CN106345472A - Method for preparing high-efficient Fenton-like catalyst of sulphur modified iron-based composite material solid acid ceramic film layer and application - Google Patents
Method for preparing high-efficient Fenton-like catalyst of sulphur modified iron-based composite material solid acid ceramic film layer and application Download PDFInfo
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- CN106345472A CN106345472A CN201610638681.3A CN201610638681A CN106345472A CN 106345472 A CN106345472 A CN 106345472A CN 201610638681 A CN201610638681 A CN 201610638681A CN 106345472 A CN106345472 A CN 106345472A
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- composite material
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- 239000005864 Sulphur Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000011973 solid acid Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 36
- -1 sulphur modified iron Chemical class 0.000 title abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 59
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 46
- 239000010962 carbon steel Substances 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 181
- 229910052742 iron Inorganic materials 0.000 claims description 90
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 89
- 230000004048 modification Effects 0.000 claims description 88
- 238000012986 modification Methods 0.000 claims description 88
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 24
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 24
- 239000002351 wastewater Substances 0.000 claims description 23
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 19
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 244000137852 Petrea volubilis Species 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 12
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 12
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- OWAQGBSFGKBQQS-UHFFFAOYSA-N phosphorous acid;sodium Chemical compound [Na].OP(O)O OWAQGBSFGKBQQS-UHFFFAOYSA-N 0.000 claims 1
- 238000005498 polishing Methods 0.000 claims 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 17
- 150000004645 aluminates Chemical class 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
-
- B01J35/657—
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- 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
- 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
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a method for preparing high-efficient Fenton-like catalyst of sulphur modified iron-based composite material solid acid ceramic film layer and an application, and relates to a preparation method of the high-efficient Fenton-like catalyst of the sulphur modified iron-based composite material solid acid ceramic film layer and the application. The invention aims to solve the shortcomings of complex separation and recycling of traditional Fenton-like catalyst and poor catalytic performance under near-neutral or neutral condition. The preparation method includes the first step of performing pretreatment of carbon steel; the second step of placing the bright carbon steel obtained in the first step in electrolyte of a stainless steel electrolytic cell as the anode, connecting the stainless steel electrolytic cell withc athode of power source as the cathode; the third step of supplying power by impulse power, and performing plasma electrolytic oxidation reaction, and obtaining the high-efficient Fenton-like catalyst of the sulphur modified iron-based composite material solid acid ceramic film layer. The invention can obtain a preparation method of the high-efficient Fenton-like catalyst of the sulphur modified iron-based composite material solid acid ceramic film layer.
Description
Technical field
The present invention relates to the preparation method of the efficient class fenton catalyst of a kind of sulphur modification iron base composite material solid acid and should
With.
Background technology
In recent years, the waste water containing persistency, difficult for biological degradation organic pollution entered in environment, carried to environment and the mankind
Carry out while high risks the also removal to sewage and bring great difficulty.Fenton oxidation method as high-level oxidation technology it
One, available fe2+And h2o2Produce strong oxidizing property hydroxyl radical free radical (oh) to aoxidize organic pollution, there is efficiency high and low
Energy consumption, low cost and Green-pollution and widely paid close attention to.However, traditional Fenton oxidation method has catalyst cannot return
The shortcomings of receipts, ph narrow range and output iron cement, in order to overcome the shortcoming of homogeneous catalyst, further develop on this basis
Class fenton catalyst.Class fenton catalyst mainly utilizes iron-based powder body material such as Zero-valent Iron, fe2o3、fe3o4And alumina load
Iron etc. carrys out catalyst h2o2Produce oh and carry out degradation of organic substances.
Traditional class fenton catalyst need to reclaim catalyst by centrifugation or filter method, and then increases its cost recovery
And its degradation efficiency is low and limit it and be widely applied under ph is for weakly acidic pH or neutrallty condition.In order to solve above-mentioned asking
Topic, can prepare the iron oxides film layer catalyst with solid acid characteristic.
Content of the invention
The invention aims to solving traditional class fenton catalyst separation and recovery complexity and in weakly acidic pH or neutral bar
The shortcoming of catalytic performance difference under part, and provide one kind to prepare the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film
The methods and applications of catalyst.
A kind of prepare the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film method be by with
Lower step completes:
First, carbon steel pre-treatment: the surface of carbon steel is carried out beat using 500# sand paper, 1500# sand paper and 2500# sand paper successively
The surface being milled to carbon steel is minute surface；Using the surface 3 times～5 times of deionized water rinsing carbon steel, finally dried up using hair-dryer, obtain
Carbon steel to light；
2nd, the carbon steel of the light obtaining in step one is placed in the electrolyte in stainless steel electrolytic groove, as anode；No
Rust steel electrolysis bath is connected with power cathode, as negative electrode；
3rd, powered using the pulse power, be 1a/cm in electric current density2～20a/cm2, supply frequency 500hz～2500hz,
10 DEG C～50 DEG C of electrolyte temperature and electrolyte ph value are for carrying out plasma electrolytic oxidation reaction under conditions of 9.0～14.0
5min～20min, obtains the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film on carbon steel surface, that is,
Complete a kind of method preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film；
Electrolyte described in step 3 is electrolyte a or electrolyte b；Described electrolyte a is by sodium aluminate, ortho phosphorous acid
Sodium, sodium thiosulfate and water composition；In described electrolyte a the concentration of sodium aluminate be 5g/l～30g/l, sodium hypophosphite dense
Spend for 0.5g/l～2g/l, the concentration of sodium thiosulfate is 0.5g/l～10g/l；Described electrolyte b is by sodium silicate, secondary phosphorous
Sour sodium, sodium peroxydisulfate and water composition；In described electrolyte b the concentration of sodium silicate be 5g/l～30g/l, sodium hypophosphite dense
Spend for 0.5g/l～2g/l, the concentration of sodium peroxydisulfate is 0.5g/l～10g/l.
The efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film is used for processing giving up containing phenol
Water.
Advantages of the present invention:
First, the electrolyte system of the present invention is simple, economical and practical, and preparation process is simple；
2nd, the present invention utilizes plasma electrolysis oxidation method first on carbon steel in aluminate or silicate electrolyte liquid system
It is prepared for the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film；
3rd, the film layer of the sulphur modification iron base composite material pottery efficient class fenton catalyst of solid acid porcelain film layer of present invention preparation
For the grey black film layer of rough porous, average pore size is 3.0 μm；
4th, the present invention can be mass-produced sulphur modification iron base composite material solid acid ceramic film efficient class Fenton catalysis
Agent；
5th, the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film of present invention preparation can be in ph
For under conditions of 7 in 8min the degradation efficiency of Pyrogentisinic Acid up to 100%；
The present invention can obtain one kind and prepare the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
Method.
Brief description
Fig. 1 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment one step 3 obtains in aluminates system
Floor height imitates the xrd collection of illustrative plates of class fenton catalyst；
Fig. 2 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the xrd collection of illustrative plates of class fenton catalyst；
Fig. 3 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the fe 2p3/2 corresponding xps spectrogram of class fenton catalyst；
Fig. 4 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the si 2p corresponding xps spectrogram of class fenton catalyst；
Fig. 5 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the s 2p corresponding xps spectrogram of class fenton catalyst；
Fig. 6 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment one step 3 obtains in aluminates system
Floor height imitates the sem figure that class fenton catalyst amplifies 1000 times；
Fig. 7 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the sem figure that class fenton catalyst amplifies 2000 times；
Fig. 8 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment one step 3 obtains in aluminates system
Floor height imitates the nh of class fenton catalyst3- tpd curve；
Fig. 9 is the sulphur modification iron base composite material ceramic film being obtained in aluminates system using embodiment one step 3
The efficiently degradation efficiency figure of the waste water containing phenol for the class fenton catalyst degraded；
Figure 10 is the sulphur modification iron base composite material ceramic membrane being obtained in silicate systems using embodiment two step 3
Floor height imitates the degradation efficiency figure of the class fenton catalyst waste water containing phenol for the degraded.
Specific embodiment
Specific embodiment one: present embodiment is that one kind prepares sulphur modification iron base composite material solid acid ceramic membrane floor height
The method of effect class fenton catalyst completes according to the following steps:
First, carbon steel pre-treatment: the surface of carbon steel is carried out beat using 500# sand paper, 1500# sand paper and 2500# sand paper successively
The surface being milled to carbon steel is minute surface；Using the surface 3 times～5 times of deionized water rinsing carbon steel, finally dried up using hair-dryer, obtain
Carbon steel to light；
2nd, the carbon steel of the light obtaining in step one is placed in the electrolyte in stainless steel electrolytic groove, as anode；No
Rust steel electrolysis bath is connected with power cathode, as negative electrode；
3rd, powered using the pulse power, be 1a/cm in electric current density2～20a/cm2, supply frequency 500hz～2500hz,
10 DEG C～50 DEG C of electrolyte temperature and electrolyte ph value are for carrying out plasma electrolytic oxidation reaction under conditions of 9.0～14.0
5min～20min, obtains the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film on carbon steel surface, that is,
Complete a kind of method preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film；
Electrolyte described in step 3 is electrolyte a or electrolyte b；Described electrolyte a is by sodium aluminate, ortho phosphorous acid
Sodium, sodium thiosulfate and water composition；In described electrolyte a the concentration of sodium aluminate be 5g/l～30g/l, sodium hypophosphite dense
Spend for 0.5g/l～2g/l, the concentration of sodium thiosulfate is 0.5g/l～10g/l；Described electrolyte b is by sodium silicate, secondary phosphorous
Sour sodium, sodium peroxydisulfate and water composition；In described electrolyte b the concentration of sodium silicate be 5g/l～30g/l, sodium hypophosphite dense
Spend for 0.5g/l～2g/l, the concentration of sodium peroxydisulfate is 0.5g/l～10g/l.
The advantage of present embodiment:
First, the electrolyte system of present embodiment is simple, economical and practical, and preparation process is simple；
2nd, present embodiment utilizes plasma electrolysis oxidation method first in aluminate or silicate electrolyte liquid on carbon steel
It is prepared for the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film in system；
3rd, the sulphur modification iron base composite material pottery efficient class fenton catalyst of solid acid porcelain film layer that prepared by present embodiment
Film layer is the grey black film layer of rough porous, and average pore size is 3.0 μm；
4th, the present embodiment efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film that can be mass-produced is urged
Agent；
5th, the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film of present embodiment preparation can
Ph be Pyrogentisinic Acid in 8min under conditions of 7 degradation efficiency up to 100%；
Present embodiment can obtain one kind to be prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and urges
The method of agent.
Specific embodiment two: the difference from specific embodiment one for the present embodiment is: the carbon described in step one
Steel is q235 carbon steel.Other are identical with specific embodiment one.
Specific embodiment three: the difference from specific embodiment one or two for the present embodiment is: adopt in step 3
The pulse power is powered, and is 1a/cm in electric current density2～10a/cm2, supply frequency 500hz～1000hz, 10 DEG C of electrolyte temperature
～30 DEG C and electrolyte ph value for carrying out plasma electrolytic oxidation reaction 5min～10min under conditions of 9.0～10.0, in carbon
Steel surface obtains the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film, that is, complete one kind and prepare sulfur to change
The method of the property efficient class fenton catalyst of iron base composite material solid acid ceramic film.Other are with specific embodiment one or two-phase
With.
Specific embodiment four: the difference from specific embodiment one to three for the present embodiment is: adopt in step 3
The pulse power is powered, and is 10a/cm in electric current density2～20a/cm2, supply frequency 1000hz～2500hz, electrolyte temperature 30
DEG C～50 DEG C and electrolyte ph value for carrying out plasma electrolytic oxidation reaction 10min～20min under conditions of 12.0～14.0,
Obtain the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film on carbon steel surface, that is, complete one kind and prepare
The method of the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film.Other with specific embodiment one to
Three is identical.
Specific embodiment five: the difference from specific embodiment one to four for the present embodiment is: described electrolyte a
The concentration of middle sodium aluminate is 5g/l～10g/l, and the concentration of sodium hypophosphite is 0.5g/l～1g/l, and the concentration of sodium thiosulfate is
0.5g/l～5g/l.Other are identical with specific embodiment one to four.
Specific embodiment six: the difference from specific embodiment one to five for the present embodiment is: described electrolyte a
The concentration of middle sodium aluminate is 10g/l～30g/l, and the concentration of sodium hypophosphite is 1g/l～2g/l, and the concentration of sodium thiosulfate is
5g/l～10g/l.Other are identical with specific embodiment one to five.
Specific embodiment seven: the difference from specific embodiment one to six for the present embodiment is: described electrolyte b
The concentration of middle sodium silicate is 5g/l～10g/l, and the concentration of sodium hypophosphite is 0.5g/l～1g/l, and the concentration of sodium peroxydisulfate is
0.5g/l～5g/l.Other are identical with specific embodiment one to six.
Specific embodiment eight: the difference from specific embodiment one to seven for the present embodiment is: described electrolyte b
The concentration of middle sodium silicate is 10g/l～30g/l, and the concentration of sodium hypophosphite is 1g/l～2g/l, and the concentration of sodium peroxydisulfate is 5g/
L～10g/l.Other are identical with specific embodiment one to seven.
Specific embodiment nine: present embodiment is the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film
Catalyst is used for processing the waste water containing phenol.
Specific embodiment ten: the difference from specific embodiment nine for the present embodiment is: sulphur modification iron-based composite wood
Material solid acid ceramic film efficient class fenton catalyst is used for the waste water containing phenol for the process and completes according to the following steps:
First the ph of the waste water containing phenol is adjusted to 3～7, then by sulphur modification iron base composite material solid acid ceramic film
Efficiently class fenton catalyst is added in the waste water containing phenol, then low whipping speed is to add under 100r/min～500r/min
Mass fraction is 30% hydrogen peroxide, then low whipping speed is stirring reaction 8min～30min under 100r/min～500r/min,
Water after being processed；The geometric area of the described efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
With the volume ratio (5cm in the waste water containing phenol2～10cm2):50ml；The concentration of the described phenol in wastewater containing phenol
For 20mg/l～50mg/l；The geometry of the described efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
Area and mass fraction are the volume ratio of 30% hydrogen peroxide is (5cm2～10cm2):0.034ml.Other and specific embodiment
Nine is identical.
Using following examples checking beneficial effects of the present invention:
A kind of embodiment one: side preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
Method completes according to the following steps:
First, carbon steel pre-treatment: the surface of carbon steel is carried out beat using 500# sand paper, 1500# sand paper and 2500# sand paper successively
The surface being milled to carbon steel is minute surface；Using the surface 5 times of deionized water rinsing carbon steel, finally dried up using hair-dryer, obtain light
Bright carbon steel；
2nd, the carbon steel of the light obtaining in step one is placed in the electrolyte in stainless steel electrolytic groove, as anode；No
Rust steel electrolysis bath is connected with power cathode, as negative electrode；
3rd, powered using the pulse power, be 15a/cm in electric current density2, supply frequency 2000hz, 30 DEG C of electrolyte temperature
With electrolyte ph value for carrying out plasma electrolytic oxidation reaction 15min under conditions of 10.0, obtain sulphur modification on carbon steel surface
Iron base composite material solid acid ceramic film efficient class fenton catalyst, that is, complete one kind and prepare sulphur modification iron base composite material admittedly
The method of body acid ceramic film efficient class fenton catalyst；
Electrolyte described in step 3 is made up of sodium aluminate, sodium hypophosphite, sodium thiosulfate and water；Described electrolysis
In liquid a, the concentration of sodium aluminate is 10g/l, and the concentration of sodium hypophosphite is 1g/l, and the concentration of sodium thiosulfate is 2g/l.
A kind of embodiment two: side preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
Method completes according to the following steps:
First, carbon steel pre-treatment: the surface of carbon steel is carried out beat using 500# sand paper, 1500# sand paper and 2500# sand paper successively
The surface being milled to carbon steel is minute surface；Using the surface 5 times of deionized water rinsing carbon steel, finally dried up using hair-dryer, obtain light
Bright carbon steel；
2nd, the carbon steel of the light obtaining in step one is placed in the electrolyte in stainless steel electrolytic groove, as anode；No
Rust steel electrolysis bath is connected with power cathode, as negative electrode；
3rd, powered using the pulse power, be 12a/cm in electric current density2, supply frequency 2000hz, 30 DEG C of electrolyte temperature
With electrolyte ph value for carrying out plasma electrolytic oxidation reaction 15min under conditions of 12.0, obtain sulphur modification on carbon steel surface
Iron base composite material solid acid ceramic film efficient class fenton catalyst, that is, complete one kind and prepare sulphur modification iron base composite material admittedly
The method of body acid ceramic film efficient class fenton catalyst；
Electrolyte described in step 3 is made up of sodium silicate, sodium hypophosphite, sodium peroxydisulfate and water；Described electrolyte
In b, the concentration of sodium silicate is 20g/l, and the concentration of sodium hypophosphite is 0.5g/l, and the concentration of sodium peroxydisulfate is 2g/l.
Fig. 1 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment one step 3 obtains in aluminates system
Floor height imitates the xrd collection of illustrative plates of class fenton catalyst；
Fig. 2 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the xrd collection of illustrative plates of class fenton catalyst；
Fig. 3 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the fe 2p3/2 corresponding xps spectrogram of class fenton catalyst；
Fig. 4 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the si 2p corresponding xps spectrogram of class fenton catalyst；
Fig. 5 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the s 2p corresponding xps spectrogram of class fenton catalyst；
Knowable to Fig. 1～Fig. 5, the sulphur modification iron base composite material that embodiment one step 3 obtains in aluminates system is solid
Body acid ceramic film efficient class fenton catalyst and the sulphur modification iron-based that obtains in silicate systems of embodiment two step 3 are multiple
Condensation material solid acid ceramic film efficient class fenton catalyst is respectively sulphur modification fe3o4/feal2o4With sulphur modification fe3o4/
sio2.
Fig. 6 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment one step 3 obtains in aluminates system
Floor height imitates the sem figure that class fenton catalyst amplifies 1000 times；
Fig. 7 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment two step 3 obtains in silicate systems
Floor height imitates the sem figure that class fenton catalyst amplifies 2000 times；
Knowable to Fig. 6～Fig. 7, the sulphur modification iron base composite material that embodiment one step 3 obtains in aluminates system is solid
Body acid ceramic film efficient class fenton catalyst and the sulphur modification iron-based that obtains in silicate systems of embodiment two step 3 are multiple
The film surface of condensation material solid acid ceramic film efficient class fenton catalyst is complicated loose structure, and average pore size is 3.0 μ
m.
Fig. 8 is the sulphur modification iron base composite material solid acid ceramic membrane that embodiment one step 3 obtains in aluminates system
Floor height imitates the nh of class fenton catalyst3- tpd curve；
As it can be observed in the picture that the sulphur modification iron base composite material solid acid that embodiment one step 3 obtains in aluminates system
Ceramic film efficient class fenton catalyst assumes a wide nh from 180 degree～770 degree3Desorption peaks, 180 degree～350 degree,
350 degree～770 degree have two obvious nh3Desorption peaks, correspond to weak acid position and strong acidic site respectively, and the latter's peak area are substantially high
In the former, the sulphur modification iron base composite material solid acid ceramic film that therefore embodiment one step 3 obtains in aluminates system
Efficiently class fenton catalyst is strong solid acids.
First the ph of the waste water containing phenol is adjusted to 7, then by 6cm2The sulphur modification iron-based that embodiment one step 3 obtains
Composite solid acid ceramic film efficient class fenton catalyst is added to 50ml ph value in 7 waste water containing phenol, then
Low whipping speed is to add the hydrogen peroxide that 0.034ml mass fraction is 30% under 150r/min, then low whipping speed is 150r/
Stirring reaction 0min～8min under min, water after being processed；The concentration of the described phenol in wastewater containing phenol is 35mg/
l.Degradation effect is as shown in Figure 9；
Fig. 9 is the sulphur modification iron base composite material ceramic film being obtained in aluminates system using embodiment one step 3
The efficiently degradation efficiency figure of the waste water containing phenol for the class fenton catalyst degraded.
First the ph of the waste water containing phenol is adjusted to 7, then by 6cm2Embodiment two step 3 is in silicate systems
The efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film obtaining is added to 50ml ph value containing for 7
Have in the waste water of phenol, then low whipping speed is to add the hydrogen peroxide that 0.034ml mass fraction is 30% under 150r/min, then
Mixing speed is stirring reaction 0min～8min under 150r/min, water after being processed；Benzene in the described waste water containing phenol
The concentration of phenol is 35mg/l.Degradation effect is as shown in Figure 10；
Figure 10 is the sulphur modification iron base composite material ceramic membrane being obtained in silicate systems using embodiment two step 3
Floor height imitates the degradation efficiency figure of the class fenton catalyst waste water containing phenol for the degraded.
Knowable to Fig. 9～10, the sulphur modification iron-based composite wood that obtained in aluminates system using embodiment one step 3
Expect the sulphur modification iron base composite material ceramic membrane floor height that ceramic film efficient class fenton catalyst and embodiment two step 3 obtain
After effect class fenton catalyst degraded 8min, phenol clearance is up to 100%.
Claims (10)
1. a kind of method preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film, its feature exists
It is according to the following steps in a kind of method preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
Complete:
First, carbon steel pre-treatment: using 500# sand paper, 1500# sand paper and 2500# sand paper, the surface of carbon steel is polishing to successively
The surface of carbon steel is minute surface；Using the surface 3 times～5 times of deionized water rinsing carbon steel, finally dried up using hair-dryer, obtain light
Bright carbon steel；
2nd, the carbon steel of the light obtaining in step one is placed in the electrolyte in stainless steel electrolytic groove, as anode；Rustless steel
Electrolysis bath is connected with power cathode, as negative electrode；
3rd, powered using the pulse power, be 1a/cm in electric current density2～20a/cm2, supply frequency 500hz～2500hz, electrolysis
10 DEG C～50 DEG C of liquid temp and electrolyte ph value for carry out under conditions of 9.0～14.0 plasma electrolytic oxidation reaction 5min～
20min, obtains the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film on carbon steel surface, that is, completes one
Plant the method preparing the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film；
Electrolyte described in step 3 is electrolyte a or electrolyte b；Described electrolyte a by sodium aluminate, sodium hypophosphite,
Sodium thiosulfate and water composition；In described electrolyte a, the concentration of sodium aluminate is 5g/l～30g/l, the concentration of sodium hypophosphite
For 0.5g/l～2g/l, the concentration of sodium thiosulfate is 0.5g/l～10g/l；Described electrolyte b is by sodium silicate, ortho phosphorous acid
Sodium, sodium peroxydisulfate and water composition；In described electrolyte b, the concentration of sodium silicate is 5g/l～30g/l, the concentration of sodium hypophosphite
For 0.5g/l～2g/l, the concentration of sodium peroxydisulfate is 0.5g/l～10g/l.
2. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent is it is characterised in that the carbon steel described in step one is q235 carbon steel.
3. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent, it is characterised in that being powered using the pulse power in step 3, is 1a/cm in electric current density2～10a/cm2, power supply
Frequency 500hz～1000hz, 10 DEG C～30 DEG C of electrolyte temperature and electrolyte ph value for carry out under conditions of 9.0～10.0 etc. from
Daughter electrolytic oxidation reaction 5min～10min, obtains sulphur modification iron base composite material solid acid ceramic membrane floor height on carbon steel surface
Effect class fenton catalyst, that is, complete one kind and prepare the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
Method.
4. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent, it is characterised in that being powered using the pulse power in step 3, is 10a/cm in electric current density2～20a/cm2, electricity
Source frequency 1000hz～2500hz, 30 DEG C～50 DEG C of electrolyte temperature and electrolyte ph value are for carrying out under conditions of 12.0～14.0
Plasma electrolytic oxidation reacts 10min～20min, obtains sulphur modification iron base composite material solid acid ceramic membrane on carbon steel surface
Floor height imitates class fenton catalyst, that is, complete one kind and prepare the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film to urge
The method of agent.
5. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent it is characterised in that in described electrolyte a the concentration of sodium aluminate be 5g/l～10g/l, sodium hypophosphite dense
Spend for 0.5g/l～1g/l, the concentration of sodium thiosulfate is 0.5g/l～5g/l.
6. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent it is characterised in that in described electrolyte a the concentration of sodium aluminate be 10g/l～30g/l, sodium hypophosphite dense
Spend for 1g/l～2g/l, the concentration of sodium thiosulfate is 5g/l～10g/l.
7. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent it is characterised in that in described electrolyte b the concentration of sodium silicate be 5g/l～10g/l, sodium hypophosphite dense
Spend for 0.5g/l～1g/l, the concentration of sodium peroxydisulfate is 0.5g/l～5g/l.
8. one kind according to claim 1 is prepared the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film and is urged
The method of agent it is characterised in that in described electrolyte b the concentration of sodium silicate be 10g/l～30g/l, sodium hypophosphite dense
Spend for 1g/l～2g/l, the concentration of sodium peroxydisulfate is 5g/l～10g/l.
9. a kind of sulphur modification iron base composite material solid acid ceramic membrane floor height according to the preparation method preparation described in claim 1
The application of effect class fenton catalyst is it is characterised in that the efficient class Fenton of sulphur modification iron base composite material solid acid ceramic film is catalyzed
Agent is used for processing the waste water containing phenol.
10. sulphur modification iron base composite material solid acid ceramic film according to claim 9 efficient class fenton catalyst
Application is it is characterised in that the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film contains benzene for process
The waste water of phenol completes according to the following steps:
First the ph of the waste water containing phenol is adjusted to 3～7, then by sulphur modification iron base composite material solid acid ceramic membrane floor height
Effect class fenton catalyst is added in the waste water containing phenol, then low whipping speed is to add matter under 100r/min～500r/min
Amount fraction is 30% hydrogen peroxide, then low whipping speed is stirring reaction 8min～30min under 100r/min～500r/min, obtains
The water to after process；The described geometric area of the efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film with
Volume ratio (5cm in waste water containing phenol2～10cm2):50ml；The concentration of the described phenol in wastewater containing phenol is
20mg/l～50mg/l；The geometric surface of the described efficient class fenton catalyst of sulphur modification iron base composite material solid acid ceramic film
The volume ratio of the long-pending hydrogen peroxide being 30% with mass fraction is (5cm2～10cm2):0.034ml.
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| CN107245749A (en) * | 2017-06-09 | 2017-10-13 | 哈尔滨工业大学 | A kind of method and application that sulfur doping out-phase fenton catalyst is prepared in titanium alloy surface |
| CN109847764A (en) * | 2019-01-09 | 2019-06-07 | 哈尔滨工业大学 | A kind of methods and applications preparing sulphur modification ferriferous oxide film layer type Fenton catalyst |
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