CN108579734A - A kind of sludge carbon electrochemical catalyst and its preparation and application - Google Patents

A kind of sludge carbon electrochemical catalyst and its preparation and application Download PDF

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Publication number
CN108579734A
CN108579734A CN201810307992.0A CN201810307992A CN108579734A CN 108579734 A CN108579734 A CN 108579734A CN 201810307992 A CN201810307992 A CN 201810307992A CN 108579734 A CN108579734 A CN 108579734A
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sludge
sludge carbon
temperature
catalyst
carbon
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何益得
于杨
张永军
黄菲
安世林
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Nanjing Tech University
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Nanjing Tech University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

Abstract

The present invention is prepared for a kind of high temperature resistant, corrosion-resistant, the excellent highly effective sludge Pd/carbon catalyst of catalytic performance, is applied to electrochemical treatments organic wastewater with difficult degradation thereby, belongs to water technology and field of environment protection.The sludge carbon chemical property is stablized, and can be stabilized in acid and alkaline solution, can improve the efficiency of electrochemical oxidation organic matter, be conducive to the development of electrochemicial oxidation organic wastewater with difficult degradation thereby technology.

Description

A kind of sludge carbon electrochemical catalyst and its preparation and application
Technical field
The present invention relates to a kind of efficient stable sludge carbon electrochemical catalyst and its preparation method and application, with sludge carbon or The sludge carbon that surface is modified uses the metal that high activity not easily runs off to prepare sludge Pd/carbon catalyst for active component as carrier, For electrochemical treatments organic industrial sewage.
Background technology
Municipal sewage plant can form a large amount of excess sludge in sewage disposal process, contain in sludge a large amount of Water, organic matter, inanimate matter, microorganism, parasite and each heavy metal species.If handling not in time, serious secondary dirt will be caused Dye, causes potentially to threaten to mankind's activity, ecological environment.Sludge is the Main By product in sewage disposal process, currently, I State's whole year sewage load is up to 550m3More than, it is contemplated that whole year generates 35,000,000 tons of the sludge or more of moisture content 80%, dewatered sludge 7000000 tons or more.Existing sludge disposal technology is simultaneously immature, and treatment effeciency is relatively low.
From the point of view of processing sludge method analysis comparison both at home and abroad, in foreign countries since the starting development of Treatment of Sludge cause is more early, More mature industrial technology is formed at present.Such as the U.S. mainly takes and throws Haifa's processing sludge early stage, as a result causes Serious water pollution phenomenon, therefore gradually abandon sludge and throw extra large method.With advances in technology, existing main methods are Sludge landfill characteristics.And at home, the processing method of sludge still based on landfill, sets the treatment technology and processing of sludge Standby to fall behind relatively, there are Treatment of Sludge rate is low, technique is not perfect, and the management level design level in processing procedure is relatively low.
As social economy continues to develop, industrialized level is continuously improved, the industry developments such as chemical industry, smelting, fiber manufacture Rapidly, industrial wastewater discharge amount increases year by year.Organic industrial sewage has great harm to human body and environment, therefore seeks height It is very urgent to imitate sewage water treatment method.High-level oxidation technology can efficiently remove the organic pollution in waste water, be widely used in Handle organic wastewater with difficult degradation thereby.Studies have shown that containing a large amount of organic matter in sludge, sludge can be prepared under the high temperature conditions Charcoal.Catalyst of the sludge carbon as high-level oxidation technology, it is possible to reduce the dosage of oxidant improves the removal rate of organic matter, Reduce the operating cost of high-level oxidation technology.
Electrochemical oxidation process in high-level oxidation technology has preferable removal effect in processing low concentration high-salt wastewater, such Waste water includes mainly coal chemical industrial waste water, pharmacy corporation waste water, membrane filtration strong brine, petrochemical industry waste water and chemical enterprise waste water Deng.During electrochemicial oxidation organic industrial sewage, adds a certain amount of catalyst and will further improve organic pollution Removal rate.Do not occur report of the sludge Pd/carbon catalyst in electrochemicial oxidation yet at present.If can using sludge carbon as Carrier prepares the catalysis material of inexpensive high activity, while can solve Treatment of Sludge problem, realizes the purpose of " treatment of wastes with processes of wastes against one another ", The sludge Pd/carbon catalyst of preparation is expected to be answered extensively on the industrialized unit of electrochemical catalytic oxidation in degradation of organic wastewater With with very high actual application prospect.
Invention content
The present invention relates to a kind of sludge carbon electric catalysts and its preparation method and application, are handled for electrocatalytic oxidation organic Industrial wastewater.
1. sludge carbon electrochemical catalyst, it is characterised in that：
(1) sludge for taking city sewage plant, dry 10~48h under 80~120 DEG C of temperature condition, later by it It crushes, using 50~300 mesh screens, obtains sewage sludge powder sample.
(2) make protection gas using nitrogen, calcine 3~7h with 300~900 DEG C of temperature conditions in reacting furnace, be cooled to room Temperature obtains sludge carbon powder.
(3) while can also be sulfuric acid, hydrochloric acid, the nitre of 10~50wt.% by the sludge carbon mass fraction obtained in (2) 1~2 kind in acid, phosphoric acid, acetic acid, perchloric acid or mass fraction be in 10~50wt.% sodium hydroxides and hydrogen peroxide 1~ 2 kinds, immersion 2~for 24 hours, control temperature, later by the sludge carbon after being impregnated, reuses deionized water between 0~90 DEG C It rinses until water outlet pH value 6~8, to treated, sludge carbon is dried, temperature control is at 10~150 DEG C to get to surface Modified sludge carbon powder.
2. active sludge carbon method for preparing catalyst is as follows：
Sludge carbon (or sludge carbon of surface modification) is immersed in RuCl3、H2PtCl6、Pd(NO3)2、RhCl3Or IrCl3In In one or more kinds of solution, with the load capacity of metallic gauge salt in salt for 0.01~5.0wt.%, at 300~900 DEG C At a temperature of, completely cut off the sludge Pd/carbon catalyst that the product that 2~8h of air calcination is obtained is required.
3. a kind of efficient stable described in sludge carbon powder or claim 2 that surface described in claim 1 is modified is dirty The application of peat electrochemical catalyst：
The catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Reaction temperature is 10~70 DEG C, mixing speed is 100~300r/min；Catalyst amounts are 0.1~5.0g/L, electrode plate Ti/RuO2+TiO2, electrode Board size is 50 × 40 × 2mm, and pole plate spacing is 10~50mm, and current density is 2~500mA/cm2.
Electrochemical catalyst of the present invention has the following advantages：
1. such catalyst has larger specific surface area, load high activity noble metal component, which can be improved largely, urges Change efficiency.
2. such catalyst is not easily decomposed during electrochemical oxidation degrades industrial wastewater organic matter, have good steady It is qualitative.
3. such catalyst raw material is derived from municipal sludge, waste rationally recycles, and beautifies the environment, and sludge cost of material It is relatively low, it is suitable for large-scale production.
The sludge carbon chemical property is stablized, and can be stabilized in acid and alkaline solution, can improve electrochemistry oxygen The efficiency for changing organic matter, is conducive to the development of electrochemicial oxidation organic wastewater with difficult degradation thereby technology.
Description of the drawings：
Sludge carbon electro-catalysis TOC removal rates acetophenone conversion and reaction time relational graph in Fig. 1 embodiments 1.
Sludge carbon electro-catalysis pollutant conversion ratio TOC removal rates and reaction time relational graph in Fig. 2 embodiments 1.
Specific implementation mode
Efficient stable sludge carbon electrochemical catalyst of the present invention, can handle organic wastewater with difficult degradation thereby, and raising has The removal rate of machine object, to promote the extensive use of electrochemical oxidation technology.
Embodiment 1：
1. taking the sludge of city sewage plant, dry 10h, is crushed later under 105 DEG C of temperature condition, Using 50 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 3h is calcined with 400 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. by sludge carbon obtained above with mass fraction be 25wt.% sulfuric acid impregnate 2h, control temperature at 20 DEG C, it Afterwards by the sludge carbon after being impregnated, reuses deionized water and rinse until water outlet pH value is 6, sludge carbon carries out to treated Drying, temperature control is at 60 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in RuCl3In solution, the load capacity with metallic gauge salt in salt is 5.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 2h is obtained is required at a temperature of 300 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 60 DEG C, mixing speed 100r/min；Catalyst amounts are 0.5g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 10mm, current density 50mA/cm2.React 180min Afterwards, acetophenone conversion 84.2%, TOC removal rates are 72.2%.
Embodiment 2：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 120 DEG C of temperature condition, Using 100 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 4h is calcined with 500 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. the phosphoric acid dip 4h for being 30wt.% with mass fraction by sludge carbon obtained above, control temperature at 40 DEG C, it Afterwards by the sludge carbon after being impregnated, reuses deionized water and rinse until water outlet pH value is 6, sludge carbon carries out to treated Drying, temperature control is at 50 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 50 DEG C, mixing speed 200r/min；Catalyst amounts are 0.8g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 20mm, current density 90mA/cm2.React 180min Afterwards, acetophenone conversion 70.2%, TOC removal rates are 65.3%.
Embodiment 3：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 120 DEG C of temperature condition, Using 200 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 7h is calcined with 600 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. by sludge carbon obtained above with mass fraction be 40wt.% nitric acid dousing for 24 hours, control temperature at 60 DEG C, Later by the sludge carbon after being impregnated, reuse deionized water and rinse until water outlet pH value is 6, to treated sludge carbon into Row drying, temperature control is at 40 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in Pd (NO3)2In solution, the load capacity with metallic gauge salt in salt is 3.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 4h is obtained is required at a temperature of 800 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 50 DEG C, mixing speed 150r/min；Catalyst amounts are 1.0g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 30mm, current density 70mA/cm2.React 180min Afterwards, acetophenone conversion 66.7%, TOC removal rates are 61.2%.
Embodiment 4：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 100 DEG C of temperature condition, Using 150 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 6h is calcined with 700 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. the salt acid soak 10h for being 30wt.% with mass fraction by sludge carbon obtained above, control temperature at 50 DEG C, Later by the sludge carbon after being impregnated, reuse deionized water and rinse until water outlet pH value is 6, to treated sludge carbon into Row drying, temperature control is at 40 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in Pd (NO3)2And IrCl3In mixed solution, with metallic gauge salt in salt Load capacity is respectively 1.0wt.%, and at a temperature of 700 DEG C, the product that isolation air calcination 5h is obtained is that required sludge carbon is catalyzed Agent.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 70 DEG C, mixing speed 200r/min；Catalyst amounts are 1.2g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 40mm, current density 80mA/cm2.React 180min Afterwards, acetophenone conversion 77.7%, TOC removal rates are 71.0%.
Embodiment 5：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 100 DEG C of temperature condition, Using 300 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 2h is calcined with 450 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. by sludge carbon obtained above with mass fraction be 30wt.% perchloric acid impregnate 3h, control temperature at 50 DEG C, Later by the sludge carbon after being impregnated, reuse deionized water and rinse until water outlet pH value is 6, to treated sludge carbon into Row drying, temperature control is at 60 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 40 DEG C, mixing speed 200r/min；Catalyst amounts are 0.7g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 50mm, current density 50mA/cm2.React 180min Afterwards, acetophenone conversion 60.1%, TOC removal rates are 55.7%.
Embodiment 6：
1. taking the sludge of city sewage plant, dry 10h, is crushed later under 105 DEG C of temperature condition, Using 50 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 3h is calcined with 400 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. sludge carbon powder is immersed in RuCl3In solution, the load capacity with metallic gauge salt in salt is 5.0wt.%, At a temperature of 300 DEG C, completely cut off the sludge Pd/carbon catalyst that the product that air calcination 2h is obtained is required.
4. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 60 DEG C, mixing speed 100r/min；Catalyst amounts are 0.5g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 10mm, current density 50mA/cm2.React 180min Afterwards, acetophenone conversion 71.4%, TOC removal rates are 61.3%.
Comparative example 1：
1. active carbon from coal is taken to impregnate 3h with the sulfuric acid that mass fraction is 30wt.%, control temperature is incited somebody to action later at 50 DEG C Active carbon from coal after to immersion reuses deionized water and rinses until water outlet pH value is 6, to treated active carbon from coal into Row drying, temperature control is at 60 DEG C to get the active carbon from coal being modified to surface.
2. the active carbon from coal is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone is initially dense Degree is 100mg/L, and reaction temperature is 40 DEG C, mixing speed 200r/min；Catalyst amounts are 0.7g/L, and electrode plate is Ti/RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 50mm, current density 50mA/cm2.Reaction After 180min, acetophenone conversion 41.7%, TOC removal rates are 36.2%.
Comparative example 2：
1. taking the salt acid soak 10h that active carbon from coal is 30wt.% with mass fraction, control temperature later will at 50 DEG C Active carbon from coal after being impregnated reuses deionized water and rinses until water outlet pH value is 6, and to treated, sludge carbon carries out Drying, temperature control is at 40 DEG C to get the sludge carbon powder being modified to surface.
2. the sludge carbon that surface is modified is immersed in Pd (NO3)2And IrCl3In mixed solution, with metallic gauge salt in salt Load capacity is respectively 1.0wt.%, and at a temperature of 700 DEG C, the product that isolation air calcination 5h is obtained is that required sludge carbon is catalyzed Agent.
3. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 70 DEG C, mixing speed 200r/min；Catalyst amounts are 1.2g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 40mm, current density 80mA/cm2.React 180min Afterwards, acetophenone conversion 50.1%, TOC removal rates are 44.2%
Comparative example 3：
1. taking the sludge of city sewage plant, dry 10h, is crushed later under 105 DEG C of temperature condition, Using 50 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, with 250 DEG C of (less than 300 DEG C of lower limits in claim 1) temperature strips in reacting furnace Part calcines 3h, is cooled to room temperature, and obtains sludge carbon powder.
3. by sludge carbon obtained above with mass fraction be 25wt.% sulfuric acid impregnate 2h, control temperature at 20 DEG C, it Afterwards by the sludge carbon after being impregnated, reuses deionized water and rinse until water outlet pH value is 6, sludge carbon carries out to treated Drying, temperature control is at 60 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in RuCl3In solution, the load capacity with metallic gauge salt in salt is 5.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 2h is obtained is required at a temperature of 300 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 60 DEG C, mixing speed 100r/min；Catalyst amounts are 0.5g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 10mm, current density 50mA/cm2.React 180min Afterwards, acetophenone conversion 50.1%, TOC removal rates are 42.9%.
Comparative example 4：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 120 DEG C of temperature condition, Using 200 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 2h is calcined (less than 3h in claim 1 with 300 DEG C of temperature conditions in reacting furnace Lower limit), it is cooled to room temperature, obtains sludge carbon powder.
3. by sludge carbon obtained above with mass fraction be 40wt.% nitric acid dousing for 24 hours, control temperature at 60 DEG C, Later by the sludge carbon after being impregnated, reuse deionized water and rinse until water outlet pH value is 6, to treated sludge carbon into Row drying, temperature control is at 40 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in Pd (NO3)2In solution, the load capacity with metallic gauge salt in salt is 3.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 4h is obtained is required at a temperature of 800 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 50 DEG C, mixing speed 150r/min；Catalyst amounts are 1.0g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 30mm, current density 70mA/cm2.React 180min Afterwards, acetophenone conversion 50.2%, TOC removal rates are 39.5%.
Comparative example 5：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 120 DEG C of temperature condition, Using 200 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, with 1000 DEG C of (less than 900 DEG C of upper limits in claim 1) temperature strips in reacting furnace Part calcines 3h, is cooled to room temperature, and obtains sludge carbon powder.
3. by sludge carbon obtained above with mass fraction be 40wt.% nitric acid dousing for 24 hours, control temperature at 60 DEG C, Later by the sludge carbon after being impregnated, reuse deionized water and rinse until water outlet pH value is 6, to treated sludge carbon into Row drying, temperature control is at 40 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in Pd (NO3)2In solution, the load capacity with metallic gauge salt in salt is 3.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 4h is obtained is required at a temperature of 800 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 50 DEG C, mixing speed 150r/min；Catalyst amounts are 1.0g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 30mm, current density 70mA/cm2.React 180min Afterwards, acetophenone conversion 40.9%, TOC removal rates are 32.8%.
Comparative example 6：
1. taking the sludge of city sewage plant, dry 20h, is crushed later under 120 DEG C of temperature condition, Using 200 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 3h is calcined with 600 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. sludge carbon obtained above is immersed in Pd (NO3)2In solution, the load capacity with metallic gauge salt in salt is 3.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 4h is obtained is required at a temperature of 600 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 50 DEG C, mixing speed 150r/min；Catalyst amounts are 1.0g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 30mm, current density 70mA/cm2.React 180min Afterwards, acetophenone conversion 50.1%, TOC removal rates are 43.8%.
Comparative example 7：
1. taking the sludge of city sewage plant, dry 10h, is crushed later under 105 DEG C of temperature condition, Using 50 mesh screens, sewage sludge powder sample is obtained.
2. making protection gas using nitrogen, 3h is calcined with 350 DEG C of temperature conditions in reacting furnace, is cooled to room temperature, obtained dirty Peat powder.
3. the salt acid soak 1h for being 5wt.% with mass fraction by sludge carbon obtained above, control temperature at 20 DEG C, it Afterwards by the sludge carbon after being impregnated, reuses deionized water and rinse until water outlet pH value is 6, sludge carbon carries out to treated Drying, temperature control is at 60 DEG C to get the sludge carbon powder being modified to surface.
4. the sludge carbon that surface is modified is immersed in RuCl3In solution, the load capacity with metallic gauge salt in salt is 3.0wt.% completely cuts off the sludge Pd/carbon catalyst that the product that air calcination 2h is obtained is required at a temperature of 400 DEG C.
5. the catalyst is for electrochemicial oxidation organic wastewater intermittent reaction condition：Acetophenone initial concentration is 100mg/L, reaction temperature are 60 DEG C, mixing speed 100r/min；Catalyst amounts are 0.5g/L, electrode plate Ti/ RuO2+TiO2, electrode board size is 50 × 40 × 2mm, and pole plate spacing is 10mm, current density 50mA/cm2.React 180min Afterwards, acetophenone conversion 48.2%, TOC removal rates are 41.3%.

Claims (5)

1. the preparation method of sludge carbon electrochemical catalyst, it is characterised in that：
(1) sludge for taking city sewage plant, dry 10~48h, is carried out later under 80~120 DEG C of temperature condition It crushes, using 50~300 mesh screens, obtains sewage sludge powder sample；
(2) make protection gas using nitrogen, calcined with 300~900 DEG C of (400-600 DEG C of preferred temperature) temperature conditions in reacting furnace 3~7h (preferred time 2-4h), is cooled to room temperature, and obtains sludge carbon powder；
(3) sulfuric acid by the sludge carbon mass fraction obtained in (2) for 10~50wt.% (preferably 20~30wt.%), salt One kind or two or more or mass fraction in acid, nitric acid, phosphoric acid, acetic acid, perchloric acid be 10~50wt.% (preferably 20~ 30wt.%) a kind in sodium hydroxide and hydrogen peroxide or 2 kinds, impregnate 2~for 24 hours, control temperature is in 0~90 DEG C of (preferred temperature 20-40 DEG C) between, later by the sludge carbon after being impregnated, reuses deionized water and rinse until water outlet pH value 6~8 is (preferable For 7), to treated, sludge carbon is dried, temperature control is 10~150 DEG C (preferably 60~80 DEG C) to get to surface Modified sludge carbon powder, can be directly as sludge carbon electrochemical catalyst.
2. the preparation method of sludge activity Pd/carbon catalyst described in accordance with the claim 1, it is characterised in that：
The sludge carbon powder that claim 1 prepares and/or the sludge carbon powder that surface is modified are immersed in RuCl3、 H2PtCl6、Pd(NO3)2、RhCl3Or IrCl3In middle one or more salting liquid, with the load of metallic gauge salt in salt Amount is 0.01~5.0wt.%, and at a temperature of 300~900 DEG C (400-600 DEG C of preferred temperature), isolation 2~8h of air calcination is obtained To product be required sludge carbon electrochemical catalyst.
3. a kind of prepared sludge carbon electrochemical catalyst obtained of claims 1 or 2.
4. application of the sludge carbon electrochemical catalyst in electrochemicial oxidation organic wastewater described in a kind of claim 3, institute It is the sludge carbon powder and/or claim 2 that the prepared surface obtained of claim 1 is modified to state sludge carbon electrochemical catalyst The sludge carbon electrochemical catalyst of prepared acquisition.
5. according to the application of sludge carbon electrochemical catalyst described in claim 4, the catalyst is used for electrochemicial oxidation Organic wastewater intermittent reaction condition is：Reaction temperature is 10~70 DEG C (preferably 30~50 DEG C), mixing speed is 100~ 300r/min (preferably 200~300r/min)；Catalyst amounts are 0.1~5.0g/L (preferably 0.5~2.0g/L), electricity Pole plate is Ti/RuO2+TiO2, electrode board size be 50 × 40 × 2mm, pole plate spacing be 10~50mm, current density be 2~ 500mA/cm2(preferably 200~300mA/cm2)。
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Application publication date: 20180928