CN114605268B - Method for catalytically synthesizing polyethylene polyamine - Google Patents
Method for catalytically synthesizing polyethylene polyamine Download PDFInfo
- Publication number
- CN114605268B CN114605268B CN202210285184.5A CN202210285184A CN114605268B CN 114605268 B CN114605268 B CN 114605268B CN 202210285184 A CN202210285184 A CN 202210285184A CN 114605268 B CN114605268 B CN 114605268B
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- Prior art keywords
- catalyst
- carrier
- reaction
- temperature
- ammonia
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 88
- -1 polyethylene Polymers 0.000 title claims abstract description 79
- 229920000768 polyamine Polymers 0.000 title claims abstract description 74
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 69
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 69
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 268
- 239000003054 catalyst Substances 0.000 claims abstract description 228
- 239000012298 atmosphere Substances 0.000 claims abstract description 130
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 105
- 230000009467 reduction Effects 0.000 claims abstract description 82
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 42
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 202
- 238000011282 treatment Methods 0.000 claims description 173
- 238000001035 drying Methods 0.000 claims description 71
- 239000001257 hydrogen Substances 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- 239000003570 air Substances 0.000 claims description 52
- 238000011068 loading method Methods 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 229910001316 Ag alloy Inorganic materials 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000005913 hydroamination reaction Methods 0.000 abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 77
- 238000011156 evaluation Methods 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 238000002791 soaking Methods 0.000 description 30
- 230000004048 modification Effects 0.000 description 27
- 238000012986 modification Methods 0.000 description 27
- 150000002431 hydrogen Chemical class 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 238000005576 amination reaction Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- 229960001124 trientine Drugs 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-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
- ULAXUFGARZZKTK-UHFFFAOYSA-N 2-aminopentan-1-ol Chemical compound CCCC(N)CO ULAXUFGARZZKTK-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical compound NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GPQWKLDEDGOJQH-UHFFFAOYSA-N ethane-1,1,1,2-tetramine Chemical compound NCC(N)(N)N GPQWKLDEDGOJQH-UHFFFAOYSA-N 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- LPGZAWSMGCIBOF-UHFFFAOYSA-N pentane-1,2-diamine Chemical compound CCCC(N)CN LPGZAWSMGCIBOF-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a method for catalytically synthesizing polyethylene polyamine. Monoethanolamine and ethylenediamine are used as main raw materials, and a polyethylene polyamine product is synthesized through a hydroamination reaction under the action of a catalyst. The catalyst consists of active metal, an auxiliary agent and a carrier: the active metal is one or the combination of Ni and Co, the assistant is one or the combination of Fe, ir, re, ru, cu, mn, B and W, and the carrier is Al 2 O 3 Activated carbon, siO 2 、Al 2 O 3 ‑SiO 2 One or a combination of (a). The carrier is modified by alkali metal or alkaline earth metal before use, wherein the alkali metal is one or a combination of Na and K. The catalyst after reduction activation is treated at high temperature in ammonia atmosphere. The catalyst prepared by the method is used for monoethanolamine and ethyleneThe hydroamination reaction of diamine has the advantages of high yield of polyethylene polyamine, high stability, high activity, etc. and has wide industrial foreground.
Description
Technical Field
The invention relates to a method for catalytically synthesizing polyethylene polyamine, in particular to a catalyst loaded by a modified carrier and an activation treatment method thereof, which are used for converting raw materials of monoethanolamine and ethylenediamine into amine products mainly comprising linear polyethylene polyamine through a catalytic amination reaction in a hydrogen atmosphere.
Background
Polyethylenepolyamines are one type of ethylene amines, including linear homologs, branched or cyclic amines of ethylene diamine. Among them, common linear polyethylenepolyamines include diethylenetriamine, triethylenetetramine (straight chain), tetraethylenepentamine (straight chain), etc., and are widely used in the fields of papermaking, lubricant additives, chelating agents, curing agents, etc. In recent years, the market of ethylenediamine in China gradually tends to be saturated, but the capacity of linear polyethylene polyamine is still low, high-quality products depend on import, and the development of downstream industries is limited. With the continuous maturity in the field of domestic chemical industry and the gradual optimization of industrial structure, the market demand for high-purity linear polyethylene polyamine products is increasing day by day.
The prior production process of polyethylene polyamine mainly comprises a dichloroethane method and a monoethanolamine method. Among them, the dichloroethane method is gradually eliminated due to the problems of severe corrosion of equipment, high energy consumption, environmental pollution, high investment cost and the like. The monoethanol amine method is a process for generating ethylene amine by reacting raw materials of monoethanolamine and liquid ammonia under the conditions of high pressure, hydrogen presence and the presence of a metal catalyst, and has the advantages of environmental friendliness, cleanness, low energy consumption, good atom economy and the like. Therefore, the ethylene polyamine is produced by adopting a dichloroethane method with a laggard technology in the industry at present, and researchers propose a process route for producing the ethylene polyamine by taking monoethanolamine, ethylenediamine and ammonia as raw materials in order to find a high-efficiency and environment-friendly production process of the ethylene polyamine. In the United states patent 4399308, lewis acid halide is used as a catalyst, when tin chloride is used as the catalyst and the reaction is carried out at 300 ℃, the selectivity of acyclic polyethylene polyamine reaches 71.4 percent, and the product mainly comprises triethylene tetramine and triaminoethylamine. The United states patents 4503253 and 4617418 adopt supported phosphoric acid or rare earth modified phosphoric acid catalysts, the conversion rate of monoethanolamine in gas phase reaction at 250-350 ℃ can reach more than 40%, the selectivity of acyclic polyethylene polyamine can reach more than 80%, the product mainly comprises diethylenetriamine, however, active components are easy to lose, and long-term operation cannot be realized. The U.S. Pat. No. 5321160 adopts Ni-Y-Ir system supported catalyst, and makes batch reaction in reactor at 200 deg.C, the conversion rate of monoethanolamine can be up to 27.8%, and the total selectivity of polyethylene polyamine is about 70.2%.
In summary, the catalytic system and process for producing polyethylenepolyamines by using the catalyst in the first place still have one or more of the following disadvantages: 1. the energy consumption is high; 2. a corrosion-susceptible device; 3. environmental pollution; 4. the linear polyethylene polyamine has low selectivity and few varieties; 5. the catalyst is not stable; 6. the side products of branched chain or cyclic amine in the product are more; 7. continuous production cannot be realized; 8. the catalyst activity is low. The present invention provides a new method for overcoming the above disadvantages.
Disclosure of Invention
The invention aims to provide a method for catalytically synthesizing polyethylene polyamine, which needs to be carried out in the presence of a supported metal catalyst and under the hydrogen condition. The method is used for the reaction of producing the polyethylene polyamine by the monoethanolamine and the ethylenediamine, and has the characteristics of high yield of linear polyethylene polyamine, rich varieties, less branched and cyclic byproducts, high catalytic activity, adjustable product distribution, good stability, green and clean reaction process and the like.
In accordance with one aspect of the present invention, there is provided a supported catalyst for the synthesis of polyethylene polyamine products.
The catalyst consists of active metal, an auxiliary agent element and a modified carrier, wherein the active metal and the auxiliary agent element are loaded on the modified carrier.
The catalyst is prepared by the following steps: and (3) loading the precursor of the active metal and the auxiliary agent element on a modified carrier through impregnation or precipitation, and drying, roasting, reducing and activating to obtain the catalyst.
The modified carrier is an alkali metal modified carrier, wherein the alkali metal is selected from one or more than two of Na and K.
The carrier is Al 2 O 3 Activated carbon, siO 2 、Al 2 O 3 -SiO 2 One or a combination of two or more of (1).
The specific surface area of the carrier is 50-1800 m 2 The pore volume is 0.2-1.2 ml/g.
In a preferable embodiment, the specific surface area of the carrier is 70 to 700m 2 The pore volume is 0.3-1.0 ml/g.
The preparation method of the modified carrier comprises the following steps: and loading a precursor of Na or K on the carrier, and roasting to obtain the modified carrier.
Wherein the precursor of Na or K is selected from carbonates, nitrates or hydrochlorides of Na or K.
The weight of Na or K accounts for 0.05-2% of the total mass of the modified carrier.
In a preferable embodiment, the weight of Na or K accounts for 0.1-1.2% of the total mass of the modified carrier.
In a more preferred embodiment, the weight of Na or K is 0.4-0.8% of the total mass of the modified carrier.
The roasting condition in the preparation method of the modified carrier is as follows: normal pressure, 300-700 deg.c for 4-10 hr in the atmosphere of one or more of air, oxygen and nitrogen and gas volume space velocity of 0-2000 hr -1 。
Alternatively, when the calcination gas volume space velocity of the modified carrier is 0h -1 That is, the firing process is carried out in a static (non-flowing) atmosphere.
Alternatively, the calcination treatment of the modified support may be performed in the following apparatus: muffle furnaces, tube furnaces, etc.
The roasting atmosphere of the preparation method of the modified carrier is as follows: when the carrier is Al 2 O 3 、SiO 2 、Al 2 O 3 -SiO 2 While being bakedThe atmosphere is preferably air or oxygen; when the selected carrier is activated carbon, nitrogen is selected as the roasting atmosphere.
The active metal of the supported catalyst is one or the combination of Ni and Co.
The weight of the active component accounts for 5-45% of the total weight of the catalyst.
In a preferred embodiment, the weight of the active component accounts for 10-30% of the total weight of the catalyst.
The auxiliary agent is one or a combination of elements Fe, ir, re, ru, cu, mn, B and W.
The weight of the auxiliary agent accounts for 0.05-10% of the total weight of the catalyst.
In a preferable scheme, the weight of the auxiliary agent accounts for 0.5-6% of the total weight of the catalyst.
The preparation method of the supported catalyst comprises the following steps: and loading the active metal and the auxiliary agent on the modified carrier by adopting at least one of an impregnation method and a precipitation method.
More specifically, when the dipping method is employed, the procedure is as follows: and (2) soaking the modified carrier in a solution containing an active metal element source and an auxiliary agent element source, drying and roasting to obtain the catalyst.
More specifically, when the precipitation method is employed, the procedure is as follows: adding the solution containing the active metal element source and the auxiliary agent element source and a precipitator into the suspension of the modified carrier, precipitating, aging, washing, drying and roasting to obtain the catalyst.
Optionally, the roasting temperature is 200-600 ℃, the roasting time is 0.5-15 h, and the roasting atmosphere is one or the combination of more than two of air, oxygen and nitrogen.
Optionally, the active component precursor comprises soluble salts of Ni and soluble salts of Co.
Optionally, the promoter precursor comprises a soluble precursor of a promoter element.
Specifically, the soluble salt of Ni used may be nickel nitrate, nickel acetate, nickel chloride, nickel sulfate or nickel citrate, preferably nickel nitrate, nickel acetate.
The soluble salt of Co can be cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate or cobalt citrate, preferably cobalt nitrate or cobalt acetate.
The soluble salt of the metal auxiliary agent is nitrate, hydrochloride or ammonium salt.
The nonmetal auxiliary agent B is boric acid.
Alternatively, the preparation method of the catalyst can adopt one or a combination of an impregnation method and a precipitation method to load the active component and the auxiliary agent on the modified carrier.
In a preferred embodiment, the active ingredient and the auxiliary agent may be supported on the modified carrier by impregnation.
Alternatively, in the impregnation method embodiment, the active component and the auxiliary agent may be supported on the modified support by co-impregnation or stepwise impregnation.
Alternatively, the impregnation method may include the steps of: preparing aqueous solution containing active component and adjuvant precursor, in which the weight of active component is 5-45% of catalyst weight, and the weight of adjuvant is 0.05-10% of catalyst weight, impregnating modified carrier with aqueous solution containing active component and adjuvant, naturally drying and roasting.
Alternatively, the impregnation method may be one impregnation or a multi-step impregnation.
Optionally, the roasting temperature is usually 200-600 ℃ and the time is 0.5-15 h.
Alternatively, the catalyst precursor may also be supported on the modified support by a precipitation method.
Alternatively, the step of preparing the catalyst by the precipitation method may be: the modified support is suspended in water, soluble precursors of the active ingredient and the auxiliary agent, such as metal salts, are added, and then the active ingredient and the auxiliary agent are precipitated onto the suspended modified support by adding a precipitating agent. Wherein the weight of the active component accounts for 5-45% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.05-10% of the weight of the catalyst. And (4) aging, washing, filtering, drying and roasting the precipitated sample.
Alternatively, the precipitant used is preferably an inorganic base, preferably sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.
Alternatively, the precipitant used may also be an ammonium salt, which may be ammonium carbonate, ammonium hydroxide or ammonium halide.
Alternatively, the precipitation temperature may be 20 to 100 ℃, preferably 40 to 60 ℃.
Optionally, the roasting temperature is usually 200-600 ℃ and the time is 0.5-15 h.
The calcined catalyst needs to be subjected to reduction activation treatment.
The operation process of the reduction activity comprises the following steps: the catalyst is treated at high temperature in a reducing atmosphere.
The process of the reduction activation treatment is carried out in a hydrogen atmosphere.
The reduction treatment conditions are as follows: the temperature is 200-600 ℃, the pressure is 0.1MPa, the time is 0.5-10 h, and the space velocity of hydrogen is 20-3000 h -1 。
Optionally, the reducing atmosphere comprises a mixture of hydrogen and an inert gas, wherein the inert gas can be nitrogen, helium, or argon.
Preferably, the reducing atmosphere is hydrogen.
According to another aspect of the invention, a method for treating a catalyst in an ammonia atmosphere at an elevated temperature is provided.
The load type catalyst after reduction activation needs to be treated in high-temperature ammonia atmosphere before being used for catalyzing and synthesizing polyethylene polyamine.
The operation process of the high-temperature ammonia atmosphere treatment comprises the following steps: the catalyst is used for high-temperature treatment in ammonia atmosphere before the reaction of catalyzing and synthesizing polyethylene polyamine.
The conditions of the high-temperature ammonia atmosphere treatment are as follows: the temperature is 300-600 ℃, the pressure is 1.5-3 MPa, and the time is 1-20 h.
In a preferred embodiment, the conditions of the high-temperature ammonia atmosphere treatment are as follows: the temperature is 350-450 ℃, the pressure is 1-4 MPa, and the time is 5-15 h.
In a more preferable embodiment, the conditions of the high-temperature ammonia atmosphere treatment are as follows: the temperature is 350-450 ℃, the pressure is 1.5-3 MPa, and the time is 8-12 h.
The ammonia source treated in the high-temperature ammonia atmosphereLiquid ammonia, the liquid hourly space velocity is 1-2 h -1 。
The catalyst treated in high temperature ammonia atmosphere may be used directly in the reaction of synthesizing polyethylene polyamine with monoethanolamine and ethylenediamine through hydrogenation.
The catalyst prepared by the method is used for the hydroamination reaction of monoethanolamine and ethylenediamine, and has the advantages of high yield of polyethylene polyamine, good stability, high activity and the like, and has wide industrial prospect.
In an alternative scheme, the high-temperature ammonia atmosphere treatment process can be carried out in situ on a reactor before the reaction for synthesizing polyethylene polyamine by the hydroamination of monoethanolamine and ethylenediamine.
According to another aspect of the invention, a process route for synthesizing polyethylene polyamine by using monoethanolamine and ethylenediamine as main raw materials through a hydro-catalytic amination reaction is provided, and the method has one or more advantages of easily available raw materials, good economy, adjustable product distribution, multiple types and high yield of linear polyethylene polyamine, capability of realizing continuous production, simple process route and easy operation.
The amination reaction takes monoethanolamine, ethylenediamine and ammonia as raw materials, adopts the catalyst provided by the invention to generate an amine product taking linear polyethylene polyamine as a main product through catalytic amination reaction under certain reaction conditions in a hydrogen atmosphere.
The polyethylene polyamine product comprises linear polyethylene polyamine, branched polyethylene polyamine and cyclic polyethylene polyamine.
The linear polyethylene polyamine refers to a compound having the following structure. Wherein n is more than or equal to 1.
Typically, 1. Ltoreq. N.ltoreq.6.
The branched polyethylene polyamine refers to an acyclic isomer of a linear polyethylene polyamine. Including but not limited to compounds of the following structure.
The cyclic polyethylene polyamine refers to a polyethylene polyamine having a cyclic structure including, but not limited to, a piperazine ring, a pyrazine ring, a morpholine ring, and the like. Including but not limited to compounds of the following structure.
The molar ratio of monoethanolamine to ethylenediamine in the raw materials is 0-5:1.
Preferably, the molar ratio of monoethanolamine to ethylenediamine in the raw material is 0-3:1.
The molar ratio of the liquid ammonia to the reaction raw materials is 0-90%.
Alternatively, when the molar ratio of liquid ammonia to the reaction raw material is 0%, that is, no liquid ammonia is added to the raw material.
Optionally, the starting material may be diluted with a solvent or may be free of other solvents.
Preferably, no additional solvent is required to be added to the feedstock.
Alternatively, the reaction raw material ammonia is selected from ammonia gas, liquid ammonia, and aqueous ammonia.
Preferably, the feed ammonia is selected from liquid ammonia.
In the present invention, the amination reaction is performed under a hydrogen atmosphere, which means under the condition of introducing hydrogen.
The amination reaction process is carried out under the hydrogen condition, wherein the molar concentration of hydrogen in the total feed materials is 1-80%.
Preferably, the molar concentration of hydrogen in the total feed material is from 3 to 40%.
Optionally, the raw materials are pumped into a preheater, preheated at 50-120 ℃ and then enter a reactor for reaction.
The amination reaction is carried out in a continuous or batch reactor.
Optionally, the continuous or batch reactor is selected from one of a fixed bed, a high pressure autoclave, a slurry bed, and a fluidized bed.
Preferably, the reactor is selected from fixed beds.
The reaction conditions of the hydrocatalytic amination are as follows: the reaction temperature is 130-210 ℃, preferably 150-200 ℃; the reaction pressure is 1-30 MPa, preferably 6-26 MPa; the total liquid hourly space velocity of the monoethanolamine and the ethylenediamine is 0.02-15 h -1 Preferably 0.1 to 10 hours -1 。
The catalytic system, the special treatment method and the application conditions thereof are also suitable for the reaction of preparing organic amines by ammoniating other unit alcohols, polyols or polyamines.
Alternatively, the monoalcohol substrate includes, but is not limited to, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 6-amino-1-hexanol, and the like.
Alternatively, the diol or polyol substrate includes, but is not limited to, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-pentanediol, 1,6-hexanediol, diethylene glycol, polyether polyol PPG-230, polyether polyol PPG-440, 1,2,6-hexanetriol, and the like.
Alternatively, the polyamines include, but are not limited to, aliphatic or aromatic diamines and the like, such as 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,2-pentanediamine, 1,6-hexanediamine, furandimethylamine (2,5-diaminomethylfuran), octanediamine, decanediamine, and the like.
The invention has the beneficial effects that:
1) The invention uses active components Ni and Co, auxiliary agent elements Fe, ir, re, ru, cu, mn, B and W, and carrier Al 2 O 3 Activated carbon, siO 2 And Al 2 O 3 -SiO 2 The combination of the two components produces synergistic catalyst effect, thereby improving the catalyst in the hydroamination reaction of the monoethanolamine and the ethylenediamineThe catalytic activity of (3).
2) The method influences the adsorption and activation capacity of the active metal to ammonia by carrying out alkali metal modification treatment on the carrier and carrying out ammonia atmosphere high-temperature treatment on the reduced catalyst, so that the ratio of the active metal to the active metal nitride is regulated and controlled, and the effect of improving the yield of the linear polyethylene polyamine in the product is achieved.
3) The catalyst of the invention is used for the hydroamination reaction of monoethanolamine and ethylenediamine, and has the effects of improving the yield of linear polyethylene polyamine and reducing the selectivity of branched chain or cyclic amine byproducts. In particular, the yield of long chain linear polyethylenepolyamines in the product can be improved. The long chain linear polyethylene polyamines include linear triethylene tetramine and higher linear ethylene diamine polymeric homologues. Meanwhile, the catalyst has high activity and good stability, and can realize long-period stable production.
4) The catalyst substrate has good adaptability, and shows excellent catalytic effect on raw materials with different ratios of monoethanolamine, ethylenediamine and ammonia.
Detailed Description
The invention is further illustrated by the following specific examples.
The active metal and adjuvant loadings in the examples and comparative examples were obtained by X-ray fluorescence spectroscopy. The catalysts in examples and comparative examples were subjected to reaction evaluation using a fixed bed reactor. The product analysis instrument is gas chromatography, and quantitative analysis is carried out by adopting an SE-30 capillary chromatographic column, an FID detector and N, N-dimethylformamide as an internal standard. Part of the analysis results are listed in table 1. Example 15 conversion data for ethylenediamine was used, and the other examples and comparative examples used monoethanolamine. Ammonia, water were not included in the calculation of product selectivity data.
The product designations of the examples and comparative examples are as follows: the selectivity of the linear polyethylene polyamine (L-polyethylene polyamine) is the sum of the selectivities of Diethylenetriamine (DETA), linear triethylene tetramine (L-TETA), linear tetraethylenepentamine (L-TEPA) and linear pentaethylenehexamine (L-PEHA). Wherein the long-chain linear polyethylene polyamine refers to linear triethylene tetramine (L-TETA), linear tetraethylene pentamine (L-TEPA) and linear pentaethylene hexamine (L-PEHA). The amine product also includes piperazine (PIP) and hydroxyethylethylenediamine (AEEA). Branched and cyclic amine by-products include triethylenediamine, tris (2-aminoethyl) amine, aminoethylpiperazine, hydroxyethylpiperazine, 1,4-piperazine diethylamine, and the like.
The loading amounts of the active metal, the additive element and the support modification additive on the catalysts described in the examples and comparative examples were measured by inductively coupled plasma atomic emission spectrometry or X-ray fluorescence spectrometry. Porous supports for use in the examples and comparative examples, wherein: the specific surface of the alumina carrier is about 350m 2 (ii)/g, pore volume about 0.4ml/g; the specific surface area of the silica carrier is about 450m 2 (iv)/g, pore volume about 0.7ml/g; the specific surface area of the alumina-silica carrier is about 400m 2 (ii)/g, pore volume about 0.4ml/g; the specific surface of the activated carbon carrier is about 650m 2 Per g, pore volume about 0.9ml/g. In the examples, the reaction evaluation of the catalyst was carried out in a fixed bed reactor, and the catalyst was subjected to an activation treatment including two steps of a reduction treatment and an ammonia atmosphere treatment before the reaction evaluation. Wherein, the catalyst adopts in-situ activation treatment, and the process is carried out on a fixed bed reactor. After the activation treatment, hydrogen is introduced into the reactor, the temperature is reduced to the required reaction temperature, the pressure is increased to the required pressure, and after the conditions are stable, reaction raw materials are injected through a pump for reaction evaluation.
In the comparative example, the evaluation of the catalyst reaction was carried out in a fixed bed reactor under the same operating conditions as in the example.
Specific catalyst preparation parameters, activation treatments and reaction conditions are shown in examples and comparative examples:
example 1
The preparation of catalyst 1 is as follows. Firstly, carrying out carrier modification treatment: 7.794 g of silicon dioxide carrier is taken and dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.014 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 0.08Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of a mixture containing 4.955 g of Ni (A)NO 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.08Na-SiO in an aqueous solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 1 is Ni10Co10Ru2/0.08Na-SiO 2 。
Catalyst 1 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 2MPa, and the liquid ammonia hourly space velocity is 1.5h -1 The treatment time was 10h.
The treated catalyst 1 was used for reaction evaluation, the reaction temperature was 170 ℃, the pressure was 12MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine to ethylenediamine to liquid ammonia was 0.3 -1 The molar concentration of hydrogen is 10%. Sampling and analyzing after the fixed bed reactor continuously reacts for 50 hours. The results are shown in Table 1.
Example 2
The preparation of catalyst 2 is as follows. Firstly, carrying out carrier modification treatment: 7.78 g of silicon dioxide carrier is taken and dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.045 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 0.25Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 g Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.25Na-SiO in an aqueous solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. To obtainCatalyst 2 is Ni10Co10Ru2/0.25Na-SiO 2 。
Catalyst 2 the high temperature ammonia atmosphere treatment process before use in the reaction was the same as in example 1.
The treated catalyst 2 was used for reaction evaluation, and the reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 3
The preparation of catalyst 3 is as follows. Firstly, carrying out carrier modification treatment: 7.753 g silicon dioxide carrier is dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.108 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 0.6Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.6Na-SiO in an aqueous solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 3 is Ni10Co10Ru2/0.6Na-SiO 2 。
Catalyst 3 the high temperature ammonia atmosphere treatment process before use in the reaction was the same as in example 1.
The treated catalyst 3 was used for reaction evaluation, and the reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 4
The preparation of catalyst 4 is as follows. Firstly, carrying out carrier modification treatment: 7.722 g silicon dioxide carrier is dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.18 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 1Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 g Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking the above 1Na-SiO in an aqueous solution 2 Naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 4 is Ni10Co10Ru2/1Na-SiO 2 。
The procedure of treating catalyst 4 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 4 was used for reaction evaluation, and the reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 5
The catalyst 5 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.66 g of silicon dioxide carrier is taken and dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.3236 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 1.8Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking the above 1.8Na-SiO in an aqueous solution 2 Naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 5 is Ni10Co10Ru2/1.8Na-SiO 2 。
The procedure of treating the catalyst 5 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 5 was used for reaction evaluation, and the reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 6
The catalyst 6 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.777 g silicon dioxide carrier is dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.054 g of sodium carbonate and 0.041 g of potassium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the space velocity of gas volume is 0h -1 To obtain a modified carrier of 0.3Na0.3K-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.3Na0.3K-SiO in water solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 6 is Ni10Co10Ru2/0.3Na0.3K-SiO 2 。
The procedure of treating the catalyst 6 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 6 was used for reaction evaluation, and the reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 7
The catalyst 7 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.654 g of alumina carrier is dried at 120 ℃ for standby. Preparing 6ml of aqueous solution containing 0.119 g of potassium nitrate, soaking the carrier by the aqueous solution, naturally drying, roasting at 600 ℃ in air atmosphere for 5h, wherein the gas volume space velocity is 200h -1 The obtained modified carrier is 0.6K-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: the 12ml sample contained 7.432 grams of Ni (NO) 3 ) 2 ·6H 2 O,2.469 g Co (NO) 3 ) 2 ·6H 2 O,1.14 g Cu (NO) 3 ) 2 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.6K-Al in an aqueous solution 2 O 3 Naturally drying the carrier in the air at 120 ℃ for 10h, and drying in the air for 40Roasting at 0 deg.c for 10 hr. Carrying out reduction treatment: the reduction condition is that the temperature is 450 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 500h -1 And the reduction time is 8h. The obtained catalyst 7 is Ni15Co5Cu3/0.6K-Al 2 O 3 。
Catalyst 7 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 320 ℃, the pressure is 2MPa, and the liquid ammonia liquid hourly space velocity is 1.8h -1 The treatment time was 10h.
The treated catalyst 7 was used for reaction evaluation, the reaction temperature was 180 ℃, the pressure was 14MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine, ethylenediamine and liquid ammonia was 0.2 -1 The molar concentration of hydrogen is 15%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 8
Catalyst 7 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 2MPa, and the liquid ammonia hourly space velocity is 1.8h -1 The treatment time was 10h.
The treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as in example 7.
Example 9
Catalyst 7 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 580 ℃, the pressure is 2MPa, and the liquid ammonia hourly space velocity is 1.8h -1 The treatment time was 10h.
The treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as in example 7.
Example 10
The catalyst 8 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.547 g of alumina-silica carrier is dried at 120 ℃ for standby. Preparing 7ml of water solution containing 0.094 g of potassium carbonate, impregnating the carrier with the water solution, naturally drying, roasting at 550 ℃ in air atmosphere for 6 hours, wherein the gas volume space velocity is 1000 hours -1 The obtained modified carrier is 0.7K-Al 2 O 3 -SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 14ml of the mixture containing 9.909 g Ni (NO) were prepared 3 ) 2 ·6H 2 O,0.988 g Co (NO) 3 ) 2 ·6H 2 O,0.288 g NH 4 ReO 4 The aqueous solution of (a) was divided into two equal portions and the following procedure was repeated 2 times: soaking 0.7K-Al in one part of the above aqueous solution 2 O 3 -SiO 2 And (3) naturally airing the carrier, drying at 120 ℃ for 10h, and roasting in air at 350 ℃ for 12h. Carrying out reduction treatment: the reduction condition is that the temperature is 460 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 200h -1 The reduction time is 10h. The obtained catalyst 8 is Ni20Co2Re2/0.7K-Al 2 O 3 -SiO 2 。
Catalyst 8 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 0.2MPa, and the liquid ammonia hourly space velocity is 2h -1 The treatment time was 10h.
The treated catalyst 8 was used for reaction evaluation, the reaction temperature was 190 ℃, the pressure was 25MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine, ethylenediamine and liquid ammonia was 1 -1 The molar concentration of hydrogen is 5%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 11
Catalyst 8 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 1.1MPa, and the liquid ammonia hourly space velocity is 2h -1 The treatment time was 10h.
The treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as in example 10.
Example 12
Catalyst 8 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 2MPa, and the liquid ammonia liquid hourly space velocity is 2h -1 The treatment time was 10h.
The treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as in example 10. And (4) evaluating the stability of the catalyst, and respectively sampling and analyzing after continuously evaluating for 50h and 2000h in a fixed bed reactor. The results are shown in Table 1, wherein the upper and lower rows of example 12 correspond to the reaction evaluation results of 50h and 2000h, respectively.
Example 13
Catalyst 8 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 4MPa, and the liquid ammonia hourly space velocity is 2h -1 The treatment time was 10h.
The treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as in example 10.
Example 14
Catalyst 8 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 4.9MPa, and the liquid ammonia hourly space velocity is 2h -1 The treatment time was 10h.
The treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as in example 10.
Example 15
The procedure of treating the catalyst 8 in the high-temperature ammonia atmosphere before the reaction was the same as in example 12.
The activated catalyst 8 is used for reaction evaluation, the reaction temperature is 190 ℃, the pressure is 25MPa, the liquid-phase feeding is ethylenediamine, and the liquid hourly space velocity of the ethylenediamine is 4h -1 The molar concentration of hydrogen was 5%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 16
The procedure of treating the catalyst 8 in the high-temperature ammonia atmosphere before the reaction was the same as in example 12.
The treated catalyst 8 was used for reaction evaluation, the reaction temperature was 190 ℃, the pressure was 25MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine, ethylenediamine and liquid ammonia was 4 -1 The molar concentration of hydrogen is 5%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 17
The catalyst 9 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.214 g of alumina carrier is dried at 120 ℃ for standby. Preparing 6.8ml of aqueous solution containing 0.134 g of sodium nitrate, soaking the carrier in the aqueous solution, naturally drying, roasting at 350 ℃ for 8h in air atmosphere, and setting the gas volume space velocity at 1500h -1 The obtained modified carrier is 0.5Na-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: adding 0.5Na-Al 2 O 3 Dispersing in water to form suspension, and stirring at 50 deg.C with medium speed. The formulation contained 7.408 grams of Co (NO) 3 ) 2 ·6H 2 O,4.955 g Ni (NO) 3 ) 2 ·6H 2 O,0.459 g IrCl 3 ·3H 2 O precursor fluid. The precipitant used is 2mol/L NaOH solution. Simultaneously dripping precursor liquid and precipitant into the above suspension at a rate of 1ml/min, maintaining pH at 9 until precipitation is complete, washing precipitate with deionized water to neutrality, filtering, air drying, drying at 120 deg.C for 10 hr, and calcining at 550 deg.C in air for 4 hr. Carrying out reduction treatment: the reduction condition is that the temperature is 450 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 2000h -1 And the reduction time is 4h. The obtained catalyst 9 was Co15Ni10Ir2.5/0.5Na-Al 2 O 3 。
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time is 2h.
The treated catalyst 9 was used for reaction evaluation, the reaction temperature was 160 ℃, the pressure was 20MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine, ethylenediamine and liquid ammonia was 0.5 -1 The molar concentration of hydrogen is 20%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 18
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 6h.
The treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Example 19
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 10h.
The treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Example 20
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 14h.
The treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Example 21
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 20h.
The treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Example 22
The catalyst 10 is prepared as follows. Firstly, carrying out carrier modification treatment: 8.201 g of active carbon carrier, dried at 120 ℃ for standby. Preparing 10ml of aqueous solution containing 0.126 g of sodium chloride, soaking the carrier by the aqueous solution, naturally drying, roasting at 400 ℃ in nitrogen atmosphere for 10h, wherein the gas volume space velocity is 100h -1 The modified support obtained was 0.6Na-C. And secondly, carrying out active metal and auxiliary agent loading: a20 ml aliquot of the mixture containing 7.408 grams of Co (NO) 3 ) 2 ·6H 2 O,0.866 g Fe (NO) 3 ) 3 0.129 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking the above 0.6Na-C carrier in a part of water solution, air drying, drying at 120 deg.C for 10 hr, and calcining at 400 deg.C in nitrogen for 4 hr. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 800h -1 And the reduction time is 5h. The catalyst 10 obtained was Co15Fe2Ru0.5/0.6Na-C.
The catalyst 10 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1.1h -1 The treatment time was 10h.
The treated catalyst 10 was used for reaction evaluation at a reaction temperature of 200 c,the pressure is 18MPa, the liquid phase feed materials are monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of the monoethanolamine to the ethylenediamine to the liquid ammonia is 1.5 -1 The molar concentration of hydrogen is 30%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 23
The catalyst 11 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.661 g silica carrier, dried at 120 ℃ for use. Preparing 7ml of aqueous solution containing 0.099 g of potassium nitrate, soaking the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 10h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 0.5K-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: the 14ml sample contained 9.909 grams of Ni (NO) 3 ) 2 ·6H 2 O,1.145 g H 3 BO 3 0.326 g Mn (NO) 3 ) 2 The aqueous solution of (a) was divided into two equal portions, and the following process was repeated 2 times: soaking the above 0.5K-SiO in an aqueous solution 2 And (3) naturally airing the carrier, drying at 120 ℃ for 10h, and roasting in air at 400 ℃ for 6h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 500h -1 And the reduction time is 5h. The obtained catalyst 11 is Ni20B2Mn1/0.5K-SiO 2 。
Catalyst 11 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1.2h -1 The treatment time was 10h.
The treated catalyst 11 was used for reaction evaluation, the reaction temperature was 185 ℃, the pressure was 15MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine to ethylenediamine to liquid ammonia was 1.5 -1 The molar concentration of hydrogen was 3%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 24
The catalyst 12 is prepared as follows. Firstly, carrying out carrier modification treatment: 7.761 g of alumina carrier, drying at 120 ℃ for later use. Fitting for mixingPlacing 6.8ml of aqueous solution containing 0.101 g of potassium nitrate, soaking the carrier by the aqueous solution, naturally drying, roasting for 10 hours at 400 ℃ in air atmosphere, wherein the gas volume space velocity is 50 hours -1 The obtained modified carrier is 0.5K-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: the resulting mixture (13.6 ml) contained 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,2.469 g Co (NO) 3 ) 2 ·6H 2 O,0.572 g H 3 BO 3 0.154 g (NH) 4 ) 2 WO 4 The aqueous solution of (a) was divided into two equal portions and the following procedure was repeated 2 times: soaking 0.5K-Al in water 2 O 3 And (3) naturally airing the carrier, drying at 120 ℃ for 10h, and roasting in air at 400 ℃ for 6h. Carrying out reduction treatment: the reduction condition is that the temperature is 450 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 500h -1 And the reduction time is 5h. The obtained catalyst 12 is Ni10Co5B1W1/0.5K-Al 2 O 3 。
The catalyst 12 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1.2h -1 The treatment time was 10h.
The treated catalyst 12 was used for reaction evaluation, the reaction temperature was 155 ℃, the pressure was 15MPa, the liquid phase feed was monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine to ethylenediamine to liquid ammonia was 1.5: 10, wherein the liquid hourly space velocity of monoethanolamine and ethylenediamine was 0.4h -1 The molar concentration of hydrogen was 8%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
Example 25
The catalyst 13 is prepared as follows. Firstly, carrying out carrier modification treatment: 9.244 g silica carrier, dried at 120 ℃ for use. Preparing 9ml of aqueous solution containing 0.206 g of sodium nitrate, soaking the carrier by the aqueous solution, naturally drying, roasting for 10 hours at 400 ℃ in air atmosphere, and controlling the gas volume space velocity to be 50 hours -1 The obtained modified carrier is 0.6Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 18ml of a mixture containing 2.477 grams of Ni (NO) 3 ) 2 ·6H 2 O,0.494 g Co (NO) 3 ) 2 ·6H 2 O,0.144 g NH 4 ReO 4 The aqueous solution of (a) was divided into two equal portions and the following procedure was repeated 2 times: soaking 0.6Na-SiO in an aqueous solution 2 And (3) naturally airing the carrier, drying at 120 ℃ for 10h, and roasting in air at 400 ℃ for 6h. Carrying out reduction treatment: the reduction condition is that the temperature is 450 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 500h -1 And the reduction time is 5h. The obtained catalyst 13 is Ni5Co1Re1/0.6Na-SiO 2 。
Catalyst 13 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1.2h -1 The treatment time was 10h.
The treated catalyst 13 was used for reaction evaluation, the reaction temperature was 185 ℃, the pressure was 15MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine to ethylenediamine to liquid ammonia was 1.5 -1 The molar concentration of hydrogen is 10%. Sampling and analyzing after the fixed bed reactor continuously reacts for 50 hours. The results are shown in Table 1.
Example 26
The catalyst 14 was prepared as follows. Firstly, carrying out carrier modification treatment: 5.268 g of alumina carrier, drying at 120 ℃ for later use. Preparing 5ml of aqueous solution containing 0.117 g of sodium nitrate, soaking the carrier by the aqueous solution, naturally drying, roasting at 500 ℃ in air atmosphere for 10h, wherein the gas volume space velocity is 200h -1 The obtained modified carrier is 0.6Na-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: adding 0.6Na-Al 2 O 3 Dispersing in water to form suspension, and stirring at 50 deg.C with medium speed. The mixture was made up to 19.819 g Ni (NO) 3 ) 2 ·6H 2 O,2.862 grams H 3 BO 3 0.367 g of IrCl 3 ·3H 2 O precursor fluid. The precipitant used was a 3mol/L NaOH solution. Simultaneously dripping precursor liquid and precipitant into the above suspension at a rate of 1ml/min, maintaining pH at 9 until precipitation is complete, washing precipitate with deionized water to neutrality, filtering, air drying, drying at 120 deg.C for 10 hr, and calcining at 400 deg.C in air for 6 hr. Carrying out reduction treatment: the reduction conditions were a temperature of 45 deg.CAt 0 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 100h -1 And the reduction time is 10h. The obtained catalyst 14 is Ni40B5Ir2/0.6Na-Al 2 O 3 。
Catalyst 14 was used for high temperature ammonia atmosphere treatment prior to reaction: the ammonia treatment temperature is 380 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1.2h -1 The treatment time was 10h.
The treated catalyst 14 was used for reaction evaluation, the reaction temperature was 185 ℃, the pressure was 15MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine to ethylenediamine to liquid ammonia was 1.5 -1 The molar concentration of hydrogen is 10%. Sampling and analyzing after the fixed bed reactor continuously reacts for 50 hours. The results are shown in Table 1.
Comparative example 1
The catalyst was 30% Ni-2% Re-1.2% 2 O 3 Prepared according to the method described in example 8 of patent WO 2013/152548.
Catalyst 30% Ni-2% Re-1.2% B/Al 2 O 3 The reduction process is as described in the example of patent WO 2013/152548.
The reduced catalyst was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 2
34% by weight of the catalyst supported on silica 3 PO 4 Prepared according to the method described in patent US 4503253, example 1. According to patent US 4503253, the catalyst does not require an activation treatment prior to use.
34% by weight of the catalyst silica 3 PO 4 For the reaction evaluation, the reaction conditions were the same as in example 1. No reaction product was detected in the product, which is indicated by "-" in Table 1-comparative example 2.
Comparative example 3
The Catalyst is acid lanthanum phosphate, and is prepared according to the method of Catalyst-B acid lanthanum phosphate in the patent US 4617418. According to patent US 4617418, the catalyst does not require an activation treatment prior to use.
Catalyst acid lanthanum phosphate was used for reaction evaluation, and the reaction conditions were the same as in example 1. No reaction product was detected in the product, which is indicated by "-" in Table 1-comparative example 3.
Comparative example 4
The catalyst is Ni-Y-Ir/Al 2 O 3 Prepared according to the method described in patent US 5321160, catalyst-19.
Catalyst Ni-Y-Ir/Al 2 O 3 The reduction process is as described in the examples of patent US 5321160.
Catalyst Ni-Y-Ir/Al 2 O 3 For the reaction evaluation, the reaction conditions were the same as in example 1.
Comparative example 5
The catalyst was a lewis acid halide, tin chloride as described in patent US 4399308, example 7.
Tin chloride catalyst was used for reaction evaluation, and the reaction conditions were the same as in example 1. No reaction product was detected in the product, which is indicated by "-" in Table 1-comparative example 5.
Comparative example 6
The catalyst 15 was prepared as follows. The support is not modified with alkali metal. 7.8 g of silicon dioxide carrier is taken and dried at 120 ℃ for standby. 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking the above SiO in an aqueous solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 15 is Ni10Co10Ru2/SiO 2 。
The procedure of treating the catalyst 15 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 15 was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 7
The catalyst 16 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.753 g diAnd drying the silicon oxide carrier at 120 ℃ for later use. The preparation (7.5 ml) contained 0.276 g Ca (NO) 3 ) 2 ·4H 2 Soaking the carrier in O water solution, air drying, calcining at 400 deg.C in air atmosphere for 6 hr with gas volume space velocity of 0 hr -1 The obtained modified carrier is 0.6Ca-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 g Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking the above 0.6Ca-SiO in an aqueous solution 2 Naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 16 is Ni10Co10Ru2/0.6Ca-SiO 2 。
The high temperature ammonia atmosphere treatment process of the catalyst 16 before use in the reaction was the same as in example 1.
The treated catalyst 16 was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 8
The catalyst 17 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.753 g silicon dioxide carrier is dried at 120 ℃ for standby. Preparation of 7.5ml of a solution containing 0.285 g of Mg (NO) 3 ) 2 The carrier is soaked by the aqueous solution, the carrier is naturally dried and roasted for 6 hours at 400 ℃ in the air atmosphere, and the gas volume space velocity is 0 hour -1 The obtained modified carrier is 0.6Mg-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.6Mg-SiO in an aqueous solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 17 is Ni10Co10Ru2/0.6Mg-SiO 2 。
The procedure of treating the catalyst 17 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 17 was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 9
The catalyst 18 is prepared as follows. Firstly, carrying out carrier modification treatment: 7.799 g silicon dioxide carrier is dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.002 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 0.01Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: 15ml of the mixture was prepared containing 4.955 g of Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.01Na-SiO in an aqueous solution 2 Naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 18 is Ni10Co10Ru2/0.01Na-SiO 2 。
The procedure of treating the catalyst 18 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 18 was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 10
The catalyst 19 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.41 g of silicon dioxide carrier is taken and dried at 120 ℃ for standby. Preparing 7.5ml of aqueous solution containing 0.899 g of sodium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 400 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 0h -1 The obtained modified carrier is 5Na-SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: the mixture was 15ml containing 4.955 g of Ni(NO 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: taking one part of water solution to dip the 5Na-SiO 2 Naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The obtained catalyst 19 is Ni10Co10Ru2/5Na-SiO 2 。
The procedure of treating the catalyst 19 in the high-temperature ammonia atmosphere before the reaction was the same as in example 1.
The treated catalyst 19 was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 11
The catalyst 20 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.753 g silicon dioxide carrier is dried at 120 ℃ for standby. The preparation 15ml contains 0.108 g of Na 2 CO 3 4.955 g Ni (NO) 3 ) 2 ·6H 2 O,4.939 grams Co (NO) 3 ) 2 ·6H 2 O,0.517 g RuCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking the above SiO in an aqueous solution 2 And naturally drying the carrier, drying at 120 ℃ for 10h, and roasting in air at 500 ℃ for 5h. Carrying out reduction treatment: the reduction condition is that the temperature is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 1000h -1 And the reduction time is 6h. The resulting catalyst 20 was Ni10Co10Ru2Na0.6/SiO 2 。
The procedure of the high-temperature ammonia atmosphere treatment of the catalyst 20 before use in the reaction was the same as in example 1.
The treated catalyst 20 was used for reaction evaluation, and the reaction conditions were the same as in example 1.
Comparative example 12
The catalyst 7 was used without high temperature ammonia atmosphere treatment prior to reaction.
Catalyst 7 was used for the reaction evaluation, and the reaction conditions were the same as in example 7.
Comparative example 13
Catalyst 7 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 240 ℃, the pressure is 2MPa, and the liquid ammonia liquid hourly space velocity is 1.8h -1 The treatment time was 10h.
The treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as in example 7.
Comparative example 14
Catalyst 7 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 750 ℃, the pressure is 2MPa, and the liquid ammonia liquid hourly space velocity is 1.8h -1 The treatment time was 10h.
The treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as in example 7.
Comparative example 15
Catalyst 8 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380 ℃, the pressure is 8MPa, and the liquid ammonia liquid hourly space velocity is 2h -1 The treatment time was 10h.
The treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as in example 10.
Comparative example 16
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 0.2h.
The treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Comparative example 17
Catalyst 9 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 100h.
The treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Comparative example 18
The catalyst 21 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.711 g of alumina carrier is dried at 120 ℃ for standby. Preparing 6.8ml of aqueous solution containing 0.143 g of sodium nitrate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 350 ℃ for 8h in air atmosphere, and degassingThe volume space velocity is 1500h -1 The obtained modified carrier is 0.5Na-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: adding 0.5Na-Al 2 O 3 Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The mixture is prepared with 8.663 g Fe (NO) 3 ) 3 0.459 g IrCl 3 ·3H 2 O precursor fluid. The precipitant used is 2mol/L NaOH solution. Simultaneously dripping precursor liquid and precipitant into the above suspension at a rate of 1ml/min, maintaining pH at 9 until precipitation is complete, washing precipitate with deionized water to neutrality, filtering, air drying, drying at 120 deg.C for 10 hr, and calcining at 550 deg.C in air for 4 hr. Carrying out reduction treatment: the reduction condition is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 2000h -1 And the reduction time is 4h. The obtained catalyst 21 was Fe20Ir2.5/0.5Na-Al 2 O 3 。
Catalyst 21 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 10h.
The treated catalyst 21 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Comparative example 19
The catalyst 22 is prepared as follows. Firstly, carrying out carrier modification treatment: 7.711 g of alumina carrier is dried at 120 ℃ for standby. Preparing 6.8ml of aqueous solution containing 0.143 g of sodium nitrate, soaking the carrier by the aqueous solution, naturally drying, roasting for 8 hours at 350 ℃ in air atmosphere, and setting the gas volume space velocity at 1500 hours -1 The obtained modified carrier is 0.5Na-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: adding 0.5Na-Al 2 O 3 Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The formulation contained 7.602 grams of Cu (NO) 3 ) 2 ·3H 2 O,0.459 g IrCl 3 ·3H 2 O precursor fluid. The precipitant used is 2mol/L NaOH solution. Dripping precursor liquid and precipitant into the above suspension at a rate of 1ml/min, maintaining pH at 9 until precipitation is complete, washing precipitate with deionized water to neutrality, filtering, air drying, and drying at 120 deg.C for 10h, roasting at 550 ℃ in air for 4h. Carrying out reduction treatment: the reduction condition is 400 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 2000h -1 And the reduction time is 4h. The obtained catalyst 22 was Cu20Ir2.5/0.5Na-Al 2 O 3 。
The procedure of treating the catalyst 22 with the high-temperature ammonia atmosphere before the reaction was the same as in comparative example 18.
The treated catalyst 22 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Comparative example 20
The catalyst 23 was prepared as follows. Firstly, carrying out carrier modification treatment: 7.711 g of alumina carrier is dried at 120 ℃ for standby. Preparing 6.8ml of aqueous solution containing 0.143 g of sodium nitrate, soaking the carrier by the aqueous solution, naturally drying, roasting for 8 hours at 350 ℃ in air atmosphere, and setting the gas volume space velocity at 1500 hours -1 The obtained modified carrier is 0.5Na-Al 2 O 3 . And secondly, carrying out active metal and auxiliary agent loading: adding 0.5Na-Al 2 O 3 Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The mixture was prepared to contain 5.309 g H 2 PtCl 6 ·6H 2 O,0.459 g IrCl 3 ·3H 2 O precursor fluid. The precipitant used is 2mol/L NaOH solution. Simultaneously dripping precursor liquid and precipitant into the above suspension at a rate of 1ml/min, maintaining pH at 9 until precipitation is complete, washing precipitate with deionized water to neutrality, filtering, air drying, drying at 120 deg.C for 10 hr, and calcining at 550 deg.C in air for 4 hr. Carrying out reduction treatment: the reduction condition is that the temperature is 300 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 2000h -1 And the reduction time is 4h. The obtained catalyst 23 was Ir20Ir2.5/0.5Na-Al 2 O 3 。
Catalyst 23 was used for high temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400 ℃, the pressure is 1.8MPa, and the liquid ammonia hourly space velocity is 1h -1 The treatment time was 10h.
The treated catalyst 23 was used for reaction evaluation, and the reaction conditions were the same as in example 17.
Comparative example 21
The catalyst 24 is prepared as follows. Firstly, the methodCarrying out carrier modification treatment: 7.547 g of alumina-silica carrier is dried at 120 ℃ for standby. Preparing 7ml of aqueous solution containing 0.094 g of potassium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 550 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 1000h -1 The obtained modified carrier is 0.7K-Al 2 O 3 -SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: the 14ml sample contained 9.909 grams of Ni (NO) 3 ) 2 ·6H 2 O,0.988 g Co (NO) 3 ) 2 ·6H 2 O,0.517 g RhCl 3 ·3H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.7K-Al in water 2 O 3 -SiO 2 And (3) naturally airing the carrier, drying at 120 ℃ for 10h, and roasting in air at 350 ℃ for 12h. Carrying out reduction treatment: the reduction condition is that the temperature is 460 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 200h -1 And the reduction time is 10h. The obtained catalyst 24 is Ni20Co2Rh2/0.7K-Al 2 O 3 -SiO 2 。
The high temperature ammonia atmosphere treatment process of the catalyst 24 before use in the reaction was the same as in example 12.
The treated catalyst 24 was used for reaction evaluation, and the reaction conditions were the same as in example 12.
Comparative example 22
The catalyst 25 is prepared as follows. Firstly, carrying out carrier modification treatment: 7.547 g of alumina-silica carrier is dried at 120 ℃ for standby. Preparing 7ml of aqueous solution containing 0.094 g of potassium carbonate, impregnating the carrier with the aqueous solution, naturally drying, roasting at 550 ℃ in air atmosphere for 6h, wherein the gas volume space velocity is 1000h -1 The obtained modified carrier is 0.7K-Al 2 O 3 -SiO 2 . And secondly, carrying out active metal and auxiliary agent loading: the 14ml sample contained 9.909 grams of Ni (NO) 3 ) 2 ·6H 2 O,0.988 g Co (NO) 3 ) 2 ·6H 2 O,1.539 g Cr (NO) 3 ) 3 ·9H 2 The aqueous solution of O, divided into two equal portions, was repeated 2 times: soaking 0.7K-Al in water 2 O 3 -SiO 2 Carrier, natureAir drying, drying at 120 deg.C for 10 hr, and calcining at 350 deg.C in air for 12 hr. Carrying out reduction treatment: the reduction condition is that the temperature is 460 ℃, the atmosphere is normal pressure hydrogen, and the volume space velocity is 200h -1 And the reduction time is 10h. The obtained catalyst 25 is Ni20Co2Cr2/0.7K-Al 2 O 3 -SiO 2 。
The procedure of treating the catalyst 25 in the high-temperature ammonia atmosphere before the reaction was the same as in example 12.
The treated catalyst 25 was used for reaction evaluation, and the reaction conditions were the same as in example 12.
Comparative example 23
The procedure of treating the catalyst 8 in the high-temperature ammonia atmosphere before the reaction was the same as in example 12.
The treated catalyst 8 was used for reaction evaluation, the reaction temperature was 190 ℃, the pressure was 25MPa, the liquid phase feeds were monoethanolamine, ethylenediamine and liquid ammonia, the molar ratio of monoethanolamine, ethylenediamine and liquid ammonia was 10h -1 The molar concentration of hydrogen is 5%. Samples were taken for analysis after 50h of continuous reaction in the fixed bed reactor. The results are shown in Table 1.
TABLE 1 evaluation results of a catalyst for preparing polyethylene polyamine by hydroamination
Table 1 evaluation results of catalysts for preparing polyethylene polyamine by hydroamination
The method has the beneficial effects of improving the substrate conversion rate and the selectivity of the linear polyethylene polyamine, and particularly improving the selectivity of the long-chain linear polyethylene polyamine in the product. Wherein the long-chain linear polyethylene polyamine comprises linear triethylene tetramine, linear tetraethylene pentamine and linear pentaethylene hexamine. From the reaction evaluation results of the catalysts shown in table 1, it can be seen from examples 1 to 6, comparative example 6, and comparative examples 9 to 10 that when the loading amount of the alkali metals Na, K pretreated with the carrier is less than 0.05% or no modification is performed, the catalysts show higher activity, but the linear polyethylene polyamine has low selectivity and the cyclic amine by-product is more; with the increase of the loading of Na and K, the activity of the catalyst shows a trend of gradually and rapidly decreasing, and meanwhile, the selectivity of linear polyethylene polyamine in the product is increased and then decreased; compared with the effect of the load capacity in the optional range of 0.05-2%, the linear polyethylene polyamine has higher selectivity when the load capacity is in the preferred range of 0.1-1.2%; at a more preferred range of 0.4 to 0.8%, the highest selectivity for long chain linear polyethylene polyamines is achieved with higher monoethanolamine conversion than would be achieved with loading levels in the preferred range of 0.1 to 1.2%. As is clear from comparative examples 7 to 8, the carrier pretreatment with Ca and Mg failed to provide the effects of Na and K, and there were problems of low activity and poor selectivity of linear polyethylenepolyamine. As is clear from comparative example 11, when the alkali metals Na and K are supported simultaneously with the active metal and the auxiliary, there are problems of low activity or poor selectivity of the linear polyethylene polyamine. As can be seen from examples 7-9 and comparative examples 12-14, the influence of the ammonia atmosphere activation treatment temperature on the catalytic performance is significant, and poor selectivity of linear polyethylene polyamine is easily caused when the ammonia atmosphere activation treatment is not carried out or the treatment temperature is lower than the optional range of 300-600 ℃; along with the increase of the ammonification treatment temperature, the conversion rate is in a trend of firstly gently and then rapidly decreasing, and the selectivity of the linear polyethylene polyamine is in a trend of firstly increasing and then decreasing; compared with the optional amination temperature of 300-600 ℃, the optimal amination temperature of 350-450 ℃ has the highest selectivity of the long-chain linear polyethylene polyamine while keeping higher conversion rate and the selectivity of the linear polyethylene polyamine; too high an activation temperature of the ammonia atmosphere may cause sintering of the catalyst, resulting in a significant decrease in activity. From the evaluation results of 50h and 2000h in example 12, it is clear that the conversion and selectivity data do not change much as the reaction time is extended to 2000h, demonstrating that the catalyst of the present invention is excellent in stability. As can be seen from examples 10 to 14 and comparative example 15, the conversion rate tended to decrease gradually and then rapidly with the increase in the treatment pressure of the ammonia atmosphere, and the selectivity of the linear polyethylene polyamine increased and then decreased; compared with the treatment pressure of 0.1-5 MPa in the optional ammonia atmosphere, the conversion rate or the selectivity of long-chain linear polyethylene polyamine is higher when the pressure is preferably 1-4 MPa; compared with the preferable ammonia atmosphere treatment pressure of 1-4 MPa, the pressure of 1.5-3 MPa is more preferable, the selectivity of the long-chain linear polyethylene polyamine is the highest, and the conversion rate is higher; when the pressure is too high, deactivation of the catalyst active metal is caused, and thus the conversion rate is significantly decreased. As can be seen from examples 15-16 and comparative example 23, the proportion of AEEA and cyclic by-products in the product gradually increased as the proportion of monoethanolamine in the starting material increased. As is clear from the results of examples 17 to 21 and comparative examples 16 to 17, as the treatment time of the ammonia atmosphere increases, the conversion rate tends to decrease gradually and rapidly, and the selectivity of the linear polyethylenepolyamine increases and then decreases; compared with the comparative example 16, when the ammonia atmosphere treatment time is in the optional range of 1-20 h, the selectivity of linear polyethylene polyamine is higher; compared with the optional treatment time range of 1-20 h, when the treatment time is preferably 5-15 h, the conversion rate or the selectivity of linear polyethylene polyamine is higher; compared with the preferable treatment time of 5-15 h, the long-chain linear polyethylene polyamine has the highest selectivity when the treatment time is more preferably 8-12 h; when the treatment time is too long, the conversion decreases significantly. As is clear from examples 22 to 26 and comparative examples 18 to 22, when the active components and auxiliary elements not defined in the present invention are used, there may be problems of low catalytic activity, poor selectivity of linear polyethylene polyamine, etc. From the above analysis, it can be seen that using the catalyst for the hydroamination to produce polyethylene polyamines can achieve one or more of the following: (1) the preparation process of the catalyst is simple and easy to operate; (2) The linear polyethylene polyamine has high selectivity, and the long-chain linear polyethylene polyamine has multiple types and high selectivity; (3) the selectivity of the generated cyclic by-product is low; (4) the catalyst has high activity; (5) the process is economical; (6) the catalyst has good stability; (7) the reaction condition is mild; (8) continuous production can be realized; and (9) the reaction process is green and clean.
Claims (13)
1. A process for the catalytic synthesis of polyethylene polyamines, characterized in that the process is carried out in the presence of a catalyst;
the catalyst consists of active metal, an auxiliary agent element and a modified carrier, wherein the active metal and the auxiliary agent element are loaded on the modified carrier;
the modified carrier is an alkali metal modified carrier; the alkali metal is selected from one or two of Na and K; the carrier is Al 2 O 3 Activated carbon, siO 2 And Al 2 O 3 -SiO 2 One or more than two of (a);
the active metal is one or two combinations of Ni and Co; the auxiliary agent is one or the combination of more than two of elements of Fe, ir, re, ru, cu, mn, B and W;
the catalyst is prepared by the following steps: impregnating or precipitating precursors of active metals and auxiliary agent elements to load the precursors on a modified carrier, and drying, roasting, reducing and activating the precursors to obtain the catalyst;
the conditions of the reduction activation treatment are as follows: the temperature is 200 to 600 ℃, the pressure is 0.1MPa, the time is 0.5 to 10h, and the hydrogen airspeed is 20 to 3000h -1 ；
Before the catalyst is used for catalyzing and synthesizing polyethylene polyamine, high-temperature ammonia atmosphere treatment is needed; the high-temperature ammonia atmosphere treatment conditions are as follows: the temperature is 300 to 600 ℃; the pressure is 0.1 to 5MPa; the time is 1 to 20h; the ammonia source is liquid ammonia, and the liquid hourly space velocity is 1 to 2h -1 The reaction raw material for catalytically synthesizing the polyethylene polyamine comprises ethylenediamine, or one or two of ethylenediamine, monoethanolamine and ammonia;
the alkali metal of the alkali metal modified carrier is Na and/or K, and the carrier modification method comprises the following steps: loading a precursor of Na and/or K on a carrier by adopting an impregnation method, and roasting to obtain a modified carrier; the weight of the Na and/or the K accounts for 0.05 to 2 percent of the total mass of the modified carrier.
2. The method of claim 1, wherein:
the weight of the active component accounts for 5 to 45 percent of the total weight of the catalyst;
the weight of the auxiliary agent accounts for 0.05 to 10 percent of the total weight of the catalyst;
the specific surface area of the carrier is 50-1800 m 2 (ii)/g; the pore volume is 0.2 to 1.2ml/g.
3. The method of claim 1, wherein:
the weight of the active component accounts for 10 to 30 percent of the total weight of the catalyst;
the weight of the auxiliary agent accounts for 0.5 to 6 percent of the total weight of the catalyst;
the specific surface area of the carrier is 70 to 700m 2 (iv) g; the pore volume is 0.3 to 1.0ml/g.
4. The method according to claim 1 or 2,
the precursor of Na and/or K is selected from one or more of carbonates, nitrates or hydrochlorides of Na and/or K;
the weight of the Na and/or K accounts for 0.05 to 2 percent of the total mass of the modified carrier;
the roasting conditions are as follows: under normal pressure, at 300-700 ℃ for 4-10 h, the atmosphere is one or the combination of more than two of air, oxygen and nitrogen, the reaction is carried out in static or flowing atmosphere, and the airspeed of the gas volume is 0-2000 h -1 。
5. The method according to claim 4, wherein the weight of Na and/or K is 0.1 to 1.2 percent of the total mass of the modified carrier.
6. The method of claim 4,
the weight of the Na and/or the K accounts for 0.4 to 0.8 percent of the total mass of the modified carrier.
7. The method according to claim 1, characterized in that the active metal and the auxiliary agent are loaded on the modified support by at least one or two of impregnation and precipitation: in particular to a method for preparing a high-performance nano-silver alloy,
dipping the modified carrier into a solution containing an active metal element source and an auxiliary agent element source, drying and roasting to obtain the catalyst;
or adding a solution containing an active metal element source and an auxiliary element source and a precipitator into the suspension of the modified carrier, precipitating, aging, washing, drying and roasting to obtain the catalyst;
the roasting conditions are as follows: the temperature is 200 to 600 ℃, the time is 0.5 to 15h, and the atmosphere is one or the combination of more than two of air, oxygen and nitrogen.
8. The method of claim 1, wherein:
the molar ratio of monoethanolamine to ethylenediamine in the reaction raw materials is 0~5: 1; the molar ratio of the liquid ammonia to the reaction raw materials is 0 to 90 percent;
the catalytic reaction process is carried out under the hydrogen condition, wherein the molar ratio of hydrogen to the total feed material is 1-80%;
the reaction conditions are as follows: the temperature is 130 to 210 ℃; the pressure is 1 to 30MPa;
the total liquid hourly space velocity of the monoethanolamine and the ethylenediamine is 0.02 to 15h -1 。
9. The method of claim 8, wherein:
the molar ratio of monoethanolamine to ethylenediamine in the reaction raw materials is 0~3: 1;
the catalytic reaction process is carried out under the hydrogen condition, wherein the molar ratio of hydrogen to the total feed material is 3-40%;
the reaction conditions are as follows: the temperature is 150 to 200 ℃; the pressure is 6 to 26MPa;
the total liquid hourly space velocity of the monoethanolamine and the ethylenediamine is 0.1 to 10h -1 。
10. The process of claim 1, wherein the reaction for catalytically synthesizing polyethylene polyamine is carried out in a reactor comprising one or both of a continuous, batch reactor; wherein the continuous reactor is selected from one or more than two of a fixed bed reactor, a continuous stirred tank reactor, a slurry bed reactor and a fluidized bed reactor; the batch reactor is selected from autoclave reactors.
11. The method of claim 10, wherein the reactor is one or both of a fixed bed reactor and an autoclave reactor.
12. The method of claim 1, wherein the high temperature ammonia atmosphere treatment conditions are: the temperature is 350 to 450 ℃; the pressure is 1 to 4MPa; the time is 5 to 15h.
13. The method according to claim 12, wherein the pressure is 1.5 to 3mpa; the time is 8 to 12h.
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| CN202210285184.5A CN114605268B (en) | 2022-03-22 | 2022-03-22 | Method for catalytically synthesizing polyethylene polyamine |
| PCT/CN2022/138260 WO2023179110A1 (en) | 2022-03-22 | 2022-12-11 | Method for synthesizing polyethylene polyamine under catalysis |
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| CN115739102B (en) * | 2022-11-14 | 2024-05-03 | 万华化学集团股份有限公司 | Preparation method of hydroamination catalyst and method for amination reaction of polyether polyol |
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| CN109908900B (en) * | 2017-12-12 | 2022-05-06 | 中国科学院大连化学物理研究所 | Supported catalyst and preparation method and application thereof |
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| CN114605268B (en) * | 2022-03-22 | 2023-02-28 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
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