FR2553089A1 - PROCESS FOR PRODUCING DIETHYLENETRIAMINE FROM MONOETHANOLAMINE - Google Patents
PROCESS FOR PRODUCING DIETHYLENETRIAMINE FROM MONOETHANOLAMINE Download PDFInfo
- Publication number
- FR2553089A1 FR2553089A1 FR8415322A FR8415322A FR2553089A1 FR 2553089 A1 FR2553089 A1 FR 2553089A1 FR 8415322 A FR8415322 A FR 8415322A FR 8415322 A FR8415322 A FR 8415322A FR 2553089 A1 FR2553089 A1 FR 2553089A1
- Authority
- FR
- France
- Prior art keywords
- phosphate
- monoethanolamine
- acid
- diethylenetriamine
- ethylenediamine
- 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 50
- 239000010452 phosphate Substances 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 48
- 239000002253 acid Substances 0.000 description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 17
- 235000011007 phosphoric acid Nutrition 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- -1 chlorine ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- 229910052773 Promethium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- KDCUNMWWJBHRSC-UHFFFAOYSA-K praseodymium(3+);phosphate Chemical compound [Pr+3].[O-]P([O-])([O-])=O KDCUNMWWJBHRSC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- QQCIBICIISNSAY-UHFFFAOYSA-K terbium(3+);phosphate Chemical compound [Tb+3].[O-]P([O-])([O-])=O QQCIBICIISNSAY-UHFFFAOYSA-K 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HQBYUMGOEJNFJB-UHFFFAOYSA-N 2-aminoethanol;azane Chemical compound N.NCCO HQBYUMGOEJNFJB-UHFFFAOYSA-N 0.000 description 1
- TYFJTEPDESMEHE-UHFFFAOYSA-N 6,8-dihydroxy-3-[2-(4-methoxyphenyl)ethyl]-3,4-dihydroisochromen-1-one Chemical compound C1=CC(OC)=CC=C1CCC1OC(=O)C2=C(O)C=C(O)C=C2C1 TYFJTEPDESMEHE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- LWSFGPKHSQZZME-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Pm+3] Chemical compound P(=O)([O-])([O-])[O-].[Pm+3] LWSFGPKHSQZZME-UHFFFAOYSA-K 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- JFILLDQSIUEZPE-UHFFFAOYSA-N azane;piperazine Chemical compound N.C1CNCCN1 JFILLDQSIUEZPE-UHFFFAOYSA-N 0.000 description 1
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 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
- IPYGWRGXZUHZSR-UHFFFAOYSA-L cadmium(2+) dihydrogen phosphate Chemical compound [Cd++].OP(O)([O-])=O.OP(O)([O-])=O IPYGWRGXZUHZSR-UHFFFAOYSA-L 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- UATXJGCWVXKVBN-UHFFFAOYSA-L dihydrogen phosphate iron(2+) Chemical compound [Fe+2].OP(O)([O-])=O.OP(O)([O-])=O UATXJGCWVXKVBN-UHFFFAOYSA-L 0.000 description 1
- MOJITMJAFATXAX-UHFFFAOYSA-M dihydrogen phosphate;rubidium(1+) Chemical compound [Rb+].OP(O)([O-])=O MOJITMJAFATXAX-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- UIUJMPLGCICBOO-UHFFFAOYSA-K dysprosium(3+);phosphate Chemical compound [Dy+3].[O-]P([O-])([O-])=O UIUJMPLGCICBOO-UHFFFAOYSA-K 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XFULIUKARWFBDF-UHFFFAOYSA-K erbium(3+);phosphate Chemical compound [Er+3].[O-]P([O-])([O-])=O XFULIUKARWFBDF-UHFFFAOYSA-K 0.000 description 1
- KKZGDLIHIDYQIY-UHFFFAOYSA-N ethanol ethene Chemical group C(C)O.C=C.C=C.C=C KKZGDLIHIDYQIY-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- KJNZTHUWRRLWOA-UHFFFAOYSA-K europium(3+);phosphate Chemical compound [Eu+3].[O-]P([O-])([O-])=O KJNZTHUWRRLWOA-UHFFFAOYSA-K 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- JAOZQVJVXQKQAD-UHFFFAOYSA-K gadolinium(3+);phosphate Chemical compound [Gd+3].[O-]P([O-])([O-])=O JAOZQVJVXQKQAD-UHFFFAOYSA-K 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZFEZZRFBMNCXLQ-UHFFFAOYSA-K holmium(3+);phosphate Chemical compound [Ho+3].[O-]P([O-])([O-])=O ZFEZZRFBMNCXLQ-UHFFFAOYSA-K 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- AUOXQXPFOXZHRO-UHFFFAOYSA-N lanthanum;phosphoric acid Chemical compound [La].OP(O)(O)=O AUOXQXPFOXZHRO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- OWNMACFMOIQGAC-UHFFFAOYSA-K lutetium(3+);phosphate Chemical compound [Lu+3].[O-]P([O-])([O-])=O OWNMACFMOIQGAC-UHFFFAOYSA-K 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- IYPZRUYMFDWKSS-UHFFFAOYSA-N piperazin-1-amine Chemical compound NN1CCNCC1 IYPZRUYMFDWKSS-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- BJRVEOKYZKROCC-UHFFFAOYSA-K samarium(3+);phosphate Chemical compound [Sm+3].[O-]P([O-])([O-])=O BJRVEOKYZKROCC-UHFFFAOYSA-K 0.000 description 1
- DYRWWVFQQONJJK-UHFFFAOYSA-K scandium(3+);phosphate Chemical compound [Sc+3].[O-]P([O-])([O-])=O DYRWWVFQQONJJK-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- OKBGNVIROKPBTK-UHFFFAOYSA-K thulium(3+);phosphate Chemical compound [Tm+3].[O-]P([O-])([O-])=O OKBGNVIROKPBTK-UHFFFAOYSA-K 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- YXNVQKRHARCEKL-UHFFFAOYSA-K ytterbium(3+);phosphate Chemical compound [Yb+3].[O-]P([O-])([O-])=O YXNVQKRHARCEKL-UHFFFAOYSA-K 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/14—Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/09—Diamines
- C07C211/10—Diaminoethanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
SELON L'INVENTION, ON PRODUIT LA DIETHYLENETRIAMINE AVEC UNE BONNE SELECTIVITE ET DE FACON PEU COUTEUSE EN FAISANT REAGIR DE L'AMMONIAC AVEC DE LA MONOETHANOLAMINE EN UNE PROPORTION MOLAIRE DE L'AMMONIAC A LA MONOETHANOLAMINE D'AU MOINS 11, EN PRESENCE D'UNE SUBSTANCE CONTENANT DU PHOSPHORE ET D'ETHYLENEDIAMINE. L'ETHYLENEDIAMINE COUTEUSE N'EST PAS CONSOMMEE AU COURS DE CE PROCEDE. APPLICATION A LA PRODUCTION INDUSTRIELLE DE DIETHYLENETRIAMINE, NOTAMMENT DANS UN SYSTEME EN CONTINU A LIT FIXE.ACCORDING TO THE INVENTION, DIETHYLENETRIAMINE IS PRODUCED WITH GOOD SELECTIVITY AND AT LOW COST BY REACTING AMMONIA WITH MONOETHANOLAMINE IN A MOLAR PROPORTION FROM AMMONIA TO MONOETHANOLAMINE AT LEAST 11, IN THE PRESENCE OF AT LEAST 11. A SUBSTANCE CONTAINING PHOSPHORUS AND ETHYLENEDIAMINE. COSTLY ETHYLENEDIAMINE IS NOT CONSUMED DURING THIS PROCESS. APPLICATION TO INDUSTRIAL PRODUCTION OF DIETHYLENETRIAMINE, ESPECIALLY IN A CONTINUOUS FIXED BED SYSTEM.
Description
Procédé pour produire de la diéthylènetriamine à partir de laProcess for producing diethylenetriamine from the
monoéthanolamine.monoethanolamine.
La présente invention concerne un procédé pour produire de The present invention relates to a method for producing
la diéthylènetriamine par ammoniolyse de la monoéthanolamine. diethylenetriamine by ammonolysis of monoethanolamine.
Au plan industriel, la diéthylènetria mine n'est produite qu'en tant que produit secondaire dans les procédés de production de léthylènediamine par réaction du 1,2-dichloroéthane avec l'ammoniac ou par réaction de la monoéthanolamine avec l'ammoniac Dans le premier de ces procédés, une grande quantité de chlorure de sodium, jusqu'à 2 fois la quantité molaire d'éthylène10 diamine, est produite en tant que produit secondaire et du chlorure de vinyle est également produit en tant que produit secondaire En conséquence, ce procédé devient coûteux lorsque l'on traite les déchets et présente l'inconvénient de corroder sévèrement l'appareillage par les 15 ions chlore De plus, dans l'un et l'autre de ces procédés, la production de diéthylènetriamine a tendance à At the industrial level, diethylenetria mine is only produced as a by-product in the processes for the production of ethylene diamine by reacting 1,2-dichloroethane with ammonia or by reacting monoethanolamine with ammonia. of these processes, a large amount of sodium chloride, up to 2 times the molar amount of ethylene diamine, is produced as a by-product and vinyl chloride is also produced as a by-product. becomes expensive when the waste is treated and has the disadvantage of severely corroding the equipment with the chlorine ions. In addition, in both of these processes, the production of diethylenetriamine tends to
dépendre de la demande en éthylènediamine sur le marché. depend on the demand for ethylenediamine on the market.
Pour produire de la diéthylènetriamine, on a également décrit un procédé selon lequel on fait réagir 20 de la monoéthanolamine avec de léthylènediamine en utilisant un composé contenant du phosphore tel que l'acide phosphorique, en tant que 'catalyseur (brevet JA publié N 6982/1981) et un procédé selon leq)ul on fait réagir la monoéthanolamine avec de l'éthylènediamine en phase liquide, en utilisant en tant que catalyseur, un composé minéral contenant de l'alumine ou de la silice en tant To produce diethylenetriamine, a process has also been described in which monoethanolamine is reacted with ethylene diamine using a phosphorus-containing compound such as phosphoric acid, as a catalyst (JA patent N 6982 / 1981) and a process according to which monoethanolamine is reacted with ethylenediamine in the liquid phase, using as catalyst a mineral compound containing alumina or silica as a catalyst.
que composant principal (brevet japonais mis à l'inspection publique N 38329/1980). as the main component (Japanese Patent Laid-Open No. 38329/1980).
:53089: 53089
Cependant, ces procédés n'ont pas jusqu'à présent atteint un niveau souhaitable de sélectivité et de productivité, car, non seulement l'éthylènediamine est comparativement chère, mais encore la conversion de l'é5 thylènediamine et la sélectivité de la diéthylènetriamine However, these processes have not heretofore achieved a desirable level of selectivity and productivity, since not only is ethylenediamine comparatively expensive, but also the conversion of ethylenediamine and the selectivity of diethylenetriamine
sont l'une et l'autre faibles.both are weak.
Le procédé décrit dans le brevet JA mis à i'inspection publique N 52322/1983 perfectionne le procédé décrit dans le brevet JA publié N 6982/1981 indiqué ci10 dessus et produit des amines non cycliques avec de bons rendements tout en réglant simultanément la production d'amines cycliques par addition d'ammoniac à raison de 0,5 à 10 fois la quantité molaire de monoéthanolamine dans la réaction de la monoéthanolamine avec l'éthylènediamine 15 en utilisant un composé contenant du phosphore tel que l'acide phosphorique, en tant que catalyseur Toutefois, dans ce procédé, la sélectivité de la diéthylènetriamine n'est pas suffisante et la monoéthanolamine, l'éthylènediamine et l'ammoniac sont consommés en produisant de la 20 diéthylènetriamine lorsqu'on utilise comme matière brute The process described in the JA patent N 52322/1983 perfects the process described in published JA patent N 6982/1981 indicated above and produces noncyclic amines in good yields while simultaneously controlling the production of cyclic amines by adding ammonia at 0.5 to 10 times the molar amount of monoethanolamine in the reaction of monoethanolamine with ethylenediamine using a phosphorus-containing compound such as phosphoric acid, as the However, in this process, the selectivity of diethylenetriamine is not sufficient and monoethanolamine, ethylenediamine and ammonia are consumed by producing diethylenetriamine when used as the raw material.
de l'éthylènediamine coûteuse.expensive ethylenediamine.
La demanderesse a étudié en détail différentes réactions de l'ammoniac avec la monoéthanolamine et découvert que la diéthylènetriamine pouvait être produite 25 avec une sélectivité remarquablement élevée en faisant réagir l'ammoniac et -la monoéthanolamine en présence The applicant has studied in detail different reactions of ammonia with monoethanolamine and discovered that diethylenetriamine could be produced with remarkably high selectivity by reacting ammonia and monoethanolamine in the presence of
d'une substance contenant du phosphore et d'éthylènediamine, dans des conditions de réaction limitées. of a substance containing phosphorus and ethylenediamine under limited reaction conditions.
Le procédé selon l'invention est caractérisé 30 en ce que l'on produit de la diéthylènetriamine en faisant réagir de l'ammoniac avec de la monoéthanolamine en présence d'une substance contenant du phosphore et d'éthylènediamine en une proportion molaire de l'ammoniac à la The process according to the invention is characterized in that diethylenetriamine is produced by reacting ammonia with monoethanolamine in the presence of a substance containing phosphorus and ethylenediamine in a molar proportion of ammonia to the
monoéthanolamine d'au moins 11.monoethanolamine of at least 11.
S. La présente invention est relative à un procédé The present invention relates to a process
pour produire de la diéthylènetriamine comme décrit cidessus. to produce diethylenetriamine as described above.
La substance contenant du phosphore utilisable dans le procédé selon l'invention comprend différents sels de l'acide phosphorique, des pyrophosphates, des composés de l'acide phosphorique ou des anhydrides de ceux-ci, de l'acide phosphoreuxou leurs anhydrides des esters alcoyliques ou aryliques de l'acide phosphorique ou de l'acide 10 phosphoreux, et des acides phosphoriques ou phosphoreux alcoyl ou aryl-substitués Cette substance peut-être The phosphorus-containing substance usable in the process according to the invention comprises various phosphoric acid salts, pyrophosphates, phosphoric acid compounds or anhydrides thereof, phosphorous acid or their anhydrides of the alkyl esters or aryls of phosphoric acid or phosphorous acid, and alkyl or aryl-substituted phosphoric or phosphorous acids. This substance may be
utilisée seule ou en mélange.used alone or as a mixture.
Parmi les sels variés de l'acide phosphorique, on préfère les phosphates diacides ou des compositions 15 leur correspondant, ou les pyrophosphates obtenus grâce à leur déshydratation Parmi les phosphates diacides et leurs compositions correspondantes, on peut citer à titre d'exemples: le phosphate diacide d'ammonium, le phosphate diacide de lithium, le phosphate diacide de sodium, le 20 phosphate diacide de potassium, le phosphate diacide de rubidium, le phosphate diacide de césium, le phosphate diacide de beryllium, le phosphate diacide de magnésium, le phosphate diacide ae calcium, le phosphate diacide de strontium, le phosphate diacide de baryum, et un produit 25 de réaction d'un composé de terre rare avec l'acide phosphorique, le produit étant une composition ayant un rapport atomique du phosphore à l'élément de terre rare de 3, tel qu'un produit de réaction de l'acide phosphorique avec un hydroxyde ou un oxyde d'éléments tels que le scandium, l'yttrium, le lanthane, le cérium, le praseodyme, le néodyme, le prométhium, le samarium, l'europium, le gadolinium, le terbium, le dysprosium, Of the various salts of phosphoric acid, diacid phosphates or their corresponding compositions, or the pyrophosphates obtained by virtue of their dehydration, are preferred. Among the diacid phosphates and their corresponding compositions, examples that may be mentioned are: phosphate ammonium diacid, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, rubidium dihydrogen phosphate, cesium diacid phosphate, beryllium diacid phosphate, magnesium dihydrogen phosphate, phosphate calcium diacid, strontium diacid phosphate, barium diacid phosphate, and a reaction product of a rare earth compound with phosphoric acid, the product being a composition having an atomic ratio of phosphorus to element rare earth of 3, such as a reaction product of phosphoric acid with a hydroxide or oxide of elements such as scandium, yttrium, lantha ne, cerium, praseodyme, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium,
l'holmium, l'erbium, le thulium l'ytterbium et le lutétium On peut également citer à titre d'exemplesle phos- holmium, erbium, thulium, ytterbium and lutetium. Examples of these are phos-
phate diacide de manganèse, le phosphate diacide de fer, le phosphate diacide de cobalt, le phosphate diacide de zinc, le phosphate diacide de cadmium, le phosphate diacide d'aluminium, le phosphate diacide de thallium, le phosphate diacide d'étain, le phosphate diacide de plomb et un produit de réaction d'un composé du chrome, du gallium, de l'indium, de l'antimoine ou du bismuth avec l'acide phosphorique, le produit étant une composition ayant un rapport atomique du phosphore au métal de 3, tel 10 qu'un produit de réaction de l'acide phosphorique avec un hydroxyde ou un oxyde dudit métal De plus, sont également compris dans l'énumération un produit de réaction d'un composé du nickel ou du cuivre avec l'acide phosphorique, le produit étant une composition ayant un 15 rapport atomique du phosphore au métal de 2, tel qu'un manganese diacidic acid, iron dihydrogen phosphate, cobalt diacid phosphate, zinc dihydrogen phosphate, cadmium dihydrogen phosphate, aluminum dihydrogen phosphate, thallium dihydrogen phosphate, tin diacid phosphate, lead dihydrogen phosphate and a reaction product of a compound of chromium, gallium, indium, antimony or bismuth with phosphoric acid, the product being a composition having an atomic ratio of phosphorus to metal Such a reaction product of phosphoric acid with a hydroxide or an oxide of said metal is also included in the enumeration of a reaction product of a nickel or copper compound with the phosphoric acid, the product being a composition having an atomic ratio of phosphorus to metal of 2, such that
produit de réaction de l'acide phosphorique avec un hydroxyde ou un oxyde dudit métal. reaction product of phosphoric acid with a hydroxide or an oxide of said metal.
Peuvent également être utilisés des pyrophosphates acides obtenus par déshydratation des phosphates dia20 cides ci-dessus ou des compositions qui leur sont équivalentes On peut de plus utiliser un produit de réaction de l'acide phosphorique avec un composé d'un métal du groupe I Va ou Va de la classification périodique des éléments, par exemple un produit ayant un rapport atomique 25 de P/Ti= 2, P/Zr= 2, P/Hf= 2, P/V= 2, P/Nb= 3 ou P/Ta= 3, tel It is also possible to use acid pyrophosphates obtained by dehydration of the above-mentioned dicarboxylic phosphates or compositions which are equivalent thereto. It is also possible to use a reaction product of phosphoric acid with a compound of a Group I metal Va or Va of the periodic table of elements, for example a product having an atomic ratio of P / Ti = 2, P / Zr = 2, P / Hf = 2, P / V = 2, P / Nb = 3 or P / Ta = 3, such
que le phosphate diacide de titanyle ou le phosphate diacide de zirconyle. titanyl dihydrogen phosphate or zirconyl diacid phosphate.
On peut encore utiliser des phosphates monoacides Des exemples de phosphates monoacides comprennent 30 le phosphate acide de diammonium, le phosphate acide de béryllium, le phosphate acide de magnésium, le phosphate acide de calcium, le phosphate acide de strontium, le phosphate acide de baryum, le phosphate acide de scandium, Monoacid phosphates may also be used. Examples of monoacid phosphates include diammonium acid phosphate, beryllium acid phosphate, magnesium acid phosphate, calcium acid phosphate, strontium acid phosphate, barium acid phosphate, the acid phosphate of scandium,
le phosphate acide d'yttrium, le phosphate acide de lan- yttrium acid phosphate, the acid phosphate of
thane le phosphate acide de cérium, le phosphate acide de praseodyme, le phosphate acide de néodyme, le phosphate acide de prométhium, le phosphate acide de samarium, le phosphate-acide d'europium, le phosphate acide de ga5 dolinium, le phosphate acide de terbium, le phosphate acide de dysprosium le phosphate acide d'holmium, le phosphate acide d'erbium, le phosphate acide de thulium, le phosphate acide d'ytterbium, le phosphate acide de lutétium, le phosphate acide de chrome, le phosphate acide 10 de manganèse, le phosphate acide de fer, le phosphate acide de cobalt, le phosphate acide de nickel, le phosphate acide de cuivre, le phosphate acide d'argent, le phosphate acide de zinc, le phosphate acide de cadmium, le phosphate acide de mercure, le phosphate acide d'alumi15 nium, le phosphate acide de gallium, le phosphate acide d'indium, le phosphate acide de thallium, le phosphate acide d'étain, le phosphate acide de plomb, le phosphate acide d'antimoine et le phosphate acide de bismuth On peut également utiliser un produit de réaction de l'acide. 20 phosphorique avec un composé d'un métal du groupe I Va ou Va de la classification périodique des -éléments, par exemple un produit ayant un rapport atomique de P-/Ti=l, thane, acidic cerium phosphate, acidic praseodymium phosphate, neodymium acid phosphate, promethium acid phosphate, samarium acid phosphate, europium phosphate-acid, dolminium acid phosphate, acid phosphate terbium, dysprosium acid phosphate, holmium acid phosphate, erbium acid phosphate, thulium acid phosphate, ytterbium acid phosphate, lutetium acid phosphate, chromium acid phosphate, acid phosphate 10 of manganese, iron acid phosphate, cobalt acid phosphate, nickel acid phosphate, copper acid phosphate, silver acid phosphate, zinc acid phosphate, cadmium acid phosphate, acid phosphate of mercury, aluminum acid phosphate, gallium acid phosphate, indium acid phosphate, thallium acid phosphate, tin acid phosphate, lead acid phosphate, antimony acid phosphate, and acid phosphate of bismuth A reaction product of the acid can also be used. Phosphoric compound with a group I metal compound Va or Va of the periodic table of the elements, for example a product having an atomic ratio of P- / Ti = 1,
P/Zr=l, P/Hf=l, P/V= 1, P/Nb=l,5 ou P/Ta= 1,5. P / Zr = 1, P / Hf = 1, P / V = 1, P / Nb = 1.5 or P / Ta = 1.5.
De plus, des sels normaux de l'acide phosphori25 que peuvent être utilisés comme par exemple le phosphate de bore, le phosphate de scandium, le phosphate d'yttrium, le phosphate de lanthane, le phosphate de cérium, le phosphate de praséodyme le phosphate de néodyme, le phosphate de prométhium, le phosphate de samarium, le phosphate d'europium, le phosphate de gadolinium, le phosphate de terbium, le phosphate de dysprosium le phosphate d'holmium, le phosphate d'erbium, le phosphate de thulium, le phosphate d'ytterbium, le phosphate de lutétium, le phosphate de chrome, le phosphate de fer, In addition, normal salts of phosphoric acid can be used such as, for example, boron phosphate, scandium phosphate, yttrium phosphate, lanthanum phosphate, cerium phosphate, praseodymium phosphate, phosphate, and the like. neodymium, promethium phosphate, samarium phosphate, europium phosphate, gadolinium phosphate, terbium phosphate, dysprosium phosphate, holmium phosphate, erbium phosphate, thulium phosphate, ytterbium phosphate, lutetium phosphate, chromium phosphate, iron phosphate,
le phosphate d'aluminium et le phosphate de bismuth. aluminum phosphate and bismuth phosphate.
En tant que composés de l'acide phosphorique, As phosphoric acid compounds,
on peut avoir recours aux suivants: l'acide orthophosphorique l'acide pyrophosphorique, l'acide métaphospho5 rique et les acides phosphoriques condensés tels que l'acide polyphosphorique. the following can be used: orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid and condensed phosphoric acids such as polyphosphoric acid.
En tant que composés de l'acide phosphoreux, As compounds of phosphorous acid,
on peut avoir recours à l'acide orthophosphoreux De plus. we can use orthophosphorous acid moreover.
les esters mono-, di-, tri-alcoyliques ou aryliques de e 10 l'acide phosphorique ou de l'acide phosphoreux peuvent être utilisés en tant que catalyseurs dans le procédé selon l'invention, les groupes alcoyle étant de préférence ceux ayant l à 8 atomes de carbone et les groupes aryle étant de préférence ceux-ayant 6 à 20 atomes de 15 carbone, c'est-à-dire le groupe phényle ou les groupes phénylalcoyl-substituéso Par exemple, on peut utiliser le phosphate de triéthyle, le phosphite de triéthyle, the mono-, di-, tri-alkyl or aryl esters of phosphoric acid or phosphorous acid may be used as catalysts in the process according to the invention, the alkyl groups being preferably those having to 8 carbon atoms and the aryl groups being preferably those having 6 to 20 carbon atoms, ie phenyl group or phenylalkyl-substituted-groups For example, triethyl phosphate may be used, triethyl phosphite,
le phosphate de phényle ou le phosphite de phényle. phenyl phosphate or phenyl phosphite.
Dans le cas des acides phosphoriques ou phos20 phoreux alcoyl ou arylsubstitués, on préfàre les groupes alcoyle et aryle ayant 1 à 8 atomes de carbone et 6 à 20 atomes de carbone, respectivement, c'est-à-dire par exemple des acides tels que l'acide phénylphosphinique, l'acide éthylphosphinique, l'acide phénylphosphonique et 25 l'acide naphtophosphonique Parmi les substances contenant du phosphore mentionnées ci-dessus, sont particulièrement préférés les phosphates diacides, les phosphates de composés du vanadium et les phosphates de composés des terres rares. 30 La quantité de substance contenant du phosphore mentionnéeci-dessus utilisée en tant que catalyseur, peut être d'environ 0,01 à 1 mole en référence à la teneur en phosphore pour 1 mole de monoéthanolamine en tant que matière brute Une quantité inférieure à 0, 01 mole ne présente pas une activité suffisante, tandis In the case of alkyl or arylsubstituted phosphoric or phosphoteric acids, alkyl and aryl groups having 1 to 8 carbon atoms and 6 to 20 carbon atoms, respectively, ie, for example acids such as phenylphosphinic acid, ethylphosphinic acid, phenylphosphonic acid and naphthophosphonic acid. Among the phosphorus-containing substances mentioned above, diacid phosphates, vanadium compound phosphates and phosphate compounds are particularly preferred. rare earth. The amount of phosphorus-containing substance mentioned above used as a catalyst may be about 0.01 to 1 mole by reference to the phosphorus content per mole of monoethanolamine as the raw material. , 01 mole does not show sufficient activity, while
qu'une quantité supérieure à 1 mole peut être non nécessaire. an amount greater than 1 mole may be unnecessary.
Selon la présente invention, l'éthylènediamine 5 est habituellement ajoutée en une quantité de 0-, 1 à 5 moles pour 1 mole de monoéthanolamine. According to the present invention, ethylenediamine is usually added in an amount of from 0. 1 to 5 moles per 1 mole of monoethanolamine.
Si l'on ajoute moins de 0,1 mole d'éthylènediamine, la sélectivité de la diéthylènetriamine devient moins bonne en raison de la production secondaire d'éthy10 lènediamine, d'aminoéthyléthanolamine, de pipérazine ou d'aminoéthylpipérazine Par ailleurs, si l'on ajoute plus de 5 moles d'éthylènediamine, le degré d'accroissement de If less than 0.1 mole of ethylenediamine is added, the selectivity of diethylenetriamine becomes less favorable due to the secondary production of ethylene diamine, aminoethylethanolamine, piperazine or aminoethylpiperazine. more than 5 moles of ethylenediamine are added, the degree of
la sélectivité de la diéthylènetriamine n'est pas significatif/tandis que l'efficacité volumique du réacteur de15 vient moins bonne. the selectivity of the diethylenetriamine is not significant / while the efficiency of the reactor de15 comes less good.
En conséquence, on ajoute de préférence de 1 à As a result, 1 to
2 moles d'éthylènediamine.2 moles of ethylenediamine.
Dans le procédé de la présente invention, on fait réagir l'ammoniac et la monoéthanolamine en une pro20 portion molaire d'ammoniac à la monoéthanolamine d'au moins 11 S'ils réagissent dans un rapport inférieur à 11, l'éthylènediamine est consommée en de larges quantités, ce qui rend le procédé inefficace La proportion molaire est de préférence de 11 à 30 Plus la proportion molaire 25 est élevée, plus la sélectivité de la diéthylènetriamine est bonne, mais plus l'efficacité volumique du réacteur est mauvaise La température de réaction est habituellement fixée à 200 à 400 C A une température inférieure à 2000 C, la vitesse de réaction est réduite, tandis qu'à une température supérieure à 4000 C, la décomposition thermique de la diéthylènetriamine augmente La température préférée est de 250 à 3000 C Bien que la durée de réaction dépende de la quantité de catalyseur utilisée et de la température de réaction, environ 30 minutes à 8 heures In the process of the present invention, ammonia and monoethanolamine are reacted in a molar proportion of monoethanolamine ammonia of at least 11. If they react in a ratio of less than 11, the ethylenediamine is consumed in the following manner. The molar proportion is preferably 11 to 30%. The higher the molar ratio, the better the selectivity of the diethylenetriamine, but the lower the volume efficiency of the reactor. reaction is usually set at 200 to 400 CA a temperature below 2000 C, the reaction rate is reduced, while at a temperature above 4000 C, the thermal decomposition of diethylenetriamine increases The preferred temperature is 250 to 3000 C Although the reaction time depends on the amount of catalyst used and the reaction temperature, about 30 minutes to 8 hours
sont habituellement suffisantes.are usually sufficient.
La réaction peut être effectuée soit en phase liquide, soit en phase gazeuse, mais de préféren 6 e en The reaction can be carried out either in the liquid phase or in the gas phase, but preferably in
phase liquide o la pression manométrique est habituel5 lement maintenue à au moins 196 105 Pa ( 200 kg/cm 2). liquid phase where the gauge pressure is usually maintained at at least 196 105 Pa (200 kg / cm 2).
Etant donné que des substances cycliques telles que la pipérazine et l'aminopipérazine sont produites dans de larges proportions en phase gazeuse, il est préférable de Since cyclic substances such as piperazine and aminopiperazine are produced in large proportions in the gas phase, it is preferable to
réaliser la réaction en phase liquide. perform the reaction in the liquid phase.
1 En mettant en oeuvre le procédé selon l'invention, tant un système en discontinu qu'un système en continu fournissent des résultats acceptables, mais le système en continu avec un lit fixe est préférable du point de vue de la séparation-du catalyseur utilisé Dans ce cas, la vitesse spatiale des réactifs est utilisée à environ 0,1 jusqu'à environ 10 g de l'ensemble des réactifs/ ml de volume de catalyseur/h, de préférence d'environ 0,2 à 2. Le catalyseur ci-dessus peut être supporté sur 20 un support tel que de la terre de diatomées, de la silice ou de l'alumine La diéthylènetriamine produite peut facilement être séparée à partir du mélange réactionnel, By carrying out the process according to the invention, both a batch system and a continuous system provide acceptable results, but the continuous system with a fixed bed is preferable from the point of view of the separation of the catalyst used. In this case, the space velocity of the reagents is used at about 0.1 to about 10 g of all reagents / ml of catalyst volume / h, preferably about 0.2 to 2. The catalyst above can be supported on a support such as diatomaceous earth, silica or alumina. The diethylenetriamine produced can easily be separated from the reaction mixture,
par exemple par distillation.for example by distillation.
Etant donné que le procédé selon l'invention 25 permet de produire de l-a diéthylènetriamine à partir de l'ammoniac et de la monoéthanolamine sans consommer Since the process according to the invention makes it possible to produce 1-diethylenetriamine from ammonia and monoethanolamine without consuming
réellement l'éthylènediamine coûteuse qui est ajoutée mais n'est pas utilisée en tant que matière brute dans le cadre de l'invention, ëe procédé présente une 30 grande valeur industrielle. In fact, the expensive ethylenediamine which is added but is not used as a raw material in the context of the invention, the process has a high industrial value.
L'invention sera illustrée plus en détail par les exemples non limitatifs qui suivent: The invention will be illustrated in more detail by the following nonlimiting examples:
Exemple 1Example 1
18,3 g ( 0,3 mole) de monoéthanolamine, 18,0 g ( 0,3 mole) d'éthytlènediamine et 3,18 g ( 0,03 mole, calcu16 e en tant que P) de phosphate diacide d'aluminium sont introduits dans un autoclave ayant une capacité de 300 ml et muni d'un agitateur magnétique Après avoir remplacé l'air de l'autoclave par de l'azote, on y introduit 56,2 g { 3,3 moles) d'ammoniac liquide et on chauffe le mélange jusqu'à 270 'C et on le maintient ensuite 3 heures à cette température, la pression manométrique étant de 274 10 Pa ( 280 kg/cm 2) La solution réactionnelle est ensuite refroidie à la température ambiante, la pression étant réduite, et la solution est retirée et analysée par 18.3 g (0.3 mole) of monoethanolamine, 18.0 g (0.3 mole) of ethylenediamine and 3.18 g (0.03 mole, calculated as P) of aluminum dihydrogen phosphate are introduced into an autoclave having a capacity of 300 ml and equipped with a magnetic stirrer. After replacing the air of the autoclave with nitrogen, 56.2 g (3.3 moles) of ammonia are introduced into it. liquid and the mixture is heated to 270 ° C. and then kept at this temperature for 3 hours, the pressure being 274 10 Pa (280 kg / cm 2). The reaction solution is then cooled to room temperature, pressure being reduced, and the solution is removed and analyzed by
chromatographie gazeuse.gas chromatography.
Conversion de la monoéthanolamine 81 % Sélectivité de la diéthylènetriamine 704 % Dans les conditions ci-dessus -proportion molaire NH 3/monoéthanolamine de 11), l'éthylènediamine reste dans la solution réactionnelle en la même quantité, 18,O g, que celle qui a été introduite Ceci signifie que la diéthylènetriamine est synthétisée par la seule réaction de 20 la monoéthanolamine et de l'ammoniac en tant que matières brutes. Conversion of monoethanolamine 81% selectivity of diethylenetriamine 704% Under the above conditions-NH 3 / monoethanolamine molar proportion of 11), the ethylenediamine remains in the reaction solution in the same amount, 18.0 g, as that which This means that diethylenetriamine is synthesized by the single reaction of monoethanolamine and ammonia as raw materials.
Exemple 2.Example 2
Le mode opératoire décrit dans l'exemple 1 est The procedure described in Example 1 is
répété si ce n'est que la quantité d'ammoniac liquide est 25 de 66 4 g ( 3,9 moles). repeated except that the amount of liquid ammonia is 664 g (3.9 moles).
Conversion de la monoéthanolamine 76 % Sélectivité de la diéthylènetriamine 74 % Sélectivité de l'éthylènediamine 2 % Conversion of monoethanolamine 76% Selectivity of diethylenetriamine 74% Selectivity of ethylenediamine 2%
Dans les conditions ci-dessus {proportion mo30 laire NH 3/monoéthanolamine de 13), la quantité d'éthylènediamine augmente par rapport à ce qu'elle était avant la réaction. Under the above conditions (NH 3 / monoethanolamine molar ratio 13), the amount of ethylenediamine increases from that prior to the reaction.
L'accroissement de la quantité d'éthylènediamine est de The increase in the amount of ethylenediamine is
2,0 % par rapport à la monoéthanolamine convertie. 2.0% based on the converted monoethanolamine.
Exemple 3.Example 3
On répète le mode opératoire décrit à l'exemple 1 si ce n'est que la quantité d'ammoniac liq uide est de 76,6 g { 4,5 moles) Conversion de la monoéthanolamine 72 % Sélectivité de la diétbylénetriamine 77 % Sélectivité de 1 'éethylènediamine 4 % The procedure described in Example 1 is repeated except that the amount of liquid ammonia is 76.6 g (4.5 mol). Conversion of monoethanolamine 72% Selectivity of diethanoletriamine 77% Selectivity of 1 'ethylenediamine 4%
Témoin 1.Witness 1.
On répète le mode opératoire décrit à l'exemple 10 si ce n'est que la quantité d'ammoniac liquide est de The procedure described in Example 10 is repeated except that the quantity of liquid ammonia is
46,0 g {i 2,7 moles).46.0 g (2.7 moles).
Conversion de la monoéthanolamine 86 % Sélectivité de la diéthylènetriamine 64 % Dans les conditions ci-dessus (proportion-mo15 laire NH 3/monoéthanolamine de 9), la quantité d'éthylènediamine décro It par rapport à ce qu'elle était avant la réaction La quantité d'éthylènediamine consommée est de 2 % par rapport à la monoéthanolamine convertie Conversion of monoethanolamine 86% Selectivity of diethylenetriamine 64% Under the above conditions (NH 3 / monoethanolamine proportion of 9), the amount of ethylenediamine declines from that before the reaction. amount of ethylenediamine consumed is 2% compared to the converted monoethanolamine
Exemples 4 à 24.Examples 4 to 24.
On répète le mode opératoire décrit à l'exemple 1 si ce n'est que l'on change les différents catalyseurs utilisés, les quantités de ceux-ci étant de 'O,O-03 mole exprimées en P Les résultats obtenus sont rassemblés dans le tableau I. The procedure described in Example 1 is repeated except that the various catalysts used are changed, the amounts thereof being 0.05 mole expressed in P. The results obtained are gathered in FIG. Table I.
' -'-
TABLEAU ITABLE I
Production de diéthylènetriamine en utilisant différents catalyseurs Exemple Monoethanol Diethylene Ethylene TriethyleneN Ex Catalyseur amine triamine diamine tétramine conversion % sélectivité % sélectivité % sélectivité % 4 3 H 3 PO 4-La(OH) 87 66 O 17 Production of diethylenetriamine using different catalysts Example Monoethanol Diethylene Ethylene TriethyleneN Ex Catalyst amine triamine diamine tetramine conversion% selectivity% selectivity% selectivity% 4 3 H 3 PO 4-La (OH) 87 66 O 17
3 4)33 4) 3
3 H 3 P 04-Y(OH)3 92 58 1 133 H 3 P 04-Y (OH) 3 92 58 1 13
6 Zr O(Hi 2 P 04)2 21 66 1 6 7 Ti O(H 2 PO 2 33 77 2 7 6 Zr O (H 2 P O) 2 21 66 1 6 7 Ti O (H 2 PO 2 33 77 2 7
2 3 74 272 3 74 27
8 VO(H 2 P 04)2 78 78 4 88 VO (H 2 P 04) 2 78 78 4 8
9 6 H 3 PO 4-Nb 205 98 60 1 9 6 H 3 P 04-Ta 205 93 64 1 9 11 BPO 4 95 70 1 1 il 12 Ca(H 2 PO 04)9 97 55 12 13 Li H 2 PO 87 70 O 15 14 Fe(H 2 PO 4) 3 83 71 1 10 3 H 3 P 04-Cr(OH)3 85 74 13 9 6 H 3 PO 4-No 205 98 60 1 9 6 H 3 P 04-Ta 205 93 64 1 9 11 BPO 4 95 70 1 1 y 12 Ca (H 2 PO 04) 9 97 55 12 13 Li H 2 PO 87 70 O 15 14 Fe (H 2 PO 4) 3 83 71 1 10 3 H 3 P 04-Cr (OH) 3 85 74 13
16 B(H 24)2: 68 62 O O 1416 B (H 24) 2: 68 62 O O 14
16 Ba(H 2 PO 4)1)6 201 Ln t o %o TABLEAU I (suite) r 16 Ba (H 2 PO 4) 1) 6 201 Ln t o% o TABLE I (cont'd) r
ExempleExample
No Catalyseur MonoéthanolamineNo Catalyst Monoethanolamine
conversion %.conversion%.
Diéthylènetriamine selectivité % Ethylènediamine selectivité % Triéthylènetétramine selectivit '% I 17 18 Diethylenetriamine selectivity% Ethylene diamine selectivity% Triethylenetetramine selectivity% I 17 18
19 20 21 22 23 2419 20 21 22 23 24
Mn(H 2 P 04)2 3 H 3 P 04-Ce(OH)3 Pb(H 2 P 04)2 TZH PIO 2 4 TQH 2 PD 4 Fe HP 207 AX(P 03)3 H 3 PO 4-gel de silice acide phénylphosphonique Mn (H 2 P 04) 2 3 H 3 P 04-Ce (OH) 3 Pb (H 2 P 04) 2 TZH PIO 2 4 TQH 2 PD 4 Fe HP 207 AX (P 03) 3 H 3 PO 4-gel Phenylphosphonic acid silica
83 91 83 77 65 80 86 9083 91 83 77 65 80 86 90
60 70 '74 61 60 60 6060 70 '74 61 60 60 60
1 0 0 O1 0 0 O
3 0 0.03 0.0
il '16 13he '16 13
13 20 17 1513 20 17 15
bobo
L ____________________________________ _____________________________________ _____________________________________ 1 L ____________________________________ _____________________________________ _____________________________________ 1
tn u 1 oo 0 o O Otn u 1 oo 0 o O O
Témoin 2.Witness 2.
18,3 g ( 0,3 mole) de monoéthanolamine, 18,0 g ( 0,3 mole) d'éthylènediamine et du lanthane-acide phosphorique en tant que catalyseur (proportion molaire P/La de 3) à raison de 0,03 mole exprimée en P, sont introduits dans un autoclave ayant une capacité de 300 ml et Auni d'un agitateur magnétique Après avoir remplacé l'air de l'autoclave par de l'azote on y introduit 25,5 g ( 1,5 mole) d'ammoniac liquide et le mélange est chauffé jusqu'à 10 270 C puis maintenu 3 heures à cette température La solution réactionnelle est ensuite refroidie à la température ambiante, la pression étant diminuée,et la solution est 18.3 g (0.3 mole) of monoethanolamine, 18.0 g (0.3 mole) of ethylenediamine and lanthanum-phosphoric acid as catalyst (molar ratio P / La of 3) at 0, Mole, expressed in P, are introduced into an autoclave having a capacity of 300 ml and equipped with a magnetic stirrer. After replacing the air of the autoclave with nitrogen, 25.5 g (1.5 g) are introduced into it. mole) of liquid ammonia and the mixture is heated to 10 270 C and then held for 3 hours at this temperature The reaction solution is then cooled to room temperature, the pressure is decreased, and the solution is
retirée et analysée par chromatographie gazeuse. removed and analyzed by gas chromatography.
Conversion de la monoéthanolamine 1 OO % Sélectivité de la diéthylènetriamine 33 % Sélectivité de la triéthylènetétramine 8 % Sélectivité de la pipérazine 14 % Sélectivité de l'aminoéthylpipérazine 17 % Dans les conditions ci-dessus (proportion mo20 laire NH 3/monoéthanolamine de 5), l'éthylènediamine est consommée à raison de 22 % par rapport à la monoéthanolamine convertie De plus, la sélectivité de la diéthylènetriamine est fortement réduite et de grandes quantités Conversion of monoethanolamine 100% Selectivity of diethylenetriamine 33% Selectivity of triethylenetetramine 8% Selectivity of piperazine 14% Selectivity of aminoethylpiperazine 17% Under the above conditions (NH 3 / monoethanolamine molar ratio of 5), ethylenediamine is consumed at a rate of 22% relative to the converted monoethanolamine In addition, the selectivity of diethylenetriamine is greatly reduced and large amounts
de substances cycliques telles que la pipérazine et l'ami25 noéthylpipérazine sont produites. cyclic substances such as piperazine and ammonia piperazine are produced.
Témoin 3.Witness 3.
On répète le mode opératoire décrit à l'exemple The procedure described in the example is repeated
1, si ce n'est que l'on n'ajoute pas d'éthylènediamine. 1, except that no ethylenediamine is added.
Conversion de la monoéthanolamine 65 % Sélectivité de la diéthylènetriamine 32 % Sélectivité de l'éthylènediamine 44 % Dans ce cas, la sélectivité de la diéthylènetriamine est également faible,alors que de l'éthylènediamine Conversion of monoethanolamine 65% Selectivity of diethylenetriamine 32% Selectivity of ethylenediamine 44% In this case, the selectivity of diethylenetriamine is also low, while ethylenediamine
est produite en une grande quantité. is produced in a large quantity.
Exemple 25.Example 25
Préparation du catalyseur.Catalyst preparation
On dissout 112,8 g de nitrate de lanthane hexahydraté dans 300 ml d'eau auxquels on ajoute 168 g de 5 terre de diatomées Tandis que l'on agite la bouillie, on y ajoute 449,5 g d'une solution aqueuse à 20 % de phosphate diacide d'ammonium Après avoir chauffé la solution et l'avoir soumise à une évaporation de l'eau, on la sèche à 120 C pendant 3 heures puis on la cuit à 112.8 g of lanthanum nitrate hexahydrate are dissolved in 300 ml of water to which 168 g of diatomaceous earth are added. While the slurry is stirred, 449.5 g of a 20% aqueous solution are added. % of ammonium dihydrogen phosphate After heating the solution and evaporation of the water, it is dried at 120 ° C. for 3 hours and then cooked at room temperature.
1 Q 4000 C pendant 3 heures.1 Q 4000 C for 3 hours.
Préparation de la diéthylènetriamine. Preparation of diethylenetriamine
Le catalyseur ainsi préparé avec des tailles d'environ 1 à 1,4 'mm ( 12 16 mesh) une proportion atomique de P/La de 3, et 40 % d'équivalent de La(H 2 P 04)3, sup15 portés sur de la terre de diatomées, est introduit en une quantité de 150 ml dans un réacteur en acier inoxydable ayant un diamètre intérieur de 15 mm et une longueur de 1 m On introduit de l'ammoniac, de la monoéthanolamine et de l'éthylènediamine en des proportions molaires de NH 3/monoéthanolamine de 18 et d'éthylènediamine/monoéthanolamine de 2, et à une vitesse de l'alimentation mixte de 1 g/ml de catalyseur/h On maintient le réacteur à 260 C et la pression manométrique de réaction à 314 105 Pa The catalyst thus prepared with sizes of about 1 to 1.4 mm (12 16 mesh) an atomic proportion of P / La of 3, and 40% equivalent of La (H 2 P 04) 3, sup15 worn. on diatomaceous earth, is introduced in an amount of 150 ml in a stainless steel reactor having an internal diameter of 15 mm and a length of 1 m. Ammonia, monoethanolamine and ethylenediamine are introduced into molar proportions of NH 3 / monoethanolamine of 18 and of ethylenediamine / monoethanolamine of 2, and at a mixed feed rate of 1 g / ml of catalyst / h The reactor is maintained at 260 ° C. and the reaction pressure at 314 105 Pa
( 320 kg/cm 2).(320 kg / cm 2).
L'analyse de la solution réactionnelle donne les résultats suivants: Conversion de la monoéthanolamine 65 % Sélectivité de la diéthylènetriamine 91 % Sélectivité de la triéthylènetétramine 6 % Sélectivité de l'éthylènediamine 2 % Un système combiné à lit fixe et en continu tel qu'utilisé dans cet exemple est préférable pour produire industriellement la diéthylènetriamine selon le procédé The analysis of the reaction solution gives the following results: Conversion of monoethanolamine 65% Selectivity of diethylenetriamine 91% Selectivity of triethylenetetramine 6% Selectivity of ethylenediamine 2% A combined fixed and continuous bed system as used in this example is preferable for industrially producing diethylenetriamine by the process
de la présente invention.of the present invention.
Si l'on désire obtenir des polyamines supérieures à la diéthylènetriamine, il est également possible If it is desired to obtain polyamines higher than diethylenetriamine, it is also possible
de les produire avec des rendements suffisants en recyclant la diéthylènetriamine ainsi produite vers le réac5 teur. to produce them with sufficient yields by recycling the diethylenetriamine thus produced to the reactor.
2553 0692553 069
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58185871A JPS6078945A (en) | 1983-10-06 | 1983-10-06 | Production of diethylenetriamine |
Publications (2)
Publication Number | Publication Date |
---|---|
FR2553089A1 true FR2553089A1 (en) | 1985-04-12 |
FR2553089B1 FR2553089B1 (en) | 1988-09-23 |
Family
ID=16178333
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR8415322A Expired FR2553089B1 (en) | 1983-10-06 | 1984-10-05 | PROCESS FOR PRODUCING DIETHYLENETRIAMINE FROM MONOETHANOLAMINE |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS6078945A (en) |
BE (1) | BE900759A (en) |
DE (1) | DE3436036A1 (en) |
FR (1) | FR2553089B1 (en) |
GB (1) | GB2147896B (en) |
IT (1) | IT1176876B (en) |
NL (1) | NL189347C (en) |
SE (1) | SE465125B (en) |
ZA (1) | ZA847588B (en) |
Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4578517A (en) * | 1983-09-16 | 1986-03-25 | Air Products And Chemicals, Inc. | Polyalkylene polyamines from alkanolamine and ammonia or amines using group IIIB metal acid phosphate catalysts |
US4605770A (en) * | 1983-12-22 | 1986-08-12 | Air Products And Chemicals, Inc. | Noncyclic polyalkylene polyamines by the reaction of an alkanolamine compound and an alkyleneamine compound in the presence of a Group IIA or Group IIIB metal acid phosphate catalyst |
JPS6154241A (en) * | 1984-08-21 | 1986-03-18 | シ−ビ−エムエム・インタ−ナシヨナル・リミタ−ダ | Water containing niobium oxide solid acid catalyst |
US4617418A (en) * | 1984-11-26 | 1986-10-14 | Air Products And Chemicals, Inc. | Polyalkylene polyamines via vapor phase reaction |
US5202489A (en) * | 1987-12-22 | 1993-04-13 | Union Carbide Chemicals & Plastics Technology Corporation | Amines catalysis |
JP2764968B2 (en) * | 1988-02-10 | 1998-06-11 | 東ソー株式会社 | Method for producing alkyleneamines |
US4927931A (en) * | 1988-11-01 | 1990-05-22 | The Dow Chemical Company | Preparation of alkyl-extended, alcohol-extended or amine-extended piperazines |
US4973569A (en) * | 1988-11-01 | 1990-11-27 | The Dow Chemical Company | Preparation of group VB metal phosphate catalysts therefor |
US4950690A (en) * | 1988-11-28 | 1990-08-21 | Air Products And Chemicals, Inc. | Process for the animation of alcohols using activated phosphorus-containing catalysts |
US5210307A (en) * | 1988-12-20 | 1993-05-11 | The Dow Chemical Company | Catalytic reforming of alkyleneamines to linearly-extended polyalkylenepolyamines |
US5166442A (en) * | 1988-12-20 | 1992-11-24 | The Dow Chemical Company | Catalytic reforming of alkyleneamines |
US4996363A (en) * | 1988-12-20 | 1991-02-26 | The Dow Chemical Company | Catalytic reforming of alkyleneamines to linearly-extended polyalkylenepolyamines |
US5011999A (en) * | 1989-02-23 | 1991-04-30 | The Dow Chemical Company | Process of preparing non-cyclic polyalkylenepolyamines employing group VB metal catalysts |
JP2764093B2 (en) * | 1989-07-14 | 1998-06-11 | 三井化学株式会社 | Preparation of acyclic ethyleneamines |
JP2764078B2 (en) * | 1989-07-14 | 1998-06-11 | 三井化学株式会社 | Preparation of acyclic ethyleneamines |
JPH0348643A (en) * | 1989-07-18 | 1991-03-01 | Mitsui Toatsu Chem Inc | Production of non-cyclic ethyleneamines |
US5082972A (en) * | 1989-07-17 | 1992-01-21 | Mitsui Toatsu Chemicals, Inc. | Process for preparation of acyclic ethyleneamines |
JP2938093B2 (en) * | 1989-07-17 | 1999-08-23 | 三井化学株式会社 | Method for producing acyclic ethyleneamines |
JP2764094B2 (en) * | 1989-07-18 | 1998-06-11 | 三井化学株式会社 | Preparation of acyclic ethyleneamines |
US5210306A (en) * | 1989-08-08 | 1993-05-11 | Union Carbide Chemicals & Plastics Technology Corporation | Promoted amines catalysis |
US5101074A (en) * | 1989-08-08 | 1992-03-31 | Union Carbide Chemicals & Plastics Technology Corporation | Vicinal di(hetro) alkylene organometalates and processes for the production of amines therewith |
US4983736A (en) * | 1989-08-08 | 1991-01-08 | Union Carbide Chemicals And Plastic Company Inc. | Amines catalysis using metallic polyphosphate condensation catalysts having a condensed structure |
US5202492A (en) * | 1989-08-08 | 1993-04-13 | Union Carbide Chemicals & Plastics Technology Corporation | Amines catalysis using metallic phosphate condensation catalysts having a cyclic structure |
US5225600A (en) * | 1989-08-08 | 1993-07-06 | Union Carbide Chemicals & Plastics Technology Corporation | Amines catalysis using group VIB metal-containing condensation catalysts |
DE69029825T2 (en) * | 1989-08-08 | 1997-06-05 | Union Carbide Chem Plastic | Process for the preparation of polyalkylene polyamines |
US5214213A (en) * | 1990-03-30 | 1993-05-25 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of linear tetraethylenepentamine and hydroxyethyldiethylenetriamine |
US5166415A (en) * | 1990-03-30 | 1992-11-24 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of diethylenetriamine and aminoethylethanolamine |
US5214215A (en) * | 1990-03-30 | 1993-05-25 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of aminoethylethanolamine |
US5225599A (en) * | 1990-03-30 | 1993-07-06 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of linear triethylenetetramine and aminoethylethanolamine |
US5231230A (en) * | 1990-03-30 | 1993-07-27 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of diethylenetriamine |
US5220071A (en) * | 1990-03-30 | 1993-06-15 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of pentaethylenehexamine and hydroxyethyltriethylenetetramine |
US5225598A (en) * | 1990-03-30 | 1993-07-06 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of linear pentaethylenehexamine and hydroxyethyldiethylenetriamine |
US5073635A (en) * | 1990-06-22 | 1991-12-17 | The Dow Chemical Company | Process of preparing linearly-extended polyalkylenepolyamines employing metal silicate catalysts |
DE10335991A1 (en) | 2003-08-01 | 2005-02-24 | Basf Ag | Process for the preparation of ethylene amines |
JP2006342745A (en) * | 2005-06-09 | 2006-12-21 | Nippon Sharyo Seizo Kaisha Ltd | Engine working machine |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0073520A1 (en) * | 1981-08-31 | 1983-03-09 | Air Products And Chemicals, Inc. | Preparation of polyalkylene polyamines from ammonia, alkyleneamine and alkanolamine |
EP0131958A1 (en) * | 1983-07-19 | 1985-01-23 | Air Products And Chemicals, Inc. | Production of non cyclic polyalkylene polyamines |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1514306A (en) * | 1967-01-11 | 1968-02-23 | P Barnier Ets | Process for obtaining and applications of long chain hydrocarbon polyamine products |
US3869527A (en) * | 1971-08-17 | 1975-03-04 | Leo Ab | Secondary phosphate esters |
GB1424513A (en) * | 1972-06-13 | 1976-02-11 | Ciba Geigy Ag | Organic phosphates |
US4036881A (en) * | 1975-06-02 | 1977-07-19 | Texaco Development Corporation | Preparation of polyalkylene polyamines |
US4324917A (en) * | 1980-08-28 | 1982-04-13 | Texaco Inc. | Preparation of polyalkylene polyamines |
CA1202328A (en) * | 1981-09-30 | 1986-03-25 | William B. Herdle | Preparation of polyalkylene polyamines |
JPH05232283A (en) * | 1992-02-26 | 1993-09-07 | Toshiba Corp | Measuring equipment of radioactive substance released on accident of nuclear power plant |
KR930020867A (en) * | 1992-03-02 | 1993-10-20 | 빈센트 비.인그라시아 | Remote Sensing Units and Drivers |
-
1983
- 1983-10-06 JP JP58185871A patent/JPS6078945A/en active Granted
-
1984
- 1984-09-26 ZA ZA847588A patent/ZA847588B/en unknown
- 1984-10-02 DE DE19843436036 patent/DE3436036A1/en active Granted
- 1984-10-02 SE SE8404920A patent/SE465125B/en not_active IP Right Cessation
- 1984-10-03 NL NLAANVRAGE8403008,A patent/NL189347C/en not_active IP Right Cessation
- 1984-10-05 FR FR8415322A patent/FR2553089B1/en not_active Expired
- 1984-10-05 GB GB08425228A patent/GB2147896B/en not_active Expired
- 1984-10-05 IT IT23028/84A patent/IT1176876B/en active
- 1984-10-05 BE BE0/213783A patent/BE900759A/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0073520A1 (en) * | 1981-08-31 | 1983-03-09 | Air Products And Chemicals, Inc. | Preparation of polyalkylene polyamines from ammonia, alkyleneamine and alkanolamine |
EP0131958A1 (en) * | 1983-07-19 | 1985-01-23 | Air Products And Chemicals, Inc. | Production of non cyclic polyalkylene polyamines |
Also Published As
Publication number | Publication date |
---|---|
IT1176876B (en) | 1987-08-18 |
IT8423028A0 (en) | 1984-10-05 |
GB2147896B (en) | 1987-04-08 |
NL189347B (en) | 1992-10-16 |
GB2147896A (en) | 1985-05-22 |
SE465125B (en) | 1991-07-29 |
NL8403008A (en) | 1985-05-01 |
GB8425228D0 (en) | 1984-11-14 |
FR2553089B1 (en) | 1988-09-23 |
BE900759A (en) | 1985-02-01 |
IT8423028A1 (en) | 1986-04-05 |
DE3436036C2 (en) | 1989-11-09 |
JPH0445505B2 (en) | 1992-07-27 |
SE8404920D0 (en) | 1984-10-02 |
NL189347C (en) | 1993-03-16 |
DE3436036A1 (en) | 1985-05-02 |
SE8404920L (en) | 1985-04-07 |
ZA847588B (en) | 1985-06-26 |
JPS6078945A (en) | 1985-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
FR2553089A1 (en) | PROCESS FOR PRODUCING DIETHYLENETRIAMINE FROM MONOETHANOLAMINE | |
EP1988998B1 (en) | Improved process for producing nickel(0)-phosphorus ligand complexes | |
KR20060129427A (en) | Removal of permanganate reducing compounds from methanol carbonylation process stream | |
WO1996040592A1 (en) | Formic acid and formaldehyde destruction in waste streams | |
WO2009063926A1 (en) | PROCESS FOR PRODUCING α,β -UNSATURATED ETHER | |
WO2017040583A1 (en) | Inhibiting cpi formation from adiponitrile | |
CN1107055C (en) | Method for preparation of lactan | |
Fadel et al. | Synthesis of enantiomerically pure (1S, 2S)‐1‐aminocyclopropanephosphonic acids from (2S)‐methylcyclopropanone acetal | |
US5202455A (en) | Process for the liquid-phase preparation of nitriles from aliphatic dicarboxylic acids | |
JPH0542436B2 (en) | ||
RU2059597C1 (en) | Method of 3-methyl-1-butyne-3-ol synthesis | |
US5082972A (en) | Process for preparation of acyclic ethyleneamines | |
JPH0859205A (en) | Production of hydroiodic acid | |
JPH07504084A (en) | Enzymatic production of N-(phosphonomethyl)glycine | |
US20090143618A1 (en) | Method for the production of formic acid formates | |
JP2938093B2 (en) | Method for producing acyclic ethyleneamines | |
JPH0348643A (en) | Production of non-cyclic ethyleneamines | |
US6841666B2 (en) | Process for the preparation of ε-caprolactam | |
BE842465A (en) | PROCESS FOR PREPARING NON-CYCLIC POLYALKYLENEPOLYAMINES | |
US4950690A (en) | Process for the animation of alcohols using activated phosphorus-containing catalysts | |
FR2624509A1 (en) | PROCESS FOR THE PREPARATION OF ACETYL CHLORIDE | |
CA1143717A (en) | Catalyst for decomposition of 1,3-dioxanes | |
JPS5939843A (en) | Preparation of glyoxal | |
US6844467B2 (en) | Method for the production of glyceric acid | |
JPH05186410A (en) | Method for purifying crude acetonitrile by extraction with caustic alkali |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ST | Notification of lapse |