CN114433064A - Method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine - Google Patents
Method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine Download PDFInfo
- Publication number
- CN114433064A CN114433064A CN202011224912.9A CN202011224912A CN114433064A CN 114433064 A CN114433064 A CN 114433064A CN 202011224912 A CN202011224912 A CN 202011224912A CN 114433064 A CN114433064 A CN 114433064A
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- CN
- China
- Prior art keywords
- carrier
- ethylenediamine
- group
- doping element
- catalyst
- Prior art date
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 79
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 title claims abstract description 61
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 38
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- -1 borate ions Chemical class 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 31
- 239000000243 solution Substances 0.000 description 43
- 239000000843 powder Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 24
- 230000009467 reduction Effects 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 21
- 238000002386 leaching Methods 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 19
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 241000219793 Trifolium Species 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 235000011128 aluminium sulphate Nutrition 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229940031098 ethanolamine Drugs 0.000 description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BSGRLBPZSRZQOR-UHFFFAOYSA-N ethene-1,1-diamine Chemical group NC(N)=C BSGRLBPZSRZQOR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229940006163 selenate ion Drugs 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- B01J29/48—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 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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Abstract
The invention relates to the field of preparation of piperazine and ethylenediamine, and discloses a method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine. The method comprises the following steps: contacting hydroxyethyl ethylenediamine with an ammonia source in the presence of hydrogen and a catalyst to react, wherein the molar ratio of hydroxyethyl ethylenediamine to ammonia source is 1:4-35, the catalyst comprises a support and an active component comprising cobalt and/or nickel and optionally a promoter supported on the support, the promoter is a combination of at least one of a group IIA metal, at least one of a group IIB metal, and at least one of a group VA metal. The invention shows higher selectivity and conversion rate when preparing piperazine and co-producing ethylenediamine, and is a new production path.
Description
Technical Field
The invention relates to the field of preparation of piperazine and ethylenediamine, in particular to a method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine.
Background
Ethylenediamine, also known as EDA for short, 1, 2-diaminoethane, diaminoethylene, Ethylenediamine, having the molecular formula C2H8N2The water-soluble epoxy resin is colorless and transparent viscous liquid, has the melting point of 8.5 ℃ and the boiling point of 116.5 ℃, is easy to dissolve in water, can be mixed and dissolved with ethanol, has the characteristics of alkalinity and surface activity, is an important chemical raw material and a fine chemical intermediate, is widely applied to the fields of epoxy resin curing agents, pesticides, medicines, low molecular weight polyamide resins, chelating agents and the like, and relates to various industries.
Piperazine, known as PIPERAzine for short, having the molecular formula C4H10N2Piperazine and its derivatives are very important fine chemical products, which are mostly used as intermediates of medicines, pesticides and dyes, and are widely used in the field of medicine, and are raw materials of various medical products, and with the continuous expansion of medical requirements, especially the continuous increase of the demand of quinolone drugs, the market demand of piperazine and its derivatives is continuously rising.
Piperazine and ethylenediamine belong to important products of ethylene amines, and the current industrial production methods of ethylene amines are mainly Ethylene Dichloride (EDC) and ethanol amine (MEA). Because the dichloroethane raw material is low in price and wide in source, the early ethylenediamine device mainly adopts an EDC method which is a series reaction, and the polyene polyamine is used as a main byproduct, but the pollution is serious, the equipment corrosion is serious, and the investment cost is high. The MEA route has relatively less pollution and lower investment cost, and becomes an important process route and a research hotspot for preparing ethylene amine products in recent years.
CN101875014A discloses a catalyst for converting monoethanolamine and ammonia into ethylenediamine in the presence of hydrogen, which comprises a main active component, an auxiliary agent and a carrier, wherein the main active auxiliary agent is Co or nickel, the auxiliary agent is at least one of Re, Fe, Cu, Ru and B, and the carrier is Al2O3Or SiO2. Under the reaction conditions: the reaction temperature is 135 plus one year, the reaction pressure of hydrogen is 6.5-8MPa, and the liquid volume space velocity of monoethanolamine is 0.35-0.65h-1. The selectivity of DETA is 7.1-9.5%.
At present, domestic ethylene diamine, piperazine and other ethylene amine products basically depend on import, and a large amount of byproducts including triethylene diamine, hydroxyethyl ethylene diamine, hydroxyethyl piperazine, N-aminoethyl piperazine and the like exist in the existing route for preparing ethylene diamine and piperazine by an ethanolamine method, and a large amount of energy consumption is needed in separation, and the yield of ethylene diamine and piperazine can be seriously influenced.
Therefore, it is necessary to develop a new route for preparing ethylenediamine and piperazine to improve the yield and selectivity of ethylenediamine and piperazine.
Disclosure of Invention
The invention aims to overcome the technical defects of low yield and selectivity and high separation energy consumption in the preparation of ethylenediamine and piperazine in the prior art, and provides a method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine.
In order to achieve the above objects, the present invention provides, in one aspect, a method for preparing piperazine and ethylenediamine from hydroxyethylethylenediamine, the method comprising: the method comprises the following steps of contacting hydroxyethyl ethylenediamine and an ammonia source for reaction in the presence of hydrogen and a catalyst, wherein the molar ratio of the hydroxyethyl ethylenediamine to the ammonia source is 1:4-35, the catalyst comprises a carrier and an active component and an optional promoter, the active component comprises cobalt and/or nickel, and the promoter is a combination of at least one of group IIA metals, at least one of group IIB metals and at least one of group VA metals, and is supported on the carrier.
Compared with the prior art, the invention has higher selectivity and conversion rate when preparing the ethylenediamine and the piperazine, has greater practical significance, provides a new route for preparing the ethylenediamine and the piperazine, and particularly can improve the selectivity of the piperazine.
Further, the inventors of the present invention have studied to find that the specific compounding of the promoter will further improve the activity of the catalyst. Moreover, the doping elements and the pore structure of the catalyst are changed to be more beneficial to improving the selectivity and the conversion rate of preparing the ethylenediamine and the piperazine by the hydroxyethyl ethylenediamine, so that the yield of the ethylenediamine and the piperazine is further improved in a mode of overcoming the technical prejudice.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine, which is characterized by comprising the following steps: the method comprises the following steps of contacting hydroxyethyl ethylenediamine and an ammonia source for reaction in the presence of hydrogen and a catalyst, wherein the molar ratio of the hydroxyethyl ethylenediamine to the ammonia source is 1:4-35, the catalyst comprises a carrier and an active component and an optional promoter, the active component comprises cobalt and/or nickel, and the promoter is a combination of at least one of group IIA metals, at least one of group IIB metals and at least one of group VA metals, and is supported on the carrier.
According to the present invention, the conditions of the contacting may include: the temperature is 120-240 ℃, preferably 130-220 ℃.
According to the present invention, the conditions of the contacting may further include: the pressure is 4-18MPa, preferably 5-17 MPa.
According to the present invention, the conditions of the contacting may further include: the liquid phase volume space velocity of the hydroxyethyl ethylenediamine is 0.05-0.6m3/(m3H), preferably from 0.1 to 0.6m3/(m3·h)。
According to the present invention, the conditions of the contacting may further include: the molar ratio of hydrogen, ammonia source and hydroxyethyl ethylenediamine is 1-4:4-35:1, preferably 1-3:5-30: 1.
According to the invention, the hydroxyethyl ethylenediamine can be reacted in a pure form or prepared into a solution, and in order to further improve the conversion rate, reduce the generation of heavy components and improve the selectivity of ethylenediamine and piperazine, the hydroxyethyl ethylenediamine is preferably reacted in a solution manner. The concentration of hydroxyethylethylenediamine in the solution is not particularly critical and may be from 10 to 80% by weight. The solvent in the solution can be various solvents which can dissolve the hydroxyethyl ethylene diamine and do not react with other reaction raw materials, can be water or organic solvents, and preferably, the solvent in the solution is selected from water and/or 1, 4-dioxane.
According to the present invention, the ammonia source is a reactant capable of providing amino groups and/or amine groups, and may be selected from at least one of ammonia, a primary amine of C1-12, and a secondary amine of C2-12, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, and diethylamine. "C1-12" refers to a primary or secondary amine having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 carbon atoms.
According to the present invention, the method may further comprise the step of separating and purifying the product of the amination reaction to obtain piperazine and ethylenediamine, respectively. The separation and purification mode can be rectification.
According to the present invention, the amination may be continuous or intermittent, and one of reaction apparatuses such as a fixed bed tubular reactor, a high-pressure stirred tank, a bubbling bed reactor, a fluidized bed reactor, and a microchannel reactor may be used.
In the present invention, the vector may be a vector commonly used in the art. According to a preferred embodiment of the invention, the support comprises alumina, doping elements and optionally other supports, including silica and/or molecular sieves; the doping element is selected from at least one of boron, fluorine, phosphorus, sulfur and selenium; the percentage of the pore volume of the carrier with a pore diameter in the range of 7-27nm is more than 65%.
According to the invention, the carrier takes doped alumina as a main body, and can be further matched with (doped) silicon oxide and the like, so that the pore channel structure of the catalyst is further improved, reactants and products are easy to diffuse in the pore channel, and the performance of the pore structure is more stable. Thus, according to a preferred embodiment of the invention, the alumina content of the support is more than 70 wt.%, preferably 75-100 wt.%, of the total amount of alumina and other supports.
According to a preferred embodiment of the invention, the content of doping element in the support is 0.05 to 4.5 wt.%, more preferably 0.07 to 2.8 wt.%, based on the total weight of the components in the support, excluding the doping element. The constituents other than the doping element mainly refer to the alumina and optionally other carriers in the carrier.
According to a preferred embodiment of the present invention, the element doped in the carrier is doped in the form of at least one of borate ion, fluoride ion, phosphate ion, sulfate ion and selenate ion. The doped elements exist in the alumina precursor and are added in the process of preparing the precursor, the doped elements are wrapped and clamped in the crystal phase of the precursor, and the doped elements mainly exist in the crystal phase of the carrier after the carrier is prepared.
According to a preferred embodiment of the invention, the percentage of the pore volume of the support having a pore diameter in the range of 7-27nm is 70-90%. According to a preferred embodiment of the invention, the percentage of the pore volume of the support with pore diameters smaller than 7nm is between 0 and 8%.
According to a preferred embodiment of the present invention, the specific surface area of the support is 110-210m2/g。
According to a preferred embodiment of the invention, the pore volume of the support is between 0.45 and 1.1 ml/g.
In the invention, the specific surface area, the pore volume and the occupation ratio of pores with different pore diameters of the carrier are measured by a nitrogen adsorption-desorption method, which is specifically disclosed in GB/T6609.35-2009.
According to the invention, the active component may be present in an amount of 8 to 45g, preferably 15 to 38g (for example, any of 15, 20, 25, 28, 30, 32, 35, 37, 38, or any intermediate value between any two of the above values) per 100g of support, calculated on the weight of the constituents other than the doping element.
According to the invention, the promoter may be present in an amount of 0.1 to 10g, preferably 0.5 to 6g (for example, any of 0.5, 1,2, 3, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 6, or any intermediate value between any two of the above values) per 100g of carrier by weight of the ingredients other than the doping element.
According to the present invention, the catalyst further contains a promoter as described above in order to exert the performance of the catalyst of the present invention more effectively, to adjust the proportion of the reaction product, and to reduce the occurrence of unwanted side reactions. The weight ratio of the IIA group metal, IIB group metal and VA group metal in the promoter is preferably 0.1-10: 0.1-10: 1, more preferably 0.2 to 8: 0.2-8: 1. preferably, the group IIA metal is selected from at least one of magnesium, calcium and barium. Preferably, the group IIB metal is selected from zinc. Preferably, the group VA metal is selected from bismuth.
In the present invention, the active ingredient and the accelerator may be supported on the carrier in a conventional manner, or may be supported in a specific order.
According to the present invention, the carrier can be prepared by using the existing method capable of obtaining the doping elements, the pore structures, and the like which satisfy the above ranges, and the obtaining of the carrier having the doping elements and the pore structures which satisfy the above ranges can be performed by those skilled in the art. According to a preferred embodiment of the invention, however, the support is prepared by a process comprising the steps of:
(1) sequentially molding, first drying and first roasting a mixture containing a doping element, an alumina precursor and optional other carrier precursors, wherein the other carrier precursors comprise a silica precursor (such as silica sol) and/or a molecular sieve precursor (such as ZSM-5);
(2) and mixing the product of the first roasting with a solution of a group IIA metal precursor, and then carrying out second drying and second roasting. The molding method may use kneading, rolling balls, or sheeting.
In the above preparation method of the carrier, it can be understood by those skilled in the art that: if the raw material for providing the carrier precursor already contains a desired amount of the doping element, shaping is carried out using such a raw material, and if the raw material for providing the carrier precursor does not contain the doping element or the content of the doping element is low (insufficient), the doping element may be additionally introduced.
In the above preparation method of the carrier, the doping element may be doped in the raw material for providing the alumina precursor, that is, the alumina precursor modified by the doping element and/or other carrier precursors may be directly used, and such alumina precursor modified by the doping element or other carrier precursors may be obtained by a commercially available or conventional method, and will not be described herein again.
In the above preparation method of the carrier, a person skilled in the art can determine the amount of a certain ingredient raw material (e.g., a carrier modifier) according to the amount of a certain ingredient (e.g., a doping element) in the final carrier, and therefore, some of the amounts of the raw materials are not shown herein.
In the above method for producing a support, the alumina precursor is preferably pseudoboehmite. The specific surface area of the pseudo-boehmite is preferably 250-330m2(ii) in terms of/g. The pore volume of the pseudoboehmite is preferably 0.5 to 1.1. The pseudoboehmite can be produced by at least one of a carbonization method, an organoaluminum hydrolysis method, an aluminum sulfate method and a nitric acid method, and particularly preferably produced by an aluminum sulfate method. The catalyst with better performance can be obtained by selecting the pseudoboehmite with a specific pore structure.
In the above method for producing a support, the conditions of the first drying and the second drying may each independently include: the temperature is 80-150 deg.C (for example, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, or any value between any two values); the time is 6-20h (e.g., 6h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 10h, 11h, 11.5h, 12h, 12.5h, 13h, 14h, 14.5h, 15h, 15.5h, 16h, 17h, 18h, 19h, 20h, or any value in between).
In the above method for producing a support, the conditions of the first calcination may include: the temperature is 500 ℃ and 650 ℃ (e.g., 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃ or any value between any two values); the time is 2-20h (e.g., 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 7h, 8h, 9h, 9.5h, 10h, 10.5h, 11h, 12h, 15h, 18h, 20h, or any value in between any two of the foregoing).
In the above method for producing a support, the conditions of the second calcination may include: the temperature is 800-; the time is 2-20h (e.g., 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 7h, 8h, 9h, 9.5h, 10h, 10.5h, 11h, 12h, 15h, 18h, 20h, or any value between any two of the foregoing).
According to the invention, the catalyst can be used after reduction. The reduction can be carried out with a gas containing hydrogen at 350-500 deg.C, preferably at 350-450 deg.C. The hydrogen gas may be pure hydrogen gas or hydrogen gas diluted with inert gas, such as a mixture of nitrogen and hydrogen. During the reduction, the reduction temperature is gradually increased, and the temperature is not increased too quickly, for example, not more than 20 ℃ per hour. Can be monitored by monitoring H in a reduction system2The generation of O determines the time of reduction, i.e. when the reduction system no longer generates new H2O, the reduction is completed, and the person skilled in the art can select the time of reduction accordingly, which will not be described in detail, for example, the reduction time may be 2 to 5 hours at the maximum temperature. The reduction may be carried out directly in the reactor, followed by a catalytic reaction. It is also possible to carry out the reduction in a separate reactor, also referred to as an off-reactor reduction, and to carry out the passivation after the reduction with a gas mixture containing oxygen, for example at temperatures of from 10 to 60 ℃ and in particular from 20 to 40 ℃ before the discharge from the reactor. The catalyst reduced and passivated outside the reactor can be filled into the reactor before useActivation with hydrogen or a mixture of hydrogen and nitrogen is carried out at, for example, 150 ℃ and 250 ℃, preferably 170 ℃ and 200 ℃. Can be monitored by monitoring H in the activated system2The generation of O determines the time of activation, i.e. when the activated system no longer generates new H2O, the activation is terminated and the skilled person will be able to select the time of activation accordingly, which will not be described in detail, for example, at the highest temperature, for example, from 1 to 5 hours, preferably from 2 to 3 hours, or it may be used without activation, depending on the degree of oxidation of the active components and promoters in the catalyst.
The present invention also provides a process for preparing a catalyst as hereinbefore described, which process comprises: the active component and the accelerant are loaded on the carrier.
It is understood that the method for preparing the catalyst may further comprise: the step of preparing the carrier according to the aforementioned method. Thus, in a preferred embodiment, the method of preparing the catalyst comprises:
(1) sequentially molding, first drying and first roasting a mixture containing a doping element, an alumina precursor and optionally other carrier precursors, wherein the other carrier precursors comprise a silicon oxide precursor and/or a molecular sieve precursor;
(2) mixing the first roasted product with a solution of a IIA metal precursor, and then carrying out second drying and second roasting;
(3) at least one of group IIA metals, at least one of group VA metals and an active component are supported on the second calcined product.
In the present invention, in the step (3), the method of supporting the active component and the accelerator on the carrier may be an impregnation method, that is, impregnating the carrier with a solution containing an active component precursor and an accelerator precursor, followed by drying and baking. The impregnation method is to soak the carrier in a solution of a suitable precursor containing the active component and the accelerator, the precursor being adsorbed and supported on the carrier. The impregnation method is subdivided and includes a dry impregnation method, a wet impregnation method, a multiple impregnation method, a mixed impregnation method, a spray impregnation method and the like. The dry and wet impregnation method refers to the state of the carrier before impregnation with the precursor of the active component, whether dry or pre-soaked with water. The multiple impregnation method is to impregnate a precursor mixed solution of one or more components for multiple times or impregnate different precursors in batches, and the multiple impregnation method needs drying and roasting after each impregnation to 'anchor' the impregnated components. The mixed impregnation method is to impregnate the active component and the precursor used as the accelerator together without precipitation reaction. The spray-dip method is to spray the dipping solution onto the continuously rotating carrier by a spray gun so that the dipping solution just fills the pore volume of the carrier to saturation. The catalyst of the present invention can be suitably selected according to the conditions of a processing plant.
The metal (active component or promoter) impregnating the support is preferably used in the form of a solution of a metal salt, such as nitrate, formate, oxalate, lactate, etc. The solvent is preferably water, and some organic solvents, such as ethanol, may also be used. Impregnation of the support with the metal salt solution may be carried out in any desired sequence, or it may be carried out continuously with a plurality of solutions containing one or more metal salts. All or a single impregnation step may be carried out in several portions, and the order of impregnation may also be varied. The concentration of the solution is selected so that the desired amount of metal is supported on the support. The impregnated support is preferably dried at 80 to 150 c, more preferably 80 to 120 c. The drying time is reasonably selected according to the conditions of the drying temperature, the amount of the dried materials, the drying equipment and the like, for example, 8 hours, and the criterion is that the water content after drying does not influence the subsequent roasting. After drying, the salt is roasted at the temperature of 150-500 ℃ to remove the crystal water in the salt or decompose the salt into oxide, and the roasting is preferably carried out at the temperature of 300-500 ℃ for 1-6 h. In the case of multiple impregnations, it is preferable to dry and calcine after each impregnation.
In the present invention, the supporting operation in step (3) does not greatly affect the microstructure of the catalyst, and therefore, the resulting catalyst has a similar pore structure to that of the support.
According to the invention, the method comprises the steps of screening the catalyst, screening out the catalyst with the composition or structure parameter meeting the requirements, and then carrying out the ammoniation reaction according to the mode.
The following will be described by way of examplesThe present invention will be described in detail. In the following examples, the dry basis (Al) of pseudo-boehmite powder2O3) The content was 70 wt%; silica sol was purchased from Qingdao ocean chemical Co., Ltd.
Preparation example 1
Pseudo-boehmite powder (specific surface area 288 m) prepared by using aluminum sulfate method2The pore volume is 0.91ml/g, the pseudo-boehmite powder contains doping element P and relative 100g of Al2O3The pseudoboehmite powder calculated contains 0.22g of P element) is kneaded by dilute acid water containing 5 vol% of nitric acid, extruded into strips with the diameter of 5mm, cut into 4mm in length, dried for 8h at 120 ℃, and then roasted for 6h at 550 ℃. 32.1g of magnesium nitrate hexahydrate (analytically pure) was dissolved in 85ml of water, and the aqueous magnesium nitrate solution was supported on 100g of the above calcined product by spray-dipping, followed by drying at 100 ℃ for 10 hours and further calcination at 820 ℃ for 5 hours to prepare the desired carrier.
186.5g of cobalt nitrate hexahydrate (technical grade, purity 98%), 6.83g of zinc nitrate hexahydrate (analytical grade) and 1.16g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to prepare a 148mL solution, which was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 120 ℃ for 4 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating and reducing by hydrogen, wherein the heating reduction rate is 20 ℃/h, and finally reducing for 3h at 430 ℃ to obtain the catalyst A-1.
Preparation example 2
Pseudo-boehmite powder (specific surface area 285 m) prepared by aluminium sulfate method2The pore volume is 0.93ml/g, the pseudo-boehmite powder contains doping element B and relative 100g of Al2O3The pseudoboehmite powder calculated contains 0.53g of B element), is kneaded by dilute acid water containing 5 vol% of nitric acid, extruded into a clover shape with the thickness of 3mm, dried for 15h at 120 ℃, and then roasted for 8h at 520 ℃. 11.8g of calcium nitrate tetrahydrate (analytically pure) was dissolved in water to give 91ml of a solution, and the aqueous calcium nitrate solution was applied to 100g of the above calcined product by spray-dipping, followed by drying at 110 ℃ for 10 hours and further calcining at 800 ℃ for 6 hours to prepare the desired carrier.
151.7g of nickel nitrate hexahydrate (technical grade, purity 98%), 6.83g of zinc nitrate hexahydrate (analytical grade) and 1.16g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to give 156mL of a solution, which was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 120 ℃ for 4 hours after each spray-leaching and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 3h at 430 ℃ to obtain the catalyst A-2.
Preparation example 3
Pseudo-boehmite powder (specific surface area 285 m) prepared by aluminium sulfate method2The pore volume is 0.9ml/g, the pseudo-boehmite powder contains doping element P and relative 100g of Al2O3The pseudoboehmite powder measured contains 0.23g of P element) is kneaded by dilute acid water containing 5 vol% of nitric acid, and the kneaded mixture is extruded into strips with the diameter of 5mm after being mixed evenly, cut into 4mm long pieces, dried for 8h at the temperature of 120 ℃ and then roasted for 6h at the temperature of 550 ℃. 32.1g of magnesium nitrate hexahydrate (analytically pure) was dissolved in 85ml of water, and the above 100g of calcined product was loaded with an aqueous magnesium nitrate solution by spray-immersion method, followed by drying at 100 ℃ for 10 hours and further calcination at 820 ℃ for 5 hours to prepare the desired carrier.
45.4g of cobalt nitrate hexahydrate (technical grade, purity 98%), 6.83g of zinc nitrate hexahydrate (analytical grade) and 1.16g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to give 146mL of solution, which was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 120 ℃ for 4 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 3h at 430 ℃ to obtain the catalyst A-3.
Preparation example 4
The carrier was prepared by the method of preparation example 1 except that the pseudo-boehmite powder and the molecular sieve powder (ZSM-5, catalyst works of southern Kai university, SiO)2/Al2O345 (molar ratio)), and adjusting the dosage of the molecular sieve ZSM-5 powder so that the content of alumina derived from pseudoboehmite in the carrier accounts for 85% of the total mass of the carrier.
176.4g of cobalt nitrate hexahydrate (technical grade, purity 98%), 4.55g of zinc nitrate hexahydrate (analytical grade) and 2.32g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to 178mL of a solution, and the solution was supported on the above-obtained carrier by spray-leaching in two passes, dried at 120 ℃ for 4 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 3h at 430 ℃ to obtain the catalyst A-4.
Preparation example 5
Pseudo-boehmite powder (specific surface area 258 m) prepared by using aluminum sulfate method2The pore volume is 0.65ml/g, the pseudo-boehmite powder contains doping element P and relative 100g of Al2O3The pseudoboehmite powder calculated, containing 0.18g of P element) was kneaded with dilute acid water containing 4.5 vol% of nitric acid, extruded into a 4mm thick clover shape, dried at 100 ℃ for 18 hours, and then calcined at 560 ℃ for 5 hours. 11.8g of calcium nitrate tetrahydrate (analytically pure) was dissolved in 73ml of water, and the aqueous calcium nitrate solution was supported on 100g of the above calcined product by spray-dipping, followed by drying at 120 ℃ for 10 hours and further calcining at 970 ℃ for 6 hours to prepare the desired carrier.
75.6g of cobalt nitrate hexahydrate (technical grade, purity 98%), 4.55g of zinc nitrate hexahydrate (analytical grade) and 2.32g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to give 124mL of a solution, and the solution was supported on the above-obtained carrier by spray-leaching in two passes, dried at 100 ℃ for 10 hours after each spray-leaching, and then calcined at 388 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 4h at 420 ℃ to obtain the catalyst A-5.
Preparation example 6
Pseudo-boehmite powder (specific surface area 318 m) prepared by using aluminium sulfate method2The pore volume is 0.93ml/g, the pseudo-boehmite powder contains doping element B and relative 100g of Al2O3The pseudoboehmite powder measured contains 3.66g of B element and is kneaded by dilute acid water containing 5 vol% of nitric acid, silica sol (JN-40, Qingdao ocean chemical Co., Ltd.) is added in the kneading process, the mixture is evenly mixed and extruded into dentate spheres with the diameter of 3.5mm, the dentate spheres are dried for 4h at 120 ℃, and then the dentate spheres are roasted for 5h at 630 ℃. 7.6g of barium nitrate (analytically pure) was usedDissolving in water to obtain 88ml solution, loading barium nitrate aqueous solution on the above 100g calcined product by spray immersion method, drying at 100 deg.C for 12 hr, and calcining at 880 deg.C for 3 hr to obtain the required carrier. Adjusting the dosage of the silica sol to achieve the ratio of the mass of the alumina to the mass of the silica in the carrier of 4: 1.
126.4g of nickel nitrate hexahydrate (technical grade, purity 98%), 4.55g of zinc nitrate hexahydrate (analytical grade) and 2.32g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to give 160mL of a solution, and the solution was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 120 ℃ for 4 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 3.5h at 420 ℃ to obtain the catalyst A-6.
Preparation example 7
The support prepared in preparation example 1 was used.
201.6g of cobalt nitrate hexahydrate (technical grade, purity 98%), 6.83g of zinc nitrate hexahydrate (analytical grade) and 1.16g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to obtain a 150mL solution, which was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 120 ℃ for 4 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 3h at 430 ℃ to obtain the catalyst A-7.
Preparation example 8
Pseudo-boehmite powder prepared by an aluminum sulfate method (the specific surface area is 290 m)2The pore volume is 0.78ml/g, the pseudo-boehmite powder contains doping element S and relative 100g of Al2O3The pseudoboehmite powder measured contains 0.88g of S element and is kneaded by dilute acid water containing 4.5 vol% of nitric acid, silica sol (JN-40, Qingdao ocean chemical Co., Ltd.) is added in the kneading process, the mixture is uniformly mixed and extruded into a clover shape with the thickness of 4mm, the clover shape is dried for 20h at the temperature of 80 ℃, and then the clover shape is roasted for 7h at the temperature of 550 ℃. 17.7g of calcium nitrate tetrahydrate (analytically pure) was dissolved in 84ml of water, and the above 100g of calcined product was loaded with an aqueous calcium nitrate solution by spray-dipping, dried at 120 ℃ for 10 hours, and then calcined at 900 ℃4h, preparing the required carrier. Adjusting the dosage of the silica sol to achieve the ratio of the mass of the alumina to the mass of the silica in the carrier of 86: 14.
100.8g of cobalt nitrate hexahydrate (technical grade, purity 98%), 2.88g of zinc nitrate hexahydrate (analytical grade) and 3.48g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to obtain a 152mL solution, which was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 100 ℃ for 10 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 4h at 430 ℃ to obtain the catalyst A-8.
Preparation example 9
Pseudo-boehmite powder (specific surface area 320 m) prepared by using aluminum sulfate method2The pore volume is 0.95ml/g, the pseudo-boehmite powder contains doping element F, and relative 100g of Al2O3The pseudoboehmite powder counted contains 0.82g of F element and is kneaded by dilute acid water containing 5.2 vol% of nitric acid, silica sol (JN-40, Qingdao ocean chemical Co., Ltd.) is added in the kneading process, the mixture is evenly mixed and extruded into a clover shape with the thickness of 3mm, the clover shape is dried for 8h at the temperature of 100 ℃, and then the clover shape is roasted for 4h at the temperature of 620 ℃. 3.8g of barium nitrate (analytically pure) is dissolved into 83ml of solution by water, and the barium nitrate aqueous solution is loaded on 100g of the roasted product by a spray-immersion method, and then dried at 120 ℃ for 8 hours and roasted at 950 ℃ for 5 hours to prepare the required carrier. The amount of silica sol used was adjusted to achieve a ratio of alumina mass to silica mass in the carrier of 89: 11.
176.4g of cobalt nitrate hexahydrate (technical grade, purity 98%), 2.88g of zinc nitrate hexahydrate (analytical grade) and 3.48g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to prepare a 160mL solution, which was loaded on the above-obtained carrier by spray-leaching in two passes, dried at 110 ℃ for 8 hours after each spray-leaching, and then calcined at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 4.5h at 420 ℃ to obtain the catalyst A-9.
Preparation example 10
Pseudo-boehmite powder (specific surface area 291 m) prepared by using aluminum sulfate method2The pore volume is 0.93ml/g, the pseudo-boehmite powder contains doping element S and relative 100g of Al2O3The pseudoboehmite powder calculated, containing 0.95g of the S element) was kneaded with dilute acid water containing 4 vol% of nitric acid, then extruded into a 3.5mm thick clover shape, dried at 100 ℃ for 8 hours, and then calcined at 600 ℃ for 5 hours. 42.7g of magnesium nitrate hexahydrate (analytically pure) was dissolved in 92ml of water, and the above 100g of calcined product was loaded with an aqueous magnesium nitrate solution by spray-dipping, followed by drying at 120 ℃ for 8 hours and further calcining at 830 ℃ for 8 hours to prepare the desired carrier.
226.8g of cobalt nitrate hexahydrate (technical grade, purity 98%), 2.88g of zinc nitrate hexahydrate (analytical grade) and 4.64g of bismuth nitrate pentahydrate (analytical grade) were dissolved in water to give 172mL of a solution, and the solution was supported on the above-obtained carrier by spray-leaching in two passes, followed by drying at 120 ℃ for 6 hours after each spray-leaching and then calcining at 400 ℃ for 4 hours. Then gradually heating up and reducing by hydrogen, wherein the heating up reduction rate is 20 ℃/h, and finally reducing for 4.5h at 420 ℃ to obtain the catalyst A-10.
Preparation example 11
A catalyst was prepared by the method of preparation example 1 except that the pseudo-boehmite powder used was doped with P in an amount of 100g in terms of Al2O3The pseudoboehmite powder measured contains 4.3g of P element. Catalyst A-11 was obtained.
Preparation example 12
A catalyst was prepared by following the procedure of preparation example 2 except that the pseudo-boehmite powder used was free of doping element and had a specific surface area of 286m2The catalyst A-12 was obtained in terms of a pore volume of 0.93 ml/g.
Preparation example 13
A catalyst was prepared by following the procedure of preparation example 2 except that the second calcination temperature was 1200 ℃ to obtain catalyst A-13.
Comparative preparation example 1
A catalyst was prepared as in preparation example 2, except that the aqueous calcium nitrate solution was replaced with an equal volume of water, and the solution for spray-impregnating the carrier was prepared by: 151.7g of nickel nitrate hexahydrate (technical grade, purity 98%) was dissolved in 158mL of water to prepare a catalyst in which only nickel was supported as an active component. Catalyst D-1 was obtained.
Comparative preparation example 2
A catalyst was prepared by following the procedure of preparation example 1 except that the solution for spray-impregnating the carrier was prepared by: 186.5g of cobalt nitrate hexahydrate (technical grade, 98% purity) and 1.16g of bismuth nitrate pentahydrate (analytical grade) were dissolved in 148mL of water. Catalyst D-2 was obtained.
Comparative preparation example 3
A catalyst was prepared according to the method of preparation example 1 except that magnesium nitrate was replaced with 8.5g of copper nitrate trihydrate to obtain catalyst D-3.
Test example 1
The elemental compositions of the support and the catalyst were analyzed by a plasma emission spectrometer, the elemental (ion) contents other than the support being each expressed in terms of the content of the support relative to 100g by weight of the components other than the doping element; the carrier prepared above was characterized by BET nitrogen adsorption desorption method, and the specific procedure was as follows, and the results are shown in table 1.
BET test
The instrument name: a full-Automatic physical and chemical adsorption Analyzer (Automatic micro & chemical Analyzer); the instrument model is as follows: ASAP2420, MICROMERICICS (Mike instruments, Inc.) USA
And (3) testing conditions are as follows: experimental gas: n is a radical of2(purity 99.999%); degassing conditions: heating to 350 deg.C at 10 deg.C/min, and vacuumizing for 4 hr; the analysis conditions are as follows: and (4) carrying out full analysis on the mesoporous isotherm. Specific surface area and pore volume were obtained.
TABLE 1
Example 1
Respectively measuring 100 ml of the catalysts A-1 to D-3 prepared in the preparation examples, loading the catalysts A-1 to D-3 into a fixed bed reactor, activating the catalysts A-1 to D-3 by using hydrogen at 220 ℃ for 2 hours, then cooling to 180 ℃, increasing the system pressure to 9.8MPa by using the hydrogen, and then using the hydrogenMetering ammonia by a metering pump, feeding the ammonia into a reaction system, preheating the ammonia to 165 ℃, feeding the ammonia into the upper end of a reactor, feeding hydroxyethyl ethylenediamine into the upper end of the reactor by the metering pump, stably feeding hydrogen into the reactor by a gas mass flowmeter, wherein the molar ratio of the hydrogen to the ammonia to the hydroxyethyl ethylenediamine is 3:20:1, and the liquid phase volume airspeed of the hydroxyethyl ethylenediamine is 0.3h-1After the catalytic ammoniation reaction is carried out in the reactor and the reaction is stable (namely, when the reaction is carried out for 20 hours), the reaction liquid is sampled and analyzed, and the analysis result is shown in Table 2.
The sampling analysis method is gas chromatography analysis, and calibration is carried out by preparing a correction factor of a standard sample;
the conversion and selectivity were calculated as the molar content of each component in the reaction solution.
nxRepresents the moles of hydroxyethylethylenediamine required to convert to one mole of product x;
the product x comprises ethylenediamine, piperazine, diethylenetriamine, N-hydroxyethyl piperazine, N-aminoethyl piperazine, monoethylamine and trace other dimerization and trimerization products;
nxrepresents the moles of hydroxyethylethylenediamine required to convert to one mole of product x;
nethylene diamineRepresents the number of moles of hydroxyethylethylenediamine required to convert one mole of ethylenediamine;
the product x comprises ethylenediamine, piperazine, diethylenetriamine, N-hydroxyethyl piperazine, N-aminoethyl piperazine, monoethylamine, and trace amounts of other dimerization and trimerization products
The selectivity of other products only needs to be n of the molecule in the formulaEthylenediamineAnd the corresponding molar content is changed into the corresponding value.
TABLE 2
Example 2
A100 ml portion of catalyst A-1 was taken and loaded in a fixed bed reactor, and activated with hydrogen at 220 ℃ for 2 hours in the same manner as in example 1, except that the reaction results were sampled and analyzed under different reaction conditions (the analysis conditions, conversion and selectivity were calculated in the same manner as in example 1) while changing the experimental conditions such as temperature, pressure, molar ratio of hydrogen to ammonia to hydroxyethylethylenediamine, liquid phase volume space velocity of hydroxyethylethylenediamine, etc., and the results are shown in Table 3.
TABLE 3
Example 3
100 milliliters of catalyst A-3 is measured and loaded in a fixed bed reactor, hydrogen is used for activating for 2 hours at 220 ℃, then the temperature is reduced to 180 ℃, the system pressure is increased to 9MPa by the hydrogen, then ammonia is metered by a metering pump and sent into a reaction system, the ammonia is preheated to 165 ℃ and enters the upper end of the reactor, a mixed solution of 30 wt% of hydroxyethyl ethylene diamine and 70 wt% of 1, 4-dioxane is sent into the upper end of the reactor by the metering pump, hydrogen is stably sent by a gas mass flowmeter, the molar ratio of the hydrogen to the ammonia to the hydroxyethyl ethylene diamine is 3:20:1, and the liquid phase volume space velocity of the hydroxyethyl piperazine is 0.3 hour-1After the catalytic amination reaction was carried out in the reactor and the reaction was stabilized (i.e., after 20 hours of reaction), a sample of the reaction solution was taken and analyzed (the analytical conditions, the conversion and the selectivity were calculated in the same manner as in example 1), and the analytical results are shown in table 4.
TABLE 4
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. A process for preparing piperazine and ethylenediamine from hydroxyethylethylenediamine, the process comprising: the method comprises the following steps of contacting hydroxyethyl ethylenediamine and an ammonia source for reaction in the presence of hydrogen and a catalyst, wherein the molar ratio of the hydroxyethyl ethylenediamine to the ammonia source is 1:4-35, the catalyst comprises a carrier and an active component and an optional promoter, the active component comprises cobalt and/or nickel, and the promoter is a combination of at least one of group IIA metals, at least one of group IIB metals and at least one of group VA metals, and is supported on the carrier.
2. The method of claim 1, wherein the conditions of the contacting comprise: the temperature is 120 ℃ and 240 ℃, the pressure is 4-18MPa, and the liquid phase volume space velocity of the hydroxyethyl ethylenediamine is 0.05-0.6m3/(m3H) the molar ratio of hydrogen, ammonia source and hydroxyethylethylenediamine is from 1 to 4:4 to 35: 1.
3. The method of claim 1, wherein the conditions of the contacting comprise: the temperature is 130 ℃ and 220 ℃, the pressure is 5-17MPa, and the liquid phase volume space velocity of the hydroxyethyl ethylenediamine is 0.1-0.6m3/(m3H) the molar ratio of hydrogen, ammonia source and hydroxyethylethylenediamine is from 1 to 3:5 to 30: 1.
4. The process according to any one of claims 1 to 3, wherein the hydroxyethylethylenediamine is reacted in the form of a solution having a hydroxyethylethylenediamine concentration of 10 to 80% by weight, the solvent of said solution being selected from water and/or 1, 4-dioxane;
and/or the ammonia source is selected from at least one of ammonia, C1-12 primary amine and C2-12 secondary amine, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine.
5. The method of any one of claims 1-4, wherein the support comprises an alumina support, a doping element, and optionally other supports including silica and/or molecular sieves; the doping element is selected from at least one of boron, fluorine, phosphorus, sulfur and selenium; the percentage of the pore volume of the carrier with a pore diameter in the range of 7-27nm is more than 65%.
6. A process as claimed in any one of claims 1 to 5, in which the alumina carrier is present in the support in an amount of more than 70% by weight, preferably 75 to 100% by weight, of the total amount of alumina carrier and other support;
and/or the content of the doping element in the carrier accounts for 0.05-4.5 wt%, preferably 0.07-2.8 wt% of the total weight of the components except the doping element in the carrier;
and/or the doping element in the carrier is doped in a mode of at least one of borate ions, fluoride ions, phosphate ions, sulfate ions and selenate ions;
and/or, the percentage of the pore volume of the carrier with the pore diameter of 7-27nm in the carrier is 70-90%, and the percentage of the pore volume of the carrier with the pore diameter of less than 7nm in the carrier is 0-8%;
and/or the specific surface area of the carrier is 110-210m2/g；
And/or the pore volume of the carrier is 0.45-1.1 ml/g;
and/or the active component is present in an amount of 8 to 45g, preferably 15 to 38g, per 100g of support, calculated on the weight of the components other than the doping element;
and/or the promoter is present in an amount of 0.1 to 10g, preferably 0.5 to 6g, per 100g of support, calculated on the weight of the constituents other than the doping element;
and/or the weight ratio of the IIA group metal, the IIB group metal and the VA group metal in the accelerant is 0.1-10: 0.1-10: 1, preferably 0.2 to 8: 0.2-8: 1;
and/or, the group IIA metal is selected from at least one of magnesium, calcium and barium;
and/or, the group IIB metal is selected from zinc;
and/or, the group VA metal is selected from bismuth.
7. The method of claim 5 or 6, wherein the support is prepared by a method comprising the steps of:
(1) sequentially molding, first drying and first roasting a mixture containing a doping element, an alumina precursor and optionally other carrier precursors, wherein the other carrier precursors comprise a silicon oxide precursor and/or a molecular sieve precursor;
(2) and mixing the product of the first roasting with a solution of the IIA metal precursor, and then carrying out second drying and second roasting.
8. The method as claimed in claim 7, wherein the alumina precursor is pseudoboehmite, and the specific surface area of the pseudoboehmite is 250-330m2The pore volume is 0.5-1.1 ml/g;
and/or, the conditions of the first calcination include: the temperature is 500-650 ℃, and the time is 2-20 h;
and/or, the conditions of the second roasting include: the temperature is 800-1100 ℃, and the time is 2-20 h.
9. The method of any one of claims 1-8, wherein the catalyst is prepared by a method comprising:
(1) sequentially molding, first drying and first roasting a mixture containing a doping element, an alumina precursor and optionally other carrier precursors, wherein the other carrier precursors comprise a silicon oxide precursor and/or a molecular sieve precursor;
(2) mixing the product of the first roasting with a solution of a IIA group metal precursor, and then carrying out second drying and second roasting;
(3) at least one of group IIA metals, at least one of group VA metals and an active component are supported on the second calcined product.
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| CN101704753A (en) * | 2009-11-17 | 2010-05-12 | 中国科学院大连化学物理研究所 | Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition |
| CN106607060A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application, and method for preparing ethanediamine through ethylene glycol hydrogenation amination |
| CN109908900A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of loaded catalyst and the preparation method and application thereof |
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| CN101704753A (en) * | 2009-11-17 | 2010-05-12 | 中国科学院大连化学物理研究所 | Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition |
| CN106607060A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst and its preparation method and application, and method for preparing ethanediamine through ethylene glycol hydrogenation amination |
| CN109908900A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of loaded catalyst and the preparation method and application thereof |
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