CN108176392A - Composite catalyst of amine salt and preparation method thereof is catalytically decomposed, prepares the method for MDA - Google Patents
Composite catalyst of amine salt and preparation method thereof is catalytically decomposed, prepares the method for MDA Download PDFInfo
- Publication number
- CN108176392A CN108176392A CN201711450846.5A CN201711450846A CN108176392A CN 108176392 A CN108176392 A CN 108176392A CN 201711450846 A CN201711450846 A CN 201711450846A CN 108176392 A CN108176392 A CN 108176392A
- Authority
- CN
- China
- Prior art keywords
- polyamines
- diamines
- diphenylmethane series
- aniline
- composite catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- -1 amine salt Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000768 polyamine Polymers 0.000 claims abstract description 120
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims abstract description 100
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 90
- 150000004985 diamines Chemical class 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000047 product Substances 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 19
- 239000012263 liquid product Substances 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 72
- 239000012071 phase Substances 0.000 claims description 68
- 239000000243 solution Substances 0.000 claims description 49
- 238000005406 washing Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 20
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000006396 nitration reaction Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- 239000012266 salt solution Substances 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 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000004821 distillation Methods 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
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 229960000359 chromic chloride Drugs 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 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 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000008859 change Effects 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
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 238000007598 dipping method 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
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 239000008098 formaldehyde solution Substances 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000007859 condensation product Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 238000003756 stirring Methods 0.000 description 21
- 230000009102 absorption Effects 0.000 description 18
- 239000004519 grease Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 13
- 238000006386 neutralization reaction Methods 0.000 description 12
- 238000007670 refining Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000012797 qualification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 3
- 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 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 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 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
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- CYGKLLHTPPFPHH-UHFFFAOYSA-N aniline;hydrate Chemical compound O.NC1=CC=CC=C1 CYGKLLHTPPFPHH-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 208000012839 conversion disease Diseases 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
- 238000007405 data analysis Methods 0.000 description 1
- 238000000151 deposition Methods 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
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- 239000002245 particle Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—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
Landscapes
- 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 present invention relates to the preparing technical fields of the diamines and polyamines of diphenylmethane series, more particularly to a kind of composite catalyst and preparation method thereof that amine salt is catalytically decomposed, prepare the method for MDA, the composite catalyst includes carrier, main active component and secondary active component, and the method for preparing the diamines and polyamines of diphenylmethane series includes：(a) under acidic catalyst, aniline carries out salt-forming reaction, generates aniline hydrochlorate；Then aniline hydrochlorate and formalin contact are subjected to condensation reaction；(b) in the presence of composite catalyst, condensation product is catalytically decomposed, obtains the gas-phase product comprising HCl and the liquid product I of the diamines and polyamines comprising diphenylmethane series.The method of the present invention makes the MDA mass of subsequent production be improved in itself, while save cost.
Description
Technical field
Preparing technical field more particularly to a kind of catalysis point the present invention relates to the diamines and polyamines of diphenylmethane series
It solves composite catalyst of amine salt and preparation method thereof, prepare the method for MDA.
Background technology
The diamines and polyamines (abbreviation MDA) of diphenylmethane series including the diamine compound of diphenylmethane series or its
The mixture of isomers, the referred to as polyamine compounds or mixture of monomer MDA (MMDA) and diphenylmethane series, referred to as
For poly- MDA (PMDA).MDA is primarily referred to as the mixture for meeting following chemical structural formula：
Wherein, n represents >=0 integer.As n=0, this kind of compound is referred to as the diamines or two of diphenylmethane series
Diaminodiphenylmethane.As n ＞ 0, this kind of compound is referred to as the polyamines of diphenylmethane series.NCO group can be passed through in form
Replace NH all in this kind of compound2Corresponding isocyanates, is accordingly called diphenylmethane obtained from group
The diisocyanate of row, the diisocyanate of the polyisocyanates of diphenylmethane series or diphenylmethane series and polyisocyanate cyanogen
Acid esters (MDI).
Industrially, the preparation method of the diamines and polyamines of diphenylmethane series, in many disclosed patents and publication
It is described in object, such as patent document WO2009037088 etc..In existing industrial production, typically pass through aniline and first
Anilinechloride is made in aldehyde under acid catalysed conditions, then condensation reaction occurs with formaldehyde and obtains MDA, is given birth to using phosgenation reaction
Monomer MDI and polymeric MDI are produced, this is well-known method in polyurethane industries among others.
According to the prior art, aniline and formaldehyde carry out condensation reaction under acid catalyst effect, and obtained acid reaction is mixed
The post processing for closing object causes by using alkali neutralization.Alkali neutralization reaction usually carries out at a temperature of 90 DEG C to 100 DEG C.Alkali metal
Alkali is suitable as, such as use NaOH aqueous solutions with the hydroxide of alkali earth metal.In alkali neutralization diphenylmethane series
Diamine salts and polyamines salt to obtain the diamines and polyamines of diphenylmethane series during, due to salt in the salt-forming reaction of front end
Sour dosage is very big, and in order to fully neutralize hydrochloric acid, caustic soda addition is also very huge, accounts for nearly the 10% of MDA manufacture costs.Meanwhile
Since the addition of caustic soda brings a large amount of neutralization waste water, equally exert heavy pressures on to environment protection emission.Also, due to neutralization reaction
Particularity, if caustic soda addition is inadequate, the diamine salts and polyamines salt of excessive acid diphenylmethane series will be to downstreams
Acid-resistant system does not cause huge corrosion.
In addition, alkali neutralization diphenylmethane series diamine salts and polyamines salt to obtain the diamines of diphenylmethane series
During polyamines, the organic phase of the diamines and polyamines containing diphenylmethane series with containing the inorganic of a large amount of inorganic salt solutions
Mutually there is also some problems on phase detachment technique, if the formation of impurity layer cannot avoid completely, then it will be eventually entered into
In one in two phases.Phase separation is carried out again when impurity layer enters organic phase, after crude product is neutralized than will be through
It crosses after the product neutralized washs to carry out being separated again and is more difficult to receive.This is because in the case where latter is separated, not only
There is a considerable amount of water, and also have naturally and be dissolved in some of which substance (such as NaOH and NaCl), then together with next
The step of impurity layer of self-neutralization reaction is further processed together, they are more difficult are disposed off in the processing step
, such as appear in the device or pipeline of distillation zone and generate salt deposit.Even if (can such as it exist to avoid the formation of impurity layer
Technical solution described in 2008/148631 A1 of patent document EP 1652835 A1 and WO), but obtain after separation of the phases
Organic phase, as dispersed phase, can cause similar in further processing steps still comprising significant percentage of water composition
Problem, so as to generate the impurity layer of entrainment.
At present, domestic and international patent document mostly with the neutralization reaction of the diamines and polyamines of diphenylmethane series and phase separation skill
Art is related, as patent document EP1652835 A1 are describeed how with the diamine salts and polyamines with diphenylmethane series in lye
Salt, the salt aqueous solution phase of generation is from the methods of separation in the organic phase containing product.Few documents refer to directly will catalytic decomposition
Hydrochloride technology is used to produce MDI fields.
Existing literature is mainly mutually divided in MDA preparation process by neutralization plus alkali and organic liquid phase with the progress of inorganic liquid phase
From the diamines and polyamines of diphenylmethane series are prepared, the impurity content in MDA products can not be fundamentally reduced, also not
Can the quality by the MDA isocyanates generated and polyurethane be improved with this.Therefore, diamine salts of diphenylmethane series and more
Amine salt diamines and polyamines that are how simple, fast, efficient, safe, being converted into diphenylmethane series at low cost are that condensation is anti-
The key technology of MDA should be prepared.
Invention content
It is an object of the present invention in view of the problems of the existing technology, a kind of catalytic decomposition the compound of amine salt is provided and is urged
Agent and preparation method thereof, the method for preparing MDA, this prepares the method for MDA and its uses gained composite catalyst fundamentally
The residual of impurity in the solution separation process of organic phase and inorganic phase is avoided, the MDA mass of subsequent production is made to obtain in itself
To raising, while save production cost.
To achieve these goals, the present invention provides a kind of composite catalyst that amine salt is catalytically decomposed, the composite catalyst
Including carrier, main active component and secondary active component；Wherein, the carrier is the carrier after low-kappa number；It is described
Carrier is selected from Nano-meter SiO_22Solid material and/or multi-walled carbon nanotube, the main active component be selected from cerium oxide, tin oxide and
Arbitrary two kinds in cuprous oxide, the secondary active component is in manganese oxide, cobalt oxide, iron oxide and chrome green
It is one or more.In a preferred embodiment of the invention, the main active component is selected from cerium oxide and tin oxide, described secondary
It is chrome green to want active component.
According to composite catalyst provided by the invention, it is preferable that the content of the main active component is vehicle weight
20-70wt%, more preferably 45-68wt%；The content of the secondary active component is the 1-10wt% of vehicle weight, more preferably
3-6wt%.
According to composite catalyst provided by the invention, it is preferable that the step of carrying out low-kappa number to the carrier includes：It will
The carrier, which is placed in the inorganic acid that mass fraction is 20-30%, to be impregnated, and is carried out a hypo acid processing, is subsequently placed in nitration mixture, adds
Heat reflux carries out quadratic acid processing.
Preferably, the inorganic acid is hydrochloric acid solution or sulfuric acid solution.
Preferably, the molar ratio of the carrier and inorganic acid is 1：10-12.
In one embodiment, the time that the carrier impregnates in mineral acid is 0.5-3h；It is removed later by washing
Inorganic acid is removed, for example, the time that the carrier impregnates in mineral acid is 1 hour.
Preferably, the nitration mixture is concentrated nitric acid and the mixed acid of the concentrated sulfuric acid, and the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1：
2-5, more preferably 1：3-4.In the present invention, the concentrated nitric acid or the concentrated sulfuric acid of selection, such as be but not limited to concentration and be more than
The concentrated nitric acid or concentration of 65wt% is more than the concentrated sulfuric acid of 70wt%.
Preferably, the mass ratio of the carrier and nitration mixture is 1：1-2.In a preferred embodiment of the invention, the load
The mass ratio of body and nitration mixture is 1：2.
In one embodiment, the temperature being heated to reflux that the carrier is placed in nitration mixture is 50-70 DEG C, return time
It is 1-3 hours；Washing removes nitration mixture therein later, for example, the carrier is placed in nitration mixture, flows back 1 hour at 70 DEG C.
In the composite catalyst of the present invention, the carrier is handled by two hypo acids, on the one hand can pre-activated catalyst carrier
Surface, the surface-active of lifting carrier improve the adhesive rate of active metal soluble-salt, and particularly active metal chloride is attached
Rate, so as to be obviously improved catalytic efficiency；On the other hand it advantageously reduces needed for gained composite catalyst catalytic decomposition amine salt
Activation energy further reduces energy expenditure, promotes economy.
The present invention also provides a kind of preparation methods of composite catalyst as described above, include the following steps：
Soluble salt solutions containing active metal with the carrier after low-kappa number are contacted and carry out dipping absorption, are added
Dispersant adjusts pH value after uniformly dispersing be 8.0-8.5, then stands, filters, washing, is dry, then solid is obtained after calcining
The composite catalyst of shape；
The soluble salt solutions containing active metal be containing arbitrary two kinds in cerium, tin, copper and containing manganese, cobalt, iron and
One or more soluble salt solutions in chromium are preferably selected from nitrate solution containing active metal and/or containing active metal
Chloride solution.
According to preparation method provided by the invention, it is preferable that the process conditions of the drying include：Drying temperature is 50-
80 DEG C, more preferably 60-70 DEG C；Drying time is 30-60h, more preferably 40-50h.
According to preparation method provided by the invention, it is preferable that the process conditions of the calcining include：At 420 DEG C -550 DEG C,
2-5h, more preferable 3-4h are calcined in more preferably 450-500 DEG C of air atmosphere.
Preferably, the chloride containing active metal arbitrary two kinds in cerium chloride, stannic chloride and stannous chloride and
It is one or more in manganous chloride, cobalt chloride, ferric trichloride and chromium trichloride.
The amount ratio of the chloride and carrier containing active metal is makes main active component in gained composite catalyst
Content be vehicle weight 20-70wt%, for example, 30wt%, 40wt%, 50wt%, preferably 60wt%, 45-68wt%；It is secondary
The content for wanting active component is the 1-10wt% of vehicle weight, for example, 2wt%, 4wt%, 8wt%, preferably 3-6wt%.
In a preferred embodiment of the invention, the chloride containing active metal is cerium chloride, stannic chloride and trichlorine
Change chromium.Wherein, cerium chloride：Stannic chloride：The molar ratio of chromium trichloride is 1-4：1-5：1；Preferably 1.4-3.8：1.7-4.2：1.
Preferably, the dispersant is polyethylene glycol 400.The addition of dispersant is the conventional selection of this field, at this
In the specific embodiment of invention, the quality of the dispersant is the 1-10% of carrier quality described in the composite catalyst,
Preferably 4-8%.
In a preferred embodiment of the invention, the preparation method of the composite catalyst specifically includes：The first step, will
Carrier material Nano-meter SiO_22And/or multi-walled carbon nanotube is placed in the hydrochloric acid of mass fraction about 30% and impregnates 1h, passes through water later
Washing filtering is placed on nitration mixture, and (volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1：3) in, 70 DEG C of reflux 1h, in being washed with distilled water to
Property, drying is for use；Chloride (such as cerium chloride, stannic chloride, chromium trichloride) containing active metal is placed in beaker by second step,
After adding distilled water stirring and dissolving, the carrier material after low-kappa number is added in, is eventually adding polyethylene glycol 400 as dispersant,
Ultrasonic wave is uniformly dispersed, and after constant temperature stirs 3-6 hours at room temperature, it is 8.0-8.5, Ran Houjing to stir lower ammonium hydroxide to the pH value that instills
It puts, filter, wash, dry, then through 450 DEG C of calcining 3h, obtain the composite catalyst of solid network structure.
Nano-meter SiO_2 of the present invention2, appearance be amorphous white powder, particle size range at 1~100 nanometer,
Micro-structure is spherical shape, in cotton-shaped and netted porous quasi- grain structure.
The present invention is combined using liquid-phase chemistry deposition technique and infusion process, and obtained composite catalyst has fine and close three
Network structure is tieed up, the main active component and secondary active component are carried on the carrier table in the form of nano spherical particle
Face.Reactive metal oxides are supported on carrier surface with nano spherical particle, and grain size is small, is uniformly dispersed, carrier limitation therein
The migration of nano-particle, can prevent nano-particle from reuniting, so as to give full play to the spy of the huge specific surface area of nanocatalyst
Point.In addition, the composite catalyst surface-active point is more, adsorption capacity is strong, the main active component of high-content can effectively reduce ammonium
Salt decomposition activation energy, shows excellent catalytic effect, and a certain amount of secondary active component makes catalyst have stronger oxidation
Reducing power, surface acidity and thermal stability.
It is a further object of the invention to provide a kind of method for the diamines and polyamines for preparing diphenylmethane series,
Include the following steps：
(a) in the presence of acidic, aniline carries out salt-forming reaction, generates aniline hydrochlorate；Then by aniline hydrochlorate and
Formalin contact carries out condensation reaction, obtains the mixture of the diamine salts comprising diphenylmethane series and polyamines salt；
(b) in the presence of composite catalyst made from composite catalyst as described above or preparation method as described above,
Step (a) mixture is catalytically decomposed, obtains the gas-phase product comprising HCl gases and comprising diphenylmethane
The liquid product I of the diamines and polyamines of row.
According to method provided by the invention, aniline can be by existing with formaldehyde reacting under acid catalysis in step (a)
Method carry out.Preferably, acidic catalyst described in step (a) is selected from the hydrochloric acid solution that mass percentage concentration is 30-33%
And/or the sulfuric acid solution that mass percentage concentration is 30-33%, preferably mass percentage concentration is the hydrochloric acid solution of 30-33%.
In the preferred embodiment of the present invention, aniline carries out salt-forming reaction with hydrochloric acid solution in step (a), generates anilinechloride.
Preferably, the molar ratio of the acidic catalyst and aniline is 0.1-1.0:1, more preferably 0.15-0.6:1, into
One step is preferably 0.3-0.5:1；The molar ratio of formaldehyde and aniline in the formalin is 0.1-0.9:1, more preferable 0.2-
0.6:1, further preferably 0.35-0.55:1；The mass percentage concentration of the formalin is preferably 36.0-37.5%.
Preferably, the technique of step (a) includes：Aniline is reacted with the salt-forming reaction of acidic catalyst for moment, Phenyl Acetic Acid (Powder)
The reaction time of salt and formaldehyde is 3-5h；The reaction temperature of aniline and acidic catalyst is 40-50 DEG C, aniline hydrochlorate and formaldehyde
Setting-up point is 45-55 DEG C.
According to method provided by the invention, it is preferable that the admission space of composite catalyst described in step (b)：Diphenyl
The diamine salts of methane series and volume of mixture=1 of polyamines salt：1-6.
The mixture of diamine salts comprising diphenylmethane series and polyamines salt can have the reactor of catalyst by load
It is catalytically decomposed.In a preferred embodiment of the invention, the reactor of catalyst decomposition is carried out selected from fixed-bed catalytic point
Solve reactor.Preferably, the process conditions of the catalytic decomposition include：Reaction pressure is 2-20KpaG, more preferably 5-
15KpaG, further preferably 8-12KpaG；Reaction temperature be 60 DEG C -100 DEG C, more preferably 75 DEG C -95 DEG C, further preferably
It is 80 DEG C -90 DEG C.In the present invention, the mixture of the diamine salts comprising diphenylmethane series and polyamines salt has catalysis in load
Residence time in the reactor of agent is depending on the amount of fill of used catalyst.
Preferably, it is undecomposed complete described mixed when the resolution ratio of the mixture that step (a) obtains is not up to 80%
It closes object and second decomposition is carried out by the decomposition reaction system of circuit return to step (b).
According to method provided by the invention, it is preferable that further include following steps：
(c) by absorbent absorption hydrochloric acid solution is made, and as the acidic catalyst in step (a) in the gas-phase product
Agent；
(d) the liquid product I is detached, washed and is refined, obtain comprising diphenylmethane series diamines and
The organic liquid phase product II of polyamines.
According to method provided by the invention, it is preferable that in step (c), the gas-phase product comprising HCl gases enters suction
Tower is received, is caught by adding in process water and draws absorptions, obtains mass percentage concentration as 30~33% hydrochloric acid solution.
Preferably, the temperature in the middle part of the absorbing tower be 40-100 DEG C, more preferably 45-80 DEG C, further preferably
50-60℃；Tower top temperature is 45-100 DEG C, more preferably 50-80 DEG C, further preferably 55-65 DEG C；Tower top pressure is -10
~10KpaG, more preferably -8~5KpaG, further preferably -6~-2KpaG.
According to method provided by the invention, it is preferable that in step (d), the separation, washing and refined include：By described in
Liquid product I has unit by what separator was separated into aqueous components and diamines and polyamines comprising diphenylmethane series
Point；The organic component of the diamines and polyamines comprising diphenylmethane series is obtained by washing step comprising aniline again
The organic phase of hydrochloride, the water phase of diamine hydrochloride and polyamines hydrochloride and the diamines and polyamines comprising diphenylmethane series；
The aqueous components one isolated by the water phase comprising anilinechloride, diamine hydrochloride and polyamines hydrochloride and from liquid product I
It rises, is sent into saline treatment process and is handled, the organic phase of the diamines and polyamines comprising diphenylmethane series is passed through into distillation
Water and aniline therein are isolated, obtains the organic liquid phase product II of the diamines and polyamines comprising diphenylmethane series.
Preferably, the washing step is：At 70-90 DEG C, by washings and the diamines comprising diphenylmethane series and
The organic component of polyamines is sufficiently mixed in a mixer.By wash with remove include diphenylmethane series diamines and
Remaining anilinechloride, diamine hydrochloride and polyamines hydrochloride in the organic component of polyamines.By diamines and polyamines, washing hydrosphere
Face adjuster control two-phase interface position.Aniline water after washing contains trace aniline and MDA and also enters surge tank, is sent into brine
Treatment process is handled.The organic phase of the diamines and polyamines comprising diphenylmethane series after washing can also pass through basin.
Wherein, the temperature of the organic phase is 50 DEG C -150 DEG C, preferably 50 DEG C -120 DEG C, particularly preferred 80 DEG C -110 DEG C.
In refining step, preferably can by distillation by water and aniline from the diamines and polyamines comprising diphenylmethane series
Organic phase in isolate.The process that its concrete operations technique can refer to described in patent document CN105324361A carries out.Essence
After system, in the organic phase of the diamines and polyamines comprising diphenylmethane series, the diamines of the diphenylmethane series and
The mass percentage of polyamines is up to more than 99.9%.
In the present invention, the diamines and polyamines of diphenylmethane series can be applied to prepare made from method as described above
Isocyanates.The diamines and polyamines of diphenylmethane series produced by the present invention can be carried out anti-by known method and phosgene
It answers, generates the diisocyanate and polyisocyanates of corresponding diphenylmethane series.In this case, the phosgenation is anti-
It should can be carried out according to known method in the prior art (such as patent document CN1651406).
The advantageous effect that technical solution of the present invention is brought is：
(1) method of the diamines and polyamines of the present invention for preparing diphenylmethane series saves cost of material, this is
Replace in traditional caustic soda and work because of diphenylmethane series diamine salts and polyamines salt is decomposed using the composite catalyst
Skill can reduce a large amount of amount of caustic soda every year；
(2) method of the diamines and polyamines of the present invention for preparing diphenylmethane series saves cost of energy, this is
Due to being added without a large amount of a concentration of 50% caustic soda, reduce the water brought into production system, less water remain in containing
In the organic phase of thick MDA, carry out distilling required steam meeting less as a result, in follow-up refining step；Also reduce washing simultaneously
Tradition neutralizes the water that salt impurity needs in technique oil phase, reduces the production quantity of condensation process effluent brine；
(3) method of the diamines and polyamines of the present invention for preparing diphenylmethane series save the maintenance of production into
This, this is because fouling (such as evaporator, stripper etc.) is notable as caused by the salt of neutralization reaction generation in downstream unit
It reduces.
Description of the drawings
Fig. 1 shows the process flow chart for the diamines and polyamines that diphenylmethane series are prepared using the method for the present invention.
Above-mentioned figure label is described as follows：
The HCI solution of the diamines and polyamines of 1- diphenylmethane series, 2- saturated vapors, the catalysis of 3- fixed-bed types
Agent reactor, 4- delivery pumps, 5- storage tanks off quality, 6- delivery pumps, 7- liquid phase circulations circuit, 8- process waters, 9- absorption towers,
10- hydrochloric acid solutions, 11- grease phase separators, 12- washings agitator tanks, 13- washings, 14- grease phase separators, 15- washings
Waste water surge tank, 16- delivery pumps, 17- include the organic phase (thick MDA) of the diamines and polyamines of diphenylmethane series, 18- conveyings
Pump, 19- wastewater treatment processes.
Specific embodiment
In order to which the technical characteristic of the present invention and content is understood in detail, the excellent of the present invention is described in more detail below
Select embodiment.Although describing the preferred embodiment of the present invention in embodiment, however, it is to be appreciated that can be in a variety of manners
Realize the present invention without should be limited by embodiments set forth herein.
The diamines and polyamines technological process that diphenylmethane series are prepared using the method for the present invention is as shown in Figure 1：Acidity is urged
Agent is with aniline by certain molar ratio reaction generation aniline hydrochlorate, and aniline hydrochlorate is with formalin by condensation reaction, generation
The HCI solution 1 of the diamines and polyamines of diphenylmethane series, and enter and be connected with 2kg/cm2The fixed bed of saturated vapor 2
In formula hydrogen-catalyst reactor 3, gas-phase product of the generation comprising HCl gases is decomposed in the presence of composite catalyst and includes hexichol
The liquid product I of the diamines and polyamines of methylmethane series；HCl gases are absorbed in absorption tower 9 by process water 8, and matter is made
It measures score and is the hydrochloric acid solution 10 of 30-33%, and return to upstream as acidic catalyst；The two of the diphenylmethane series of generation
If 1 rates of decomposing and transforming of HCI solution of amine and polyamines is below standard, by the delivery pump 4 of bottom of towe, send to off quality
It is cached in storage tank 5, then returns in fixed-bed type hydrogen-catalyst reactor 3 by liquid phase circulation circuit 7 by delivery pump 6 that the reaction was continued.
The liquid product I of the qualified diamines and polyamines comprising diphenylmethane series of generation, which is sent into grease phase separator 11, to be layered simultaneously
It is detached；Aqueous components and oil phase are isolated, the oil phase isolated is the diamines and polyamines comprising diphenylmethane series
Organic component is passed to washings agitator tank 12, enters in grease phase separator 14 after being washed by washings 13 and is layered simultaneously
It is detached, the oil phase isolated is the organic phase (thick MDA) 17 of the diamines and polyamines comprising diphenylmethane series, is led to
Delivery pump 16 is crossed to send to the thick MDA refining steps in downstream；That isolates includes anilinechloride, diamine hydrochloride and polyamines hydrochloric acid
The water phase of salt enters washes surge tank 15 together with the aqueous components that grease phase separator 11 is isolated, and passes through delivery pump 18
It send to waste water downstream treatment process 19.
First, raw material sources
Aniline is self-control with formaldehyde, and preparation method is known to the skilled in the art.In principle, aniline or formaldehyde can
It is prepared by any desired method.
Aniline used in the present invention is by fixed bed or fluid bed, in the gas phase prepared by catalytic hydrogenation of nitrobenzene；
Formaldehyde used in the present invention by fixed bed reactors catalysis oxidation prepare.
Obtained aniline mass fraction is more than 99.5%, and phenol content is less than 0.0020%, and moisture is less than
0.2%；
Obtained formaldehyde exists in the form of a solution, formaldehyde mass fraction be 36% ± 0.5% (generally 36%), methanol
Content is about 0.8%.
In the present invention, if not otherwise specified, the content is mass content.If not otherwise specified, examination used below
Agent is pure to analyze.
Nano-meter SiO_22, grain size be 30 ± 5nm, Hangzhou Wanjing New Material Co., Ltd..
2nd, test method
Liquid chromatogram test process is as follows：
1st, operating parameter
1) instrument model：Shimadzu liquid chromatogram, with autosampler, diode array detector；
2) parameter：Flow velocity is 1ml/min, and sample size is 10 μ L, and mobile phase is ultra-pure water, methanol；
3) quantitative approach：4,4-MDA outer marking quantitatives, other components area normalization.
2nd, sample is configured
1) 4,4-MDA purity determines：4,4-MDA is taken to be dissolved in methanol, direct gas phase analysis determines that its area normalization is pure
Degree；
2) configuration of MDA standard specimens：45-50mg (accurately to 0.1mg) 4,4-MDA is weighed respectively, until in 50mL volumetric flasks, is added
Constant volume after methanol dissolving, concussion is uniform, spare；
3) pre-treatment of sample：It weighs in 0.2g (accurately to 0.1mg) MDA to 10mL sample bottles, add methylene chloride dissolving
Afterwards plus methanol is to bottleneck, and concussion is uniform, is transferred in Shimadzu liquid phase bottle and treats that sample introduction is analyzed.
3rd, sample analysis
After instrument stabilizer, under selected chromatographic condition, the 10 μ L of sample prepared are extracted with autosampler, sample introduction obtains
Chromatogram.
4th, result counts：
Pass through outer marking quantitative and area normalization, statistical data analysis.
The preparation example 1 of composite catalyst：
By 0.5mol (30g) Nano-meter SiO_22It is placed at 20 DEG C in the hydrochloric acid of 5mol mass fractions about 30% and impregnates 1h, it
Add in 10mol distilled water afterwards, after stirring frequency is washing filtering under conditions of 400r/min, be placed in 60g nitration mixture (concentrated nitric acid and
The volume ratio of the concentrated sulfuric acid is 1：3) in, flow back 1h at 70 DEG C, with 15mol distilled water under conditions of stirring frequency is 400r/min
Washing is dried for use to neutrality, at 65 DEG C；17.255g cerium chlorides (0.07mol), 19.798g stannic chlorides are weighed respectively
(0.076mol), 2.88g chromium trichlorides (0.018mol) three molar ratio are 3.8:4.2:1 in beaker, adds in 5mol distillations
Water after stirring and dissolving, adds in the carrier material after low-kappa number, finally 20 under conditions of stirring frequency is 400r/min
0.005mol polyethylene glycol 400s are added at DEG C as dispersant, ultrasonic wave is uniformly dispersed, 20 DEG C of constant temperature, stirring frequency 400r/
After being stirred 4 hours under min, it is 8.0~8.5 (dropwise addition frequency is 50 drops/min) to instill ammonium hydroxide to pH value in whipping process, so
1 hour is stood afterwards, machine is filtered and filters 1 hour, the rear 5mol distilled water that adds in washs under conditions of stirring frequency is 400r/min,
And it is 45 hours dry at 65 DEG C, it is finally calcined 3.5 hours in 480 DEG C of air atmospheres, obtains the compound of solid network structure and urge
Agent.In obtained composite catalyst, measured through this field conventional method of analysis (ICP elemental analyses)：Its chief active group
Point cerium oxide, tin oxide content be the 66.26% of vehicle weight, the content of secondary active component chrome green is carrier weight
The 4.01% of amount.
The preparation example 2 of composite catalyst：
By 0.5mol (30g) Nano-meter SiO_22It is placed at 20 DEG C in the hydrochloric acid of 5mol mass fractions about 30% and impregnates 1h, it
Add in 10mol distilled water afterwards, after stirring frequency is washing filtering under conditions of 400r/min, be placed in 60g nitration mixture (concentrated nitric acid and
The volume ratio of the concentrated sulfuric acid is 1：3) in, flow back 1h at 70 DEG C, with 15mol distilled water under conditions of stirring frequency is 400r/min
Washing is dried for use to neutrality, at 65 DEG C；8.856g cerium chlorides (0.036mol), 9.36g stannic chlorides are weighed respectively
(0.036mol), 5.76g chromium trichlorides (0.036mol) three molar ratio are 1:1:1 in beaker, adds in 5mol distilled water and exists
Under conditions of stirring frequency is 400r/min after stirring and dissolving, the carrier material after low-kappa number is added in, finally at 20 DEG C
0.005mol polyethylene glycol 400s are added in as dispersant, ultrasonic wave is uniformly dispersed, 20 DEG C of constant temperature, stirring frequency 400r/min
After lower stirring 4 hours, it is 8.0~8.5 (dropwise addition frequency is 50 drops/min) to instill ammonium hydroxide to pH value in whipping process, Ran Houjing
It puts 1 hour, filters machine and filter 1 hour, the rear 5mol distilled water that adds in washs under conditions of stirring frequency is 400r/min, and
65 DEG C of dryings 45 hours, finally calcine 3.5 hours in 480 DEG C of air atmospheres, obtain the composite catalyst of solid network structure.
In obtained composite catalyst, measured through this field conventional method of analysis (ICP elemental analyses)：Its main active component aoxidizes
Cerium, tin oxide content be the 34.08% of vehicle weight, the content of secondary active component chrome green is vehicle weight
8.03%.
Embodiment 1
The technological process of the diamines and polyamines of diphenylmethane series is prepared as shown in Figure 1, acid catalyst hydrochloric acid solution (matter
Measure it is a concentration of 31.5%) mixed with aniline material (mass concentration be 99.9% industrial aniline), the molar ratio of the two is
0.35：Reaction generation anilinechloride at 0 DEG C of Isosorbide-5-Nitrae.Formalin material (a concentration of 36.5wt%) and anilinechloride material
Mixing is reacted, and the control of the molar ratio of formaldehyde and aniline is 0.42 in formalin：At 1,50 DEG C in cascade reactor into
The diamines and polyamines HCI solution 1 of 3 hours generation diphenylmethane series of row reaction.
The diamines and polyamines HCI solution 1 of the diphenylmethane series of generation, into being connected with 2kg/cm2Saturated vapor
2 fixed-bed type hydrogen-catalyst reactor 3, reactor 3 is built-in to fill out composite catalyst made from preparation example 2 and its loadings is
100L, residence time 0.25h, reaction temperature control is at 80 DEG C, and pressure control is in 6~10KpaG, and the two of diphenylmethane series
Amine and polyamines hydrochloride are decomposed into the gas-phase product comprising HCl gases and comprising two by the decomposition of composite catalyst
The liquid product I of the diamines and polyamines of phenylmethane series, sampling oil phase analysis catalytic decomposition conversion ratio, is listed in table 2 at this.
The HCl gases generated will be decomposed to be absorbed by process water 8 in absorption tower 9, the salt of output a concentration of 31.2%
Acid solution 10, and upstream is returned to as acidic catalyst.Temperature in 9 tower of absorption tower is 50 DEG C, and the temperature of 9 tower top of absorption tower is
55 DEG C, the pressure -2KpaG of tower top.Turn if the HCI solution 1 of the diamines and polyamines of the diphenylmethane series of generation decomposes
Rate is below standard, then by the delivery pump of bottom of towe 4, send into storage tank 5 off quality and cache, then pass through liquid phase by delivery pump 6
Circulation loop 7 returns in fixed-bed type hydrogen-catalyst reactor 3 that the reaction was continued.Include diphenylmethane series the two of generation qualification
The liquid product I of amine and polyamines, which is sent, to be layered and is detached into grease phase separator 11；Aqueous components and oil phase are isolated, point
The oil phase separated out is the organic component of the diamines and polyamines comprising diphenylmethane series, is passed to washings agitator tank 12,
By washings 13 through exchanging heat to mixer 12 is entered after 80 DEG C, under stirring with the diamines comprising diphenylmethane series
It is sufficiently mixed with the organic component of polyamines.Enter in grease phase separator 14 after washing and be layered and detached, isolate
Oil phase be the diamines and polyamines comprising diphenylmethane series organic phase (thick MDA) 17, by its by delivery pump 16 send to
The thick MDA refining steps in downstream, finally obtain the MDA after refining, and composition is listed in Table 1 below.That isolates includes aniline hydrochloric acid
It is useless that the water phase of salt, diamine hydrochloride and polyamines hydrochloride enters washing together with the aqueous components that grease phase separator 11 is isolated
Water surge tank 15 is sent by delivery pump 18 to waste water downstream treatment process 19.Statistics wastewater flow rate is listed in Table 2 below.
Embodiment 2
The technological process of the diamines and polyamines of diphenylmethane series is prepared as shown in Figure 1, acid catalyst hydrochloric acid solution (matter
Measure it is a concentration of 31.5%) mixed with aniline material (mass concentration be 99.9% industrial aniline), the molar ratio of the two is
0.35：Reaction generation anilinechloride at 0 DEG C of Isosorbide-5-Nitrae.Formalin material (a concentration of 36.5wt%) and anilinechloride material
Mixing is reacted, and the control of the molar ratio of formaldehyde and aniline is 0.42 in formalin：At 1,50 DEG C in cascade reactor into
The diamines and polyamines HCI solution 1 of 3 hours generation diphenylmethane series of row reaction.
The diamines and polyamines HCI solution 1 of the diphenylmethane series of generation, into being connected with 2kg/cm2Saturated vapor
2 fixed-bed type hydrogen-catalyst reactor 3, reactor 3 is built-in to fill out composite catalyst made from preparation example 2 and its loadings is
200L, residence time 0.5h, at 85 DEG C, pressure is controlled in 7~10KpaG, the diamines of diphenylmethane series for reaction temperature control
With polyamines hydrochloride by the decomposition of composite catalyst, it is decomposed into the gas-phase product comprising HCl gases and comprising hexichol
The liquid product I of the diamines and polyamines of methylmethane series, sampling oil phase analysis catalytic decomposition conversion ratio, is listed in table 2 at this.
The HCl gases generated will be decomposed to be absorbed by process water 8 in absorption tower 9, the salt of output a concentration of 31.2%
Acid solution 10, and upstream is returned to as acidic catalyst.Temperature in 9 tower of absorption tower is 55 DEG C, and the temperature of 9 tower top of absorption tower is
60 DEG C, the pressure -3KpaG of tower top.Turn if the HCI solution 1 of the diamines and polyamines of the diphenylmethane series of generation decomposes
Rate is below standard, then by the delivery pump of bottom of towe 4, send into storage tank 5 off quality and cache, then pass through liquid phase by delivery pump 6
Circulation loop 7 returns in fixed-bed type hydrogen-catalyst reactor 3 that the reaction was continued.Include diphenylmethane series the two of generation qualification
The liquid product I of amine and polyamines, which is sent, to be layered and is detached into grease phase separator 11；Aqueous components and oil phase are isolated, point
The oil phase separated out is the organic component of the diamines and polyamines comprising diphenylmethane series, is passed to washings agitator tank 12,
By washings 13 through exchanging heat to mixer 12 is entered after 85 DEG C, under stirring with the diamines comprising diphenylmethane series
It is sufficiently mixed with the organic component of polyamines.Enter in grease phase separator 14 after washing and be layered and detached, isolate
Oil phase be the diamines and polyamines comprising diphenylmethane series organic phase (thick MDA) 17, by its by delivery pump 16 send to
The thick MDA refining steps in downstream, finally obtain the MDA after refining, and composition is listed in Table 1 below.That isolates includes aniline hydrochloric acid
It is useless that the water phase of salt, diamine hydrochloride and polyamines hydrochloride enters washing together with the aqueous components that grease phase separator 11 is isolated
Water surge tank 15 is sent by delivery pump 18 to waste water downstream treatment process 19.Statistics wastewater flow rate is listed in Table 2 below.
Embodiment 3
The technological process of the diamines and polyamines of diphenylmethane series is prepared as shown in Figure 1, acid catalyst hydrochloric acid solution (matter
Measure it is a concentration of 31.5%) mixed with aniline material (mass concentration be 99.9% industrial aniline), the molar ratio of the two is
0.35：Reaction generation anilinechloride at 0 DEG C of Isosorbide-5-Nitrae.Formalin material (a concentration of 36.5wt%) and anilinechloride material
Mixing is reacted, and the control of the molar ratio of formaldehyde and aniline is 0.42 in formalin：At 1,50 DEG C in cascade reactor into
The diamines and polyamines HCI solution 1 of 3 hours generation diphenylmethane series of row reaction.
The diamines and polyamines HCI solution 1 of the diphenylmethane series of generation, into being connected with 2kg/cm2Saturated vapor
2 fixed-bed type hydrogen-catalyst reactor 3, reactor 3 is built-in to fill out composite catalyst made from preparation example 1 and its loadings is
300L, residence time 0.75h, reaction temperature control is at 90 DEG C, and pressure control is in 8~10KpaG, and the two of diphenylmethane series
Amine and polyamines hydrochloride are decomposed into the gas-phase product comprising HCl gases and comprising two by the decomposition of composite catalyst
The liquid product I of the diamines and polyamines of phenylmethane series, sampling oil phase analysis catalytic decomposition conversion ratio, is listed in table 2 at this.
The HCl gases generated will be decomposed to be absorbed by process water 8 in absorption tower 9, the salt of output a concentration of 31.3%
Acid solution 10, and upstream is returned to as acidic catalyst.Temperature in 9 tower of absorption tower is 60 DEG C, and the temperature of 9 tower top of absorption tower is
65 DEG C, the pressure -5KpaG of tower top.Turn if the HCI solution 1 of the diamines and polyamines of the diphenylmethane series of generation decomposes
Rate is below standard, then by the delivery pump of bottom of towe 4, send into storage tank 5 off quality and cache, then pass through liquid phase by delivery pump 6
Circulation loop 7 returns in fixed-bed type hydrogen-catalyst reactor 3 that the reaction was continued.Include diphenylmethane series the two of generation qualification
The liquid product I of amine and polyamines, which is sent, to be layered and is detached into grease phase separator 11；Aqueous components and oil phase are isolated, point
The oil phase separated out is the organic component of the diamines and polyamines comprising diphenylmethane series, is passed to washings agitator tank 12,
By washings 13 through exchanging heat to mixer 12 is entered after 90 DEG C, under stirring with the diamines comprising diphenylmethane series
It is sufficiently mixed with the organic component of polyamines.Enter in grease phase separator 14 after washing and be layered and detached, isolate
Oil phase be the diamines and polyamines comprising diphenylmethane series organic phase (thick MDA) 17, by its by delivery pump 16 send to
The thick MDA refining steps in downstream, finally obtain the MDA after refining, and composition is listed in Table 1 below.That isolates includes aniline hydrochloric acid
It is useless that the water phase of salt, diamine hydrochloride and polyamines hydrochloride enters washing together with the aqueous components that grease phase separator 11 is isolated
Water surge tank 15 is sent by delivery pump 18 to waste water downstream treatment process 19.Statistics wastewater flow rate is listed in Table 2 below.
Embodiment 4
The technological process of the diamines and polyamines of diphenylmethane series is prepared as shown in Figure 1, acid catalyst hydrochloric acid solution (matter
Measure it is a concentration of 31.5%) mixed with aniline material (mass concentration be 99.9% industrial aniline), the molar ratio of the two is
0.35：Reaction generation anilinechloride at 0 DEG C of Isosorbide-5-Nitrae.Formalin material (a concentration of 36.5wt%) and anilinechloride material
Mixing is reacted, and the control of the molar ratio of formaldehyde and aniline is 0.42 in formalin：At 1,50 DEG C in cascade reactor into
The diamines and polyamines HCI solution 1 of 3 hours generation diphenylmethane series of row reaction.
The diamines and polyamines HCI solution 1 of the diphenylmethane series of generation, into being connected with 2kg/cm2Saturated vapor
2 fixed-bed type hydrogen-catalyst reactor 3, reactor 3 is built-in to fill out composite catalyst made from preparation example 1 and its loadings is
400L, residence time 1h, reaction temperature control at 90 DEG C, pressure control in 8~10KpaG, the diamines of diphenylmethane series and
Polyamines hydrochloride is decomposed into the gas-phase product comprising HCl gases and comprising diphenyl by the decomposition of composite catalyst
The liquid product I of the diamines and polyamines of methane series, sampling oil phase analysis catalytic decomposition conversion ratio, is listed in table 2 at this.
The HCl gases generated will be decomposed to be absorbed by process water 8 in absorption tower 9, the salt of output a concentration of 31.3%
Acid solution 10, and upstream is returned to as acidic catalyst.Temperature in 9 tower of absorption tower is 60 DEG C, and the temperature of 9 tower top of absorption tower is
65 DEG C, the pressure -5KpaG of tower top.Turn if the HCI solution 1 of the diamines and polyamines of the diphenylmethane series of generation decomposes
Rate is below standard, then by the delivery pump of bottom of towe 4, send into storage tank 5 off quality and cache, then pass through liquid phase by delivery pump 6
Circulation loop 7 returns in fixed-bed type hydrogen-catalyst reactor 3 that the reaction was continued.Include diphenylmethane series the two of generation qualification
The liquid product I of amine and polyamines, which is sent, to be layered and is detached into grease phase separator 11；Aqueous components and oil phase are isolated, point
The oil phase separated out is the organic component of the diamines and polyamines comprising diphenylmethane series, is passed to washings agitator tank 12,
By washings 13 through exchanging heat to mixer 12 is entered after 90 DEG C, under stirring with the diamines comprising diphenylmethane series
It is sufficiently mixed with the organic component of polyamines.Enter in grease phase separator 14 after washing and be layered and detached, isolate
Oil phase be the diamines and polyamines comprising diphenylmethane series organic phase (thick MDA) 17, by its by delivery pump 16 send to
The thick MDA refining steps in downstream, finally obtain the MDA after refining, and composition is listed in Table 1 below.That isolates includes aniline hydrochloric acid
It is useless that the water phase of salt, diamine hydrochloride and polyamines hydrochloride enters washing together with the aqueous components that grease phase separator 11 is isolated
Water surge tank 15 is sent by delivery pump 18 to waste water downstream treatment process 19.Statistics wastewater flow rate is listed in Table 2 below.
Comparative example 1
The diamines and polyamines hydrochloride of diphenylmethane series is handled with technique using in traditional caustic soda, generates diphenyl
The diamines and polyamines of methane series.Fixed-bed type hydrogen-catalyst reactor 3 is changed to neutralization caustic soda in technological process and adds in stirring
Kettle, and cancel absorption tower 9, subsequent wash water washing process remains unchanged.
(mass concentration is 99.9% industry to acidic catalyst hydrochloric acid material (mass concentration 31.5%) with aniline material
Aniline) it is mixed, the molar ratio of the two is 0.35：Reaction generation anilinechloride at 0 DEG C of Isosorbide-5-Nitrae.Formalin material (concentration
For 36.5wt%) it is reacted with the mixing of anilinechloride material, the molar ratio of formaldehyde and aniline, which controls, in formalin exists
0.42：1, the 3 hours diamines and polyamines hydrochloric acid for generating diphenylmethane series of reaction is carried out in cascade reactor at 50 DEG C
Salting liquid 1.The diamines and polyamines HCI solution 1 of the diphenylmethane series of generation into stirred tank is neutralized, uses mass concentration
Sodium hydroxide solution for 50% is neutralized, and flowmeter metering caustic soda addition is included in table 2, by salt water phase and includes hexichol
The liquid phase organic layer of the diamines and polyamines of methylmethane series detach in simultaneously sampling and measuring and conversion ratio, is included in table 2.To packet
The liquid phase organic layer of diamines and polyamines containing diphenylmethane series carries out washing and refining step such as embodiment 1, finally obtains
MDA after refined, composition are listed in Table 1 below.The water phase that neutralization reaction generates is beaten together with the water phase that washing step generates under
Wastewater treatment process is swum, statistics wastewater flow rate is listed in Table 2 below.
The liquid-phase chromatographic analysis Comparative result of MDA in 1 product of table
2 reaction conversion ratio of table and cost result comparison
The experimental result brief summary of embodiment and comparative example：
Find that aniline and formaldehyde carry out instead under acidic catalyst effect by the comparison of above example and comparative example
Should, the diamine salts of obtained diphenylmethane series and the mixture of polyamines salt decompose, simultaneously by novel composite catalyst
In the diamines and polyamines of the diphenylmethane series obtained after washing, the desired product 4 of embodiment 3 and 4,4-MDA contents and MDA
Total content is higher than using the correspondence MDA contents that in traditional lye and technique lab scale generates, and side reaction product N- methyl MDA contains
Amount is lower, and by-product tricyclic more than polyamine content is lower；In addition, without caustic soda consumption, the waste water of embodiment 3 and 4 in preparation process
In the more traditional lye of amount and technique also reduces 28%.Therefore, which more improves product quality, energy-saving and ring
Guarantor's advantage.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
1. a kind of composite catalyst that amine salt is catalytically decomposed, which is characterized in that the composite catalyst includes carrier, chief active group
Divide and secondary active component；Wherein, the carrier is the carrier after low-kappa number；The carrier is selected from Nano-meter SiO_22Solid
Material and/or multi-walled carbon nanotube, the main active component in cerium oxide, tin oxide and cuprous oxide arbitrary two
Kind, the secondary active component is one or more in manganese oxide, cobalt oxide, iron oxide and chrome green.
2. composite catalyst according to claim 1, which is characterized in that the content of the main active component is carrier weight
The 20-70wt% of amount, more preferably 45-68wt%；The content of the secondary active component is the 1-10wt% of vehicle weight, more
It is preferred that 3-6wt%.
3. composite catalyst according to claim 1 or 2, which is characterized in that the step of low-kappa number is carried out to the carrier
Suddenly include：The carrier is placed in the inorganic acid that mass fraction is 20-30% and is impregnated, carries out a hypo acid processing；It is subsequently placed in
In nitration mixture, it is heated to reflux carrying out quadratic acid processing；
Preferably, the inorganic acid is hydrochloric acid solution or sulfuric acid solution；
Preferably, the nitration mixture is concentrated nitric acid and the mixed acid of the concentrated sulfuric acid, and the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1：2-5,
More preferably 1：3-4；
Preferably, the mass ratio of the carrier and nitration mixture is 1：1-2.
4. the preparation method of a kind of composite catalyst as described in any one of claim 1-3, which is characterized in that including as follows
Step：
Soluble salt solutions containing active metal with the carrier after low-kappa number are contacted and carry out dipping absorption, add dispersion
Agent adjusts pH value after uniformly dispersing be 8.0-8.5, then stands, filters, washing, is dry, then solid-like is obtained after calcining
The composite catalyst；
The soluble salt solutions containing active metal are containing arbitrary two kinds in cerium, tin, copper and containing in manganese, cobalt, iron and chromium
One or more soluble salt solutions, be preferably selected from the nitrate solution containing active metal and/or the chlorine containing active metal
Compound solution；
Preferably, arbitrary two kind and dichloro of the chloride containing active metal in cerium chloride, stannic chloride and stannous chloride
Change one or more in manganese, cobalt chloride, ferric trichloride and chromium trichloride；
Preferably, the dispersant is polyethylene glycol 400.
5. preparation method according to claim 4, which is characterized in that the process conditions of the calcining include：420 DEG C-
550 DEG C, 2-5h, preferably 3-4h are calcined in preferably 450-500 DEG C of air atmosphere.
A kind of 6. method for the diamines and polyamines for preparing diphenylmethane series, which is characterized in that include the following steps：
(a) in the presence of acidic, aniline carries out salt-forming reaction, generates aniline hydrochlorate；Then by aniline hydrochlorate and formaldehyde
Solution contact carries out condensation reaction, obtains the mixture of the diamine salts comprising diphenylmethane series and polyamines salt；
(b) in the composite catalyst as described in any one of claim 1-3 or the preparation method as described in claim 4 or 5
In the presence of composite catalyst obtained, mixture obtained by step (a) is catalytically decomposed, obtains including the gas phase of HCl gases
The liquid product I of product and diamines and polyamines comprising diphenylmethane series.
7. according to the method described in claim 6, it is characterized in that, acidic catalyst described in step (a) is selected from quality percentage
A concentration of 30~33% hydrochloric acid solution and/or mass percentage concentration is 30~33% sulfuric acid solution, preferably quality percentage
A concentration of 30~33% hydrochloric acid solution；
Preferably, the molar ratio of the acidic catalyst and aniline is 0.1~1.0:1, more preferably 0.15~0.6:1, into one
Step preferably 0.3~0.5:1；The molar ratio of formaldehyde and aniline in the formalin is 0.1~0.9:1, more preferable 0.2~
0.6:1, further preferably 0.35~0.55:1；
Preferably, the technique of step (a) includes：The reaction time of aniline hydrochlorate and formaldehyde is 3-5h；Aniline and acidic catalyst
Salt-forming reaction temperature for 40-50 DEG C, the setting-up point of aniline hydrochlorate and formaldehyde is 45-55 DEG C.
8. the method described according to claim 6 or 7, which is characterized in that the filling body of composite catalyst described in step (b)
Product：The diamine salts of diphenylmethane series and volume of mixture=1 of polyamines salt：1-6；
Preferably, the process conditions of the catalytic decomposition include：Reaction pressure is 2-20KpaG, more preferably 5-15KpaG, into
One step is preferably 8-12KpaG；Reaction temperature is 60 DEG C -100 DEG C, more preferably 75 DEG C -95 DEG C, further preferably 80 DEG C -90
℃。
9. according to the method described in any one of claim 6-8, which is characterized in that the method further includes following steps：
(c) by absorbent absorption hydrochloric acid solution is made, and as the acidic catalyst in step (a) in the gas-phase product；
(d) the liquid product I is detached, washed and is refined, obtain including the diamines and polyamines of diphenylmethane series
Organic liquid phase product II.
10. according to the method described in claim 9, it is characterized in that, in step (d), the liquid product I is filled by detaching
Put the organic component for being separated into aqueous components and the diamines and polyamines comprising diphenylmethane series；Described it will include diphenyl again
The organic component of the diamines and polyamines of methane series is obtained comprising anilinechloride, diamine hydrochloride and more by washing step
The organic phase of the water phase of amine hydrochlorate and diamines and polyamines comprising diphenylmethane series；Then diphenylmethane will be included
The organic phase of the diamines and polyamines of row is separated by distillation out water and aniline therein, obtains including the two of diphenylmethane series
The organic liquid phase product II of amine and polyamines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711450846.5A CN108176392B (en) | 2017-12-27 | 2017-12-27 | Composite catalyst for catalytic decomposition of amine salt, preparation method thereof and method for preparing MDA (multidrug resistance) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711450846.5A CN108176392B (en) | 2017-12-27 | 2017-12-27 | Composite catalyst for catalytic decomposition of amine salt, preparation method thereof and method for preparing MDA (multidrug resistance) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108176392A true CN108176392A (en) | 2018-06-19 |
| CN108176392B CN108176392B (en) | 2020-09-08 |
Family
ID=62547939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711450846.5A Active CN108176392B (en) | 2017-12-27 | 2017-12-27 | Composite catalyst for catalytic decomposition of amine salt, preparation method thereof and method for preparing MDA (multidrug resistance) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108176392B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438254A (en) * | 2018-10-29 | 2019-03-08 | 万华化学集团股份有限公司 | A kind of preparation method of the diphenylmethane series diamines and polyamines of low big molecular impurity content |
| CN111905753A (en) * | 2020-08-10 | 2020-11-10 | 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 |
| CN112169807A (en) * | 2020-09-01 | 2021-01-05 | 润泰化学（泰兴）有限公司 | Catalyst for synthesizing isobutyronitrile by ammoniation of isobutylaldehyde and preparation method and application thereof |
| CN112279441A (en) * | 2020-09-30 | 2021-01-29 | 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 |
| CN115124431A (en) * | 2022-06-30 | 2022-09-30 | 万华化学集团股份有限公司 | Preparation method of diamine and polyamine 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 |
|---|
| J.S.M. DA SILVA ETAL.: "Chloride salt of conducting polyaniline synthesized in the presence of", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| R.LEVI ETAL.: "Catalytic Wet Air Oxidation of Aniline with Nanocasted Mn-Ce-Oxide Catalyst", 《ENVIRON. SCI. TECHNOL》 * |
| 吴鼎泉等: "B10H10、B12H12二茂铁季铵盐热分解机理的研究", 《武汉大学学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438254A (en) * | 2018-10-29 | 2019-03-08 | 万华化学集团股份有限公司 | A kind of preparation method of the diphenylmethane series diamines and polyamines of low big molecular impurity content |
| CN109438254B (en) * | 2018-10-29 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of diphenylmethane series diamine and polyamine with low macromolecular impurity content |
| CN111905753A (en) * | 2020-08-10 | 2020-11-10 | 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 |
| 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 |
| CN112169807A (en) * | 2020-09-01 | 2021-01-05 | 润泰化学（泰兴）有限公司 | Catalyst for synthesizing isobutyronitrile by ammoniation of isobutylaldehyde and preparation method and application thereof |
| 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 |
| CN112279441A (en) * | 2020-09-30 | 2021-01-29 | 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 |
| CN115124431A (en) * | 2022-06-30 | 2022-09-30 | 万华化学集团股份有限公司 | Preparation method of diamine and polyamine of diphenylmethane series with low N methyl impurity content |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108176392B (en) | 2020-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108176392A (en) | Composite catalyst of amine salt and preparation method thereof is catalytically decomposed, prepares the method for MDA | |
| CN101049562A (en) | Catalyst for preparing halogeno anilin through catalytic hydrogenation of halogeno nitrobenzene and preparation method | |
| CN101934234B (en) | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof | |
| CN105749936A (en) | Metal composite catalyst for selective dechloridation and preparation method thereof | |
| CN108947099A (en) | A kind of advanced oxidation processes treatment process device and method of the waste water containing sodium phenolate | |
| CN105837391A (en) | Application of metal-free hydrogenation catalyst to catalysis of benzene hydrogenation | |
| CN107266357A (en) | A kind of synthetic method of 2,3 dichloropyridine | |
| CN1861525B (en) | Treatment process of active hargil waste acid | |
| CN111905753A (en) | Catalyst for catalyzing amine salt conversion, preparation method of catalyst and preparation method of DAM | |
| CN105713657B (en) | Hydrocracking method | |
| EP3971135A1 (en) | Catalyst for preparing phosgene and preparation method therefor, and method for preparation of phosgene and comprehensive utilization of energy thereof | |
| CN110170333A (en) | One kind is for ethane to ethylene catalyst under carbon dioxide atmosphere and preparation method thereof | |
| CN106853376A (en) | A kind of preparation method and applications of benzene and the catalyst of methanol alkylation reaction | |
| CN104056665A (en) | Application of ionic liquid-modified mesoporous material in decomposition of cyclohexyl hydroperoxide | |
| CN107597173A (en) | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof | |
| EP2697189B2 (en) | Improved process for the production of hexamethylenediamine | |
| CN103772240B (en) | Method for preparation of methylene diphenyl diisocyanate (MDI) | |
| WO2022067747A1 (en) | Method for controlling toc in effluent brine in dam production process | |
| CN106582798A (en) | Catalyst for MTP (methanol-to-propylene) through conversion and preparation method of catalyst | |
| CN208632327U (en) | A kind of advanced oxidation processes treatment process device of the waste water containing sodium phenolate | |
| CN107638888A (en) | New catalyst and preparation method thereof used in one kind production MEK | |
| CN104028268B (en) | A kind of micron order elemental copper catalyst and its preparation method and application | |
| CN104945223B (en) | A kind of method that load molecular sieve catalysis toluene synthesizes ortho-chlorotolu'ene | |
| CN101792206A (en) | Copper polysilicate, preparation method thereof and application thereof in water treatment | |
| Ischia et al. | Synthesis, characterization and photocatalytic activity of TiO 2 powders prepared under different gelling and pressure conditions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240422 Address after: 264006 No. 59, Chongqing Street, Yantai Economic and Technological Development Zone, Shandong Province Patentee after: Wanhua Chemical Group Co.,Ltd. Country or region after: China Patentee after: Wanhua chemical (Ningbo) Co.,Ltd. Patentee after: Wanhua Chemical Group (Fujian) Isocyanate Co.,Ltd. Address before: 264002 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Patentee before: Wanhua Chemical Group Co.,Ltd. Country or region before: China Patentee before: Wanhua chemical (Ningbo) Co.,Ltd. |
|
| TR01 | Transfer of patent right |