CN103495419A - Activated carbon used for three-dimensional electrode, preparation of activated carbon and application of activated carbon to treatment of waste water containing non-biodegradable organic matter - Google Patents
Activated carbon used for three-dimensional electrode, preparation of activated carbon and application of activated carbon to treatment of waste water containing non-biodegradable organic matter Download PDFInfo
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Abstract
The invention relates to activated carbon used for a three-dimensional electrode, preparation of the activated carbon and application of activated carbon to treatment of waste water containing non-biodegradable organic matter. The process for preparing the activated carbon includes the steps of mixing a mixture of various types of lignocellulose with organic nitrogen-containing compounds, placing the mixture obtained in the first step in a phosphoric acid solution to soak the mixture, and sequentially conducting kneading, granulation, curing, carbonization, activation, washing, soda boiling, secondary washing, pickling, salt soaking and solidification to obtain the product. The comprehensive performance indexes of the activated carbon used for the three-dimensional electrode include the polygon stumpy shape, the polygonal short-column-shaped particle size ranging from 4mm to 5mm, the iodine adsorption value larger than or equal to 1600mg/g, the mass nitrogen content ranging from 1.5% to 3.5%, the mass copper (CuO) content ranging from 3.0% to 5.0%, the organic matter degradation rate larger than or equal to 92%, the granule hardness which is achieved through the ball-milling method and is larger than or equal to 90% and the apparent density ranging from 0.7g/g to 2.5g/g. The activated carbon has the advantages that catalytic activity is improved, operating cost is reduced, the activated carbon has an extremely strong adsorption effect, meanwhile, product hardness is improved, and maintenance expenses are reduced.
Description
Technical field
The present invention relates to special typed active carbon and manufacture field; Be particularly related to a kind of active carbon preparation and preparation and application that is applicable to the hardly degraded organic substance waste water treatment.
Background technology
The processing 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 is processed waste water possess skills economic indicator advanced person, the characteristics such as nontoxic, clean, more and more is subject to people's attention.The deep oxidation technology (AOPs) of the people such as Glaze proposition in 1992 provides an important approach (W.H.Glaze for administering organic pollution, F.BeltranandT.Tuhkanen, WaterPollutionRes.J.Canada, 1992,17:33) be characterized in taking full advantage of free radical, particularly the extremely strong oxidisability of hydroxyl radical free radical (.OH), understand oxidative degradation organic pollution up hill and dale.
Three-diemsnional electrode electrocatalysis oxidation reaction device is a kind of device that hydroxyl radical free radical (.OH) can effectively be provided.It comprises anode and cathode.This kind of reactor except selecting better suited anode and cathode electrode material and suitable electrode spacing and electrode shape, structure, arrange, the factor such as area, finding a kind of particulate material that is suitable as three-diemsnional electrode is of paramount importance, the most primary the most key place that can three-diemsnional electrode electrocatalysis oxidation reaction device bring into play higher performance.
Three-diemsnional electrode mostly selects active carbon or carbon modified class material as the three-diemsnional electrode particle at present.Although it have advantages of the scope of application than wide, material source is many, price is relatively low, also have following shortcoming: 1. catalytic capability is low, when in the specific sewage of special type, Cucumber content is high, its usefulness is lower; 2. because its particle surface hardness is very low, easily damaged and particle is diminished and lose electroactive in course of reaction; 3. because its bulk density is little, easily for example, with non-conductive particle (quartz sand), separate, 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 increase cost to sewage disposal without value.
In order to overcome the deficiency of above-mentioned technology, preparation and the application process thereof of the present invention the proposes active carbon that a kind of economy, efficient, eco-friendly three-diemsnional electrode uses.
Summary of the invention
The object of the present invention is to provide a kind of have certain degree of hardness and large active carbon and preparation and the application on the refractory organic waste water treatment for three-diemsnional electrode of catalytic activity.
The objective of the invention is to realize by following scheme:
Three-diemsnional electrode is prepared as follows with active carbon:
Its operation is as follows: by between the mixture of multiple lignocellulosic and nitrogen-containing organic compound, mixed, afterwards the mixture of lignocellulosic and nitrogen-containing organic compound being placed in to phosphoric acid solution floods, kneaded afterwards and granulation, the product of granulation is respectively through overcuring and charing, product after charing is activated again, then the product after activation is washed respectively, soda boiling, secondary washing, pickling, is soaked salt, solidify to obtain product;
Wherein said concrete steps of soaking salt are: by active carbon after pickling, add 7%～13% copper nitrate solution, after flooding 20～26 hours, drain the recovery copper nitrate.
Further: by described mixing multiple lignocellulosic and the nitrogen-containing organic compound that is prepared into emulsion; Described wood fibre comprises through screening removes foreign material dry, keeps stalk, bamboo, sawdust, wood powder, pericarp, shell, kernel, brown coal, pitch, paper pulp, the paper mill black liquor of moisture 5%--15% and length 20-30mm; Described nitrogen-containing organic compound comprises cyanate, melamine, urea, MU, Lauxite, poly-amino resins, melmac, chitin, marine alga etc.; The mixture of lignocellulosic and the weight ratio between nitrogen-containing organic compound are 1:1-7.
The mixture of lignocellulosic and nitrogen-containing organic compound is placed in phosphoric acid solution and floods, and the weight ratio that its immersion condition is 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 mediated for the product of dipping is put into to kneader, and the condition of kneading is temperature 150-260 ℃, time 2-5 hour.
Described granulation is carried out in to the tooth comminutor, produces polygon short cylinder particle, and its particle diameter is 3-4mm.
Described slaking, carbonization, for granulation product being placed in the heating converter, keep turn/min of rotating speed 5-10, slaking under the condition of furnace temperature 160-260 ℃, and the curing time is 24-64 hour; Adjust afterwards temperature and carry out carbonization to 300-400 ℃, carbonization time is 1-3 hour.
Described activation, for the heating converter of starting to exchange fire between the product of carbonization is placed in, under the condition that is turn/min of 5-10 at rotating speed, remains on temperature 450-600 ℃, reaction time 1-6 hour.
Washing: phosphoric acid is reclaimed in the product water extraction after activating dries;
Soda boiling: add doubly 10～15%NaOH solution of volume 3-4 through the washing active carbon, pressure 0.12-0.15MPa, boiling 1-3 hour, standing 12-24 hour ceases fire;
Secondary washing: the active carbon after soda boiling is washed with water to pH5-6;
Pickling: above-mentioned washing charcoal, add 15%～25%HNO3, flood 20～28 hours, after draining, then use water rinse 1-2 time, use the microcellular structure that improves active carbon;
Solidify: soak after salt active carbon need to be under 100～120C dry 1-3 hour, solidify 1--3 hour in 250-300 ℃.
Three-diemsnional electrode is as follows with the Properties of Activated Carbon index comprehensive:
Shape: polygon short cylinder granular size 4-5mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) amount: 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 is the application on the hardly degraded organic substance waste water treatment with active carbon: three-diemsnional electrode is placed between three phase three-diemsnional electrode reactor anode and cathode with active carbon, organic wastewater is placed in to 3 D electrode reactor, carry out electrolysis.
Advantage of the present invention is as follows:
(1) have and improve the effect that catalytic activity reduces operating cost
Because reactor of the present invention is to using cheap electric energy as excitation energy, take air as raw material, produce two electron reductions on granule electrode, 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 extremely strong hydroxyl radical free radical of oxidisability:
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, and extremely strong suction-operated is arranged, thereby the organic matter in water is played to enrichment; Activated carbon surface has special nitrogen-containing functional group and Nanometer Copper or its oxide, and extremely strong catalytic action is arranged; So that the highly active OH-in granule electrode surface before by the hydrone cancellation, has an opportunity to contact with organic molecule, so can be quickly and effectively and mineralising organic pollution up hill and dale; Reaction equation is as follows:
OH-+R → CO
2+ inorganic ions (3)
(in formula, R is organic matter)
By above (1)-(3), analyze known: cheap electric energy and raw material, and rapid-action speed, inevitable decrease operating cost, estimation can be saved electric energy more than 30%.
(3) electrode active carbon of the present invention mainly adopts the nitride modification, makes in active carbon to form a certain amount of nitrogen-containing functional group, pyridine and pyrroles's key; Adopt the 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, and according to test: containing 2% formaldehyde waste water, at normal pressure, under temperature 60 C, electrolysis 30min. degradation rate reaches more than 97%, and electrolysate is the nontoxic lower fatty acid easily be degraded by microorganisms or its esters; Therefore, activated carbon electrodes of the present invention can replace being loaded with the activated carbon electrodes of platinum, ruthenium or rare earth metal fully; Owing to avoiding adopting rare precious metal, be raw material, thereby the manufacturing cost that greatly reduces electrode and reactor is conducive to suitability for industrialized production.
(4) improve the hardness of active carbon, reduce wear, reduce maintenance cost
The hardness of common wooden granular activated carbon (ball-milling method) is 85% left and right; The hardness of wood substance grain active carbon of the present invention (ball-milling method) is more than 90%; When using at the three-dimensional electrode reactor bed, because hardness is large, be difficult for fragmentation while repeatedly stirring in solution, often do not change, thereby, 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, for fear of short circuit current, in the conduction active-carbon electrode of being everlasting, mix non-conductive particle; Due to the proportion of electrically conductive particles is little and non-conductive particle than great, lamination usually occurs in the difference due to proportion when both stir between solution; The bulk density that strengthens granular activated carbon is conducive to avoid interparticle separated from one another, improves current efficiency.
The 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 are filled electrode, 5 air inlet pipe, 6 negative electrodes, 7 porous air distribution plates.
The specific embodiment
Below in conjunction with Figure of description and embodiment, content of the present invention is elaborated:
As shown in Figure 1: three-diemsnional electrode of the present invention is prepared as follows with active carbon:
By between the mixture of multiple lignocellulosic and nitrogen-containing organic compound, mixed, afterwards the mixture of lignocellulosic and nitrogen-containing organic compound being placed in to phosphoric acid solution floods, kneaded afterwards and granulation, the product of granulation is respectively through overcuring and charing, product after charing is activated again, then the product after activation is washed respectively, soda boiling, secondary washing, pickling, is soaked salt, solidify to obtain product;
Wherein said concrete steps of soaking salt are: by active carbon after pickling, add 7%～13% copper nitrate solution, after flooding 20～26 hours, drain the recovery copper nitrate; By the modification to above-mentioned active carbon, load cheap metal and metal oxide thereof, the charcoal particle that makes it to have larger catalytic activity;
Further: by mixing of multiple lignocellulosic and the nitrogen-containing organic compound that is prepared into emulsion; Described wood fibre comprises through screening removes foreign material dry, keeps stalk, bamboo, sawdust, wood powder, pericarp, shell, kernel, brown coal, pitch, paper pulp, the paper mill black liquor of moisture 5%--15% and length 20-30mm; On wood fibre is selected, can also select wood fibre commonly used 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; The mixture of lignocellulosic and the weight ratio between nitrogen-containing organic compound are 1:1-7; Nitrogen-containing organic compound is made to emulsion in advance, can improve the uniformity of mixing; The interpolation itrogenous organic substance can improve the nitrogen content of product quality, improves 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 the weight ratio that its immersion condition is 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%.Hydrolysis and the saccharification of the favourable stalk of high concentration phosphorus acid solution and sawdust.The intensity of granular activated carbon and other physicochemical property are subject to the impact of phosphorus bits ratio and dipping kneading condition.In the constant situation of other condition, the phosphoric acid ratio is large, and transitional pore is flourishing, absorption property is good but intensity is lower; On the contrary, the phosphorus bits are less than little pore volume, capacity is large, and absorption affinity is low, but intensity is high,
Described kneading is mediated for the product of dipping is put into to kneader, and the condition of kneading is temperature 150-260 ℃, time 2-5 hour.
Described granulation is carried out in to the tooth comminutor, produces polygon short cylinder particle, and its particle diameter is 3-4mm.
Described slaking, carbonization, for granulation product being placed in the heating converter, keep turn/min of rotating speed 5-10, slaking under the condition of furnace temperature 160-260 ℃, and the curing time is 24-64 hour; Adjust afterwards temperature and carry out carbonization to 300-400 ℃, 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 surpass 1.5%.
Described activation, for the heating converter of starting to exchange fire between the product of carbonization is placed in, under the condition that is turn/min of 5-10 at rotating speed, remains on temperature 450-600 ℃, reaction time 1-6 hour.
Wherein take lignocellulosic and itrogenous organic substance as raw material, and phosphoric acid is catalyst, the purpose by charing and activation be there is certain degree of hardness in order to make, the granular activated carbon of definite shape, certain catalytic capability;
Washing: phosphoric acid is reclaimed in the product water extraction after activating dries; The quality index of carbonized material is: iodine number > 1600mg/g; Hardness (ball-milling method) > 90%.
Soda boiling: add doubly 10～15%NaOH solution of volume 3-4 through the washing active carbon, pressure 0.12-0.15MPa, boiling 1-3 hour, standing 12-24 hour ceases fire;
Secondary washing: the active carbon after soda boiling is washed with water to pH5-6;
Pickling: above-mentioned washing charcoal, add 15%～25%HNO3, flood 20～28 hours, after draining, then use water rinse 1-2 time, use the microcellular structure that improves active carbon;
Solidify: soak after salt active carbon need to be under 100～120C dry 1-3 hour, solidify 1--3 hour in 250-300C.
Three-diemsnional electrode is as follows with the Properties of Activated Carbon index comprehensive:
Shape: polygon short cylinder granular size 4-5mm.,
Iodine sorption value >=1600mg/g,
Quality nitrogen content 1.5-3.5%,
Quality cupric (CuO) amount: 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 is placed between three phase three-diemsnional electrode reactor anode and cathode with active carbon, sewage is placed in to 3 D electrode reactor, carry out electrolysis.
Concrete operations are: the present invention is placed in the dimension electrode reactor, and 3 D electrode reactor comprises: electrolytic cell 2, anode 3, negative electrode 6, granular activated carbon are filled 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 that is provided with a porous sieve plate (7) certain flow rate apart from 30mm place, bottom is blasted in system by air pump in reactor bottom, 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 the 20g activated carbon granule is put between three phase three-diemsnional electrode reactor anode and cathode, annotated the waste water of people 500mL, COD content 300mg/L, add the Na of 30g/L
2sO
4as supporting electrolyte. adopt DH1716 mono-7A type dc source, control voltage under 20.0V, waste water is carried out to electrolysis.Take out appropriate solution through the certain hour interval from reactor, under the 1000r/min rotating speed after centrifugal 10min, if carry out the mensuration of indices. 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 is measured COD value remaining after wastewater degradation.
The present invention will be described below to exemplify part embodiment
Example 1
The Lauxite emulsion that takes the moisture 10% chrysanthemum rice grass chopping of 10kg, moisture 10% sawdust of 10kg and 40kg moisture 50% mixes, then adds 70% phosphatase 24 0kg dipping 24 hours;
Above-mentioned acidleach thing moves into Z-type kneader, 150 ℃ of temperature, and 3 hours time, raw material are converted into the sticking material of tool group;
Above-mentioned material is rolled into a ball and is moved into the tooth comminutor, and extrusion molding also is cut into uniform granule, and shape size is 3 * 3mm. approximately.
Above-mentioned wet granular moves into revolving burner, keeps turn/min of rotating speed 5, passes into 160 ℃ of thermal currents and is heated, and makes furnace charge slaking gradually, 64 hours time;
The revolving burner that particle after above-mentioned slaking is started to exchange fire and heated between moving into, turn/min of rotating speed 5, utilize fire coal or fuel oil that furnace temperature is elevated to 300 ℃, and time 2 h, make the abundant charing of furnace charge;
Above-mentioned carbonized material is in same stove, and turn/min of rotating speed 5, be raised to 550 ℃ to furnace temperature, furnace charge fully activated in 3 hours, passes into nitrogen during activation as protection gas;
The cooling rear immigration plastic channel of above-mentioned activated material adds 2 times of water to carry out phosphoric acid extraction at every turn, just stops washing when the washings pH reaches 5-6;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 3 times of 12%NaOH solution, pressure 0.12-0.15MPa scope, and boiling 2 hours, cease fire standing 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, with after water rinse 2 times, add 7% copper nitrate solution, after flooding 25 hours, drain the recovery copper nitrate;
After above-mentioned Activated Carbon with Cu water washes away surperficial copper nitrate, the sample that first takes a morsel is dry under 105 ℃, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, must again soak the salt operation; Qualified Activated Carbon with Cu, 100 ℃ of dryings 3 hours, is solidified 2 hours under 300 ℃.
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) amount: 4.0%,
To degradation effect of organic compound >=92%,
Pellet hardness (ball-milling method) >=90%,
Apparent density 1.5g/g.
Example 2
The Lauxite emulsion that takes the moisture 10% chrysanthemum rice grass chopping of 10kg, moisture 10% sawdust of 10kg and 140kg moisture 50% mixes, then adds 70% phosphatase 11 30kg dipping 24 hours.
Above-mentioned acidleach thing moves into Z-type kneader, 260 ℃ of temperature, and 5 hours time, raw material are converted into the sticking material of tool group;
Above-mentioned material is rolled into a ball and is moved into the tooth comminutor, and extrusion molding also is cut into uniform granule, and shape size is 3 * 3mm. approximately.
Above-mentioned wet granular moves into revolving burner, keeps turn/min of rotating speed 7, passes into 260 ℃ of thermal currents and is heated, and makes furnace charge slaking gradually, 24 hours time;
The revolving burner that particle after above-mentioned slaking is started to exchange fire and heated between moving into, turn/min of rotating speed 8, utilize fire coal or fuel oil that furnace temperature is elevated to 400 ℃, 1 hour time, makes the abundant charing of furnace charge;
Above-mentioned carbonized material is in same stove, and turn/min of rotating speed 8 is raised to 600 ° to furnace temperature, furnace charge is fully activated in 5 hours, passes into nitrogen during activation as protection gas;
The cooling rear immigration plastic channel of above-mentioned activated material adds 2 times of water to carry out phosphoric acid extraction at every turn, and the washings pH reaches at 6 o'clock just stops washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, and boiling 1 hour, cease fire standing 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, with after water rinse 1 time, add 15% copper nitrate solution, after flooding 24 hours, drain the recovery copper nitrate;
After above-mentioned Activated Carbon with Cu water washes away surperficial copper nitrate, the sample that first takes a morsel is dry under 105 ℃, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, must again soak the salt operation; Qualified Activated Carbon with Cu, 120 ℃ of dryings 2 hours, is solidified 1 hour under 300 ℃.
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) amount: 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
The Lauxite emulsion that takes the moisture 10% chrysanthemum rice grass chopping of 10kg, moisture 10% sawdust of 10kg and 40kg moisture 50% mixes, then adds 70% phosphatase 24 0kg dipping 24 hours
Above-mentioned acidleach thing moves into Z-type kneader, 200 ℃ of temperature, and 3 hours time, raw material are converted into the sticking material of tool group;
Above-mentioned material is rolled into a ball and is moved into the tooth comminutor, and extrusion molding also is cut into uniform granule, and shape size is 3 * 3mm. approximately.
Above-mentioned wet granular moves into revolving burner, keeps turn/min of rotating speed 10, passes into 260 ℃ of thermal currents and is heated, and makes furnace charge slaking gradually, 48 hours time;
The revolving burner that particle after above-mentioned slaking is started to exchange fire and heated between moving into, turn/min of rotating speed 10, utilize fire coal or fuel oil that furnace temperature is elevated to 300 ℃, 3 hours time, makes the abundant charing of furnace charge;
Above-mentioned carbonized material is in same stove, and turn/min of rotating speed 8, be raised to 450 ℃ to furnace temperature, furnace charge fully activated in 6 hours, passes into nitrogen during activation as protection gas;
The cooling rear immigration plastic channel of above-mentioned activated material adds 4 times of water to carry out phosphoric acid extraction at every turn, just stops washing when the washings pH reaches 5-6;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, and boiling 3 hours, cease fire standing 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, with after water rinse 1 time, add 10% copper nitrate solution, after flooding 24 hours, drain the recovery copper nitrate;
After above-mentioned Activated Carbon with Cu water washes away surperficial copper nitrate, the sample that first takes a morsel is dry under 105 ℃, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, must again soak the salt operation; Qualified Activated Carbon with Cu, 120 ℃ of dryings 3 hours, is solidified 1 hour under 300 ℃.
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) amount: 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
The Lauxite emulsion that takes the moisture 10% chrysanthemum rice grass chopping of 10kg, the moisture 10% sawdust 60kg moisture 50% of 10kg mixes, then adds 70% phosphatase 24 0kg dipping 24 hours
Above-mentioned acidleach thing moves into Z-type kneader, 150 ℃ of temperature, and 5 hours time, raw material are converted into the sticking material of tool group;
Above-mentioned material is rolled into a ball and is moved into the tooth comminutor, and extrusion molding also is cut into uniform granule, and shape size is 3 * 3mm. approximately.
Above-mentioned wet granular moves into revolving burner, keeps turn/min of rotating speed 10, passes into 260 ℃ of thermal currents and is heated, and makes furnace charge slaking gradually, 48 hours time;
The revolving burner that particle after above-mentioned slaking is started to exchange fire and heated between moving into, turn/min of rotating speed 10, utilize fire coal or fuel oil that furnace temperature is elevated to 400 ℃, 3 hours time, makes the abundant charing of furnace charge;
Above-mentioned carbonized material is in same stove, and turn/min of rotating speed 10, be raised to 600 ° to furnace temperature, furnace charge fully activated in 6 hours, passes into nitrogen during activation as protection gas;
The cooling rear immigration plastic channel of above-mentioned activated material adds 4 times of water to carry out phosphoric acid extraction at every turn, and the washings pH reaches at 5 o'clock just stops washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, and boiling 3 hours, cease fire standing 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, with after water rinse 2 times, add 15% copper nitrate solution, after flooding 28 hours, drain the recovery copper nitrate;
After above-mentioned Activated Carbon with Cu water washes away surperficial copper nitrate, the sample that first takes a morsel is dry under 105 ℃, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, must again soak the salt operation; Qualified Activated Carbon with Cu, 120 ℃ of dryings 3 hours, is solidified 1 hour under 300 ℃.
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) amount: 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
The Lauxite emulsion that takes the moisture 10% chrysanthemum rice grass chopping of 10kg, moisture 10% sawdust of 10kg and 40kg moisture 50% mixes, then adds 70% phosphatase 24 0kg dipping 24 hours
Above-mentioned acidleach thing moves into Z-type kneader, 190 ℃ of temperature, and 4 hours time, raw material are converted into the sticking material of tool group;
Above-mentioned material is rolled into a ball and is moved into the tooth comminutor, and extrusion molding also is cut into uniform granule, and shape size is 4 * 4mm. approximately.
Above-mentioned wet granular moves into revolving burner, keeps turn/min of rotating speed 6, passes into 230 ℃ of thermal currents and is heated, and makes furnace charge slaking gradually, 33 hours time;
The revolving burner that particle after above-mentioned slaking is started to exchange fire and heated between moving into, turn/min of rotating speed 7, utilize fire coal or fuel oil that furnace temperature is elevated to 400 ℃, 3 hours time, makes the abundant charing of furnace charge;
Above-mentioned carbonized material is in same stove, and turn/min of rotating speed 8, be raised to 600 ° to furnace temperature, furnace charge fully activated in 5 hours, passes into nitrogen during activation as protection gas;
The cooling rear immigration plastic channel of above-mentioned activated material adds 3 times of water to carry out phosphoric acid extraction at every turn, and the washings pH reaches at 5 o'clock just stops washing;
Above-mentioned rinsing charcoal drains rear immigration pressure cooker, adds 4 times of 10%NaOH solution, pressure 0.12-0.15MPa scope, and boiling 2 hours, cease fire standing 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, with after water rinse 1 time, add 25% copper nitrate solution, after flooding 20 hours, drain the recovery copper nitrate;
After above-mentioned Activated Carbon with Cu water washes away surperficial copper nitrate, the sample that first takes a morsel is dry under 105 ℃, measures copper-loaded (CuO) amount of active carbon; If copper content is less than 3.0%, must again soak the salt operation; Qualified Activated Carbon with Cu, 120 ℃ of dryings 3 hours, is solidified 3 hours under 250 ℃.
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) amount: 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 is placed between three phase three-diemsnional electrode reactor anode and cathode with active carbon, organic wastewater is placed in to 3 D electrode reactor, carry out electrolysis.
So-called degradation of organic waste water; the Degrading experiment of waste water is to carry 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 are filled electrode 4, porous air distribution plate 7, air inlet pipe 5) compositions such as power supply 1, air pump.This structure is prior art, and the present invention just is placed in granular activated carbon by three-diemsnional electrode with active carbon and fills in the scope of electrode.
The mensuration of sample quality
First by NAC
1-NAC
5each 20g of activated carbon granule puts between three phase three-diemsnional 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, controls voltage under 20.0V, and waste water is carried out to electrolysis.Through the 30min time, appropriate solution is taken out at interval from reactor, and under the 1000r/min rotating speed after centrifugal 10min, according to GB11914-89, the mensuration-dichromate titration of COD is measured the COD value of remnants after wastewater degradation.
Will do blank test before test, method of operating is with identical above, but obstructed electric current is write down test value.Result of the test should be deducted the adsorptive value of active carbon for the first time.This experiment adopts 10 mean values.
Result of the test is as following table:
* annotate: the experimental data that upper table is 1.5 hours
As can be known from the above table: the processing of three-diemsnional electrode active carbon of the present invention to acid red simulation industrial wastewater, high degradation rate is 95.3%, minimum 93.40%, average 94.29%; Detect and illustrate that adopting the inventive method to utilize lignocellulosic to prepare three-diemsnional electrode is highly effective by the granular activated carbon method, the product degradation property is very excellent, with low cost, is easy to industrialization.
Claims (10)
1. the preparation of a three-diemsnional electrode use active carbon, it is characterized in that: its operation is as follows: by between the mixture of multiple lignocellulosic and nitrogen-containing organic compound, mixed, afterwards the mixture of lignocellulosic and nitrogen-containing organic compound being placed in to phosphoric acid solution floods, kneaded afterwards and granulation, the product of granulation is respectively through overcuring and charing, product after charing is activated again, then the product after activation is washed respectively, soda boiling, secondary washing, pickling, is soaked salt, solidify to obtain product;
Wherein said concrete steps of soaking salt are: by active carbon after pickling, add 7%～13% copper nitrate solution, after flooding 20～26 hours, drain the recovery copper nitrate.
2. the preparation of active carbon for three-diemsnional electrode according to claim 1 is characterized in that: described mixing multiple lignocellulosic and the nitrogen-containing organic compound that is prepared into emulsion; Described wood fibre comprises through screening removes foreign material dry, keeps stalk, bamboo, sawdust, wood powder, pericarp, shell, kernel, brown coal, pitch, paper pulp, the paper mill black liquor of moisture 5%--15% and length 20-30mm; Described nitrogen-containing organic compound comprises cyanate, melamine, urea, MU, Lauxite, poly-amino resins, melmac, chitin, marine alga;
The mixture of lignocellulosic and the weight ratio between nitrogen-containing organic compound are 1:1-7.
3. the preparation of active carbon for three-diemsnional electrode 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, the weight ratio that its immersion condition is 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 of active carbon for three-diemsnional electrode according to claim 1, it is characterized in that: described kneading is mediated for the product of dipping is put into to kneader, and the condition of kneading is temperature 150-260 ℃, time 2-5 hour.
5. the preparation of active carbon for three-diemsnional electrode according to claim 1, it is characterized in that: described granulation is carried out in to the tooth comminutor, produces polygon short cylinder particle, and its particle diameter is 3-4mm.
6. the preparation of active carbon for three-diemsnional electrode according to claim 1, it is characterized in that: described slaking, carbonization are for being placed on granulation product in the heating converter, keep turn/min of rotating speed 5-10, slaking under the condition of furnace temperature 160-260 ℃, the curing time is 24-64 hour; Adjust afterwards temperature and carry out carbonization to 300-400 ℃, carbonization time is 1-3 hour.
7. the preparation of active carbon for three-diemsnional electrode according to claim 1, it is characterized in that: described activation is the heating converter of starting to exchange fire between the product of carbonization is placed in, under the condition that is turn/min of 5-10 at rotating speed, remain on temperature 450-600 ℃, reaction time 1-6 hour.
8. the preparation of active carbon for three-diemsnional electrode according to claim 1 is characterized in that:
Washing, soda boiling, secondary washing, pickling, curing operation are specific as follows;
Washing: phosphoric acid is reclaimed in the product water extraction after activating dries;
Soda boiling: add doubly 10～15%NaOH solution of volume 3-4 through the washing active carbon, pressure 0.12-0.15MPa, boiling 1-3 hour, standing 12-24 hour ceases fire;
Secondary washing: the active carbon after soda boiling is washed with water to pH5-6;
Pickling: above-mentioned washing charcoal, add 15%～25%HNO3, flood 20～28 hours, after draining, then use water rinse 1-2 time, use the microcellular structure that improves active carbon;
Solidify: soak after salt active carbon need to be under 100～120 ℃ dry 1-3 hour, solidify 1--3 hour in 250-300 ℃.
9. according to the described a kind of described three-diemsnional electrode active carbon 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 cupric (CuO) amount: 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. a kind of described three-diemsnional electrode according to claim 8 application on the hardly degraded organic substance waste water treatment with active carbon: it is characterized in that: three-diemsnional electrode is placed between three phase three-diemsnional electrode reactor anode and cathode with active carbon, organic wastewater is placed in to 3 D electrode reactor, carries out electrolysis.
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