JP5073914B2 - トリエチレンジアミンを選択的に合成するための方法 - Google Patents
トリエチレンジアミンを選択的に合成するための方法 Download PDFInfo
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- JP5073914B2 JP5073914B2 JP2003510666A JP2003510666A JP5073914B2 JP 5073914 B2 JP5073914 B2 JP 5073914B2 JP 2003510666 A JP2003510666 A JP 2003510666A JP 2003510666 A JP2003510666 A JP 2003510666A JP 5073914 B2 JP5073914 B2 JP 5073914B2
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- Prior art keywords
- zeolite
- catalyst
- teda
- process according
- metal
- Prior art date
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000015572 biosynthetic process Effects 0.000 title abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000010457 zeolite Substances 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000008569 process Effects 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 29
- 239000002184 metal Substances 0.000 abstract description 29
- DXOHZOPKNFZZAD-UHFFFAOYSA-N 2-ethylpiperazine Chemical compound CCC1CNCCN1 DXOHZOPKNFZZAD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000001629 suppression Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 25
- 239000007858 starting material Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000001354 calcination Methods 0.000 description 11
- 238000010791 quenching Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 Co Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 150000004885 piperazines Chemical class 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
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- 238000005406 washing Methods 0.000 description 6
- 241001550224 Apha Species 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052733 gallium Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 150000002739 metals Chemical group 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 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 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- VARKIGWTYBUWNT-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanol Chemical compound OCCN1CCN(CCO)CC1 VARKIGWTYBUWNT-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- CJNRGSHEMCMUOE-UHFFFAOYSA-N 2-piperidin-1-ylethanamine Chemical compound NCCN1CCCCC1 CJNRGSHEMCMUOE-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 125000005595 acetylacetonate group Chemical class 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- RZZUXGKNTFNJGF-UHFFFAOYSA-N nitrosilyl nitrate Chemical class [N+](=O)(O[SiH2][N+](=O)[O-])[O-] RZZUXGKNTFNJGF-UHFFFAOYSA-N 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/08—Bridged systems
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
Description
(MI・MIIO2)・aMIIIO2・bH2O
[式中、MIは、1価のアルカリ金属イオンの1当量、プロトン、アンモニウム基であるか、あるいは2価のアルカル土類金属イオンの半当量であり、
MIIは、Al3+、B3+、Sb3+,As3+、Cr3+、V3+、Ga3+またはFe3+の1当量であり、
MIIIは、Si4+、Ge4+、Ti4+またはZr4+の1当量であり、
aは15〜200であり、かつ、
bは0〜8である]を示す。
(II=酸化状態2、III=酸化状態3、IV=酸化状態4)
通常、前記ゼオライトは、SiO2−源と金属−源(たとえば、M=Al、Zn、Be、B、Fe、Co、Ni、V、Mo、Mn、As、Sb、Bi、La、Ga、In、Y、Sc、Cr、Ti、Zr、Ge、Hfおよび/またはSnであり、前記に示したような酸化状態である)との混合物を、テンプレートとしての窒素含有塩基、たとえば、テトラアルキルアンモニウム塩中で、必要である場合にはさらに、塩基性化合物(たとえばアルカリ)を添加して、耐圧容器中で、高い温度で、数時間または数日に亘って反応させることによって製造され、その際、結晶質の生成物が形成される。これは分離(たとえば、濾別、噴霧乾燥または沈殿によって)し、洗浄し、乾燥し、かつ高温でか焼され、有機性窒素塩基を除去する(以下参照)。二者択一的に、ゼオライトの形成が保証される場合には、テンプレートを用いずに合成することも可能である。このようにして得られた粉末中において、金属(たとえば、M=Al、Zn、Be、B、Fe、Co、Ni、V、Mo、Mn、As、Sb、Bi、La、Ga、In、Y、Sc、Cr、Ti、Zr、Ge、Hfおよび/またはSnであり、前記に示したような酸化状態である)は、少なくとも部分的に、ゼオライト格子の範囲内で、4−,5−または6−倍の配位結合を有する種々の量で存在する。
(すべてのAHDA数はDIN ISO 6271による)
液体溶剤中へのTEDA蒸気の通過は、急冷装置、たとえば、好ましくは流下薄膜型凝縮器(fall-film condenser)(薄層型凝縮器(thin-film condenser)、散布型凝縮器(spray condenser)または流下型凝縮器(down-flow condenser))中でか、あるいはノズル装置中でおこなわれる。その際、TEDA蒸気は、液体溶剤に並流または向流で、TEDA蒸気に供給することができる。前記のように、TEDA蒸気を急冷装置中へ通過させることは有利である。フォールフィルム型凝縮器の頂部での液体溶剤を接線的供給、または1個または複数個のノズルを介しての液体供給は、急冷装置内壁の完全な湿潤を達成するために、さらに有利である。
反応に使用されたアミンに対するWHSV(重量空間速度)は0.01〜6h−1、好ましくは0.05〜1h−1、特に好ましくは0.1〜1h−1である。
反応器供給物(前記に示した組成のもの)を、蒸発器中で250〜500℃の温度で、気相に変換し、この場合は、蒸発器は、実際の反応器の一部分であってもよく、かつ触媒上を通過させる。反応器出口で、ガス状で得られる反応器搬出物は、ポンプによって循環される液体の反応器搬出物によって、20〜100℃の温度で、好ましくは80℃で急冷される。これらの液体反応器搬出物は、以下のようにして後処理された:第1蒸留工程において、低沸点成分、たとえばアセトアルデヒド、エチルアミン、アンモニアおよび水、ならびに合成中において副生成物として形成されるヘテロ環式化合物を分離除去する。第2蒸留工程において、反応器搬出物からピペラジンを放出させ、この場合、これは、再度、反応器供給物に再循環させる。分離除去されたピペラジン流は、20質量%のTEDAを含有していてもよい(二者択一的に、水およびピペラジンの同時の除去が可能であり、この場合、これらは一緒になって反応器供給物中に再循環することができる)。第3蒸留工程において、重要な生成物であるTEDAが反応搬出物から蒸留され、かつ、必要である場合には、たとえば、下流の晶出工程で(たとえば、以下に記載されている)、さらに後処理される。
単一の出発材料(PIP)のみの使用、
供給物中の水のわずかな過剰量(<60質量%)、
高いPIP変換率(>80質量%)、
高いTEDA選択率(>90%)、
EtPIP形成がわずかであることからのTEDAの簡単な後処理、
長い触媒寿命(>1000h)を有し、かつ再生可能な触媒。
実施例
A 触媒の製造
ゼオライト粉末(ALISIPENTA,Na−ZSM−5の型のアルモシリケート、モジュール1000)を、20%NH4Cl溶液で3回に亘って交換し、洗浄し、かつ500℃で5時間に亘ってか焼した。その後に粉末を、3回、8時間に亘って酸処理(5%濃度のHCl、室温)し、毎回水で洗浄することで中性にし、かつ500℃で3時間に亘ってか焼した。最終的に、ゼオライト粉末を、20質量%のSiO2(製造された2mmの押出物の全質量に対して)で押出し、かつ500℃で5時間に亘ってか焼した。
B 方法の実施
触媒を気相装置中で使用した(加熱された管型反応器;長さ:1000mm、直径6mm)。出発材料混合物:50%PIP、50.0%水(すべて質量%)。出発材料の水性混合物を、直接的に反応器中に汲み上げ、かつ、触媒上に大気圧下で通過させる前に、上に、反応温度350℃〜370℃で蒸発させた。空間速度:0.2kg 出発材料混合物/触媒kg/h。反応生成物を、反応器出口でコンデンサ中で凝縮させ、捕集し、かつアリコートをガスクロマトグラフィーにより分析した。
GC−分析:
カラム:RTX−5、30m;温度プログラム:80℃−5℃/分−280℃、検出器:FID
第1表:
ピペラジン(PIP)からのトリエチレンジアミン(TEDA)の合成
Claims (10)
- ゼオライト触媒の骨格がSiO 2 とAl 2 O 3 からなるゼオライト触媒上で、ピペラジンのみを原料としてトリエチレンジアミンを製造するための方法において、ゼオライトがSiO 2 /Al 2 O 3 モル比400〜5000を有することを特徴とする、トリエチレンジアミンを製造するための方法。
- 特にペンタシル型のゼオライトを使用する、請求項1に記載の方法。
- ゼオライトが、ZSM−5型またはZSM−11型であるか、あるいはこれらの混合された構造である、請求項2に記載の方法。
- 触媒が、少なくとも部分的にH−形で使用される、請求項1から3までのいずれか1項に記載の方法。
- 250〜500℃で実施する、請求項1から4までのいずれか1項に記載の方法。
- ピペラジンを、水および/または有機性希釈剤との混合物として使用する、請求項1から5までのいずれか1項に記載の方法。
- ピペラジン変換率が80%を上廻る、請求項1から6までのいずれか1項に記載の方法。
- 回分的にかまたは連続的に実施する、請求項1から7までのいずれか1項に記載の方法。
- 気相中で実施する、請求項8に記載の方法。
- 流動触媒床または固定触媒床上で実施する、請求項8に記載の方法。
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DE10132499A DE10132499A1 (de) | 2001-07-05 | 2001-07-05 | Verfahren zur selektiven Synthese von Triethylendiamin |
DE10132499.5 | 2001-07-05 | ||
PCT/EP2002/007430 WO2003004499A1 (de) | 2001-07-05 | 2002-07-04 | Verfahren zur selektiven synthese von triethylendiamin |
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JP2005500324A JP2005500324A (ja) | 2005-01-06 |
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US (1) | US6958397B2 (ja) |
EP (1) | EP1406904B1 (ja) |
JP (1) | JP5073914B2 (ja) |
KR (1) | KR20040023639A (ja) |
CN (1) | CN1228339C (ja) |
AT (1) | ATE341551T1 (ja) |
DE (2) | DE10132499A1 (ja) |
ES (1) | ES2272786T3 (ja) |
WO (1) | WO2003004499A1 (ja) |
Families Citing this family (10)
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DE10326137A1 (de) | 2003-06-06 | 2004-12-23 | Basf Ag | Verfahren zur Erhöhung der Schneidhärte eines Formkörpers enthaltend ein kristallines Alumosilikat und Verwendung dieser Formkörper mit erhöhter Schneidhärte in chemischen Syntheseverfahren, insbesondere in einem Verfahren zur Herstellung von Triethylendiamin (TEDA) durch Umsetzung von Ethylendiamin (EDA) und/oder Piperazin (PIP) |
DE10356184A1 (de) | 2003-12-02 | 2005-07-07 | Basf Ag | Zeolithisches Material vom Pentasil-Strukturtyp, seine Herstellung und seine Verwendung |
DE102004013588A1 (de) * | 2004-03-19 | 2005-10-06 | Basf Ag | Verfahren zur Herstellung von Triethylendiamin aus Monoethanolamin |
DE102004024274A1 (de) * | 2004-05-15 | 2005-12-01 | Basf Ag | Verfahren zur Herstellung einer Lösung von reinem Triethylendiamin (TEDA) |
DE102004029544A1 (de) | 2004-06-18 | 2006-01-05 | Basf Ag | Formkörper enthaltend ein mikroporöses Material und mindestens ein siliciumhaltiges Bindemittel, Verfahren zu seiner Herstellung und seine Verwendung als Katalysator, insbesondere in einem Verfahren zur Herstellung von Triethylendiamin (TEDA) |
US20100204438A1 (en) * | 2007-09-03 | 2010-08-12 | Basf Se | Method for producing teda derivatives |
DE102009027791B4 (de) | 2009-07-17 | 2013-02-21 | Basf Se | Zusammensetzung enthaltend Triethylendiamin, Monethylenglykol und Borhydrid |
US8440586B2 (en) * | 2010-02-26 | 2013-05-14 | Corning Incorporated | Low pressure drop extruded catalyst filter |
CN108906116B (zh) * | 2018-07-18 | 2021-01-29 | 西安近代化学研究所 | 一种用于合成2-甲基三乙烯二胺的催化剂和制备方法及应用 |
CN115920589B (zh) * | 2022-12-21 | 2023-08-11 | 可迪尔空气技术(北京)有限公司 | 一种低浓度污水池废气的处理方法 |
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JPS5337876B2 (ja) * | 1973-07-19 | 1978-10-12 | ||
JPS60260574A (ja) * | 1984-04-10 | 1985-12-23 | ユニオン・カ−バイド・コ−ポレ−シヨン | 1−アザビシクロ〔2.2.2〕オクタン又は1,4−ジアザビシクロ〔2.2.2〕オクタンの合成 |
US4804758A (en) * | 1986-10-08 | 1989-02-14 | Basf Aktiengesellschaft | Preparation of 1,4-diazabicyclo[2.2.2]octanes |
DE3735214A1 (de) * | 1987-10-17 | 1989-04-27 | Huels Chemische Werke Ag | Verfahren zur herstellung von 1,4-diazabicyclo(2.2.2)-octan aus piperazin |
US5731449A (en) * | 1996-09-23 | 1998-03-24 | Air Products And Chemicals, Inc. | Triethylendiamine synthesis with base-treated zeolites as catalysts |
US5741906A (en) * | 1996-11-15 | 1998-04-21 | Air Products And Chemicals, Inc. | Production of triethylenediamine using surface acidity deactivated zeolite catalysts |
US6084096A (en) * | 1998-04-09 | 2000-07-04 | Air Products And Chemicals, Inc. | Triethylenediamine and piperazine synthesis using zeolite catalysts modified with a silicon-containing compound |
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2001
- 2001-07-05 DE DE10132499A patent/DE10132499A1/de not_active Withdrawn
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2002
- 2002-07-04 AT AT02782456T patent/ATE341551T1/de not_active IP Right Cessation
- 2002-07-04 CN CNB028135210A patent/CN1228339C/zh not_active Expired - Lifetime
- 2002-07-04 KR KR10-2004-7000036A patent/KR20040023639A/ko not_active Application Discontinuation
- 2002-07-04 ES ES02782456T patent/ES2272786T3/es not_active Expired - Lifetime
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JP2005500324A (ja) | 2005-01-06 |
DE50208348D1 (de) | 2006-11-16 |
CN1524083A (zh) | 2004-08-25 |
US20040236106A1 (en) | 2004-11-25 |
EP1406904A1 (de) | 2004-04-14 |
KR20040023639A (ko) | 2004-03-18 |
CN1228339C (zh) | 2005-11-23 |
EP1406904B1 (de) | 2006-10-04 |
US6958397B2 (en) | 2005-10-25 |
DE10132499A1 (de) | 2003-01-23 |
WO2003004499A1 (de) | 2003-01-16 |
ES2272786T3 (es) | 2007-05-01 |
ATE341551T1 (de) | 2006-10-15 |
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