eller jodid, eller ammoniumbromid (dvs. bromvannstoff i et surt sy-stem) uten et metall, er mindre gunstige enn med manganklorid. A light colored terephthalic acid product is obtained with a weight yield of approx. 1.18% in (75% of theoretical yield).. Similar results are obtained with manganese or cobalt bromide as catalyst. With the manganese chloride templates, however, only approx. 25-30 weight percent yield (a four to five-fold difference) is achieved under comparable conditions. The results obtained with manganese fluoride, acetate or iodide, or ammonium bromide (ie, hydrogen bromide in an acidic system) without a metal, are less favorable than with manganese chloride.
Eksempel 2: Example 2:
Forannevnte eksempel gjentas under The aforementioned example is repeated below
bruk av: use of:
125 deler para-cymol 125 » eddiksyre 125 parts para-cymol 125 » acetic acid
1,2 » .manganacetat 0,95 » ammoniumbromid 1.2 » .manganese acetate 0.95 » ammonium bromide
og et tereftalsyreutbytte på 58,6 % av teoretisk utbytte oppnås, hvilket tilsvarer 73 % vektutbytte. Med manganbromid oppnås lignende resultater'(73 vektprosent utbytte). I et lignende forsøk under bruk av bare to deler manganacetat som katalysator var utbyttet imidlertid ikke over 7 vektprosent (10 gangers differanse), og under bruk av manganklorid var det enda lavere. and a terephthalic acid yield of 58.6% of theoretical yield is obtained, which corresponds to 73% weight yield. Similar results are obtained with manganese bromide (73% yield by weight). In a similar experiment using only two parts of manganese acetate as catalyst, the yield was, however, no more than 7 percent by weight (a 10-fold difference), and when using manganese chloride it was even lower.
Under bruk av nedenfor angitte kullvannstoffer som utgangsmateriale og katalysatoren i eksempel 2, oppnåddes de angitte produkter i sammenlignbare utbytter: Using the coal hydrosubstances specified below as starting material and the catalyst in Example 2, the specified products were obtained in comparable yields:
Eksempel 21 : Example 21 :
De markerte forskjeller mellom :manganbromid og manganklorid som katalysator iakttas ved oksydasjonen av f. eks. slike kullvannstoffer som p-xyol og p-diiso-propyl-benzol. Sammenlignbare og repro-duserbare forsøk gir da utbytter som er an- ■ gitt nedenfor: The marked differences between manganese bromide and manganese chloride as a catalyst are observed in the oxidation of e.g. such hydrocarbons as p-xyol and p-diiso-propyl-benzene. Comparable and reproducible experiments then yield yields that are ■ stated below:
I forsøk som er sammenlignbare med eksemplene 3—20, bortsett fra bruk av manganklorid som katalysator, oppnås be-traktelig lavere utbytter av de respektive syrer i hvert tilfelle. In experiments comparable to examples 3-20, apart from the use of manganese chloride as catalyst, considerably lower yields of the respective acids are obtained in each case.
Eksempel 22: Example 22:
En prosess utføres i et apparat .som, i kombinasjon har et korrosjonsbestandig trykkoksydasjonskar og en vannkjølt kondensator montert over reaksjonskaret. Re-•åksjonsdelen er omviklet med et nikron-'.bånd opp til en høyde av ca. y3. Når oksy-vdasjonen er i gang, innføres luft under :trykk til reaksjonskaret gjennom en gass-ifordeler anbragt like over bunnen, og den •øvre ende av kondensatoren er lukket. Av-•gassutløp finner sted gjennem et rør på toppen av kondensatoren og passerer gjennom -en nålkontrollventil; >en kvikksølv-gassmåler for innløp og en tørrisutskiller <er anbragt foran utløpet. Reaksjonskaret •beskikkes ved å tilsette avveide mengder av hver reaksjonsdeltager gjennom toppen av kondensatoren, som derpå lukkes, og; .trykket av .reaksjonskaret økes til ca. 30' kg/cm-' med luft. Derpå beskikkes reak- l sjonskaret med 7.5 deler 95 % p-xylol, 150 deler eddiksyre, en del manganacetattetra-hydrait og 0,75 deler ammoniumbromid. Trykket holdes ved 30 kg/cm-, og reaksjonssonen oppvarmes til 195° C. Utløps-kontroll ventilen reguleres slik at strøm-ningshastigheten av .gass gjennom utløps-gassmåleren er 3000 volumdeler/time/ volum av reaksjonsblandingen. Når temperaturen når 195° C, stoppes den ytre oppvarmning og temperaturen øker på grunn av den eksoterme reaksjon. Etter •den .begynnende reaksjon tilføres ytre varme for å opprettholde en reaksjons-temperatur :på 195—200° C for ialt 1,5 timer..Etter fullendelse av reaksjonen, som vist ved 20—21 % surstoffinnhold for ut-løpsgassen ;(Orsat gassanalyse), får reaksjonskaret avkjøle til ca. 85° C og trykket senkes. De -flytende jprodukter fjernes ved 150—:200° C ved å påføre trykkutjevning fra en kvelstof f sylinder gjennom kondensatoren. Reaksjonsvæsken tappes ut ved å åpne en forbindelse i lufttilførselslednin-gen. Bunnflensen fjernes, og det faste produkt skrapes ut fra reaksj onskaret. De faste og flytende produkter forenes og filtreres. Det uoppløselige tereftalsyreresiduum vaskes to ganger med 75 deler varm eddiksyre og tørres. Et vektutbytte på 115 % tereftalsyre oppnås (syretall 672, teoretisk •6.75). , I et kontrollforsøk med paraxylol og ;en gitt mengde metallbromid under hruk av en .blanding av >mangan og koboltbro-.mid i like deler, er utbyttet tereftalsyre ca. 12 vektprosent eller litt høyere enn når det A process is carried out in an apparatus which, in combination, has a corrosion-resistant pressure oxidation vessel and a water-cooled condenser mounted above the reaction vessel. The reaction part is wrapped with a nicron band up to a height of approx. y3. When the oxidation is underway, air is introduced under pressure to the reaction vessel through a gas distributor placed just above the bottom, and the •upper end of the condenser is closed. Off-•gas outlet takes place through a pipe on top of the condenser and passes through -a needle check valve; >a mercury gas meter for inlet and a dry ice separator <is placed in front of the outlet. The reaction vessel •is equipped by adding weighed quantities of each reaction participant through the top of the condenser, which is then closed, and; The pressure of the reaction vessel is increased to approx. 30' kg/cm-' with air. Then the reac- l reaction vessel with 7.5 parts 95% p-xylene, 150 parts acetic acid, one part manganese acetate tetrahydrate and 0.75 parts ammonium bromide. The pressure is maintained at 30 kg/cm-, and the reaction zone is heated to 195° C. The outlet control valve is regulated so that the flow rate of gas through the outlet gas meter is 3000 parts by volume/hour/volume of the reaction mixture. When the temperature reaches 195°C, the external heating is stopped and the temperature increases due to the exothermic reaction. After the initial reaction, external heat is supplied to maintain a reaction temperature of 195-200° C for a total of 1.5 hours. After completion of the reaction, as shown at 20-21% oxygen content for the outlet gas; Orsat gas analysis), the reaction vessel is allowed to cool to approx. 85° C and the pressure is lowered. The -liquid jproducts are removed at 150—:200° C by applying pressure equalization from a nitrogen f cylinder through the condenser. The reaction liquid is drained by opening a connection in the air supply line. The bottom flange is removed, and the solid product is scraped out of the reaction vessel. The solid and liquid products are combined and filtered. The insoluble terephthalic acid residue is washed twice with 75 parts of hot acetic acid and dried. A weight yield of 115% terephthalic acid is obtained (acid number 672, theoretical •6.75). , In a control experiment with paraxylol and a given amount of metal bromide under the crushing of a mixture of >manganese and cobalt bromide in equal parts, the yield of terephthalic acid is approx. 12 percent by weight or slightly higher than that
-brukes metallbromid alene. - metal bromide is used alone.
Tereftalsyre oppnås i utmerkede utbytter ved å erstatte katalysatorkompo-nentene som ble -brukt i eksempel 22 med de materialer som angis nedenfor: Terephthalic acid is obtained in excellent yields by replacing the catalyst components used in Example 22 with the materials indicated below:
Eksempel: Brukt materiale: Example: Material used:
<*> Materialene blandes og inndampes til tørrhet og det resulterende materiale brukes som katalysator. <*> The materials are mixed and evaporated to dryness and the resulting material is used as a catalyst.
Eksempel 44: Example 44:
75 deler trietylbenzol oksyderes i over-ensstemmelse med fremgangsmåten i eksempel 24 i tre timer ved 200—215° C i nærvær av 150 deler eddiksyre, 1 del manganacetat og 0,75 deler ammoniumbromid. Reaksjonskarinnholdet tappes fra og filtreres. Filterkaken slemmes opp med 50 deler eddiksyre (vasking) og filtreres. Den tørre vekt av den trebasiske syre som oppnås er 28,7 g, hvilket tilsvarer et vektutbytte på 38 %. 75 parts of triethylbenzene are oxidized in accordance with the method in example 24 for three hours at 200-215° C. in the presence of 150 parts of acetic acid, 1 part of manganese acetate and 0.75 parts of ammonium bromide. The reaction vessel contents are drained off and filtered. The filter cake is slurried with 50 parts acetic acid (washing) and filtered. The dry weight of the tribasic acid obtained is 28.7 g, which corresponds to a weight yield of 38%.
Eksempel 45: Ammoniumbromidet utelates fra sat-sen i reaksjonskaret beskrevet i eksempel 44. Bare 1 del tribasisk syre oppnåddes, hvilket tilsvarer et vektutbytte på 1,3 %. Example 45: The ammonium bromide is omitted from the batch in the reaction vessel described in Example 44. Only 1 part of tribasic acid was obtained, which corresponds to a weight yield of 1.3%.
Eksempel 46: Fremgangsmåten utføres i et apparat som i kombinasjon har en korrosjonsbestandig trykkoksydasjonsreaktor og en vannkjølt kondensator anordnet over reaktoren. Reaksjonskaret er foret med ni-krombånd til en høyde av ca. 30 cm. Når oksydasjonen er i gang, innføres luft under trykk til reaksjonskaret gjennom en gass-fordeler anbragt like over bunnen, og den Example 46: The method is carried out in an apparatus which, in combination, has a corrosion-resistant pressure oxidation reactor and a water-cooled condenser arranged above the reactor. The reaction vessel is lined with ni-chromium tape to a height of approx. 30 cm. When the oxidation is underway, pressurized air is introduced into the reaction vessel through a gas distributor placed just above the bottom, and the
øvre ende av kondensatoren forsegles. Gassutluftning skjer gjennom et rør på toppen av kondensatoren og går gjennom en nålekontrollventil. Videre er anordnet en strømningsmåler (kviksølv i glass) og en tørrisavskiller foran utluftningen til atmosfæren. Reaktoren beskikkes ved å tilsette avveide mengder av hver reaksjbns-komponent gjennom toppen av kondensatoren, som derpå lukkes og reaktortrykket økes til ca. 28 kg/cm-' med luft. Reaksjonskaret beskikkes derpå med 75 g 95 %'s paraxylol, 150 g eddiksyre, og katalysatoren fremstilles ved å blande 1 g ceriumhydrok-syd, 1 g ammoniumbromid og 50 ml. 20 %'s bromhydrogensyre, og inndampning til tørrhet. upper end of the condenser is sealed. Gas venting occurs through a tube on top of the condenser and passes through a needle check valve. Furthermore, a flow meter (mercury in glass) and a dry ice separator are arranged in front of the vent to the atmosphere. The reactor is coated by adding weighed amounts of each reaction component through the top of the condenser, which is then closed and the reactor pressure is increased to approx. 28 kg/cm-' with air. The reaction vessel is then coated with 75 g of 95% paraxylene, 150 g of acetic acid, and the catalyst is prepared by mixing 1 g of cerium hydroxide, 1 g of ammonium bromide and 50 ml. 20% hydrobromic acid, and evaporation to dryness.
Trykket holdes ved ca. 28 kg/cm- og reaksjonskaret oppvarmes til ca. 195° C. Utløpskontrollventilen reguleres slik at strømningshastigheten for gass gjennom utløpsstrømningsmåleren er 300 volum pr. time pr. volum reaksjonsblanding. Når temperaturen når 195° C, stoppes den ytre oppvarmning og temperaturen stiger på grunn av reaksjonens eksoterme karakter. Etter den begynnende reaksjon tilføres ytre varme for å holde reaksjonstemperaturen på 195 til 205° C i alt iy2 time. Etter avslutning av reaksjonen, som vises ved 20—21 % oksygeninnhold i utløpsgassen The pressure is maintained at approx. 28 kg/cm and the reaction vessel is heated to approx. 195° C. The outlet control valve is regulated so that the flow rate of gas through the outlet flow meter is 300 volumes per hour per volume of reaction mixture. When the temperature reaches 195° C, the external heating is stopped and the temperature rises due to the exothermic nature of the reaction. After the initial reaction, external heat is added to keep the reaction temperature at 195 to 205° C. for a total of 1y2 hours. After completion of the reaction, which appears at 20-21% oxygen content in the outlet gas
(Orsatgassanalyse), får reaksjonskaret av-kjøle seg til 85° C og avgasses. De flytende produkter fjernes ved 65 til 90° C ved å på-føre trykk fra en nitrogensylinder gjennom kondensatoren. Reaktorvæsken tappes av (Orsate gas analysis), the reaction vessel is allowed to cool to 85° C and degassed. The liquid products are removed at 65 to 90°C by applying pressure from a nitrogen cylinder through the condenser. The reactor liquid is drained off
ved å åpne en forbindelse i luftmatnings-ledninger. Bunnflensen fjernes og det faste produkt skrapes ut fra reaksjonskaret. De faste og flytende produkter forenes og filtreres. Det uoppløselige tereftalsyre-resi-duum vaskes to ganger med 75 deler varm eddiksyre og tørkes. Et vektsutbytte på 117 % tereftalsyre oppnås. by opening a connection in the air supply lines. The bottom flange is removed and the solid product is scraped out of the reaction vessel. The solid and liquid products are combined and filtered. The insoluble terephthalic acid residue is washed twice with 75 parts of warm acetic acid and dried. A weight yield of 117% terephthalic acid is obtained.
Eksempel 47: Example 47:
En katalysator fremstilles ved å for-dampe 3 g neodymiumammoniumnitrat, 2 g ammoniumbromid og 40 ml 20 %'s bromhydrogensyre. Katalysatoren tilsettes til 100 g paradiisopropylbenzol og 100 g eddiksyre og blandingen oksyderes i 15 mi-nutter ved 156° C og to timer ved 200 til 215° C. Reaktorvæskene filtreres og bunn-fallet vaskes med eddiksyre. Det rå tereftalsyreprodukt oppnådd ved direkte filtrering av reaksjons væsken veier 3,2 g, og har et syretall på 573. Kuminsyreproduktet ut-vunnet ved natriumbikarbonatekstraksjon veier 20,8 g (syretall 332; teoretisk for kuminsyre 342). Således oppnås ca. 3 %'s utbytte på tereftalsyre og 20 %'s utbytte for kuminsyre. A catalyst is prepared by evaporating 3 g of neodymium ammonium nitrate, 2 g of ammonium bromide and 40 ml of 20% hydrobromic acid. The catalyst is added to 100 g of paradiisopropylbenzene and 100 g of acetic acid and the mixture is oxidized for 15 minutes at 156° C. and two hours at 200 to 215° C. The reactor liquids are filtered and the precipitate is washed with acetic acid. The crude terephthalic acid product obtained by direct filtration of the reaction liquid weighs 3.2 g, and has an acid number of 573. The cumic acid product obtained by sodium bicarbonate extraction weighs 20.8 g (acid number 332; theoretical for cumic acid 342). Thus, approx. 3% yield on terephthalic acid and 20% yield on cumic acid.
Flere forskjellige karboksylsyrer kan brukes som reaksjonsmedium. Hvis alle fordeler ikke er nødvendige, kan forskjellige karboksylsyrer, inkludert mellomoksy-dasjonsproduktene av materialet som oksyderes, brukes med fordel. F. eks. ved et enkelt forsøk som i eksempel 1 oppnås uten bruk av eddiksyre et lavt utbytte på tereftalsyre (ca. 8 til 20 vektprosent) sammen med en stor mengde fenyleddiksyre. Ved utvinning av førstnevnte og tilbakeføring av sistnevnte syre sammen med tilmåtet nytt kullvannstoff og ved å arbeide ved temperaturer over smeltepunktet for fenyleddiksyre kan en i det vesentlige fullstendig omdannelse av det tilmatede kullvannstoff til tereftalsyre oppnås. Several different carboxylic acids can be used as reaction medium. If all advantages are not required, various carboxylic acids, including the intermediate oxidation products of the material being oxidized, can be used with advantage. For example in a simple experiment as in example 1, without the use of acetic acid, a low yield of terephthalic acid (approx. 8 to 20 percent by weight) is obtained together with a large amount of phenylacetic acid. By extracting the former and returning the latter acid together with a moderate amount of new coal hydrogen and by working at temperatures above the melting point of phenylacetic acid, an essentially complete conversion of the fed coal hydrogen to terephthalic acid can be achieved.
Generelt, ifølge nærværende oppfinnelse, er det mulig å oppnå utbytter av karboksylsyrer med over 50 vektprosent pr. omgang og således redusere mengden av nødvendig tilbakeføring for å oppnå høye endelige utbytter og i mange tilfeller unn-gå nødvendigheten av tilbakeføring. In general, according to the present invention, it is possible to obtain yields of carboxylic acids of over 50% by weight per round and thus reduce the amount of necessary return in order to achieve high final yields and in many cases avoid the necessity of return.
Fremgangsmåten etter nærværende oppfinnelse kan utføres som en kontinuerlig prosess, en halv-kontinuerlig prosess eller på satsbasis. Vann kan fjernes for å opprettholde ønsket konsentrasjon, f. eks. ved destillasjon ved tilsetning av eddik-syreanhydrid eller lignende. The method according to the present invention can be carried out as a continuous process, a semi-continuous process or on a batch basis. Water can be removed to maintain the desired concentration, e.g. by distillation with the addition of acetic acid anhydride or the like.
Blant ytterligere metaller som kan brukes sammen med brom for å oksydere en alifatisk substituert, aromatisk forbindelse til en karboksyaromatisk forbindelse skal nevnes aluminium, vismut, kadmium, jern (II), palladium, bly og neodymium. Additional metals which can be used together with bromine to oxidize an aliphatically substituted aromatic compound to a carboxyaromatic compound include aluminium, bismuth, cadmium, iron (II), palladium, lead and neodymium.
Ønskede eller sammenlignbare resultater kan oppnås ved forskjellige modifika-sjoner av hva som er anført foran innenfor det brede området angitt her, således: trykket skal være tilstrekkelig til å opprettholde en flytende fase, som, hvis et oppløsningsmiddel brukes, skal inneholde i det minste noe av det nevnte oppløsnings-middel. Vanligvis vil trykket ligge i området fra atmosfæretrykk opp til 100—105 kg/cm-. Desired or comparable results can be obtained by various modifications of what is stated above within the broad range indicated here, thus: the pressure should be sufficient to maintain a liquid phase, which, if a solvent is used, should contain at least some of the said solvent. Usually the pressure will be in the range from atmospheric pressure up to 100-105 kg/cm-.
Det substituerte, aromatiske materiale som mates inn i reaksjonskaret, kan være et alkylbenzol (med en til seks metyl- og lignende alkyl-grupper), i teknisk ren form og fri for forurensninger eller materialer som kan gripe inn i oksydasjonsreaksjonen. Det kan være en blanding av isomere materialer eller en slik blanding inneholdende lavere eller høyere homologer. Den kan også inneholde noen alifatiske kullvann-stoffmaterialer med lignende kokeområder. Blandinger av alkylaromatiske stoffer kan brukes, omdannet til de tilsvarende blandinger av aromatiske karboksylsyrer, hvilke syrer derpå kan skilles fra, f. eks. ved fysiske midler som destillasjon, eller ved en kombinasjon av kjemiske og fysiske midler som esterifisering fulgt av fraksjo-nering. The substituted, aromatic material which is fed into the reaction vessel can be an alkylbenzene (with one to six methyl and similar alkyl groups), in technically pure form and free of impurities or materials that can intervene in the oxidation reaction. It may be a mixture of isomeric materials or such a mixture containing lower or higher homologues. It may also contain some aliphatic coal water materials with similar boiling ranges. Mixtures of alkylaromatic substances can be used, converted to the corresponding mixtures of aromatic carboxylic acids, which acids can then be separated from, e.g. by physical means such as distillation, or by a combination of chemical and physical means such as esterification followed by fractionation.
Alifatiske substituenter i den aromatiske kjerne kan være bifunksjonelle grupper bundet til to forskjellige aromatiske kullstoffatomer, f. eks. ftalid eller tetra-hydronaftalon. Sistnevnte forbindelse fore-skriver to alifatiske kullstoffatomer for hvert substituert aromatisk kullstoffatom. Dette er innenfor området 1 til 4 alifatiske kullstoffatomer pr. substituert aromatisk kullstoffatom som foran nevnt. Alle eller noen av de aromatiske kullstoffatomer kan være substituert med en alifatisk gruppe og to eller flere av substituentene kan omdannes til tilsvarende karboksylsyregrup-per. Aliphatic substituents in the aromatic nucleus can be bifunctional groups attached to two different aromatic carbon atoms, e.g. phthalide or tetrahydronaphthalone. The latter compound prescribes two aliphatic carbon atoms for each substituted aromatic carbon atom. This is within the range of 1 to 4 aliphatic carbon atoms per substituted aromatic carbon atom as mentioned above. All or some of the aromatic carbon atoms can be substituted with an aliphatic group and two or more of the substituents can be converted into corresponding carboxylic acid groups.
Delvise oksydasjonsprodukter av forannevnte materialer kan også behandles overensstemmende med nærværende oppfinnelse, f. eks. alkaryler eller lignende, hvor de alifatiske substituenter omdannes til surstoffholdige mellomproduktderivater som alkoholer, aldehyder, ketoner, perok-syd-forbindelser o.l. Partial oxidation products of the aforementioned materials can also be treated in accordance with the present invention, e.g. alkaryls or the like, where the aliphatic substituents are converted into oxygen-containing intermediate product derivatives such as alcohols, aldehydes, ketones, peroxide compounds and the like.
De substituerte homocykliske, aromatiske forbindelser som behandles i overens-stemmelse med oppfinnelsen kan inneholde en aromatisk kjerne eller kan være flerkjernede; f. eks. benzol, naftalen, antra-cen, fenantren. difenyl, trifenyl o.l., som har ovenfor nevnte alifatiske substituenter. Disse inkluderer metylbenzoly etylbenzol, n-propylbenzol, i-propylbenzol, n-butylbenzol, sek-butylbenzol, cykloheksyl-benzol1, dimetylbenzol, dietylbenzol, di-n-propylbenzol, di-i-propylbenzol, di-n-butylbenzol, di-sek-butylbenzol, trimetylbenzol, trietylbenzol, tri-n-propylbenzol, tri-i-propylbenzol, tri-n-butylbenzol, tri-sek-butylbenzol, etyltoluol, etyl-n-propyltoluol, etyl<1->i-propyltoluol, etyl-sek-butyftoHiol, dietyl<1->toluol, dietyl-n-propyltoluol, dietyl-r-propyltoluol, dietyl-sek-butyltoluol, trietylto-luol, trietyl-n-propyltoluol, trietyl-i-propyltoluol, trietyl-sek-butyltoluol, n-propyletylbenzol, i-propyletylbenzol, n-butylbenzol<1>, sek-butyletylbenzol, dimetyletylbenzol, di-n-propyletylibenzol, di-i-propyletylbenzol, di-n-butyletylbenzol, di-sek-butyletylbenzol, trimetyl-etylbenzol, tetra-etylbenzol, tri-n-propyletylbenzol, tri-i-propyletylbenzol, tri-n-butyletylbenzol, tri-sek-butyletylbenzol, i-propyl-n-propylbenzol, n-butyl-n-propylbenzol, sek-butyl-n-propylbenzol, dimetyl-n-propylbenzol, di-i-propyl-n-propylbenzol, di-n-butyl-n-propylbenzol, di-sek-butyl-n-propylbenzol, trimetyl-n-propylbenzol, trietyl-n-propylbenzol, tri-i-propylbenzol, tyl-n-propylbenzol, trimetyl-n-propylben - zol, tri-n-propylbenzol, tri-i-propylbenzol, tri-n-butyl-n-propylbenzol, tri-sek-butyl-n-propyl-benzol, n-butyl-i-propylbenzol, sek-butyl-i-propylbenzol, dimetyl-i-propylbenzol, dietyl-i-propylbenzol, di-i-propylbenzol, di-n-propyl-i-propylbenzol, di-sek-butyl-i-propylbenzol, trimetyl-i-propylbenzol, trietyl-i-propylbenzol, tri-i-propylbenzol, tri-n-butyl-i- propylbenzol, i-butyl-n-butylbenzol, dimetyl-i-butylbenzol, djetyl-i-butylbenzol, di-n-propyl-i-butylbenzol, di-i-propyl-i-butylbenzol, di-n-butyl-i-butylbenzol, di-sek-butyl-i-butylbenzol, trimetyl-i-butylbenzol, trietyl-i-butylbenzol, tri-n-propyl-i-butylbenzol, tri-i-propyl-i-butylbenzol, dimetyl-sek-butylbenzol, dietyl-sek-butylbenzol, di-n-propyl-sek-butylbenzol, di-i-propyl-sek-butylbenzol, di-n-butyl-sek-butylbenzol, trimetyl-sek-butylbenzol, trietyl-sek-butylbenzol, tri-n-'propyl-sek-butylbenzol, tri-i-propylLsek-butylbenzol, tri-n-butyl-sek-butylbenzol, og tilsvarende (eller høyere} substituerte ^flerkjernede materialer. Også alfa-metyl-inaftalen, beta-metylnaf talen, dimetylbife-nyl, metylacetofénoner, fenyleddiksyrer, acetobenzoesyrer og l,3-dimetyl-4'-kloro-<i>benzol (isoftalsyrederivatet som er et resul-tat fra sistnevnte kan omdannes til det tilsvarende fenol ved å erstatte klorogruppen med en hydroksylgruppe på kjent måte) 'kan anvendes som utgangsmateriale. The substituted homocyclic aromatic compounds treated in accordance with the invention may contain an aromatic nucleus or may be polynuclear; e.g. benzene, naphthalene, anthracene, phenanthrene. diphenyl, triphenyl and the like, which have the above-mentioned aliphatic substituents. These include methylbenzoly ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, sec-butylbenzene, cyclohexyl-benzene1, dimethylbenzene, diethylbenzene, di-n-propylbenzene, di-i-propylbenzene, di-n-butylbenzene, di-sec -butylbenzene, trimethylbenzene, triethylbenzene, tri-n-propylbenzene, tri-i-propylbenzene, tri-n-butylbenzene, tri-sec-butylbenzene, ethyltoluene, ethyl-n-propyltoluene, ethyl<1->i-propyltoluene, ethyl- sec-butyphtoHiol, diethyl<1->toluene, diethyl-n-propyltoluene, diethyl-r-propyltoluene, diethyl-sec-butyltoluene, triethyltoluene, triethyl-n-propyltoluene, triethyl-i-propyltoluene, triethyl-sec-butyltoluene , n-propylethylbenzene, i-propylethylbenzene, n-butylbenzene<1>, sec-butylethylbenzene, dimethylethylbenzene, di-n-propylethylbenzene, di-i-propylethylbenzene, di-n-butylethylbenzene, di-sec-butylethylbenzene, trimethylethylbenzene, tetra-ethylbenzene, tri-n-propylethylbenzene, tri-i-propylethylbenzene, tri-n-butylethylbenzene, tri-sec-butylethylbenzene, i-propyl-n-propylbenzene, n-butyl-n-propylbenzene, sec-butyl-n- propylbenzene, dimethyl-n-propylbenzene, di-i-propyl-n-propylbenzene, di-n-butyl-n-propylbenzene, di-sec-butyl-n-propylbenzene, trimethyl-n-propylbenzene, triethyl-n-propylbenzene, tri- i-propylbenzene, tyl-n-propylbenzene, trimethyl-n-propylbenzene, tri-n-propylbenzene, tri-i-propylbenzene, tri-n-butyl-n-propylbenzene, tri-sec-butyl-n-propyl- benzene, n-butyl-i-propylbenzene, sec-butyl-i-propylbenzene, dimethyl-i-propylbenzene, diethyl-i-propylbenzene, di-i-propylbenzene, di-n-propyl-i-propylbenzene, di-sec- butyl-i-propylbenzene, trimethyl-i-propylbenzene, triethyl-i-propylbenzene, tri-i-propylbenzene, tri-n-butyl-i-propylbenzene, i-butyl-n-butylbenzene, dimethyl-i-butylbenzene, diethyl- i-butylbenzene, di-n-propyl-i-butylbenzene, di-i-propyl-i-butylbenzene, di-n-butyl-i-butylbenzene, di-sec-butyl-i-butylbenzene, trimethyl-i-butylbenzene, triethyl-i-butylbenzene, tri-n-propyl-i-butylbenzene, tri-i-propyl-i-butylbenzene, dimethyl-sec-butylbenzene, diethyl-sec-butylbenzene, di-n-propyl-sec-butylbenzene, di- i-propyl-sec-butylbenzene, di-n-butyl-sec-buty lbenzene, trimethyl-sec-butylbenzene, triethyl-sec-butylbenzene, tri-n-'propyl-sec-butylbenzene, tri-i-propylLsec-butylbenzene, tri-n-butyl-sec-butylbenzene, and similarly (or higher} substituted ^multi-core materials. Also alpha-methyl-inaphthalene, beta-methylnaphthalene, dimethylbiphenyl, methylacetophenones, phenylacetic acids, acetobenzoic acids and 1,3-dimethyl-4'-chloro-<i>benzene (the isophthalic acid derivative which is a result of the latter can be converted into the corresponding phenol by replacing the chloro group with a hydroxyl group in a known manner) can be used as starting material.
Claims (4)
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DK124165A DK113166B (en) | 1965-03-11 | 1965-03-11 | Two-stage compressor. |
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DE (1) | DE1503419A1 (en) |
DK (1) | DK113166B (en) |
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1966
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SE321537B (en) | 1970-03-09 |
DK113166B (en) | 1969-02-24 |
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