CN108176392B - Composite catalyst for catalytic decomposition of amine salt, preparation method thereof and method for preparing MDA (multidrug resistance) - Google Patents
Composite catalyst for catalytic decomposition of amine salt, preparation method thereof and method for preparing MDA (multidrug resistance) Download PDFInfo
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- CN108176392B CN108176392B CN201711450846.5A CN201711450846A CN108176392B CN 108176392 B CN108176392 B CN 108176392B CN 201711450846 A CN201711450846 A CN 201711450846A CN 108176392 B CN108176392 B CN 108176392B
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- Prior art keywords
- acid
- polyamine
- aniline
- diamine
- diphenylmethane series
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- 238000000034 method Methods 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 21
- -1 amine salt Chemical class 0.000 title claims abstract description 18
- 230000036457 multidrug resistance Effects 0.000 title description 2
- 229920000768 polyamine Polymers 0.000 claims abstract description 124
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims abstract description 119
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 150000004985 diamines Chemical class 0.000 claims abstract description 92
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000012071 phase Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000047 product Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 239000007791 liquid phase Substances 0.000 claims abstract description 34
- 239000003377 acid catalyst Substances 0.000 claims abstract description 20
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 19
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 62
- 230000008569 process Effects 0.000 claims description 61
- 238000005406 washing Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 9
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- 229960000359 chromic chloride Drugs 0.000 claims description 7
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012263 liquid product Substances 0.000 claims 1
- 239000007859 condensation product Substances 0.000 abstract 1
- YQYUWUKDEVZFDB-UHFFFAOYSA-N mmda Chemical compound COC1=CC(CC(C)N)=CC2=C1OCO2 YQYUWUKDEVZFDB-UHFFFAOYSA-N 0.000 description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 238000003756 stirring Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 18
- 238000006386 neutralization reaction Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 14
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 238000012546 transfer Methods 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 150000003840 hydrochlorides Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- CYGKLLHTPPFPHH-UHFFFAOYSA-N aniline;hydrate Chemical compound O.NC1=CC=CC=C1 CYGKLLHTPPFPHH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of preparation of diamine and polyamine of diphenylmethane series, in particular to a composite catalyst for catalytic decomposition of amine salt, a preparation method thereof and a method for preparing MDA, wherein the composite catalyst comprises a carrier, a main active component and a secondary active component, and the method for preparing diamine and polyamine of diphenylmethane series comprises the following steps: (a) under the condition of an acid catalyst, aniline is subjected to salt forming reaction to generate aniline acid salt; then, the aniline acid salt is contacted with formaldehyde solution for condensation reaction; (b) and (3) in the presence of a composite catalyst, carrying out catalytic decomposition on the condensation product to obtain a gas-phase product containing HCl and a liquid-phase product I containing diamine and polyamine of diphenylmethane series. The method of the invention essentially improves the quality of the subsequently produced MDA and saves the cost at the same time.
Description
Technical Field
The invention relates to the technical field of preparation of diamine and polyamine of diphenylmethane series, in particular to a composite catalyst for catalytic decomposition of amine salt, a preparation method thereof and a method for preparing MDA.
Background
Diamines and polyamines of the diphenylmethane series (MDA for short) include diamine compounds of the diphenylmethane series or mixtures of isomers thereof, referred to as monomeric MDA (mmda), and polyamine compounds of the diphenylmethane series or mixtures thereof, referred to as polymeric MDA (pmda). MDA refers primarily to a mixture that conforms to the following chemical structural formula:
wherein n represents an integer of 0 or more. When n ═ 0, such compounds are known as diamines of the diphenylmethane series or diaminodiphenylmethane. When n > 0, these compounds are referred to as polyamines of the diphenylmethane series. All NH groups in such compounds may be formally substituted by NCO groups2The corresponding isocyanates obtained by radical polymerization are referred to as diisocyanates of the diphenylmethane series, polyisocyanates of the diphenylmethane series or diisocyanates and polyisocyanates of the diphenylmethane series (MDI), respectively.
The preparation of di-and polyamines of the diphenylmethane series is described industrially in numerous published patents and publications, for example in WO2009037088 and the like. In the existing industrial production, aniline hydrochloride is prepared from aniline and formaldehyde under the acid catalysis condition, then the aniline hydrochloride and formaldehyde are subjected to condensation reaction to obtain MDA, and then the MDA is subjected to phosgenation reaction to produce monomeric MDI and polymeric MDI, which are well known methods in the polyurethane industry.
According to the prior art, aniline and formaldehyde are subjected to a condensation reaction under the action of an acid catalyst, and the work-up of the acidic reaction mixture obtained is initiated by neutralization with a base. The base neutralization reaction is usually carried out at a temperature of 90 ℃ to 100 ℃. Suitable bases are hydroxides of alkali and alkaline earth elements, for example aqueous NaOH solution. In the process of neutralizing diamine salts and polyamine salts of diphenylmethane series with alkali to obtain diamine and polyamine of diphenylmethane series, because the amount of hydrochloric acid used in the front-end salt forming reaction is large, the amount of caustic soda added is also huge to fully neutralize the hydrochloric acid, and accounts for nearly 10% of the MDA manufacturing cost. Meanwhile, the addition of caustic soda brings about a large amount of neutralization wastewater, and also causes huge pressure on environmental-friendly discharge. Moreover, due to the particularity of the neutralization reaction, if the amount of caustic soda is not enough, excessive amounts of diamine and polyamine salts of the acidic diphenylmethane series will cause great corrosion to downstream non-acid-resistant equipment.
In addition, in the neutralization of diamine salts and polyamine salts of the diphenylmethane series with a base to obtain diamines and polyamines of the diphenylmethane series, the organic phase containing diamines and polyamines of the diphenylmethane series and the inorganic phase containing a large amount of an aqueous solution of an inorganic salt also have problems in terms of phase separation technology, and if the formation of a rag layer cannot be completely avoided, it will end up in one of the two phases. When the rag layer enters the organic phase, neutralization of the crude product followed by phase separation is more acceptable than washing the neutralized product followed by phase separation. This is because in the case of the latter phase separation, not only a considerable amount of water but naturally also some substances dissolved therein (e.g. NaOH and NaCl) are then taken, together with the impurity layer from the neutralization reaction, to a further processing step in which they are more difficult to dispose of, for example salt deposits which may occur in the apparatus or pipes of the distillation zone. Even if the formation of an impurity layer can be avoided (as in the solutions described in patent documents EP1652835 a1 and WO 2008/148631 a 1), the organic phase obtained after phase separation still contains a considerable proportion of aqueous constituents as dispersed phase, which in further processing steps leads to similar problems, resulting in an entrained impurity layer.
At present, the patent documents at home and abroad are mostly related to the neutralization reaction and phase separation technology of diamine and polyamine of diphenylmethane series, for example, the patent document EP 1652835A 1 describes how to neutralize diamine salt and polyamine salt of diphenylmethane series with alkali liquor, and the separation of the generated salt-containing aqueous phase from the product-containing organic phase. Few documents mention the direct use of the catalytic hydrochloride decomposition technique in the field of MDI production.
In the prior literature, in the process of preparing MDA, diamine and polyamine in diphenylmethane series are prepared mainly by neutralizing and adding alkali and carrying out phase separation on an organic liquid phase and an inorganic liquid phase, so that the impurity content in MDA products cannot be reduced fundamentally, and the quality of isocyanate and polyurethane generated by MDA cannot be improved. Therefore, how to convert diamine and polyamine salts of diphenylmethane series into diamine and polyamine of diphenylmethane series simply, rapidly, efficiently, safely and at low cost is a key technology for preparing MDA by condensation reaction.
Disclosure of Invention
The invention aims to provide a composite catalyst for catalytic decomposition of amine salt, a preparation method thereof and a method for preparing MDA (methyl methacrylate), aiming at the problems in the prior art, the method for preparing MDA and the composite catalyst prepared by the method fundamentally avoid the residue of impurities in the process of separating organic phase and inorganic phase solutions, so that the quality of the subsequently produced MDA is essentially improved, and the production cost is saved.
In order to achieve the above object, the present invention provides a composite catalyst for catalytically decomposing an amine salt, the composite catalyst comprising a carrier, a primary active component and a secondary active component; wherein the carrier is pretreated by acid; the carrier is selected from nano SiO2The composite material comprises a solid material and/or multi-wall carbon nano tubes, wherein the main active components are selected from any two of cerium oxide, tin oxide and cuprous oxide, and the secondary active components are selected from one or more of manganese oxide, cobalt oxide, ferric oxide and chromium oxide. In a preferred embodiment of the invention, the primary active component is selected from cerium oxide and tin oxide and the secondary active component is chromium oxide.
According to the composite catalyst provided by the invention, preferably, the content of the main active component is 20-70 wt% of the weight of the carrier, and more preferably 45-68 wt%; the secondary active ingredient is present in an amount of 1 to 10 wt%, more preferably 3 to 6 wt%, based on the weight of the carrier.
According to the composite catalyst provided by the present invention, preferably, the step of acid-pretreating the carrier comprises: and (2) soaking the carrier in 20-30% of inorganic acid by mass, performing primary acid treatment, then placing the carrier in mixed acid, and performing heating reflux to perform secondary acid treatment.
Preferably, the inorganic acid is a hydrochloric acid solution or a sulfuric acid solution.
Preferably, the molar ratio of the carrier to the inorganic acid is 1: 10-12.
In one embodiment, the support is impregnated in the mineral acid for a time of 0.5 to 3 hours; the mineral acid is then removed by washing with water, for example, the support is immersed in the mineral acid for a period of 1 hour.
Preferably, the mixed acid is a mixed acid of concentrated nitric acid and concentrated sulfuric acid, and the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 2-5, more preferably 1: 3-4. In the present invention, concentrated nitric acid or concentrated sulfuric acid is selected, such as but not limited to concentrated nitric acid with a concentration of more than 65 wt% or concentrated sulfuric acid with a concentration of more than 70 wt%.
Preferably, the mass ratio of the carrier to the mixed acid is 1: 1-2. In a preferred embodiment of the present invention, the mass ratio of the carrier to the mixed acid is 1: 2.
in one embodiment, the carrier is placed in the mixed acid and heated and refluxed at the temperature of 50-70 ℃ for 1-3 hours; the mixed acid is then removed by washing with water, for example, the carrier is placed in the mixed acid and refluxed at 70 ℃ for 1 hour.
In the composite catalyst, the carrier is subjected to acid treatment twice, so that on one hand, the surface of the catalyst carrier can be pre-activated, the surface activity of the carrier is improved, the attachment rate of soluble salts of active metals, particularly the attachment rate of chlorides of the active metals, is improved, and the catalytic efficiency is obviously improved; on the other hand, the method is beneficial to reducing the activation energy required by the obtained composite catalyst for catalytically decomposing the amine salt, further reducing the energy consumption and improving the economy.
The invention also provides a preparation method of the composite catalyst, which comprises the following steps:
contacting soluble salt solution containing active metal with a carrier pretreated by acid for impregnation and adsorption, adding a dispersing agent for uniform dispersion, adjusting the pH value to 8.0-8.5, standing, performing suction filtration, washing, drying, and calcining to obtain the solid composite catalyst;
the soluble salt solution containing the active metal is any two of cerium, tin and copper, and one or more of manganese, cobalt, iron and chromium, and is preferably selected from nitrate solution containing the active metal and/or chloride solution containing the active metal.
According to the preparation method provided by the invention, preferably, the drying process conditions comprise: the drying temperature is 50-80 ℃, and more preferably 60-70 ℃; the drying time is 30-60h, more preferably 40-50 h.
According to the preparation method provided by the invention, preferably, the calcination process conditions include: calcining at 420-550 deg.C, preferably 450-500 deg.C in air atmosphere for 2-5h, preferably 3-4 h.
Preferably, the active metal-containing chloride is selected from any two of cerium chloride, tin chloride and cuprous chloride and one or more of manganese dichloride, cobalt chloride, ferric trichloride and chromium trichloride.
The amount ratio of the active metal-containing chloride to the carrier is such that the content of the main active component in the resulting composite catalyst is 20 to 70 wt%, for example, 30 wt%, 40 wt%, 50 wt%, 60 wt%, preferably 45 to 68 wt%, based on the weight of the carrier; the secondary active component is present in an amount of 1 to 10 wt%, e.g. 2 wt%, 4 wt%, 8 wt%, preferably 3 to 6 wt% based on the weight of the carrier.
In a preferred embodiment of the invention, the active metal-containing chloride is cerium chloride, tin chloride and chromium trichloride. Wherein, cerium chloride: tin chloride: the molar ratio of the chromium trichloride is 1-4: 1-5: 1; preferably 1.4 to 3.8: 1.7-4.2: 1.
preferably, the dispersant is polyethylene glycol 400. The amount of dispersant added is a matter of routine choice in the art, and in a particular embodiment of the invention, the mass of the dispersant is 1-10%, preferably 4-8% of the mass of the support in the composite catalyst.
In a preferred embodiment of the present invention, the preparation method of the composite catalyst specifically comprises: firstly, nano SiO as carrier material2And/or immersing the multi-walled carbon nano-tube in hydrochloric acid with the mass fraction of about 30% for 1h, washing and filtering the multi-walled carbon nano-tube by water, then putting the multi-walled carbon nano-tube in mixed acid (the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 1: 3), refluxing for 1h at 70 ℃, washing the multi-walled carbon nano-tube to be neutral by distilled water, and drying the multi-walled carbon nano-tube for later use; secondly, placing chlorides containing active metals (such as cerium chloride, stannic chloride and chromium trichloride) in a beaker, adding distilled water, stirring and dissolving, adding a carrier material pretreated by acid, finally adding polyethylene glycol 400 as a dispersing agent, dispersing uniformly by ultrasonic waves, stirring at room temperature for 3-6 hours, then dripping ammonia water under stirring until the pH value is 8.0-8.5, then standing, filtering, washing, drying, and calcining at 450 ℃ for 3 hours to obtain the composite catalyst with a solid network structure.
The nanometer SiO of the invention2The powder is amorphous white powder, the particle size range is 1-100 nanometers, and the microstructure is spherical and is a flocculent and reticular porous quasi-particle structure.
The composite catalyst prepared by combining a liquid phase chemical deposition method and an impregnation method has a compact three-dimensional network structure, and the main active component and the secondary active component are loaded on the surface of the carrier in the form of spherical nano particles. The active metal oxide is loaded on the surface of the carrier by spherical nano particles, the particle size is small, the dispersion is uniform, the carrier limits the migration of the nano particles, and the agglomeration of the nano particles can be prevented, so that the characteristic of huge specific surface area of the nano catalyst is fully exerted. In addition, the composite catalyst has multiple surface active points and strong adsorption capacity, the high-content main active component can effectively reduce the decomposition activation energy of ammonium salt, and the excellent catalytic effect is presented, and a certain amount of secondary active component enables the catalyst to have stronger oxidation-reduction capacity, surface acidity and thermal stability.
It is another object of the present invention to provide a process for the preparation of di-and polyamines of the diphenylmethane series, comprising the steps of:
(a) in the presence of an acid catalyst, aniline is subjected to a salt forming reaction to generate aniline acid salt; then, the aniline acid salt is contacted with formaldehyde solution for condensation reaction to obtain a mixture containing diamine salt and polyamine salt of diphenylmethane series;
(b) subjecting the mixture of step (a) to catalytic decomposition in the presence of a composite catalyst as described above or a composite catalyst prepared by the preparation method as described above to obtain a gas phase product comprising HCl gas and a liquid phase product I comprising di-and polyamines of the diphenylmethane series.
According to the process provided by the present invention, the reaction of aniline and formaldehyde in step (a) under acid catalysis can be carried out by known methods. Preferably, the acid catalyst in step (a) is selected from a hydrochloric acid solution with a mass percentage concentration of 30-33% and/or a sulfuric acid solution with a mass percentage concentration of 30-33%, preferably a hydrochloric acid solution with a mass percentage concentration of 30-33%. In a preferred embodiment of the present invention, aniline is salified with a hydrochloric acid solution in step (a) to form aniline hydrochloride.
Preferably, the molar ratio of the acidic catalyst to aniline is 0.1-1.0:1, more preferably 0.15-0.6:1, even more preferably 0.3-0.5: 1; the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.1-0.9:1, more preferably 0.2-0.6:1, and still more preferably 0.35-0.55: 1; the mass percentage concentration of the formaldehyde solution is preferably 36.0-37.5%.
Preferably, the process of step (a) comprises: the salt forming reaction of aniline and an acid catalyst is an instant reaction, and the reaction time of aniline acid salt and formaldehyde is 3-5 h; the reaction temperature of aniline and acid catalyst is 40-50 deg.c, and the condensation reaction temperature of aniline acid salt and formaldehyde is 45-55 deg.c.
According to the method provided by the present invention, preferably, the loading volume of the composite catalyst in the step (b): mixture volume of diamine and polyamine salts of diphenylmethane series ═ 1: 1-6.
The mixture comprising diamine and polyamine salts of the diphenylmethane series can be catalytically decomposed by means of a reactor loaded with a catalyst. In a preferred embodiment of the present invention, the reactor in which the catalyst decomposition is carried out is selected from fixed bed catalytic decomposition reactors. Preferably, the process conditions of the catalytic decomposition include: the reaction pressure is 2 to 20KpaG, more preferably 5 to 15KpaG, and still more preferably 8 to 12 KpaG; the reaction temperature is 60 ℃ to 100 ℃, more preferably 75 ℃ to 95 ℃, and still more preferably 80 ℃ to 90 ℃. In the present invention, the residence time of the mixture comprising diamine and polyamine salts of the diphenylmethane series in the catalyst-loaded reactor is determined depending on the loading of the catalyst used.
Preferably, when the decomposition rate of the mixture obtained in the step (a) is less than 80%, the mixture which is not decomposed completely is returned to the decomposition reaction system in the step (b) through a loop to perform secondary decomposition.
According to the method provided by the invention, the method preferably further comprises the following steps:
(c) absorbing the gas-phase product by an absorbent to prepare a hydrochloric acid solution, and using the hydrochloric acid solution as an acid catalyst in the step (a);
(d) and separating, washing and refining the liquid-phase product I to obtain an organic liquid-phase product II containing diamine and polyamine of diphenylmethane series.
According to the method provided by the invention, preferably, in the step (c), the gas-phase product containing the HCl gas enters an absorption tower, and is added with process water for capturing and absorption, so as to obtain a hydrochloric acid solution with the mass percentage concentration of 30-33%.
Preferably, the temperature of the middle part of the absorption tower is 40-100 ℃, more preferably 45-80 ℃, and further preferably 50-60 ℃; the temperature at the top of the column is 45-100 ℃, more preferably 50-80 ℃, and further preferably 55-65 ℃; the pressure at the top of the column is-10 to 10KpaG, more preferably-8 to 5KpaG, and still more preferably-6 to-2 KpaG.
According to the method provided by the present invention, preferably, in the step (d), the separating, washing and refining comprises: separating the liquid-phase product I into an aqueous component and an organic component containing di-and polyamines of the diphenylmethane series by a separation device; then, subjecting the organic component containing the diamine and the polyamine of the diphenylmethane series to a water washing step to obtain an aqueous phase containing aniline hydrochloride, diamine hydrochloride and polyamine hydrochloride and an organic phase containing the diamine and the polyamine of the diphenylmethane series; and (2) sending the aqueous phase containing aniline hydrochloride, diamine hydrochloride and polyamine hydrochloride together with the aqueous component separated from the liquid phase product I to a brine treatment process for treatment, and separating the water and aniline in the organic phase containing diamine and polyamine of the diphenylmethane series through distillation to obtain an organic liquid phase product II containing diamine and polyamine of the diphenylmethane series.
Preferably, the water washing process comprises: the washing water is thoroughly mixed with the organic components comprising di-and polyamines of the diphenylmethane series in a mixer at from 70 to 90 ℃. Residual aniline hydrochloride, diamine hydrochloride and polyamine hydrochloride in organic components containing diamines and polyamines of the diphenylmethane series are removed by water washing. The position of the two-phase interface is controlled by diamine, polyamine and a washing water interface regulator. And (4) the aniline water after washing contains a trace amount of aniline and MDA, and the aniline water enters a buffer tank and is sent to a brine treatment process for treatment. The washed organic phase containing di-and polyamines of the diphenylmethane series can also be passed to a storage tank. Wherein the temperature of the organic phase is from 50 ℃ to 150 ℃, preferably from 50 ℃ to 120 ℃, particularly preferably from 80 ℃ to 110 ℃.
In the purification step, water and aniline can be separated from the organic phase containing diamine and polyamine of the diphenylmethane series preferably by distillation. The specific operation process can be carried out by referring to the process described in patent document CN 105324361A. After refining, in the organic phase containing the diamine and polyamine of the diphenylmethane series, the mass percentage content of the diamine and polyamine of the diphenylmethane series can reach more than 99.9 percent.
In the present invention, the di-and polyamines of the diphenylmethane series prepared as described above can be used for the preparation of isocyanates. The di-and polyamines of the diphenylmethane series prepared according to the invention can be reacted with phosgene by known methods to give the corresponding di-and polyisocyanates of the diphenylmethane series. In this case, the phosgenation reaction can be carried out according to a method known in the art (e.g., patent document CN 1651406).
The technical scheme of the invention has the following beneficial effects:
(1) the method for preparing diamine and polyamine of diphenylmethane series saves the cost of raw materials, because the composite catalyst is used for decomposing diamine salt and polyamine salt of diphenylmethane series to replace the traditional caustic soda neutralization process, and a large amount of caustic soda can be reduced each year;
(2) the method for preparing diamine and polyamine of diphenylmethane series saves energy cost, because a large amount of caustic soda with the concentration of 50 percent is not added, the amount of water brought into a production system is reduced, and less water remains in an organic phase containing crude MDA, thereby less steam is required for distillation in the subsequent refining process; meanwhile, the water quantity required for washing salt impurities in the oil phase in the traditional neutralization process is reduced, and the generation quantity of waste brine in the condensation process is reduced;
(3) the process for the preparation of di-and polyamines of the diphenylmethane series according to the invention saves maintenance costs of production, since the fouling caused by salts produced by the neutralization reaction (e.g. evaporators, strippers, etc.) in downstream units is significantly reduced.
Drawings
FIG. 1 shows a process scheme for the preparation of di-and polyamines of the diphenylmethane series by the process of the present invention.
The numbers in the above figures are illustrated as follows:
1-hydrochloride solution of diamine and polyamine of diphenylmethane series, 2-saturated water vapor, 3-fixed bed type catalyst reactor, 4-transfer pump, 5-unqualified quality storage tank, 6-transfer pump, 7-liquid phase circulation loop, 8-process water, 9-absorption tower, 10-hydrochloric acid solution, 11-oil-water phase separator, 12-washing water stirring tank, 13-washing water, 14-oil-water phase separator, 15-washing wastewater buffer tank, 16-transfer pump, 17-organic phase (crude MDA) containing diamine and polyamine of diphenylmethane series, 18-transfer pump and 19-wastewater treatment process.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The technological process for preparing diamine and polyamine of diphenylmethane series by adopting the method of the invention is shown in figure 1: the acid catalyst reacts with aniline according to a certain molar ratio to generate aniline acid salt, the aniline acid salt and formaldehyde solution undergo condensation reaction to generate a hydrochloride solution 1 of diamine and polyamine of diphenylmethane series, and 2kg/cm of solution is introduced2Decomposing in a fixed bed catalyst reactor 3 saturated with water vapor 2 in the presence of a composite catalyst to produce a gas phase product containing HCl gas and a liquid phase product I containing diamines and polyamines of the diphenylmethane series; the HCl gas is absorbed in an absorption tower 9 through process water 8 to prepare a hydrochloric acid solution 10 with the mass fraction of 30-33%, and the hydrochloric acid solution is returned to the upstream to be used as an acid catalyst; if the generated hydrochloride solution 1 of diamine and polyamine of diphenylmethane series does not reach the standard, the solution is conveyed to a storage tank 5 with unqualified quality for buffering through a conveying pump 4 at the bottom of the tower, and then is pumped back to the fixed bed type catalyst reactor 3 through a liquid phase circulation loop 7 by a conveying pump 6 for continuous reaction. Sending the qualified liquid phase product I containing diamine and polyamine of diphenylmethane series to an oil-water phase separator 11 for layering and separation; separating an aqueous component and an oil phase, wherein the separated oil phase is an organic component containing diamine and polyamine of diphenylmethane series, sending the organic component to a washing water stirring tank 12, washing the organic component by washing water 13, then entering an oil-water phase separator 14 for layering and separation, the separated oil phase is an organic phase (crude MDA)17 containing diamine and polyamine of diphenylmethane series, and sending the organic phase to a downstream crude MDA refining process by a delivery pump 16; the separated aqueous phase containing aniline hydrochloride, diamine hydrochloride, and polyamine hydrochloride is sent to a washing wastewater buffer tank 15 together with the aqueous component separated in the oil-water phase separator 11, and sent to a downstream wastewater treatment process 19 by a transfer pump 18.
Firstly, the source of raw materials
Aniline and formaldehyde are self-made and the methods for their preparation are known to those skilled in the art. In principle, aniline or formaldehyde can be prepared by any desired method.
The aniline used according to the invention is prepared by catalytic hydrogenation of nitrobenzene in the gas phase in a fixed bed or fluidized bed; the formaldehyde used in the present invention is prepared by catalytic oxidation in a fixed bed reactor.
The mass fraction of the prepared aniline is more than 99.5%, the content of phenol is less than 0.0020%, and the content of moisture is less than 0.2%;
the prepared formaldehyde exists in the form of solution, the mass fraction of the formaldehyde is 36% +/-0.5% (generally 36%), and the content of the methanol is about 0.8%.
In the present invention, the contents are all mass contents unless otherwise specified. Unless otherwise specified, the reagents used below were analytical grade.
Nano SiO2Particle size of 30 + -5 nm, Hangzhou Wanjing New Material Co., Ltd.
Second, testing method
The liquid chromatography test procedure was as follows:
1. operating parameters
1) The instrument model is as follows: shimadzu liquid chromatography, automatic sample injector, diode array detector;
2) parameters are as follows: the flow rate is 1ml/min, the sample injection amount is 10 mu L, and the mobile phase is ultrapure water and methanol;
3) the quantitative method comprises the following steps: external standard quantity of 4,4-MDA and area normalization of other components.
2. Sample configuration
1)4, determination of purity of 4, 4-MDA: dissolving 4,4-MDA in methanol, directly carrying out gas phase analysis, and determining the area normalized purity;
2) configuration of MDA standard: respectively weighing 45-50mg (accurate to 0.1mg) of 4,4-MDA into a 50mL volumetric flask, adding methanol to dissolve, fixing the volume, and shaking uniformly for later use;
3) pretreatment of a sample: weighing 0.2g (accurate to 0.1mg) of MDA into a 10mL sample bottle, adding dichloromethane to dissolve, adding methanol to the bottle mouth, shaking uniformly, transferring to Shimadzu liquid phase bottle for sample injection analysis.
3. Sample analysis
After the instrument is stabilized, under the selected chromatographic condition, 10 μ L of the prepared sample is extracted by an automatic sample injector and subjected to sample injection to obtain a chromatogram.
4. And (4) counting results:
and (4) counting and analyzing data through external standard quantification and area normalization.
Preparation example 1 of composite catalyst:
0.5mol (30g) of nano SiO2Soaking in 5mol of hydrochloric acid with the mass fraction of about 30% at 20 ℃ for 1h, then adding 10mol of distilled water, washing and filtering under the condition of stirring frequency of 400r/min, placing in 60g of mixed acid (the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 1: 3), refluxing for 1h at 70 ℃, washing to neutrality by using 15mol of distilled water under the condition of stirring frequency of 400r/min, and drying at 65 ℃ for later use; 17.255g of cerium chloride (0.07mol), 19.798g of stannic chloride (0.076mol) and 2.88g of chromium trichloride (0.018mol) are respectively weighed in a beaker in a molar ratio of 3.8:4.2:1, adding 5mol of distilled water, stirring and dissolving under the condition that the stirring frequency is 400r/min, adding the carrier material pretreated by acid, finally adding 0.005mol of polyethylene glycol 400 as a dispersant at 20 ℃, uniformly dispersing by ultrasonic waves, stirring for 4 hours at constant temperature of 20 ℃ and stirring frequency of 400r/min, ammonia water is dripped in during the stirring process until the pH value is 8.0-8.5 (the dripping frequency is 50 drops/min), then the mixture is kept stand for 1 hour, filtering for 1 hour by a suction filter, adding 5mol of distilled water, washing under the condition of stirring frequency of 400r/min, and drying at 65 ℃ for 45 hours, and finally calcining at 480 ℃ for 3.5 hours in the air atmosphere to obtain the composite catalyst with the solid net structure. Among the prepared composite catalysts, measured by a conventional analytical method in the art (ICP elemental analysis): the content of the main active components cerium oxide and tin oxide is 66.26 percent of the weight of the carrier, and the content of the secondary active component chromium sesquioxide is 4.01 percent of the weight of the carrier.
Preparation example 2 of composite catalyst:
0.5mol (30g) of nano SiO2Soaking in 5mol of hydrochloric acid with a mass fraction of about 30% at 20 deg.C for 1 hr, adding 10mol of distilled water, and stirring at a certain frequencyWashing and filtering under the condition of 400r/min, placing in 60g of mixed acid (the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 1: 3), refluxing for 1h at 70 ℃, washing to be neutral by 15mol of distilled water under the condition of stirring frequency of 400r/min, and drying for later use at 65 ℃; 8.856g of cerium chloride (0.036mol), 9.36g of stannic chloride (0.036mol) and 5.76g of chromium trichloride (0.036mol) are respectively weighed in a molar ratio of 1:1:1 in a beaker, adding 5mol of distilled water, stirring and dissolving under the condition that the stirring frequency is 400r/min, adding the carrier material pretreated by acid, finally adding 0.005mol of polyethylene glycol 400 as a dispersant at 20 ℃, uniformly dispersing by ultrasonic waves, stirring for 4 hours at constant temperature of 20 ℃ and stirring frequency of 400r/min, ammonia water is dripped in during the stirring process until the pH value is 8.0-8.5 (the dripping frequency is 50 drops/min), then the mixture is kept stand for 1 hour, filtering for 1 hour by a suction filter, adding 5mol of distilled water, washing under the condition of stirring frequency of 400r/min, and drying at 65 ℃ for 45 hours, and finally calcining at 480 ℃ for 3.5 hours in the air atmosphere to obtain the composite catalyst with the solid net structure. Among the prepared composite catalysts, measured by a conventional analytical method in the art (ICP elemental analysis): the content of the main active components of cerium oxide and tin oxide is 34.08 percent of the weight of the carrier, and the content of the secondary active component of chromium sesquioxide is 8.03 percent of the weight of the carrier.
Example 1
The process flow for preparing diamine and polyamine of diphenylmethane series is shown in figure 1, acid catalyst hydrochloric acid solution (mass concentration is 31.5%) and aniline material (industrial aniline with mass concentration is 99.9%) are mixed, and the molar ratio of the two is 0.35: reacting at 1 and 40 ℃ to generate aniline hydrochloride. Mixing a formaldehyde solution material (with the concentration of 36.5 wt%) and an aniline hydrochloride material for reaction, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is controlled to be 0.42: the reaction was carried out in a cascade reactor at 1, 50 ℃ for 3 hours to give a solution 1 of a hydrochloride of a diamine and a polyamine of the diphenylmethane series.
The resulting diamine and polyamine hydrochloride solution 1 of diphenylmethane series was introduced into a reactor containing 2kg/cm of the solution2A fixed bed type catalyst reactor 3 saturated with steam 2, wherein the reactor 3 is filled with the composite catalyst prepared in the preparation example 2, the filling amount is 100L, and the retention time isThe reaction temperature is controlled to be 80 ℃ and the pressure is controlled to be 6-10 KpaG, the diamine and polyamine hydrochlorides of the diphenylmethane series are decomposed into a gas-phase product containing HCl gas and a liquid-phase product I containing the diamine and polyamine of the diphenylmethane series through the decomposition effect of the composite catalyst, and the sampled oil phase is analyzed to analyze the catalytic decomposition conversion rate and is listed in Table 2.
The HCl gas produced by the decomposition is absorbed in an absorption column 9 by means of process water 8, yielding a hydrochloric acid solution 10 with a concentration of 31.2% and returned upstream as an acid catalyst. The temperature in the absorber 9 was 50 ℃ and the temperature at the top of the absorber 9 was 55 ℃ and the pressure at the top was-2 KpaG. If the generated hydrochloride solution 1 of diamine and polyamine of diphenylmethane series does not reach the standard, the solution is conveyed to a storage tank 5 with unqualified quality for buffering through a conveying pump 4 at the bottom of the tower, and then is pumped back to the fixed bed type catalyst reactor 3 through a liquid phase circulation loop 7 by a conveying pump 6 for continuous reaction. Sending the qualified liquid phase product I containing diamine and polyamine of diphenylmethane series to an oil-water phase separator 11 for layering and separation; separating out an aqueous component and an oil phase, wherein the separated oil phase is an organic component containing diamine and polyamine of diphenylmethane series, sending the organic component to a washing water stirring tank 12, exchanging heat to 80 ℃ through washing water 13, then entering a mixer 12, and fully mixing the organic component containing diamine and polyamine of diphenylmethane series under the stirring action. The washed mixture is separated into layers in an oil-water phase separator 14, the separated oil phase is an organic phase (crude MDA)17 containing diamine and polyamine of diphenylmethane series, and the organic phase is sent to a downstream crude MDA refining process by a transfer pump 16, and finally refined MDA is obtained, wherein the composition of the refined MDA is shown in Table 1. The separated aqueous phase containing aniline hydrochloride, diamine hydrochloride, and polyamine hydrochloride is sent to a washing wastewater buffer tank 15 together with the aqueous component separated in the oil-water phase separator 11, and sent to a downstream wastewater treatment process 19 by a transfer pump 18. Statistical wastewater amounts are listed in table 2.
Example 2
The process flow for preparing diamine and polyamine of diphenylmethane series is shown in figure 1, acid catalyst hydrochloric acid solution (mass concentration is 31.5%) and aniline material (industrial aniline with mass concentration is 99.9%) are mixed, and the molar ratio of the two is 0.35: reacting at 1 and 40 ℃ to generate aniline hydrochloride. Mixing a formaldehyde solution material (with the concentration of 36.5 wt%) and an aniline hydrochloride material for reaction, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is controlled to be 0.42: the reaction was carried out in a cascade reactor at 1, 50 ℃ for 3 hours to give a solution 1 of a hydrochloride of a diamine and a polyamine of the diphenylmethane series.
The resulting diamine and polyamine hydrochloride solution 1 of diphenylmethane series was introduced into a reactor containing 2kg/cm of the solution2A fixed bed type catalyst reactor 3 saturated with water vapor 2, wherein the composite catalyst prepared in preparation example 2 is filled in the reactor 3, the filling amount is 200L, the retention time is 0.5h, the reaction temperature is controlled at 85 ℃, the pressure is controlled at 7-10 KpaG, diamine and polyamine hydrochlorides of diphenylmethane series are decomposed into a gas phase product containing HCl gas and a liquid phase product I containing diamine and polyamine of diphenylmethane series through the decomposition effect of the composite catalyst, the oil phase is sampled, and the catalytic decomposition conversion rate is analyzed and listed in Table 2.
The HCl gas produced by the decomposition is absorbed in an absorption column 9 by means of process water 8, yielding a hydrochloric acid solution 10 with a concentration of 31.2% and returned upstream as an acid catalyst. The temperature in the absorber 9 was 55 ℃ and the temperature at the top of the absorber 9 was 60 ℃ and the pressure at the top was-3 KpaG. If the generated hydrochloride solution 1 of diamine and polyamine of diphenylmethane series does not reach the standard, the solution is conveyed to a storage tank 5 with unqualified quality for buffering through a conveying pump 4 at the bottom of the tower, and then is pumped back to the fixed bed type catalyst reactor 3 through a liquid phase circulation loop 7 by a conveying pump 6 for continuous reaction. Sending the qualified liquid phase product I containing diamine and polyamine of diphenylmethane series to an oil-water phase separator 11 for layering and separation; separating out an aqueous component and an oil phase, wherein the separated oil phase is an organic component containing diamine and polyamine of diphenylmethane series, sending the organic component to a washing water stirring tank 12, exchanging heat to 85 ℃ through washing water 13, then entering a mixer 12, and fully mixing the organic component containing diamine and polyamine of diphenylmethane series under the stirring action. The washed mixture is separated into layers in an oil-water phase separator 14, the separated oil phase is an organic phase (crude MDA)17 containing diamine and polyamine of diphenylmethane series, and the organic phase is sent to a downstream crude MDA refining process by a transfer pump 16, and finally refined MDA is obtained, wherein the composition of the refined MDA is shown in Table 1. The separated aqueous phase containing aniline hydrochloride, diamine hydrochloride, and polyamine hydrochloride is sent to a washing wastewater buffer tank 15 together with the aqueous component separated in the oil-water phase separator 11, and sent to a downstream wastewater treatment process 19 by a transfer pump 18. Statistical wastewater amounts are listed in table 2.
Example 3
The process flow for preparing diamine and polyamine of diphenylmethane series is shown in figure 1, acid catalyst hydrochloric acid solution (mass concentration is 31.5%) and aniline material (industrial aniline with mass concentration is 99.9%) are mixed, and the molar ratio of the two is 0.35: reacting at 1 and 40 ℃ to generate aniline hydrochloride. Mixing a formaldehyde solution material (with the concentration of 36.5 wt%) and an aniline hydrochloride material for reaction, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is controlled to be 0.42: the reaction was carried out in a cascade reactor at 1, 50 ℃ for 3 hours to give a solution 1 of a hydrochloride of a diamine and a polyamine of the diphenylmethane series.
The resulting diamine and polyamine hydrochloride solution 1 of diphenylmethane series was introduced into a reactor containing 2kg/cm of the solution2A fixed bed type catalyst reactor 3 saturated with water vapor 2, wherein the composite catalyst prepared in the preparation example 1 is filled in the reactor 3, the filling amount is 300L, the retention time is 0.75h, the reaction temperature is controlled at 90 ℃, the pressure is controlled at 8-10 KpaG, diamine and polyamine hydrochlorides of diphenylmethane series are decomposed into a gas phase product containing HCl gas and a liquid phase product I containing diamine and polyamine of diphenylmethane series through the decomposition effect of the composite catalyst, the oil phase is sampled, and the catalytic decomposition conversion rate is analyzed and listed in Table 2.
The HCl gas produced by the decomposition is absorbed in an absorption column 9 by means of process water 8, yielding a hydrochloric acid solution 10 with a concentration of 31.3% and returned upstream as an acid catalyst. The temperature in the absorber 9 was 60 ℃ and the temperature at the top of the absorber 9 was 65 ℃ and the pressure at the top was-5 KpaG. If the generated hydrochloride solution 1 of diamine and polyamine of diphenylmethane series does not reach the standard, the solution is conveyed to a storage tank 5 with unqualified quality for buffering through a conveying pump 4 at the bottom of the tower, and then is pumped back to the fixed bed type catalyst reactor 3 through a liquid phase circulation loop 7 by a conveying pump 6 for continuous reaction. Sending the qualified liquid phase product I containing diamine and polyamine of diphenylmethane series to an oil-water phase separator 11 for layering and separation; separating out an aqueous component and an oil phase, wherein the separated oil phase is an organic component containing diamine and polyamine of diphenylmethane series, sending the organic component to a washing water stirring tank 12, exchanging heat to 90 ℃ through washing water 13, then entering a mixer 12, and fully mixing the organic component containing diamine and polyamine of diphenylmethane series under the stirring action. The washed mixture is separated into layers in an oil-water phase separator 14, the separated oil phase is an organic phase (crude MDA)17 containing diamine and polyamine of diphenylmethane series, and the organic phase is sent to a downstream crude MDA refining process by a transfer pump 16, and finally refined MDA is obtained, wherein the composition of the refined MDA is shown in Table 1. The separated aqueous phase containing aniline hydrochloride, diamine hydrochloride, and polyamine hydrochloride is sent to a washing wastewater buffer tank 15 together with the aqueous component separated in the oil-water phase separator 11, and sent to a downstream wastewater treatment process 19 by a transfer pump 18. Statistical wastewater amounts are listed in table 2.
Example 4
The process flow for preparing diamine and polyamine of diphenylmethane series is shown in figure 1, acid catalyst hydrochloric acid solution (mass concentration is 31.5%) and aniline material (industrial aniline with mass concentration is 99.9%) are mixed, and the molar ratio of the two is 0.35: reacting at 1 and 40 ℃ to generate aniline hydrochloride. Mixing a formaldehyde solution material (with the concentration of 36.5 wt%) and an aniline hydrochloride material for reaction, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is controlled to be 0.42: the reaction was carried out in a cascade reactor at 1, 50 ℃ for 3 hours to give a solution 1 of a hydrochloride of a diamine and a polyamine of the diphenylmethane series.
The resulting diamine and polyamine hydrochloride solution 1 of diphenylmethane series was introduced into a reactor containing 2kg/cm of the solution2A fixed bed type catalyst reactor 3 of saturated steam 2, wherein the reactor 3 is filled with the composite catalyst prepared in the preparation example 1, the filling amount is 400L, the retention time is 1h, the reaction temperature is controlled at 90 ℃, the pressure is controlled at 8-10 KpaG, and diphenylmethane seriesThe diamine and polyamine hydrochloride of (1) was decomposed into a gas phase product containing HCl gas and a liquid phase product I containing diamines and polyamines of the diphenylmethane series by decomposition of the composite catalyst, where a sample of the oil phase was analyzed for catalytic decomposition conversion rates, as shown in table 2.
The HCl gas produced by the decomposition is absorbed in an absorption column 9 by means of process water 8, yielding a hydrochloric acid solution 10 with a concentration of 31.3% and returned upstream as an acid catalyst. The temperature in the absorber 9 was 60 ℃ and the temperature at the top of the absorber 9 was 65 ℃ and the pressure at the top was-5 KpaG. If the generated hydrochloride solution 1 of diamine and polyamine of diphenylmethane series does not reach the standard, the solution is conveyed to a storage tank 5 with unqualified quality for buffering through a conveying pump 4 at the bottom of the tower, and then is pumped back to the fixed bed type catalyst reactor 3 through a liquid phase circulation loop 7 by a conveying pump 6 for continuous reaction. Sending the qualified liquid phase product I containing diamine and polyamine of diphenylmethane series to an oil-water phase separator 11 for layering and separation; separating out an aqueous component and an oil phase, wherein the separated oil phase is an organic component containing diamine and polyamine of diphenylmethane series, sending the organic component to a washing water stirring tank 12, exchanging heat to 90 ℃ through washing water 13, then entering a mixer 12, and fully mixing the organic component containing diamine and polyamine of diphenylmethane series under the stirring action. The washed mixture is separated into layers in an oil-water phase separator 14, the separated oil phase is an organic phase (crude MDA)17 containing diamine and polyamine of diphenylmethane series, and the organic phase is sent to a downstream crude MDA refining process by a transfer pump 16, and finally refined MDA is obtained, wherein the composition of the refined MDA is shown in Table 1. The separated aqueous phase containing aniline hydrochloride, diamine hydrochloride, and polyamine hydrochloride is sent to a washing wastewater buffer tank 15 together with the aqueous component separated in the oil-water phase separator 11, and sent to a downstream wastewater treatment process 19 by a transfer pump 18. Statistical wastewater amounts are listed in table 2.
Comparative example 1
The diamine and polyamine hydrochlorides of the diphenylmethane series are treated by a conventional caustic soda neutralization process to form the diamines and polyamines of the diphenylmethane series. The fixed bed type catalyst reactor 3 is changed into the neutralization caustic soda and added into the stirring kettle in the process flow, the absorption tower 9 is eliminated, and the subsequent washing procedure of washing water is kept unchanged.
Mixing an acidic catalyst hydrochloric acid material (mass concentration is 31.5%) and an aniline material (industrial aniline with mass concentration of 99.9%), wherein the molar ratio of the acidic catalyst hydrochloric acid material to the aniline material is 0.35: reacting at 1 and 40 ℃ to generate aniline hydrochloride. Mixing a formaldehyde solution material (with the concentration of 36.5 wt%) and an aniline hydrochloride material for reaction, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is controlled to be 0.42: 1, at 50 ℃ in a cascade reactor for 3 hours to form a solution 1 of a hydrochloride of a diamine and a polyamine of the diphenylmethane series. The resulting diamine and polyamine hydrochloride solution 1 of diphenylmethane series was fed into a neutralization agitation tank, neutralized with a sodium hydroxide solution having a mass concentration of 50%, the amount of caustic soda added was measured by a flow meter and shown in Table 2, and a brine phase and a liquid phase organic layer containing diamine and polyamine of diphenylmethane series were separated and sampled to measure the neutralization conversion rate and shown in Table 2. The liquid phase organic layer containing diamine and polyamine of diphenylmethane series was subjected to water washing and refining process as in example 1, and finally refined MDA was obtained, the composition of which is shown in table 1. The aqueous phase from the neutralization reaction was sent to the downstream wastewater treatment process along with the aqueous phase from the water wash process, and the statistical wastewater amounts are listed in table 2.
TABLE 1 comparison of results of liquid chromatography analysis of MDA in products
TABLE 2 comparison of reaction conversion and cost results
The experimental results of the examples and comparative examples are summarized:
through comparison of the above examples and comparative examples, it is found that, in the mixture of diamine salts and polyamine salts of diphenylmethane series obtained by reacting aniline and formaldehyde under the action of an acidic catalyst, in the diamine and polyamine of diphenylmethane series obtained by decomposing and washing with a novel composite catalyst, the content of 4,4-MDA and the total content of MDA of the desired products of examples 3 and 4 are higher than the corresponding MDA content generated by using a conventional alkali liquor neutralization process trial, the content of N-methyl MDA as a side reaction product is lower, and the content of polyamine with more than tricyclic ring as a side product is lower; in addition, no caustic soda is consumed in the preparation process, and the waste water amount of the examples 3 and 4 is reduced by 28 percent compared with the traditional alkali liquor neutralization process. Therefore, the novel process has the advantages of improving the product quality, saving energy, reducing consumption and protecting environment.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (27)
1. The composite catalyst for catalytically decomposing amine salt consists of carrier, main active component and secondary active component; wherein the carrier is pretreated by acid; the carrier is nano SiO2The solid material comprises main active components of cerium oxide and tin oxide, and secondary active components selected from one or more of manganese oxide, cobalt oxide, iron oxide and chromium oxide;
the step of acid pre-treating the support comprises: placing the carrier in 20-30% of inorganic acid for soaking, and performing primary acid treatment; then placing the mixture into mixed acid, heating and refluxing the mixture to perform secondary acid treatment; the inorganic acid is a hydrochloric acid solution or a sulfuric acid solution; the mixed acid is mixed acid of concentrated nitric acid and concentrated sulfuric acid, and the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 2-5; the mass ratio of the carrier to the mixed acid is 1: 1-2;
the content of the main active component is 20-70 wt% of the weight of the carrier; the content of the secondary active component is 1-10 wt% of the weight of the carrier;
the catalytic decomposition of the amine salt is as follows: and (2) in the presence of the composite catalyst, carrying out catalytic decomposition on the mixture containing diamine salt and polyamine salt of the diphenylmethane series to obtain a gas-phase product containing HCl gas and a liquid-phase product I containing diamine and polyamine of the diphenylmethane series.
2. The composite catalyst according to claim 1, wherein the content of the main active component is 45-68 wt% of the weight of the carrier.
3. The composite catalyst according to claim 1, wherein the secondary active component is present in an amount of 3 to 6 wt% based on the weight of the support.
4. The composite catalyst according to claim 1, wherein the volume ratio of concentrated nitric acid to concentrated sulfuric acid is 1: 3-4.
5. A method for preparing the composite catalyst according to any one of claims 1 to 4, comprising the steps of:
contacting soluble salt solution containing active metal with a carrier pretreated by acid for impregnation and adsorption, adding a dispersing agent for uniform dispersion, adjusting the pH value to 8.0-8.5, standing, performing suction filtration, washing, drying, and calcining to obtain the solid composite catalyst;
the soluble salt solution containing active metal is a soluble salt solution containing cerium, tin and one or more of manganese, cobalt, iron and chromium.
6. The method according to claim 5, wherein the soluble salt solution containing the active metal is selected from a nitrate solution containing the active metal and/or a chloride solution containing the active metal.
7. The method according to claim 6, wherein the active metal-containing chloride is selected from the group consisting of cerium chloride and tin chloride, and one or more of manganese dichloride, cobalt chloride, ferric trichloride and chromium trichloride.
8. The method according to claim 5, wherein the dispersant is polyethylene glycol 400.
9. The method according to claim 5, wherein the calcination process conditions include: calcining for 2-5h in air atmosphere at 420-550 ℃.
10. The method of claim 9, wherein the calcining process conditions include: calcining in air atmosphere of 450-500 ℃.
11. The method of claim 9, wherein the calcining process conditions include: calcining for 3-4h in air atmosphere.
12. A process for the preparation of di-and polyamines of the diphenylmethane series comprising the steps of:
(a) in the presence of an acid catalyst, aniline is subjected to a salt forming reaction to generate aniline acid salt; then, the aniline acid salt is contacted with formaldehyde solution for condensation reaction to obtain a mixture containing diamine salt and polyamine salt of diphenylmethane series;
(b) subjecting the mixture obtained in step (a) to catalytic decomposition in the presence of a composite catalyst according to any one of claims 1 to 4 or a composite catalyst prepared by the preparation process according to any one of claims 5 to 11 to obtain a gaseous product comprising HCl gas and a liquid product I comprising di-and polyamines of the diphenylmethane series.
13. The method according to claim 12, wherein the acidic catalyst in step (a) is selected from a hydrochloric acid solution with a mass percentage concentration of 30-33% and/or a sulfuric acid solution with a mass percentage concentration of 30-33%.
14. The method according to claim 12, wherein the molar ratio of the acidic catalyst to aniline is 0.1-1: 1; the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.1-0.9: 1.
15. The method according to claim 14, wherein the molar ratio of the acidic catalyst to aniline is 0.15-0.6: 1.
16. The method of claim 15, wherein the molar ratio of the acidic catalyst to aniline is 0.3 to 0.5: 1.
17. The method according to claim 14, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.2-0.6: 1.
18. The method according to claim 17, wherein the molar ratio of formaldehyde to aniline in the formaldehyde solution is 0.35-0.55: 1.
19. The method of claim 12, wherein the process of step (a) comprises: the reaction time of the aniline acid salt and the formaldehyde is 3-5 h; the salt-forming reaction temperature of the aniline and the acid catalyst is 40-50 ℃, and the condensation reaction temperature of the aniline acid salt and the formaldehyde is 45-55 ℃.
20. The method according to any one of claims 12 to 19, wherein the loading volume of the composite catalyst in step (b): mixture volume of diamine and polyamine salts of diphenylmethane series ═ 1: 1-6.
21. The method according to any one of claims 12-19, wherein the process conditions of the catalytic decomposition comprise: the reaction pressure is 2-20 KpaG; the reaction temperature is 60-100 ℃.
22. The method of claim 21, wherein the process conditions of the catalytic decomposition comprise: the reaction pressure is 5-15 KpaG.
23. The method of claim 22, wherein the process conditions of the catalytic decomposition comprise: the reaction pressure is 8-12 KpaG.
24. The method of claim 21, wherein the process conditions of the catalytic decomposition comprise: the reaction temperature is 75-95 ℃.
25. The method of claim 24, wherein the process conditions of the catalytic decomposition comprise: the reaction temperature is 80-90 ℃.
26. The method according to any of claims 12-19, 22-25, further comprising the step of:
(c) absorbing the gas-phase product by an absorbent to prepare a hydrochloric acid solution, and using the hydrochloric acid solution as an acid catalyst in the step (a);
(d) and separating, washing and refining the liquid-phase product I to obtain an organic liquid-phase product II containing diamine and polyamine of diphenylmethane series.
27. The process according to claim 26, wherein in step (d), the liquid phase product I is separated by a separation device into an aqueous component and an organic component comprising di-and polyamines of the diphenylmethane series; then, subjecting the organic component containing the diamine and the polyamine of the diphenylmethane series to a water washing step to obtain an aqueous phase containing aniline hydrochloride, diamine hydrochloride and polyamine hydrochloride and an organic phase containing the diamine and the polyamine of the diphenylmethane series; and then, the organic phase containing the diamine and the polyamine of the diphenylmethane series is distilled to separate water and aniline in the organic phase to obtain an organic liquid phase product II containing the diamine and the polyamine of the diphenylmethane series.
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| CN111905753B (en) * | 2020-08-10 | 2023-04-07 | 万华化学集团股份有限公司 | Catalyst for catalyzing amine salt conversion, preparation method of catalyst and preparation method of DAM |
| CN112169807B (en) * | 2020-09-01 | 2023-02-28 | 润泰化学（泰兴）有限公司 | Catalyst for synthesizing isobutyronitrile by ammoniation of isobutylaldehyde and preparation method and application thereof |
| CN112279441B (en) * | 2020-09-30 | 2023-01-17 | 万华化学集团股份有限公司 | Treatment method of drained water generated in MDA preparation process |
| CN114057583A (en) * | 2021-10-26 | 2022-02-18 | 菏泽永辉复合材料有限公司 | Preparation method of 4,4 '-diaminodiphenylmethane and 4, 4' -diaminodiphenylmethane |
| CN115124431B (en) * | 2022-06-30 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method of di-and polyamines of diphenylmethane series with low N-methyl impurity content |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460544A (en) * | 2003-05-26 | 2003-12-10 | 中国科学院广州地球化学研究所 | Preparation method of nano ZnO-SnO2 composite oxide photo-catalyst |
| CN101148415A (en) * | 2007-11-02 | 2008-03-26 | 华东理工大学 | Method for preparing 4,6-dialkoxy-1,3-phenylene diamine hydrochlorate |
| CN101774928A (en) * | 2010-02-10 | 2010-07-14 | 烟台万华聚氨酯股份有限公司 | Method for preparing m-xylylenediamine |
| CN102341343A (en) * | 2009-03-31 | 2012-02-01 | 三菱综合材料株式会社 | Method for producing bis(fluorosulfonyl)imide salt, method for producing fluorosulfate, and method for producing bis(fluorosulfonyl)imide onium salt |
| CN105503654A (en) * | 2008-03-01 | 2016-04-20 | 拜耳材料科技股份有限公司 | Process for preparing methylenediphenyl diisocyanate |
| CN106083504A (en) * | 2016-06-01 | 2016-11-09 | 中国工程物理研究院化工材料研究所 | A kind of based on energetic compound [Mn (BTO) (H2o)2]nefficient catalytic decompose ammonium perchlorate method |
| CN106103394A (en) * | 2014-03-12 | 2016-11-09 | 巴斯夫欧洲公司 | The method that formates decomposes |
-
2017
- 2017-12-27 CN CN201711450846.5A patent/CN108176392B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460544A (en) * | 2003-05-26 | 2003-12-10 | 中国科学院广州地球化学研究所 | Preparation method of nano ZnO-SnO2 composite oxide photo-catalyst |
| CN101148415A (en) * | 2007-11-02 | 2008-03-26 | 华东理工大学 | Method for preparing 4,6-dialkoxy-1,3-phenylene diamine hydrochlorate |
| CN105503654A (en) * | 2008-03-01 | 2016-04-20 | 拜耳材料科技股份有限公司 | Process for preparing methylenediphenyl diisocyanate |
| CN102341343A (en) * | 2009-03-31 | 2012-02-01 | 三菱综合材料株式会社 | Method for producing bis(fluorosulfonyl)imide salt, method for producing fluorosulfate, and method for producing bis(fluorosulfonyl)imide onium salt |
| CN101774928A (en) * | 2010-02-10 | 2010-07-14 | 烟台万华聚氨酯股份有限公司 | Method for preparing m-xylylenediamine |
| CN106103394A (en) * | 2014-03-12 | 2016-11-09 | 巴斯夫欧洲公司 | The method that formates decomposes |
| CN106083504A (en) * | 2016-06-01 | 2016-11-09 | 中国工程物理研究院化工材料研究所 | A kind of based on energetic compound [Mn (BTO) (H2o)2]nefficient catalytic decompose ammonium perchlorate method |
Non-Patent Citations (3)
| Title |
|---|
| B10H10、B12H12二茂铁季铵盐热分解机理的研究;吴鼎泉等;《武汉大学学报》;19901231;第64-70页 * |
| Catalytic Wet Air Oxidation of Aniline with Nanocasted Mn-Ce-Oxide Catalyst;R.LEVI etal.;《Environ. Sci. Technol》;20081231;第5165–5170页 * |
| Chloride salt of conducting polyaniline synthesized in the presence of;J.S.M. da Silva etal.;《Journal of Molecular Structure》;20160801;第337-344页 * |
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