CN106277225A - The method producing regular iron-carbon micro-electrolysis filler with high ferro copper ashes - Google Patents
The method producing regular iron-carbon micro-electrolysis filler with high ferro copper ashes Download PDFInfo
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- CN106277225A CN106277225A CN201610825289.XA CN201610825289A CN106277225A CN 106277225 A CN106277225 A CN 106277225A CN 201610825289 A CN201610825289 A CN 201610825289A CN 106277225 A CN106277225 A CN 106277225A
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- copper ashes
- high ferro
- carbon micro
- iron
- electrolysis filler
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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
- C02F1/46104—Devices therefor; Their operating or servicing
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
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Abstract
The present invention provides a kind of method that high ferro copper ashes produces regular iron-carbon micro-electrolysis filler, belongs to technical field of resource utilization.After high ferro copper ashes is crushed by described preparation method, it is prepared as carbonaceous pelletizing after mixing with carbonaceous reducing agent, binding agent, additive and water, carbonaceous pelletizing reduction roasting under the conditions of 1100～1300 DEG C of starvations after drying, it is thus achieved that regular iron-carbon micro-electrolysis filler.This technique achieves the efficient utilization of high ferro copper ashes to environmental pollutants, has the advantage that raw material sources are extensive, flow process is short, low cost, added value of product are high.The regular iron-carbon micro-electrolysis filler that the present invention provides is applied to Industrial Wastewater Treatment, can effectively reduce COD and the colourity of waste water, run using effect stable.
Description
Technical field
The present invention relates to technical field of resource utilization, particularly relate to one high ferro copper ashes and produce regular iron-carbon micro-electrolysis
The method of filler.
Background technology
Copper ashes is the waste residue produced during copper concentrate pyrometallurgical smelting refines, and the most often produces one ton of copper and will produce 2.2 tons of copper
Slag.The annual copper ashes yield of China is up to 1 500 ten thousand t, and accumulative heap product is with ton copper ashes.The copper ashes that different smelting processes produce becomes
Difference is had though dividing, but ferrum, copper content the highest (Fe, Cu content is generally up to 30%～50% and 0.5%～2.1%), far
Higher than China's iron ore payable grade (TFe > 27%) and copper mining grade (Cu > 0.3%), it addition, possibly together with in a large number in slag
Cobalt, the noble metal such as antimony.The existence of a large amount of waste copper slags, not only takies a large amount of soil, also results in environmental pollution.At copper mine and iron mine
In the case of resource increasingly reduces and steps up with environmental requirement, how to realize comprehensive utilization and the Green Development of resource,
Become the task of top priority of society and enterprise development.At present, substantial amounts of scholar's research reclaims valuable metal from copper ashes, including electric furnace
Dilution method, floatation, magnetic method etc., although can realize the recovery of copper, but have that copper recovery is low, tailings copper grade high, ferrum
The unserviceable problem of component.
Micro electrolysis tech is the technique that a kind of Applied Electrochemistry principle processes waste water, and also referred to as internal electrolysis utilizes anode
Between (ferrum) and negative electrode (carbon), pollutant are processed by the potential difference of 1.2V, high toxicity, height big particular for organic concentration
Colourity, the process of difficult biochemical waste water, can significantly cut down chroma in waste water and COD, improve its biodegradability；Additionally, micro electrolysis tech
The most adsorbable, reduce various heavy metal ion, therefore, micro electrolysis tech is widely used in printing and dyeing, papermaking, chemical industry, electroplates, prints
The process of all types of industries waste water such as wiring board, pharmacy.
Conventional iron carbon micro-electrolysis filler is by iron filings and activated carbon physical mixed in proportion, constitutes ferrum carbon fixation bed, but because of
Abrasive grit (anode) and carbon granules (negative electrode) physical separation, the electric current density that light electrolysis produces is little, and water treatment effect is poor；Abrasive grit surface
Easily get rusty passivation, cause packing layer to harden, form channel, need frequent backwash packing layer or change filler, adding light electrolysis
The complexity of technique.Therefore, the development of hardening resistant micro-electrolysis filler, it appears the most necessary.In recent years, domestic iron-carbon micro-electrolysis is filled out
With market sale development quickly, product is mainly by metal iron powder, activated carbon, non-ferrous metal catalyst and binding agent in the production of material
Composition, blended, molding and sintering make, and filler has realized Regularization, overcomes filler and hardens problem.But, still suffer from as
Lower problem: filler material cost is high, product price is high, cost of water treatment rises；Sintering temperature is low, and filling-material structure is loose, waste water
During process, loss is fast；Conventional ferrum carbon filler produces and uses commercial metals iron powder, and commercial metals iron powder is passivated because of surface oxidation,
Directly applying in filler, activity is low, and electric current density is little, can be improved the activity of metal iron powder by acidleach, but too increase
Production cost and environmental protection risk.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high ferro copper ashes and produces the side of regular iron-carbon micro-electrolysis filler
Method.
The method specifically includes following steps:
(1) copper ashes carbonaceous pelletizing is prepared: high ferro copper ashes is crushed to-2mm, the high ferro copper ashes after then crushing and carbonaceous
Reducing agent, additive and binding agent add water after mixing by a certain percentage pelletizing or pressure ball, are prepared as carbonaceous pelletizing；
(2) reduction roasting: step (1) gained carbonaceous pelletizing is dried, at sintering temperature 1100～1300 DEG C of isolating oxygens
Product after the roasting of reduction roasting generation containing metal iron grain and carbon granules under the conditions of gas, after roasting, product is cold under the conditions of starvation
But, regular iron-carbon micro-electrolysis filler is obtained.In roasting process, iron mineral is reduced to the metallic iron sun as micro-electrolysis stuffing
Pole, carbon residue is as negative electrode；Copper-bearing mineral is reduced to metallic copper, can be as the catalyst of micro-electrolysis stuffing；Additive can promote
The intensity of iron-carbon micro-electrolytic material after iron mineral reduction and raising roasting.
Wherein, in step (1), the iron content of high ferro copper ashes used is more than 30%, the relatively low copper ashes of iron content by ore dressing or
Smelting means improve iron content and can also be used for producing regular iron-carbon micro-electrolysis filler after more than 30%.
Carbonaceous reducing agent in step (1) be the one in anthracite, bituminous coal, activated carbon, coke, semicoke, petroleum coke or
Multiple combination；
Additive in step (1) is the one in limestone, Calx, slaked lime, sodium carbonate, sodium sulfate, fluorite, Borax
Or multiple combination；
Binding agent in step (1) is one or more in bentonite, molasses, starch, waterglass；
In step (1), the mass ratio of high ferro copper ashes, carbonaceous reducing agent, additive and binding agent is: 100:(30～60): (1
～20): (0.5～10).
In step (2), reduction roasting is carried out under the conditions of starvation, and after roasting, product cools down under the conditions of starvation.
Having the beneficial effect that of the technique scheme of the present invention:
In such scheme, directly produced regular iron-carbon micro-electrolysis filler by high ferro copper ashes, have raw material sources extensively, stream
Short and the eco-friendly feature of journey, gained iron-carbon micro-electrolytic material is applied to process industrial wastewater, can effectively reduce the COD of waste water
And colourity, run using effect stable.
Accompanying drawing explanation
Fig. 1 is the method flow diagram of the high ferro copper ashes production regular iron-carbon micro-electrolysis filler of the present invention.
Detailed description of the invention
For making the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
The present invention provides a kind of method that high ferro copper ashes produces regular iron-carbon micro-electrolysis filler, technological process such as Fig. 1 institute
Show that the step such as including dispensing, pelletizing, drying, reduction roasting, cooling is explained below in conjunction with specific embodiment.
Embodiment 1
The multielement analysis of certain high ferro copper ashes is shown in Table 1, with being front crushed to-2mm.Carbonaceous reducing agent used is anthracite, coal
Matter is analyzed as shown in table 2, and with being front crushed to-1mm, additive is limestone, with being front crushed to-1mm.
The multielement analysis of table 1 high ferro copper ashes
| Composition | TFe | Al2O3 | SiO2 | MgO | CaO |
| Content (%) | 41.07 | 4.10 | 34.64 | 0.32 | 1.43 |
| Composition | K2O | Na2O | TiO2 | Cu | S |
| Content (%) | 0.61 | 0.21 | 0.45 | 0.31 | 0.21 |
The Industrial Analysis result of table 2 coal
High ferro copper ashes: anthracite: limestone: bentonite 100:50:17:5 in mass ratio weighs mixing, then adds 12%
Water mixes.Mixed material is being prepared as carbonaceous pelletizing on roller ball press, by carbonaceous pelletizing 105 DEG C of drying.By carbon containing ball
Group puts in atmosphere furnace, and inflated with nitrogen protection is warming up to 1150 DEG C, is then incubated 3h, and roasting is the coldest with stove after terminating
But, regular iron-carbon micro-electrolysis filler is obtained.
The application regular iron-carbon micro-electrolysis filler prepared of the present embodiment process certain silk dye transfer waste water (colourity about 800 times,
COD is about 1400mg/L, pH:5.3～5.5), pH is adjusted to about 3, under conditions of hydraulic detention time is 9h, waste water color
Degree clearance is 87%, COD removal efficiency 48%；Reactor runs 1 month continuously, and do not find significantly to harden phenomenon, runs
Relatively stable.
Embodiment 2
The multielement analysis of certain high ferro copper ashes is shown in Table 3, with being front crushed to-2mm.
The multielement analysis of table 3 high ferro copper ashes
| Composition | TFe | Cu | Al2O3 | SiO2 | MgO | CaO |
| Content (%) | 39.23 | 1.47 | 4.12 | 30.64 | 0.32 | 5.43 |
| Composition | K2O | Na2O | TiO2 | P | S | |
| Content (%) | 0.35 | 0.39 | 0.32 | 0.22 | 0.76 |
High ferro copper ashes: carbonaceous reducing agent: binding agent: additive 100:48:5:8 in mass ratio weighs mixing, then adds
The water mixing of 12%.Carbonaceous reducing agent consist of anthracite: bituminous coal: activated carbon: coke: semicoke: the mass ratio of petroleum coke is
40:20:10:10:10:10, anthracite, bituminous coal, activated carbon, coke, semicoke, petroleum coke are industrial products；Binding agent forms
For waterglass: bentonite: starch: molasses mass ratio is 20:40:10:30, waterglass, bentonite, starch, molasses are
Industrial products；Additive consists of limestone: Calx: slaked lime: sodium carbonate: sodium sulfate: fluorite: Borax mass ratio is 20:20:
10:10:15:15:10, limestone, Calx, slaked lime, fluorite, sodium carbonate, sodium sulfate, Borax are industrial products.Will mixing
Material is being prepared as carbonaceous pelletizing on roller ball press, by carbonaceous pelletizing 105 DEG C of drying.Carbonaceous pelletizing is put into atmosphere furnace
In, inflated with nitrogen protection is warming up to 1270 DEG C, is then incubated 2h, and roasting cools down under nitrogen protection with stove after terminating, and obtains regular
Change iron-carbon micro-electrolysis filler.
Regular iron-carbon micro-electrolysis filler prepared by application the present embodiment processes certain industry coking chemical waste water, and its COD is
14000mg/L, colourity is about 11500 times.Wastewater pH is adjusted to about 3, and under conditions of hydraulic detention time is 7h, COD goes
Except rate is 52, chroma removal rate is 83%.Running 6 weeks continuously, run treatment effect stable, do not find substantially to harden phenomenon.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, it is also possible to make some improvements and modifications, these improvements and modifications are also
Should be regarded as protection scope of the present invention.
Claims (7)
1. the method producing regular iron-carbon micro-electrolysis filler with high ferro copper ashes, it is characterised in that: comprise the steps:
(1) prepare copper ashes carbonaceous pelletizing: high ferro copper ashes is crushed to-2mm, will broken after high ferro copper ashes and carbonaceous reducing agent,
Additive and binding agent add water after mixing by a certain percentage pelletizing or pressure ball, are prepared as carbonaceous pelletizing；
(2) reduction roasting: step (1) gained carbonaceous pelletizing is dried, at sintering temperature 1100～1300 DEG C of starvation bars
Product after the roasting of reduction roasting generation containing metal iron grain and carbon granules under part, after roasting, product cools down under the conditions of starvation,
Obtain regular iron-carbon micro-electrolysis filler.
High ferro copper ashes the most according to claim 1 produces the method for regular iron-carbon micro-electrolysis filler, it is characterised in that:
The iron content of high ferro copper ashes used is more than 30%.
High ferro copper ashes the most according to claim 1 produces the method for regular iron-carbon micro-electrolysis filler, it is characterised in that:
Carbonaceous reducing agent used is one or more combinations in anthracite, bituminous coal, activated carbon, coke, semicoke, petroleum coke.
High ferro copper ashes the most according to claim 1 produces the method for regular iron-carbon micro-electrolysis filler, it is characterised in that:
Additive used is one or more combinations in limestone, Calx, slaked lime, sodium carbonate, sodium sulfate, fluorite, Borax.
High ferro copper ashes the most according to claim 1 produces the method for regular iron-carbon micro-electrolysis filler, it is characterised in that:
Binding agent used is one or more combinations in bentonite, molasses, starch, waterglass.
High ferro copper ashes the most according to claim 1 produces the method for regular iron-carbon micro-electrolysis filler, it is characterised in that:
The mass ratio of high ferro copper ashes used, carbonaceous reducing agent, additive and binding agent is 100:(30～60): (0～20): (0.5～
10)。
High ferro copper ashes the most according to claim 1 produces the method for regular iron-carbon micro-electrolysis filler, it is characterised in that:
Reduction roasting is carried out under the conditions of starvation, and after roasting, product cools down under the conditions of starvation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830211A (en) * | 2017-03-08 | 2017-06-13 | 江西理工大学 | A kind of method that dyeing waste water is processed with low-grade iron ore |
| CN107012316A (en) * | 2017-04-07 | 2017-08-04 | 江西理工大学 | The method that many first micro-electrolysis stuffings of Regularization Fe Ni C are produced with lateritic nickel ore |
| CN109055720A (en) * | 2018-09-06 | 2018-12-21 | 钢研晟华科技股份有限公司 | A method of iron powder is prepared based on the modified copper ashes with cryogenic vulcanization reduction of alkaline process |
| CN109626511A (en) * | 2019-01-29 | 2019-04-16 | 中环清源(北京)科技有限公司 | Electrochemistry-light electrolysis coupling device and technology for Laboratory Waste Water Treatment |
| CN111644144A (en) * | 2020-06-16 | 2020-09-11 | 四川时代绿洲环境修复股份有限公司 | Water body dephosphorization magnetic material and preparation method and application thereof |
| CN114408885A (en) * | 2021-12-28 | 2022-04-29 | 中节能工业节能有限公司 | Reducing agent for producing yellow phosphorus by thermal method and preparation method thereof |
| CN115475951A (en) * | 2022-09-01 | 2022-12-16 | 江西理工大学 | Silicate-loaded micro-nano zero-valent iron sulfide with core-shell structure and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830211A (en) * | 2017-03-08 | 2017-06-13 | 江西理工大学 | A kind of method that dyeing waste water is processed with low-grade iron ore |
| CN106830211B (en) * | 2017-03-08 | 2020-12-01 | 江西理工大学 | Method for treating printing and dyeing wastewater by using low-grade iron ore |
| CN107012316A (en) * | 2017-04-07 | 2017-08-04 | 江西理工大学 | The method that many first micro-electrolysis stuffings of Regularization Fe Ni C are produced with lateritic nickel ore |
| CN109055720A (en) * | 2018-09-06 | 2018-12-21 | 钢研晟华科技股份有限公司 | A method of iron powder is prepared based on the modified copper ashes with cryogenic vulcanization reduction of alkaline process |
| CN109626511A (en) * | 2019-01-29 | 2019-04-16 | 中环清源(北京)科技有限公司 | Electrochemistry-light electrolysis coupling device and technology for Laboratory Waste Water Treatment |
| CN111644144A (en) * | 2020-06-16 | 2020-09-11 | 四川时代绿洲环境修复股份有限公司 | Water body dephosphorization magnetic material and preparation method and application thereof |
| CN114408885A (en) * | 2021-12-28 | 2022-04-29 | 中节能工业节能有限公司 | Reducing agent for producing yellow phosphorus by thermal method and preparation method thereof |
| CN114408885B (en) * | 2021-12-28 | 2023-08-29 | 中节能工业节能有限公司 | Reducing agent for producing yellow phosphorus by thermal method and preparation method thereof |
| CN115475951A (en) * | 2022-09-01 | 2022-12-16 | 江西理工大学 | Silicate-loaded micro-nano zero-valent iron sulfide with core-shell structure and preparation method and application thereof |
| CN115475951B (en) * | 2022-09-01 | 2023-10-10 | 江西理工大学 | Silicate supported micro-nano zero-valent iron sulfide with core-shell structure and preparation method and application thereof |
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