CN105366773B - A kind of regular iron-carbon micro-electrolysis filler and preparation method thereof - Google Patents
A kind of regular iron-carbon micro-electrolysis filler and preparation method thereof Download PDFInfo
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- CN105366773B CN105366773B CN201510941513.7A CN201510941513A CN105366773B CN 105366773 B CN105366773 B CN 105366773B CN 201510941513 A CN201510941513 A CN 201510941513A CN 105366773 B CN105366773 B CN 105366773B
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
- C02F2103/325—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Abstract
The invention belongs to Environmental Engineering Material technical field, and in particular to a kind of regular iron-carbon micro-electrolysis filler and preparation method thereof.The preparation method is using Iron concentrate, pulverized bituminous coal as raw material, using paper mill sludge after dries pulverizing as pore creating material, using copper powder as catalyst, and add binding agent, it is compressing after well mixed, and dry and obtain dry bulb filler, the Iron concentrate direct-reduction in the dry bulb filler is generated by anode metal iron by high-temperature roasting, prepares iron-carbon micro-electrolysis filler.The granularity of the anode metal iron of the iron-carbon micro-electrolysis filler is less than 10 μm.Regular iron-carbon micro-electrolysis filler provided by the invention has the characteristics that iron carbon one, micropore framework formula alloy structure, porosity are high, activity is strong, current density is big, it is applied to Industrial Wastewater Treatment, the COD and colourity, raising biodegradability of waste water can effectively be reduced, and various heavy metal ion can be removed, operation using effect is stable.
Description
Technical field
The invention belongs to Environmental Engineering Material technical field, and in particular to a kind of regular iron-carbon micro-electrolysis filler and its system
Preparation Method.
Background technology
Micro electrolysis tech is a kind of technique of Applied Electrochemistry principle processing waste water, also referred to as internal electrolysis, utilizes anode
1.2V potential difference is handled pollutant between (iron) and negative electrode (carbon), particular for organic concentration is big, high toxicity, height
The processing of colourity, difficult biochemical waste water, chroma in waste water and COD can be significantly cut down, improve its biodegradability；In addition, micro electrolysis tech
Also adsorbable, the various heavy metal ion of reduction, therefore, micro electrolysis tech is widely used in printing and dyeing, papermaking, chemical industry, plating, printing
The processing of all types of industries waste water such as wiring board, pharmacy.
Traditional iron-carbon micro-electrolysis filler is by iron filings and activated carbon physical mixed in proportion, forms iron carbon fixation bed, but because
Abrasive grit (anode) and carbon granules (negative electrode) physical separation, current density caused by light electrolysis is small, and water treatment effect is poor；Abrasive grit surface
Easy passivation of getting rusty, causes packing layer hardened, forms channel, need to frequently backwash packing layer or change filler, add light electrolysis
The complexity of technique.Therefore, the development of hardening resistant micro-electrolysis filler, it appears very necessary.In recent years, domestic iron-carbon micro-electrolysis is filled out
The production of material and market sale development are quick, and product is mainly by metal iron powder, activated carbon, non-ferrous metal catalyst and binding agent
Composition, blended, shaping and sintering are made, and filler has realized Regularization, overcomes the hardened problem of filler.But still suffer from as
Lower problem：Filler material cost is high, and product price is high, cost of water treatment rises；Sintering temperature is low, and filling-material structure is loose, waste water
It is lost during processing fast；The production of conventional iron carbon filler directly uses commercially available metal iron powder, commercial metals iron powder because of surface oxidation and
It is passivated, directly applies in filler, activity is low, and current density is small.
Paper mill sludge is to handle the remaining solid waste of paper waste, often produces 1 ton of paper, can produce the dirt of water content 80%
About 1.2 tons of mud, paper mill sludge complicated component, water content are high, intractability is big, and it is total that its disposal costs can account for pulping wastewater treatment
More than the 50% of expense, paper mill sludge disposal have turned into the problem of puzzlement papermaking enterprise operation.
Biomass is enriched in paper mill sludge, content of organics 50~65%, and organic matter is mainly cellulose, hemicellulose, wood
The macromolecule organics such as quality, inorganic matter are mostly the fillers such as calcium carbonate, talcum.
The content of the invention
For the high cost and technological deficiency of existing iron-carbon micro-electrolysis filler, the invention discloses a kind of regular iron-carbon is micro-
Electrolysis filler and preparation method thereof, the preparation method is using Iron concentrate and bituminous coal cheap and easy to get as primary raw material, paper mill sludge
For pore creating material, handled through shaping, high-temperature roasting, the flourishing iron-carbon micro-electrolysis filler of iron carbon one, hole, iron anode activity is made
Height, while high-efficient purification function is ensured, thoroughly solves the problems such as being passivated and be hardened, and reduce filler production cost.
The present invention is achieved by the following technical solutions：
A kind of preparation method of regular iron-carbon micro-electrolysis filler, the preparation method is using Iron concentrate, pulverized bituminous coal as original
Material, using paper mill sludge after dries pulverizing as pore creating material, using copper powder as catalyst, and adds binding agent, is pressed into after well mixed
Type, and dry and obtain dry bulb filler, it is by high-temperature roasting that the Iron concentrate direct-reduction generation in the dry bulb filler is positive
Pole metallic iron, prepares iron-carbon micro-electrolysis filler.
Further, the preparation method includes：Papermaking after the preparation of Iron concentrate, the preparation of pulverized bituminous coal, dries pulverizing
The preparation of sludge, the preparation of catalyst, compressing and high temperature firing steps.
Further, the preparation method specifically includes following steps：
（1）The preparation of Iron concentrate：The Iron concentrate is obtained after ironmaking is crossed into 200 mesh sieves with Iron concentrate；
（2）The preparation of pulverized bituminous coal：The pulverized bituminous coal is by bituminous coal obtain after crushed 200 mesh sieves, the cigarette
The weight/mass percentage composition of fixed carbon is more than 80% in coal coal dust；
（3）The preparation of paper mill sludge after dries pulverizing：The solid waste in paper waste is collected, obtains wet paper mill sludge,
The wet paper mill sludge is placed at 80~120 DEG C and dried, 100 mesh sieves are crossed after crushing, that is, obtain papermaking after the dries pulverizing
Sludge；
（4）The preparation of catalyst：The catalyst was the copper powder obtained after 200 mesh sieves；
（5）It is compressing：By weight percentage, take 40~70 parts of the Iron concentrate, 10~30 parts of the pulverized bituminous coal,
5~8 parts of 8~15 parts of paper mill sludge, 1~3 part of the catalyst and binding agent after the dries pulverizing；By above-mentioned parts by weight
Paper mill sludge, catalyst and binding agent are well mixed after Iron concentrate, coal dust, dries pulverizing, obtain compound, toward the mixing
In material plus water mixes, and it is 10~15% to control moisture content in the compound, and the compound after adding water to mix is put into high pressure pressure
It is compressing in ball equipment, wet bulb filler is obtained, the wet bulb filler is dried at 75~90 DEG C, obtains dry bulb filler；
（6）High-temperature roasting：By step（5）The obtained dry bulb filler is placed in the high temperature furnace with air exclusion,
High-temperature roasting 1~3 hour at 1230~1280 DEG C, isolation air is cooled to less than 400 DEG C, and after taking out natural cooling, institute is made
State iron-carbon micro-electrolysis filler.
Further, step（5）Described in binding agent be sodium metasilicate, one or both of bentonite.
A kind of regular iron-carbon micro-electrolysis filler, according to a kind of preparation method system of regular iron-carbon micro-electrolysis filler
Standby to obtain, the granularity of the anode metal iron of the Iron concentrate direct-reduction generation is less than 10 μm, and the iron-carbon micro-electrolysis is filled out
Material is using iron as anode, and using carbon as negative electrode, the mass ratio of the iron of the anode and the carbon of the negative electrode is (3.2~8.2):1.
Further, the iron-carbon micro-electrolysis filler has a porous honeycomb Regularization structure, and outward appearance is in elliposoidal, diameter
For 10~30mm, the iron-carbon micro-electrolysis filler interior porosity is 32~55%.
The advantageous effects of the present invention：
（1）The filler Anodic metallic iron of the present invention is to be reduced directly by Iron concentrate and generated, and the fine size of metallic iron, is divided
Cloth density is big, high with negative electrode carbon contact probability, and the anode metal iron surface for being reduced directly generation by Iron concentrate does not have
Oxide layer, electrochemical corrosion activity are high.
（2）The preparing raw material of pore creating material is paper mill sludge solid waste, and the present invention is using paper mill sludge as pore creating material, papermaking
Organic matter is completely broken down gasification in the high-temperature roasting stage in sludge, and the iron-carbon micro-electrolysis filler for causing to prepare contains many
Tiny micropore, hole is flourishing, specific surface area is big；And filler is in integrally porous honeycomb structure, internal voids rate up to 32~
55%, suitable porosity is advantageous to increase the contact area of gas-solid-liquid three-phase, and the mass transfer that can be reacted with pharmaceutics wastewater
Process.
（3）High temperature firing steps, dry bulb filler is after high-temperature roasting at 1230~1280 DEG C, a small amount of iron and carbon in filler
React, form a small amount of carbon and ooze the carbonization iron compound in metallic iron（Fe3C）, carbonization iron compound can improve anode
Electron transfer efficiency between (iron) and negative electrode (carbon), improve the Inner electrolysis efficiency of iron-carbon micro-electrolysis filler.
（4）The addition of pore creating material and the high-temperature roasting of 1230~1280 DEG C of combination make the micro- of the preparation of the present invention in the present invention
Electrolysis filler has the integration of iron carbon, micropore framework formula alloy structure, and filling intensity is high, is not pulverized easily during wastewater treatment, filler
Service life is grown, not hardened, is not passivated, and treatment effect is stable.
（5）In use, metallic iron can be consumed constantly the filler of the present invention, and carbon and inorganic binder can be from filler tables
Emaciated face falls, and flows into next section of waste water treatment process, can continue to play a part of absorption and bio-carrier.
（6）The filler primary raw material source of the present invention is wide, and price is low, and can utilize solid waste paper mill sludge, filler production
Product cost is low, simple production process, is easy to industrialized production, there is good application prospect.
Brief description of the drawings
Fig. 1 is a kind of preparation flow schematic diagram of regular iron-carbon micro-electrolysis filler of the present invention；
Fig. 2 is a kind of regular iron-carbon micro-electrolysis filler sample appearance figure of the present invention；
Fig. 3 is a kind of scanning electron microscope (SEM) photograph in regular iron-carbon micro-electrolysis filler section of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiied
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to the thin of the present invention
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
Embodiment 1
A kind of preparation method of regular iron-carbon micro-electrolysis filler, the preparation method is using Iron concentrate, pulverized bituminous coal as original
Material, using paper mill sludge after dries pulverizing as pore creating material, using copper powder as catalyst, and adds binding agent, is pressed into after well mixed
Type, and dry and obtain dry bulb filler, it is by high-temperature roasting that the Iron concentrate direct-reduction generation in the dry bulb filler is positive
Pole metallic iron, prepares iron-carbon micro-electrolysis filler.
The Iron concentrate that the present invention uses is product obtained from iron-bearing mineral purifies through ore dressing process in iron ore mine, mainly into
It is divided into various iron oxide；And commercially available iron powder is used in the technology of preparing of conventional iron-carbon micro-electrolysis filler, commercially available iron powder is storing
During easily aoxidize.
Iron-carbon micro-electrolysis filler Anodic metallic iron of the present invention has following compared with conventional fillers Anodic metallic iron
Advantage：Firstly, since the anode metal iron in filler of the present invention is newly-generated in high-temperature calcination process direct-reduction by Iron concentrate,
Therefore surface does not aoxidize, and activity is strong, and routine techniques prepares the sun that the commercially available iron powder added during filler is the filler
Pole metallic iron, commercially available iron powder can aoxidize during storage, generate one layer of iron oxide film, reduce filler Anodic metallic iron
With the electron transfer efficiency between negative electrode carbon, thus as anode metal iron when surface-active it is low；Secondly, the present invention prepares
Filler in anode metal iron granularity it is thinner, less than 10 μm, and the granularity for the metal iron powder that conventional fillers use is more 50
~200 μm, so, when iron content is identical in filler, anode metal iron in filler of the present invention is because granularity is small, the quantity of anode iron
Greatly, it is high with negative electrode carbon contact probability, thus the Inner electrolysis activity of the iron-carbon micro-electrolysis filler of the invention prepared is stronger.
The preparation method includes：The system of paper mill sludge after the preparation of Iron concentrate, the preparation of pulverized bituminous coal, dries pulverizing
Standby, catalyst preparation, compressing and high temperature firing steps.
The preparation method specifically includes following steps：
（1）The preparation of Iron concentrate：Using ironmaking Iron concentrate as raw material, 200 mesh sieves are crossed, obtain the Iron concentrate, it is standby；
（2）The preparation of pulverized bituminous coal：Bituminous coal is crushed, 200 mesh sieves is crossed, obtains the pulverized bituminous coal, it is standby, it is described
The weight/mass percentage composition of fixed carbon is more than 80% in coal dust；
（3）The preparation of paper mill sludge after dries pulverizing：The solid waste in paper waste is collected, obtains wet paper mill sludge,
The wet paper mill sludge is placed at 80~120 DEG C and dried, 100 mesh sieves are crossed after crushing, that is, obtain papermaking after the dries pulverizing
Sludge；
Drying temperature can not be higher than 120 DEG C in the present invention, and the content of organic matter is high in paper mill sludge, if entering higher than 120 DEG C
Row high temperature dries (such as at 300 DEG C), and the organic matter in sludge may evaporate, and cause the change of organic matter property, separately
Outside, drying will also result in energy waste under high temperature；
The present invention by the paper mill sludge after drying cross 100 mesh sieves be obtain one that suitable porosity needs to control it is important
Parameter.Because suitable porosity is advantageous to increase the contact area of gas-solid-liquid three-phase, the mass transport process of pharmaceutics wastewater reaction.
Sludge powder after 100 mesh sieves point can leave sizeable hole, if but screen size mistake after high-temperature roasting in filler
Slightly (i.e. mesh number is too small), follow-up paper mill sludge powder skewness in filler can be caused, it is irregular in turn result in distribution of pores；When
Screen size is meticulous (i.e. mesh number is excessive), although sludge powder can uniformly mix with filler material, the voidage of filler after roasting
Can be too small.
（4）The preparation of catalyst：The catalyst was the copper powder that 200 mesh sieves obtain；
（5）It is compressing：By weight percentage, take 40~70 parts of the Iron concentrate, 10~30 parts of the pulverized bituminous coal,
5~8 parts of 8~15 parts of paper mill sludge, 1~3 part of the catalyst and binding agent after the dries pulverizing；By above-mentioned parts by weight
Paper mill sludge, catalyst and binding agent are well mixed after Iron concentrate, coal dust, dries pulverizing, and into the compound plus water mixes
It is even, compound is obtained, and it is 10~15% to control moisture content in the compound, and the compound is put into high pressure pressure ball equipment
In it is compressing, obtain wet bulb filler, the wet bulb filler dried at 75~90 DEG C, obtains dry bulb filler；
By the moisture control of compound 10~15%, drawn by systematic substantial amounts of experiment, at this
It is under moisture content that compound is compressing, the intensity highest of the wet bulb filler of acquisition, and in subsequent high temperature（1230~1280
℃）Efflorescence not easy to crack in roasting process, the filling-material structure intensity burnt out are high.
（6）High-temperature roasting：By step（5）The obtained dry bulb filler is placed in the high temperature furnace with air exclusion, with stove
Outer air exclusion, high-temperature roasting 1~3 hour at 1230~1280 DEG C, then completely cut off air and be cooled to less than 400 DEG C, take out certainly
So cooling, the iron-carbon micro-electrolysis filler is made.
, can be to filling out if the binding agent engages power selected is big in the production process of the iron-carbon micro-electrolysis filler of routine
Material is without sintering；If binding agent engages power is little, and the intensity requirement of filler is higher, then selection is at 1000 DEG C or so
It is sintered, so that the intensity increase of filler, will not efflorescence when being used so as to filler.
Different from conventional art, high temperature sintering step of the present invention is essential, and high temperature of the present invention is calcined
Condition must control for：1230 ~ 1280 DEG C of temperature range, it is calcined 1 ~ 3 hour, under conditions of the high-temperature roasting, raw material
In Iron concentrate can by direct-reduction generate metal abrasive grit, and generate the metal abrasive grit granularity it is small（Less than 10 μ
m）, be evenly distributed, surface is not oxidized and activity is strong.
And high temperature firing steps, dry bulb filler after high-temperature roasting at 1230~1280 DEG C, in filler a small amount of iron with
Carbon reacts, and forms a small amount of carbon and oozes the carbonization iron compound in metallic iron（Fe3C）, carbonization iron compound can improve sun
Electron transfer efficiency between pole (iron) and negative electrode (carbon), improve the Inner electrolysis efficiency of iron-carbon micro-electrolysis filler.
The process of high-temperature roasting at 1230~1280 DEG C, the high temperature furnace are using strong close with the mode that outside air completely cuts off
The fire door of closing property covers tightly fire door, and because high temperature furnace and outside air completely cut off, in filler with addition of coal dust in roasting process it is raw
Into carbon monoxide so that high temperature furnace forms reducing atmosphere in roasting process, protects the metallic iron of direct-reduction not by air
Oxidation.
After high-temperature roasting terminates at 1230~1280 DEG C, the stage that isolation air is cooled to 400 DEG C needs also exist for completely cutting off
Air is highly important, can keep weak reducing atmosphere in high temperature furnace with air exclusion outside stove, is cooled to furnace
The filler prepared is taken out from stove again after 400 DEG C, the metallic iron that reduction can be avoided to obtain is oxidized.
The addition of pore creating material and the high-temperature roasting of 1230~1280 DEG C of combination make the micro-electrolysis stuffing tool of the preparation of the present invention
There are the integration of iron carbon, micropore framework formula alloy structure, filling intensity is high, is not pulverized easily during wastewater treatment, filler service life length,
It is not hardened, it is not passivated, treatment effect is stable.
Step（5）Described in binding agent be sodium metasilicate, one or both of bentonite.
A kind of regular iron-carbon micro-electrolysis filler, according to a kind of preparation method system of regular iron-carbon micro-electrolysis filler
Standby to obtain, the granularity of the anode metal iron of the Iron concentrate direct-reduction generation is less than 10 μm, and the iron-carbon micro-electrolysis is filled out
Material is using iron as anode, and using carbon as negative electrode, the mass ratio of the iron of the anode and the carbon of the negative electrode is (3.2~8.2):1.
The iron-carbon micro-electrolysis filler has porous honeycomb Regularization structure（As shown in Figure 3）, outward appearance is in elliposoidal（Such as
Shown in Fig. 2）, a diameter of 10~30mm, the iron-carbon micro-electrolysis filler interior porosity is 32~55%.
Embodiment 2
By Iron concentrate, coal dust, paper mill sludge, copper powder and sodium metasilicate in mass ratio 50:25:15:2:8 uniformly mixing, then adjust
The moisture content for saving compound is 10%, and the wet filling ball of elliposoidal is pressed into high pressure pressure ball equipment, a diameter of 15mm, and in drying
Dried in machine at 80 DEG C, filler stem ball is placed in the high temperature furnace with air exclusion, be calcined 3 hours at 1230 DEG C, completely cut off air
Less than 400 DEG C are cooled to, takes out natural cooling, regular iron-carbon micro-electrolysis filler is made.Obtained filler have iron carbon one,
Porous honeycomb Regularization structure, iron carbon mass ratio are 4.1:1, interior porosity 54%.
The regular iron-carbon micro-electrolysis filler prepared using the present embodiment handles the leaded and simulation of a copper ion huge sum of money
Belong to waste water, lead, the initial concentration of copper ion are 100mg/L, hydraulic detention time 45min in the simulation heavy metal wastewater thereby
When, after microelectrolysis processing, lead ion clearance 94.3%, copper ion clearance 99.2%, it is hardened continuously to run 14 days no-arbitrary pricings
Phenomenon.
Embodiment 3
By the papermaking after the ironmaking Iron concentrate of 200 mesh sieves excessively, the excessively dries pulverizing of the pulverized bituminous coal of 200 mesh, 100 mesh of mistake
Sludge, the copper powder and bentonite in mass ratio 58 for crossing 200 mesh:20:15:2:5 uniformly mixing, obtain compound, then adjust mixing
The moisture content of material is 15%, and compound is pressed into elliposoidal wet bulb filler, a diameter of 20mm, by described in high pressure pressure ball equipment
Wet filling ball dried under drying machine obtain dry bulb filler, drying temperature be 90 DEG C, by the dry bulb filler be placed in air every
In exhausted high temperature furnace, it is calcined at 1250 DEG C 2.5 hours, then, isolation air is cooled to less than 400 DEG C, takes out natural cooling, system
Obtain regular iron-carbon micro-electrolysis filler.The obtained iron-carbon micro-electrolysis filler has iron carbon one, porous honeycomb Regularization
Structure, iron carbon mass ratio are 5.2:1, interior porosity 46%.
The regular iron-carbon micro-electrolysis filler prepared using the present embodiment handles methylene blue stimulated dye wastewater, institute
Methylene blue stimulated dye wastewater Methylene Blue initial concentration 300mg/L is stated, when hydraulic detention time is 30min, through micro- electricity
After solution processing, methylene blue clearance 97.2%, 14 days no-arbitrary pricing hardened phenomenons are continuously run.
Embodiment 4
By the papermaking after the ironmaking Iron concentrate of 200 mesh sieves excessively, the excessively dries pulverizing of the pulverized bituminous coal of 200 mesh, 100 mesh of mistake
Sludge, the copper powder and bentonite in mass ratio 62 for crossing 200 mesh:15:13:3:7 uniformly mixing, obtain compound, then adjust mixing
The moisture content of material is 13%, and compound is pressed into elliposoidal wet bulb filler, a diameter of 25mm, by described in high pressure pressure ball equipment
Wet filling ball dried under drying machine obtain dry bulb filler, drying temperature be 80 DEG C, by the dry bulb filler be placed in air every
In exhausted high temperature furnace, it is calcined at 1270 DEG C 2 hours, then, isolation air is cooled to less than 400 DEG C, takes out natural cooling, is made
Regular iron-carbon micro-electrolysis filler.The obtained iron-carbon micro-electrolysis filler has iron carbon one, porous honeycomb Regularization knot
Structure, iron carbon mass ratio are 6.4:1, interior porosity 42%.
The regular iron-carbon micro-electrolysis filler prepared using the present embodiment handles certain beer brewery water, the waste water
Initial COD is 18000mg/L, and when hydraulic detention time is 150min, after microelectrolysis processing, COD clearances are 64.6%, fortune
Row is stable.
Embodiment 5
By the papermaking after the ironmaking Iron concentrate of 200 mesh sieves excessively, the excessively dries pulverizing of the pulverized bituminous coal of 200 mesh, 100 mesh of mistake
Sludge, the copper powder and bentonite in mass ratio 68 for crossing 200 mesh:11:10:2:6 uniformly mixing, obtain compound, then adjust mixing
The moisture content of material is 13%, and compound is pressed into elliposoidal wet bulb filler, a diameter of 25mm, by described in high pressure pressure ball equipment
Wet filling ball dried under drying machine obtain dry bulb filler, drying temperature be 85 DEG C, by the dry bulb filler be placed in air every
In exhausted high temperature furnace, it is calcined at 1280 DEG C 1.5 hours, then, isolation air is cooled to less than 400 DEG C, takes out natural cooling, system
Obtain regular iron-carbon micro-electrolysis filler.The obtained iron-carbon micro-electrolysis filler has iron carbon one, porous honeycomb Regularization
Structure, iron carbon mass ratio are 7.7:1, interior porosity 36%.
The regular iron-carbon micro-electrolysis filler prepared using the present embodiment handles certain chemical industrial park waste water, the chemical industry
The initial COD of garden waste water is 9300mg/L, and when hydraulic detention time is 120min, after microelectrolysis processing, COD clearances are
57.3%, 20 days no-arbitrary pricing hardened phenomenons are continuously run, it is stable.
Claims (4)
1. a kind of preparation method of regular iron-carbon micro-electrolysis filler, it is characterised in that the preparation method is with Iron concentrate, bituminous coal
Coal dust is raw material, using paper mill sludge after dries pulverizing as pore creating material, using copper powder as catalyst, and adds binding agent, is well mixed
It is compressing afterwards, and dry and obtain dry bulb filler, the Iron concentrate in the dry bulb filler is directly gone back by high-temperature roasting
It is primary into anode metal iron, prepare iron-carbon micro-electrolysis filler；
The preparation method specifically includes following steps：
（1）The preparation of Iron concentrate：The Iron concentrate is obtained after ironmaking is crossed into 200 mesh sieves with Iron concentrate；
（2）The preparation of pulverized bituminous coal：The pulverized bituminous coal is by bituminous coal obtain after crushed 200 mesh sieves, the bituminous coal coal
The weight/mass percentage composition of fixed carbon is more than 80% in powder；
（3）The preparation of paper mill sludge after dries pulverizing：The solid waste in paper waste is collected, wet paper mill sludge is obtained, by institute
State wet paper mill sludge and be placed at 80~120 DEG C and dry, 100 mesh sieves are crossed after crushing, that is, obtain paper mill sludge after the dries pulverizing；
（4）The preparation of catalyst：The catalyst was the copper powder obtained after 200 mesh sieves;
（5）It is compressing：By weight percentage, 40~70 parts of the Iron concentrate, 10~30 parts of the pulverized bituminous coal, described is taken
5~8 parts of 8~15 parts of paper mill sludge, 1~3 part of the catalyst and binding agent after dries pulverizing；By the iron essence of above-mentioned parts by weight
Paper mill sludge, catalyst and binding agent are well mixed after powder, coal dust, dries pulverizing, obtain compound, into the compound
Water is added to mix, and it is 10~15% to control moisture content in the compound, the compound after adding water to mix is put into high pressure pressure ball sets
It is compressing in standby, wet bulb filler is obtained, the wet bulb filler is dried at 75~90 DEG C, obtains dry bulb filler；
（6）High-temperature roasting：By step（5）The obtained dry bulb filler is placed in the high temperature furnace with air exclusion, 1230~
High-temperature roasting 1~3 hour at 1280 DEG C, isolation air is cooled to less than 400 DEG C, and after taking out natural cooling, the iron carbon is made
Micro-electrolysis stuffing；
In high temperature firing steps, dry bulb filler is after high-temperature roasting at 1230~1280 DEG C, and a small amount of iron is sent out with carbon in filler
Raw reaction, forms a small amount of carbon and oozes the carbonization iron compound Fe in metallic iron3C。
A kind of 2. preparation method of regular iron-carbon micro-electrolysis filler according to claim 1, it is characterised in that step（5）
Described in binding agent be sodium metasilicate, one or both of bentonite.
3. a kind of regular iron-carbon micro-electrolysis filler, a kind of regular iron-carbon micro-electrolysis filler according to claim 1 or claim 2
Preparation method prepares, it is characterised in that the granularity of the anode metal iron of the Iron concentrate direct-reduction generation is less than
10 μm, the iron-carbon micro-electrolysis filler is using iron as anode, using carbon as negative electrode, the quality of the iron of the anode and the carbon of the negative electrode
Than for (3.2~8.2):1.
A kind of 4. regular iron-carbon micro-electrolysis filler according to claim 3, it is characterised in that the iron-carbon micro-electrolysis filler
With porous honeycomb Regularization structure, outward appearance is in elliposoidal, a diameter of 10~30mm, the iron-carbon micro-electrolysis filler internal holes
Gap rate is 32~55%.
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| CN105858821B (en) * | 2016-04-18 | 2019-05-21 | 河南弘康环保科技有限公司 | Iron-carbon micro-electrolysis filler and its preparation method and application |
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| CN107021547B (en) * | 2017-05-10 | 2021-03-19 | 代纯伟 | Preparation method of iron-carbon micro-electrolysis filler and product thereof |
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| CN109650492A (en) * | 2019-01-16 | 2019-04-19 | 马步真 | A kind of iron-carbon micro-electrolysis filler and preparation method thereof |
| CN109911992B (en) * | 2019-03-20 | 2021-11-19 | 浙江省环境保护科学设计研究院 | Preparation method and application of iron-based multi-metal alloy micro-electrolysis filler |
| CN112320897B (en) * | 2020-10-09 | 2022-07-22 | 新昌中国计量大学企业创新研究院有限公司 | Spherical iron-carbon micro-electrolysis filler and preparation method thereof |
| CN113979516A (en) * | 2021-11-12 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Iron-carbon-copper alloy micro-electrolysis composite material and preparation method and application thereof |
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