CN100336796C - Process for preparing 4-amino diphenylamine - Google Patents
Process for preparing 4-amino diphenylamine Download PDFInfo
- Publication number
- CN100336796C CN100336796C CNB2004100689839A CN200410068983A CN100336796C CN 100336796 C CN100336796 C CN 100336796C CN B2004100689839 A CNB2004100689839 A CN B2004100689839A CN 200410068983 A CN200410068983 A CN 200410068983A CN 100336796 C CN100336796 C CN 100336796C
- Authority
- CN
- China
- Prior art keywords
- aminodiphenylamine
- preparing
- reaction
- hydrogenation
- water
- 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.)
- Expired - Lifetime
Links
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 149
- 239000003054 catalyst Substances 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 95
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 238000009833 condensation Methods 0.000 claims abstract description 34
- 230000005494 condensation Effects 0.000 claims abstract description 34
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000007670 refining Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 150000001875 compounds Chemical class 0.000 claims description 75
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 49
- 239000011552 falling film Substances 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 238000006482 condensation reaction Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 22
- -1 sulfate radical Chemical class 0.000 claims description 21
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- 150000004678 hydrides Chemical class 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 230000002829 reductive effect Effects 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000007046 ethoxylation reaction Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 125000005270 trialkylamine group Chemical group 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006148 magnetic separator Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- LZTAFOFVUWLZLV-UHFFFAOYSA-N C(O)CN.CN(C)C Chemical compound C(O)CN.CN(C)C LZTAFOFVUWLZLV-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- DBUFGTBLIAQSPT-UHFFFAOYSA-N ethanamine;ethylazanium;hydrogen carbonate Chemical compound CCN.CC[NH3+].OC([O-])=O DBUFGTBLIAQSPT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- FEXZQQGGZRKWMV-UHFFFAOYSA-N C([O-])([O-])=O.OCC[NH3+].C[NH+](C)C Chemical compound C([O-])([O-])=O.OCC[NH3+].C[NH+](C)C FEXZQQGGZRKWMV-UHFFFAOYSA-N 0.000 claims description 2
- CHIBTYAITBTOIG-UHFFFAOYSA-N CCC[NH3+].CCC[NH3+].[O-]C([O-])=O Chemical compound CCC[NH3+].CCC[NH3+].[O-]C([O-])=O CHIBTYAITBTOIG-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 238000003809 water extraction Methods 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 20
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 241000282326 Felis catus Species 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- YKLKUNBKAPXTEZ-UHFFFAOYSA-M methyl carbonate;tetramethylazanium Chemical compound COC([O-])=O.C[N+](C)(C)C YKLKUNBKAPXTEZ-UHFFFAOYSA-M 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WJZPIORVERXPPR-UHFFFAOYSA-L tetramethylazanium;carbonate Chemical compound [O-]C([O-])=O.C[N+](C)(C)C.C[N+](C)(C)C WJZPIORVERXPPR-UHFFFAOYSA-L 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- 229910000545 Nickel–aluminium alloy Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- KUECCNRXHBAQOG-UHFFFAOYSA-N azane;ethyl hydrogen carbonate Chemical compound [NH4+].CCOC([O-])=O KUECCNRXHBAQOG-UHFFFAOYSA-N 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LMASIWYRIYEBTQ-UHFFFAOYSA-M ethyl carbonate;tetraethylazanium Chemical compound CCOC([O-])=O.CC[N+](CC)(CC)CC LMASIWYRIYEBTQ-UHFFFAOYSA-M 0.000 description 1
- HCWMUANODLPMEO-UHFFFAOYSA-M ethyl sulfate;tetraethylazanium Chemical compound CCOS([O-])(=O)=O.CC[N+](CC)(CC)CC HCWMUANODLPMEO-UHFFFAOYSA-M 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004845 hydriding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- JGJWEFUHPCKRIJ-UHFFFAOYSA-M methyl sulfate;tetramethylazanium Chemical compound C[N+](C)(C)C.COS([O-])(=O)=O JGJWEFUHPCKRIJ-UHFFFAOYSA-M 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- APBDREXAUGXCCV-UHFFFAOYSA-L tetraethylazanium;carbonate Chemical compound [O-]C([O-])=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC APBDREXAUGXCCV-UHFFFAOYSA-L 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a method for preparing 4-aminodiphenylamine from nitrobenzene and aniline as raw material, which comprises the working procedures of condensation, hydrogenation, separation, recovery and recycle of a composite base catalyst, separation and recycle of an arbitrary composite powdery catalyst at least partially regenerated, separation, recovery and recycle of aniline, arbitrarily separation, recovery and recycle of hydrogenation solvent, and refining, wherein a composite base catalyst is used as a condensation catalyst, and a composite powdery catalyst is used as a hydrogenation catalyst. The method can be in a continuous process. The two catalysts selected in the method of the present invention have low prices and high catalytic activity. The method has the advantages of mild reaction condition, few byproducts and continuous preparing process and is suitable for industrial scale production. The content of the prepared 4-aminodiphenylamine can be higher than 99 wt%, and the yield of industrial scale production can be higher than 95%.
Description
Technical field
The present invention relates to prepare the method for 4-aminodiphenylamine, specifically being specifically related to oil of mirbane, aniline is raw material, adopts two kinds of composite catalysts and cyclical operation technical process, prepares the method for 4-aminodiphenylamine continuously.
Background technology
The 4-aminodiphenylamine is the intermediate of important antioxidants and stablizer, is important chemical product in rubber industry and the polymer industry.According to the difference of using raw material, the method for producing the 4-aminodiphenylamine at present has: (1) aniline process is a raw material with p-Nitrophenyl chloride and aniline, and reaction generates 4 nitrodiphenyl amine under catalyst action, is the 4-aminodiphenylamine with sodium sulfide reducing then; (2) formylaniline method is the feedstock production formylaniline with formic acid and aniline, reacts in the presence of acid binding agent (for example salt of wormwood) with p-Nitrophenyl chloride to generate 4 nitrodiphenyl amine again, prepares the 4-aminodiphenylamine with sodium sulfide reducing then; (3) pentanoic method, it promptly is raw material with the pentanoic, in organic solvent, carry out nitrosification with nitrite, obtain N nitrosodiphenyl amine, again with anhydrous hydrogen chloride reset 4-nitrosodiphenylamine hydrochloride, with in the alkali and generate the 4-nitrosodiphenylamine, get the 4-aminodiphenylamine with sodium sulfide reducing at last.Although these method raw material differences are all used traditional Sodium Sulphide to make reductive agent and are produced the 4-aminodiphenylamine.The shortcoming of these reactions is severe reaction conditions, complicated operation, and the energy consumption height, yield is low, cost height and the contaminate environment etc. with " three wastes " produce.
Also have a route to be to use oil of mirbane or oil of mirbane and aniline or nitrosobenzene to carry out condensation reaction in the route of preparation 4-aminodiphenylamine, prepare the method for 4-aminodiphenylamine then with hydrogen hydrogenation as raw material.In fact, under the effect of alkali, oil of mirbane and aniline reaction generated the 4-nitrosodiphenylamine and 4 nitrodiphenyl amine has all had report (Wohl, ChemischeBerichte, 34 at 1901 and 1903, p.2442 (1901) and Wohl, Chemische Berichte, 36, p.4135 (1903)), just yield is relatively low, so never obtain paying attention to and development.Entered since the nineties, in the world this route is researched and developed again, obtained that some are progressive (referring to DE19734055.5, DE19810929.6, DE 19709124.5).There are some common shortcomings in these methods: the one, and selected catalyzer costs an arm and a leg, and is applied to industrial-scale production and can causes production cost too high, and comparing with present production technique does not have advantage.For example, price costlinesses such as the precious metal palladium that tetraalkylammonium hydroxide that condensation reaction is used and fluorochemical and hydrogenation adopt, platinum, rhodium, because the unstable of tetraalkylammonium hydroxide, to recovery set with having brought certain degree of difficulty, noble metal hydrogenation catalyst select for use then requirement to raw material and equipment all than higher; The 2nd, yield is lower, only is the way of testing laboratory, and this also is to be difficult to an industrialized major reason; The 3rd, operate more loaded down with trivial detailsly, be unfavorable for continuous operation, make industrial scale be restricted; The 4th, separation difficulty, product purity are not high.
At US 6,395, in 933, disclose at a certain temperature with oil of mirbane and substituted aniline, in the presence of highly basic and phase-transfer catalyst, synthesize the method for 4-aminodiphenylamine.The yield of this method is undesirable, and side reaction is a lot; In the 4 nitrodiphenyl amine and 4-nitrosodiphenylamine mixture that produces in synthetic, the ratio of 4 nitrodiphenyl amine is excessive, causes in the hydrogenation hydrogen consumption excessive, has increased production cost; And need oxygenant, therefore be difficult to be fit to industrialized production.
In WO9300324, oil of mirbane and aniline are disclosed in suitable solvent, under the effect of alkali, the content of control proton material in solution, the method for 4-aminodiphenylamine is produced in reaction under suitable temperature.Solvent and the content of control proton material in solution must be arranged in this patent, the introducing of solvent has brought energy consumption to increase and has brought separating difficulty, control proton material is controlled to reaction and has been brought difficulty, especially in later stage of condensation reaction, the content (mainly be meant and be dewatered to a relatively little content) of the proton material in the control solution can prolong the time of reaction, take away the aniline of a part, more to the difficult more proton material of sloughing of later stage, control proton material is big to certain range operation difficulty, is unfavorable for industrial production; Control proton material can make expensive tetraalkyl quaternary amine alkali catalyzer decompose fast in the scope of 0.5-4% the time, causes production cost to increase.
Summary of the invention
The objective of the invention is to select to be used for catalyzer and a technical process that is suitable for industrial-scale production condensation and hydrogenation, inexpensive and superior performance, prepare the 4-aminodiphenylamine continuously.The present invention uses compound alkaline catalysts as condensation catalyst, use composite powder powder catalyzer as hydrogenation catalyst, comprise condensation, hydrogenation, separation I (Separation and Recovery with recycle compound alkaline catalysts and Separation and Recovery and recycle optional partial regeneration at least after composite powder powder catalyzer), separates II (Separation and Recovery and recycle aniline and optionally separating reclaims and recycle hydrogenation solvent), make with extra care in five operations, prepare the 4-aminodiphenylamine with continuous processing.
In the technical process of the present invention, " separate I " is meant separations, reclaims and recycles the composite powder powder catalyzer behind the optional partial regeneration at least and separate, reclaim and recycle compound alkaline catalysts, and " separation II " is meant separation, reclaims and recycles aniline and optionally separating, reclaims and recycle hydrogenation solvent.
" optionally separating, reclaim and recycle hydrogenation solvent " of the present invention is meant, when making water as hydrogenation solvent, choose wantonly and reclaim and recycle described water, when using alcoholic solvent, should separate, reclaim and recycle described alcohols hydrogenation solvent as hydrogenation solvent.
The method of the 4-of preparation aminodiphenylamine of the present invention comprises: with oil of mirbane, aniline and compound alkaline catalysts by a certain percentage, to the condensation operation, reaction generates the condensated liquid (7) that contains 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt by the volume pump continuously feeding; Condensated liquid (7) and hydrogenation solvent (comprising additional hydrogenation solvent (2) and the optional hydrogenation solvent (5) that reclaims) continuously feeding by a certain percentage is to hydrogenation process, under the katalysis of (comprising additional composite powder powder catalyzer (1) and the optional regenerated composite powder powder catalyzer (4) that recycles) of composite powder powder catalyzer and hydrogen reaction, obtain containing the hydride (8) of 4-aminodiphenylamine; Hydride (8) is fed to and separates upward preface of I, obtain (a) composite powder powder catalyzer (4) in this separation, it directly loops back hydrogenation process or loops back hydrogenation process behind the partial regeneration at least, (b) compound alkaline catalysts (3), it loops back condensation operation and (c) organic phase (9) that obtains of evaporation obtains when concentrating water and extraction; With separate the water that obtains in the I operation and extract after organic phase (9) deliver to respectively and separate the II operation, obtain (a) aniline (6) in this separation, it loops back the condensation operation, (b) separated the 4-aminodiphenylamine crude product (10) of most of aniline, randomly (c), hydrogenation solvent (5), it loops back hydrogenation process; 4-aminodiphenylamine crude product (10) is fed to refining step, isolates (a) part aniline (6) at this, it loops back condensation operation and (b) 4-aminodiphenylamine finished product.Whole process flow is carried out continuously.
In condensation reaction, the mol ratio of oil of mirbane and aniline is 1: 1-1: 15; Temperature of reaction be 20-150 (℃), preferred 50-90 (℃), control reaction temperature is not higher than 90 ℃ can be so that the rate of decomposition of compound alkaline catalysts be less than 0.5% in the condensation course; Reaction pressure is absolute pressure 0.005-0.1 (MPa); The residence time of material in whole condensation reaction be 3.5-6 (hour).
The compound alkaline catalysts that condensation reaction is used contains tetraalkylammonium hydroxide, alkali metal hydroxide, three kinds of components of tetraalkylammonium salt, the optional water that also contains, wherein tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt three concentration expressed in percentage by weight summation are 10%-100%, be preferably 25%-38%, and the mol ratio of tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt is (0-9): (0.5-3): (0.5-3).Be used in combination the tetraalkylammonium hydroxide and cheap alkali metal hydroxide or oxide compound and tetraalkylammonium salt of a part, reached and used highly purified tetraalkylammonium hydroxide in the prior art as the same purpose of catalyzer.In the condensation reaction mixture, the mol ratio of hydroxide ion and oil of mirbane is 1 in the compound alkaline catalysts: 4-4: 1.
The compound alkaline catalysts that condensation reaction is adopted can prepare by the following method: controlled temperature is at 0-90 ℃, tetraalkylammonium hydroxide, alkali metal hydroxide or oxide compound, tetraalkylammonium salt are pressed (0-9): (0.5-3): molar ratio (0.5-3) stirs in water, promptly gets aqueous compound alkaline catalysts.After obtaining aqueous compound alkaline catalysts, optional add benzene azeotropic and slough moisture fully, obtain not having water combined alkaline catalysts.Described raw material tetraalkylammonium hydroxide, alkali metal hydroxide or oxide compound, tetraalkylammonium salt all can be solid form or aqueous solution form.
In industrial process, reactant inevitably will with the air in the external world in, the carbonic acid gas that is mingled with in the hydrogen contacts with carbon monoxide, causes the amount of tetraalkylammonium hydroxide to reduce, and changes into the tetraalkyl ammonium carbonate salts.Only be in the reaction of catalyzer, to change into the minimizing that ammonium salt has caused catalytic amount with the tetraalkylammonium hydroxide, must increasing the amount of catalyzer, getting rid of ammonium salt.Adopt the technology that compound alkaline catalysts of the present invention then need not be complicated, only need to improve the alkali metal hydroxide in the compound alkaline catalysts or the ratio of oxide compound and get final product.
The present invention adopts described compound alkaline catalysts under certain conditions, and oil of mirbane and aniline condensation are generated 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt.In the condensation reaction of the present invention, can use the compound alkaline catalysts of anhydrous type to make oil of mirbane and aniline change into 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt, under the anhydrous environment of system, the selectivity and the transformation efficiency of reaction reach requirement.
The method for preparing the 4-aminodiphenylamine of the present invention, adopt compound alkaline catalysts, because tetraalkylammonium hydroxide, alkali metal hydroxide, the comprehensive action of three kinds of materials of tetraalkylammonium salt, condensation reaction can be to water, proton materials such as methyl alcohol are controlled harshly, avoid the loss of the compound alkaline catalysts that causes because of the control of proton material and the operational trouble that causes as far as possible, that is to say proton materials such as in reaction, not having moisture or in solution system the content of proton material such as moisture content than in higher, condensation reaction can be carried out as usual, transformation efficiency and selectivity are unaffected, so just reduced the difficulty of controlling of reaction, and reduced the aniline amount of taking out of, made the production of suitability for industrialized more of described method because of dehydration and azeotropic.And use its rate of decomposition of compound alkaline catalysts to reduce than single tetraalkylammonium hydroxide.
In a preferred embodiment of the invention, condensation reaction is following carries out: by volume pump with oil of mirbane, aniline and compound alkaline catalysts in proportion continuously feeding to falling film reactor heat to carry out condensation reaction; Condensated liquid in the falling film reactor is discharged from the falling film reactor bottom and is entered A reactor, to proceed condensation reaction; The condensated liquid of part A reactor bottom returns falling film reactor again by recycle pump, constitutes the local circulation system of condensation reaction of the present invention like this.This recycle system mainly is made of falling film reactor and A reactor, and material constantly circulates in this system by the condensation recycle pump.Keep the amount of condensated liquid can in falling film reactor, form uniform film in the working cycle.The falling film reactor heating agent adopts alcohol vapor or hot water or steam or methanol vapor, and the preferably ethanol steam makes that temperature is very even in the system, has avoided the local superheating phenomenon.Reaction solution does not almost have back-mixing in the falling film reactor, greatly reduces the touch opportunity of product and raw material thing, makes side reaction drop to bottom line.By a local circulation system that has falling film reactor, accelerated the speed of response of condensation reaction, reduced the reaction times, make the reaction times that reaches more than ten hour originally shorten to 3.5-6 hour.
In the condensation operation of the present invention, oil of mirbane and aniline reaction have generated the 4-nitrosodiphenylamine, and oil of mirbane can also generate 4 nitrodiphenyl amine with the reaction of 4-nitrosodiphenylamine, and oil of mirbane self is reduced into nitrosobenzene simultaneously.Nitrosobenzene energy and aniline reaction generate nitrogen benzide, and this reaction pair main reaction is disadvantageous, have reduced the selectivity of reaction.The amount that oil of mirbane is relative at first is bigger reacting, and along with the carrying out of reaction, oil of mirbane is gradually transformed into the 4-nitrosodiphenylamine, and the amount of oil of mirbane reduces gradually.Owing to adopt continuous film reactor, reduced add fashionable oil of mirbane with after the 4-nitrosodiphenylamine that generates contact that (concentration of oil of mirbane is relative higher but 4-nitrosodiphenylamine concentration is relatively low when entering reactor and beginning to react with the chance of reaction, 4-nitrosodiphenylamine concentration was higher relatively but nitro phenenyl concentration is relatively low when reaction finished), reduced oil of mirbane is reduced into nitrosobenzene by the 4-nitrosodiphenylamine chance, also just reduced the reaction that oil of mirbane and aniline generate nitrogen benzide, therefore film type reaction is all higher than mixing reaction preference and yield entirely continuously.
In the condensation reaction that oil of mirbane and aniline carry out in the presence of compound alkaline catalysts, main side reaction is to generate such byproducts as azobenzene and azophenlyene.The amount of aniline is big more, and the side reaction that oil of mirbane is converted into azophenlyene is just few more.Another one by product in this reaction is a nitrogen benzide, and nitrogen benzide is easy to be converted into aniline, recycled in process of production at hydrogenation process.So the mol ratio of oil of mirbane and aniline is chosen as 1 among the present invention: 1-1: 15.
The method of the 4-of preparation aminodiphenylamine of the present invention can not introduced solvent in system, just carry out condensation reaction under suitable oil of mirbane and aniline conditions of mixture ratios, has obtained good yield.
The present invention utilizes aforesaid method to improve the yield of condensation reaction, and reaction is carried out to the direction of needs.
It may occur to persons skilled in the art that condensation reaction of the present invention can be adopted more multistage tandem reactor.
In the condensation operation, along with the carrying out of reaction, the compound alkaline catalysts that the condensation operation is used will lose a part inevitably.Can only add alkali metal hydroxide and two components of tetraalkylammonium salt in the compound alkaline catalysts when adding catalyzer, both mol ratios are 4: 1-1: 4.Can adopt alkalimetal oxide to replace alkali metal hydroxide, its consumption can convert by corresponding oxyhydroxide and get.
The method for preparing the 4-aminodiphenylamine of the present invention, described tetraalkylammonium salt has following general formula:
[(R1)(R2)(R3)(R4)N]
+ nX
n-
Wherein R1, R2, R3, R4 are identical or inequality, are respectively the alkyl with 1-4 carbon atom, X
N-Be selected from halogen root, sulfate radical, carbonate, phosphate radical, bicarbonate radical, bisulfate ion, alkyl (C1-C2) carbonate, alkyl (C1-C2) sulfate radical etc., n=1-2.
The method for preparing the 4-aminodiphenylamine of the present invention, at least one has hydrophilic substituent group alkyl R1, the R2 of described tetraalkylammonium salt, R3, R4, and this hydrophilic substituent group is selected from the group that hydroxyl, methoxyl group, polyethers, cationic polyamide, polyester, the many ammoniums of many ethene, strong water-soluble contain quaternary ammonium salt.
The method for preparing the 4-aminodiphenylamine of the present invention, described tetraalkylammonium salt limiting examples comprises: many methylated triethylene tetramines vitriol, the diethylenetriamine that methylates carbonate more, N, N-dimethyl-N, N-dimethoxy ethyl ammonium carbonate, N-methyl-N, N, N-trimethoxy ethyl ammonium carbonate, N, N, N-trimethylammonium-N-hydroxyethyl ammonium carbonate, chlorination trimethylammonium hydroxyethyl ammonium, N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) ethyl carbonate ammonium, N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) propyl ammonium carbonate, N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) propyl ammonium hydrochloride, N, N-dimethyl-N, N-two (ethoxylation (1-4 mole EO) propyl group) ammonium carbonate, tetramethyl-ammonium carbonate, the methyl carbonic acid tetramethyl-ammonium, tetraethyl ammonium carbonate, ethyl carbonate tetraethyl ammonium, tetramethyl-ammonium vitriol, methylsulfuric acid tetramethyl-ammonium, tetraethyl ammonium vitriol and ethylsulfuric acid tetraethyl ammonium.
The method for preparing the 4-aminodiphenylamine of the present invention, the structural formula of the tetraalkylammonium hydroxide of using in the described compound alkaline catalysts is R '
4N
+OH
-, wherein R ' represents to contain the alkyl of 1-2 carbon atom independently.Can adopt corresponding tetraalkylammonium salt and alkali to react in polar solvent prepares.
Alkali metal hydroxide or oxide compound comprise the oxyhydroxide or the oxide compound of lithium, sodium, potassium or rubidium, for example sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium oxide or potassium oxide.
Alkyl carbonic acid tetra-allkylammonium that adopts among the present invention or alkylsurfuric acid tetra-allkylammonium are to be reacted in polar solvent by trialkylamine and dialkyl carbonate (C1-C2) ester or sulfuric acid dialkyl group (C1-C2) ester to make.
The method for preparing the 4-aminodiphenylamine of the present invention, the temperature of reaction of described preparation alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium be 50-200 (℃), preferred temperature be 60-150 (℃), the pressure of reaction is gauge pressure 0.1-3 (MPa).In general, pressure and selected temperature, solvent types and consumption have substantial connection, and promptly the solvent consumption is few more, and system pressure is high more; Temperature is high more, and pressure is big more.The pressure of the present invention's reaction preferably is controlled at 0.4-2 (MPa), can obtain the product of higher yields.
The proportioning of raw material trialkylamine that the reaction of preparation alkyl carbonic acid tetra-allkylammonium of the present invention or alkylsurfuric acid tetra-allkylammonium is selected and dialkyl carbonate (C1-C2) ester or sulfuric acid dialkyl group (C1-C2) ester is 2: 1-1: 2 (moles).If the ratio of trialkylamine is excessive, then superfluous in reaction system, thus bring difficulty for the operation of subsequent technique, and contaminate environment; If the ratio of trialkylamine is too small, then dialkyl carbonate (C1-C2) ester or sulfuric acid dialkyl group (C1-C2) ester surplus cause the loss of dialkyl carbonate (C1-C2) ester or sulfuric acid dialkyl group (C1-C2) ester when next step reacts, and increase production cost.
The trialkylamine that the reaction of preparation alkyl carbonic acid tetra-allkylammonium of the present invention or alkylsurfuric acid tetra-allkylammonium is adopted and the reaction times of dialkyl carbonate (C1-C2) acid esters or sulfuric acid dialkyl group (C1-C2) ester are 1.5-6 hour.Initial reaction stage speed is fast, and exothermic phenomenon is obvious, and along with the consumption gradually of raw material, reaction slows down, and heat release reduces gradually.In reaction, can control certain reaction temperature, pressure by the consumption of constantly regulating water coolant.
The selected polar solvent of condensation reaction comprises methyl alcohol or ethanol or Virahol among the present invention, and solvent load is 1-10 a times of trialkylamine weight.
In hydrogenation of the present invention, can adopt hydrogen is reductive agent.Temperature of reaction is 50-100 ℃, and pressure is absolute pressure 0.2-3.0 (MPa), the reaction times be 2-7 (hour), gas-liquid volume ratio is 10: 1-1500: 1, the solid-liquid weight ratio is 0.5: 100-16: 100.Gas promptly refers to hydrogen, and liquid comprises hydrogenation solvent and condensated liquid, and solid is meant composite powder powder catalyzer.
Among the present invention, hydrogenation can adopt alcohols and/or water to make hydrogenation solvent.Alcohols particular methanol, ethanol or Virahol.The weight ratio of hydrogenation solvent and condensated liquid is 1: 10-5: 10.Hydrogenation solvent is pure time-like, need separate after hydrogenation and recycle.When hydrogenation solvent was water, the extraction back only need concentrate and promptly get compound alkaline catalysts of the present invention, and the water of condensation optional recycle that obtains in the concentration process is returned hydrogenation process.
The composite powder powder catalyst pack of using in the hydrogenation of the present invention is nickeliferous, aluminium and elements A, described A is selected from least a among Fe, Cu, Co, Mn, Cr, Mo, B, the P, wherein the weight percentage of nickel is 25%-99.9%, and the gross weight percentage composition of aluminium, elements A is 0.1%-75%.The particle diameter of catalyzer can be 40-300 (order).
Above-mentioned be selected from modulation auxiliary agent A at least a among Fe, Cu, Cr, Co, Mn, Mo, B and the P and can modify nickel-aluminium alloy crystalline state, reach and improve the hydrogenation selectivity, improve the purpose of catalyst activity.
Composite powder powder catalyzer of the present invention can prepare by the following method: with nickel powder, aluminium powder and elements A are by after the required mixed, and 40-300 purpose powder is pulverized in fusion under the condition of high temperature after the discharging, handle with hydroxide aqueous solution then.The oxyhydroxide weight percent concentration is 5%-50%, temperature of reaction be 50-90 (℃).
In order to improve the effect that the magnetic separator that adopts reclaims hydrogenation catalyst in follow-up technology, preferably adopt iron as the modulation auxiliary agent at least, to increase the ferromegnetism of composite powder powder catalyzer.Therefore, in a preferred embodiment of the invention, composite powder powder catalyzer of the present invention can be prepared as follows: ratio is as required got nickel powder, aluminium powder, iron powder, and optional other modulation auxiliary agent A that is selected from Cu, Cr, Co, Mn, Mo, B and P, in electric induction furnace, be melt into the alloy shape, lean on the pressure of gas to be sprayed onto by nozzle on the bronze drum of high speed rotating the alloy of fusing, rapid quenching, refrigerative speed can reach 10
5-10
6K/S.Cooled alloy is rolled into 40-300 (order) with ball mill, the powder of preferred 100-200 (order), then with weight percent concentration be 5%-50% hydroxide aqueous solution 50-90 (℃) processing.
According to a preferred embodiment of the present invention, hydrogenation can carry out in the following manner: condensated liquid, the composite powder powder catalyzer of hydrogenation solvent and recovery and the fresh composite powder powder catalyzer that replenishes are as required delivered into one-level by the solid-liquid e Foerderanlage, secondary and optional more senior hydrogenation reactor, hydrogen enters reactor with the form of bubbling from each reactor bottom by the hydrogen recycle machine, under above-mentioned hydrogenation condition, carry out hydrogenation, generation contains the thick hydride of 4-aminodiphenylamine, to be separated with magnetic separator through settling vessel by the composite powder powder catalyzer that thick hydride is carried secretly, with the isolating composite powder powder catalyzer solid-liquid that contains high density very of hydride mutually, recycle to reenter A reactor by a solid-liquid mix conveying appliance, obtain containing the hydride of 4-aminodiphenylamine simultaneously.
In hydrogenation process, composite powder powder catalyzer of the present invention is a solid matter.Hydrogenation catalyst circulates at industrial general employing pump, but often damages pump chamber easily with the catalyzer that pump circulation contains the high density powdery metal, carries the effect neither be very desirable.The present invention utilizes a kind of solid-liquid e Foerderanlage of Venturi-type, and the no pump circulation that the power of pump carries out when using condensated liquid into, realize the circulation of composite powder powder catalyzer in hydro genation system, increased the concentration of catalyzer in condensated liquid greatly, significantly reduced the loss of catalyzer.
According to a kind of embodiment preferred, in the continuous hydrogenation process, the composite powder powder catalyzer in the thick hydride reclaims by sedimentation and magnetic separator, circulates by Venturi-type solid-liquid e Foerderanlage, and circulating hydrogen adopts the form of bubbling to enter reactor.Whole hydriding process takes continuously feeding, the placed in-line complete mixing flow mode of staged reactor to carry out.Hydrogenation solvent can recycle.
The hydride that has reclaimed part composite powder powder catalyzer through sedimentation and magnetic separator enters and separates the I operation, pass through remaining composite powder powder catalyzer in the filtered and recycled hydride at this, and directly loop back hydrogenation process or looping back hydrogenation process behind the partial regeneration at least.
In the hydrogenation of the present invention, carry out continuously when a small amount of hydrogenation catalyst upgrades, can remain the high density of reactive system inner catalyst optional.The method that such catalyst recirculation is used remains in the higher scope gross activity all-the-time stable ground of system inner catalyst, has avoided the problem that catalyst activity lowers gradually in the method for employing fixed bed catalyst.The user of magnetic separator the recovery of catalyzer, the design of solid-liquid mix conveying appliance is used and composite powder powder catalyzer has been formed circulate in hydrogenation process.
In the present invention, the inactivation of catalyzer generally all is because inorganics or organism carbon distribution blocking catalyst hole cause the catalyst activity position to be capped, and causes the reduction of catalyst activity.Therefore, the present invention adopts the alkaline solution solution washing of higher concentration to take regenerated catalyst in conjunction with ultrasonic oscillation, and the described alkaline solution concentration that is weight percentage is the alkali metal hydroxide aqueous solution of 5%-50%.Ultrasonic oscillation helps to remove inorganics settling or organism carbon distribution, does not have dissolved aluminium and the alkaline solution of high density can catalyst-solvent when the first time, alkali was molten, forms new loose shape pore structure, thereby increases catalyst activity.
The method for preparing the 4-aminodiphenylamine of the present invention, reclaim the hydrogenation catalyst that contains magnetic by sedimentation and magnetic withdrawer, design a kind of solid-liquid mix conveying appliance of Venturi-type, use reinforced power and send catalyzer back to hydrogenation reactor, realized composite powder powder catalyst recirculation, and, greatly reduce the consumption of catalyzer with the original activity of recovery of regenerating after the catalyzer filtration, increased active lifetime of catalyst.
Filtrate is with extraction agent and help the extraction agent extraction, obtains organic phase and water, and wherein organic phase is delivered to and separated the II operation, and water obtains compound alkaline catalysts of the present invention after one or more levels concentrates, loop back the condensation operation.
Particularly, in the present invention, be extraction agent with water, the volume ratio of it and hydride is 0.5: 1-5: 1, be preferably 0.8: 1-1.2: 1.For helping extraction agent, the example includes but not limited to the polyethers organism: polyglycol ether, as Polyethylene glycol dimethyl ether (molecular weight 200-1000), polyoxyethylene glycol diethyl ether (molecular weight 200-1000) and polyoxyethylene glycol methyl ethyl ether (molecular weight 200-1000); Polypropylene glycol ether is as polypropylene glycol dme (molecular weight 200-1000), polypropylene glycol diethyl ether (molecular weight 200-1000) and polypropylene glycol methyl ethyl ether (molecular weight 200-1000); Fatty alcohol-polyoxyethylene ether, for example wherein the carbon number of Fatty Alcohol(C12-C14 and C12-C18) is 12-18, the polyoxyethylated polymerization degree is those of 3-15.The volume ratio of itself and extraction agent water is 0.0001: 1-0.005: 1.The extraction pressure be 0.005-0.1 (MPa), the temperature of extraction be 0-80 (℃), the extraction time 2-5 (hour).Behind the separatory, obtain containing the upper strata water of hydrogenation solvent and compound alkaline catalysts and mainly contain aniline and the organic phase of 4-aminodiphenylamine and a small amount of organic impurity thereof.
The method for preparing the 4-aminodiphenylamine of the present invention, one or more levels gas of concentrated employing of the water behind the hydrogenation help stream falling film evaporation apparatus.Gas helps the shell side of stream falling-film evaporator to adopt steam heating, and another part steam promptly helps head piece by the steam port at the top of one-level falling-film evaporator, enters tube side, and water helps the lower concentration water import of stream falling-film evaporator to enter in the tube side from gas.With steam is power-assist power, and steam and water direction of motion are in the same way.Described gas help the stream falling-film evaporator comprise shell side (2 '), tube side (3 '), be installed in shell side (2 ') upper end steam inlet (8 '), be installed in shell side (2 ') lower end vapor condensation water out (1 '), be installed in tube side (3 ') top lower concentration water import (6 '), be installed in the high density water outlet (9 ') of tube side (3 ') bottom, be installed in helping of tube side (3 ') top and flow steam inlet (5 ', 7 '), be installed in the distributing disc (4 ') of lower concentration water import (6 ') below.
In described falling-film evaporator, under the drive of steam, water is membranaceous from top to bottom in inside tube and flows by distributing disc, and the control residence time is 2-60 (second), its temperature be 30-105 (℃).The pressure of the shell side steam that adopts when concentrating is absolute pressure 0.005-0.1 (MPa).By adopting gas to help the stream falling-film evaporator, utilize steam to drive water and flow from top to bottom, accelerated liquid flow velocity, controlled the residence time, simultaneously under higher temperature, the low boiling substance of aqueous phase is evaporated in large quantities.Can reduce the decomposition of the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium so to greatest extent.If hydrogenation solvent is an alcohol, then the condensation product (it be the mixture of alcohol and water) that obtains of evaporant condensation can send and separate the II operation with the recovery hydrogenation solvent; If hydrogenation solvent is alcohol/water mixture, condensation product (it is the mixture of alcohol and water) the capable of circulation time hydrogenation process that obtain of evaporant condensation or send and separate the II operation then to reclaim alcohol; If hydrogenation solvent is a water, capable of circulation time hydrogenation process of the condensation product that obtains of evaporant condensation (it is water) then.
In separation II operation of the present invention, obtain aniline from separating the evaporation through the organic phase of extraction that the I operation sends here, it loops back the condensation operation, and the tower bottoms that has separated most of aniline send refining step.The working pressure of vaporizer is absolute pressure 0.005-0.1 (MPa), tower still temperature be 120-320 (℃), gas phase temperature be 60-190 (℃).
At hydrogenation solvent is under the situation of alcohol or alcohol/water mixture, obtains alcohol as hydrogenation solvent with separating the condensed water phase time obtains in the I operation evaporator condensation thing rectifying, and it loops back hydrogenation process.
In separating the II operation, separated in the organic phase of most of aniline, contained 4-aminodiphenylamine, aniline, nitrogen benzide and azophenlyene etc.In one embodiment of the present invention, refining step adopts three tower continuous rectifications and batch fractionating to carry out, the wherein said purified organic phase for the treatment of is gone in No. 1 rectifying tower by pump delivery, takes overhead out aniline, azophenlyene and nitrogen benzide, and the discharging of tower still is a crude product 4-aminodiphenylamine; The cat head discharging of No. 1 rectifying tower enters rectifying tower No. 3, and No. 3 the rectifying tower cat head steams aniline, and its content is about 99%, can directly loop back the condensation operation, remaining azophenlyene of tower still and nitrogen benzide; No. 1 rectifying tower tower bottoms is by pump delivery to 2 tower, No. 2 the rectifying tower cat head distills out finished product 4-aminodiphenylamine, tower still feed liquid runs up to a certain amount of, enter the batch still distillation, distill out a small amount of 4-aminodiphenylamine remaining in the feed liquid, and it is returned rectifying tower No. 2, other material slag is emitted at the bottom of by still.
In above-mentioned process for refining of the present invention, the vacuum tightness of No. 1 rectifying tower is 0.09-0.098 (MPa), and reflux ratio is 2: 1-10: 1, tower top temperature be 80-130 (℃), tower still temperature be 260-290 (℃); The vacuum tightness of No. 2 rectifying tower is 0.09-0.098 (MPa), and reflux ratio is 1: 0.5-1: 4, tower top temperature be 140-190 (℃), tower still temperature be 260-300 (℃); The vacuum tightness of No. 3 rectifying tower is 0.09-0.098 (MPa), and reflux ratio is 1: 0.5-1: 2, tower top temperature be 80-120 (℃), tower still temperature be 120-170 (℃); The tower still vacuum tightness of batch fractionating is 0.09-0.098 (MPa), tower top temperature be 235-250 (℃), tower still temperature be 280-330 (℃).The tower still temperature of No. 2 rectifying tower is relatively low, can reduce the coking degree of 4-aminodiphenylamine like this, and account for total amount reach 96% or higher 4-aminodiphenylamine can separate at the cat head of No. 2 rectifying tower of relatively low tower still temperature, thereby the amount of carrying out 4-aminodiphenylamine in the feed liquid of batch distillation significantly reduces.
In the method for preparing the 4-aminodiphenylamine of the present invention, selected compound alkaline catalysts and composite powder powder Catalyst Production cost are low, the catalytic activity height; Whole process of preparation can be carried out continuously, is suitable for industrial-scale production; In the condensation operation, adopted compound alkaline catalysts greatly to reduce the difficulty of controlling of reaction, made the moisture in the reaction system no longer become the factor that reaction restricts; Compound alkaline catalysts decomposition is significantly less than single tetraalkylammonium hydroxide catalyzer; The selection of the proportioning of falling film reactor and reaction raw materials improves the selectivity of reaction; Need not solvent; The hydrogenation temperature is lower, the reaction conditions gentleness, and the hydrogenation catalyst toxin immunity is good, and by product is few, transformation efficiency and selectivity height; The composite powder powder catalyzer that has adopted the magnetic withdrawer to reclaim during hydrogenation to contain magnetic; By a kind of solid-liquid mix conveying appliance of Venturi-type, and use reinforced power and send hydrogenation catalyst back to hydrogenation reactor; Carry out the regeneration of catalyzer with the method for chemistry and/or physics, reduced the consumption of catalyzer; Selected after hydrogenation, to reclaim compound alkaline catalysts, and separated compound alkaline catalysts as extraction agent with containing the water that helps extraction agent; Extraction back water adopts one to imitate or multiple-effect gas helps the stream falling-film evaporator to concentrate to carry out the recovery of compound alkaline catalysts; Whole process is continuous, and labour intensity is low, does not produce corrosive liquid, basically eliminate to the pollution of environment.The purity of 4-aminodiphenylamine can be higher than 99%, and the yield of the technological process of whole industrial-scale production can be higher than 95%.
Description of drawings
Fig. 1 is the process flow sheet of an embodiment of the method for preparing the 4-aminodiphenylamine of the present invention.
Fig. 2 is that the gas that is used for one embodiment of the invention helps the synoptic diagram that flows falling-film evaporator.
Fig. 3 is the process flow sheet of refining step of the present invention
Reference numeral
1-composite powder powder catalyzer
The 2-hydrogenation solvent
3-recycles compound alkaline catalysts
4-recycles the composite powder powder catalyzer behind the optional partial regeneration at least
5-recycles hydrogenation solvent
6-recycles aniline
1 '-vapor condensation water out, 2 '-shell side
3 '-tube side 4 '-distributing disc
5 ', 7 '-help the stream steam inlet
The import of 6 '-lower concentration water
8 '-steam inlet
The outlet of 9 '-high density water
Embodiment
Embodiment given below is in order to further specify the mode of the present invention of implementing, and not in officely where is construed as limiting in the face of the present invention.
The preparation of compound alkaline catalysts:
In being furnished with 1000 milliliters of three-necked flasks of condenser and agitator, the tetramethyl ammonium hydroxide aqueous solution (0.50 mole), 10 gram sodium hydroxide (0.25 mole), the 346 gram 30% tetramethyl-ammonium carbonate aqueous solutions (0.5 mole) that add 227.5 grams, 20% (weight) with random order, under 72-77 ℃, stir, promptly make compound alkaline catalysts, concentration 27.3% (weight).
Composite powder powder Preparation of catalysts:
Get nickel powder 46 and restrain, aluminium powder 51 grams, iron powder 3 grams mix the back and be melt into the alloy shape in electric induction furnaces, lean on the pressure of gas to be sprayed onto by nozzle on the copper wheel of high speed rotating the alloy that melts, and (refrigerative speed can reach 10 to quenching rapidly
5-10
6K/S).Cooled alloy is rolled into Powdered with ball mill, sieve to obtain 40-300 purpose powder 99.7 grams.In capacity is 500 milliliters the there-necked flask that thermometer and agitator are housed, the 375 gram concentration of packing into are the NaOH aqueous solution of 20% (weight), slowly add the above-mentioned powder that makes, 60 ℃ of stir process 4 hours, use the deionized water wash solid to neutral then, promptly obtain composite powder powder catalyzer.
Under vacuum, open described compound alkaline catalysts, aniline and oil of mirbane transferpump simultaneously, regulate flow to 150 kilograms/hour of aniline, 30 kilograms/hour in oil of mirbane, 200 kilograms/hour of compound alkaline catalystss, said components oil of mirbane, aniline and compound alkaline catalysts continuously feeding to falling film reactor are heated to carry out condensation reaction: the condensated liquid in the falling film reactor is discharged from the bottom and is entered A reactor, to proceed condensation reaction; The condensated liquid of part A reactor bottom returns falling film reactor again by recycle pump, forms the local circulation system.The heating agent of falling film reactor adopts 78-90 ℃ of alcohol vapor.Control reaction temperature is 75 ℃, and pressure is 0.008MPa (absolute pressure), 1 meter of circulating fluid flow rate 3/ hour.The material overflow of A reactor is to second reactor.The service temperature of second reactor is identical with A reactor with processing condition such as pressure.The total residence time of control material in falling film reactor, A reactor and second reactor is 5 hours.After condensation reaction is stable, can use the compound alkaline catalysts that reclaims by following embodiment method, only add the fresh compound alkaline catalysts of small part by embodiment 1 preparation, the mol ratio of hydroxide radical and oil of mirbane is not less than 1: 1 in the control reaction system.The material that second reactor is discharged by analysis, oil of mirbane≤0.1%, moisture are 24.9%, 4-nitrosodiphenylamine and 4 nitrodiphenyl amine content are 16.1% (weight).
Under vacuum, open described compound alkaline catalysts, aniline and oil of mirbane transferpump simultaneously, regulate flow to 150 kilograms/hour of aniline, 30 kilograms/hour in oil of mirbane, 200 kilograms/hour of compound alkaline catalystss, with said components oil of mirbane, aniline and compound alkaline catalysts in proportion continuously feeding to falling film reactor heat to carry out condensation reaction; Condensated liquid in the falling film reactor is discharged from the bottom and is entered A reactor, to proceed condensation reaction; The condensated liquid of part A reactor bottom returns falling film reactor again by recycle pump, forms the local circulation system.The heating agent of falling film reactor adopts 78-90 ℃ of alcohol vapor.。75 ℃ of control reaction temperature, pressure 0.008MPa (absolute pressure), 1 meter of circulating fluid flow rate
3/ hour.The material overflow of A reactor is to second reactor.The service temperature of second reactor is identical with A reactor with processing condition such as pressure.The total residence time of control material in falling film reactor, A reactor and second reactor is 5 hours.After condensation reaction is stable, use the compound alkaline catalysts that reclaims.According to sodium hydroxide: the ratio of tetraalkylammonium salt (is the tetramethyl-volatile salt according to embodiment 1) 1: 1 (mole) is added alkaline catalysts, and the concentration of hydroxide ion and the mol ratio of oil of mirbane are not less than 1: 1 in the control reaction system.The material that second reactor is discharged by analysis, oil of mirbane≤0.1%, moisture 15.6%, 4-nitrosodiphenylamine and 4 nitrodiphenyl amine content are 17.6% (weight).
Hydrogenation
The condensated liquid that to do by the method for embodiment 3 is fed to the one-level hydrogenation reactor after the filtration, this reactor has the magnetic stirrer of sealing, cooling and heating system.Use hydrogen exchange, and pressurising is to 1.3MPa.Start the hydrogen recycle machine, the flow that keeps recycle hydrogen 1 standard cubic meter/hour, and circulating hydrogen enters hydrogenation reactor with the form of bubbling, the gas-liquid mass transfer effect when improving reaction.The flow of the condensated liquid of control oil of mirbane and aniline is 306 kilograms/hour, the flow of methyl alcohol be 60 liters (48Kg)/hour.Add the above-mentioned composite powder powder catalyzer that makes simultaneously in reactor, making solid-to-liquid ratio is 6: 100 (weight ratio).Hydro-reduction liquid overflows to the second order reaction still from the first order reaction still, overflows to the third order reaction still again, overflows to subsider then, and temperature of reaction 75-80 ℃, pressure 1.3MPa, total residence time is 5 hours.Under the effect of magnetic separator, can reclaim described composite powder powder catalyzer most possibly.The solidliquid mixture that contains big concentration solid catalyst of subsider bottom is used reinforced power through the solid-liquid e Foerderanlage of Venturi-type and is turned back to the one-level hydrogenation reactor again.Can judge activity of such catalysts in the hydrogenation by monitoring reduction reaction terminal point situation, thereby whether decision needs to add composite powder powder hydrogenation catalyst.
Hydro-reduction liquid detects through high performance liquid chromatography, does not contain 4 nitrodiphenyl amine and 4-nitrosodiphenylamine.
Separate I
The hydride of producing according to the method for embodiment 5, behind sedimentation and magnetic Separation and Recovery composite powder powder catalyzer, carry out filtered and recycled magnetic and separate unrenewable extremely fine composite powder powder hydrogenation catalyst, recycle after the regeneration and turn back to hydrogenation process.The hydro-reduction liquid that does not contain solid catalyst is delivered to continuously the top of extraction tower with 360 liters/hour flow with volume pump, simultaneously extraction agent water is with 360 liters of/hour identical flows, and helping the extractant molecules amount is the Polyethylene glycol dimethyl ether of 400-800 enters extraction tower continuously with 0.4 liter of/hour flow bottom.After the extraction, obtain water, obtain organic phase at the bottom of the tower from cat head.The extraction time is 3 hours, and extracting pressure is a normal pressure.The compound alkaline catalysts of methyl alcohol in the hydro-reduction liquid and condensation all is extracted into aqueous phase by water, and the water amount that obtains is 540 liters/hour, and organic phasor is 180 liters/hour.
Be preheating to 80 ℃ water with volume pump with 540 liters/hour flow, be fed to gas and help stream falling-film evaporator top, gas helps stream falling-film evaporator shell side to heat with 120 ℃ of water vapors, the residence time of material in this vaporizer is 10 seconds.The one-level concentrated solution is sent into shell and tube secondary falling-film evaporator under the 0.1MPa pressure (absolute pressure), and about 10 seconds of the residence time of material in this vaporizer, the liquid-vapor mixture temperature of coming out from the secondary falling-film evaporator is 80-95 ℃.After the secondary vapour liquid separator separated, the rate of recovery of compound alkaline catalysts can reach 99.7% in the whole enrichment process then.Compound alkaline catalysts is looped back the condensation operation.
Embodiment 7
Separate II
The gas phase that falling-film evaporator is evaporated obtains containing the methanol-water solution of the about 28 weight % of methyl alcohol after condensation.This methanol-water solution separates with pump continuously feeding to rectifying tower, and cat head obtains the methyl alcohol greater than 99 weight %, and the hydrogenation process that can be recycled back, tower still are water.Survey tower still water with gas-chromatography, methanol content can be less than 0.3 weight %.
The organic phase that extracting and separating is obtained is sent into shell and tube climbing-film evaporation separator and is isolated most of aniline.The working pressure of climbing-film evaporation separator (absolute pressure) is 0.01MPa, and shell side is with 180 ℃ of steam heating.Obtain 75-105 ℃ gas phase and 160 ℃ liquid phase through the separation of climbing-film evaporation separator top vapour liquid separator.Detect condensed gaseous phase materials with chromatogram, record aniline content and reach 99 weight %.Most of aniline steams in this operation, and the aniline that steams retraction capable of circulation closes the raw material of operation as condensation reaction, and liquid phase material is the crude product of 4-aminodiphenylamine, comprises 78.1% 4-aminodiphenylamine, other organic impuritys of 21.75% aniline and surplus.
Embodiment 8
Refining
With the crude product (containing 4-aminodiphenylamine 78.1%, aniline 21.75%, nitrogen benzide 0.05%, azophenlyene 0.1%) of 4-aminodiphenylamine, send into rectifying tower continuously No. 1 by toothed gear pump with 120 kilograms of/hour flows.270 ℃ of control tower still temperature, 110 ℃ of tower top temperatures, vacuum tightness be at 0.094MPa, reflux ratio 5: 1.Light constituent aniline, nitrogen benzide, three kinds of materials of azophenlyene are from the cat head extraction, and flow is about 26.2 kilograms/hour, and send into rectifying tower No. 3.150 ℃ of No. 3 rectifying Tata still temperature, 90 ℃ of tower top temperatures, vacuum tightness 0.094MPa, reflux ratio 1: 1, cat head distills out aniline with 24 kilograms/hour flow, and what the tower still was remaining is nitrogen benzide, azophenlyene.No. 1 the rectifying tower tower bottoms is sent into rectifying tower No. 2.280 ℃ of No. 2 rectifying Tata still temperature, tower top temperature is controlled at 170 ℃, and vacuum tightness is 0.097MPa, reflux ratio 1: 1.It is finished product 4-aminodiphenylamine that the cat head of No. 2 rectifying tower obtains.No. 2 the rectifying tower tower bottoms is sent into batch still.The still temperature of batch still is 285-320 ℃, vacuum tightness 0.094MPa, and the top temperature remains on 235-250 ℃, steams remaining 4-aminodiphenylamine, and loops back No. 2 rectifying tower and distill again.Whole 4-aminodiphenylamine process for refining carries out continuously.The finished product 4-aminodiphenylamine purity that obtains is 99.1%, 72 ℃ of fusing points, 72.4 ℃ at zero pour.The industrial-scale production yield of this technological process is 95.1%.
The renovation process of catalyzer
Get by filtering composite powder powder catalyzer 20 grams that hydride reclaims, add and be equipped with in 100 milliliters of there-necked flasks of whipping appts and thermometer, add 20 milliliters 40% sodium hydroxide solution again.This mixture under agitation is warming up to 90 ℃, maintains under this temperature and reacted 1 hour.After reaction finishes, catalyzer is put into ultrasonic cleaner cleaned 30 minutes, water repeatedly washs up to the pH of washing water value and is 7-8, and the solid of gained is the compound powder catalyst after the regeneration.
Embodiment 10
The preparation of compound alkaline catalysts
In being furnished with 500 milliliters of three-necked flasks of condenser and agitator, add entry 230 grams, random order adds five hydronium(ion) oxidation tetramethyl-ammoniums, 91 grams (containing 0.50 mole of tetramethyl ammonium hydroxide), sodium hydroxide 20 grams (0.5 mole), chlorination trimethylammonium hydroxyethyl ammonium 70 grams (0.5 mole), 75 ± 2 ℃ of controlled temperature, stir, make compound alkaline catalysts, concentration is 32.85 (weight %).
Embodiment 11
The preparation of compound alkaline catalysts
In being furnished with 500 milliliters of three-necked flasks of condenser and agitator, add entry 230 grams, be not sequentially added into five hydronium(ion) oxidation tetramethyl-ammoniums, 91 grams (containing 0.50 mole of tetramethyl ammonium hydroxide), sodium hydroxide 20 gram (0.5 mole), methyl carbonic acid tetramethyl-ammonium [(CH
3)
4N]
+[CO
3CH
3]
-74.5 gram (0.5 mole), 75 ± 2 ℃ of control mixing temperatures stir, and make compound alkaline catalysts, concentration 33.7 (weight %).
Embodiment 12
Is being furnished with condenser, in 500 milliliters of four-hole boiling flasks of agitator and water trap, add entry 150 grams, be not sequentially added into five hydronium(ion) oxidation tetramethyl-ammoniums, 91 grams (containing 0.50 mole of tetramethyl ammonium hydroxide 50%), sodium hydroxide 20 gram (0.5 mole), methyl carbonic acid tetramethyl-ammonium [(CH
3)
4N]
+[CO
3CH
3]
-74.5 gram (0.5 mole) adds 25 gram benzene, temperature rising reflux has water and oil reservoir in water trap, and oil reservoir comes back to four-hole boiling flask, and water layer is told, and till the liquid that steams does not have water, obtains not having water combined alkaline catalysts.
Embodiment 13
Methyl carbonic acid tetramethyl-ammonium [(CH
3)
4N]
+[CO
3CH
3]
-Preparation
Have whipping appts at one, in 1.5 liters the autoclave of heating unit, add methylcarbonate 90 grams (1.0 moles), Trimethylamine 99 59 grams (1.0 moles), methyl alcohol 510 grams (15 moles).Start stirring after airtight, be warmed up to 140 ℃, pressure is 1.5MPa, maintains 4 hours this following reaction times of temperature.Cool to 50 ℃ then, discharging to 1 rises in the there-necked flask, obtain the methanol solution of methyl carbonic acid tetramethyl-ammonium, a part of methyl alcohol, cool to room temperature are sloughed in decompression, the adularescent crystal is separated out, filter, oven dry is made recrystallization with methyl alcohol again, obtains methyl carbonic acid tetramethyl-ammonium 119.5 grams, stratographic analysis purity is 99.2%, and yield is 80.2%
Embodiment 14
With 1-chloro-2,3-propylene oxide 92.5 grams (1 mole) and N methyldiethanol amine 3 grams (1 mole), with 2 gram sodium hydroxide, add 700 gram water again, add one and have stirring, heating in the reactor of temperature measuring equipment, is started stirring, be warmed up to 120 ℃ gradually, feed ethylene oxide gas, keep reactor pressure 0.3Mpa to reactor, logical again oxyethane after reaction pressure reduces, amount up to the oxyethane that feeds reaches 150 grams, continues to react 2 hours the ClCH that obtains under this condition
2[CH
2CH
2O]
2-5H feeds Trimethylamine 99 gas 60 grams again, is warmed up to 140 ℃, and pressure is 1.5MPa, maintains 4 hours this following reaction times of temperature.Cool to room temperature then, dehydrate, obtain N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) propyl ammonium hydrochloride 105 grams according to ordinary method.
Embodiment 15
The preparation of tetramethyl ammonium hydroxide:
Have whipping appts at one, in 1.5 liters the autoclave of heating unit, add methylcarbonate 90 grams (1.0 moles), Trimethylamine 99 59 grams (1.0 moles), methyl alcohol 510 grams (15 moles).Start stirring after airtight, be warmed up to 140 ℃, pressure is 1.5MPa, maintains 4 hours this following reaction times of temperature.Cool to room temperature then, discharging to 1 rises in the there-necked flask, adds the soup compound that 148 gram (2.0 moles) calcium hydroxides and 350 gram water are mixed with.Stir down and steam methyl alcohol, filter and obtain 355 gram tetramethyl ammonium hydroxide solutions with heating in 8 hours.Analysis knows that tetramethyl ammonium hydroxide content is 24.4%, and the entire reaction yield is 95.2%.
Embodiment 16
The preparation of tetraethyl ammonium hydroxide
Have whipping appts at one, in 1.5 liters the autoclave of heating unit, add ethyl sulfate 154 grams (1.0 moles), triethylamine 101 grams (1.0 moles), ethanol 690 gram (15 moles) starts stirring after airtight, is warmed up to 140 ℃ and keeps, pressure is 1.0MPa, maintains 4 hours this following reaction times of temperature.Cool to room temperature then, discharging to 1 rises there-necked flask, adds sodium hydroxide 80 grams (2.0 moles), heating under agitation, and control reaction temperature is 45 ℃, reacts 4 hours.Filter, filtrate steams part ethanol earlier, adds 500 gram water, steams ethanol (wherein having portion water to be pulled away) when adding entry, obtains 604 gram tetraethyl ammonium hydroxide solution.Analysis knows that tetraethyl ammonium hydroxide content is 23.3% (weight), and the entire reaction yield is 95.7%.
Embodiment 17
The amount of aniline and oil of mirbane is to the influence of reaction
Mini-reactor and a falling film reactor and the recycle pump composition local circulation system that vacuum system and temperature controlling system are housed, cumulative volume is 1 liter.Fill aniline earlier, the flow set of recycle pump is 2 liters/hour.With oil of mirbane: aniline: OH in the compound alkaline catalysts
-Mol ratio be that the mixed solution of 1: 1: 1.8 the compound alkaline catalysts that contains among oil of mirbane, aniline and the embodiment 1 preparation is fed to reactor with 200 milliliters/hour, the residence time is 5 hours, keeping system temperature is 75 ℃, and pressure is 0.008MPa (absolute pressure).Displace aniline Deng reaction solution, after the reaction solution composition is stable, sampling analysis, the basic existence that detects less than oil of mirbane.Calculate the selectivity of reaction according to the 4-nitrosodiphenylamine of reaction generation and the total mole number of 4 nitrodiphenyl amine.
Adopt same condition, just change the proportioning of oil of mirbane and aniline, obtain the results are shown in Table 1.
The amount of table 1 aniline and oil of mirbane is to the influence of reaction
| Numbering | Oil of mirbane: aniline (mole) | Reaction preference (%) |
| 1 | 1∶1 | 90.2 |
| 2 | 1∶3 | 96.1 |
| 3 | 1∶5 | 99.1 |
| 4 | 1∶10 | 99.3 |
From table data as can be seen, the mol ratio that increases aniline and oil of mirbane can improve the selectivity of reaction, increases target product, reduces by product.But in actual applications, if the amount of aniline is excessive, the consumption of the consumption that can increase aniline when separating energy when separating.
Embodiment 18
Water is to the influence of condensation reaction:
In a continuous reaction apparatus, the local circulation system that vacuum pump is housed and forms by thermometric heating system, film reactor and recycle pump, cumulative volume is 1 liter, fill aniline earlier, the flow of recycle pump is 2 liters/hour, will contain oil of mirbane, aniline, the mixed solution of compound alkaline catalysts enters reactor with certain speed, keeps oil of mirbane: aniline: molar ratio be 1: 7, oil of mirbane: compound alkaline catalysts OH
-Molar ratio is 1: 1.15, keeping system temperature is 75 ℃, pressure is 0.008MPa (absolute pressure), displace aniline Deng reaction solution, after the reaction solution composition is stable, adjust reaction time by regulating feed rate, up to detecting oil of mirbane≤0.1%, reach at 97% o'clock according to the 4-nitrosodiphenylamine of reaction generation and the yield of 4 nitrodiphenyl amine calculating, measure the moisture content in reaction solution exit, the result who obtains is as follows:
| Sequence number | Compound alkaline catalysts three component ratios (mol ratio) | Product water content (%) |
| Tetramethyl ammonium hydroxide: N, N-dimethyl-N, N-two (ethoxylation (1-4 mole EO) propyl group) ammonium carbonate: sodium hydroxide | ||
| 1 | 5∶2∶2 | 5.1 |
| 2 | 3∶2∶2 | 10.2 |
| 3 | 2∶2∶2 | 15.4 |
| 4 | 1∶2∶1 | 17.5 |
| 5 | 0.5∶2∶0.5 | 19.8 |
| 6 | Make catalyzer with tetramethyl ammonium hydroxide | 1.2 |
Can see, along with N in the compound alkaline catalysts, N-dimethyl-N, the raising of N-two (ethoxylation (1-4 mole EO) propyl group) ammonium carbonate ratio, the water content during reaction end is improving.Adopt compound alkaline catalysts of the present invention, the wide ranges of the moisture content that allows in the reaction mixture when reaction finishes a lot, when in system, containing, also can obtain satisfied yield than higher water-content.Because few more at reaction later stage moisture, the efficient of dehydration is low more, and the inventive method has reduced the difficulty of reaction.And if only adopt tetramethyl ammonium hydroxide as catalyzer, then system must be dewatered to 1.2%, 97% yield is just arranged, this has brought difficulty for control of reaction, has also increased energy consumption.
Embodiment 19
With embodiment 12 prepared anhydrous composite catalysts, pack into aniline 651 gram and one to have whipping appts, in the four-hole boiling flask of thermometer, start stirring, keeping temperature is 75 ℃, pressure is 0.008MPa (absolute pressure), aniline comes back in the four-hole boiling flask after aniline that distills out and the layering of water azeotrope, water content drips oil of mirbane 123 grams less than 0.5% in system, and the dropping time is 2 hours, kept 4 hours, continue dehydration when keeping, the yield of chromatographically 4-nitrosodiphenylamine and 4 nitrodiphenyl amine is 97.4%, and water content is less than 0.5% in the detection architecture.
Embodiment 20
Film type reaction and the full comparison that mixes reaction result continuously
OH in control aniline, oil of mirbane and the compound alkaline catalysts
-Ratio be 7.5: 1: 1.5 (mol/mol), temperature of reaction is 75 ℃, the reaction times is 5 hours, pressure is 0.005MPa (absolute pressure), more continuous film type reaction and complete mix reaction the results are shown in Table 2 and table 3.
Table 2: the full result who mixes reaction
| Sequence number | Oil of mirbane transformation efficiency | Yield % | |
| 1 | 98.1 | 94.6 | |
| 2 | 98.3 | 95.1 | |
| 3 | 98.1 | 94.8 |
Table 3: continuous film type reaction
| Sequence number | Oil of mirbane transformation efficiency | Yield % | |
| 1 | 99.2 | 97.6 | |
| 2 | 99.9 | 98.1 | |
| 3 | 99.5 | 97.8 |
Embodiment 21
Hydrogenation at intermittence embodiment
In having 1 liter autoclave of whipping appts, temperature regulating device, add the condensated liquid that 500 grams contain 17.5%4-nitrosodiphenylamine and 3.0%4-nitrodiphenylamine.Composite powder powder catalyzer 5 grams that add preparation in the 150 gram ethanol and the embodiment of the invention 2.Behind hydrogen exchange three times, pressurising is to 0.8MPa.Under agitation, reaction mixture is warmed up to 100 ℃, and maintains under this temperature reaction 4 hours.Reaction finishes postcooling, pressure release discharging.Use the efficient liquid phase chromatographic analysis reaction solution, find not contain 4-nitrosodiphenylamine and 4 nitrodiphenyl amine in the reaction solution, the content of 4-aminodiphenylamine is 14.6% (chromatogram content).
The comparison of composite powder powder catalyzer and noble metal catalyst
Compare with Pd/C catalyzer that contains palladium 5% (weight) and composite powder powder catalyzer of the present invention.Test is carried out under the described processing condition of above-mentioned hydrogenation at intermittence embodiment, add the amount unanimity of catalyzer, two kinds of equal recovery sets of catalyzer were used after reaction finished.Apply mechanically within 21 times two kinds of catalyst recovery, all detect less than 4-nitrosodiphenylamine in both reaction solutions, the 21st cover time spent, with containing 0.1% 4 nitrodiphenyl amine in the Pd/C catalyzer gained reaction solution, and with detecting less than 4 nitrodiphenyl amine in the reaction solution of composite powder powder catalyzer gained of the present invention.The toxin immunity that shows catalyzer of the present invention is better than noble metal catalyst.
Claims (29)
1. method for preparing the 4-aminodiphenylamine, this method is a raw material with oil of mirbane and aniline, comprise condensation, hydrogenation, separating I is that Separation and Recovery is chosen the composite powder powder catalyzer of partial regeneration at least wantonly with recycling compound alkaline catalysts and Separation and Recovery and recycling, separate II and be Separation and Recovery and recycle aniline and optionally separating reclaims and recycle hydrogenation solvent, refining five operations, use compound alkaline catalysts as condensation catalyst, use composite powder powder catalyzer as hydrogenation catalyst, the compound alkaline catalysts that is adopted contains tetraalkylammonium hydroxide, alkali metal hydroxide, and three kinds of components of tetraalkylammonium salt, it is characterized in that described tetraalkylammonium salt has following general formula:
[(R1)(R2)(R3)(R4)N]
+ nX
n-
Wherein R1, R2, R3, R4 are identical or inequality, are respectively the alkyl with 1-4 carbon atom, and at least one among described R1, R2, R3, the R4 has hydrophilic substituent group, X
N-Be selected from halogen root, sulfate radical, carbonate, phosphate radical, bicarbonate radical, bisulfate ion, alkyl (C1-C2) carbonate, alkyl (C1-C2) sulfate radical, n=1-2.
2. according to the method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that described hydrophilic substituent group is selected from the group that hydroxyl, methoxyl group, polyethers, cationic polyamide, polyester, the many ammoniums of many ethene, strong water-soluble contain quaternary ammonium salt.
3. according to the method for preparing the 4-aminodiphenylamine of claim 2, it is characterized in that described alkyl has the tetraalkylammonium salt of hydrophilic substituent group for being selected from many methylated triethylene tetramines vitriol, the diethylenetriamine that methylates carbonate more, N, N-dimethyl-N, N-dimethoxy ethyl ammonium carbonate, N-methyl-N, N, N-trimethoxy ethyl ammonium carbonate, N, N, N-trimethylammonium-N-hydroxyethyl ammonium carbonate, chlorination trimethylammonium hydroxyethyl ammonium, N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) ethyl ammonium carbonate, N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) propyl ammonium carbonate, N, N, N-trimethylammonium-N-ethoxylation (1-4 mole EO) propyl ammonium hydrochloride, N, N-dimethyl-N, the tetraalkylammonium salt that contains hydrophilic substituent of N-two (ethoxylation (1-4 mole EO) propyl group) ammonium carbonate.
4. according to the method for preparing the 4-aminodiphenylamine of claim 1, the condition that it is characterized in that condensation reaction is that the mol ratio of oil of mirbane and aniline is 1: 1-1: 15, and temperature of reaction is 20-150 ℃, reaction pressure is absolute pressure 0.005-0.1MPa, and the reaction times is 3.5-6 hour.
5. according to the method for preparing the 4-aminodiphenylamine of claim 1 or 4, it is characterized in that the mol ratio of hydroxide ion and oil of mirbane is 1 in the compound alkaline catalysts: 4-4: 1.
6. according to the method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that the mol ratio of tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt in the compound alkaline catalysts=(0-9): (0.5-3): (0.5-3), tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt three concentration expressed in percentage by weight summation are 10%-100%.
7. according to the method for preparing the 4-aminodiphenylamine of claim 6, it is characterized in that the compound alkaline catalysts that is adopted prepares by the following method: controlled temperature is at 0-90 ℃, tetraalkylammonium hydroxide, alkali metal hydroxide or oxide compound, tetraalkylammonium salt molar ratio is on request stirred in water, promptly get aqueous compound alkaline catalysts, wherein said raw material tetraalkylammonium hydroxide, alkali metal hydroxide or oxide compound, tetraalkylammonium salt are solid form or aqueous solution form.
8. according to the method for preparing the 4-aminodiphenylamine of claim 6, it is characterized in that described compound alkaline catalysts prepares by the following method: controlled temperature is at 0-90 ℃, tetraalkylammonium hydroxide, alkali metal hydroxide or oxide compound, tetraalkylammonium salt molar ratio is on request stirred in water, add benzene azeotropic then and slough moisture fully, obtain not having water combined alkaline catalysts, wherein said raw material tetraalkylammonium hydroxide, alkali metal hydroxide or oxide compound, tetraalkylammonium salt are solid form or aqueous solution form.
9. according to the method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that described tetraalkylammonium salt, react in polar solvent by trialkylamine and dialkyl carbonate (C1-C2) ester or sulfuric acid dialkyl group (C1-C2) ester and make.
10. the method for preparing the 4-aminodiphenylamine according to claim 9 is characterized in that preparing in the reaction of described tetraalkylammonium salt, and reaction pressure is 0.1-3MPa; Temperature of reaction is 50-200 ℃; Reaction times is 1.5-6 hour; The mol ratio of trialkylamine and dialkyl carbonate (C1-C2) ester or sulfuric acid dialkyl group (C1-C2) ester is 2: 1-1: 2; Selected polar solvent is methyl alcohol, ethanol or Virahol; The consumption of polar solvent be trialkylamine weight 1-10 doubly.
11., it is characterized in that condensation reaction carries out under oxygen free condition according to the method for preparing the 4-aminodiphenylamine of claim 1.
12. the method for preparing the 4-aminodiphenylamine according to claim 1 is characterized in that in the condensation reaction, need not control the proton material.
13. the method for preparing the 4-aminodiphenylamine according to claim 1 is characterized in that in the condensation reaction solvent-free.
14. the method for preparing the 4-aminodiphenylamine according to claim 1, it is characterized in that only needing in the condensation reaction to add the compound alkaline catalysts of part, only replenish tetraalkylammonium salt and alkali metal hydroxide or two compositions of alkalimetal oxide in the compound alkaline catalysts in the reaction process at the initial stage of reaction.
15., it is characterized in that the condensation operation is to reach in the optional subsequent reactor in the recycle system that is formed by condensation recycle pump, falling film reactor and A reactor to carry out according to the method for preparing the 4-aminodiphenylamine of claim 1.
16., it is characterized in that the heating agent of described falling film reactor adopts alcohol vapor, hot water, steam or methanol vapor according to the method for preparing the 4-aminodiphenylamine of claim 15.
17. the method for preparing the 4-aminodiphenylamine according to claim 1, the condition that it is characterized in that hydrogenation is: employing hydrogen is reductive agent, gas-liquid volume ratio is 10: 1-1500: 1, the solid-liquid weight ratio is 0.5: 100-16: 100, solvent and condensated liquid weight ratio are 1: 10-5: 10, gas refers to hydrogen, liquid comprises solvent and condensated liquid, solid refers to composite powder powder catalyzer, the temperature of hydrogenation is 50-100 ℃, the pressure of reactor is absolute pressure 0.2-3.0MPa, and the reaction times is 2-7 hour.
18. the method for preparing the 4-aminodiphenylamine according to claim 1, it is characterized in that the composite powder powder catalyst pack that hydrogenation adopts is nickeliferous, aluminium and elements A, described A is selected from least a among Fe, Cu, Co, Mn, Cr, Mo, B and the P, wherein the weight percentage of nickel is 25%-99.9%, and the gross weight percentage composition of aluminium and elements A is 0.1%-75%.
19. the method for preparing the 4-aminodiphenylamine according to claim 18, it is characterized in that the composite powder powder catalyzer that hydrogenation adopts prepares by the following method: with nickel powder, aluminium powder and elements A are by after the required mixed, fusion at high temperature, pulverize powdered after the quenching discharging, handle with hydroxide aqueous solution then.
20., it is characterized in that utilizing magnetic separator to reclaim the composite powder powder catalyzer of magnetic behind the hydrogenation according to the method for preparing the 4-aminodiphenylamine of claim 1 or 18.
21. according to the method for preparing the 4-aminodiphenylamine of claim 1 or 18, it is characterized in that, send the composite powder powder catalyzer that reclaims back to hydrogenation reactor by reinforced power by Venturi-type solid-liquid mix conveying appliance.
22., it is characterized in that the composite powder powder catalyzer of inactivation is regenerated by vibration of ultrasonic wave and/or with the highly basic processing according to the method for preparing the 4-aminodiphenylamine of claim 1 or 18.
23. according to the method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that solvent that hydrogenation uses as alcohols or/and water.
24. the method for preparing the 4-aminodiphenylamine according to claim 1, it is characterized in that the hydride behind the hydrogenation helps the water extraction agent of extraction agent to extract with comprising polyethers, wherein the volume ratio of extraction agent and hydride is 0.5: 1-5: 1, extracted time 2-5 hour.
25. the method for preparing the 4-aminodiphenylamine according to claim 24, it is characterized in that described polyethers helps extraction agent to be selected from polyglycol ether, polypropylene glycol ether and fatty alcohol-polyoxyethylene ether, and composition thereof, the volume ratio of itself and water extraction agent is 0.0001: 1-0.005: 1.
26., it is characterized in that the water that obtains after the hydride extraction adopts one or more levels gas to help the stream falling-film evaporator to concentrate and reclaims compound alkaline catalysts according to the method for preparing the 4-aminodiphenylamine of claim 1.
27. the method for preparing the 4-aminodiphenylamine according to claim 26, it is characterized in that described gas helps the stream falling-film evaporator to comprise shell side (2 '), tube side (3 '), be installed in the steam inlet (8 ') of shell side (2 ') upper end, be installed in the vapor condensation water out (1 ') of shell side (2 ') lower end, be installed in the lower concentration water import (6 ') at tube side (3 ') top, be installed in the high density water outlet (9 ') of tube side (3 ') bottom, be installed in helping of tube side (3 ') top and flow steam inlet (5 ', 7 '), be installed in the distributing disc (4 ') of lower concentration water import (6 ') below.
28. according to the method for preparing the 4-aminodiphenylamine of claim 26 or 27, it is characterized in that the pressure when water concentrates is absolute pressure 0.005-0.1MPa, the residence time is 2-60 second, helps the stream vapor pressure to remain on 0.01-0.5MPa.
29. the method for preparing the 4-aminodiphenylamine according to claim 1, it is characterized in that refining three tower continuous rectifications and the batch fractionating of adopting, wherein the vacuum tightness of 1,2, No. 3 rectifying tower is 0.09-0.098MPa independently of one another, tower still temperature is respectively 260-290 ℃, 260-300 ℃ and 120-170 ℃, reflux ratio is respectively 2: 1-10: 1,1: 0.5-1: 4 and 1: 0.5-1: 2, the tower still vacuum tightness of batch fractionating is 0.09-0.098MPa, and tower still temperature is 280-330 ℃.
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| JP4500302B2 (en) | 2003-07-04 | 2010-07-14 | チアンス・シノケム・テクノロジー・カンパニー・リミテッド | Method for producing 4-aminodiphenylamine |
| CN102259029B (en) * | 2010-05-24 | 2014-12-10 | 江苏圣奥化学科技有限公司 | Solid alkali catalyst |
| CN108623475A (en) * | 2017-03-20 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of method that quaternary ammonium alkali collection puts recycling in order |
| CN108558675A (en) * | 2018-04-25 | 2018-09-21 | 南通理工学院 | Synthesis method of 4-aminodiphenylamine |
| CN112300007B (en) * | 2019-07-26 | 2023-06-13 | 中石化南京化工研究院有限公司 | Catalytic hydrogenation method for 4-nitrodiphenylamine and 4-nitrosodiphenylamine-containing condensate |
| CN114409550B (en) * | 2022-02-14 | 2023-10-13 | 万华化学集团股份有限公司 | Quaternary ammonium salt type cationic antistatic agent and preparation method and application thereof |
| CN115318280B (en) * | 2022-07-25 | 2023-05-30 | 万华化学（宁波）有限公司 | Method for regenerating and recovering catalyst and byproduct o-aminophenol from aniline tar |
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| CN1460673A (en) * | 2003-07-04 | 2003-12-10 | 王农跃 | Method for preparing 4-aminodiphenylamine |
| CN1460674A (en) * | 2003-07-04 | 2003-12-10 | 兰溪市钱塘合成新材料有限公司 | Method for preparing tetraalkylammonium hydroxide |
| CN1470330A (en) * | 2003-07-04 | 2004-01-28 | 郭长玉 | Composite base catalyst and its preparing method |
| CN1475476A (en) * | 2003-07-04 | 2004-02-18 | 茅晓晖 | Separation method of composition containing 4-aminodiamine and its equipment |
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| CN1460673A (en) * | 2003-07-04 | 2003-12-10 | 王农跃 | Method for preparing 4-aminodiphenylamine |
| CN1460674A (en) * | 2003-07-04 | 2003-12-10 | 兰溪市钱塘合成新材料有限公司 | Method for preparing tetraalkylammonium hydroxide |
| CN1470330A (en) * | 2003-07-04 | 2004-01-28 | 郭长玉 | Composite base catalyst and its preparing method |
| CN1475476A (en) * | 2003-07-04 | 2004-02-18 | 茅晓晖 | Separation method of composition containing 4-aminodiamine and its equipment |
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