CN104844436B - 一种香兰素的清洁生产方法 - Google Patents
一种香兰素的清洁生产方法 Download PDFInfo
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- CN104844436B CN104844436B CN201510270186.7A CN201510270186A CN104844436B CN 104844436 B CN104844436 B CN 104844436B CN 201510270186 A CN201510270186 A CN 201510270186A CN 104844436 B CN104844436 B CN 104844436B
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- acid
- solution
- silver powder
- vanillic aldehyde
- reaction
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 70
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 239000010946 fine silver Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 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 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 22
- OLSDAJRAVOVKLG-UHFFFAOYSA-N 3-hydroxymandelic acid Chemical compound OC(=O)C(O)C1=CC=CC(O)=C1 OLSDAJRAVOVKLG-UHFFFAOYSA-N 0.000 claims description 20
- 229940073735 4-hydroxy acetophenone Drugs 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000006482 condensation reaction Methods 0.000 claims description 15
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 14
- XHUBSJRBOQIZNI-UHFFFAOYSA-N (4-Hydroxy-3-methoxyphenyl)ethanol Chemical compound COC1=CC(CCO)=CC=C1O XHUBSJRBOQIZNI-UHFFFAOYSA-N 0.000 claims description 13
- 229960001867 guaiacol Drugs 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
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- 241000732800 Cymbidium Species 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000012485 toluene extract Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- -1 methoxyl group Chemical group 0.000 abstract description 8
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- VKVOJYUPJRVDPP-UHFFFAOYSA-N 2,2-dihydroxy-2-phenylacetic acid Chemical compound OC(=O)C(O)(O)C1=CC=CC=C1 VKVOJYUPJRVDPP-UHFFFAOYSA-N 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
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- 238000003786 synthesis reaction Methods 0.000 description 7
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 7
- 235000012141 vanillin Nutrition 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 235000015424 sodium Nutrition 0.000 description 5
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229940107700 pyruvic acid Drugs 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- GRNCTJVYPJXPAY-UHFFFAOYSA-N 2-methoxyphenol;sodium Chemical compound [Na].COC1=CC=CC=C1O GRNCTJVYPJXPAY-UHFFFAOYSA-N 0.000 description 1
- HBMCQTHGYMTCOF-UHFFFAOYSA-N 4-hydroxyphenyl acetate Chemical compound CC(=O)OC1=CC=C(O)C=C1 HBMCQTHGYMTCOF-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229940047586 chemet Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000016768 molybdenum Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开一种采用硝酸银在碱性条件下氧化3‑甲氧基‑4‑羟基苯乙醇酸联合生产香兰素和超细银粉的清洁生产方法。采用向反应器中并流加入硝酸银溶液、3‑甲氧基‑4‑羟基苯乙醇酸溶液和氢氧化钠溶液,反应生成3‑甲氧基‑4‑羟基苯乙酮酸钠溶液和超细银粉,过滤分离生成的银粉,先后用去离子水和乙醇洗涤,干燥后得到超细银粉,银粉还原收率99.4%‑100%。将分离银粉后的滤液酸化,3‑甲氧基‑4‑羟基苯乙酮酸脱羧基生成香兰素,用甲苯萃取其中的香兰素,回收甲苯溶剂,残留物在乙醇水溶液中重结晶得到香兰素,甲氧基‑4‑羟基苯乙醇酸氧化收率为95.7%‑98.5%。本发明以硝酸银为氧化剂制备香兰素,提高了氧化收率和缩短了氧化反应时间。本发明能同时制备二种实用精细化工产品,原料得到充分利用,减少了废弃物产生,生产成本降低,工艺过程安全环保。
Description
技术领域
本发明涉及一种香兰素的清洁生产方法,特别是用硝酸银在碱性条件下氧化3-甲氧基-4-羟基苯乙醇酸联合生产香兰素和超细银粉的清洁生产方法,可同时得到二种实用精细化工产品,属于化工新材料和环境保护领域。
背景技术
香兰素(英文名Vanillin),化学名3-甲氧基-4-羟基苯甲醛,化学式C8H8O3,分子量152.2,为白色针状结晶,熔点81-83℃,沸点284℃,微溶于水,溶于乙醇和氯仿中,具有香荚兰香气及浓郁的奶香。香兰素是世界上生产量最大的合成香料之一, 也是合成药物和化工产品的重要中间体,中国香兰素生产能力2.5万吨,已成为世界最大的香兰素生产国。
香兰素工业生产路线很多,从生产成本和环境保护考虑,目前国内外普遍采用乙醛酸法工艺路线。发明人曾在《江苏化工》1993年,第3期,第13-16页详细介绍了乙醛酸法合成香兰素工艺研究情况。愈创木酚与乙醛酸在碱性条件下缩合生成3-甲氧基-4 -羟基苯乙醇酸,它在碱性条件下被铜离子氧化生成3-甲氧基-4-羟基苯乙酮酸,然后在酸性条件下脱去羧基生成香兰素,优化缩合反应温度为50-80℃,原料乙醛酸、愈创木酚和氢氧化钠摩尔比为1:1.5-2:2-3 ,缩合反应液的pH 8-11 ,缩合反应时间1.5-3小时,缩合反应收率74%-78% 。优化的氧化反应温度为85-95℃,氧化反应液pH10-11,氧化反应时间5-7小时,氧化产率89.5%-93.5%。
吉化集团公司在中国专利 CN101012161(2007-08-08)中披露了对乙醛酸法合成香兰素缩合反应的改进,采用季胺盐类催化剂,原料乙醛酸、愈创木酚和氢氧化钠摩尔比为1:1.1-1.2:2.2-2.3 ,优化的缩合温度为27-29℃,缩合反应时间为3.5-5小时,缩合反应收率81.3%-85.8%。吉化集团公司在中国专利 CN1537675(2004-10-20) 中披露了对乙醛酸法合成香兰素氧化反应的改进,采用含钼元素的多元催化剂,优化的氧化反应温度为91-95℃,氧化反应时间7-8小时,氧化反应收率95.0%-98.7%。
乙醛酸法合成香兰素工艺路线国外上世纪七十年代就实现了工业化,日本公开特许公报JP5404463(1979-04-09)和美国专利US4165341(1979-08-21) 披露了用硅、铝及其化合物作缩合催化剂合成香兰素3-烷氧基-4-羟基苯乙醇酸工艺,日本公开特许公报JP55022614(1980-02-18)和JP49034975(1974-09-19) 披露了用铜、钴、铈、铁、铬、钼等元素的化合物作氧化催化剂合成香兰素工艺。
国内外乙醛酸法合成香兰素生产规模和技术水平不断提高,但生产成本居高不下,企业生产效益并没有相应提高,主要是实际合成收率和反应时间与实验室研究结果相差很大。例如,香兰素工业生产中采用空气催化氧化法,氧化反应收率86%-90%,氧化反应时间12-24小时,由于香兰素合成中间体3-甲氧基-4-羟基苯乙醇酸不够稳定,在较高温度下长时间的氧化过程中存在比较严重的分解或聚合现象。
研究发现如果采用氧化铜进行化学氧化,则氧化反应收率高达98%以上,氧化反应时间仅1.5-2.5小时,存在的问题是生成的氧化亚铜以胶体形式存在,很难与反应液分离和实现循环使用,需要选择氧化反应完成后容易比较分离的氧化剂。采用氧化银进行氧化可望解决氧化反应时间长、氧化收率低和超细银粉分离的难题,但如果不能解决超细银粉的再利用问题,则生产成本比较高。
银粉是电子产业中应用最为广泛和用量最大的一种贵金属粉末,是生产触摸屏等各种电子元器件产品的基本和关键功能材料。电子信息产业的迅速发展,带动了超细银粉及导电浆料市场的发展。银粉也是太阳能电池导电银浆的重要组成部分,太阳能电池产业的快速发展进一步促进了超细银粉的市场需求。导电银浆成膜后的高导电率和致密性等关键技术指标主要由超细银粉的性能决定的,而超细银粉性能主要取决于其形貌结构特征、粉末的粒度及其分布等形态特征。对于太阳能电池导电银浆,只有符合特定条件的银粉配制的导电浆料才具备良好的丝网印刷性能,经过烧结后才能形成具有较高方阻和细栅线的正面银电极。
银粉的制备方法有高能球磨法、喷雾热分解法(SP法)、等离子体蒸发冷凝法、化学液相还原法和微乳液法等,其中化学液相还原法因生产设备简单、工艺比较容易控制、低成本、低能耗等优点得到了广泛重视。
美国CHEMET公司专利US4456474(1984-06-26)公开了超细银粉制备的传统工艺,将硝酸银水溶液通过高压喷头雾化喷入高速搅拌下的含有铜离子、表面活性剂、水合肼的氢氧化铵水溶液中,在常温下反应15-40分钟,过滤分离沉淀,水洗,干燥,得到0.6 - 2.5μm,比表面积0.6-2.0m2/g的高纯银粉。针对传统方法是间歇式工艺和产品质量不够稳定的缺点,台湾科学院专利US5413617(1995-05-09)公开一种可控制比表面积的银粉制备工艺,先将含表面活性剂和水合肼还原剂的水溶液与银氨溶液连续加入低温反应槽,在5-20℃下反应7-60分钟,然后转入高温反应槽,在40-60℃下继续完成反应,过滤分离沉淀,得到微细银粉。
在微细银粉制备的还原反应过程中,还原剂的选择非常重要,文献报道的银粉制备无机还原剂主要有水合肼、羟胺、双氧水、次亚磷酸钠、连二亚硫酸钠、硼氢化钠、硫酸亚铁、亚硫酸钾等,其中水合肼还原剂受到广泛重视和深入研究;文献报道的银粉制备有机还原剂主要有抗坏血酸、甲醛、甲酸、酒石酸钾钠、乙醇、甘油、葡萄糖、还原糖、三乙醇胺、氢醌等,其中甲醛和抗坏血酸还原剂受到广泛重视和深入研究。
微细银粉制备还原剂存在的不足包括:(1)还原剂水合肼、甲醛和氢醌有毒,刺激性很强,环保和安全方面问题突出;(2)还原剂硼氢化钠、氢醌成本过高,影响银粉生产效益;(3)还原剂抗坏血酸对还原体系酸度、浓度和温度等条件变化敏感,生产条件不易控制;(4)大多数还原剂需要与大量分散剂配合使用,导致后续的银粉分离困难;(5)常用还原剂的投料比过大,缺少安全稳定的新型还原剂。
在以上超细银粉生产工艺中,还原剂被氧化生成大量无用的废弃物,这些污染物的处理过程比较麻烦,目前仅因为产品生产的高附加值和生产规模较小,环境污染问题没有受到充分重视。随着超细银粉市场需求和生产规模不断扩大,急需要开发能够将还原剂有效利用的清洁生产工艺。
发明内容
本发明的目的是提供一种采用硝酸银在碱性条件下氧化3-甲氧基-4-羟基苯乙醇酸联合生产香兰素和超细银粉的清洁生产方法,使反应原料得到充分利用,采取的技术方案和生产步骤为:
(1)向反应瓶中同时滴加乙醛酸、愈创木酚和氢氧化钠溶液,控制投料时原料摩尔比为:乙醛酸:愈创木酚:氢氧化钠 = 1:1.0-1.2:2-5,控制温度为20-40℃和pH11-13下加料1-2小时,加料完成后继续反应4-6小时结束缩合反应;
(2)用质量百分浓度为10%的硫酸中和缩合反应液至pH5-6,用甲苯萃取分离未转化的愈创木酚,得到香兰素合成中间体3-甲氧基-4-羟基苯乙醇酸(MHMA)缩合反应液,测定其中MHMA的含量;
(3)向带搅拌的玻璃反应器中并流加入硝酸银溶液、氢氧化钠溶液和3-甲氧基-4-羟基苯乙醇酸溶液,反应生成3-甲氧基-4-羟基苯乙酮酸钠溶液和超细银粉,控制原料摩尔比为:硝酸银:MHMA:氢氧化钠 = 1:0.45-0.50:1.0-1.2,加料速度控制在保持反应液中生成的沉淀为灰白色,维持反应液温度20-40℃和pH11-13下反应0.5-1小时;
(4)投料完成后升高温度至50-60℃,继续搅拌反应0.5-1小时,使MHMA完全氧化,再 加入甲酸使过量的硝酸银还原回收,控制硝酸银和甲酸摩尔比为1:0.02-0.1;
(5)过滤分离生成的银粉,先后用去离子水和乙醇洗涤,在80℃下干燥得到超细银粉产品,银粉颗粒呈近球状,表面光滑和有光泽,粒径分布窄,平均粒径 1.2-1.8μm,振实密度 4.7-5.2g/mL,质量符合太阳能电池银浆制备要求,以硝酸银计的摩尔收率为99.4%-100%;
(6)在搅拌下向分离银粉后的滤液中加入质量百分浓度为10%的硫酸,使溶液酸化至pH1-2,溶液中的3-甲氧基-4-羟基苯乙酮酸脱羧基生成香兰素,控制脱羧反应温度30-50℃;
(7)用甲苯萃取脱羧反应液中的香兰素,有机相用少量水洗,测定其中香兰素含量,以MHMA计的摩尔收率为96.8%-98.5%;
(8)减压蒸馏有机相回收甲苯溶剂,将残留物在乙醇水溶液中重结晶得到白色香兰素。
本发明中原料硝酸银是试剂硝酸银或将工业银溶于过量硝酸制得的硝酸银溶液,工业硝酸银原料中掺杂的少量硝酸对发明实施没有影响。
本发明中香兰素合成中间体3-甲氧基-4-羟基苯乙醇酸,又名3-甲氧基-4-羟基扁桃酸,分子结构中有活泼的羟基和羧基,容易氧化生成3-甲氧基-4-羟基苯乙酮酸,这些多官能团化合物具有银粉制备分散剂作用,即使没有外加有机分散剂,也可以将银晶粒尺寸限制在微米或亚微米范围。
本发明硝酸银氧化3-甲氧基-4-羟基苯乙醇酸,同时制备3-甲氧基-4-羟基苯乙酮酸和银粉在碱性条件下进行,反应中需要不断加入氢氧化钠或氢氧化钾溶液控制反应液pH11-13,反应液碱度过高时,后续酸化需要消耗大量酸液,同时使银粉过细和不易分离。
由于3-甲氧基-4-羟基苯乙醇酸生产成本高,应尽量选择硝酸银过量,使MHMA完全氧化转化,过量硝酸银的可用少量甲酸还原为银粉回收。本发明反应的开始阶段,加入的原料硝酸银溶液直接与MHMA反应形成黑色银晶核和3-甲氧基-4-羟基苯乙酮酸;在后续反应阶段,原料硝酸银溶液首先与反应液中含有的3-甲氧基-4-羟基苯乙酮酸反应生成3-甲氧基-4-羟基苯乙酮酸银配位体,3-甲氧基-4-羟基苯乙酮酸银再和MHMA反应生成银原子和生成3-甲氧基-4-羟基苯乙酮酸,还原生成的银原子在先前形成的银晶核上均匀生长为几微米的银晶粒,3-甲氧基-4-羟基苯乙酮酸银配位体的形成和进一步还原成银原子的反应循环进行。
本发明反应过程比较复杂,实际参加还原反应的不一定是丙酮酸银配位体,可以是其离解形成的少量银离子,银离子浓度主要由丙酮酸银配位体稳定常数决定,受硝酸银加入速度和反应温度影响较小,由于银离子浓度比较稳定,还原反应条件容易控制。
本发明中MHMA氧化生成的3-甲氧基-4-羟基苯乙酮酸作为分散剂在银晶粒表面吸附,可有效地抑制银晶核的过快长大,同时每一个银晶核表面的分散剂吸附层都占据着一定的空间,使已经形成的银晶粒无法聚结,处于充分分散的状态,银粉粒径得以控制。
本发明中3-烷氧基-2-羟基苯乙醇酸和香兰素含量测定采用液相色谱法,采用岛津LC-10液相色谱仪。色谱柱:Kromasil-C18(5μm,250 mm×4.6mm);流动相: 正己烷:异丙醇:冰醋酸=91:4:5( 体积比);流速:1mL/min;检测波长:280nm ;柱温:40℃。
发明的优点和有益效果体现在:
(1)本发明以硝酸银为氧化剂氧化3-甲氧基-4-羟基苯乙醇酸制备香兰素,提高了缩短了氧化反应时间、避免了分解或聚合副反应,提高了氧化收率;
(2)本发明在制备香兰素的同时,能得到适合太阳能电池导电银浆用超细银粉产品,提供了一条超细银粉生产或降低生产成本的新途径;
(3)本发明可同时生产二种实用精细化工产品,原料得到充分利用,减少了废弃物产生,生产成本降低,生产过程安全环保。
具体实施方式
实施例1
将一配有搅拌器、冷凝器和恒压滴液漏斗的1000mL四口反应瓶安装在恒温水浴上,向其中加入59.5g愈创木酚(0.48 mo1)和100mL4.8mol/L的氢氧化钠(0.48 mo1),生成愈创木酚钠溶液,通过二支恒压滴液漏斗中分别加入74.1g40%乙醛酸(0.4mo1)和100mL4.8mol/L的氢氧化钠(0.48 mo1),控制温度为20-40℃和pH11-13下加料1-2小时,加料完成后继续反应4-6小时结束缩合反应。用质量百分浓度为10%的硫酸约200mL中和缩合反应液至pH5-6,,用100mL甲苯分二次萃取其中分离未转化的愈创木酚,得到香兰素合成中间体3-甲氧基-4-羟基苯乙醇酸缩合反应液,测定其中MHMA的含量为0.66mol/L(0.33mo1)。
向带搅拌的玻璃反应器中并流加入硝酸银溶液220 mL3 mol/L (0.66mo1)、氢氧化钠溶液150 mL4.8 mol/L (0.66mo1)和以上3-甲氧基-4-羟基苯乙醇酸溶液,反应生成3-甲氧基-4-羟基苯乙酮酸钠溶液和超细银粉,加料速度控制在保持反应液中生成的沉淀为灰白色,维持反应液温度20-40℃和pH11-13下反应0.5-1小时,投料完成后升高温度至50-60℃,继续搅拌反应0.5-1小时,使MHMA完全反应,再加入6.9g20%甲酸溶液(0.03mo1)使过量硝酸银还原。
过滤分离生成的银粉,先后用300mL去离子水和乙醇洗涤,在80℃下干燥得到超细银粉产品71.0 g,银粉颗粒呈近球状,表面光滑,平均粒径 1.6μm,振实密度 4.8g/mL,质量符合太阳能电池银浆制备要求,以硝酸银计的摩尔收率为99.6%。
在搅拌下向分离银粉后的滤液中加入质量百分浓度为10%的硫酸约400mL,使溶液酸化至pH1-2,溶液中的3-甲氧基-4-羟基苯乙酮酸在酸性条件下脱羧基生成香兰素,控制脱羧反应温度30-50℃。用500mL甲苯分三次萃取脱羧反应液中的香兰素,有机相用少量水洗,测定其中香兰素含量0.64mol/L (0.325mo1) ,以MHMA计的摩尔收率为98.5%。减压蒸馏有机相回收甲苯溶剂,将残留物在乙醇水溶液中重结晶得到白色香兰素49.5 g 。
实施例2
按 实施例同样方法得到香兰素合成中间体3-甲氧基-4-羟基苯乙醇酸缩合反应液,测定其中MHMA的含量为0.66mol/L (0.32mo1)。
向带搅拌的玻璃反应器中并流加入硝酸银溶液237 mL3 mol/L (0.71mo1)、氢氧化钠溶液150 mL4.8 mol/L (0.66mo1)和以上3-甲氧基-4-羟基苯乙醇酸溶液,反应生成3-甲氧基-4-羟基苯乙酮酸钠溶液和超细银粉,加料速度控制在保持反应液中生成的沉淀为灰白色,维持反应液温度20-40℃和pH11-13下反应0.5-1小时,投料完成后升高温度至50-60℃,继续搅拌反应0.5-1小时,使MHMA完全反应,再加入12.0g20%甲酸溶液(0.05mo1)使过量硝酸银还原。
过滤分离生成的银粉,先后用300mL去离子水和乙醇洗涤,在80℃下干燥得到超细银粉产品76.5 g,银粉颗粒呈近球状,表面光滑,平均粒径 1.7μm,振实密度 4.9g/mL,质量符合太阳能电池银浆制备要求,以硝酸银计的摩尔收率为99.8%。
在搅拌下向分离银粉后的滤液中加入质量百分浓度为10%的硫酸约400mL,使溶液酸化至pH1-2,溶液中的3-甲氧基-4-羟基苯乙酮酸在酸性条件下脱羧基生成香兰素,控制脱羧反应温度30-50℃。用500mL甲苯分三次萃取脱羧反应液中的香兰素,有机相用少量水洗,测定其中香兰素含量0.64mol/L (0.31mo1) ,以MHMA计的摩尔收率为96.8%。减压蒸馏有机相回收甲苯溶剂,将残留物在乙醇水溶液中重结晶得到白色香兰素47.2 g。
Claims (1)
1.一种香兰素的清洁生产方法,其特征在于采用硝酸银在碱性条件下氧化3-甲氧基-4-羟基苯乙醇酸联合生产香兰素和超细银粉,使反应原料得到充分利用,采取的技术方案和生产步骤为:
(1)向反应瓶中同时滴加乙醛酸、愈创木酚和氢氧化钠溶液,控制投料时原料摩尔比为:乙醛酸:愈创木酚:氢氧化钠 = 1:1.0-1.2:2-5,控制温度为20-40℃和pH11-13下加料1-2小时,加料完成后继续反应4-6小时结束缩合反应;
(2)用质量百分浓度为10%的硫酸中和缩合反应液至pH5-6,用甲苯萃取分离未转化的愈创木酚,得到香兰素合成中间体3-甲氧基-4-羟基苯乙醇酸(MHMA)缩合反应液,测定其中MHMA的含量;
(3)向带搅拌的玻璃反应器中并流加入硝酸银溶液、3-甲氧基-4-羟基苯乙醇酸溶液和氢氧化钠溶液,反应生成3-甲氧基-4-羟基苯乙酮酸钠溶液和超细银粉,控制原料摩尔比为:硝酸银:MHMA:氢氧化钠 = 1:0.45-0.55:1.0-1.2,加料速度控制在保持反应液中生成的沉淀为灰白色,维持反应液温度20-40℃和pH11-13下反应0.5-1小时;
(4)投料完成后升高温度至50-60℃,继续搅拌反应0.5-1小时,使MHMA完全氧化,再 加入甲酸溶液使过量的硝酸银还原回收,控制硝酸银和甲酸摩尔比为1:0.02-0.1;
(5)过滤分离生成的银粉,先后用去离子水和乙醇洗涤,在80℃下干燥得到超细银粉产品,质量符合太阳能电池银浆制备要求,以硝酸银计的银粉摩尔收率为99.4%-100%;
(6)在搅拌下向分离银粉后的滤液中加入质量百分浓度为10%的硫酸,使溶液酸化至pH1-2,溶液中的3-甲氧基-4-羟基苯乙酮酸脱羧基生成香兰素,控制脱羧反应温度30-50℃;
(7)用甲苯萃取脱羧反应液中的香兰素,有机相用少量水洗,测定其中香兰素含量,以MHMA计的摩尔收率为96.8%-98.5%;
(8)减压蒸馏有机相回收甲苯溶剂,将残留物在乙醇水溶液中重结晶得到白色香兰素。
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