CN117399004A - Iron-loaded coal gasification fine slag catalyst and preparation method and application thereof - Google Patents
Iron-loaded coal gasification fine slag catalyst and preparation method and application thereof Download PDFInfo
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- CN117399004A CN117399004A CN202311334888.8A CN202311334888A CN117399004A CN 117399004 A CN117399004 A CN 117399004A CN 202311334888 A CN202311334888 A CN 202311334888A CN 117399004 A CN117399004 A CN 117399004A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000003245 coal Substances 0.000 title claims abstract description 116
- 238000002309 gasification Methods 0.000 title claims abstract description 112
- 239000002893 slag Substances 0.000 title claims abstract description 111
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 87
- 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 abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000011068 loading method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000002351 wastewater Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 10
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 208000033126 Colobomatous microphthalmia Diseases 0.000 description 120
- 208000034367 isolated with coloboma microphthalmia Diseases 0.000 description 120
- 239000000243 solution Substances 0.000 description 49
- 239000011148 porous material Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
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- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to an iron-loaded coal gasification fine slag catalyst and a preparation method and application thereof. The method comprises the following steps: mixing coal gasification fine slag and an activating agent, placing the mixture in an activating device, roasting the mixture at 800 ℃ in a protective gas atmosphere, sequentially carrying out acid washing and water washing, and drying to obtain modified coal gasification fine slag active carbon; and (3) respectively mixing the modified coal gasification fine slag active carbon and ferric nitrate in water, stirring at room temperature, drying, and roasting at 300 ℃ in an activator under a protective gas atmosphere to obtain the iron-supported coal gasification fine slag catalyst, wherein the iron loading amount in the catalyst is 2-3wt.%. The invention prepares the loaded Fe by adopting a dipping-calcining method 3+ Fine coal gasification slag catalyst of Fe 3+ The method can accelerate the speed of producing hydroxyl free radicals by decomposing hydrogen peroxide in Fenton reaction, improves the degradation treatment capacity of the catalyst on phenol, and has low preparation cost, easy recovery and repeated use.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an iron-loaded coal gasification fine slag catalyst and a preparation method and application thereof.
Background
Phenol in industrial wastewater is a typical toxic substance that can cause cell damage by affecting the coagulation and degradation processes of proteins in living organisms. The phenol derivatives have a wide variety, wide sources and serious harm, and are the difficult problems in the current water pollution treatment in China, wherein the phenol has serious harm to the environment.
The common method for industrially treating phenol-containing wastewater is Fenton (Fenton) oxidation, which has the outstanding advantages of wide application range, convenient operation, high degradation efficiency and the like, and is a technology for catalytically oxidizing organic pollutants by generating active free radicals, particularly hydroxyl free radicals, through chemical reaction under proper conditions. The hydroxyl radical has very strong oxidizing power and can completely decompose organic matters. The Fenton method was unexpectedly discovered by French chemist Fenton in an experiment more than 120 years ago, when he discovered that Fe2+ mixed with H2O2 produced a strong oxidizing effect. However, fenton's reagent was not used to remove persistent organic contaminants during industrial production until the 70 s of the 20 th century. The Fenton method comprises the following specific reaction processes:
Fe+H 2 O 2 →Fe 3+ +OH - +·OH (1)
H 2 O 2 +Fe 3+ →Fe 2+ +HO 2 ·+H + (2)
Fe 2+ +·OH→Fe 3+ +OH - (3)
Fe 2+ +HO 2 ·→Fe 3+ HO 2 (4)
Fe 3+ HO 2 ·→Fe 2+ +O 2 +H + (5)
at present, the Fenton method is widely applied to wastewater treatment, but the used homogeneous catalyst is easy to run off in the treatment process and causes secondary pollution, and the problems of high cost and difficult disposal of iron sludge are also existed.
Coal is an important energy source and accounts for over 70% of the energy consumption. However, the coal burning causes ecological environment pollution, clean utilization of coal is urgently needed, and coal gasification technology is one of the effective ways of clean utilization of coal. However, this technique produces a large amount of coal gasification fine slag, and the discharge amount of coal gasification fine slag in 2022 is reported to exceed 2000 ten thousand tons. The piling and landfill of coal gasification fine slag occupies a large area of land, and the discharged percolate also causes heavy metal pollution to soil and water due to high carbon content and heavy metal content; but simultaneously, because of the high temperature (800-1300 ℃) and chilling effect in the gasification process, the coal gasification fine slag has the characteristics of large specific surface area and even and developed pores, and is favorable for the high-value utilization of the coal gasification fine slag. Therefore, the research on treating the phenol-containing wastewater by using the heterogeneous Fenton catalyst prepared by taking the coal gasification fine slag as the catalyst carrier is significant in promoting the industrial and healthy development of coal chemical industry in China.
Disclosure of Invention
In order to solve the problems, the invention provides an iron-loaded coal gasification fine slag catalyst and a preparation method and application thereof, and the invention prepares the loaded Fe by taking coal gasification fine slag which has extremely low price and needs large-scale high-value application as a carrier and adopting a dipping-calcining method 3+ Fine coal gasification slag catalyst of Fe 3+ The loading rate of the catalyst is 2-3%, the surface of the catalyst has free hydroxyl free radicals, which is helpful for improving the degradation capability of the catalyst to phenol and Fe 3+ The method can accelerate the speed of producing hydroxyl free radicals by decomposing hydrogen peroxide in Fenton reaction, the hydroxyl free radicals can effectively decompose and treat phenol, and the removal rate of phenol in phenol-containing wastewater can exceed 90% by degrading phenol in a heterogeneous Fenton (Fenton) system. The catalyst has the advantages of low preparation cost, easy recovery, repeated use and higher treatment capacity.
The invention solves the technical problems through the following technical proposal.
The first object of the invention is to provide a preparation method of an iron-supported coal gasification fine slag catalyst, which comprises the following steps:
mixing coal gasification fine slag and an activating agent, dehydrating and drying, placing the mixture in an activating device, roasting at 800 ℃ in a protective gas atmosphere, sequentially carrying out acid washing and water washing to neutrality after roasting, and drying to obtain modified coal gasification fine slag active carbon;
and dissolving the obtained modified coal gasification fine slag active carbon in water to obtain a modified coal gasification fine slag active carbon solution, dissolving ferric nitrate in water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, stirring at room temperature, drying to obtain a mixture, placing the mixture in an activator, roasting at 300 ℃ in a protective gas atmosphere, and obtaining the iron-loaded coal gasification fine slag catalyst after roasting is finished, wherein the iron loading amount in the catalyst is 2-3 wt%.
Preferably, the mass ratio of the activator to the coal gasification fine slag activator is 0.5-3: 1.
preferably, the activator is one of potassium hydroxide, zinc chloride and phosphoric acid.
Preferably, in the step of preparing the modified coal gasification fine slag active carbon, the dehydration and drying temperature is 105-200 ℃, the time is 2-6h, the roasting time is 80min, and the drying temperature is 105 ℃ and the time is 12h.
Preferably, the mass volume ratio of the modified coal gasification fine slag active carbon to the water is 3g:100mL, wherein the mass volume ratio of the ferric nitrate to the water is 0.15g:100mL.
Preferably, the volume ratio of the modified coal gasification fine slag active carbon solution to the ferric nitrate solution is 1:1.
Preferably, the stirring time at room temperature is 5 hours, the rotating speed is 10rpm, the drying temperature is 105-110 ℃ and the time is 12 hours.
Preferably, in the roasting process of the mixture, the protective gas is nitrogen, the roasting time is 1h, and the heating rate is 10 ℃/min.
The second purpose of the invention is to provide the iron-supported coal gasification fine slag catalyst prepared by the preparation method.
The second purpose of the invention is to provide the application of the iron-supported coal gasification fine slag catalyst in the catalytic degradation of phenolic wastewater, wherein the catalyst is added into the phenolic wastewater, the pH value is regulated, hydrogen peroxide is added for catalysis, the dosage of the catalyst is 2-4 g/L, the concentration of the phenolic wastewater is 20-50 mg/L, the dosage of the hydrogen peroxide is 10mL/L, the pH value is 5, and the catalysis temperature is 60-80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention takes coal gasification fine slag which has extremely low price and needs large-scale high-value application as a carrier and adopts a dipping-calcining method to prepare the loaded Fe 3+ Fine coal gasification slag catalyst of Fe 3+ The loading rate of the catalyst is 2-3%, the collapse of the holes is generated in the modification process of the loaded iron, the formed holes are more zigzag and long, the surface area of the holes is increased, the volume of the holes is reversely reduced, the mesoporous is taken as the main material, and the surface of the catalyst is provided withFree hydroxyl radical, which is helpful to improve the degradation capability of the catalyst to phenol, fe 3+ The method can accelerate the speed of producing hydroxyl free radicals by decomposing hydrogen peroxide in Fenton reaction, the hydroxyl free radicals can effectively decompose and treat phenol, and the removal rate of phenol in phenol-containing wastewater can exceed 90% by degrading phenol in a heterogeneous Fenton (Fenton) system. The catalyst has the advantages of low preparation cost, easy recovery, repeated use and higher treatment capacity.
(2) The Fe/MAC catalyst prepared by the method has the iron loading capacity of 2.8 wt%, and is added into phenol-containing wastewater to catalyze, and the highest removal rate of the Fe/MAC catalyst to phenol can reach 98.21%. The problems of secondary pollution of iron to wastewater and catalyst separation in the traditional Fenton method are relieved to a great extent, and the Fe/MAC catalyst is low in preparation cost, easy to recycle, reusable and high in treatment capacity.
Drawings
FIG. 1 is an SEM image of the Fe/MAC catalyst of the present invention, in FIG. 1, (a) is coal gasification fine slag, (b) is the MAC catalyst of comparative example 1, (c) is the Fe/MAC catalyst of example 1, and (d) is the Fe/MAC catalyst of example 1 after phenol solution treatment;
FIG. 2 is a schematic diagram of N of the Fe/MAC catalyst of the present invention 2 In FIG. 2, (a) is the comparative example 1MAC catalyst and (b) is the example 1Fe/MAC catalyst;
FIG. 3 shows pore size distribution curves of the Fe/MAC catalyst of the present invention, wherein in FIG. 3, (a) is the MAC catalyst of comparative example 1 and (b) is the Fe/MAC catalyst of example 1;
FIG. 4 is a Fourier infrared spectrum of a Fe/MAC catalyst of the present invention;
FIG. 5 is a standard curve of a phenol solution of the present invention;
FIG. 6 is a graph showing the effect of the Fe/MAC catalyst of the present invention on phenol removal at various reaction times;
FIG. 7 is a graph showing the effect of the Fe/MAC catalyst of the present invention on phenol removal at various temperatures;
FIG. 8 is a graph showing the effect of the Fe/MAC catalyst of the present invention on phenol removal at various phenol concentrations;
FIG. 9 shows the effect of Fe/MAC catalyst of the present invention on phenol removal rate at various dosage levels.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the technical terms used in the present invention are only for describing specific embodiments, and are not intended to limit the scope of the present invention, and various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention may be purchased commercially or prepared by existing methods unless otherwise specifically described.
The invention provides a preparation method of an iron-supported coal gasification fine slag catalyst, which comprises the following steps:
mixing coal gasification fine slag and an activating agent, dehydrating and drying, placing the mixture in an activating device, roasting at 800 ℃ in a protective gas atmosphere, sequentially carrying out acid washing and water washing to neutrality after roasting, and drying to obtain modified coal gasification fine slag active carbon;
and dissolving the obtained modified coal gasification fine slag active carbon in water to obtain a modified coal gasification fine slag active carbon solution, dissolving ferric nitrate in water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, stirring at room temperature, drying to obtain a mixture, placing the mixture in an activator, roasting at 300 ℃ in a protective gas atmosphere, and obtaining the iron-loaded coal gasification fine slag catalyst after roasting is finished, wherein the iron loading amount in the catalyst is 2-3 wt%. .
The invention prepares the loaded Fe by adopting a dipping-calcining method 3+ The Fe/MAC catalyst of coal gasification fine slag has the loading of iron of 2.8wt.% and the added hydrogen peroxide is kept to be 1mL, the pH is adjusted to be 5, the concentration of phenol solution is 40mg/L, and the catalyst is addedAdding 0.2g of catalyst at 70 ℃, adding hydrogen peroxide into phenolic wastewater for catalysis, wherein the highest removal rate of the Fe/MAC catalyst to phenol can reach 98.21%. The problems of secondary pollution of iron to wastewater and catalyst separation in the traditional Fenton method are relieved to a great extent, and the Fe/MAC catalyst is low in preparation cost, easy to recycle, reusable and high in treatment capacity.
In a specific embodiment, the mass ratio of the activator to the coal gasification fine slag activator is 0.5-3: 1.
in a specific embodiment, the activator is one of potassium hydroxide, zinc chloride, and phosphoric acid.
In a specific embodiment, in the step of preparing the modified coal gasification fine slag active carbon, the dehydration and drying temperature is 105-200 ℃, the time is 2-6h, the roasting time is 80min, and the drying temperature is 105 ℃ and the time is 12h.
In a specific embodiment, the mass-to-volume ratio of the modified coal gasification fine slag active carbon to the water is 3g:100mL, wherein the mass volume ratio of the ferric nitrate to the water is 0.15g:100mL.
In a specific embodiment, the volume ratio of the modified coal gasification fine slag active carbon solution to the ferric nitrate solution is 1:1.
In a specific embodiment, the stirring time at room temperature is 5 hours, the rotation speed is 10rpm, the drying temperature is 105-110 ℃ and the time is 12 hours.
In a specific embodiment, during the roasting process of the mixture, the protective gas is nitrogen, the roasting time is 1h, and the heating rate is 10 ℃/min.
The iron-supported coal gasification fine slag catalyst prepared by the preparation method is prepared.
The iron-supported coal gasification fine slag catalyst is applied to catalytic degradation of phenolic wastewater, the catalyst is added into the phenolic wastewater, the pH value is regulated, hydrogen peroxide is added for catalysis, the dosage of the catalyst is 2-4 g/L, the concentration of the phenolic wastewater is 20-50 mg/L, the dosage of the hydrogen peroxide is 10mL/L, the pH value is 5, and the catalysis temperature is 60-80 ℃.
The Fe/MAC catalyst prepared by the method has the iron loading capacity of 2.8 wt%, and is added into phenol-containing wastewater to catalyze, and the highest removal rate of the Fe/MAC catalyst to phenol can reach 98.21%. The problems of secondary pollution of iron to wastewater and catalyst separation in the traditional Fenton method are relieved to a great extent, and the Fe/MAC catalyst is low in preparation cost, easy to recycle, reusable and high in treatment capacity.
The following is further illustrated by specific examples.
Example 1
The preparation method of the iron-supported coal gasification fine slag catalyst comprises the following steps:
s1, uniformly mixing coal gasification fine slag and an activating agent KOH according to a mass ratio of 2:1, dehydrating and drying at 200 ℃ for 120min, placing in a tube furnace, roasting at 800 ℃ for 80min in a nitrogen protection atmosphere, cooling to room temperature after roasting, eluting a reaction product and residual KOH by using hydrochloric acid, repeatedly eluting to obtain clear supernatant by using deionized water, enabling the pH value to be neutral and stable, and drying at 105 ℃ for 12h to obtain alkali modified coal gasification fine slag active carbon, wherein the alkali modified coal gasification fine slag active carbon is named as MAC;
s2, dissolving 3g of the modified coal gasification fine slag active carbon obtained in S1 in 100mL of water to obtain a modified coal gasification fine slag active carbon solution, dissolving 0.15g of ferric nitrate in 100mL of water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, placing the mixture into a constant-temperature magnetic stirrer, stirring at room temperature for 5 hours at the rotating speed of 10rpm, drying at 105 ℃ for 12 hours after stirring, placing the mixture into a tubular furnace, heating to 300 ℃ for roasting at the heating rate of 10 ℃/min around the protective atmosphere of nitrogen, keeping for 1 hour, keeping the nitrogen flow rate at 100cc/min, and cooling to the room temperature after roasting is finished to obtain the iron-loaded coal gasification fine slag catalyst, namely an Fe/MAC catalyst, wherein the iron loading amount in the catalyst is 2.8wt.%.
Example 2
The preparation method of the iron-supported coal gasification fine slag catalyst comprises the following steps:
s1, uniformly mixing coal gasification fine slag and an activating agent KOH according to a mass ratio of 3:1, dehydrating and drying at 150 ℃ for 180min, placing in a tube furnace, roasting at 800 ℃ for 80min in a nitrogen protection atmosphere, cooling to room temperature after roasting, eluting a reaction product and residual KOH by using hydrochloric acid, repeatedly eluting to obtain clear supernatant by using deionized water, enabling the pH value to be neutral and stable, and drying at 105 ℃ for 12h to obtain alkali modified coal gasification fine slag active carbon, wherein the alkali modified coal gasification fine slag active carbon is named as MAC;
s2, dissolving 3g of the modified coal gasification fine slag active carbon obtained in S1 in 100mL of water to obtain a modified coal gasification fine slag active carbon solution, dissolving 0.15g of ferric nitrate in 100mL of water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, placing the mixture into a constant-temperature magnetic stirrer, stirring at room temperature for 5 hours at the rotating speed of 10rpm, drying at 105 ℃ for 12 hours after stirring, placing the mixture into a tubular furnace, heating to 300 ℃ in a nitrogen protection atmosphere at the heating rate of 10 ℃/min, keeping for 1 hour, keeping the nitrogen flow rate of 100cc/min, and cooling to room temperature after the roasting is finished to obtain the iron-loaded coal gasification fine slag catalyst, namely the Fe/MAC catalyst.
The experiment proves that the characterization data of the iron-supported coal gasification fine slag catalyst obtained in the embodiment have no substantial difference with that of the embodiment 1.
Example 3
The preparation method of the iron-supported coal gasification fine slag catalyst comprises the following steps:
s1, uniformly mixing coal gasification fine slag and an activating agent KOH according to the mass ratio of 0.5:1, dehydrating and drying at 180 ℃ for 180min, placing in a tube furnace, roasting at 800 ℃ for 80min in a nitrogen protection atmosphere, cooling to room temperature after roasting, eluting a reaction product and residual KOH by using hydrochloric acid, repeatedly eluting supernatant by using deionized water to be clear and stable to a neutral pH value, and drying at 105 ℃ for 12h to obtain alkali modified coal gasification fine slag active carbon, wherein the alkali modified coal gasification fine slag active carbon is named as MAC;
s2, dissolving 3g of the modified coal gasification fine slag active carbon obtained in S1 in 100mL of water to obtain a modified coal gasification fine slag active carbon solution, dissolving 0.15g of ferric nitrate in 100mL of water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, placing the mixture into a constant-temperature magnetic stirrer, stirring at room temperature for 5 hours at the rotating speed of 10rpm, drying at 105 ℃ for 12 hours after stirring, placing the mixture into a tubular furnace, heating to 300 ℃ in a nitrogen protection atmosphere at the heating rate of 10 ℃/min, keeping for 1 hour, keeping the nitrogen flow rate of 100cc/min, and cooling to room temperature after the roasting is finished to obtain the iron-loaded coal gasification fine slag catalyst, namely the Fe/MAC catalyst.
The experiment proves that the characterization data of the iron-supported coal gasification fine slag catalyst obtained in the embodiment have no substantial difference with that of the embodiment 1.
Example 4
The preparation method of the iron-supported coal gasification fine slag catalyst comprises the following steps:
s1, uniformly mixing coal gasification fine slag and an activating agent KOH according to a mass ratio of 1:1, dehydrating and drying at 150 ℃ for 200min, placing in a tube furnace, roasting at 800 ℃ for 80min in a nitrogen protection atmosphere, cooling to room temperature after roasting, eluting a reaction product and residual KOH by using hydrochloric acid, repeatedly eluting to obtain clear supernatant by using deionized water, enabling the pH value to be neutral and stable, and drying at 105 ℃ for 12h to obtain alkali modified coal gasification fine slag active carbon, wherein the alkali modified coal gasification fine slag active carbon is named as MAC;
s2, dissolving 3g of the modified coal gasification fine slag active carbon obtained in S1 in 100mL of water to obtain a modified coal gasification fine slag active carbon solution, dissolving 0.15g of ferric nitrate in 100mL of water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, placing the mixture into a constant-temperature magnetic stirrer, stirring at room temperature for 5 hours at the rotating speed of 10rpm, drying at 105 ℃ for 12 hours after stirring, placing the mixture into a tubular furnace, heating to 300 ℃ in a nitrogen protection atmosphere at the heating rate of 10 ℃/min, keeping for 1 hour, keeping the nitrogen flow rate of 100cc/min, and cooling to room temperature after the roasting is finished to obtain the iron-loaded coal gasification fine slag catalyst, namely the Fe/MAC catalyst.
The experiment proves that the characterization data of the iron-supported coal gasification fine slag catalyst obtained in the embodiment have no substantial difference with that of the embodiment 1.
Comparative example 1
The preparation method of the coal gasification fine slag catalyst comprises the following steps:
uniformly mixing coal gasification fine slag and an activating agent KOH according to a mass ratio of 2:1, dehydrating and drying the mixture at 200 ℃ for 120min, placing the mixture in a tube furnace, roasting the mixture at 800 ℃ for 80min in a nitrogen protection atmosphere, cooling the mixture to room temperature after roasting, eluting a reaction product and residual KOH by using hydrochloric acid, repeatedly eluting the reaction product and the residual KOH by using deionized water until supernatant is clear, enabling the pH value to be neutral and stable, and drying the mixture at 105 ℃ for 12h to obtain the alkali modified coal gasification fine slag catalyst which is named as MAC.
The Fe/MAC catalyst prepared in example 1 and the MAC catalyst of comparative example 1 were analyzed for surface microscopic morphology using a Sigma300 type field emission scanning electron microscope (manufactured by Chuiss, germany). Fig. 1 is an SEM image of the Fe/MAC catalyst of the present invention, in fig. 1, (a) is coal gasification fine slag (b) is comparative example 1MAC catalyst, (c) is example 1Fe/MAC catalyst, and (d) is example 1Fe/MAC catalyst after phenol solution treatment. As can be seen from fig. 1 (a), the micro morphology of the gasified fine slag is complex, the nano-scale pores with a plurality of irregular structures are distributed on the micro morphology, as can be seen from fig. 1 (b) and (c), at the 100nm size fraction, irregular particles are attached to the surfaces of the MAC and Fe/MAC catalysts, and as can be seen from fig. 1 (c), larger irregular crystalline substances are attached to the surfaces, and the combined energy spectrum analysis shows that iron is successfully attached to the mac—the Fe/MAC catalyst is successfully prepared.
Comparing FIGS. 1 (c) and (d), the Fe/MAC catalyst has greatly changed the surface morphology after adsorbing and catalyzing and degrading phenol, but the iron loading on the Fe/MAC catalyst can still be observed, the pore structure still exists, and the pore structure becomes more developed and loose due to the change of the content of carbon elements, and the following energy spectrum element content analysis is combined: the used Fe/MAC catalyst still has the capability of repeated catalysis, which proves that the Fe/MAC catalyst prepared by the experiment has good stability.
The results of elemental content analysis by an energy spectrometer for the Fe/MAC catalyst and the Fe/MAC catalyst after treating the phenol solution of example 1 are shown in tables 1 and 2. As is clear from Table 1, the modified activated carbon catalyst significantly supported iron element with a loading rate of about 2.80%. As is clear from Table 2, the Fe/MAC catalyst had a catalyst iron loading of 2.69% and a loss of about 3.93% after treating the phenol solution. This indicates that the Fe/MAC catalyst can be fully reused and greatly reduces the treatment strength of iron sludge.
TABLE 1 elemental content analysis of example 1Fe/MAC catalyst
| Element(s) | Mass percent | Atomic percent |
| CK | 3.74 | 6.73 |
| OK | 47.39 | 63.94 |
| MgK | 0.32 | 0.28 |
| AlK | 7.81 | 6.25 |
| SiK | 21.92 | 16.85 |
| SK | 0.43 | 0.29 |
| CaK | 0.72 | 0.39 |
| FeL | 7.25 | 2.80 |
| ZrL | 10.41 | 2.46 |
| Total amount of | 100.00 |
TABLE 2 elemental content analysis of Fe/MAC catalyst after phenol solution treatment
| Element(s) | Weight percent | Atomic percent |
| CK | 35.51 | 52.65 |
| OK | 27.35 | 30.45 |
| AlK | 5.90 | 3.89 |
| SiK | 12.49 | 7.92 |
| SK | 0.55 | 0.30 |
| CaK | 0.77 | 0.34 |
| FeL | 8.43 | 2.69 |
| ZrL | 9.00 | 1.76 |
| Total amount of | 100.00 |
BET analysis was performed on the Fe/MAC catalyst prepared in example 1 and the MAC catalyst of comparative example 1 using a NOVA2000 type specific surface area and microporous analyzer (manufactured by Kanta Co., ltd.).
FIG. 2 is a schematic diagram of N of the Fe/MAC catalyst of the present invention 2 In FIG. 2, (a) is the comparative example 1MAC catalyst and (b) is the example 1Fe/MAC catalyst. As can be seen from FIG. 2, the adsorption curves of the MAC and Fe/MAC catalysts are both IV-type curves of mesoporous materials, and have hysteresis loops and hairsThe fine coagulation phenomenon occurs. The larger the loop, the more secondary pores in the sample, and the larger the pore size distribution range. In general, the pore size can be divided into micropores < 2nm, mesopores of 2 to 50nm and macropores > 50 nm.
As is clear from Table 3, the specific surface area of the coal gasification fine slag after alkali modification is 157.5845m 2 The/g drops to 53.905m 2 And/g, which is caused by the high temperature treatment to destroy the internal structure, increase the particle size and reduce the surface free energy. At the same time pore volume is from 0.21cm 3 The/g drop to 0.13cm 3 The/g also indicates reduced porosity in the MAC, reduced specific surface area and reduced adsorption performance. Fe/MAC catalyst specific surface area after iron loading is 53.905m from MAC 2 Increase/g to 60.3774m 2 The pore volume is reduced from 0.13cm/g to 0.0729cm/g of the MAC, which indicates that the pore collapse is generated in the modification process of the loaded iron, the formed pore is more tortuous and long, the surface area of the pore is increased, the pore volume is reduced instead, and the corresponding average pore diameter is also increased from 4.85nm to 5.08nm of the MAC (the average pore diameter of the more tortuous and long Kong Cechu is larger).
The pore volume also indicates the density of the object, and Kong Rongyue greatly indicates that the strength and hardness of the object become low. As is clear from Table 3, the Fe/MAC catalyst has the smallest pore volume, the largest density and 3.87g/cm -1 So its hardness and strength were the greatest in all 3 samples, conforming to the above relationship (the effect of iron loading on density was essentially negligible, since the iron loading was only 2.8%).
TABLE 3 specific surface area, pore size, pore volume and Density of catalysts
| Name of the name | Specific surface area (m) 2 /g) | Pore volume (cm/g) | Average pore diameter (nm) | Density (g/cm) 3 ) |
| Coal gasification fine slag | 157.5845 | 0.21 | 2.66 | 1.27 |
| Comparative example 1 | 53.905 | 0.13 | 4.85 | 1.45 |
| Example 1 | 60.3774 | 0.0729 | 5.08 | 3.87 |
FIG. 3 shows pore size distribution curves of the Fe/MAC catalyst of the present invention, and in FIG. 3, (a) is the MAC catalyst of comparative example 1, and (b) is the Fe/MAC catalyst of example 1. As can be seen from FIG. 3, the pore size distribution curves of comparative example 1MAC and example 1Fe/MAC show that the main pore size distribution ranges are 2.4 to 6nm and 1.78 to 10nm, respectively, and the mesoporous is the main.
Fourier infrared analysis was performed on comparative example 1MAC and example 1Fe/MAC catalysts, fig. 4 is a fourier infrared spectrum of the Fe/MAC catalyst of the present invention, fig. 4, curve 1 being a MAC catalyst and curve 2 being a Fe/MAC catalyst. As can be seen from FIG. 4, the characteristic peak area of Fe/MAC is 3440cm at wave number -1 The wavelength is-OH association telescopic vibration absorption peak, which shows that the surface of the catalyst has free hydroxyl radicalIs helpful to improve the degradation capability of the catalyst to phenol. At 2362cm -1 The C.ident.C stretching vibration absorption peak is at 1722cm -1 The carboxyl C=O stretching vibration absorption peak is at 1500cm -1 There is a telescopic vibration absorption peak of-C=C-, at 1214cm -1 There is a C-O stretching vibration absorption peak or a C-O-C stretching vibration absorption peak, except for a slight difference in peak intensity. At a wave number of 1065cm -1 The peak area after iron loading was slightly increased compared to the peak area without iron loading, here the-CN telescopic vibration absorption peak.
Application example 1
The simulated phenol wastewater experiments using the Fe/MAC catalyst of example 1 and the MAC catalyst of comparative example 1 included the following steps:
weighing a certain amount of Fe/MAC catalyst, placing the catalyst into a 250mL conical flask, adding 100mL of simulated phenol wastewater with a certain concentration, adjusting the pH value, adding a certain amount of hydrogen peroxide (the mass fraction is 30%), placing the conical flask into a magnetic stirrer, fully stirring, sampling at certain intervals, and filtering by using a needle tube type filter head. Then, the mass concentration of the phenol solution after filtration was measured by an ultraviolet spectrophotometer (UV-2450 type ultraviolet, visible spectrophotometer, manufactured by Shimadzu corporation), and the removal rate was calculated according to the formula. The temperature, catalyst addition, initial concentration of phenol solution and reaction time were then varied and the effect of these factors on simulating the effect of the degradation treatment of phenol wastewater was determined.
Phenol solutions of 2mg/L, 10mg/L, 20mg/L, 40mg/L and 80mg/L are respectively prepared, an ultraviolet spectrophotometry shows that the absorption peak of phenol at the wavelength of 270nm is most obvious, and the absorbance is measured to obtain a standard curve of the phenol aqueous solution. FIG. 5 is a standard curve of a phenol solution of the present invention. As shown in fig. 5, the phenol solution satisfies a linear relationship over a wide concentration range (2 to 80 mg/L): y=0.01711x+0.00324, and the coefficient is r 2 ＝0.99647。
When the added hydrogen peroxide was kept at 1mL, the pH was adjusted to 5, and other conditions were unchanged, the COD (chemical oxygen demand) removal effect (the reaction temperature was 25 ℃ C.) was examined when the MAC and Fe/MAC catalysts (the added amounts were 0.05 g) were reacted with phenol solutions having concentrations of 40mg/L for 1, 2, 3, 4, and 5 hours. FIG. 6 shows the effect of the Fe/MAC catalyst of the present invention on phenol removal at various reaction times. As shown in FIG. 6, comparing the effect of the MAC and Fe/MAC catalysts on treating simulated phenol wastewater, the removal rate of phenol is relatively low and is only 19.76% at maximum when the wastewater is treated by the MAC; the Fe/MAC catalyst removal rate is relatively high and can reach 66.60 percent at most. The Fe/MAC catalyst is loaded with ferric ions, so that the speed of producing hydroxyl free radicals by decomposing hydrogen peroxide in Fenton reaction can be increased, and the hydroxyl free radicals can be effectively decomposed to treat phenol. Meanwhile, the Fe/MAC catalyst has certain adsorption capacity due to the large specific surface area and the tortuous pore structure, so that the effect of treating wastewater by the Fe/MAC catalyst is better under the same condition.
When the added hydrogen peroxide was kept at 1mL, the pH was adjusted to 5, and other conditions were unchanged, the COD removal effect of the reaction of the MAC and Fe/MAC catalysts (the added amounts were 0.2 g) with phenol solutions having a concentration of 40mg/L at temperatures of 30, 40, 50, 60, 70, 80 and 90℃was examined, and FIG. 7 shows the effect of the Fe/MAC catalyst of the present invention on the removal rate of phenol at different temperatures. As can be seen from FIG. 7, under the same conditions, the removal rates of Fe/MAC and MAC on phenol increase with the increase of temperature, and the removal rates of phenol reach the highest at 70 and 60 ℃ respectively, and 98.21% and 89.99% respectively (the removal effect of Fe/MAC catalyst on phenol is easily affected by the reaction temperature and is better than that of MAC at the reaction temperature of 30-90 ℃, because the molecules of Fe/MAC catalyst are greatly activated with the increase of temperature, so that the frequency of interaction is increased and the molecules migrate to the active site, the reaction rate is accelerated, and the hydroxyl radical is generated more quickly. Compared with the Fe/MAC catalyst, the removal effect of the MAC on the phenol is more obviously affected by the temperature when the temperature is 40-60 ℃, but the removal rate of the MAC on the phenol is greatly reduced when the temperature is 60-90 ℃, because the MAC reaches the adsorption saturation point when the temperature is 60 ℃, and the removal rate is rapidly reduced when the temperature is increased again. To be filled withThe experimental temperature was set to 90℃at maximum because H at too high a temperature 2 O 2 Will decompose into O 2 And H 2 O, the reaction rate is not increased and reduced.
When the added hydrogen peroxide was kept at 1mL, the pH was adjusted to 5, and other conditions were unchanged, the COD removal effects (the reaction temperature was 25 ℃ C.) of the reactions of the MAC and Fe/MAC catalysts (the added amounts were 0.05 g) with the simulated phenol solutions having the initial concentrations of 10, 20, 30, 40 and 50mg/L, respectively, were examined, and FIG. 8 shows the effect of the Fe/MAC catalyst of the present invention on the phenol removal rate at different phenol concentrations. As can be seen from FIG. 8, as the initial concentration of the simulated wastewater increases, the removal rate of phenol by the charged Fe/MAC catalyst and the MAC catalyst gradually increases. Overall, fe/MAC catalysts perform better than MAC. The removal effect of the catalyst on phenol was best when the initial concentration was 50mg/L, and the removal rates of the Fe/MAC catalyst and MAC were 48.23% and 32.71%, respectively. As can be seen from FIG. 8, the Fe/MAC catalyst has poor degradation effect on the phenol solution with the concentration of less than 20 mg/L. This is because the amount of Fe/MAC catalyst used is unchanged under the same conditions. The number of hydroxyl radicals generated in the same reaction system is fixed, and the molar quantity of phenol which is oxidized and degraded theoretically is fixed. However, the molar amount of phenol in the solution is initially below a level that results in a low distribution density of phenol that reduces the ability of OH to capture phenol and other organics, indicating that low initial concentrations of phenol solution can result in poor removal efficiency. To maximize catalyst utilization, a suitable initial concentration of phenol solution is 50mg/L. The COD removal rate of the MAC is not good because the purpose of degrading and treating phenol is achieved mainly through the self adsorption performance.
When the added hydrogen peroxide was kept at 1mL, the pH was adjusted to 5, and other conditions were unchanged, the COD removal effect of the reaction of the MAC and Fe/MAC catalysts (the added amounts were 0.2 g) with phenol solutions with a concentration of 40mg/L at temperatures of 30, 40, 50, 60, 70, 80 and 90℃was examined, and FIG. 9 shows the effect of the Fe/MAC catalysts of the present invention on the phenol removal rate at different added amounts. As can be seen from fig. 9, the amount of the catalyst used has a large influence on the phenol removal rate under other conditions. It is observed that the COD removal rate increases and decreases with increasing Fe/MAC catalyst usage. When the catalyst amount was 0.35g, the COD removal rate reached a peak value of 78.42%, but when the catalyst amount was 0.4g, the removal rate was reduced to 61.01%. While changing the amount of the MAC catalyst increases the COD removal rate, when the input exceeds 0.2g, the COD removal rate decreases rapidly. The results show that: when the catalyst input amount is not more than 0.35g, the Fe/MAC catalyst COD removal rate is proportional to the increase in the input amount, and is more susceptible to the input amount than MAC. In summary, the optimal dosage of the simulated phenol wastewater by using the MAC treatment at 25 ℃ is 0.2g, the phenol removal rate is up to 62.40%, the optimal dosage of the Fe/MAC catalyst is 0.35g, and the removal rate is up to 78.42%.
In conclusion, the invention adopts the impregnation-calcination method to prepare the loaded Fe 3+ The Fe/MAC catalyst of coal gasification fine slag has the loading of iron of 2.8 wt%, the added hydrogen peroxide is kept to be 1mL, the pH is adjusted to be 5, the concentration of phenol solution is 40mg/L, the adding amount of the catalyst is 0.2g, the temperature is 70 ℃, the catalyst is added into phenol-containing wastewater, hydrogen peroxide is added for catalysis, and the removal rate of the Fe/MAC catalyst to phenol can reach 98.21 percent at most. The problems of secondary pollution of iron to wastewater and catalyst separation in the traditional Fenton method are relieved to a great extent, and the Fe/MAC catalyst is low in preparation cost, easy to recycle, reusable and high in treatment capacity.
It should be noted that, when numerical ranges are referred to in the present invention, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and because the adopted step method is the same as the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The preparation method of the iron-supported coal gasification fine slag catalyst is characterized by comprising the following steps of:
mixing coal gasification fine slag and an activating agent, dehydrating and drying, placing the mixture in an activating device, roasting at 800 ℃ in a protective gas atmosphere, sequentially carrying out acid washing and water washing to neutrality after roasting, and drying to obtain modified coal gasification fine slag active carbon;
dissolving the obtained modified coal gasification fine slag active carbon in water to obtain a modified coal gasification fine slag active carbon solution, dissolving ferric nitrate in water to obtain a ferric nitrate solution, mixing the modified coal gasification fine slag active carbon solution and the ferric nitrate solution, stirring at room temperature, drying to obtain a mixture, placing the mixture in an activator, roasting at 300 ℃ in a protective gas atmosphere, and obtaining the iron-loaded coal gasification fine slag catalyst after roasting, wherein the iron loading amount in the catalyst is 2-3 wt%.
2. The method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein the mass ratio of the activator to the coal gasification fine slag activator is 0.5-3: 1.
3. the method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein the activator is one of potassium hydroxide, zinc chloride and phosphoric acid.
4. The method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein in the step of preparing the modified coal gasification fine slag active carbon, the dehydration and drying temperature is 105-200 ℃, the time is 2-6h, the shielding gas is nitrogen, the roasting time is 80min, the heating rate is 10 ℃/min, and the drying temperature is 105 ℃ and the time is 12h.
5. The method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein the mass-to-volume ratio of the modified coal gasification fine slag active carbon to water is 3g:100mL, wherein the mass volume ratio of the ferric nitrate to the water is 0.15g:100mL.
6. The method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein the volume ratio of the modified coal gasification fine slag active carbon solution to the ferric nitrate solution is 1:1.
7. The method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein the stirring time at room temperature is 5 hours, the rotating speed is 10rpm, the drying temperature is 105-110 ℃ and the time is 12 hours.
8. The method for preparing the iron-supported coal gasification fine slag catalyst according to claim 1, wherein the shielding gas is nitrogen in the roasting process of the mixture, the roasting time is 1h, and the heating rate is 10 ℃/min.
9. An iron-supported coal gasification fine slag catalyst prepared by the preparation method of any one of claims 1 to 8.
10. The application of the iron-supported coal gasification fine slag catalyst in catalytic degradation of phenolic wastewater, which is characterized in that the catalyst is added into the phenolic wastewater, the pH value is regulated, hydrogen peroxide is added for catalysis, the dosage of the catalyst is 2-4 g/L, the concentration of the phenolic wastewater is 20-50 mg/L, the dosage of the hydrogen peroxide is 10mL/L, the pH value is 5, and the catalysis temperature is 60-80 ℃.
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