CN103495419B - Three-diemsnional electrode active carbon and preparation method thereof and the application on refractory organic waste water treatment - Google Patents
Three-diemsnional electrode active carbon and preparation method thereof and the application on refractory organic waste water treatment Download PDFInfo
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Abstract
The present invention relates to a kind of three-diemsnional electrode active carbon and preparation thereof and the application on refractory organic waste water treatment.Its technique is as follows: mixed with between nitrogen-containing organic compound by the mixture of multiple lignocellulosic, be placed in phosphoric acid solution and flood, kneading successively, granulation, slaking, charing, activation, washing, soda boiling, secondary washing, pickling, leaching salt, solidification obtain product; Three-diemsnional electrode Properties of Activated Carbon index comprehensive is as follows: shape: polygon short cylinder granular size 4-5mm, iodine sorption value >=1600mg/g, quality nitrogen content 1.5-3.5%, quality cupric (CuO) is measured: 3.0-5.0%, to degradation effect of organic compound >=92%, pellet hardness (ball-milling method) >=90%, apparent density 0.7-2.5g/g.Product of the present invention has the effect improving catalytic activity reduction operating cost; Have extremely strong suction-operated, product hardness provides simultaneously, reduces the advantages such as maintenance cost.
Description
Technical field
The present invention relates to special typed active carbon and manufacture field; Active carbon of hardly degraded organic substance waste water treatment and its preparation method and application is applicable in particular to a kind of.
Background technology
The process of bio-refractory organic pollution is focus and the difficult point of our times Industrial Wastewater Treatment.Once proposed many processing methods for this Study on Problems person, wherein electrochemical process process waste water possesses skills economic indicator advanced person, the feature such as nontoxic, clean, is more and more subject to people's attention.The advanced oxidation processes (AOPs) that the people such as Glaze in 1992 proposes provides an important approach (W.H.Glaze for administering organic pollution, F.BeltranandT.Tuhkanen, WaterPollutionRes.J.Canada, 1992,17:33) be characterized in making full use of free radical, the particularly extremely strong oxidisability of hydroxyl radical free radical (.OH), meeting oxidative degradation organic pollution up hill and dale.
Three-diemsnional electrode electrocatalysis oxidation reaction device is a kind of device that effectively can provide hydroxyl radical free radical (.OH).It comprises anode and cathode.This kind of reactor, except selecting better suited anode and cathode electrode material and the factor such as suitable electrode spacing and electrode shape, structure, arrangement, area, finds a kind of particulate material being suitable as three-diemsnional electrode to be of paramount importance, the most primary the most key place that can three-diemsnional electrode electrocatalysis oxidation reaction device play higher performance.
Current three-diemsnional electrode mostly selects active carbon or carbon modified class material as three-diemsnional electrode particle.Although it has the scope of application compared with the advantage wide, material source is many, price is relatively low, also have following shortcoming: 1. catalytic capability is low, in the specific sewage of special type during Cucumber content height, its usefulness is lower; 2. because its particle surface hardness is very low, easily damaged and particle is diminished and loses electroactive in course of reaction; 3. be easily separated with non-conductive particle (such as quartz sand) because its bulk density is little, short circuit current increases, and current efficiency is low, also increases operating cost; 4. though the advantage of the discarded rear non-secondary pollution of carbon granule, also increases cost to sewage disposal without value.
In order to overcome the deficiency of above-mentioned technology, the present invention proposes preparation method and the application process thereof of the active carbon of a kind of economy, efficient, eco-friendly three-diemsnional electrode.
Summary of the invention
The object of the present invention is to provide and a kind ofly there is certain degree of hardness and large three-diemsnional electrode active carbon of catalytic activity and preparation method thereof and the application on refractory organic waste water treatment.
The object of the invention is to be realized by following scheme:
The preparation method of three-diemsnional electrode active carbon is as follows:
Its operation is as follows: mixed with between nitrogen-containing organic compound by the mixture of multiple lignocellulosic, afterwards the mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution to flood, carry out kneading afterwards and granulation, the product of granulation is respectively through slaking and charing, product after charing activates again, then to activation after product wash respectively, soda boiling, secondary washing, pickling, leaching salt, solidification acquisition product;
The concrete steps of wherein said leaching salt are: by active carbon after pickling, add 7% ~ 13% copper nitrate solution, flood after 20 ~ 26 hours, drain recovery copper nitrate.
Further: by described by multiple lignocellulosic and the mixing of nitrogen-containing organic compound being prepared into emulsion; Described wood fibre comprises through screening removing foreign material and dry, keep moisture 5%--15% and the stalk of length 20-30mm, bamboo, sawdust, wood powder, pericarp, shell, kernel, brown coal, pitch, paper pulp, paper mill black liquor; Described nitrogen-containing organic compound comprises cyanate, melamine, urea, MU, Lauxite, poly-amino resins, melmac, chitin, marine alga etc.; Weight ratio between the mixture of lignocellulosic and nitrogen-containing organic compound is 1:1-7.
The mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution and floods, and its immersion condition is the weight ratio of phosphoric acid solution and mixture is 1-1.5:1, and dip time is no less than 24 hours, and wherein the mass concentration of phosphoric acid solution is 70-85%.
Described kneading is the product of dipping is put into kneader mediate, and the condition of kneading is temperature 150-260 DEG C, time 2-5 hour.
Described granulation is carried out in tooth comminutor, produces polygon short cylinder particle, and its particle diameter is 3-4mm.
Described slaking, charing are for being placed on granulation product in heating converter, and keep rotating speed 5-10 to turn/min, slaking under the condition of furnace temperature 160-260 DEG C, the curing time is 24-64 hour; Adjust temperature afterwards to carbonize to 300-400 DEG C, carbonization time is 1-3 hour.
Described activation be the product of charing is placed between to start to exchange fire heating converter, rotating speed be 5-10 turn/condition of min under, remain on temperature 450-600 DEG C, reaction time 1-6 hour.
Washing: the products in water extraction and recovery phosphoric acid after activation is dried;
Soda boiling: add volume 3-4 doubly 10 ~ 15%NaOH solution through washing active carbon, pressure 0.12-0.15MPa, boiling 1-3 hour, cease fire and leave standstill 12-24 hour;
Secondary is washed: wash with water to pH5-6 by the active carbon after soda boiling;
Pickling: above-mentioned washing charcoal, adds 15% ~ 25%HNO3, floods 20 ~ 28 hours, after draining, then uses water rinse 1-2 time, uses the microcellular structure improving active carbon;
Solidification: after leaching salt, active carbon needs dry 1-3 hour under 100 ~ 120C, solidifies 1--3 hour in 250-300 DEG C.
Three-diemsnional electrode Properties of Activated Carbon index comprehensive is as follows:
Shape: polygon short cylinder granular size 4-5mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) is measured: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 0.7-2.5g/g.
The application of three-diemsnional electrode active carbon on hardly degraded organic substance waste water treatment: be placed between three-phase three-dimensional electrode reactor anode and cathode by three-diemsnional electrode active carbon, organic wastewater is placed in 3 D electrode reactor, carries out electrolysis.
Advantage of the present invention is as follows:
(1) there is the effect improving catalytic activity reduction operating cost
Because reactor of the present invention is using cheap electric energy as excitation energy, be raw material with air, granule electrode produces two electron reductions, produce the H with certain oxidisability
2o
2, its reaction equation is as follows:
O
2+2H
++2e
-→H
2O
2(1)
The H of these nascent states
2o
2under the catalysis of activated carbon particles, produce the hydroxyl radical free radical that oxidisability is extremely strong:
H
2O
2+M
XO
Y(M)+H
+→OH.+M
X-+H
2O(2)
(in formula, M is metal)
(2) granule electrode used is special active carbon, has very big specific area, has extremely strong suction-operated, thus plays enrichment to the organic matter in water; Activated carbon surface has special nitrogen-containing functional group and Nanometer Copper or its oxide, has extremely strong catalytic action; So that the highly active OH-in granule electrode surface before by hydrone cancellation, has an opportunity and organic molecule contacts, therefore can quickly and effectively and up hill and dale mineralising organic pollution; Reaction equation is as follows:
OH-+R → CO
2+ inorganic ions (3)
(in formula R system organic matter)
Analyze known by above (1)-(3): cheap electric energy and raw material, and rapid-action speed, significantly must reduce operating cost, estimation can save electric energy more than 30%.
(3) electrode active carbon of the present invention mainly adopts nitride modification, makes to be formed in active carbon
A certain amount of nitrogen-containing functional group, pyridine and pyrroles's key; Adopt copper compound modification to make activated carbon surface be uniformly distributed the particulate of a large amount of nano level copper or copper compound, make carbon surface form countless catalytic active centers; These two measures can improve the catalytic capability of electrode activity charcoal greatly, according to test: containing 2% formaldehyde waste water at normal pressure, and under temperature 60 C, electrolysis 30min. degradation rate reaches more than 97%, and electrolysate is the nontoxic lower fatty acid that is easily degraded by microorganisms or its esters; Therefore, activated carbon electrodes of the present invention can replace the activated carbon electrodes being loaded with platinum, ruthenium or rare earth metal completely; Owing to avoiding adopting rare precious metal to be raw material, the manufacturing cost thus greatly reducing electrode and reactor is conducive to suitability for industrialized production.
(4) improve the hardness of active carbon, reduce wear, reduce maintenance cost
The hardness (ball-milling method) of common wooden granular activated carbon is about 85%; The hardness (ball-milling method) of wood substance grain active carbon of the present invention is more than 90%; When being used in three-dimensional electrode reactor bed, because hardness is large, not easily broken when repeatedly stirring in the solution, often do not change, thus, reduce maintenance cost.
(5) increase bulk density, avoid the separation of particle between stuff and other stuff, improve current efficiency
Common wooden granular activated carbon bulk density is at 350mg/ml-450mg/ml; The bulk density of wood substance grain charcoal of the present invention is at 450mg/ml-1.5mg/ml; In addition, in 3 D electrode reactor, in order to avoid short circuit current, in electrical conductive activities carbon resistance rod of being everlasting, mix non-conductive particle; Proportion due to electrically conductive particles is little and non-conductive particle specific gravity large, and the difference when both stir between solution due to proportion usually lamination occurs; The bulk density of increase products active carbon is conducive to avoiding interparticle separated from one another, improves current efficiency.
Accompanying drawing explanation
The nitrogenous copper-loaded granular activated carbon technological process of production schematic diagram of Fig. 1;
Fig. 23 D electrode reactor schematic diagram;
Label declaration: 1 power supply, 2 electrolytic cells, 3 anodes, 4 granular activated carbons fill electrode, 5 air inlet pipe, 6 negative electrodes, 7 porous air distribution plates.
Detailed description of the invention
Below in conjunction with Figure of description and embodiment, content of the present invention is described in detail:
As shown in Figure 1: the preparation method of three-diemsnional electrode active carbon of the present invention is as follows:
The mixture of multiple lignocellulosic is mixed with between nitrogen-containing organic compound, afterwards the mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution to flood, carry out kneading afterwards and granulation, the product of granulation is respectively through slaking and charing, product after charing activates again, then to activation after product wash respectively, soda boiling, secondary washing, pickling, leaching salt, solidification acquisition product;
The concrete steps of wherein said leaching salt are: by active carbon after pickling, add 7% ~ 13% copper nitrate solution, flood after 20 ~ 26 hours, drain recovery copper nitrate; By the modification to above-mentioned active carbon, load cheap metal and metal oxide thereof, make it the charcoal particle with larger catalytic activity;
Further: by multiple lignocellulosic and the mixing of nitrogen-containing organic compound being prepared into emulsion; Described wood fibre comprises through screening removing foreign material and dry, keep moisture 5%--15% and the stalk of length 20-30mm, bamboo, sawdust, wood powder, pericarp, shell, kernel, brown coal, pitch, paper pulp, paper mill black liquor; On wood fibre is selected, can also select wood fibre conventional in existing production process of activated carbon, described nitrogen-containing organic compound comprises cyanate, melamine, urea, MU, Lauxite, poly-amino resins, melmac, chitin, marine alga etc.; Nitrogen-containing organic compound is including but not limited to above-mentioned substance; Weight ratio between the mixture of lignocellulosic and nitrogen-containing organic compound is 1:1-7; Nitrogen-containing organic compound is made emulsion in advance, the uniformity of mixing can be improved; Add the nitrogen content that itrogenous organic substance can improve product quality, improve the catalytic capability of active carbon.Wherein the emulsion of itrogenous organic substance can be bought to market, or consults other documents and prepare voluntarily.
The mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution and floods, and its immersion condition is the weight ratio of phosphoric acid solution and mixture is 1-1.5:1, and dip time is no less than 20-24 hour, and wherein the mass concentration of phosphoric acid solution is 70-85%.The hydrolysis of the favourable stalk of high concentration phosphorus acid solution and sawdust and saccharification.The intensity of granular activated carbon and other physicochemical property are by phosphorus bits ratio and the impact of flooding kneading conditions.When other condition is constant, phosphoric acid ratio is large, and transitional pore is flourishing, absorption property is good but intensity is lower; On the contrary, phosphorus bits are less than little then pore volume, capacity large, and absorption affinity is low, but intensity is high,
Described kneading is the product of dipping is put into kneader mediate, and the condition of kneading is temperature 150-260 DEG C, time 2-5 hour.
Described granulation is carried out in tooth comminutor, produces polygon short cylinder particle, and its particle diameter is 3-4mm.
Described slaking, charing are for being placed on granulation product in heating converter, and keep rotating speed 5-10 to turn/min, slaking under the condition of furnace temperature 160-260 DEG C, the curing time is 24-64 hour; Adjust temperature afterwards to carbonize to 300-400 DEG C, carbonization time is 1-3 hour.The quality index of carbonized material is: hardness (ball-milling method) >97%; After carbon granule boils 1 hour in boiling water, its hydrotrope must not more than 1.5%.
Described activation be the product of charing is placed between to start to exchange fire heating converter, rotating speed be 5-10 turn/condition of min under, remain on temperature 450-600 DEG C, reaction time 1-6 hour.
Wherein with lignocellulosic and itrogenous organic substance for raw material, phosphoric acid is catalyst, is to make the granular activated carbon with certain degree of hardness, definite shape, certain catalytic capability by the object carbonizing and activate;
Washing: the products in water extraction and recovery phosphoric acid after activation is dried; The quality index of carbonized material is: iodine number >1600mg/g; Hardness (ball-milling method) >90%.
Soda boiling: add volume 3-4 doubly 10 ~ 15%NaOH solution through washing active carbon, pressure 0.12-0.15MPa, boiling 1-3 hour, cease fire and leave standstill 12-24 hour;
Secondary is washed: wash with water to pH5-6 by the active carbon after soda boiling;
Pickling: above-mentioned washing charcoal, adds 15% ~ 25%HNO3, floods 20 ~ 28 hours, after draining, then uses water rinse 1-2 time, uses the microcellular structure improving active carbon;
Solidification: after leaching salt, active carbon needs dry 1-3 hour under 100 ~ 120C, solidifies 1--3 hour in 250-300C.
Three-diemsnional electrode Properties of Activated Carbon index comprehensive is as follows:
Shape: polygon short cylinder granular size 4-5mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) is measured: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 0.7-2.5g/g.
Three-diemsnional electrode active carbon is placed between three-phase three-dimensional electrode reactor anode and cathode, sewage is placed in 3 D electrode reactor, carry out electrolysis.
Concrete operations are: the present invention be placed in dimension electrode reactor, 3 D electrode reactor comprises: electrolytic cell 2, anode 3, negative electrode 6, granular activated carbon fill the compositions such as electrode 4, porous air distribution plate 7, air inlet pipe 5, power supply 1, air pump.
3 D electrode reactor electrolytic cell (2) diameter 90mm, high 160mm, the air being provided with a porous sieve plate (7) certain flow rate apart from 30mm place, bottom is blasted in system in reactor bottom by air pump, then passes through this porous sieve plate (7) and carry out even gas distribution. and structure of reactor is as shown in Figure 2.
2, experimental technique
First put between three-phase three-dimensional electrode reactor anode and cathode by 20g activated carbon granule, the waste water of note people 500mL, COD content 300mg/L, adds the Na of 30g/L
2sO
4as supporting electrolyte. adopt DH1716 mono-7A type dc source, control voltage, under 20.0V, carries out electrolysis to waste water.From reactor, appropriate solution is taken out, under 1000r/min rotating speed after centrifugal 10min, if carry out the mensuration of indices through certain hour interval. without specified otherwise, aeration quantity all maintains 2.5L/min, and polar plate spacing is 3cm.
(3) analytical method of degradation solution, according to GB11914-89, the mensuration-dichromate titration of COD carrys out the rear remaining COD value of wastewater measurement degraded.
The present invention will be described to exemplify section Example below
Example 1
Take the moisture 10% chrysanthemum rice grass chopping of 10kg, the Lauxite emulsion of moisture 10% sawdust of 10kg and 40kg moisture 50% mixes, then add 70% phosphatase 24 0kg and flood 24 hours;
Above-mentioned acidleach thing moves into Z-type kneader, temperature 150 DEG C, and 3 hours time, raw material are converted into the sticking material group of tool;
Above-mentioned material group moves into tooth comminutor, and extrusion molding is also cut into uniform granule, and shape size is 3 × 3mm. about.
Above-mentioned wet granular moves into revolving burner, keeps rotating speed 5 turns/min, passes into 160 DEG C of thermal currents and heat, make furnace charge slaking gradually, 64 hours time;
Particle after above-mentioned slaking is started to exchange fire between moving into the revolving burner of heating, rotating speed 5 turns/min, utilizes coal-fired or fuel oil furnace temperature to be elevated to 300 DEG C, time 2 h, furnace charge is fully carbonized;
Above-mentioned carbonized material is in same stove, and rotating speed 5 turns/min, is raised to 550 DEG C furnace temperature, furnace charge is fully activated in 3 hours, passes into nitrogen as protection gas during activation;
Move into plastic channel after above-mentioned activated material cooling, add 2 times of water at every turn and carry out phosphoric acid extraction, when aqueous rinse solution pH value reaches 5-6, just stop washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 3 times of 12%NaOH solution, pressure 0.12-0.15MPa scope, boiling 2 hours, ceases fire and leaves standstill 16 hours;
After above-mentioned alkali cleaning charcoal drains and reclaims alkali lye, till being washed with water to pH=7.3;
Above-mentioned alkali cleaning charcoal moves into plastic channel, adds 15%HNO
3, flood 28 hours, after draining, after water rinse 2 times, add 7% copper nitrate solution, flood after 25 hours, drain recovery copper nitrate;
After above-mentioned Activated Carbon with Cu washes surperficial copper nitrate with water, the sample that first takes a morsel is dry at 105 DEG C, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, salt operation again must be soaked; Qualified Activated Carbon with Cu, 100 DEG C of dryings 3 hours, is solidified 2 hours at 300 DEG C.
This product called after NAC
1
Product parameters is as follows:
Shape: polygon short cylinder granular size 4.3mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 3.2%,
Quality cupric (CuO) is measured: 4.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 1.5g/g.
Example 2
Take the moisture 10% chrysanthemum rice grass chopping of 10kg, the Lauxite emulsion of moisture 10% sawdust of 10kg and 140kg moisture 50% mixes, then add 70% phosphatase 11 30kg and flood 24 hours.
Above-mentioned acidleach thing moves into Z-type kneader, temperature 260 DEG C, and 5 hours time, raw material are converted into the sticking material group of tool;
Above-mentioned material group moves into tooth comminutor, and extrusion molding is also cut into uniform granule, and shape size is 3 × 3mm. about.
Above-mentioned wet granular moves into revolving burner, keeps rotating speed 7 turns/min, passes into 260 DEG C of thermal currents and heat, make furnace charge slaking gradually, 24 hours time;
Particle after above-mentioned slaking is started to exchange fire between moving into the revolving burner of heating, rotating speed 8 turns/min, utilizes coal-fired or fuel oil that furnace temperature is elevated to 400 DEG C, 1 hour time, furnace charge is fully carbonized;
Above-mentioned carbonized material is in same stove, and rotating speed 8 turns/min is raised to 600 ° furnace temperature, furnace charge is fully activated in 5 hours, passes into nitrogen as protection gas during activation;
Move into plastic channel after above-mentioned activated material cooling, add 2 times of water at every turn and carry out phosphoric acid extraction, when aqueous rinse solution pH value reaches 6, just stop washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, boiling 1 hour, ceases fire and leaves standstill 24 hours;
After above-mentioned alkali cleaning charcoal drains and reclaims alkali lye, till being washed with water to pH=8;
Above-mentioned alkali cleaning charcoal moves into plastic channel, adds 20%HNO
3, flood 24 hours, after draining, after water rinse 1 time, add 15% copper nitrate solution, flood after 24 hours, drain recovery copper nitrate;
After above-mentioned Activated Carbon with Cu washes surperficial copper nitrate with water, the sample that first takes a morsel is dry at 105 DEG C, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, salt operation again must be soaked; Qualified Activated Carbon with Cu, 120 DEG C of dryings 2 hours, is solidified 1 hour at 300 DEG C.
This product called after NAC
2
Product parameters is as follows:
Shape: polygon short cylinder granular size 4mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) is measured: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 0.7-2.5g/g.
Example 3
Take the moisture 10% chrysanthemum rice grass chopping of 10kg, the Lauxite emulsion of moisture 10% sawdust of 10kg and 40kg moisture 50% mixes, then add 70% phosphatase 24 0kg and flood 24 hours
Above-mentioned acidleach thing moves into Z-type kneader, temperature 200 DEG C, and 3 hours time, raw material are converted into the sticking material group of tool;
Above-mentioned material group moves into tooth comminutor, and extrusion molding is also cut into uniform granule, and shape size is 3 × 3mm. about.
Above-mentioned wet granular moves into revolving burner, keeps rotating speed 10 turns/min, passes into 260 DEG C of thermal currents and heat, make furnace charge slaking gradually, 48 hours time;
Particle after above-mentioned slaking is started to exchange fire between moving into the revolving burner of heating, rotating speed 10 turns/min, utilizes coal-fired or fuel oil that furnace temperature is elevated to 300 DEG C, 3 hours time, furnace charge is fully carbonized;
Above-mentioned carbonized material is in same stove, and rotating speed 8 turns/min, is raised to 450 DEG C furnace temperature, furnace charge is fully activated in 6 hours, passes into nitrogen as protection gas during activation;
Move into plastic channel after above-mentioned activated material cooling, add 4 times of water at every turn and carry out phosphoric acid extraction, when aqueous rinse solution pH value reaches 5-6, just stop washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, boiling 3 hours, ceases fire and leaves standstill 12 hours;
After above-mentioned alkali cleaning charcoal drains and reclaims alkali lye, till being washed with water to pH=8;
Above-mentioned alkali cleaning charcoal moves into plastic channel, adds 20%HNO
3, flood 24 hours, after draining, after water rinse 1 time, add 10% copper nitrate solution, flood after 24 hours, drain recovery copper nitrate;
After above-mentioned Activated Carbon with Cu washes surperficial copper nitrate with water, the sample that first takes a morsel is dry at 105 DEG C, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, salt operation again must be soaked; Qualified Activated Carbon with Cu, 120 DEG C of dryings 3 hours, is solidified 1 hour at 300 DEG C.
This product called after NAC
3
Product parameters is as follows:
Shape: polygon short cylinder granular size 4.6mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) is measured: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 0.7-2.5g/g.
Example 4
Take the moisture 10% chrysanthemum rice grass chopping of 10kg, the Lauxite emulsion of the moisture 10% sawdust 60kg moisture 50% of 10kg mixes, then add 70% phosphatase 24 0kg and flood 24 hours
Above-mentioned acidleach thing moves into Z-type kneader, temperature 150 DEG C, and 5 hours time, raw material are converted into the sticking material group of tool;
Above-mentioned material group moves into tooth comminutor, and extrusion molding is also cut into uniform granule, and shape size is 3 × 3mm. about.
Above-mentioned wet granular moves into revolving burner, keeps rotating speed 10 turns/min, passes into 260 DEG C of thermal currents and heat, make furnace charge slaking gradually, 48 hours time;
Particle after above-mentioned slaking is started to exchange fire between moving into the revolving burner of heating, rotating speed 10 turns/min, utilizes coal-fired or fuel oil that furnace temperature is elevated to 400 DEG C, 3 hours time, furnace charge is fully carbonized;
Above-mentioned carbonized material is in same stove, and rotating speed 10 turns/min, is raised to 600 ° furnace temperature, furnace charge is fully activated in 6 hours, passes into nitrogen as protection gas during activation;
Move into plastic channel after above-mentioned activated material cooling, add 4 times of water at every turn and carry out phosphoric acid extraction, when aqueous rinse solution pH value reaches 5, just stop washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, boiling 3 hours, ceases fire and leaves standstill 15 hours;
After above-mentioned alkali cleaning charcoal drains and reclaims alkali lye, till being washed with water to pH=8;
Above-mentioned alkali cleaning charcoal moves into plastic channel, adds 20%HNO
3, flood 24 hours, after draining, after water rinse 2 times, add 15% copper nitrate solution, flood after 28 hours, drain recovery copper nitrate;
After above-mentioned Activated Carbon with Cu washes surperficial copper nitrate with water, the sample that first takes a morsel is dry at 105 DEG C, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, salt operation again must be soaked; Qualified Activated Carbon with Cu, 120 DEG C of dryings 3 hours, is solidified 1 hour at 300 DEG C.
This product called after is NAC
4
Product parameters is as follows:
Shape: polygon short cylinder granular size 4.5mm,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) is measured: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 0.7-2.5g/g.
Example 5
Take the moisture 10% chrysanthemum rice grass chopping of 10kg, the Lauxite emulsion of moisture 10% sawdust of 10kg and 40kg moisture 50% mixes, then add 70% phosphatase 24 0kg and flood 24 hours
Above-mentioned acidleach thing moves into Z-type kneader, temperature 190 DEG C, and 4 hours time, raw material are converted into the sticking material group of tool;
Above-mentioned material group moves into tooth comminutor, and extrusion molding is also cut into uniform granule, and shape size is 4 × 4mm. about.
Above-mentioned wet granular moves into revolving burner, keeps rotating speed 6 turns/min, passes into 230 DEG C of thermal currents and heat, make furnace charge slaking gradually, 33 hours time;
Particle after above-mentioned slaking is started to exchange fire between moving into the revolving burner of heating, rotating speed 7 turns/min, utilizes coal-fired or fuel oil that furnace temperature is elevated to 400 DEG C, 3 hours time, furnace charge is fully carbonized;
Above-mentioned carbonized material is in same stove, and rotating speed 8 turns/min, is raised to 600 ° furnace temperature, furnace charge is fully activated in 5 hours, passes into nitrogen as protection gas during activation;
Move into plastic channel after above-mentioned activated material cooling, add 3 times of water at every turn and carry out phosphoric acid extraction, when aqueous rinse solution pH value reaches 5, just stop washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, boiling 2 hours, ceases fire and leaves standstill 17 hours;
After above-mentioned alkali cleaning charcoal drains and reclaims alkali lye, till being washed with water to pH=8;
Above-mentioned alkali cleaning charcoal moves into plastic channel, adds 20%HNO
3, flood 24 hours, after draining, after water rinse 1 time, add 25% copper nitrate solution, flood after 20 hours, drain recovery copper nitrate;
After above-mentioned Activated Carbon with Cu washes surperficial copper nitrate with water, the sample that first takes a morsel is dry at 105 DEG C, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, salt operation again must be soaked; Qualified Activated Carbon with Cu, 120 DEG C of dryings 3 hours, is solidified 3 hours at 250 DEG C.
This product called after is NAC
5
Product parameters is as follows:
Shape: polygon short cylinder granular size 5mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) is measured: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 0.7-2.5g/g.
Example 6-example 10
Three-diemsnional electrode active carbon is placed between three-phase three-dimensional electrode reactor anode and cathode, organic wastewater is placed in 3 D electrode reactor, carry out electrolysis.
So-called degradation of organic waste water; the Degrading experiment of waste water carries out in general small-size three-dimensional electrolysis groove (as Fig. 2), and the structure of small-sized three-dimensional electrolytic cell is as follows: comprising: electrolytic cell 2, anode 3, negative electrode 6, granular activated carbon fill electrode 4, porous air distribution plate 7, air inlet pipe 5) composition such as power supply 1, air pump.This structure is prior art, and three-diemsnional electrode active carbon is just placed in granular activated carbon and fills in the scope of electrode by the present invention.
The mensuration of sample quality
First by NAC
1-NAC
5the each 20g of activated carbon granule puts between three-phase three-dimensional electrode reactor anode and cathode, injects the waste water (replacing 300mg/LCOD) of 500mL acid red simulation industrial wastewater, acid red content 300mg/L, adds the Na of 15g
2sO
4as supporting electrolyte. aeration quantity 2.5L/min, polar plate spacing is that 3cm. adopts DH1716 mono-7A type dc source, and control voltage, under 20.0V, carries out electrolysis to waste water.Through the 30min time, appropriate solution is taken out at interval from reactor, and under 1000r/min rotating speed after centrifugal 10min, according to GB11914-89, the mensuration-dichromate titration of COD carrys out the rear remaining COD value of wastewater measurement degraded.
Will do blank test before test, method of operating is with identical above, but obstructed electric current, write down test value.Result of the test should deduct the adsorptive value of active carbon for the first time.This experiment employing 10 mean values.
Result of the test is as following table:
* note: upper table is the experimental data of 1.5 hours
As can be known from the above table: three-diemsnional electrode active carbon of the present invention is to the process of acid red simulation industrial wastewater, and most high degradation rate is 95.3%, minimum 93.40%, average 94.29%; Detect and illustrate that it is highly effective for adopting the inventive method to utilize lignocellulosic to prepare three-diemsnional electrode granular activated carbon method, product degradation property is very excellent, with low cost, is easy to industrialization.
Claims (10)
1. the preparation method of a three-diemsnional electrode active carbon, it is characterized in that: its operation is as follows: the mixture of multiple lignocellulosic is mixed with between nitrogen-containing organic compound, afterwards the mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution to flood, carry out kneading afterwards and granulation, the product of granulation is respectively through slaking and charing, product after charing activates again, then to activation after product wash respectively, soda boiling, secondary washing, pickling, leaching salt, solidification acquisition product;
The concrete steps of wherein said leaching salt are: by active carbon after pickling, add 7% ~ 13% copper nitrate solution, flood after 20 ~ 26 hours, drain recovery copper nitrate.
2. the preparation method of three-diemsnional electrode active carbon according to claim 1, is characterized in that: described by multiple lignocellulosic and the mixing of nitrogen-containing organic compound being prepared into emulsion; Described lignocellulosic comprises through screening removing foreign material and dry, keep moisture 5%--15% and the stalk of length 20-30mm, bamboo, sawdust, wood powder, pericarp, shell, kernel, paper pulp, paper mill black liquor; Described nitrogen-containing organic compound comprises cyanate, melamine, urea, MU, Lauxite, poly-amino resins, melmac, chitin, marine alga;
Weight ratio between the mixture of lignocellulosic and nitrogen-containing organic compound is 1:1-7.
3. the preparation method of three-diemsnional electrode active carbon according to claim 1, it is characterized in that: the mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution and floods, its immersion condition is the weight ratio of phosphoric acid solution and mixture is 1-1.5:1, dip time is no less than 24 hours, and wherein the mass concentration of phosphoric acid solution is 70-85%.
4. the preparation method of three-diemsnional electrode active carbon according to claim 1, is characterized in that: described kneading is the product of dipping is put into kneader mediate, and the condition of kneading is temperature 150-260 DEG C, time 2-5 hour.
5. the preparation method of three-diemsnional electrode active carbon according to claim 1, is characterized in that: described granulation is carried out in tooth comminutor, produces polygon short cylinder particle, and its particle diameter is 3-4mm.
6. the preparation method of three-diemsnional electrode active carbon according to claim 1, it is characterized in that: described slaking, charing are for being placed in heating converter by granulation product, keep rotating speed 5-10 to turn/min, slaking under the condition of furnace temperature 160-260 DEG C, the curing time is 24-64 hour; Adjust temperature afterwards to carbonize to 300-400 DEG C, carbonization time is 1-3 hour.
7. the preparation method of three-diemsnional electrode active carbon according to claim 1, it is characterized in that: described activation be the product of charing is placed between to start to exchange fire heating converter, rotating speed be 5-10 turn/condition of min under, remain on temperature 450-600 DEG C, reaction time 1-6 hour.
8. the preparation method of three-diemsnional electrode active carbon according to claim 1, is characterized in that:
Washing, soda boiling, secondary washing, pickling, curing operation are specific as follows;
Washing: the products in water extraction and recovery phosphoric acid after activation is dried;
Soda boiling: add volume 3-4 doubly 10 ~ 15%NaOH solution through washing active carbon, pressure 0.12-0.15MPa, boiling 1-3 hour, cease fire and leave standstill 12-24 hour;
Secondary is washed: wash with water to pH5-6 by the active carbon after soda boiling;
Pickling: above-mentioned washing charcoal, adds 15% ~ 25%HNO3, floods 20 ~ 28 hours, after draining, then uses water rinse 1-2 time, uses the microcellular structure improving active carbon;
Solidification: after leaching salt, active carbon needs dry 1-3 hour at 100 ~ 120 DEG C, solidifies 1--3 hour in 250-300 DEG C.
9., according to described three-diemsnional electrode active carbon prepared by preparation method described in any one of claim 1-7, it is characterized in that:
This Properties of Activated Carbon index comprehensive is as follows:
Shape: polygon short cylinder granular size 4-5mm,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality copper content, in CuO: 3.0-5.0%,
To degradation effect of organic compound >=92%,
Pellet hardness, ball-milling method >=90%,
Apparent density 0.7-2.5g/g.
10. the application of a kind of three-diemsnional electrode active carbon according to claim 9 on hardly degraded organic substance waste water treatment: it is characterized in that: three-diemsnional electrode active carbon is placed between three-phase three-dimensional electrode reactor anode and cathode, organic wastewater is placed in 3 D electrode reactor, carries out electrolysis.
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| CN104821233A (en) * | 2015-04-03 | 2015-08-05 | 安徽江威精密制造有限公司 | Copper alloy-clad straw-based composite electrode material and preparation method thereof |
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| CN108217865B (en) * | 2017-12-26 | 2020-11-10 | 北京理工大学 | Method for desalting by using three-dimensional carbon electrode |
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| CN111170319A (en) * | 2020-02-15 | 2020-05-19 | 太原理工大学 | Method for preparing high-performance activated carbon for automobile carbon tank by using mycelia |
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