CN1403428A - Catalytic hydrogenation and dehalogenation process of phenoxy phenol halide compound - Google Patents
Catalytic hydrogenation and dehalogenation process of phenoxy phenol halide compound Download PDFInfo
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- CN1403428A CN1403428A CN 02132909 CN02132909A CN1403428A CN 1403428 A CN1403428 A CN 1403428A CN 02132909 CN02132909 CN 02132909 CN 02132909 A CN02132909 A CN 02132909A CN 1403428 A CN1403428 A CN 1403428A
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- dehalogenation method
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title description 5
- -1 phenoxy phenol halide compound Chemical class 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 150000002989 phenols Chemical class 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- 150000008282 halocarbons Chemical class 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003586 protic polar solvent Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000007529 inorganic bases Chemical class 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 239000003849 aromatic solvent Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 125000000951 phenoxy group Polymers [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 37
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical class OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000006298 dechlorination reaction Methods 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000004904 shortening Methods 0.000 description 9
- 229960003500 triclosan Drugs 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KZNRNQGTVRTDPN-UHFFFAOYSA-N 2-chloro-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(Cl)=C1 KZNRNQGTVRTDPN-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 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
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
一种多卤代苯氧基卤代苯酚类化合物的催化加氢脱卤方法，采用过渡金属催化剂，使卤代烃在常温、常压、液相溶剂中加氢反应，该催化剂是由活性组份与载体组成。活性组份是Pd、Rh、Pt、Ni、Co、Fe、Zn、Cd、Ir中的一种或多种，活性组份占催化剂总量的0.5％～5.0％。反应压力为0.05MPa～1.0MPa，反应温度控制在20－120℃。本发明制备简单，不需要特殊设备。脱卤反应条件温和，操作易于控制，催化剂用量少，卤素的去除率高。A method for catalytic hydrodehalogenation of polyhalogenated phenoxyhalogenated phenol compounds, using a transition metal catalyst to hydrogenate halogenated hydrocarbons at normal temperature, normal pressure, and in a liquid phase solvent. The catalyst is composed of an active group Parts and carrier composition. The active component is one or more of Pd, Rh, Pt, Ni, Co, Fe, Zn, Cd and Ir, and the active component accounts for 0.5%-5.0% of the total amount of the catalyst. The reaction pressure is 0.05MPa-1.0MPa, and the reaction temperature is controlled at 20-120°C. The preparation of the present invention is simple and does not require special equipment. The dehalogenation reaction conditions are mild, the operation is easy to control, the amount of catalyst is small, and the removal rate of halogen is high.
Description
Background technology
The present invention relates to a kind of method of shortening dehalogenation of phenyl polyhalide oxygen base halogenated phenol compounds.
Technical field
The triclosan compounds is a class phenyl polyhalide oxygen base halogenated phenol compounds, and its structural formula is:
X=Cl wherein, Br, m=1～4, n=1～5
As sterilant, degerming agent, structurally Yu dioxin, polychlorobiphenyl are closely similar, under illumination or heating condition, are easy to form dioxin, therefore are known as dioxin precursor compound (Predioxins) by widely for this triclosan compounds.This compounds is in nature degraded difficulty, and accumulation in vivo damages the mankind easily, is discharged in the environment and can pollutes.
The heterogeneous catalyzed hydration dehalogenation method not only early has application in the production of fine chemicals, and important use is also arranged in environment protection, it can will be difficult to the high toxicity of handling with ordinary method or cause that the halohydrocarbon of serious environmental pollution is converted into tractable or recycling compound; For example it has been applied in the catalytic hydrogenation and dechlorinations of organochlorine for environmental pollutant such as chloroparaffin, chlorobenzene, chlorophenol, polychlorobiphenyl.Common hydrogenation catalyst is with group VIII metal (loading on the inorganic carrier) or title complex, carries out catalytic hydrogenation reaction with alcohol, organic acid salt or hydrogen as hydrogen source.European patent (1990, EP 352,164) is with Pd (OAc)
2Be catalyzer, at PPh
3And NEt
3Exist down, chlorobenzene and the reaction of hydrogen generation hydrodehalogenation generate benzene, and transformation efficiency only is 41%; United States Patent (USP) (1986, US 4,618,686) is catalyzer with Pd/C, adds phosphoric acid salt again, can make the polychlorinated biphenyl dechlorination; United States Patent (USP) (1971, US 3,595,931) is used Pd/Al
2O
3As catalyzer, in the presence of KOH, make 2-chloro-p-Xylol and hydrogen at high temperature carry out the gas-phase reaction of catalytic hydrogenation and dechlorination, generate dimethylbenzene, transformation efficiency is near 100%, and transformation efficiency is lower during low temperature.
Although the heterogeneous catalytic hydrogenation method has been used for the dehalogenation degraded of environment halogenated organic pollutent, about the document and the patent of triclosan compounds hydrodehalogenation are not appeared in the newspapers.
Summary of the invention
The purpose of this invention is to provide under a kind of mild conditions the method for above-mentioned phenyl polyhalide oxygen base halogenated phenol compounds reductive dehalogenation, make these dioxin precursor compounds effective dehalogenation in liquid phase solvent, and the product behind the hydrodehalogenation can be reclaimed.
For achieving the above object, the invention provides and a kind ofly under mild conditions, phenyl polyhalide oxygen base halogenated phenol compounds is carried out the shortening dehalogenation, adopt highly active transition metal loaded catalyst, as reductive agent, make phenyl polyhalide oxygen base halogenated phenol compounds in low temperature, normal pressure, liquid phase, carry out the method for shortening dehalogenation with hydrogen.
Shortening dehalogenation to halogenated organic compounds is to reduce such organic compound toxicity, reduce the important method of environmental pollution, the general metallic element of selecting is as the activity of such catalysts component, the group VIII metal component is for other metal components, hydrogen had higher absorption and activation, can under the condition of gentleness, activate hydrogen and C-Cl key, reduce the activation energy of reaction, thereby made hydrodehalogenation become possibility.The existence of carrier can reduce the grain fineness number of metal component, and active constituent is uniformly dispersed, and has increased the surface-area of active constituent, has saved the consumption of active constituent, has reduced cost, and the active centre is provided, and has also improved the stability of catalyzer simultaneously.The present invention selects gac, aluminium sesquioxide, silica gel etc. as carrier, with the group VIII metallic element as active ingredient, comprise Pd, Rh, Pt, Ni, Co, Fe, Zn, Cd, Ir etc., the consumption of active constituent is generally 0.5%～5% of catalyst quality, and wherein the loaded catalyst of Pd, Rh, Pt, Ni isoreactivity component is best.
In the liquid phase catalytic hydrogenation dechlorination reaction, choice of Solvent has material impact to reaction, mainly shows dissolving and the dispersive ability of solvent to reactant, to the dissolving power of hydrogen and to the influence of mechanism of catalytic reaction.In the present invention, solvent can be aromaticity solvent such as benzene,toluene,xylene, alkane solvents such as normal hexane, Skellysolve A, sherwood oil, hexanaphthene etc., heterocyclic solvents such as tetrahydrofuran (THF), dioxane, pyridine etc., polar protic kind solvent such as methyl alcohol, ethanol, Virahol, or in these solvents one or more.The dechlorination reaction of triclosan speed of reaction in polar aprotic solvent and non-polar solvent is the fastest, and its polar protic solvent is the best to select the dehydrated alcohol system, and non-polar solvent is the best to select normal hexane.Add entry in ethanol, can further improve speed of reaction, add fast response and carry out, in mole, dehydrated alcohol and water ratio control are between 2: 1～1: 2 scope, and pure water optimum amount ratio is 0.8: 1～1: 0.8.
Temperature and pressure also is the important factor that influences the shortening dehalogenation, in catalyzed reaction, and 10 ℃ of every risings, speed of reaction just increases by 2～4 times, but temperature is too high, also can increase energy expenditure, also can cause catalyst active center to assemble, the increase of grain fineness number has reduced reactive behavior.In hydrodehalogenation reaction catalyzed, pressure increases, help the dissolving of hydrogen in solvent, this will help the carrying out that react, but concerning the shortening dehalogenation, can generate hydrogen halide in the reaction process, too high pressure will help the carrying out of reversed reaction, this will be disadvantageous to the hydrodehalogenation reaction, therefore must select suitable temperature and pressure.Temperature of reaction of the present invention is controlled at 20～120 ℃, 50～70 ℃ of the bests; Reaction pressure is that 0.05MPa～1.0MPa is preferable, and optimum pressure is 0.05MPa～0.15MPa.
In shortening dehalogenation process, the hydrogen halide that generates makes the serious inactivation of catalyzer, has influenced shortening dehalogenation generation to carry out, and alkali can solve the inactivation of catalyzer effectively as the absorption agent of hydrogen halide, the effect of promotor is also played in the adding of alkali in addition, has further accelerated the carrying out of reaction.Acid absorber can be mineral alkali such as sodium hydroxide, sodium bicarbonate, yellow soda ash, potassium hydroxide, ammoniacal liquor etc. among the present invention, also can be organic bases such as pyridine, pyrroles, triethylamine, diethylamine, ethamine, thanomin etc., perhaps one or more in these alkali; Selecting triethylamine the best, with sodium hydroxide the best, consumption is in mole in the ethanol aqueous systems in ethanol system, the mol ratio of mineral alkali and halogen species be 2: 1～1: 4 preferable, 0.8: 1～1: 0.8th, the best, organic bases is excessive to be good.Through the hydrogenation place to after the decreasing ratio of phenyl polyhalide oxygen base halogenated phenol compounds halogen in the short period of time just can reach 100%, reaction system adds alkali and has improved dechlorination reaction speed, has also improved catalyst stability.
Method provided by the present invention, the precious metal of its use and transition metal loaded catalyst are active high, and preparation is simple, does not need specific installation.Dehalogenation reaction mild condition, operation is easy to control, and catalyst levels is few, and the clearance height of halogen is a kind of method of simple and effective degraded phenyl polyhalide oxygen base halogenated phenol compounds.
Embodiment
Elaborate the present invention below by example.
Example 1, Preparation of catalysts
A certain amount of Palladous chloride is dissolved in the concentrated hydrochloric acid, is impregnated into behind the dilute with water in the gac, again evaporate to dryness under constantly stirring.With the solid that the obtains logical hydrogen reduction in back that is crushed into powder, sealing is preserved then, obtains the palladium/carbon catalyst of different content.The palladium/carbon catalyst of different content is listed in table 1
Example 2, according to example 1 described Preparation of catalysts process, except that active constituent with carrier is different, remaining process is all identical, prepares the loaded catalyst of different carriers, different activities component, the catalyzer of preparation is listed in table 1.
The catalyzer of table 1 different carriers, different activities component
The active constituent carrier
Pd Rh Pt Ni
0.5％Rh， 0.5％Pt，
0.5％Pd，2.0％Pd，5.0％Pd
2.0%Ni, gac
2.0％Rh， 2.0％Pt，
1.0％Pd-5.0％Ni，1.0％Pd
5.0％Ni
5.0％Co，1.0％Pd-1.0％Rh
5.0%Rh 5.0%Pt three oxygen 2.0%Pd, 2.0%Rh, 2.0%Pt, 2.0%Ni changes two aluminium 5.0%Pd 5.0%Rh 5.0%Pt 5.0%Ni
2.0%Pd, 2.0%Rh, 2.0%Pt, 2.0%Ni, silica gel
5.0％Pd 5.0％Rh 5.0％Pt 5.0％Ni
The preparation of example 3, Raney Ni (Raney nickel)
A certain amount of NaOH is soluble in water, outside in the beaker of packing into ice-cooled.The Ni-Al alloy that adds a certain amount of grinding powder is constantly adding on a small quantity one by one under the stirring condition, till adding.At 115-120 ℃ of following heating 4h, add 440 milliliters NaOH solution again, keep after for some time until no longer including H
2Generate, add entry after the cooling.Remove upper clear supernate with decantation, add water again and stir, treat that post precipitation removes upper clear supernate again, cleaning catalyst so repeatedly, till washing lotion is neutral reaction to stone class reagent, use 95% washing with alcohol then 5 times, be stored in the ethanol with the glass stopper capping.
Triclosan hydrodechlorination in example 4, the different solvents
Take by weighing the 5%Pd/C catalyzer of 15mg example 1 preparation, join in the there-necked flask of 30ml, adding concentration is 2 of 5000ppm, 4,4 '-the adjacent dihydroxy diphenyl ether solution of trichlorine 15ml, the aqueous solution of solvent toluene, tetrahydrofuran (THF), hexanaphthene, normal hexane, ethanol, Virahol and alcohols, temperature of reaction is controlled at 50 ℃, reaction pressure is a normal pressure, is reflected at logical hydrogen under the magnetic agitation, concrete outcome such as table 2.
Triclosan hydrogenation catalyst: 5%Pd/C in table 2 different solvents, temperature: 50 ℃
Solvent mol ratio Cl: Pd reaction times/min dechlorination efficiency %
Toluene 40: 1 180 79
Tetrahydrofuran (THF) 37: 1 180 34
Hexanaphthene 82: 1 120 95
Sherwood oil 78: 1 120 82
Normal hexane 95: 1 30 85
Virahol 101: 1 30 96
Dehydrated alcohol 97: 1 30 95
Alcohol-water 105: 1 30 100
Example 5, differing temps are to the influence of triclosan hydrogenation
Operating process according to example 4, under differing tempss such as 20 ℃, 30 ℃, 50 ℃, 70 ℃, 120 ℃, in dehydrated alcohol, alcohol-water, normal hexane, toluene equal solvent, when catalyzer exists, triclosan can both be by reduction dechlorination well, and the result is as shown in table 3.
Triclosan hydrogenating reduction under table 3 differing temps
Catalyzer: 5%Pd/C
Temperature/℃ solvent mol ratio Cl: Pd reaction times/min dechlorination efficiency %
25 alcohol-waters 97: 1 60 100
30 normal hexanes 93: 1 60 64
30 dehydrated alcohols 96: 1 60 83
50 normal hexanes 102: 1 60 100
50 dehydrated alcohols 98: 1 60 100
50 alcohol-waters 105: 1 30 100
70 normal hexanes 94: 1 30 96
70 dehydrated alcohols 97: 1 30 97
70 alcohol-waters 100: 1 20 100
120 toluene 76: 1 180 100
The hydrogenation of triclosan under example 6, the different concns
According to the operating process of example 4,15ml is dense cross be respectively 20ppm, 600pmm, 4500ppm, 10000ppm the triclosan ethanol solution at 50 ℃ of hydrodechlorinations, the results are shown in Table 4.
The triclosan hydrodechlorination of table 4 different concns
Catalyzer: 5%Pd/C, temperature: 50 ℃
Concentration/ppm mol ratio Cl: Pd reaction times/min dechlorination efficiency %
30 1∶1 15 100
600 17∶1 15 98
4500 120∶1 60 100
10000 270∶1 60 85
Example 7, Different Alkali are to the influence of triclosan compounds hydrodechlorination
According to the operating process of example 4, in reaction system, add alkali such as a certain amount of sodium hydroxide, sodium bicarbonate, yellow soda ash, triethylamine, temperature of reaction is controlled at 50 ℃, reaction pressure is a normal pressure, be reflected at logical hydrogen 15min under the magnetic agitation, the extrusion rate of chlorine specifically sees Table 5 at 90%-100%.
Table 5 Different Alkali is to the influence of triclosan compounds hydrodechlorination
Catalyzer: 5%Pd/C, temperature: 50 ℃
Mol ratio dechlorination efficiency %
Mol ratio Cl:
The alkali solvent
Alkali: chlorine atom Pd 5min 10min 15min
1: 1 alcohol-water of sodium hydroxide 92: 1 65 78 97
2: 1 alcohol-waters of sodium hydroxide 95: 1 27 34 45
1: 1 dehydrated alcohol of sodium hydroxide 97: 1 35 49 60
1: 1 alcohol-water of sodium bicarbonate 89: 1 67 80 100
1: 1 dehydrated alcohol of sodium bicarbonate 93: 1 71 93 99
1: 1 alcohol-water of yellow soda ash 95: 1 42 74 99
1: 1 dehydrated alcohol of yellow soda ash 97: 1 47 93 99
4: 1 alcohol-waters of triethylamine 91: 1 43 63 91
4: 1 dehydrated alcohols of triethylamine 92: 1 99 100 100
Example 8, different catalysts are to the influence of triclosan compounds hydrodechlorination
Take by weighing a certain amount of different catalysts, join in the reactor, add the adjacent dihydroxy diphenyl ether solution of 2,4,4 of 5000ppm '-trichlorine 15ml respectively, under normal pressure, 50 ℃ of control reaction temperature, logical hydrogen 60min, the extrusion rate of chlorine is 100%, result such as table 6.
Table 6 different catalysts is to the temperature that influences of dechlorination: 50 ℃, and solvent: dehydrated alcohol
Mol ratio
Catalyzer (chlorine atom: dechlorination efficiency % metal)
0.5％Pd/C 900∶1 27
2.0％Pd/C 65∶1 70
5.0％Pd/C 97∶1 100
5.0％Pd/Al
2O
3 85∶1 100
5.0％Rh/C 88∶1 100
5.0％Pt/SiO
2 92∶1 95
5.0％Pt/Al
2O
3 89∶1 100
5.0％Rh/Al
2O
3 83∶1 100
Raney?Ni 1∶14 25
The recovery of example 9, resultant
According to the operating process of example 4, after reaction finishes,, reclaim catalyzer with reaction solution and catalyzer filtering separation, with the solution decompression distillation, removed multi-solvent then, leave standstill cooling then, separate out precipitation, filtering separation obtains the adjacent dihydroxy diphenyl ether of resultant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102921143A (en) * | 2012-10-30 | 2013-02-13 | 中国科学院烟台海岸带研究所 | Method for efficiently degrading chlorinated phenolic compound |
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| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
| CN110035820A (en) * | 2016-12-19 | 2019-07-19 | 豪夫迈·罗氏有限公司 | Catalyst, preparation method based on nitrogenous biopolymer and its purposes in method for hydrogenation, reductive dehalogenation and oxidation |
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| CN108002991B (en) * | 2017-12-20 | 2021-01-05 | 陕西师范大学 | Visible light catalytic halogenated aromatic hydrocarbon dehalogenation method without photooxidation-reduction catalyst |
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