CN104925913B - For removing catalyst particle electrode of hardly degraded organic substance and ammonia nitrogen and its preparation method and application in decontamination sewage - Google Patents
For removing catalyst particle electrode of hardly degraded organic substance and ammonia nitrogen and its preparation method and application in decontamination sewage Download PDFInfo
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- CN104925913B CN104925913B CN201510341044.5A CN201510341044A CN104925913B CN 104925913 B CN104925913 B CN 104925913B CN 201510341044 A CN201510341044 A CN 201510341044A CN 104925913 B CN104925913 B CN 104925913B
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- shell carbon
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- active fruit
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- 239000002245 particle Substances 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 239000010865 sewage Substances 0.000 title description 4
- 238000005202 decontamination Methods 0.000 title description 2
- 230000003588 decontaminative effect Effects 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910052751 metal Inorganic materials 0.000 claims abstract description 88
- 239000002184 metal Substances 0.000 claims abstract description 85
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 14
- 201000010099 disease Diseases 0.000 claims abstract description 7
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 69
- 229910017052 cobalt Inorganic materials 0.000 claims description 42
- 239000010941 cobalt Substances 0.000 claims description 42
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 36
- 229910052748 manganese Inorganic materials 0.000 claims description 35
- 239000011572 manganese Substances 0.000 claims description 35
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 238000003911 water pollution Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 230000033558 biomineral tissue development Effects 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 description 39
- 239000008187 granular material Substances 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 239000010936 titanium Substances 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 239000000470 constituent Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 8
- 238000004088 simulation Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- GUTLYIVDDKVIGB-AHCXROLUSA-N Cobalt-55 Chemical compound [55Co] GUTLYIVDDKVIGB-AHCXROLUSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- -1 printing and dyeing Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 description 1
- 229940093265 berberine Drugs 0.000 description 1
- QISXPYZVZJBNDM-UHFFFAOYSA-N berberine Natural products COc1ccc2C=C3N(Cc2c1OC)C=Cc4cc5OCOc5cc34 QISXPYZVZJBNDM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to stain disease process field, and in particular to catalyst particle electrode that hardly degraded organic substance and ammonia nitrogen synchronously remove in stain disease and its preparation method and application.The electrode includes the metal component of particle diameter for 1mm 5mm active fruit shell carbon and load thereon, and the content of the metal component is the 0.8wt% 2.5wt% of activated carbon gross mass.The particle-catalytic electrode filler of the present invention, with catalytic activity it is high, it is cheap and easy to get, prepare simple, COD and ammonia nitrogen degradation removal efficiency are high, water outlet mineralization degree is high, unit COD energy consumptions are low, can be used continuously the characteristics of, the processing suitable for difficult for biological degradation, containing high concentration organic contaminant and high ammonia-nitrogen wastewater.
Description
Technical field
The present invention relates to stain disease process field, and in particular to hardly degraded organic substance and ammonia nitrogen synchronously remove in stain disease
Catalyst particle electrode and its preparation method and application.
Background technology
Waste water caused by the industries such as agricultural chemicals, printing and dyeing, chemical industry, medicine and refuse landfill is mostly difficult degradation organic waste
Water, organic pollution that high concentration is usually contained in these waste water, that having bio-toxicity and stability is strong, using conventional life
After the processing of object space method, still there is part hardly degraded organic substance can not obtain degraded and remove, discharge of wastewater is not reached requirement.
The one kind of electrochemical oxidation technology as high-level oxidation technology, have can carry out at normal temperatures, take up an area it is small, be easy to real
Now automate, degrade completely and the advantages of non-secondary pollution, increasingly attract people's attention.Electrochemical oxidation mainly includes flat
Plate two-dimensional electrode method and three dimensional particles electrode method.Traditional flat board two-dimensional electrode method middle plateform electrode area and the face body ratio of solution
Relatively small, unit cell body treating capacity is small, and current efficiency is low.Based on Three-dimensional Electrode Method is between two-dimentional electrolytic cell plate electrode
Granular or other clastic working electrode materials are loaded as the 3rd electrode, make particle loaded electrode material surface powered, and
Electrochemical reaction occurs for granule electrode surface.Compared with two-dimensional electrode, the specific surface area increase of three-diemsnional electrode, and because particle
Spacing is small, and mass transfer effect is improved, and extends conversion zone and produces the ability of hydroxyl radical free radical, thus has higher electricity
Flow efficiency.
Metal supported catalyst forms catalyst particle electrode, under DC Electric Field, granule electrode on granule electrode
The combination of electrochemical reaction and catalytic action is realized on surface, improves the degraded removal effect of organic pollution.Gold-supported
Category is usually common transition metal and some rare metals, and they all have certain catalytic activity.Chinese patent literature
CN201210270047.0 prepares the clay and γ-Al of the metallic elements such as load Fe, Cu2O3Bipolar three-dimensional electrode catalysis
Agent filler, the processing for difficult for biological degradation organic wastewater；Chinese patent literature CN201310719743.X is prepared with γ-Al2O3
For carrier loaded MnO2、CuO、Fe2O3Deng one or more of collectively as Bipolar Micro-Electrode electrode in conventional metal oxide,
It is aided with ozone-enhanced catalysis oxidation again via hollow fiber separating film water outlet, realizes the efficient drop of difficult for biological degradation organic pollution
Solution；Chinese patent literature CN201310182361.8 is using activated carbon granule and porous ceramic ring compound particle as carrier, load
Ce, Mn, Co element prepare pretreatment and the sewage of low concentration that compound particle electrode is used for high-concentration hardly-degradable organic pollution
Advanced treating.But these catalyst particle electrodes (are inorganic matter i.e. by organic matter degradation in terms of the mineralising of hardly degraded organic substance
Matter) it is still insufficient, and also processing target is more single, can only individually remove hardly degraded organic substance or ammonia nitrogen in waste water, it is difficult to
The two is removed simultaneously, while energy expenditure is still higher, and in the preparation of catalyst particle electrode, for granule electrode sheet
Property not excessive consideration of the body as carrier.
The content of the invention
There is high degradation efficiency, mineralization rate height, unit COD for hardly degraded organic substance it is an object of the invention to provide one kind
It is low to handle energy consumption, while can remove ammonia nitrogen, and the catalyst particle electrode that preparation process is simple and cheap and easy to get.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst particle electrode.
Another object of the present invention is to provide the application of above-mentioned catalyst particle electrode.
For 1mm-5mm active fruit shell carbon and it is carried on according to the three-dimensional catalytic granule electrode of the present invention, including particle diameter
Metal component thereon, the content of the metal component are the 0.8wt%-2.5wt% of activated carbon gross mass.
It is right for the active fruit shell carbon that particle diameter is 1-2mm, the total mol concentration preferred 0.2-0.3mol/L of metal salt solution
The preferred 0.3mol/L of total mol concentration of metal salt solution, it is 3-5mm for particle diameter in the active fruit shell carbon that particle diameter is 2-3mm
Active fruit shell carbon, the preferred 0.4-0.5mol/L of total mol concentration of metal salt solution.
The main composition of catalytic metal is ferro-cobalt element, and two element proportion sums should be greater than total metal molar component
80%, wherein cobalt element proportion should be maintained at more than 50%, and remaining metal component is carried by manganese and nickel element in addition to ferro-cobalt
For.
The method of three-dimensional catalytic granule electrode produced according to the present invention comprises the following steps：
(1) pre-process：A certain amount of active fruit shell carbon is taken, is cleaned up, is dried for standby repeatedly with deionized water.
(2) activate：Activated carbon obtained by step (1) is subjected to surface active with diluted acid, used after drying.
(3) load：The active fruit shell carbon of gained in step (2) is taken, is impregnated in isometric metal salt solution, vibration is anti-
Ying Hou, drying.
(4) it is calcined：Active fruit shell carbon in (3) is placed in N2Protective condition simultaneously completely cuts off in the environment of air, in certain high
Certain time is calcined under the conditions of temperature, obtains catalyst particle electrode.
The active fruit shell carbon carrier of above-mentioned steps (1) described selection has the high rate of adsorption and high-adsorption-capacity capacity, right
In equal organic pollution, the rate of adsorption of active fruit shell carbon is other activated carbons (such as coal mass active carbon, cocoanut active charcoal)
2-4 times, saturated adsorption capacity is 3-10 times of other activated carbons.
Further, above-mentioned steps (1) described deionized water is cleaned to pH value between 6.5-7.5 repeatedly, and drying temperature is
50-80 DEG C, drying time 6-8h.
Above-mentioned steps (2) the surface active condition is：Active fruit shell carbon is impregnated in the dilute nitre of 1mol/L of 1.5-2 times of volume
In acid solution, and 20-30min is boiled, the activation degree that concentration of nitric acid is too low to cause activated carbon is inadequate, too high then to destroy activity
The internal structure of charcoal；Then cleaned with deionized water to pH value between 6.5-7.5, then be cleaned by ultrasonic 20-30min, in 103-105
3-5h is dried under the conditions of DEG C.The ash that ultrasonic procedure can remove inside activated carbon grades impurity, and drying temperature need to be controlled in 103-105
DEG C, to ensure that moisture removes completely.
Above-mentioned steps (3) described metal salt is preferred：Cobalt nitrate, cobaltous sulfate, ferric nitrate, ferrous sulfate, iron chloride, nitric acid
Manganese, manganese chloride, nickel nitrate, nickel sulfate.
Further, the metal ion total mole number in above-mentioned steps (3) described aqueous metal salt is 0.2-0.5mol/
L, each metal molar percentage are：Cobalt 50%-60%, iron 30%-40%, manganese 5%-15%, nickel 5%-15%, each component mole
Percentage sum is 100%.Metal ion total moles ratio shared by cobalt element should be more than 50%, iron cobalt element proportion it
With more than 80%, residual metallic element is made up of manganese and nickel.
Further, above-mentioned steps (3) the oscillating reactions condition is：In rotating speed 120-180rpm shaken cultivation case
Constant temperature (25-30 DEG C) oscillating reactions 8-10h；Drying condition is：103-105 DEG C of dry 3-5h.Temperature control in incubator exists
25-30 DEG C, this temperature range active fruit shell carbon is maximum to the adsorbance of metal component；Rotating speed control is 120-180rpm, rotating speed
It is too low can cause to vibrate it is uneven, it is too high, influence adsorption process.Drying temperature is controlled at 103-105 DEG C, drying time 3-5h,
Moisture is removed completely.
Above-mentioned steps (4) described sintering temperature is 550-750 DEG C, roasting time 3-6h.Sintering temperature is too low or too high
When, the catalytic activity for loading the catalytic metal component of formation on the activated carbon is relatively low.
The preparation method of the catalyst particle electrode of the present invention, it is active fruit shell carbon and metal active group with abundant micropore
Divide integrally to sinter at 550-750 DEG C and form, preparation method is simple.The particle-catalytic electrode being prepared using this method is three
Packing material is used as in dimension electrode system, the high rate of adsorption and high-adsorption-capacity of granule electrode carrier had both been remained, and had made organic
Pollutant in large quantities and can be adsorbed promptly on granule electrode surface, and the addition of catalytic metal component substantially increases again urges
Change activity, help to adsorb organic macromolecule pollutant on granule electrode surface and promptly degrade and mineralising, be not easy it
Resulted in blockage on granule electrode surface, greatly enhance particle-catalytic electrode service life and waste water in the reactor
Residence time, and then can greatly reduce processing cost.
The catalyst particle electrode of the present invention is handled under the same conditions as being contrasted under packing material, and two-dimensional system
Organic wastewater with difficult degradation thereby, COD clearance can be improved to more than 95% from 30%~35%.For the color removal of waste water from dyestuff
Rate can be promoted to more than 98% from 40%~50%.Compared to the catalyst particle electrode COD of load unit element clearance 74%
~80%, also it is obviously improved.In addition, the catalyst particle electrode of the present invention handles the organic waste containing ammonia nitrogen as packing material
During water, the clearance of ammonia nitrogen can reach more than 80%.
On the other hand, the catalyst particle electrode of the present invention, can under very low current density (＜ 2mA/cm2) produce very
Catalytic effect well, in 5mA/cm2Current density under, in general organic pollution permineralization, mineralization rate can be reached
More than 98%.(COD when handling the organic wastewater of high concentration>When 2000mg/L), unit COD consumes energy in 10kWh/kgCOD
Hereinafter, equivalent to the 1/7~1/3 of general catalyst particle electrode unit COD power consumptions (30~60kWh/kgCOD).And
After long-term use, when some regions of surface are covered by the organic pollution of some extremely difficult degradeds, pass through high current in the short time
The method of density can reactivate particle-catalytic electrode, substantially increase the service life of particle-catalytic electrode.
The catalyst particle electrode of the present invention, compared with existing activated carbon supported metal granule electrode, there is advantages below：
1) high catalytic efficiency.Under appropriate flow condition, can dynamic continuous processing sewage, treatment effect is stable；2) energy consumption is low.Processing
During high concentrated organic wastewater, unit COD power consumptions are only the 1/5~1/3 of general activated carbon catalysis granule electrode unit COD power consumptions；
3) mineralization rate is high.Mineralization degree need not be improved by electric current is improved, also can be organic by general under the conditions of low current density
Pollutant permineralization, mineralization rate reach more than 98%；4) ammonia nitrogen can be removed simultaneously.The activated carbon supported metal particle electricity of in general
Pole processing target is more single, the one kind that can only be gone in removal organic polluter or ammonia nitrogen.
The present invention have selected the active fruit shell carbon with high absorption property as catalyst particle carrier, shortens organic matter and arrives
Up to the time on granule electrode surface, and the quantity that organic matter in the unit interval reaches particle surface is added, make catalyst particle electric
Pole forms the efficient degradation process of a hardly degraded organic substance " absorption-catalysis-degraded remove ", constitute new absorption-
Catalytic degradation three-dimensional electrodes system.Compared with general catalyst particle electrode, catalyst particle electrode catalyst of the invention activity is high,
More than 98% mineralization degree can be reached to hardly degraded organic substance, while hardly degraded organic substance is removed, in waste water
Ammonia nitrogen can also reach more than 80% removal effect, unit COD (COD) power consumption as little as 4-10kWh/kgCOD,
Waste water residence time in the reactor and processing cost are greatly reduced.
In summary, particle-catalytic electrode filler of the invention, have catalytic activity it is high, it is cheap and easy to get, prepare it is simple,
COD and ammonia nitrogen degradation removal efficiency are high, water outlet mineralization degree is high, unit COD energy consumptions are low, the characteristics of being used continuously, and are applied to
Difficult for biological degradation, the processing containing high concentration organic contaminant and high ammonia-nitrogen wastewater.
Embodiment
Embodiment 1
The catalyst particle electrode material of this example, include 2~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 2.5wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 2~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
6h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 1.5 times of volumes, and boils 25min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 25min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.5mol/L metal salt solutions
Molar percentage be：Cobalt 50%, iron 40%, manganese 5%, nickel 5%, each component mole percent sum are 100%.Cobalt is with nitric acid
The mode of cobalt is added, and iron is added in a manner of ferric nitrate, and manganese is added in the form of manganese chloride, and nickel is added in a manner of nickel sulfate),
4h is dried under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition and the environment for completely cutting off air
In, it is calcined 4h under the conditions of 600 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles simulation Acid Red B waste water from dyestuff, and in influent COD=140~150mg/L, absorbance is 3.4~3.5, and electric current is
Handled under conditions of 0.2A, water outlet, which reaches, after 30min stablizes, and the clearance to COD and colourity is respectively 92.5% He
98.9%.
Embodiment 2
The catalyst particle electrode material of this example, include 4~5mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 1.9wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 4~5mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 60 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 1.5 times of volumes, and boils 20min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 25min, 5h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.5mol/L metal salt solutions
Molar percentage be：Cobalt 55%, iron 35%, manganese 5%, nickel 5%, each component mole percent sum are 100%.Cobalt is with sulfuric acid
The mode of cobalt is added, and iron is added in a manner of iron chloride, and manganese is added in the form of manganese chloride, and nickel is added in a manner of nickel sulfate),
4h is dried under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition and the environment for completely cutting off air
In, it is calcined 5h under the conditions of 550 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles simulation Acid Red B waste water from dyestuff, and in influent COD=140~150mg/L, absorbance is 3.4~3.5, and electric current is
Handled under conditions of 0.2A, water outlet, which reaches, after 30min stablizes, and the clearance to COD and colourity is respectively 91.2% He
97.2%.
Embodiment 3
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 1.6wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 2.5 times of volumes, and boils 30min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 30min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.4mol/L metal salt solutions
Molar percentage be：Co 60 %, iron 30%, manganese 5%, nickel 5%, each component mole percent sum are 100%.Cobalt is with nitric acid
The mode of cobalt is added, and iron is added in a manner of ferrous sulfate, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel nitrate
Enter), dry 3h under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition simultaneously completely cuts off air
In environment, 3h is calcined under the conditions of 750 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles simulation Acid Red B waste water from dyestuff, and in influent COD=140~150mg/L, absorbance is 3.4~3.5, and electric current is
Handled under conditions of 0.2A, water outlet, which reaches, after 30min stablizes, and the clearance to COD and colourity is respectively 90.4% He
96.8%.
Embodiment 4
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 1.2wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 1.5 times of volumes, and boils 30min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 30min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.3mol/L metal salt solutions
Molar percentage be：Cobalt 50%, iron 30%, manganese 15%, nickel 5%, each component mole percent sum are 100%.Cobalt is with sulphur
The mode of sour cobalt is added, and iron is added in a manner of ferrous sulfate, and manganese is added in the form of manganese chloride, and nickel is added in a manner of nickel nitrate
Enter), dry 3h under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition simultaneously completely cuts off air
In environment, 4h is calcined under the conditions of 650 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles simulation Acid Red B waste water from dyestuff, and in influent COD=140~150mg/L, absorbance is 3.4~3.5, and electric current is
Handled under conditions of 0.2A, water outlet, which reaches, after 30min stablizes, and the clearance to COD and colourity is respectively 88.2% He
90.9%.
Embodiment 5
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 0.8wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 2 times of volumes, and boils 30min, so
Cleaned afterwards with deionized water to pH value 7 or so, then be cleaned by ultrasonic 30min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon be impregnated in isometric total mole number in 0.2mol/L metal salt solutions (wherein each metal active constituent
Molar percentage is：Cobalt 50%, iron 30%, manganese 5%, nickel 15%, each component mole percent sum are 100%.Cobalt is with nitric acid
The mode of cobalt is added, and iron is added in a manner of ferrous sulfate, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel nitrate
Enter), dry 3h under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition simultaneously completely cuts off air
In environment, 4h is calcined under the conditions of 700 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles simulation Acid Red B waste water from dyestuff, and in influent COD=140~150mg/L, absorbance is 3.4~3.5, and electric current is
Handled under conditions of 0.2A, water outlet, which reaches, after 30min stablizes, and the clearance to COD and colourity is respectively 87.6% He
90.1%.
Embodiment 6
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 2.3wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
6h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 2 times of volumes, and boils 25min, so
Cleaned afterwards with deionized water to pH value 7 or so, then be cleaned by ultrasonic 25min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon be impregnated in isometric total mole number in 0.5mol/L metal salt solutions (wherein each metal active constituent
Molar percentage is：Cobalt 50%, iron 35%, manganese 10%, nickel 5%, each component mole percent sum are 100%.Cobalt is with nitric acid
The mode of cobalt is added, and iron is added in a manner of ferric nitrate, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel sulfate),
3h is dried under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition and the environment for completely cutting off air
In, it is calcined 5h under the conditions of 600 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode Treatment of Wastewater in Coking raw water, in influent COD=2650~2890mg/L, NH3- N=120~140mg/L, electrical conductivity are
10.81~11.14ms/cm, electric current are handled under conditions of being 0.6A, and water outlet, which reaches, after 60min stablizes, the removal to COD
Rate reaches more than 80%, reaches more than 90% to the clearance of ammonia nitrogen, unit COD energy consumptions are 6~8kWh/kg COD.
Embodiment 7
The catalyst particle electrode material of this example, include 4~5mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 1.7wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 4~5mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 1.5 times of volumes, and boils 25min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 25min, 5h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.4mol/L metal salt solutions
Molar percentage be：Cobalt 55%, iron 30%, manganese 5%, nickel 10%, each component mole percent sum are 100%.Cobalt is with nitre
The mode of sour cobalt is added, and iron is added in a manner of iron chloride, and manganese is added in the form of manganese sulfate, and nickel is added in a manner of nickel sulfate
Enter), dry 3h under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition simultaneously completely cuts off air
In environment, 4h is calcined under the conditions of 550 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode Treatment of Wastewater in Coking bio-chemical effluent.In influent COD=170~190mg/L, NH3- N=18~21mg/L, electrical conductivity are
5.3~5.6ms/cm, current condition are handled under conditions of being 0.3A, and water outlet, which reaches, after 60min stablizes, the removal to COD
Rate reaches 85%~87%, reaches more than 95% to the clearance of ammonia nitrogen.
Embodiment 8
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 2.0wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 2 times of volumes, and boils 25min, so
Cleaned afterwards with deionized water to pH value 7 or so, then be cleaned by ultrasonic 30min, 5h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon be impregnated in isometric total mole number in 0.4mol/L metal salt solutions (wherein each metal active constituent
Molar percentage is：Cobalt 50%, iron 30%, manganese 10%, nickel 10%, each component mole percent sum are 100%.Cobalt is with sulfuric acid
The mode of cobalt is added, and iron is added in a manner of iron chloride, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel sulfate),
3h is dried under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition and the environment for completely cutting off air
In, it is calcined 4h under the conditions of 700 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode Treatment of Wastewater in Coking raw water, in influent COD=2460~2710mg/L, NH3- N=110~135mg/L, electrical conductivity are
10.12~11.56ms/cm, electric current are handled under conditions of being 0.6A, and water outlet, which reaches, after 60min stablizes, the removal to COD
Rate reaches 78%~80%, reaches 90%~92% to the clearance of ammonia nitrogen, unit COD energy consumptions are less than 8kWh/kg COD.
Embodiment 9
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 2.5wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 2.5 times of volumes, and boils 30min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 30min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.5mol/L metal salt solutions
Molar percentage be：Cobalt 55%, iron 35%, manganese 5%, nickel 5%, each component mole percent sum are 100%.Cobalt is with sulfuric acid
The mode of cobalt is added, and iron is added in a manner of ferrous sulfate, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel nitrate
Enter), dry 5h under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition simultaneously completely cuts off air
In environment, 5h is calcined under the conditions of 650 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, it is stainless using ruthenium titanium electrode as anode
Steel mesh is negative electrode, and catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using being back to back
The mode Treatment of Wastewater in Coking bio-chemical effluent of water.In influent COD=160~190mg/L, NH3- N=21~26mg/L, electrical conductivity
For 7.61~7.85ms/cm, current condition carries out long-term disposal under conditions of being 0.3A, after 60min water outlet reach stable, it is right
COD clearance reaches 80% or so, reaches more than 90% to the clearance of ammonia nitrogen.After continuous processing one week, under effect slightly has
Drop, COD clearance is 70%~72%, and the clearance of ammonia nitrogen is 80% or so.When electric current is increased to 0.6A, continue 6h
After subtract back 0.3A, COD clearance and can reaches 80% or so after stable water outlet.
Embodiment 10
The catalyst particle electrode material of this example, include 1~3mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 2.4wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 1~3mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 2 times of volumes, and boils 30min, so
Cleaned afterwards with deionized water to pH value 7 or so, then be cleaned by ultrasonic 25min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon be impregnated in isometric total mole number in 0.5mol/L metal salt solutions (wherein each metal active constituent
Molar percentage is：Cobalt 55%, iron 30%, manganese 10%, nickel 5%, each component mole percent sum are 100%.Cobalt is with nitric acid
The mode of cobalt is added, and iron is added in a manner of iron chloride, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel sulfate),
3h is dried under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition and the environment for completely cutting off air
In, it is calcined 4h under the conditions of 650 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles phenolic waste water, and in influent COD=2000mg/L, electric current is handled under conditions of being 0.6A, after 50min water outlet reach
To stabilization, 82%~84% is reached to COD clearance.
Embodiment 11
The catalyst particle electrode material of this example, include 4~5mm of diameter active fruit shell carbon and active metal component, institute
The content for stating metal component is the 2.0wt% of activated carbon gross mass, and preparation method comprises the following steps：
A certain amount of 4~5mm of diameter active fruit shell carbon is taken, is cleaned up repeatedly with deionized water to pH value 7 or so,
8h is dried under the conditions of 80 DEG C, then active fruit shell carbon is dipped in the 1mol/L dilute nitric acid solutions of 1.5 times of volumes, and boils 20min,
Then cleaned with deionized water to pH value 7 or so, then be cleaned by ultrasonic 25min, 4h is dried under the conditions of 103 DEG C.Again will be modified
Active fruit shell carbon afterwards is impregnated in isometric total mole number as (wherein each metal active constituent in 0.5mol/L metal salt solutions
Molar percentage be：Cobalt 55%, iron 35%, manganese 5%, nickel 5%, each component mole percent sum are 100%.Cobalt is with sulfuric acid
The mode of cobalt is added, and iron is added in a manner of iron chloride, and manganese is added in the form of manganese nitrate, and nickel is added in a manner of nickel sulfate),
3h is dried under the conditions of 103 DEG C.The active fruit shell carbon after drying is finally placed in N again2Protective condition and the environment for completely cutting off air
In, it is calcined 5h under the conditions of 600 DEG C.
The catalyst particle electrode material of acquisition is applied in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net
For negative electrode, catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode, using continuous flow
Mode handles simulation berberine waste water, in influent COD=1820~2310mg/L, NH3- N=76~130mg/L, electric current are
Handled under conditions of 0.6A, water outlet, which reaches, after 60min stablizes, and reaches 76%~80% to COD clearance, to ammonia nitrogen
Clearance reaches 86%~90%, and unit COD energy consumptions are 8~10kWh/kg COD.
Comparative example 1
By different granule electrode materials applications in 3 D electrode reactor, using ruthenium titanium electrode as anode, titanium net is the moon
Pole, granule electrode material are formed three-diemsnional electrode oxidation system between being filled in anode and cathode, handled by the way of continuous flow
Acid Red B waste water from dyestuff is simulated, in influent COD=140~150mg/L, absorbance is 3.4~3.5, and electric current is 0.2A condition
Under handled, flow 15mL/min, as a result as shown in table 1.
The treatment effect of the different types of activated carbon particles electrode pair waste water from dyestuff of table 1
When doing granule electrode using active fruit shell carbon, the treatment effect of three-diemsnional electrode is substantially better than other kinds of activity
Charcoal, is not only embodied in COD clearance, and percent of decolourization is also clearly.It is catalyzed being formed to active fruit shell carbon supported catalyst metal
After granule electrode, the COD clearances and percent of decolourization of waste water from dyestuff can be lifted further, wherein COD clearances by loading before
72% be promoted to 87%~92%, percent of decolourization is also promoted to more than 90%.
Comparative example 2
Particle diameter is used to load the particle-catalytic electrode of multiple metallic element as carrier, preparation for 1-2mm active fruit shell carbon,
The total mol concentration of metal salt solution is 0.3mol/L, is loaded respectively by following mole of composition：
Composition 1：Cobalt 30%, iron 50%, nickel 10%, manganese 10%；
Composition 2：Cobalt 30%, iron 30%, nickel 20%, manganese 20%；
Composition 3：Cobalt 50%, iron 30%, nickel 15%, manganese 5%；
Composition 4：Cobalt 50%, iron 20%, nickel 15%, manganese 15%；
Composition 5：Cobalt 70%, iron 20%, nickel 5%, manganese 5%；
Composition 6：Cobalt 70%, iron 10%, nickel 10%, manganese 10%.
Wherein, the addition form of cobalt can be cobalt nitrate, and the addition form of iron can be ferric nitrate, and the addition form of nickel can be nitre
Sour nickel, the addition form of manganese can be manganese nitrate, and other preparation processes are identical in addition to ratio.The particle-catalytic electrode prepared is filled out
Material is filled between anode and cathode, is formed three-diemsnional electrode oxidation system, is handled simulation Acid Red B respectively by the way of continuum micromeehanics
Waste water from dyestuff.In influent COD=140~150mg/L, the concentration of electrolyte sodium sulphate is 0.03mol/L, and electric current is 0.2A bar
Handled under part, after flow 15mL/min, 40min water outlet reach stable state, COD clearance is respectively 76.9%,
79.4%, 88.2%, 89.4%, 95.1%, 91.2%.
Comparative example 3
Using the active fruit shell carbon of different-grain diameter as granule electrode, a mole composition for carried metal component is cobalt 70%, iron
20%th, nickel 5%, manganese 5%, prepare catalyst particle electrode material at different conditions.Applied in 3 D electrode reactor, with ruthenium
Ti electrode is anode, and titanium net is negative electrode, and catalyst particle electrode material forms three-diemsnional electrode oxidation system between being filled in anode and cathode,
Simulation Acid Red B waste water from dyestuff is handled by the way of continuous flow, in influent COD=140~150mg/L, absorbance is
3.4~3.5, the concentration of electrolyte sodium sulphate is 0.03mol/L, and electric current is handled under conditions of being 0.2A, flow 15mL/
Min, as a result as shown in table 2.
The treatment effect of the catalyst particle electrode pair waste water from dyestuff prepared under the different condition of table 2
When using particle diameter for 1-2mm active fruit shell carbon as carrier, the preferred 0.2- of total mol concentration of metal salt solution
0.3mol/L, now increase loaded metal component content and unobvious are lifted to treatment effect；Use shell of the particle diameter for 2-3mm
When activated carbon is as carrier, the preferred 0.3mol/L of total mol concentration of metal salt solution, shell activity of the particle diameter for 4-5mm is used
When charcoal is as carrier, the active metal component content of load is higher, and the treatment effect of catalyst particle electrode is better, now metal salt
The preferred 0.4-0.5mol/L of total mol concentration of solution.
Claims (3)
1. the catalyst particle electrode that hardly degraded organic substance and ammonia nitrogen synchronously remove in stain disease, it is characterised in that the electrode bag
The metal component of particle diameter for 1mm-5mm active fruit shell carbon and load thereon is included, the content of the metal component is activity
The 0.8wt%-2.5wt% of charcoal gross mass, the total moles based on metal component, contain cobalt 50%-60%, iron 30%-40%, manganese
5%-15%, nickel 5%-15%, wherein, the preparation method of the catalyst particle electrode comprises the following steps：
(1) pre-process：Active fruit shell carbon is cleaned repeatedly with deionized water to pH value between 6.5-7.5, drying temperature 50-80
DEG C, drying time 6-8h；
(2) activate：Activated carbon obtained by step (1) is subjected to surface active with diluted acid, used after drying, wherein, the surface is lived
The condition of change is：Active fruit shell carbon is impregnated in the 1mol/L dilute nitric acid solutions of 1.5-2 times of volume, and boils 20-30min, so
Cleaned afterwards with deionized water to pH value between 6.5-7.5, then be cleaned by ultrasonic 20-30min, 3-5h is dried under the conditions of 103 DEG C；
(3) load：The active fruit shell carbon of gained in step (2) is taken, is impregnated in isometric metal salt solution, the metal salt
It is anti-for cobalt nitrate, cobaltous sulfate, ferric nitrate, ferrous sulfate, iron chloride, manganese nitrate, manganese chloride, nickel nitrate and/or nickel sulfate, vibration
Ying Hou, drying,
Wherein, the metal ion total mole number in the metal salt solution is 0.2-0.5mol/L, wherein, it is 1- for particle diameter
2mm active fruit shell carbon, the total mol concentration of metal salt solution is 0.2-0.3mol/L, is lived for the shell that particle diameter is 2-3mm
Property charcoal, the total mol concentration of metal salt solution is 0.3mol/L, for particle diameter be 4-5mm active fruit shell carbon, metal salt solution
Total mol concentration be 0.4-0.5mol/L,
Wherein, oscillating reactions condition is：The oscillating reactions 8-10h under the conditions of rotating speed 120-180rpm, 25-30 DEG C of temperature；
(4) it is calcined：Active fruit shell carbon in (3) is placed in N2Protective condition simultaneously completely cuts off in the environment of air, in 550-750 DEG C of height
Temperature roasting 3-6h, obtains catalyst particle electrode.
2. the catalyst particle electrode that hardly degraded organic substance and ammonia nitrogen synchronously remove in stain disease according to claim 1, its
It is characterised by, the metal component includes cobalt, iron, and cobalt and iron account for more than the 80% of total metal molar component ratio, wherein cobalt institute
More than 50%, remainder is made up of accounting example manganese, nickel metal component.
3. the catalyst particle electrode that hardly degraded organic substance and ammonia nitrogen synchronously remove in stain disease described in claim 1 is controlled in water pollution
Application in terms of reason.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341044.5A CN104925913B (en) | 2015-06-18 | 2015-06-18 | For removing catalyst particle electrode of hardly degraded organic substance and ammonia nitrogen and its preparation method and application in decontamination sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341044.5A CN104925913B (en) | 2015-06-18 | 2015-06-18 | For removing catalyst particle electrode of hardly degraded organic substance and ammonia nitrogen and its preparation method and application in decontamination sewage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104925913A CN104925913A (en) | 2015-09-23 |
| CN104925913B true CN104925913B (en) | 2017-12-08 |
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| CN109336225A (en) * | 2018-12-03 | 2019-02-15 | 北京林业大学 | The mosaic electrode and preparation method thereof removed for nitrate nitrogen in sewage treatment plant tail water |
| CN112495388A (en) * | 2020-10-23 | 2021-03-16 | 华南师范大学 | Electrocatalyst for heterogeneous catalytic treatment of refractory landfill leachate and preparation method and application thereof |
| CN114477377B (en) * | 2020-10-27 | 2023-07-21 | 中国石油化工股份有限公司 | Electrode material for three-dimensional electrode, and preparation method and application thereof |
| CN113582297A (en) * | 2021-07-29 | 2021-11-02 | 北京林业大学 | Preparation method and application of nickel-iron double-element loaded particle electrode |
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| CN114105259B (en) * | 2021-12-01 | 2024-06-11 | 南京环保产业创新中心有限公司 | Cu-Co-PAC particle electrode, preparation method and application thereof |
| CN114249391A (en) * | 2021-12-15 | 2022-03-29 | 盐城工学院 | Preparation method of activated carbon column loaded nickel phosphate particle electrode |
| CN114249389A (en) * | 2021-12-15 | 2022-03-29 | 盐城工学院 | Preparation method of nickel hydroxide activated carbon column three-dimensional particle electrode |
| CN114249390A (en) * | 2021-12-15 | 2022-03-29 | 盐城工学院 | Preparation method of cobalt-nickel phosphate activated carbon-based particle electrode |
| CN114409028B (en) * | 2022-02-11 | 2024-04-16 | 中海油天津化工研究设计院有限公司 | Three-dimensional particle electrode for wastewater treatment and preparation method thereof |
| CN115974239B (en) * | 2023-02-23 | 2024-04-19 | 广东工业大学 | Particle electrode and preparation method and application thereof |
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| CN102867654B (en) * | 2012-09-10 | 2015-08-19 | 中国科学院大连化学物理研究所 | A kind of graphitization active carbon electrode material for ultracapacitor and preparation method |
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