CN100441297C - Supported metal phthalocyanine photocatalyst and its preparing method - Google Patents
Supported metal phthalocyanine photocatalyst and its preparing method Download PDFInfo
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- CN100441297C CN100441297C CNB200610098315XA CN200610098315A CN100441297C CN 100441297 C CN100441297 C CN 100441297C CN B200610098315X A CNB200610098315X A CN B200610098315XA CN 200610098315 A CN200610098315 A CN 200610098315A CN 100441297 C CN100441297 C CN 100441297C
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- metal phthalocyanine
- polydivinylbenezene
- chloromethylation
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title description 2
- 239000011347 resin Substances 0.000 claims abstract description 84
- 229920005989 resin Polymers 0.000 claims abstract description 84
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000010792 warming Methods 0.000 claims description 44
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 239000011592 zinc chloride Substances 0.000 claims description 20
- 235000005074 zinc chloride Nutrition 0.000 claims description 20
- 239000004088 foaming agent Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 7
- 229920000159 gelatin Polymers 0.000 claims description 7
- 239000008273 gelatin Substances 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 5
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 2
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000002352 surface water Substances 0.000 abstract description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 238000013019 agitation Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 7
- YMGGYIAXCYFLGD-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene toluene Chemical compound CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C YMGGYIAXCYFLGD-UHFFFAOYSA-N 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000002421 finishing Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical compound C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- -1 step C) in Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The supported metal phthalocyanine photocatalyst consists of cross-linked polydivinyl benzene resin as catalyst and metal phthalocyanine with photocatalytic activity and covalent bonded with the carrier. The preparation process includes the following steps: suspension polymerization and chloromethylation reaction to obtain chloromethylated polydivinyl benzene resin, and Friedel-Crafts reaction to bind metal phthalocyanine to the post cross-linked resin carrier, with metal phthalocyanine accounting for 0.25-1.5 wt% of the catalyst. The catalyst has both adsorption and photocatalysis functions, and may be used in the photocatalytic treatment of chlorophenol and similar pollutant in industrial waste water, city domestic sewage, surface water and drinking water.
Description
Technical field
The present invention relates to a kind of photochemical catalyst and preparation method thereof, a kind of supported metal phthalocyanine photocatalyst and preparation method thereof of more specifically saying so.
Background technology
Photocatalysis oxidation technique is widely used in handling the research of the organic pollution in the water body as a kind of high-level oxidation technology.Wherein, with TiO
2Be main conductor photocatalysis because its reaction condition gentleness is nontoxic, non-secondary pollution, advantage such as the photochemical catalytic oxidation non-selectivity of pollutant is received much concern.Yet, be used for exciting the ultraviolet light of titanium dioxide only to account for 4～5% of sunshine gross energy, electronics and hole that optical excitation produces are compound easily, make that the photo-quantum efficiency of catalyst is low; On the other hand, the undesirable relatively difficulty of catalyst recovery that causes of titanium dioxide granule settling property in the aqueous solution is so just limited its industrial applications.
In the last few years, people utilized metal phthalocyanine at visible region the character of strong absorption to be arranged, and carried out the research of the organic pollution in dissolved oxygen in the catalytic activation water under the visible radiation or the hydrogen peroxide oxidation water, to realize the visible light catalytic oxidation.Though such catalyst catalytic efficiency is higher, separates and reclaim and reuse relatively difficulty.These visible light catalysts are loaded to the recovery and the recycling that can realize catalyst on ion exchange resin or the organoclay by electrostatic interaction or by suction-operated, and make catalyst more stable.This type of document has and is published in Langmuir in recent years; Environ.Sci.Technol.; Appl.Catal.B:Environ.; Chem.Commun. the related article of going up: (1) Xiong Z.; Xu Y.; Zhu L.; Zhao J.Langmuir 2005,21:10602; (2) Xiong Z.; Xu Y.; Zhu L.; Zhao J.Environ.Sci.Technol.2005,39:651; (3) Alvaro M.; Carbonell E.; Espl á M.; Garcia H.Appl.Catal.B:Environ.2005,57:37; (4) Hu M.; Xu Y.; Zhao J.Langmuir 2004,20:6302; (5) Tao X.; Ma W.; Li J.; HuangY.; Zhao J.; Yu J.Chem.Commun.2003,1:80; (6) Suzuki M., Ohta Y.; Nagae H.; Ichinohe T.; Kimura M.; Hanabusa K.; Shirai H.,
D.Chem.Commun.2000,3:213.
Institute of Chemistry, Academia Sinica has applied in 2002 that (application number: 02126545.3), its key step is: strong basic anion-exchange resin, styrene/divinylbenzene and the acrylic/divinylbenzene that a) with commercial benzol ethene/divinylbenzene of buying is the band quaternary ammonium group of EVA is that the weak basic anion exchange resin and the styrene/ethylene yl pyridines anion exchange resin of the band amido of EVA carries out pre-treatment with conventional method to " a kind of solid-phase photocatalyst and preparation method thereof " patent; B) the certain density water-soluble metal phthalocyanine aqueous solution of configuration; C) the water-soluble metal phthalocyanine solution that configures is loaded on the ion exchange resin by ion-exchange.Prepared solid-phase photocatalyst is used for No. two oranges of visible light photocatalytic degradation and acid brilliant pink dyestuff.The solid-phase photocatalyst of above-mentioned preparation is to be carrier with ion exchange resin, described metal phthalocyanine is the water-soluble metal phthalocyanine that has electron withdraw group, and load on the carrier by ion exchange, the advantage of this solid-phase photocatalyst is that the preparation method is simple, but in use may cause the loss of activated centre metal phthalocyanine, and then influence the photocatalytic activity of catalyst.Literature search shows do not have poly-divinylbenzene directly to obtain the report of supported metal phthalocyanine photocatalyst and preparation method thereof by the mode supported metal phthalocyanine of covalent bonding in the existing document as yet.
Summary of the invention
1. invent technical problem to be solved
The purpose of this invention is to provide a kind of supported metal phthalocyanine photocatalyst, can be at dissolved oxygen in the activated water under the radiation of visible light or hydrogen peroxide, thus effective chlorophenol pollutant in the catalytic degradation water makes chlorophenol pollutant be able to effective removal.Another object of the present invention also is to provide a kind of preparation method of supported metal phthalocyanine photocatalyst.
2. technical scheme
A kind of supported metal phthalocyanine photocatalyst, the metal phthalocyanine with photocatalytic activity by carrier and load is formed, it is characterized in that: described carrier is the crosslinked polydivinylbenezene resin that contains chloromethyl, and the weight percentage of metal phthalocyanine in catalyst is 0.25%～1.5%.
Described phthalocyanine is not for being with any substituent water-insoluble metal phthalocyanine, be selected from a kind of in non-water-soluble zinc phthalocyanine, aluminium phthalocyanine, the iron-phthalocyanine, equal reference literature is synthetic, and (document is: dyestuff and dyeing, 2004,41 (3): 150 and Hu M., Xu Y., Chen Z.Chinese J.Chem.2003,21:1092.); Described metal phthalocyanine is linked on the crosslinked polydivinylbenezene resin carrier in back by the Friedel-Crafts reaction key, and the quality percentage composition of described metal phthalocyanine in catalyst is 0.25%～1.5%; Described supported metal phthalocyanine photocatalyst is that blue-green is spherical, has more by force at visible region (610-690nm) to absorb, and specific area is at 200～500m
2Between/the g.
The preparation method of a kind of supported metal phthalocyanine photocatalyst of the present invention may further comprise the steps:
A) with the divinylbenzene be monomer, utilize toluene to make pore-foaming agent, make dispersant with in gelatin, polyvinyl alcohol, the lauryl sodium sulfate one or more, make initator with benzoyl peroxide, adopt suspension polymerization, be prepared into polydivinylbenezene, with ethanol or acetone is solvent, with apparatus,Soxhlet's extracting 8～12 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin;
B) steps A gained polydivinylbenezene resin is soaked in the chloromethyl ether of 2～4 times of its volumes, 20%～60% the anhydrous zinc chloride that adds its weight is made catalyst, under 25 ℃～40 ℃ temperature, carry out chloromethylation, up to chlorinity reach stop more than 5% the reaction, leach the resin spheroid, water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying;
C) step B gained chloromethylation polydivinylbenezene resin is joined in the solvent of 2～4 times of its volumes, by the metal phthalocyanine: the chlorinity mol ratio is to add metal phthalocyanine at 0.01～0.05: 1 in the resin, swelling 12～24 hours, the anhydrous zinc chloride that adds chloromethylation polydivinylbenezene weight resin 20%～60% is in two batches made catalyst, be warming up to 85 ℃～100 ℃, reacted 4～6 hours, after be warming up to 120 ℃～130 ℃ the reaction 8～12 hours, leach the resin spheroid, water, ethanol, acetone is fully washing successively, with ethanol or acetone is solvent, with apparatus,Soxhlet's extracting 12～24 hours, obtain the resin-carried metal phthalocyanine photocatalyst of chloromethylation polydivinylbenezene through vacuum drying.
The preparation method of described a kind of supported metal phthalocyanine photocatalyst, in the steps A, toluene is pore-foaming agent, and content is 40%～70% of divinylbenzene weight, dispersant is 0.5%～1.5% at the percentage by weight of aqueous phase.
The preparation method of described a kind of supported metal phthalocyanine photocatalyst, step C) in, solvent is N, dinethylformamide (DMF) or methyl-sulfoxide (DMSO).
The preparation method of described a kind of supported metal phthalocyanine photocatalyst, it is characterized in that: step C), chloromethylation polydivinylbenezene resin, metal phthalocyanine added in the solvent swelling 12～24 hours simultaneously, phase I is warming up to 85 ℃～100 ℃ reactions 4～6 hours, second stage is warming up to 120 ℃～130 ℃ reactions 8～12 hours, with metal phthalocyanine by realizing the back cross-linking reaction of resin when the Friedel-Craffs binding is to carrier.The consumption of the metal phthalocyanine by control chloromethylation polydivinylbenezene resin chlorinity, adding and reaction time can obtain the metal phthalocyanine photocatalyst of different specific areas, different loads amount.Usually chloromethylation polydivinylbenezene resin chlorinity is high more, and adding metal phthalocyanine amount is many more, and the reaction time is long more, and metal phthalocyanine loaded amount is many more.
3. beneficial effect
The invention provides a kind of supported metal phthalocyanine photocatalyst and preparation method thereof, the supported metal phthalocyanine photocatalyst that makes by the present invention has absorption and light-catalysed dual-use function, the photocatalysis treatment that can be used for chlorophenol pollutant in industrial wastewater, city domestic sewage and surface water and the drinking water, mineralising reaction to a certain degree also can take place, and catalyst is easy to reclaim and reuse simultaneously.It has light transmission good, be easy to from reaction system, separate, easy and simple to handle, advantage such as can be recycled.
Description of drawings
Fig. 1 is the 4-chlorophenol aqueous solution (0.2mM) photocatalytic degradation effect under illumination condition
Curve a: catalyst-free, have only the dark reaction of hydrogen peroxide
The dark reaction of curve b:1g/l catalyst and hydrogen peroxide (by embodiment 1 preparation)
Curve c: catalyst-free, have only the light reaction of hydrogen peroxide
The light reaction of curve d:1g/l catalyst and hydrogen peroxide (by embodiment 1 preparation)
The light degradation experiment condition: light-catalyzed reaction has in the cylindrical refractory Photoreactor that magnetic stirs, dischargeable capacity is 500mL one to be carried out, be inserted with a halogen tungsten lamp in the middle of the reactor, between lamp and reactant liquor, there is the quartzy condensation chuck of pair of lamina to separate, logical recirculated cooling water in the chuck, experimentation control temperature is about 20 ℃-35 ℃.The concentration of hydrogen peroxide is 10mM, and following experiment condition is identical.
Curve a is under unglazed photograph and the catalyst-free condition among Fig. 1, even there is hydrogen peroxide to exist, the 4-chlorophenol is also degraded hardly; Curve b has catalyst and hydrogen peroxide to have dark reaction down, and except the concentration reduction that catalyst causes the absorption of 4-chlorophenol, the 4-chlorophenol is not almost degraded; Curve 3 is a catalyst-free, and degradation reaction to a certain degree takes place the 4-chlorophenol under illumination and hydrogen peroxide existence condition; Curve 4 is the degradation reaction that the 4-chlorophenol takes place under catalyst, illumination and the hydrogen peroxide existence condition, and illumination degraded 97% after 300 minutes, and reaction stopped to stir 5 minutes after finishing, and catalyst can be deposited to container bottom fully, is easy to separate with solution.
Fig. 2 is the effect of catalyst (by embodiment 1 preparation) 6 the photocatalytic degradation 4-chlorophenols that circulate continuously, shows that catalyst is active after reusing 6 times obviously not reduce.
Fig. 3 is catalyst (by embodiment 2 a preparation) photocatalytic degradation 4-chlorophenol, 2,4-two chlorophenols, 2,4, and the effect of 6-trichlorophenol shows the degraded that catalyst not only can photocatalysis 4-chlorophenol, can also photocatalysis 2,4-two chlorophenols, 2,4, the degraded of 6-trichlorophenol.
The specific embodiment
Further specify the present invention by following examples.
Embodiment 1
A) suspension polymerisation
Divinylbenzene (55.6%) monomer adds a certain amount of diluted sodium hydroxide solution or monomer is directly removed polymerization inhibitor through the resin column that strong basic anion-exchange resin is housed.
Add the 120g divinylbenzene in the 1000mL beaker, toluene 80g, benzoyl peroxide 1.2g, the back that stirs is standby.
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add 600g distilled water, add the 8g gelatin, 0.04g lauryl sodium sulfate is as dispersant, be warming up to 50 ℃, be stirred to dissolving fully, add the 1mL methylene blue, stir, add the above-mentioned divinylbenzene toluene solution for preparing; Adjust suitable mixing speed and make the oil droplet size to fit, be warming up to 60 ℃, be warming up to 80 ℃ with 2 ℃/10min again with 5 ℃/10min, and be incubated 4 hours, and progressively be warming up to 90 ℃ again, be incubated 6 hours, after reaction is finished, leach resin, use hot wash earlier, dry, be solvent again with acetone, with apparatus,Soxhlet's extracting 10 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin.
B) chloromethylation
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add the 75g steps A) gained polydivinylbenezene resin, the 300mL chloromethyl ether soaks more than the 2h down in 20 ℃-25 ℃, stir down, add the 15g anhydrous zinc chloride, the control temperature is not higher than 25 ℃, behind the stirring 0.5h, add the 15g anhydrous zinc chloride again, after stirring 0.5h, be warming up to 36 ℃, insulation 12h.Reaction leaches the resin spheroid after finishing, and water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying, and chlorinity is 13.0%.
C) load and back cross-linking reaction
In the 1000mL there-necked flask, add 75g step B) gained chloromethylation polydivinylbenezene resin, add 400mL N, dinethylformamide (DMF), zinc phthalocyanine 1.6g, stir swelling 12h under the room temperature after, add the 20g zinc chloride and stir 1h, progressively be warming up to 85 ℃～100 ℃, reacted 6 hours, after be warming up to 120 ℃～125 ℃ the reaction 12 hours, leach the resin spheroid, water, ethanol, acetone fully washed, and are solvent with ethanol or acetone, with apparatus,Soxhlet's extracting 12 hours.Obtain the resin-carried metal phthalocyanine photocatalyst of chloromethylation polydivinylbenezene through vacuum drying.
The synthetic catalyst of present embodiment is that blue-green is spherical, and the load capacity of zinc phthalocyanine is 0.6%, and particle diameter is the 80-300 micron, and the BET specific area is 267m
2/ g, chlorinity are 3.6%.
Embodiment 2
A) suspension polymerisation
Add the 120g divinylbenzene in the 1000mL beaker, toluene 60g, benzoyl peroxide 1.2g, the back that stirs is standby.
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add 600g distilled water, add the 4g polyvinyl alcohol, 4g gelatin and 0.8g lauryl sodium sulfate are warming up to 50 ℃ as dispersant, be stirred to dissolving fully, add the 2mL methylene blue, stir, add the above-mentioned divinylbenzene toluene solution for preparing; Adjust suitable mixing speed and make the oil droplet size to fit, be warming up to 60 ℃, be warming up to 80 ℃ with 2 ℃/10min again with 5 ℃/10min, and be incubated 4 hours, and progressively be warming up to 90 ℃ again, be incubated 6 hours, after reaction is finished, leach resin, use hot wash earlier, dry, be solvent again with acetone, with apparatus,Soxhlet's extracting 10 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin.
B) chloromethylation
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add the 75g steps A) gained polydivinylbenezene resin, the 200mL chloromethyl ether soaks more than the 2h down in 20 ℃-25 ℃, stir down, add the 10g anhydrous zinc chloride, the control temperature is not higher than 25 ℃, behind the stirring 0.5h, add the 15g anhydrous zinc chloride again, after stirring 0.5h, be warming up to 36 ℃, insulation 4h.Reaction leaches the resin spheroid after finishing, and water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying, and chlorinity is 11.7%.
C) load and back cross-linking reaction
Operating condition is with embodiment 1.
The synthetic catalyst of present embodiment is blue spherical, and the load capacity of zinc phthalocyanine is 0.8%, and particle diameter is the 50-150 micron, and the BET specific area is 320.5m
2/ g, chlorinity are 2.9%.
Embodiment 3
A) suspension polymerisation
Add the 120g divinylbenzene in the 1000mL beaker, toluene 60g, benzoyl peroxide 1.2g, the back that stirs is standby.
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add 600g distilled water, add the 8g polyvinyl alcohol, 0.8g lauryl sodium sulfate is as dispersant, be warming up to 50 ℃, be stirred to dissolving fully, add the 2mL methylene blue, stir, add the above-mentioned divinylbenzene toluene solution for preparing; Adjust suitable mixing speed and make the oil droplet size to fit, be warming up to 60 ℃, be warming up to 80 ℃ with 2 ℃/10min again with 5 ℃/10min, and be incubated 4 hours, and progressively be warming up to 90 ℃ again, be incubated 6 hours, after reaction is finished, leach resin, use hot wash earlier, dry, be solvent again with acetone, with apparatus,Soxhlet's extracting 10 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin.
B) chloromethylation
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add the 75g steps A) gained polydivinylbenezene resin, the 200mL chloromethyl ether soaks more than the 2h down in 20 ℃-25 ℃, stir down, add the 10g anhydrous zinc chloride, the control temperature is not higher than 25 ℃, behind the stirring 0.5h, add the 5g anhydrous zinc chloride again, after stirring 0.5h, be warming up to 36 ℃, insulation 3h.Reaction leaches the resin spheroid after finishing, and water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying, and chlorinity is 5.2%.
C) load and back cross-linking reaction
Operating condition is with embodiment 1.Just change the zinc phthalocyanine into aluminium phthalocyanine 3.0g, solvent changes methyl-sulfoxide (DMSO) into.
The synthetic catalyst of present embodiment is blue spherical, and the load capacity of aluminium phthalocyanine is 0.25%, and the BET specific area is 210.6m
2/ g, chlorinity are 2.1%.
Embodiment 4
A) suspension polymerisation
Add the 120g divinylbenzene in the 1000mL beaker, toluene 48g, benzoyl peroxide 1.2g, the back that stirs is standby.
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add 600g distilled water, add the 2.5g gelatin, 0.5g lauryl sodium sulfate is as dispersant, be warming up to 50 ℃, be stirred to dissolving fully, add the 1mL methylene blue, stir, add the above-mentioned divinylbenzene toluene solution for preparing; Adjust suitable mixing speed and make the oil droplet size to fit, be warming up to 60 ℃, be warming up to 80 ℃ with 2 ℃/10min again with 5 ℃/10min, and be incubated 4 hours, and progressively be warming up to 90 ℃ again, be incubated 6 hours, after reaction is finished, leach resin, use hot wash earlier, dry, be solvent again with acetone, with apparatus,Soxhlet's extracting 10 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin.
B) chloromethylation
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add the 75g steps A) gained polydivinylbenezene resin, the 300mL chloromethyl ether soaks down more than the 2h, under the stirring in 20 ℃-25 ℃, add the 20g anhydrous zinc chloride, the control temperature is not higher than 25 ℃, behind the stirring 0.5h, adds the 25g anhydrous zinc chloride again, be warming up to 39 ℃ after stirring 0.5h, insulation 10h.Reaction leaches the resin spheroid after finishing, and water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying.Chlorinity is: 12.5%.
C) load and back cross-linking reaction
In the 1000mL there-necked flask, add 75g step B) gained chloromethylation polydivinylbenezene resin, add 400mL N, dinethylformamide (DMF), zinc phthalocyanine 2.0g, stir swelling 12h under the room temperature after, add the 40g zinc chloride and stir 1h, progressively be warming up to 85 ℃～100 ℃, reacted 6 hours, after be warming up to 120 ℃～125 ℃ the reaction 12 hours, leach the resin spheroid, water, ethanol, acetone fully washed, and are solvent with ethanol or acetone, with apparatus,Soxhlet's extracting 12 hours.Obtain the resin-carried metal phthalocyanine photocatalyst of chloromethylation polydivinylbenezene through vacuum drying.
The synthetic catalyst of present embodiment is blue spherical, and the load capacity of zinc phthalocyanine is 1.0%, and the BET specific area is 282.3m
2/ g, chlorinity are 4.5%.
Embodiment 5
A) suspension polymerisation
Add the 120g divinylbenzene in the 1000mL beaker, toluene 84g, benzoyl peroxide 1.2g, the back that stirs is standby.
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add 600g distilled water, add the 5.5g gelatin, 0.5g lauryl sodium sulfate is as dispersant, be warming up to 50 ℃, be stirred to dissolving fully, add the 1mL methylene blue, stir, add the above-mentioned divinylbenzene toluene solution for preparing; Adjust suitable mixing speed and make the oil droplet size to fit, be warming up to 60 ℃, be warming up to 80 ℃ with 2 ℃/10min again with 5 ℃/10min, and be incubated 4 hours, and progressively be warming up to 90 ℃ again, be incubated 6 hours, after reaction is finished, leach resin, use hot wash earlier, dry, be solvent again with acetone, with apparatus,Soxhlet's extracting 10 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin.
B) chloromethylation
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add the 75g steps A) gained polydivinylbenezene resin, the 300mL chloromethyl ether soaks more than the 2h down in 20 ℃-25 ℃, stir down, add the 20g anhydrous zinc chloride, the control temperature is not higher than 25 ℃, behind the stirring 0.5h, add the 25g anhydrous zinc chloride again, after stirring 0.5h, be warming up to 36 ℃, insulation 12h.Reaction leaches the resin spheroid after finishing, and water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying.Chlorinity is 14.7%
C) load and back cross-linking reaction
In the 1000mL there-necked flask, add 75g step B) gained chloromethylation polydivinylbenezene resin, add 400mLN, dinethylformamide (DMF), zinc phthalocyanine 3.6g, stir swelling 12h under the room temperature after, add the 35g zinc chloride and stir 1h, progressively be warming up to 85 ℃～100 ℃, reacted 6 hours, after be warming up to 120 ℃～125 ℃ the reaction 4 hours, leach the resin spheroid, water, ethanol, acetone fully washed, and are solvent with ethanol or acetone, with apparatus,Soxhlet's extracting 12 hours.Obtain the resin-carried metal phthalocyanine photocatalyst of chloromethylation polydivinylbenezene through vacuum drying.
The synthetic catalyst of present embodiment is blue spherical, and the load capacity of zinc phthalocyanine is 1.5%, and the BET specific area is 490.5m
2/ g, chlorinity are 6.4%.
Embodiment 6
A) suspension polymerisation
Add the 120g divinylbenzene in the 1000mL beaker, toluene 48g, benzoyl peroxide 1.2g, the back that stirs is standby.
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add 600g distilled water, add the 8.5g gelatin, 0.5g lauryl sodium sulfate is as dispersant, be warming up to 50 ℃, be stirred to dissolving fully, add the 1mL methylene blue, stir, add the above-mentioned divinylbenzene toluene solution for preparing; Adjust suitable mixing speed and make the oil droplet size to fit, be warming up to 60 ℃, be warming up to 80 ℃ with 2 ℃/10min again with 5 ℃/10min, and be incubated 4 hours, and progressively be warming up to 90 ℃ again, be incubated 6 hours, after reaction is finished, leach resin, use hot wash earlier, dry, be solvent again with acetone, with apparatus,Soxhlet's extracting 10 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin.
B) chloromethylation
In the there-necked flask of 1000mL band mechanical agitation, reflux condensing tube, add the 75g steps A) gained polydivinylbenezene resin, the 300mL chloromethyl ether soaks more than the 2h down in 20 ℃-25 ℃, stir down, add the 10g anhydrous zinc chloride, the control temperature is not higher than 25 ℃, behind the stirring 0.5h, add the 15g anhydrous zinc chloride again, after stirring 0.5h, be warming up to 36 ℃, insulation 12h.Reaction leaches the resin spheroid after finishing, and water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying.Chlorinity is 10.6%
C) load and back cross-linking reaction
In the 1000mL there-necked flask, add 75g step B) gained chloromethylation polydivinylbenezene resin, add 400mLN, N dimethyl formamide (DMF), iron-phthalocyanine 2.6g, stir swelling 12h under the room temperature after, add the 15g zinc chloride and stir 1h, progressively be warming up to 85 ℃～100 ℃, reacted 6 hours, after be warming up to 120 ℃～125 ℃ the reaction 12 hours, leach the resin spheroid, water, ethanol, acetone fully washed, and are solvent with ethanol or acetone, with apparatus,Soxhlet's extracting 12 hours.Obtain the resin-carried metal phthalocyanine photocatalyst of chloromethylation polydivinylbenezene through vacuum drying.
The synthetic catalyst of present embodiment is blue spherical, and the load capacity of iron-phthalocyanine is 0.8%, and the BET specific area is 386.3m
2/ g, chlorinity are 5.8%.
Claims (7)
1, a kind of supported metal phthalocyanine photocatalyst, the metal phthalocyanine with photocatalytic activity by carrier and load is formed, it is characterized in that: described carrier is a chloromethylation polydivinylbenezene resin, and the weight percentage of metal phthalocyanine in catalyst is 0.25%～1.5%.
2, supported metal phthalocyanine photocatalyst according to claim 1 is characterized in that chlorinity is 5%～15% in the carrier chloromethylation polydivinylbenezene resin.
3, supported metal phthalocyanine photocatalyst according to claim 1 is characterized in that: described metal phthalocyanine is selected from a kind of in non-water-soluble zinc phthalocyanine, aluminium phthalocyanine, the iron-phthalocyanine.
4, supported metal phthalocyanine photocatalyst according to claim 1 is characterized in that the supported metal phthalocyanine photocatalyst specific area is 200～500m
2/ g.
5,, it is characterized in that may further comprise the steps according to the preparation method of each described a kind of supported metal phthalocyanine photocatalyst of claim 1～4:
A) with the divinylbenzene be monomer, utilize toluene to make pore-foaming agent, make dispersant with in gelatin, polyvinyl alcohol, the lauryl sodium sulfate one or more, make initator with benzoyl peroxide, adopt suspension polymerization, be prepared into the polydivinylbenezene resin, with ethanol or acetone is solvent, with apparatus,Soxhlet's extracting 8～12 hours,, obtain spherical polydivinylbenezene resin through vacuum drying again to remove residual pore-foaming agent toluene in the resin;
B) steps A gained polydivinylbenezene resin is soaked in the chloromethyl ether of 2～4 times of its volumes, 20%～60% the anhydrous zinc chloride that adds its weight is made catalyst, under 25 ℃～40 ℃ temperature, carry out chloromethylation, up to chlorinity reach stop more than 5% the reaction, leach the resin spheroid, water, ethanol, acetone are washed chloromethylation mother liquor remaining in the most resin, obtain chloromethylation polydivinylbenezene resin through vacuum drying;
C) step B gained chloromethylation polydivinylbenezene resin is joined in the solvent of 2～4 times of its volumes, by the metal phthalocyanine: the chlorinity mol ratio is to add metal phthalocyanine at 0.01～0.05: 1 in the resin, swelling 12～24 hours, the anhydrous zinc chloride that adds chloromethylation polydivinylbenezene weight resin 20%～60% is in two batches made catalyst, be warming up to 85 ℃～100 ℃, reacted 4～6 hours, after be warming up to 120 ℃～130 ℃ the reaction 8～12 hours, leach the resin spheroid, water, ethanol, acetone is fully washing successively, with ethanol or acetone is solvent, with apparatus,Soxhlet's extracting 12～24 hours, obtain the resin-carried metal phthalocyanine photocatalyst of chloromethylation polydivinylbenezene through vacuum drying.
6, the preparation method of a kind of supported metal phthalocyanine photocatalyst according to claim 5, it is characterized in that: in the steps A, toluene is pore-foaming agent, and content is 40%～70% of divinylbenzene weight, and dispersant is 0.5%～1.5% at the percentage by weight of aqueous phase.
7. according to the preparation method of claim 5 or 6 described a kind of supported metal phthalocyanine photocatalysts, it is characterized in that: among the step C, volume is that the solvent of 2～4 times of chloromethylation polydivinylbenezene resins is N, dinethylformamide or methyl-sulfoxide.
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| CN101186719B (en) * | 2007-12-04 | 2012-02-29 | 南京大学 | Composite function resin, preparation method thereof, and method for treating phthalate pollution of water body |
| CN102600898A (en) * | 2012-02-27 | 2012-07-25 | 盐城师范学院 | Photocatalyst of ordered mesoporous polymer loading with metal phthalocyanine and preparation method of photocatalyst |
| CN102861557A (en) * | 2012-09-14 | 2013-01-09 | 东南大学 | Nonpolar adsorption resin for adsorbing organic compounds and regeneration method for nonpolar adsorption resin |
| CN103102472B (en) * | 2013-01-09 | 2015-05-20 | 河北科技大学 | Synthesis and application of copolymer of 1% of DVB crosslinking skeleton of chloromethylate polystyrene resin and 1,4-naphthoquinone |
| CN106000466B (en) * | 2016-05-19 | 2019-01-22 | 中北大学 | The immobilized metal phthalocyanine catalyst and its methods for making and using same of synchronized compound and the preparation of immobilized method |
| CN108160113B (en) * | 2017-12-15 | 2020-06-16 | 东南大学 | Resin-supported metal phthalocyanine catalyst and preparation method and application thereof |
| CN108543525A (en) * | 2018-03-22 | 2018-09-18 | 安徽皖东树脂科技有限公司 | The preparation method of the absorption resin of Phenol-Containing Wastewater Treatment |
| CN115069305B (en) * | 2022-07-06 | 2023-05-26 | 中钢集团鞍山热能研究院有限公司 | Immobilized metal phthalocyanine catalyst and preparation method and application thereof |
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