CN103539225B - Internal-circulating fluidized bed electro-catalytic reactor for treating chemical organic wastewater and operation conditions of reactor - Google Patents
Internal-circulating fluidized bed electro-catalytic reactor for treating chemical organic wastewater and operation conditions of reactor Download PDFInfo
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- CN103539225B CN103539225B CN201310525732.8A CN201310525732A CN103539225B CN 103539225 B CN103539225 B CN 103539225B CN 201310525732 A CN201310525732 A CN 201310525732A CN 103539225 B CN103539225 B CN 103539225B
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Abstract
The invention discloses an internal-circulating fluidized bed electro-catalytic reactor, and belongs to the technical field of electrochemical treatment of high-concentration organic wastewater. The reactor comprises an electrolytic tank, electrode slots, a Pt-loaded titanium based anode plate on the basis of modification of NiO-FeO-ZnO, a stainless steel cathode plate, an Ag-loaded MnO2-CeO2 doped activated aluminum oxide particle electrode containing a CuO interlayer, a buffering funnel, an air inlet pipe, a wire and a stabilized voltage and current power supply; the top part of the buffering funnel is connected with the bottom part of the electrolytic tank; the air inlet pipe is mounted at the bottom part of the buffering funnel; four electrode slots are formed in the electrolytic tank and used for allowing the stainless steel cathode plate and the Pt-loaded titanium based anode plate on the basis of the modification of NiO-FeO-ZnO to be plugged; the Ag-loaded MnO2-CeO2 doped activated aluminum oxide particle electrode containing the CuO interlayer is uniformly fed into the electrolytic tank. The manufactured internal-circulating fluidized bed electro-catalytic reactor has the beneficial effects of being efficient in treatment of chemical organic wastewater, low in cost and simple to operate.
Description
Technical field
The invention belongs to the electrochemical treatment technical field of high concentrated organic wastewater, be specifically related to a kind of Internal Circulating Fluidized Bed electric catalysis reactor and operational conditions of processing chemical industrial organic wastewater.
Background technology
Electro-catalytic oxidation technology carrys out the organic pollutant in degrading waste water by producing the active group of the strong oxidizing properties such as hydroxyl radical free radical, there is non-secondary pollution, cost is low, suitability is strong, efficiency high, has application potential processing aspect high density, bio-refractory waste water.For strengthening the electrocatalysis treatment effect of bio-refractory waste water, improving electrolyzer unit volume effecting reaction area, mass transfer effect and current efficiency is very crucial problem, therefore needs the efficient electric catalysis reactor of development of new.Meanwhile, the exploitation of reactor and the electrode preparation that matches are with it combined and carried out, it is one of emphasis of research at present that the catalytic efficiency of electrode is not fully exerted.Therefore select applicable electrode materials and to its modification, to improve the surface catalysis performance of electrode, just become the new problem of electrochemist's research.Over nearly 30 years, titanium substrate anode plate has developed into the principal mode of metal oxide electrode, modifies at present the metal oxide that titanium electrode uses and mainly contains ruthenium oxide, manganese oxide, plumbous oxide, platinum oxide, iridium oxide, tin-antimony oxide etc.The surface microstructure of electro catalytic electrode and state are the important factors that affects electrocatalysis characteristic, and the preparation method of electrode directly has influence on the surface tissue of electrode, thereby to select suitable electrode preparation method be to improve the vital key link of electrode electro catalytic activity.Also lack at present the research of being prepared by the exploitation of reactor and the electrode that matches with it to the aspect that combines.
Summary of the invention
The object of this invention is to provide a kind of Internal Circulating Fluidized Bed electric catalysis reactor and operational conditions of processing chemical industrial organic wastewater.Particular content of the present invention is as follows:
Internal Circulating Fluidized Bed electric catalysis reactor is by electrolyzer (1), electrode slot (2), the supporting Pt titanium substrate anode plate (3) of modifying based on NiO-FeO-ZnO, stainless steel cathode plate (4), containing the loaded Ag doped with Mn O in CuO middle layer
2-CeO
2activated alumina granule electrode (5), surge hopper (6), inlet pipe (7), electric wire (8), current regulator power supply (9) form.The top of surge hopper (6) is connected with the bottom of electrolyzer (1), the height of surge hopper (6) is 1/2nd of electrolyzer (1) height, the length of surge hopper (6) bottom is 1/5th of the cross-section face length of electrolyzer, and the wide of surge hopper (6) bottom is 1/5th of the cross-section face width of electrolyzer; In the bottom of surge hopper (6), be installed into tracheae (7); 4 electrode slots (2) are installed altogether on electrolyzer (1), every two slots are a pair of, lay respectively on the front and opposite walls of electrolyzer (1), on slot, be uniformly distributed the screens that width is 2mm, be used for the supporting Pt titanium substrate anode plate (3) that inserts stainless steel cathode plate (4) and modify based on NiO-FeO-ZnO, the spacing of screens is 10mm; With electric wire (8), stainless steel cathode plate (4) is connected with current regulator power supply (9) with the supporting Pt titanium substrate anode plate (3) of modifying based on NiO-FeO-ZnO; Finally by the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode (5) evenly drops in electrolyzer (1).When using Internal Circulating Fluidized Bed electric catalysis reactor to process chemical industrial organic wastewater, best working conditions is: pH value is 5.5, and voltage is 15V, and the treatment time is 120min.
Wherein, the described supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO is prepared by the following method:
(1) with No. 240 aluminum oxide water-proof abrasive papers, titanium plate surface is polished to occurring metalluster, then put it in culture dish, pour 50mL acetone into, in 40kHz ultrasonic washing instrument, with detergent solution, clean oil removing 30min, take out and first with tap water, rinse, use again deionized water rinsing, be then placed on and in 40kHz ultrasonic washing instrument, use washed with de-ionized water 15min;
(2) titanium sheet step (1) being obtained is placed on etching 2h in 10% oxalic acid solution, then take out and first with tap water, rinse, with being placed on after deionized water rinsing in 40kHz ultrasonic instrument, use washed with de-ionized water 15min again, after drying, be kept in dehydrated alcohol standby;
(3) titanium plate surface that utilizes glow discharge to obtain step (2) carries out pre-treatment 10min, then on MS56A type high-vacuum multi-target magnetic control sputtering machine, complete magnetron sputtering platinum plating and obtain substance A, wherein cathode targets is platinized platinum, titanium sheet is as anode substrate, operator scheme is radio-frequency sputtering, and vacuum tightness is 8.0 * 10
-2pa, power is 100W, argon pressure is 1pa;
(4) propyl carbinol, Virahol, isopropylcarbinol, dehydrated alcohol are mixed in equal-volume ratio, obtain solution A; By Ni (NO
3)
2.6H
2o is soluble in water, and to make concentration be the solution of 0.5mol/L and add 5 nitric acid in case hydrolysis obtains solution B; By Fe (NO
3)
39H
2o is soluble in water makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution C; By Zn (NO
3)
26H
2o is soluble in water makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution D;
(5) by solution B, solution C, solution D by volume 10:10:1 mix, obtain solution E 1, by solution E 1 with solution A equal-volume than mixing, after shaking up, be divided into 4 parts of equivalent, obtain solution F1-1, solution F1-2, solution F1-3, solution F1-4;
(6) by solution B, solution C, solution D by volume 5:5:1 mix, obtain solution E 2, by solution E 2 with solution A equal-volume than mixing, after shaking up, be divided into 2 parts of equivalent, obtain solution F2-1, solution F2-2;
(7) by solution B, solution C, solution D by volume 1:1:1 mix, obtain solution E 3, by solution E 3 with solution A equal-volume than mixing, after shaking up, be divided into 3 parts of equivalent, obtain solution F3-1, solution F3-2, solution F3-3;
(8) by solution B, solution C, solution D by volume 1:1:5 mix, obtain solution E 4, by solution E 4 with solution A equal-volume than mixing, after shaking up, be divided into 2 parts of equivalent, obtain solution F4-1, solution F4-2;
(9) by solution B, solution C, solution D by volume 1:1:10 mix, obtain solution E 5, by solution E 5 with solution A equal-volume than mixing, after shaking up, be divided into 4 parts of equivalent, obtain solution F5-1, solution F5-2, solution F5-3, solution F5-4;
(10) substance A step (3) being obtained is immersed in solution F1-1, and evenly floods under magnetic stirring apparatus effect, after 3h, takes out and dries, and then dry 10h under 100 ℃ of conditions, obtains substance B 1;
(11) substance B 1 is immersed in solution F1-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance B 2;
(12) substance B 2 is immersed in solution F1-3, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance B 3;
(13) substance B 3 is immersed in solution F1-4, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance B 4;
(14) substance B 4 is immersed in solution F2-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance C 1;
(15) substance C 1 is immersed in solution F2-2, under magnetic stirring apparatus effect, after even dipping 3h, takes out and dry, under 100 ℃ of conditions, dry 10h, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance C 2;
(16) substance C 2 is immersed in solution F3-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material D1;
(17) material D1 is immersed in solution F3-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material D2;
(18) material D2 is immersed in solution F3-3, under magnetic stirring apparatus effect, after even dipping 3h, takes out and dry, under 100 ℃ of conditions, dry 10h, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material D3;
(19) material D3 is immersed in solution F4-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material E1;
(20) material E1 is immersed in solution F4-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material E2;
(21) material E2 is immersed in solution F5-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material F1;
(22) material F1 is immersed in solution F5-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material F2;
(23) material F2 is immersed in solution F5-3, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material F3;
(24) material F3 is immersed in solution F5-4, and evenly flood under magnetic stirring apparatus effect, after 3h, take out and dry, then under 100 ℃ of conditions, be dried 10h, dried material is placed in to retort furnace roasting 4h under 600 ℃ of conditions, and the material obtaining is the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO.
The described loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode is prepared by the following method:
(1) γ-Al that is 3-5mm by 300g particle diameter
2o
3ball 500ml deionized water wash, repeated washing 3 times, then puts into 200ml dehydrated alcohol and soaks 10h, and with after 500ml washed with de-ionized water 1 time, under 80 ℃ of conditions, dry 10h, obtains particulate matter A;
(2) AgNO that is 0.5mol/L by 50ml concentration
3add in 150ml Virahol, obtain solution A;
(3) particulate matter A step (1) being obtained adds in the solution A that step (2) obtains, and in shaking table, shake 3h, filtration obtains particulate matter B and microemulsion X, the washing with alcohol particulate matter B that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter C;
(4) particulate matter C step (3) being obtained is placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter D;
(5) particulate matter D step (4) being obtained adds in the microemulsion X that step (3) obtains, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter E, the washing with alcohol particulate matter E that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, is then placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter F;
(6) Ce (NO that is 0.5mol/L by 10ml concentration
3)
2the CuCl that solution and 100ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 10ml concentration be the MnCl of 0.5mol/L
2solution, is divided into 5 parts of equivalent after shaking up, obtain solution B
1, solution B
2, solution B
3, solution B
4, solution B
5;
(7) solution B that particulate matter F step (5) being obtained adds step (6) to obtain
1in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G1, the washing with alcohol particulate matter G1 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
1;
(8) particulate matter H step (7) being obtained
1the solution B that adds step (6) to obtain
2in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G2, the washing with alcohol particulate matter G2 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
2;
(9) particulate matter H step (8) being obtained
2the solution B that adds step (6) to obtain
3in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G3, the washing with alcohol particulate matter G3 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
3;
(10) particulate matter H step (9) being obtained
3the solution B that adds step (6) to obtain
4in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G4, the washing with alcohol particulate matter G4 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
4;
(11) particulate matter H step (10) being obtained
4the solution B that adds step (6) to obtain
5in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G5, the washing with alcohol particulate matter G5 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
5; By H
5be placed in retort furnace roasting 4h under 580 ℃ of conditions, obtain particulate matter I;
(12) Ce (NO that is 0.5mol/L by 20ml concentration
3)
2the CuCl that solution and 80ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 20ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution C;
(13) particulate matter I step (11) being obtained adds in the solution C that step (12) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter J, the washing with alcohol particulate matter J that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter K;
(14) Ce (NO that is 0.5mol/L by 40ml concentration
3)
2the CuCl that solution and 40ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 40ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution D;
(15) particulate matter K step (13) being obtained adds in the solution D that step (14) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter L, the washing with alcohol particulate matter L that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter M;
(16) Ce (NO that is 0.5mol/L by 45ml concentration
3)
2the CuCl that solution and 15ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 60ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution E;
(17) particulate matter M step (15) being obtained adds in the solution E that step (16) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter N, the washing with alcohol particulate matter N that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter O;
(18) Ce (NO that is 0.5mol/L by 15ml concentration
3)
2the CuCl that solution and 5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 100ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution F;
(19) particulate matter O step (17) being obtained adds in the solution F that step (18) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter P, the washing with alcohol particulate matter P that is 95% by 100mL mass concentration, repeated washing 2 times, then under 80 ℃ of conditions, be dried 10h, obtain particulate matter Q, Q is placed in to retort furnace roasting 4h under 580 ℃ of conditions, and the particulate matter obtaining is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode.
The invention has the beneficial effects as follows, Internal Circulating Fluidized Bed electric catalysis reactor is high to chemical industrial organic wastewater processing efficiency, cost is low, simple to operate.
Accompanying drawing explanation
Accompanying drawing 1 is the skeleton view of Internal Circulating Fluidized Bed electric catalysis reactor.In accompanying drawing 1,1 is electrolyzer, and 2 is electrode slot, and 3 is the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO, and 4 is stainless steel cathode plate, and 5 is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode, 6 is surge hopper, and 7 is inlet pipe, and 8 is electric wire, and 9 is current regulator power supply.
Embodiment
Embodiment
(1) preparation process of Internal Circulating Fluidized Bed electric catalysis reactor is as follows:
The length of electrolyzer is 60mm, and wide is 50mm, and height is 120mm.The length at surge hopper top is 60mm, and wide is 50mm, and the length of bottom is 12mm, and wide is 10mm, and height is 60mm, and surge hopper is connected with the bottom of electrolyzer, in the bottom of surge hopper, the inlet pipe that diameter is 8mm is installed.Have 4 electrode slots, every two slots are a pair of, lay respectively on the front and opposite walls of electrolyzer, slot is below 35mm apart from the distance of bottom of electrolytic tank, slot is above 85mm apart from the distance of bottom of electrolytic tank, on each slot, be uniformly distributed the screens that width is 2mm, the spacing of screens is 10mm, for intubating length, is that 60mm, width are stainless steel cathode plate and the supporting Pt titanium substrate anode plate based on NiO-FeO-ZnO modification that 40mm, thickness are 2mm.With electric wire, stainless steel cathode plate is connected with current regulator power supply with the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO.Finally by the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode evenly drops in electrolyzer.
(2) the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO is prepared by following process:
By length, be that 60mm, width are that the titanium sheet that 40mm, thickness are 2mm occurs metalluster with No. 240 aluminum oxide water-proof abrasive paper polishings to surface, then put it in culture dish, pour 50mL acetone into, in 40kHz ultrasonic washing instrument, with detergent solution, clean oil removing 30min, then take out first and rinse with 500mL tap water, use again 100mL deionized water rinsing, then be placed on and in 40kHz ultrasonic washing instrument, use washed with de-ionized water 15min; Then the titanium sheet after cleaning is placed on to 100mL mass concentration and is etching 2h in 10% oxalic acid solution, take out first and rinse with 500mL tap water, use again 100mL deionized water rinsing, be placed on again in 40kHz ultrasonic instrument and use washed with de-ionized water 15min, after drying, be kept in dehydrated alcohol standby;
Taking-up is kept at the titanium sheet in dehydrated alcohol, utilize glow discharge to carry out pre-treatment 10min to its surface, then on MS56A type high-vacuum multi-target magnetic control sputtering machine, complete magnetron sputtering platinum plating and obtain substance A, wherein cathode targets is platinized platinum, titanium sheet is as anode substrate, operator scheme is radio-frequency sputtering, and vacuum tightness is 8.0 * 10
-2pa, power is 100W, argon pressure is 1pa;
150mL propyl carbinol, 150mL Virahol, 150mL isopropylcarbinol and 150mL dehydrated alcohol are mixed, obtain 600mL solution A; By 29.1 grams of Ni (NO
3)
2.6H
2o is dissolved in 200mL water and makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution B; By 40.4 grams of Fe (NO
3)
39H
2o is dissolved in 200mL water and makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution C; By 29.7 grams of Zn (NO
3)
26H
2o is dissolved in 200mL water and makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution D;
50mL solution B, 50mL solution C, 5mL solution D are mixed, obtain 105mL solution E 1, by the broad liquid E1 of 105mL with 105mL solution A than mixing, after shaking up, be divided into 4 parts of equivalent, obtain 52.5mL solution F1-1,52.5mL solution F1-2,52.5mL solution F1-3,52.5mL solution F1-4;
25mL solution B, 25mL solution C, 5mL solution D are mixed, obtain 55mL solution E 2,55mL solution E 2 is mixed with 55mL solution A, after shaking up, be divided into 2 parts of equivalent, obtain 55mL solution F2-1,55mL solution F2-2;
25mL solution B, 25mL solution C, 25mL solution D are mixed, obtain 75mL solution E 3,75mL solution E 3 is mixed with 75mL solution A, after shaking up, be divided into 3 parts of equivalent, obtain 50mL solution F3-1,50mL solution F3-2,50mL solution F3-3;
10mL solution B, 10mL solution C, 50mL solution D are mixed, obtain 70mL solution E 4,70mL solution E 4 is mixed with 70mL solution A, after shaking up, be divided into 2 parts of equivalent, obtain 70mL solution F4-1,70mL solution F4-2;
10mL solution B, 10mL solution C, 100mL solution D are mixed, obtain 120mL solution E 5,120mL solution E 5 is mixed with 120mL solution A, after shaking up, be divided into 4 parts of equivalent, obtain 60mL solution F5-1,60mL solution F5-2,60mL solution F5-3,60mL solution F5-4;
Substance A is immersed in 52.5mL solution F1-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance B 1;
B1 is immersed in 52.5mL solution F1-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance B 2;
B2 is immersed in 2 to 52.5mL solution F1-3, and evenly flood under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance B 3;
B3 is immersed in 3 to 52.5mL solution F1-4, and evenly flood under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance B 4;
B4 is immersed in 55mL solution F2-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance C 1;
C1 is immersed in 55mL solution F2-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance C 2;
C2 is immersed in 50mL solution F3-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material D1;
D1 is immersed in 50mL solution F3-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material D2;
D2 is immersed in 50mL solution F3-3, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material D3;
Material D3 is immersed in 70mL solution F4-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material E1;
Material E1 is immersed in 70mL solution F4-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material E2;
E2 is immersed in 60mL solution F5-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material F1;
F1 is immersed in 60mL solution F5-2, under magnetic stirring apparatus effect, evenly floods, after 3h, taking-up is dried 10h after drying under 100 ℃ of conditions, and dried material is placed in to retort furnace roasting 4h under 600 ℃ of conditions, obtains material F2;
F2 is immersed in 60mL solution F5-3, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material F3;
F3 is immersed in 60mL solution F5-4, and evenly flood under magnetic stirring apparatus effect, after 3h, take out and dry, then under 100 ℃ of conditions, be dried 10h, dried material is placed in to retort furnace roasting 4h under 600 ℃ of conditions, and the material obtaining is the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO.
(3) contain the loaded Ag doped with Mn O in CuO middle layer
2-CeO
2activated alumina granule electrode is prepared by the following method:
γ-the Al that is 3-5mm by 300g particle diameter
2o
3ball 500ml deionized water wash, repeated washing 3 times, then puts into 200ml dehydrated alcohol and soaks 10h, and with after 500ml washed with de-ionized water 1 time, under 80 ℃ of conditions, dry 10h, obtains particulate matter A.
The AgNO that is 0.5mol/L by 50ml concentration
3add in 150ml Virahol, obtain solution A.Particulate matter A is joined in solution A, and shake 3h in shaking table, filter and obtain particulate matter B and microemulsion X, the washing with alcohol particulate matter B that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter C; Particulate matter C is placed in to retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter D; Particulate matter D is joined in microemulsion X, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter E, the washing with alcohol E that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, is then placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter F.
Ce (the NO that is 0.5mol/L by 10ml concentration
3)
2the CuCl that solution and 100ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 10ml concentration be the MnCl of 0.5mol/L
2solution, is divided into 5 parts of equivalent after shaking up, obtain solution B
1, solution B
2, solution B
3, solution B
4, solution B
5;
Particulate matter F is joined to solution B
1in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G1, the washing with alcohol particulate matter G1 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
1; By particulate matter H
1join solution B
2in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G2, the washing with alcohol particulate matter G2 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
2; By particulate matter H
2join solution B
3in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G3, the washing with alcohol particulate matter G3 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
3; By particulate matter H
3join solution B
4in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G4, the washing with alcohol particulate matter G4 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
4; By particulate matter H
4join solution B
5in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G5, the washing with alcohol particulate matter G5 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
5; By H
5be placed in retort furnace roasting 4h under 580 ℃ of conditions, obtain particulate matter I.
Ce (the NO that is 0.5mol/L by 20ml concentration
3)
2the CuCl that solution and 80ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 20ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution C.
Particulate matter I is joined in solution C, and shake 3h in shaking table; Remove by filter liquid and obtain particulate matter J, the washing with alcohol particulate matter J that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter K.
Ce (the NO that is 0.5mol/L by 40ml concentration
3)
2the CuCl that solution and 40ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 40ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution D.
Particulate matter K is joined in solution D, and shake 3h in shaking table; Remove by filter liquid and obtain particulate matter L, the washing with alcohol particulate matter L that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter M.
Ce (the NO that is 0.5mol/L by 45ml concentration
3)
2the CuCl that solution and 15ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 60ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution E.
Particulate matter M is joined in solution E, and shake 3h in shaking table; Remove by filter liquid and obtain particulate matter N, the washing with alcohol particulate matter N that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter O.
Ce (the NO that is 0.5mol/L by 15ml concentration
3)
2the CuCl that solution and 5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 100ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution F.
Particulate matter O is joined in solution F, and in shaking table, shake 3h; Remove by filter liquid and obtain particulate matter P, the washing with alcohol particulate matter P that is 95% by 100mL mass concentration, repeated washing 2 times, then under 80 ℃ of conditions, be dried 10h, obtain particulate matter Q, Q is placed in to retort furnace roasting 4h under 580 ℃ of conditions, and the particulate matter obtaining is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode.
(4) degradation experiment
The Internal Circulating Fluidized Bed electric catalysis reactor that uses the present invention to obtain has carried out Degrading experiment to chemical industrial organic wastewater, result shows that this reactor can efficiently remove Coal Gas Washing Cycling Water organic compound, when influent COD is 856mg/L, in pH value, be 5.5, voltage is 15V, treatment time is under 120min condition, and the COD after processing in water outlet is reduced to 82mg/L, and processing efficiency reaches 90.42%.
Claims (2)
1. an Internal Circulating Fluidized Bed electric catalysis reactor, it is characterized in that, this Internal Circulating Fluidized Bed electric catalysis reactor is by electrolyzer, electrode slot, the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO, stainless steel cathode plate, containing the loaded Ag doped with Mn O in CuO middle layer
2-CeO
2activated alumina granule electrode, surge hopper, inlet pipe, electric wire and current regulator power supply form; The top of surge hopper is connected with the bottom of electrolyzer, and the height of surge hopper is 1/2nd of electrolyzer height, and the length of surge hopper bottom is 1/5th of the cross-section face length of electrolyzer, and the wide of surge hopper bottom is 1/5th of the cross-section face width of electrolyzer; Bottom at surge hopper is installed into tracheae; 4 electrode slots are installed altogether on electrolyzer, for the supporting Pt titanium substrate anode plate that inserts stainless steel cathode plate and modify based on NiO-FeO-ZnO; Loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode is evenly distributed in electrolyzer; Wherein, the described supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO is prepared by the following method:
(1) with No. 240 aluminum oxide water-proof abrasive papers, titanium plate surface is polished to occurring metalluster, then put it in culture dish, pour 50mL acetone into, in 40kHz ultrasonic washing instrument, with detergent solution, clean oil removing 30min, take out and first with tap water, rinse, use again deionized water rinsing, be then placed on and in 40kHz ultrasonic washing instrument, use washed with de-ionized water 15min;
(2) titanium sheet step (1) being obtained is placed on etching 2h in 10% oxalic acid solution, then take out and first with tap water, rinse, with being placed on after deionized water rinsing in 40kHz ultrasonic instrument, use washed with de-ionized water 15min again, after drying, be kept in dehydrated alcohol standby;
(3) titanium plate surface that utilizes glow discharge to obtain step (2) carries out pre-treatment 10min, then on MS56A type high-vacuum multi-target magnetic control sputtering machine, complete magnetron sputtering platinum plating and obtain substance A, wherein cathode targets is platinized platinum, titanium sheet is as anode substrate, operator scheme is radio-frequency sputtering, and vacuum tightness is 8.0 * 10
-2pa, power is 100W, argon pressure is 1pa;
(4) propyl carbinol, Virahol, isopropylcarbinol, dehydrated alcohol are mixed in equal-volume ratio, obtain solution A; By Ni (NO
3)
2.6H
2o is soluble in water, and to make concentration be the solution of 0.5mol/L and add 5 nitric acid in case hydrolysis obtains solution B; By Fe (NO
3)
39H
2o is soluble in water makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution C; By Zn (NO
3)
26H
2o is soluble in water makes the solution that concentration is 0.5mol/L, adds 5 nitric acid in case hydrolysis obtains solution D;
(5) by solution B, solution C, solution D by volume 10:10:1 mix, obtain solution E 1, by solution E 1 with solution A equal-volume than mixing, after shaking up, be divided into 4 parts of equivalent, obtain solution F1-1, solution F1-2, solution F1-3, solution F1-4;
(6) by solution B, solution C, solution D by volume 5:5:1 mix, obtain solution E 2, by solution E 2 with solution A equal-volume than mixing, after shaking up, be divided into 2 parts of equivalent, obtain solution F2-1, solution F2-2;
(7) by solution B, solution C, solution D by volume 1:1:1 mix, obtain solution E 3, by solution E 3 with solution A equal-volume than mixing, after shaking up, be divided into 3 parts of equivalent, obtain solution F3-1, solution F3-2, solution F3-3;
(8) by solution B, solution C, solution D by volume 1:1:5 mix, obtain solution E 4, by solution E 4 with solution A equal-volume than mixing, after shaking up, be divided into 2 parts of equivalent, obtain solution F4-1, solution F4-2;
(9) by solution B, solution C, solution D by volume 1:1:10 mix, obtain solution E 5, by solution E 5 with solution A equal-volume than mixing, after shaking up, be divided into 4 parts of equivalent, obtain solution F5-1, solution F5-2, solution F5-3, solution F5-4;
(10) substance A step (3) being obtained is immersed in solution F1-1, and evenly floods under magnetic stirring apparatus effect, after 3h, takes out and dries, and then dry 10h under 100 ℃ of conditions, obtains substance B 1;
(11) substance B 1 is immersed in solution F1-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance B 2;
(12) substance B 2 is immersed in solution F1-3, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance B 3;
(13) substance B 3 is immersed in solution F1-4, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance B 4;
(14) substance B 4 is immersed in solution F2-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains substance C 1;
(15) substance C 1 is immersed in solution F2-2, under magnetic stirring apparatus effect, after even dipping 3h, takes out and dry, under 100 ℃ of conditions, dry 10h, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains substance C 2;
(16) substance C 2 is immersed in solution F3-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material D1;
(17) material D1 is immersed in solution F3-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material D2;
(18) material D2 is immersed in solution F3-3, under magnetic stirring apparatus effect, after even dipping 3h, takes out and dry, under 100 ℃ of conditions, dry 10h, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material D3;
(19) material D3 is immersed in solution F4-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material E1;
(20) material E1 is immersed in solution F4-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material E2;
(21) material E2 is immersed in solution F5-1, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material F1;
(22) material F1 is immersed in solution F5-2, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, is placed in retort furnace roasting 4h under 600 ℃ of conditions by dried material, obtains material F2;
(23) material F2 is immersed in solution F5-3, and evenly floods under magnetic stirring apparatus effect, after 3h, take out and dry, then dry 10h under 100 ℃ of conditions, obtains material F3;
(24) material F3 is immersed in solution F5-4, and evenly flood under magnetic stirring apparatus effect, after 3h, take out and dry, then under 100 ℃ of conditions, be dried 10h, dried material is placed in to retort furnace roasting 4h under 600 ℃ of conditions, and the material obtaining is the supporting Pt titanium substrate anode plate of modifying based on NiO-FeO-ZnO.
2. a kind of Internal Circulating Fluidized Bed electric catalysis reactor according to claim 1, is characterized in that, the loaded Ag doped with Mn O containing CuO middle layer in this Internal Circulating Fluidized Bed electric catalysis reactor
2-CeO
2activated alumina granule electrode is prepared by the following method:
(1) γ-Al that is 3-5mm by 300g particle diameter
2o
3ball 500ml deionized water wash, repeated washing 3 times, then puts into 200ml dehydrated alcohol and soaks 10h, and with after 500ml washed with de-ionized water 1 time, under 80 ℃ of conditions, dry 10h, obtains particulate matter A;
(2) AgNO that is 0.5mol/L by 50ml concentration
3add in 150ml Virahol, obtain solution A;
(3) particulate matter A step (1) being obtained adds in the solution A that step (2) obtains, and in shaking table, shake 3h, filtration obtains particulate matter B and microemulsion X, the washing with alcohol particulate matter B that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter C;
(4) particulate matter C step (3) being obtained is placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter D;
(5) particulate matter D step (4) being obtained adds in the microemulsion X that step (3) obtains, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter E, the washing with alcohol particulate matter E that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, is then placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter F;
(6) Ce (NO that is 0.5mol/L by 10ml concentration
3)
2the CuCl that solution and 100ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 10ml concentration be the MnCl of 0.5mol/L
2solution, is divided into 5 parts of equivalent after shaking up, obtain solution B
1, solution B
2, solution B
3, solution B
4, solution B
5;
(7) solution B that particulate matter F step (5) being obtained adds step (6) to obtain
1in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G1, the washing with alcohol particulate matter G1 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
1;
(8) particulate matter H step (7) being obtained
1the solution B that adds step (6) to obtain
2in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G2, the washing with alcohol particulate matter G2 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
2;
(9) particulate matter H step (8) being obtained
2the solution B that adds step (6) to obtain
3in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G3, the washing with alcohol particulate matter G3 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
3;
(10) particulate matter H step (9) being obtained
3the solution B that adds step (6) to obtain
4in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G4, the washing with alcohol particulate matter G4 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
4;
(11) particulate matter H step (10) being obtained
4the solution B that adds step (6) to obtain
5in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G5, the washing with alcohol particulate matter G5 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
5; By H
5be placed in retort furnace roasting 4h under 580 ℃ of conditions, obtain particulate matter I;
(12) Ce (NO that is 0.5mol/L by 20ml concentration
3)
2the CuCl that solution and 80ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 20ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution C;
(13) particulate matter I step (11) being obtained adds in the solution C that step (12) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter J, the washing with alcohol particulate matter J that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter K;
(14) Ce (NO that is 0.5mol/L by 40ml concentration
3)
2the CuCl that solution and 40ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 40ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution D;
(15) particulate matter K step (13) being obtained adds in the solution D that step (14) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter L, the washing with alcohol particulate matter L that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter M;
(16) Ce (NO that is 0.5mol/L by 45ml concentration
3)
2the CuCl that solution and 15ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 60ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution E;
(17) particulate matter M step (15) being obtained adds in the solution E that step (16) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter N, the washing with alcohol particulate matter N that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter O;
(18) Ce (NO that is 0.5mol/L by 15ml concentration
3)
2the CuCl that solution and 5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 100ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution F:
(19) particulate matter O step (17) being obtained adds in the solution F that step (18) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter P, the washing with alcohol particulate matter P that is 95% by 100mL mass concentration, repeated washing 2 times, then under 80 ℃ of conditions, be dried 10h, obtain particulate matter Q, Q is placed in to retort furnace roasting 4h under 580 ℃ of conditions, and the particulate matter obtaining is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode.
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