CN108686656A - A kind of α-Fe2O3/ gangue composite photo-catalyst and its preparation method and application - Google Patents
A kind of α-Fe2O3/ gangue composite photo-catalyst and its preparation method and application Download PDFInfo
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- CN108686656A CN108686656A CN201810403670.6A CN201810403670A CN108686656A CN 108686656 A CN108686656 A CN 108686656A CN 201810403670 A CN201810403670 A CN 201810403670A CN 108686656 A CN108686656 A CN 108686656A
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- Prior art keywords
- gangue
- catalyst
- molysite
- composite photo
- aqueous solution
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- 229910003145 α-Fe2O3 Inorganic materials 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- -1 chlorophenol class compound Chemical class 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 230000000593 degrading effect Effects 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 16
- 239000003245 coal Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 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 6
- 239000000243 solution Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 28
- 238000007146 photocatalysis Methods 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical class OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical class OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Catalysts (AREA)
Abstract
The present invention relates to a kind of α-Fe2O3/ gangue composite photo-catalyst comprising the following raw material is prepared through boiling reflux:The aqueous solution of pretreated gangue and molysite;The aqueous solution of the molysite is with α-Fe2O3The mass ratio of quality meter and pretreated gangue is 0.5 ~ 5:100.The invention further relates to the method and its application for preparing above-mentioned composite photo-catalyst.The present invention product can under ultraviolet irradiation condition effective degrading chlorophenol class compound.The preparation method of the present invention has the characteristics that raw material is few, simple for process, the reaction time is short, condition is relatively mild, environmentally safe, is a kind of green synthesis process, industrialization easy to implement.
Description
Technical field
The invention belongs to photochemical catalyst preparation fields, and in particular to a kind of α-Fe2O3/ gangue composite photo-catalyst, its system
Preparation Method and its application in degrading chlorophenol class compound.
Background technology
It is at normal temperatures and pressures inorganic molecules by organic pollutant degradation that photocatalysis technology, which can directly utilize luminous energy, and
And have the characteristics that low energy consumption, easy to operate, reaction condition is mild, secondary pollution is small, it is a kind of ideal environmental pollution improvement
Technology.Be becoming tight fossil energy day, today of environmental pollution getting worse, the importance of photocatalysis technology is self-evident,
Core is exactly to research and develop the photochemical catalyst of function admirable.
Common catalysis material is mainly TiO2,SnO2,CdS,WO3,ZrO2And Fe2O3Deng some n-type semiconductor chemical combination
Object.α-Fe2O3Not only energy gap is relatively narrow, and light abstraction width extends to visible region, can be good at utilizing sunlight, and
And with the nontoxic good characteristics such as inexpensive of high chemical stability, resistance to acid and alkali, fast light burn into, only photocatalysis efficiency needs to be carried
It is high.
Because the activity of photochemical catalyst is in close relations with its granule size, granularity is smaller, and specific surface area is bigger, and photocatalysis is lived
Property is higher, so semiconductor light-catalyst is micro-/ nano particle mostly.But during photocatalysis degradation organic contaminant, micro-/
Nano particle also can cause secondary agglomeration because of undersized, and deposit and be difficult to recycle after use, easily form the disadvantage of secondary pollution.
This, which has become, restricts the big technical bottleneck that micro-/ nano semiconductor light-catalyst promotes and applies.
As a kind of effective ways to solve the above problems, micro-/ nano semiconductor light-catalyst it is immobilized in recent years by
Domestic and foreign scholars have been arrived more and more to pay close attention to.Currently, common solid support method is generally divided into, film forming is immobilized and carrier is solid
Two kinds of loadization, the latter's multiselect use activated carbon, carbon nanotube etc. with flourishing pore structure and large specific surface area to do carrier.By
More expensive in their prices, process of industrialization is very slow.
Gangue is grey black rock lower than coal with a kind of phosphorus content of coal seam association, symbiosis in coal forming process.
The solid waste discharged in this coal mining, washing and process accounts for about the 15% ~ 20% of coal production.It is a large amount of not sharp
Gangue is arbitrarily accumulated, not only land occupation, but also pollution environment.Carrying out the comprehensive utilization of gangue in a deep going way has become China
The fundamental way of coal industry in-depth transition and sustainable development.Natural gangue complicated component, compact structure, but it is modified
Afterwards, the inorganic mineral in gangue is partially converted into amorphous state by crystalline state, and structure becomes loose, specific surface area increases, hole
Gap structure is flourishing, and absorption property significantly improves.
So far there is not yet related α-Fe2O3The report of/gangue composite photo-catalyst.If being that absorption carries with modified gangue
Body loads micro-/ nano α-Fe2O3Particle forms α-Fe2O3/ gangue composite photo-catalyst, can not only gangue become give up into
Treasured realizes efficiently using for resource, also will be helpful to improve micro-/ nano α-Fe2O3Photocatalysis efficiency.Therefore, a kind of work is found
Skill is simple, the at low cost, α-Fe of energy consumption less, environmentally protective2O3/ gangue composite photo-catalyst preparation method has important show
Sincere justice.
Invention content
The object of the present invention is to provide a kind of α-Fe2O3/ gangue composite photo-catalyst and preparation method thereof.The preparation side
Method has the characteristics that raw material is few, simple for process, the reaction time is short, condition is relatively mild, environmentally safe, is a kind of green conjunction
At technique, industrialization easy to implement.Prepared product can under ultraviolet irradiation condition effective degrading chlorophenol class compound.
The present invention adopts the following technical scheme that:
A kind of α-Fe2O3/ gangue composite photo-catalyst comprising the following raw material is prepared through boiling reflux:Pretreated coal
The aqueous solution of spoil and molysite;The aqueous solution of the molysite is with α-Fe2O3Quality meter and the mass ratio of pretreated gangue are
0.5~5:100。
The aqueous solution parameter of the molysite is calculated by following formula:
m α-Fe2O3= C The aqueous solution of molysite×V The aqueous solution of molysite×M α-Fe2O3
In formula,C- molar concentration, mol/L;V- volume, L;M- molal weight, g/mol;m- quality, g.
Further, the pretreated gangue be gangue through crush, ground 150 ~ 300 mesh sieve after, in 700
It is spare after ~ 900 DEG C of 1.5 ~ 3 h of calcining.
Preferably, the pretreated gangue is forged for gangue through crushing, after ground 200 mesh sieve in 800 DEG C
It burns spare after 2 h.
Further, the molysite includes ferric nitrate, iron chloride or ferric sulfate.
Further, Fe in the aqueous solution of the molysite3+A concentration of 0.4 mol/L of ion.
A kind of above-mentioned α-Fe2O3The preparation method of/gangue composite photo-catalyst comprising following steps:
(1)Gangue is taken, 150 ~ 300 mesh sieve is crossed after crushing, grinding, 1.5 ~ 3 h is calcined in 700 ~ 900 DEG C, is pre-processed
Gangue afterwards;
(2)Prepare Fe3+Ion concentration is the aqueous solution of the molysite of 0.4 mol/L;
(3)Take step(2)5 mL of aqueous solution of prepared molysite is added distilled water and is settled to 100 mL, then adds into solution
Enter step(1)Obtained pretreated gangue, 1 h of magnetic agitation;
The aqueous solution of the molysite is with α-Fe2O3Quality meter, α-Fe2O3Mass ratio with pretreated gangue is 0.5 ~ 5:
100;
(4)Regulating step(3)3 h of boiling reflux after the pH to 9 ~ 11 of obtained reaction system;
(5)Through filtering, water washing and after natural drying is distilled, α-Fe are obtained2O3/ gangue composite photo-catalyst.
Wherein, the step(1)In, gangue crosses 200 mesh sieve after crushing, grinding, and calcination temperature is 800 DEG C, calcining
Time is 2 h.
Wherein, the step(2)In, the molysite is ferric nitrate, iron chloride or ferric sulfate.
Wherein, the step(3)In, the α-Fe2O3Mass ratio with pretreated gangue is 1 ~ 4:100, preferably
It is 3:100.
Wherein, the step(4)In, the pH value of the reaction system is 10.
Wherein, the step(4)In, adjust reaction system using the sodium hydrate aqueous solution of 6 mol/L and 0.1 mol/L
PH value.
A kind of above-mentioned α-Fe2O3Application of/gangue the composite photo-catalyst in degrading chlorophenol class compound.
The beneficial effects of the present invention are:Natural gangue granularity is larger, quality is hard, compact structure, it is difficult to directly answer
With.Usually first it is crushed, be ground up, sieved and calcination processing.It crushes, grinding makes the grain size of natural gangue become rapidly
Small, lattice is distorted, and specific surface area accordingly becomes larger, but the structure of coal gangue particle still densification at this time, and adsorptivity is still very
Difference does not show activity substantially when being chemically reacted.After high-temperature calcination processing, gangue not only has certain ingredient to volatilize, and one
A little inorganic compounds also occur that crystalline state changes, and then the short texture degree of gangue and chemism is made to greatly improve.Although
Above-mentioned processing can be played the role of improving gangue performance, but this for gangue is used as adsorbent, effect is remote
It is not nearly enough.Gangue after calcining will be further processed with substances such as acid or alkali again.
Acid solution can dissolve the oxide of Al, Fe, Ca in gangue, increase the porosity of coal gangue particle, to enhance
The adsorption capacity of gangue.Aqueous slkali can not only then dissolve some metal oxides in gangue, increase coal gangue particle
Porosity, suitable alkali can also react with the oxide of Si in gangue and Al, generate the boiling with preferable adsorption capacity
Stone molecular sieve.
It is well known that photochemical catalyst absorption is degraded, the ability of object is to influence a key factor of its photocatalysis efficiency.
Modified gangue large specific surface area, more micropores have good adsorptivity, are not only advantageous to chemically load α-Fe2O3Light
Catalyst, the α-Fe of formation2O3/ gangue composite photo-catalyst can also realize α-Fe2O3, both gangues synergistic effect,
So that catalyst surface is remained higher pollutant concentration, promotes α-Fe2O3With the electronics transfer between the object molecule that is degraded,
Improve α-Fe2O3Photocatalysis efficiency.
Our early-stage study is found, using molysite and alkali as reactant, using boiling reflux, under the conditions of 9 ~ 11 pH
It can obtain the good micro-/ nano α-Fe of photocatalysis performance2O3Particle, this discovery make a step prepare α-Fe2O3/ gangue
Compound is possibly realized.The alkali being present in reaction system can be modified gangue and be adsorbed with modified gangue
Fe3+Ion reacts to obtain α-Fe2O3, thus by α-Fe2O3It is supported on modified gangue.Raw material needed for this method is few,
It is simple for process, the reaction time is short, condition is relatively mild, environmentally safe, be a kind of green synthesis process.
Description of the drawings
Fig. 1 is modified gangue, pure α-Fe2O3And α-Fe2O3The XRD spectra of/gangue compound.
In Fig. 1, a is modified gangue, and b is pure α-Fe2O3, c is α-Fe2O3/ gangue compound.
Fig. 2 is pure α-Fe2O3And different quality ratio α-Fe2O3/ gangue compound photocatalytic degradation pentachlorophenol efficiency is at any time
Between the curve that changes.
Specific implementation mode
In order to deepen the understanding of the present invention, the present invention is described in detail below with reference to the accompanying drawings and embodiments, should
Embodiment is exemplary, and is only used for explaining the present invention, is not constituted and is limited to protection domain.
Embodiment 1
The gangue of Shanxi riding comfort model is derived from after crushing and being fully ground, crosses 200 mesh sieve, and it is spare to calcine 2 h in 700 DEG C.
Meanwhile preparing Fe3+Ion concentration is the molysite aqueous solution of 0.4 mol/L, and the sodium hydroxide of 6 mol/L and 0.1 mol/L are water-soluble
Liquid is spare.
By 5 mL iron nitrate aqueous solutions(Fe3+Ion concentration is 0.4 mol/L)It is introduced into three-necked flask, with distilled water constant volume
100 mL, are added the pretreated bastard coal mountain flour of calculation amount, after 1 h of magnetic agitation, be slowly added dropwise into bottle 6 mol/L and
The sodium hydrate aqueous solution of 0.1 mol/L, the pH value that the addition by controlling sodium hydrate aqueous solution adjusts reaction system are
9,3 h of boiling reflux.Through filtering, distilling water washing, naturally dry, α-Fe are obtained2O3/ gangue composite photo-catalyst.
Embodiment 2 ~ 6 and comparative example 1 ~ 2
Embodiment 2 ~ 6 and comparative example 1 ~ 2 are identical as the operating procedure of embodiment 1, differ only in type, the bastard coal of molysite used
Stone calcination temperature, gangue dosage and pH value of reaction system, it is specific as shown in table 1.
1 embodiment 2 ~ 6 of table and comparative example 1 ~ 2
。
1 XRD characterization of effect example
Fig. 1 is modified gangue, pure α-Fe2O3And α-Fe2O3The XRD spectra of/gangue compound.Occur 2 simultaneously in Fig. 1 cθThe diffraction maximum of modified gangue at=21.18 °, 26.64 °(Fig. 1 a)With 2θ=24.08 °, 33.19 °, 35.67 °, 40.84
°, hexagonal structure α-Fe at 49.47 °, 53.97 °, 57.46 °, 62.39 °, 63.96 °2O3(JCPDS 33-0664)Diffraction
Peak(Fig. 1 b), it was demonstrated that product is really α-Fe2O3/ gangue compound.Because of α-Fe2O3It is covered on the surface of modified gangue,
So α-Fe2O3Belong to α-Fe in/gangue compound2O3The purer α-Fe of each diffraction peak intensity2O3Variation is little, and belongs to and change
The diffraction peak intensity of property gangue more unsupported α-Fe2O3It significantly reduces before.
2 α-Fe of effect example2O3The photocatalysis performance of/gangue compound is evaluated
Chlorophenols compound is a kind of typical " three causes(Carcinogenic, teratogenesis, mutagenesis)" organic pollution, it is widely used in giving birth to
Produce preservative, dyestuff, herbicide and agrochemical.Meanwhile during incineration of waste, association with pulp bleaching, Creation During Chlorination in Domestic Water
It is possible that generating chlorophenols by-product.Common chlorophenols compound has 2,4- Dichlorophenols, 2,4,6- trichlorophenols, 2,3,4,6- tetra-
Chlorophenol and pentachlorophenol etc..This kind of a large amount of of organic compound use, are insufficient and adjoint to the understanding of its toxicity and harm in early days
And come long-standing neglect, result in its continuous accumulation in the environment, to water environment and human health cause directly destroy and
Potential threat.However, conventional method for treating water and biotechnology is difficult effective degrading chlorophenol class compound.In recent years, with light
Catalysis is that the high-level oxidation technology of representative is quickly grown in terms of pollutant environmental improvement, is applied to degrading chlorophenol class compound
Research also achieve notable achievement.
Photocatalysis performance evaluation experimental is the results show that made α-Fe2O3/ gangue compound is to above-mentioned chlorophenols compound
There is preferable degradation effect.The photocatalysis performance evaluation experimental step and data carried out using pentachlorophenol as target degradation product is as follows:
100 mL pentachlorophenol solutions are added in beaker(10 mg/L, pH 9 ~ 10)With 0.1 g α-Fe2O3/ gangue compound
Powder is protected from light 30 min of strong stirring, and pentachlorophenol is made to reach adsorption-desorption balance in catalyst surface.Then in magnetic agitation
Under, using 125 W high voltage mercury lamp radiations(Lamp and 10 cm of liquid level distance)And start timing.Interval sampling, centrifuges, takes
Clear liquid measures it in pentachlorophenol maximum absorption wavelength through filtering with microporous membrane, with ultraviolet-visible spectrophotometer(λ max = 220
nm)The absorbance at place, and according to the degradation rate of following formula calculating pentachlorophenol(η):
η=(A 0−A t)/A 0×100%
In formula,A 0For the absorbance of pentachlorophenol solution before illumination;A tFor the absorbance of pentachlorophenol solution after light application time t.
Fig. 2 is pure α-Fe2O3And different quality ratio α-Fe2O3/ gangue compound photocatalytic degradation pentachlorophenol efficiency is at any time
Between the curve that changes.Blank assay shows, when ultraviolet light, pentachloro- Phenol degradation rate is only 46.92% after 180 min, the phenomenon
For the selfdecomposition of pentachlorophenol.While ultraviolet light, pure α-Fe are put into2O3Or α-Fe2O3/ gangue composite photo-catalyst, phase
With in light application time, the degradation rate of pentachlorophenol significantly improves.It has been observed that all α-Fe2O3The photocatalysis of/gangue compound
Activity is above pure α-Fe2O3, this confirms α-Fe2O3α-Fe in/gangue compound2O3It is implicitly present in and cooperates between gangue
Effect.However, α-Fe2O3It is not the bigger the better with the mass ratio of gangue, mass ratio 3:100 α-Fe2O3/ gangue is multiple
It closes object and shows highest photocatalytic activity, pentachloro- Phenol degradation rate is close to 90% in 180 min.
Embodiment described above is only that the preferred embodiment of the present invention is described, and but it is not limited to this, this
The technical staff in field is easy to understand the spirit of the present invention according to above-described embodiment, and makes different amplification and variation, but
Without departing from the spirit of the present invention, all within protection scope of the present invention.
Claims (10)
1. a kind of α-Fe2O3/ gangue composite photo-catalyst, which is characterized in that it includes that the following raw material is prepared through boiling reflux:
The aqueous solution of molysite and pretreated gangue;The aqueous solution of the molysite is with α-Fe2O3Quality meter and pretreated bastard coal
The mass ratio of stone is 0.5 ~ 5:100.
2. α-Fe according to claim 12O3/ gangue composite photo-catalyst, which is characterized in that described pretreated
Gangue be gangue through crush, ground 150 ~ 300 mesh sieve after, in 700 ~ 900 DEG C calcine 1.5 ~ 3 h after it is spare.
3. α-Fe according to claim 12O3/ gangue composite photo-catalyst, which is characterized in that the molysite includes nitre
Sour iron, iron chloride or ferric sulfate.
4. α-Fe according to claim 12O3/ gangue composite photo-catalyst, which is characterized in that the molysite it is water-soluble
Fe in liquid3+A concentration of 0.4 mol/L of ion.
5. a kind of claim 1 ~ 4 any one of them α-Fe2O3The preparation method of/gangue composite photo-catalyst, feature exist
In comprising following steps:
(1)Gangue is taken, 150 ~ 300 mesh sieve is crossed after crushing, grinding, 1.5 ~ 3 h is calcined in 700 ~ 900 DEG C, is pre-processed
Gangue afterwards;
(2)Prepare Fe3+Ion concentration is the aqueous solution of the molysite of 0.4 mol/L;
(3)Take step(2)5 mL of aqueous solution of prepared molysite is added distilled water and is settled to 100 mL, then adds into solution
Enter step(1)Obtained pretreated gangue, 1 h of magnetic agitation;
The aqueous solution of the molysite is with α-Fe2O3Quality meter, α-Fe2O3Mass ratio with pretreated gangue is 0.5 ~ 5:
100;
(4)Regulating step(3)3 h of boiling reflux after the pH to 9 ~ 11 of obtained reaction system;
(5)Through filtering, water washing and after natural drying is distilled, α-Fe are obtained2O3/ gangue composite photo-catalyst.
6. preparation method according to claim 5, which is characterized in that the step(1)In, gangue is through crushing, grinding
200 mesh sieve is crossed afterwards, and calcination temperature is 800 DEG C, and calcination time is 2 h.
7. preparation method according to claim 5, which is characterized in that the step(2)In, the molysite be ferric nitrate,
Iron chloride or ferric sulfate.
8. preparation method according to claim 5, which is characterized in that the step(3)In, the α-Fe2O3With pretreatment
The mass ratio of gangue afterwards is 1 ~ 4:100, preferably 3:100.
9. preparation method according to claim 5, which is characterized in that the step(4)In, the pH value of the reaction system
It is 10.
10. a kind of α-Fe as described in claim 1 ~ 42O3/ gangue composite photo-catalyst is in degrading chlorophenol class compound
Using.
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