CN104174401B - A kind of sulphur load spinel oxides Fenton Catalysts and its preparation method - Google Patents
A kind of sulphur load spinel oxides Fenton Catalysts and its preparation method Download PDFInfo
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- CN104174401B CN104174401B CN201410440630.0A CN201410440630A CN104174401B CN 104174401 B CN104174401 B CN 104174401B CN 201410440630 A CN201410440630 A CN 201410440630A CN 104174401 B CN104174401 B CN 104174401B
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- sulphur load
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 16
- 239000011029 spinel Substances 0.000 title claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000005864 Sulphur Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910000708 MFe2O4 Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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Abstract
The invention provides a kind of sulphur load spinel oxides Fenton Catalysts and its preparation method, described sulphur load spinel oxides is MFe2O4, M=Zn, Co, Ni. By sulphur load spinel oxides MFe2O4Catalyst is applied to Fenton reaction, replaces traditional molysite catalyst, forms novel heterogeneous reaction system, has not only effectively reduced cost, has increased catalytic efficiency, widens the pH scope of application, and can adopt simple magnetic technology to recycle. And can, for its distinctive optical absorption characteristics, adopt Photo-Fenton GC-MS, and reduce the addition of hydrogen peroxide, improve catalytic efficiency. The present invention, taking common chemical products as raw material, prepares heterogeneous Fenton catalyst by chemical synthesis process, is that one has multi-functional catalyst material. All raw material is cheap and easy to get, and process route is fairly simple, non-environmental-pollution, and simplified technique, can realize industry and transform.
Description
Technical field
The invention belongs to catalyst preparation field, be specifically related to a kind of sulphur load spinel oxides Fenton Catalysts and its preparation method.
Background technology
Along with industrialized development, the mankind are also deepening gradually to the destruction of environment, and China is also one of shortage of water resources and with serious pollution country. Along with environmental protection campaign is in global rise, the research of water treatment agent and production become and become more and more important. Exploitation has world-class water treatment agent has become the task of top priority. Therefore, the innovation of wastewater processing technology is more and more paid attention to.
Nowadays, a large amount of dye wastewaters that give off from textile industry cause water resource to be heavily polluted, and derive a series of environmental problem, and the dyestuff of most of textiles is the systems that contain azo bond or aromatic ring structure. Removing efficiently azo dye wastewater is the key of Development of Textile Industry, and because the chemical stability of azo dyes is fine, conventional biological degradation method is difficult to remove. Therefore need to adopt high-level oxidation technology to substitute conventional biological degradation method.
In high-level oxidation technology, Fenton technology be a small investment, simple to operate, can control preferably and reduce contaminated wastewater, the effective means of protection of the environment. But traditional Fenton technology exists and produces a large amount of iron containing sludges, the pH scope of application narrow (pH=2-3), catalyst after water treatment and affected and the shortcomings such as inactivation by anion in water. Therefore, by changing catalyst system, adopt heterogeneous catalysis, can effectively address the above problem. The kind of heterogeneous Fenton catalyst is also in continuous increase. Wherein it should be noted that magnetic spinel type oxide is very promising heterogeneous catalysis of new generation. Compared with conventional iron salt catalyst, it has, and consumption is little, catalytic efficiency is high, catalysis speed is fast, and the generation of thoroughly stopping iron containing sludge solves and is difficult to reclaim, and processing cost is high and cause the problem of secondary pollution. In addition sulphur load spinel oxides MFe,2O4(M=Zn, Co, Ni) has the larger pH scope of application, has a good application prospect.
Summary of the invention
The object of the present invention is to provide a kind of sulphur load spinel oxides Fenton Catalysts and its preparation method, by sulphur load spinel oxides MFe2O4Catalyst is applied to Fenton reaction, replaces traditional molysite catalyst, forms novel heterogeneous reaction system, has not only effectively reduced cost, has increased catalytic efficiency, widens the pH scope of application, and can adopt simple magnetic technology to recycle. And can, for its distinctive optical absorption characteristics, adopt Photo-Fenton GC-MS, and reduce the addition of hydrogen peroxide, improve catalytic efficiency. The present invention, taking common chemical products as raw material, prepares heterogeneous Fenton catalyst by chemical synthesis process, is that one has multi-functional catalyst material. All raw material is cheap and easy to get, and process route is fairly simple, non-environmental-pollution, and simplified technique, can realize industry and transform.
For achieving the above object, the present invention adopts following technical scheme:
A kind of sulphur load spinel oxides Fenton catalyst is MFe2O4，M=Zn、Co、Ni。
Taking the one in ferric nitrate and zinc nitrate, cobalt nitrate, nickel nitrate as raw material, under the existence of solvent and alkali, adopt the auxiliary coprecipitation of hydro-thermal to make catalyst. Comprise the following steps:
(1), by water-soluble to the one in zinc nitrate, cobalt nitrate, nickel nitrate and ferric nitrate, magnetic agitation, to dissolving completely, is made mixed solution;
(2) mixed solution is heated in 80-100 DEG C of water-bath, constant temperature 0.5-2h, adds ethylene glycol, uses sodium hydroxide solution homogeneous precipitation, continues heating 1-3h, suction filtration, and washing of precipitate for several times, obtains catalyst precursor;
(3) by presoma 100-110 DEG C of dry 10-14h under vacuum condition, obtain pressed powder;
(4) pressed powder is proceeded in the autoclave with tetrafluoroethene liner, process 12-18h, programmed cooling is cooling, filters, washs for several times, 100-110 DEG C of dry 10-14h under vacuum condition; Be immersed in 1MH2SO40.5-2h in solution, filters under room temperature and washs 2-4 time, 100-110 DEG C of oven dry, and at 500-900 DEG C, roasting 2-4h, obtains catalyst powder.
Remarkable advantage of the present invention is: spinel oxides MFe2O4(M=Zn, Co, Ni) is widely used magnetic material, shows extraordinary ferromagnetism under normal temperature, and the carrier that is therefore often used as catalyst reclaims to realize magnetic. By preparation method's optimization, not only can show good catalytic activity but also there is stable superparamagnetism, can carry out simple, effectively magnetic separation recovery. Except having magnetic, under ultraviolet light and visible ray, also show strong absorption, illustrate that it has photolytic activity. Based on above feature, the sulphur load spinel oxides MFe that this method can be prepared2O4Catalyst is applied to Fenton reaction, replaces traditional molysite catalyst, forms novel heterogeneous reaction system, has not only effectively reduced cost, has increased catalytic efficiency, widens the pH scope of application, and can adopt simple magnetic technology to recycle. And can, for its distinctive optical absorption characteristics, adopt Photo-Fenton GC-MS, and reduce the addition of hydrogen peroxide, improve catalytic efficiency. The handling rate of azo structure contained organic wastewater is reached as high as to 95.3% under certain condition. The present invention, taking common chemical products as raw material, prepares heterogeneous Fenton catalyst by chemical synthesis process, is that one has multi-functional catalyst material. All raw material is cheap and easy to get, and process route is fairly simple, non-environmental-pollution, and has simplified technique, can realize industry and transform.
Detailed description of the invention
Embodiment 1
(1) take the Co (NO that mass ratio is 1:13)2·6H2O and Fe (NO3)3·6H2O also makes solution, and magnetic agitation is until dissolving is completely standing.
(2) put into 90 DEG C of water-baths and heat, constant temperature 1h, adds ethylene glycol, with slightly excessive NaOH precipitating reagent homogeneous precipitation, continues the heating 2h. method of suction filtration and makes sedimentation and filtration washing for several times, obtains catalyst precursor. By presoma 105 DEG C of oven dry 12h under vacuum condition, obtain pressed powder.
(3) powder is proceeded in the autoclave with tetrafluoroethene liner, temperature be at 180 DEG C, process 12h more than. After programmed cooling is cooling, filter, wash for several times, under vacuum condition, dry 12h for 105 DEG C. The sample obtaining is immersed in 1MH2SO41h in solution, filters under room temperature and washs 3 times, 105 DEG C of oven dry, and roasting 2h at 500 DEG C, obtains CATALYST Co Fe2O4Powder.
The application of described catalyst is to choose methylene orange (MO) as simulation dyestuff degradation product. Reaction is used homemade glass reactor (150mL) and is equipped with magnetic stirring apparatus, by sulphur load C oFe2O4Catalyst 50mg, being distributed to concentration is that 10mg/L volume is in the MO solution of 100mL, can select pH=3-9, stirs after 30min in camera bellows, adding mass fraction is 30% hydrogen peroxide 2mL, gets 5mLMO clarified solution carry out the detection of UV-visible spectrum every 20min. MO is after catalytic degradation 120min, and the clearance of MO is 97.2%.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (2)
1. a preparation method for sulphur load spinel oxides Fenton catalyst, is characterized in that: described sulphur load spinel oxides is MFe2O4, M=Zn, Co, Ni; Taking the one in ferric nitrate and zinc nitrate, cobalt nitrate, nickel nitrate as raw material, under the existence of solvent and alkali, adopt the auxiliary coprecipitation of hydro-thermal to make catalyst; Comprise the following steps:
(1), by water-soluble to the one in zinc nitrate, cobalt nitrate, nickel nitrate and ferric nitrate, magnetic agitation, to dissolving completely, is made mixed solution;
(2) mixed solution is heated in 80-100 DEG C of water-bath, constant temperature 0.5-2h, adds ethylene glycol, uses sodium hydroxide solution homogeneous precipitation, continues heating 1-3h, suction filtration, and washing of precipitate for several times, obtains catalyst precursor;
(3) by presoma 100-110 DEG C of dry 10-14h under vacuum condition, obtain pressed powder;
(4) pressed powder is proceeded in the autoclave with tetrafluoroethene liner, process 12-18h, programmed cooling is cooling, filters, washs for several times, 100-110 DEG C of dry 10-14h under vacuum condition; Be immersed in 1MH2SO40.5-2h in solution, filters under room temperature and washs 2-4 time, 100-110 DEG C of oven dry, and at 500-900 DEG C, roasting 2-4h, obtains catalyst powder.
2. the sulphur load spinel oxides Fenton catalyst that according to claim 1 prepared by method is applied to Fenton reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410440630.0A CN104174401B (en) | 2014-09-02 | 2014-09-02 | A kind of sulphur load spinel oxides Fenton Catalysts and its preparation method |
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| CN201410440630.0A CN104174401B (en) | 2014-09-02 | 2014-09-02 | A kind of sulphur load spinel oxides Fenton Catalysts and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108975463A (en) * | 2018-09-07 | 2018-12-11 | 宜兴市滨元环保设备有限公司 | A kind of Fenton's reaction tower of improvement |
| CN110102314B (en) * | 2019-04-16 | 2022-07-29 | 中山大学 | S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, catalytic system, preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 《Facile reduction of nitrophenols: Comparativecatalytic efficiency of MFe2O4 (M [ Ni, Cu, Zn) nano ferrites》;Ankita Goyal et al.;《international journal of hydrogen energy》;20140208(第39期);4895-4908 * |
| Liangjun Liu etal.《Highly Active S-Modified ZnFe2O4 Heterogeneous Catalyst and Its Photo-Fenton Behavior under UV Visible Irradiation》.《Industrial & Engineering Chemistry Research》.2011,(第50期),7220. * |
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