CN109911992A - A kind of preparation method and application of iron-based more metal alloy micro-electrolysis stuffings - Google Patents
A kind of preparation method and application of iron-based more metal alloy micro-electrolysis stuffings Download PDFInfo
- Publication number
- CN109911992A CN109911992A CN201910212990.8A CN201910212990A CN109911992A CN 109911992 A CN109911992 A CN 109911992A CN 201910212990 A CN201910212990 A CN 201910212990A CN 109911992 A CN109911992 A CN 109911992A
- Authority
- CN
- China
- Prior art keywords
- iron
- powder
- electrolysis
- micro
- metal alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a kind of preparation method and application of iron-based more metal alloy micro-electrolysis stuffings, it is easy in the treatment of waste water for existing iron-carbon micro-electrolysis filler hardened, the low problem for the treatment of effeciency, by iron powder and copper, nickel, zinc, one or two kinds of metal catalytic components of manganese are by being prepared iron-based more metal alloy powder with the method ball milling of mechanical force and chemical, again by iron-based more metal alloy powder, charcoal, the mixing of the raw materials such as clay and pore creating material, suitable water and binder is added through mediating, cutting, it is granulated, raw material ball is made after the processes such as polishing, continuous sintering becomes iron-based more metal alloy micro-electrolysis stuffings of higher-strength under oxygen deficient atmospheres.The pretreatments of the industrial wastewaters before biochemical processing process such as the micro-electrolysis stuffing that the present invention is prepared can be used for printing and dyeing, chemical industry, plating, papermaking, it can also be used to the waste water treatments such as advanced treating of sewage treatment plant field.
Description
Technical field
The invention belongs to sewage treatment fields, and in particular to a kind of industrial wastewater catalysis reduction pretreatment material and application side
Method.
Background technique
In field of sewage treatment, China's water treatment technology is based on bioanalysis, but the toxic organic matter in industrial wastewater
It is often difficult to be difficult to greatly divide part using chemical oxidation by Biochemical method qualified discharge with hardly degraded organic substance
Sub- organic matter is thoroughly degraded to inorganic matter.However, most of toxic organic matter and the relatively easy chemistry of hardly degraded organic substance are also
Original, and reduzate is greatly reduced the toxic action of microorganism, so that wastewater biological degradability is improved.
Currently, studying more mature chemical reduction process both at home and abroad is Fe-C Micro Electrolysis Method, mechanism mainly has cathode
Electrocatalytic effect, iron direct-reduction, the reduction of nascent state H, the polymeric precipitation of hydroxyl iron complex etc., engineer application table
Bright, this method is to the persistent organic pollutants in the industrial wastewaters such as waste water from dyestuff, dyeing waste water, paper waste, wastewater from chemical industry
Removal have preferable effect.For example, the azo that Recalcitrant chemicals matter is mainly derived from azo dyes in waste water from dyestuff has
Machine pollutant, azo substance not only has specific color, and molecular structure is complicated, and biodegradability is poor, most of
With potential murder by poisoning, azo bond therein have it is electron-withdrawing, be not easy oxidative degradation.On the contrary, azo bond is broken after being reduced
Generation aromatic amine is oxidized easily or by aerobic degradation, and has preferable decolorizing effect.
But it with the development of iron-carbon micro-electrolysis technology, is also gradually highlighted in waste water treatment engineering using upper defect.It passes
The micro electrolysis tech raw materials of system are mainly iron filings, charcoal, such as the unitary or binary micro-electrolysis stuffing of early stage, between the two
It is physical contact, is easily passivated hardened generations separation layer in use process and ineffective, which results in frequently replacing filler,
Heavy workload, it is at high cost, influence treatment effect and efficiency.The patent of invention of Patent No. CN101838034A discloses a kind of high
Efficiency, hardening resistant micro-electrolysis material and preparation method thereof increase the porosity and specific surface of filler using high temperature boring technique
Product so as to improve filler treatment effect and increases service life.But there are the consumption of iron for this method fastly, it is biggish to joined specific gravity
Bentonite, bentonite will not consume in reaction process, cause the sludge quantity generated larger, and after the iron consumption of filler surface,
Internal iron is surrounded by clay, so that reaction effect is begun to decline.
Therefore, in order to improve micro-electrolysis stuffing to the treatment effeciency of waste water, add again on the basis of binary micro-electrolysis stuffing
A kind of or even various metals or nonmetallic, come from different backgrounds and possess different abilities micro-electrolysis stuffing.By the way that another metal and its shape is added in iron surface
Strengthen reduction reaction at bimetallic, essence is still the electrochemical corrosion reaction of iron, simultaneously because another standard being added
The electrode potential metal higher than iron is right as cathodic metal and iron formation galvanic couple electricity, plays catalysis reduction to pollutant,
Middle Zero-valent Iron loses the reaction of electronics in acid waste water as the reaction basis of whole system, and pollutant can be in zeroth order iron surface
Electrically realized reduction is obtained, electronics can also be obtained in bimetallic cathode surface and is restored, reduction ratio between the two is with anti-
Answer the difference of pollutant and reaction condition and difference.At present the ternary micro-electrolysis filler system appeared in the newspapers include Co-Fe-C,
Cu-Fe-C, Ni-Fe-C and Al-Fe-C etc., but current theoretical research is also in initial stage, due to different cathodic metals
There are different standard oxidizing potentials and different surface naturies, so processing difference on effect is obvious between each filler systems, it is of the same race
Filler systems can also be very different the reduction efficiency of different pollutants, and partly cause may is that the structure of pollutant and anti-
Answer the difference of approach.
In addition, mass ratio of cathodic metal and the ironing surface coverage mode of zeroth order, cathode and anode etc. is to reduction efficiency
There is certain influence.
The patent No. is that the patent of invention of CN107199037A discloses a kind of modified ozone in Cu/Fe bimetallic material surface and urges
The preparation method of agent mainly plates a small amount of copper in steel material surface in the method for chemical plating, forms the simple substance of endless all standing
Copper film is formed passivating film in bimetallic surface, the damage of catalyst is reduced with this in acid or neutral solution Strong oxdiative environment
Consumption.The chemical plating method needs to do steel degreasing and rust removal pretreatment, then with nitric acid or H2O2It is real for oxidant modified catalyst
Border is complicated for operation and controllability is poor, it is difficult to application.Therefore, the preparation process that improves polynary iron-carbon micro-electrolysis filler, control
Making its cost is the key factor realizing large-scale application and promoting.
Summary of the invention
The purpose of the invention is to effectively solve existing iron-carbon micro-electrolysis filler to be easy hardened, processing in the treatment of waste water
The problem of low efficiency, proposes a kind of preparation method of iron-based more metal alloy micro-electrolysis stuffings, includes the following steps:
(1) iron powder and various metals catalyst component that mass ratio is 40~60:7~17 are set in horizontal bispin stirring ball-milling
It is standby interior by the way that iron-based more metal alloy powder are prepared with the method ball milling of mechanical force and chemical；
(2) it is 47~77:17~27 according to mass ratio by raw materials such as iron-based more metal alloy powder, charcoal, clay and pore creating materials:
The proportion of 15~25:0.5~1 is uniformly mixed；
(3) water is added in the raw material after mixing and adhesive is kneaded into cuboid bulk in vacuum deairing machine, cut,
It is granulated and obtains raw material ball after polishing；
(4) by obtained raw material ball by the heating roasting of tube furnace staged, sintering obtains the iron under anoxic atmosphere
Quito metal alloy micro-electrolysis stuffing.
Preparation method of the invention, firstly, iron powder and various metals catalyst component are passed through the method with mechanical force and chemical
Iron-based more metal alloy powder are prepared in high-energy ball milling；Then, by iron-based more metal alloy powder, charcoal (preferably sludge carbon), clay
It is uniformly mixed according to a certain ratio with raw materials such as pore creating materials；And suitable water and binder kneading is added in uniformly mixed raw material
At cuboid bulk, then through cutting and granulating working procedure, then it is polished after raw material ball is made；Finally, raw material ball is put into tube furnace
Self-feeder hopper in, continue through tube furnace staged heating roast area, continuous sintering becomes under oxygen deficient atmospheres
Iron-based more metal alloy micro-electrolysis stuffings of higher-strength.
Preferably, the iron powder is one or two kinds of mixtures of cast iron powder, reduced iron powder, and the particle size range of iron powder is 80
~200 mesh.
Preferably, the metal catalytic component is copper metal powder, zinc metal powder, nickel metal powder, manganese Metal powder
One of end or various metals mixture of powders, the particle size range of metal catalytic component are 120~200 mesh.
Preferably, the charcoal is bamboo charcoal, charcoal or sludge carbon.
Preferably, the clay is white bind, kaolin or attapulgite.
Preferably, the pore creating material is sodium carbonate, calcium carbonate or sodium metasilicate；
Preferably, the adhesive refers to sodium carboxymethylcellulose or starch.
Preferably, the temperature range of tube furnace staged heating roasting is 1150-1200 DEG C, calcining time 1-
2 hours.
Preferably, the mass ratio of iron powder and metal catalytic component is 45~55:15~17 in step (1)；Iron powder be 45~
When 55 powder, metal catalytic component total amount accounts for 13~15 mass parts.It is further preferred that metal catalytic component is copper powder and zinc powder group
The mass ratio of conjunction, copper powder and nickel powder combination or copper powder and manganese powder combination, copper powder and other metal powders is 12:1~3.Step (2)
In the raw materials such as iron-based more metal alloy powder, charcoal, clay and pore creating material according to mass ratio be 55~65:20~27:15~20:0.5
~1 proportion.
Most preferably, mass ratio is stirred into ball in horizontal bispin for the iron powder of 50:12:3, copper powder and zinc powder mixed powder
Iron, copper, Zinc alloy powder is prepared in ball milling in mill equipment, then, by iron, copper, Zinc alloy powder, charcoal, kaolin and sodium metasilicate
It is matched according to 60:20:18:0.8 mass ratio.
The present invention also provides a kind of applications such as iron-based more metal alloy micro-electrolysis stuffings, include the following steps:
Iron-based more metal alloy micro-electrolysis stuffings are added in micro-electrolysis reactor, filler admission space is 50-
75%, adjusting influent waste water pH is 3.5~4.8, is reacted under the conditions of aeration aerating, and micro-electrolysis reactor water outlet adjusts pH and arrives
Through precipitation and separation after 6.8~7.5.
Application of the invention, which is directed in the industrial wastewaters such as printing and dyeing, chemical industry, contains toxic organics and hardly degraded organic substance
Wastewater treatment, be added iron-based more metal alloy micro-electrolysis stuffings in micro-electrolysis reactor, filler admission space is 50-
75%, adjusting influent waste water pH is 3.5~4.8, is reacted under the conditions of aeration aerating, and filler passes through catalysis reduction and catalysis oxidation
Synergistic effect Organic Pollutants in Wastewater is decomposed, through micro-electrolysis reactor water outlet adjust pH to 6.8~7.5 after, generate
More metal hydroxy complex compound floc sludges after precipitation and separation, treated enter biochemical treatment unit or advanced oxidation unit
Further advanced treating.
Beneficial effects of the present invention:
The preparation process of iron-based more metal alloys of the invention uses mechanochemical method, passes through stirring ball-milling equipment inner cylinder
Strong impact force that internal ball-milling medium relative motion generates, Strong shear power, strong frictional force and strong extruding force comes so that different metal
Powder surface generates strong plastic deformation, generates specific surface area increase, texture portion disordering, distortion of lattice and crystal grain
The a series of physical chemical effect such as change in size realizes metal powder alloying in Process During High Energy Ball Milling, is conducive to improve iron
The surface reaction activity and uniformity consistency of Quito metal alloy.Therefore, iron-based more metal alloy light electrolysis prepared by the present invention
The prosperity of filler porosity, large specific surface area, current density is big in acid waste water, and Zero-valent Iron and catalytic metal component are uniformly distributed
In filler micropore, it can effectively avoid iron powder from being oxidized or form passivating film with the ionic reaction in waste water and make filler mutual
Between adhesion and then hardened blocking, ensure that filler keeps the collaboration of efficient catalysis reduction and oxidation to make for a long time in waste water
With.
In addition, iron-based more metal alloy micro-electrolysis stuffings provided by the present invention be aerated in waste water can forming quantity it is numerous
Small primary battery, electrode potential difference is up to 1.2V between catalytic metal component and iron, and the micro-current of generation can excite waste water to produce
The hydrogen of raw nascent state and the oxygen of nascent state, the hydrogen and oxygen of these nascent states have very strong reproducibility and oxidisability, can to give up
Strong redox reaction occurs for water, can destroy chromophoric group or auxochrome group in waste water, by macromolecule contaminant chain rupture,
Degradable compound is converted by compound difficult to degrade.Meanwhile the Fe that iron consumption generates in filler2+Quilt during oxygenic aeration
It is oxidized to Fe3+, Fe3+Hydrolysate have stronger Coagulation and Adsorption performance, filler light electrolysis catalysis reduction after plus alkali adjust
The ferrous hydroxide and ferric hydroxide colloid generated after pH can further adsorb COD in waste water, ammonia nitrogen, total phosphorus, after flocculation sedimentation
Separation removal Pollutants in Wastewater.
Compared with traditional iron carbon filler, iron-based more metal alloy micro-electrolysis stuffings have removal efficiency in the treatment of waste water
Advantage high, waste water applicability is wide, long service life and integrated operation are at low cost can be used for printing and dyeing, chemical industry, plating, papermaking etc.
Pretreatment of the industrial wastewater before biochemical processing process, it can also be used to the waste water treatments such as advanced treating of sewage treatment plant field.
Detailed description of the invention
Fig. 1 is the preparation flow figure of iron-based more metal alloy micro-electrolysis stuffings.
Fig. 2 and Fig. 3 is the TEM figure of iron-based more metal alloy micro-electrolysis stuffings.
Fig. 4 is the XRD diagram of iron-based more metal alloy micro-electrolysis stuffings.
Fig. 5 is the EDS spectrogram of iron-based more metal alloy micro-electrolysis stuffings.
Specific embodiment
It is easy problem hardened, that treatment effeciency is low in the treatment of waste water for existing iron-carbon micro-electrolysis filler, firstly, by iron
Powder and various metals catalyst component are by being prepared iron-based more metal alloy powder with the method high-energy ball milling of mechanical force and chemical；So
Afterwards, the raw materials such as iron-based more metal alloy powder, charcoal (preferably sludge carbon), clay and pore creating material are uniformly mixed according to a certain ratio,
Suitable water is added and binder kneading is agglomerating, and suitable water and binder is added in vacuum pugging in uniformly mixed raw material
Be kneaded into machine cuboid bulk, then through cutting and granulating working procedure, then it is polished after raw material ball is made, under oxygen deficient atmospheres, will
Raw material ball, which continues through tube furnace staged and is warming up to 1150-1200 DEG C, to be roasted 1~2 hour, obtained after cooling higher-strength and
Iron-based more metal alloy micro-electrolysis stuffings of more porosity, the preparation flow figure of iron-based more metal alloy micro-electrolysis stuffings are shown in figure
1。
In wastewater treatment, iron-based more metal alloy micro-electrolysis stuffings of 50-75% are filled in micro-electrolysis reactor, are adjusted
Saving influent waste water pH is 3.5~4.8, and under the conditions of aeration aerating, filler is restored by catalysis and the synergistic effect of catalysis oxidation
Organic Pollutants in Wastewater is decomposed, after the water outlet of micro-electrolysis reactor adjusts pH to 6.8~7.5, more metal hydroxyls of generation
Base complex floc sludge mud-water separation after precipitation, realize reduction chain rupture to macromolecular in waste water, Recalcitrant chemicals or
Oxidation removal.
Embodiment 1:
Firstly, by iron powder and copper powder the high-energy ball milling preparation in horizontal bispin stirring ball-milling equipment that mass ratio is 50:10
Iron-copper powder is obtained, then, by iron-copper powder, sludge carbon, white bind and sodium carbonate according to mass ratio 55:17:25:0.5
Preferred raw material is weighed, above-mentioned raw materials are put into biaxial rneader and are stirred 30min, vacuum deairing machine is then delivered to and adds
Enter suitable quantity of water and sodium carboxymethylcellulose be kneaded into cuboid bulk, then through cutting and granulating working procedure, then it is polished after grain is made
The raw material ball of diameter 15mm.Raw material ball is put into the self-feeder of tube furnace, the heating roasting of tube furnace staged is continued through,
Under oxygen deficient atmospheres, sintering final temperature is 1150 DEG C, and the residence time is maintained at 2h or so, and continuous sintering becomes the iron-based of higher-strength
More metal alloy micro-electrolysis stuffings, after measured, the specific surface area of this iron-based more metal alloy micro-electrolysis stuffing are 65.6m2/g。
It is process object with certain printing and dyeing mill's sewage, wherein dyeing waste water is dark purple, and initial COD is 2156mg/L, and pH is
7.1.Above-mentioned iron-based more metal alloy micro-electrolysis stuffings are added in micro-electrolysis reactor, filler admission space is 50%, is adjusted
For wastewater pH to 4.0 or so, air aeration reacts 1h.Reaction water outlet be it is light brown, pH is increased to 6.2, then adjust water outlet pH to
7.5 or so, blackish green FeOOH precipitating is generated, finally determining supernatant COD is 625mg/L, and COD removal rate is
60.8%.
Embodiment 2:
Firstly, the setting in horizontal bispin stirring ball-milling for the iron powder of 50:12:3, copper powder and zinc powder mixed powder by mass ratio
Iron, copper, Zinc alloy powder is prepared in standby interior high-energy ball milling, then, by iron, copper, Zinc alloy powder, charcoal, kaolin and sodium metasilicate
Preferred raw material is weighed according to mass ratio 60:20:18:0.8, above-mentioned raw materials are put into biaxial rneader and are stirred 30min,
It is then delivered to vacuum deairing machine addition suitable quantity of water and sodium carboxymethylcellulose is kneaded into cuboid bulk, then cut and be granulated
Process, then it is polished after the raw material ball of partial size 10mm is made.Raw material ball is put into the self-feeder of tube furnace, is continued through
The heating roasting of tube furnace staged, under oxygen deficient atmospheres, sintering final temperature is 1180 DEG C, and the residence time is maintained at 1.5h or so, even
The continuous iron-based more metal alloy micro-electrolysis stuffings for being sintered into higher-strength.
It is process object with certain printing and dyeing mill's sewage, wherein dyeing waste water is dark purple, and initial COD is 3035mg/L, and pH is
7.3.Above-mentioned iron-based more metal alloy micro-electrolysis stuffings are added in micro-electrolysis reactor, filler admission space is 55%, is adjusted
For wastewater pH to 3.5 or so, air aeration reacts 1h.Reaction water outlet is contaminated with red floccule, and supernatant is colourless, pH after standing
8.3 are increased to, finally determining supernatant COD is 405mg/L, and COD removal rate is 87%.
Embodiment 3:
Firstly, the setting in horizontal bispin stirring ball-milling for the iron powder of 40:12:2, copper powder and nickel powder mixed powder by mass ratio
Iron, copper, nickel alloy powder is prepared in standby interior high-energy ball milling, then, by iron, copper, nickel alloy powder, bamboo charcoal, attapulgite and carbonic acid
Calcium weighs preferred raw material according to mass ratio 60:25:22:0.5, and above-mentioned raw materials are put into biaxial rneader and are stirred
30min, is then delivered to vacuum deairing machine addition suitable quantity of water and starch is kneaded into cuboid bulk, then is cut and be granulated work
Sequence, then it is polished after the raw material ball of partial size 12mm is made.Raw material ball is put into the self-feeder of tube furnace, pipe is continued through
The heating roasting of formula furnace staged, under oxygen deficient atmospheres, sintering final temperature is 1200 DEG C, and the residence time is maintained at 1h or so, continuous to burn
Form iron-based more metal alloy micro-electrolysis stuffings for higher-strength.
It is process object with certain factory, chemical company waste water, which is in glassy yellow through membrane process treated film concentrate,
COD is 145mg/L, pH 7.6.Above-mentioned iron-based more metal alloy micro-electrolysis stuffings, filler dress are added in micro-electrolysis reactor
Filling out volume is 55%, adjusts wastewater pH to 3.5 or so, air aeration reacts 1h.In light yellow, water outlet pH is 6.5 for reaction water outlet,
Water outlet pH to 7.0 or so is adjusted, there is a small amount of white precipitate, measurement water outlet COD is 44mg/L, and COD removal rate is 70%.
Embodiment 4:
Firstly, the setting in horizontal bispin stirring ball-milling for the iron powder of 55:12:1, copper powder and manganese powder mixed powder by mass ratio
Iron, copper, manganese alloy powder is prepared in standby interior high-energy ball milling, then, by iron, copper, manganese alloy powder, bamboo charcoal, attapulgite and silicic acid
Sodium weighs preferred raw material according to mass ratio 65:20:18:1, and above-mentioned raw materials are put into biaxial rneader and are stirred 30min,
It is then delivered to vacuum deairing machine addition suitable quantity of water and starch is kneaded into cuboid bulk, then through cutting and granulating working procedure, then pass through
The raw material ball of partial size 18mm is made after polishing.Raw material ball is put into the self-feeder of tube furnace, tube furnace rank is continued through
Ladder type heating roasting, under oxygen deficient atmospheres, sintering final temperature is 1200 DEG C, and the residence time is maintained at 1.5h or so, continuous sintering at
For iron-based more metal alloy micro-electrolysis stuffings of higher-strength.
It is process object with certain factory, chemical company waste water, the waste water is through double membrane process treated film concentrate in bright orange
Color, COD 145mg/L, pH 7.6.Using micro-electrolysis stuffing catalysis reduction and heterogeneous Fenton group technology, in light electrolysis
Above-mentioned iron-based more metal alloy micro-electrolysis stuffings are added in reactor, filler admission space is 55%, adjusts wastewater pH to 3.5 left sides
The right side, air aeration react 1h.In light yellow, water outlet pH is 6.5 for water outlet after reaction, micro-electrolysis stuffing catalytic reduction reaction be discharged into
Enter heterogeneous Fenton oxidation unit, water outlet water outlet after adjusting pH to 7.0 or so coagulating sedimentation be it is colourless, measure and be discharged COD and be
27mg/L, COD removal rate are 81%.
The reaction mechanism that iron-based more metal alloy micro-electrolysis stuffings handle waste water is analyzed and examined or check for further characterization, to iron
Quito metal alloy micro-electrolysis stuffing is shown in Fig. 2, figure using the characterization result of transmission electron microscope, X-ray diffractometer and energy disperse spectroscopy respectively
3, Fig. 4 and Fig. 5 (being characterized with the filler that embodiment 2 is prepared).Analysis is the result shows that iron-based more metal alloy light electrolysis
The prosperity of filler porosity, large specific surface area, Zero-valent Iron and alloying element are evenly distributed in filler micropore, can effectively avoid iron powder
It is oxidized or forms passivating film with the ionic reaction in waste water and make the mutual adhesion of filler hardened blocking in turn, ensure that
Filler keeps efficient waste treatment capacity for a long time.
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (10)
1. a kind of preparation method of iron-based more metal alloy micro-electrolysis stuffings, which comprises the steps of:
(1) iron powder and metal catalytic component that mass ratio is 40~60:7~17 are passed through in horizontal bispin stirring ball-milling equipment
Iron-based more metal alloy powder are prepared with the method ball milling of mechanical force and chemical；
It (2) is 47~77:17~27:15~25:0.5 according to mass ratio by iron-based more metal alloy powder, charcoal, clay and pore creating material
~1 proportion is uniformly mixed；
(3) water and adhesive is added in raw material that mixing mixes to be mediated in vacuum deairing machine as cuboid block, then through cutting
Raw material ball is generated after cutting, be granulated and polishing；
(4) by gained raw material ball by the heating roasting of tube furnace staged, sintering obtains described iron-based mostly golden under anoxic atmosphere
Belong to alloy micro-electrolysis stuffing.
2. preparation method according to claim 1, which is characterized in that the iron powder is one kind of cast iron powder or reduced iron powder
Or two kinds of mixtures, the particle size range of iron powder are 80-200 mesh.
3. preparation method according to claim 1, which is characterized in that the metal catalytic component is copper metal powder, zinc
The mixture of one of metal powder, nickel metal powder, manganese Metal powder or any several metal powders, metal catalytic component
Particle size range be 120~200 mesh.
4. preparation method according to claim 1, which is characterized in that the charcoal is bamboo charcoal, charcoal or sludge carbon.
5. preparation method according to claim 1, which is characterized in that the clay is white bind, kaolin or concave convex rod
Soil.
6. preparation method according to claim 1, which is characterized in that the pore creating material is sodium carbonate, calcium carbonate or silicic acid
Sodium.
7. preparation method according to claim 1, which is characterized in that the adhesive is sodium carboxymethylcellulose or shallow lake
Powder.
8. preparation method according to claim 1, which is characterized in that the humidity province of the tube furnace staged heating roasting
Between be 1150-1200 DEG C, calcining time be 1-2 hours.
9. a kind of iron-based more metal alloys that the preparation method as described in any one of claim 1~8 claim is prepared are micro-
Electrolysis filler.
10. a kind of application of iron-based more metal alloy micro-electrolysis stuffings as claimed in claim 9, which is characterized in that including as follows
Step:
Iron-based more metal alloy micro-electrolysis stuffings are added in micro-electrolysis reactor, filler admission space is 50-75%, is adjusted
Saving influent waste water pH is 3.5~4.8, is reacted under the conditions of aeration aerating, and micro-electrolysis reactor water outlet adjusts pH to 6.8~7.5
By precipitation and separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910212990.8A CN109911992B (en) | 2019-03-20 | 2019-03-20 | Preparation method and application of iron-based multi-metal alloy micro-electrolysis filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910212990.8A CN109911992B (en) | 2019-03-20 | 2019-03-20 | Preparation method and application of iron-based multi-metal alloy micro-electrolysis filler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109911992A true CN109911992A (en) | 2019-06-21 |
| CN109911992B CN109911992B (en) | 2021-11-19 |
Family
ID=66965891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910212990.8A Active CN109911992B (en) | 2019-03-20 | 2019-03-20 | Preparation method and application of iron-based multi-metal alloy micro-electrolysis filler |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109911992B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586126A (en) * | 2019-09-29 | 2019-12-20 | 威海中远造船科技有限公司 | Catalyst and method for sewage treatment at normal temperature and normal pressure |
| CN111517590A (en) * | 2020-06-11 | 2020-08-11 | 北京工业大学 | Tower type iron-carbon micro-electrolysis-nitrification sludge denitrification device and method |
| CN111547903A (en) * | 2020-05-13 | 2020-08-18 | 南京工业大学 | Biochar-based micro-electrolysis filler and application thereof in chemical wastewater treatment |
| CN111620514A (en) * | 2020-04-28 | 2020-09-04 | 生态环境部华南环境科学研究所 | Method for treating sewage in biofilter based on sponge iron composite filler |
| CN111847768A (en) * | 2020-06-28 | 2020-10-30 | 魏毅宏 | Ion exchange resin production wastewater treatment system and method |
| CN111892235A (en) * | 2020-06-24 | 2020-11-06 | 张建东 | High-efficient degradation waste water zero discharge system |
| CN112875810A (en) * | 2021-01-12 | 2021-06-01 | 北京市高速公路交通工程有限公司 | Multielement microelectrolysis filler and preparation method thereof |
| CN112979009A (en) * | 2021-01-27 | 2021-06-18 | 中日友好环境保护中心(生态环境部环境发展中心) | Process for removing tetrabromobisphenol A in wastewater based on iron-carbon micro-electrolysis technology |
| CN113441148A (en) * | 2020-03-27 | 2021-09-28 | 中国石化扬子石油化工有限公司 | Catalytic material for improving biodegradability of petrochemical wastewater, preparation method and application |
| 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 |
| CN113979515A (en) * | 2021-10-27 | 2022-01-28 | 沈阳建筑大学 | Iron-carbon micro-electrolysis particles for sewage treatment and preparation method thereof |
| CN114409078A (en) * | 2022-01-10 | 2022-04-29 | 南京工业大学 | Preparation and application method of sludge carbon-based functional material for improving A/O biochemical treatment efficiency of coal chemical wastewater |
| CN114478058A (en) * | 2022-01-10 | 2022-05-13 | 中国石化集团南京化学工业有限公司 | Sludge carbon-based micro-electrolysis filler for improving biochemical property of chemical wastewater and preparation method and application thereof |
| CN115779926A (en) * | 2022-12-02 | 2023-03-14 | 中海石油环保服务（天津）有限公司 | Multi-metal catalytic oxidation filler and preparation method and application thereof |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276021A (en) * | 2011-06-08 | 2011-12-14 | 煤炭科学研究总院杭州环保研究院 | Multi-component oxidized micro-electrolysis filler and preparation method thereof |
| CN104003483A (en) * | 2014-06-19 | 2014-08-27 | 福州大学 | Bamboo charcoal-based microelectrolysis porous ceramsite filler and preparing method thereof |
| CN104086033A (en) * | 2014-08-05 | 2014-10-08 | 段希福 | Treatment method of copper-containing industrial wastewater |
| CN104628091A (en) * | 2015-01-24 | 2015-05-20 | 杨强 | Multi-element catalytic microelectrolysis packing as well as preparation method and application thereof |
| CN105110427A (en) * | 2015-09-30 | 2015-12-02 | 王磊 | Composite micro-electrolysis filler as well as preparation method and application thereof |
| CN105366773A (en) * | 2015-12-16 | 2016-03-02 | 北京科技大学 | Structured iron-carbon micro-electrolysis filling material and preparation method thereof |
| CN105712443A (en) * | 2016-01-28 | 2016-06-29 | 同济大学 | Powder metallurgy iron-based catalyzed internal electrolysis filler and preparation method thereof |
| CN105967283A (en) * | 2016-06-24 | 2016-09-28 | 山东木齐健康科技有限公司 | High-activity wastewater treatment micro-electrolysis material and preparation method thereof |
| CN106495291A (en) * | 2016-12-07 | 2017-03-15 | 河海大学 | A kind of polynary micro-electrolysis stuffing and its preparation method and application |
| CN104761024B (en) * | 2015-04-22 | 2017-03-15 | 湖北泉盛环保科技股份有限公司 | Efficient heterogeneous catalytic oxidation iron-carbon micro-electrolysis filler and preparation method thereof |
| CN106631098A (en) * | 2016-09-29 | 2017-05-10 | 中冶华天工程技术有限公司 | A preparing method of precious metal-iron-carbon microelectrolysis ceramsite used for water treatment |
| CN106809922A (en) * | 2017-01-23 | 2017-06-09 | 五邑大学 | A kind of preparation method of multi-element metal micro-electrolysis stuffing |
| CN106865839A (en) * | 2017-03-06 | 2017-06-20 | 河海大学 | A kind of technique using polynary micro-electrolysis stuffing deep-treating organic waste water |
| CN107055696A (en) * | 2017-01-05 | 2017-08-18 | 长沙汇聚环境技术有限公司 | A kind of difficult biochemical waste water processing micro-electrolysis stuffing and preparation method thereof |
| CN107572635A (en) * | 2017-11-06 | 2018-01-12 | 广东石油化工学院 | A kind of preparation method of waste water light electrolysis iron carbon filler |
| CN107935129A (en) * | 2018-01-10 | 2018-04-20 | 南华大学 | A kind of preparation method of iron sludge base biology carbon micro-electrolysis filler and its application in uranium-containing waste water is handled |
| CN107986399A (en) * | 2017-11-16 | 2018-05-04 | 浙江海洋大学 | A kind of iron-carbon micro-electrolysis filler and preparation method thereof |
| CN108178246A (en) * | 2017-12-20 | 2018-06-19 | 无锡市拜沃特环保科技有限公司 | A kind of environment-friendly type light electrolysis haydite and preparation method thereof |
| CN108609694A (en) * | 2018-04-03 | 2018-10-02 | 浙江师范大学 | The preparation method of iron-carbon micro-electrolysis filler |
| CN108689455A (en) * | 2018-04-03 | 2018-10-23 | 浙江师范大学 | A kind of iron-carbon micro-electrolysis filler and its application method |
| CN109110883A (en) * | 2018-09-21 | 2019-01-01 | 中国矿业大学(北京) | A kind of preparation of compound carbon-based nano zero valence iron micro-electrolysis material and the method for handling stibium-containing wastewater |
-
2019
- 2019-03-20 CN CN201910212990.8A patent/CN109911992B/en active Active
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276021A (en) * | 2011-06-08 | 2011-12-14 | 煤炭科学研究总院杭州环保研究院 | Multi-component oxidized micro-electrolysis filler and preparation method thereof |
| CN104003483A (en) * | 2014-06-19 | 2014-08-27 | 福州大学 | Bamboo charcoal-based microelectrolysis porous ceramsite filler and preparing method thereof |
| CN104086033A (en) * | 2014-08-05 | 2014-10-08 | 段希福 | Treatment method of copper-containing industrial wastewater |
| CN104628091A (en) * | 2015-01-24 | 2015-05-20 | 杨强 | Multi-element catalytic microelectrolysis packing as well as preparation method and application thereof |
| CN104761024B (en) * | 2015-04-22 | 2017-03-15 | 湖北泉盛环保科技股份有限公司 | Efficient heterogeneous catalytic oxidation iron-carbon micro-electrolysis filler and preparation method thereof |
| CN105110427A (en) * | 2015-09-30 | 2015-12-02 | 王磊 | Composite micro-electrolysis filler as well as preparation method and application thereof |
| CN105366773A (en) * | 2015-12-16 | 2016-03-02 | 北京科技大学 | Structured iron-carbon micro-electrolysis filling material and preparation method thereof |
| CN105712443A (en) * | 2016-01-28 | 2016-06-29 | 同济大学 | Powder metallurgy iron-based catalyzed internal electrolysis filler and preparation method thereof |
| CN105967283A (en) * | 2016-06-24 | 2016-09-28 | 山东木齐健康科技有限公司 | High-activity wastewater treatment micro-electrolysis material and preparation method thereof |
| CN106631098A (en) * | 2016-09-29 | 2017-05-10 | 中冶华天工程技术有限公司 | A preparing method of precious metal-iron-carbon microelectrolysis ceramsite used for water treatment |
| CN106495291A (en) * | 2016-12-07 | 2017-03-15 | 河海大学 | A kind of polynary micro-electrolysis stuffing and its preparation method and application |
| CN107055696A (en) * | 2017-01-05 | 2017-08-18 | 长沙汇聚环境技术有限公司 | A kind of difficult biochemical waste water processing micro-electrolysis stuffing and preparation method thereof |
| CN106809922A (en) * | 2017-01-23 | 2017-06-09 | 五邑大学 | A kind of preparation method of multi-element metal micro-electrolysis stuffing |
| CN106865839A (en) * | 2017-03-06 | 2017-06-20 | 河海大学 | A kind of technique using polynary micro-electrolysis stuffing deep-treating organic waste water |
| CN107572635A (en) * | 2017-11-06 | 2018-01-12 | 广东石油化工学院 | A kind of preparation method of waste water light electrolysis iron carbon filler |
| CN107986399A (en) * | 2017-11-16 | 2018-05-04 | 浙江海洋大学 | A kind of iron-carbon micro-electrolysis filler and preparation method thereof |
| CN108178246A (en) * | 2017-12-20 | 2018-06-19 | 无锡市拜沃特环保科技有限公司 | A kind of environment-friendly type light electrolysis haydite and preparation method thereof |
| CN107935129A (en) * | 2018-01-10 | 2018-04-20 | 南华大学 | A kind of preparation method of iron sludge base biology carbon micro-electrolysis filler and its application in uranium-containing waste water is handled |
| CN108609694A (en) * | 2018-04-03 | 2018-10-02 | 浙江师范大学 | The preparation method of iron-carbon micro-electrolysis filler |
| CN108689455A (en) * | 2018-04-03 | 2018-10-23 | 浙江师范大学 | A kind of iron-carbon micro-electrolysis filler and its application method |
| CN109110883A (en) * | 2018-09-21 | 2019-01-01 | 中国矿业大学(北京) | A kind of preparation of compound carbon-based nano zero valence iron micro-electrolysis material and the method for handling stibium-containing wastewater |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586126A (en) * | 2019-09-29 | 2019-12-20 | 威海中远造船科技有限公司 | Catalyst and method for sewage treatment at normal temperature and normal pressure |
| CN113441148A (en) * | 2020-03-27 | 2021-09-28 | 中国石化扬子石油化工有限公司 | Catalytic material for improving biodegradability of petrochemical wastewater, preparation method and application |
| CN111620514A (en) * | 2020-04-28 | 2020-09-04 | 生态环境部华南环境科学研究所 | Method for treating sewage in biofilter based on sponge iron composite filler |
| CN111547903A (en) * | 2020-05-13 | 2020-08-18 | 南京工业大学 | Biochar-based micro-electrolysis filler and application thereof in chemical wastewater treatment |
| CN111517590A (en) * | 2020-06-11 | 2020-08-11 | 北京工业大学 | Tower type iron-carbon micro-electrolysis-nitrification sludge denitrification device and method |
| CN111517590B (en) * | 2020-06-11 | 2022-07-08 | 北京工业大学 | Tower type iron-carbon micro-electrolysis-nitrification sludge denitrification device and method |
| CN111892235A (en) * | 2020-06-24 | 2020-11-06 | 张建东 | High-efficient degradation waste water zero discharge system |
| CN111847768A (en) * | 2020-06-28 | 2020-10-30 | 魏毅宏 | Ion exchange resin production wastewater treatment system and method |
| CN112875810A (en) * | 2021-01-12 | 2021-06-01 | 北京市高速公路交通工程有限公司 | Multielement microelectrolysis filler and preparation method thereof |
| CN112979009A (en) * | 2021-01-27 | 2021-06-18 | 中日友好环境保护中心(生态环境部环境发展中心) | Process for removing tetrabromobisphenol A in wastewater based on iron-carbon micro-electrolysis technology |
| CN112979009B (en) * | 2021-01-27 | 2022-07-29 | 中日友好环境保护中心(生态环境部环境发展中心) | Process for removing tetrabromobisphenol A in wastewater based on iron-carbon micro-electrolysis technology |
| CN113979515A (en) * | 2021-10-27 | 2022-01-28 | 沈阳建筑大学 | Iron-carbon micro-electrolysis particles for sewage treatment and preparation method thereof |
| CN113979515B (en) * | 2021-10-27 | 2023-09-22 | 沈阳建筑大学 | Iron-carbon micro-electrolysis particle for sewage treatment 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 |
| CN114409078A (en) * | 2022-01-10 | 2022-04-29 | 南京工业大学 | Preparation and application method of sludge carbon-based functional material for improving A/O biochemical treatment efficiency of coal chemical wastewater |
| CN114478058A (en) * | 2022-01-10 | 2022-05-13 | 中国石化集团南京化学工业有限公司 | Sludge carbon-based micro-electrolysis filler for improving biochemical property of chemical wastewater and preparation method and application thereof |
| CN115779926A (en) * | 2022-12-02 | 2023-03-14 | 中海石油环保服务（天津）有限公司 | Multi-metal catalytic oxidation filler and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109911992B (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109911992A (en) | A kind of preparation method and application of iron-based more metal alloy micro-electrolysis stuffings | |
| CN104761024B (en) | Efficient heterogeneous catalytic oxidation iron-carbon micro-electrolysis filler and preparation method thereof | |
| Dai et al. | Mechanism of enhanced electrochemical degradation of highly concentrated aspirin wastewater using a rare earth La-Y co-doped PbO2 electrode | |
| CN102659221B (en) | Electro-catalytic oxidation material for wastewater treatment, preparation method and application | |
| CN107021547B (en) | Preparation method of iron-carbon micro-electrolysis filler and product thereof | |
| CN107055696A (en) | A kind of difficult biochemical waste water processing micro-electrolysis stuffing and preparation method thereof | |
| CN104773888A (en) | Iron-carbon inner electrolysis-Fenton oxidation-electrolytic electrocatalytic oxidation combined wastewater treatment method and device | |
| CN100402441C (en) | Method for treating sewage by catalytic iron internal electrogravimetry and its filler | |
| CN104261518B (en) | A kind of manganese charcoal catalyzed internal electrocatalysis filler and preparation method thereof and application | |
| CN204873961U (en) | Magnetism catalysis - electric fenton reaction device | |
| Wang et al. | Enhanced removal of copper by electroflocculation and electroreduction in a novel bioelectrochemical system assisted microelectrolysis | |
| CN109608021A (en) | Deep dehydration method for sludge | |
| CN105417643A (en) | Oxidation and reduction double-effect micro electrolysis combined reactor and application thereof | |
| CN105712443A (en) | Powder metallurgy iron-based catalyzed internal electrolysis filler and preparation method thereof | |
| Feng et al. | Accelerated Rhodamine B removal by enlarged anode electric biological (EAEB) with electro-biological particle electrode (EPE) made from steel converter slag (SCS) | |
| CN101723488B (en) | Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof | |
| CN104743652A (en) | Method for processing degradation-resistant organic wastewater and multi-element catalyst adopted by method | |
| CN108249644A (en) | A kind of removal device and method of waste water phosphite | |
| Feng et al. | Enhancing the anode performance of microbial fuel cells in the treatment of oil-based drill sludge by adjusting the stirring rate and supplementing oil-based drill cuttings | |
| CN104709996A (en) | Method for simultaneously treating hexavalent chrome wastewater and organic dye wastewater | |
| Wang et al. | Synthesis of a ternary microscopic ball-shaped micro-electrolysis filler and its application in wastewater treatment | |
| CN109574386A (en) | A kind for the treatment of of Perfume Wastewater processing system | |
| Saad et al. | Removal of cadmium from simulated wastewaters using a fixed bed bio-electrochemical reactor | |
| CN1193938C (en) | Catalytic aluminium internally electrolyzing process of treating sewage | |
| CN209583892U (en) | A kind for the treatment of of Perfume Wastewater processing system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |