CN109437629A - A kind of composite scrap tailing porous material and its preparation method and application - Google Patents

A kind of composite scrap tailing porous material and its preparation method and application Download PDF

Info

Publication number
CN109437629A
CN109437629A CN201811465905.0A CN201811465905A CN109437629A CN 109437629 A CN109437629 A CN 109437629A CN 201811465905 A CN201811465905 A CN 201811465905A CN 109437629 A CN109437629 A CN 109437629A
Authority
CN
China
Prior art keywords
tailing
haydite
raw material
discarded
iron tailings
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
Application number
CN201811465905.0A
Other languages
Chinese (zh)
Other versions
CN109437629B (en
Inventor
丁燕
杜熠
梁金生
高贵阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Technology
Original Assignee
Hebei University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hebei University of Technology filed Critical Hebei University of Technology
Priority to CN201811465905.0A priority Critical patent/CN109437629B/en
Publication of CN109437629A publication Critical patent/CN109437629A/en
Application granted granted Critical
Publication of CN109437629B publication Critical patent/CN109437629B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/027—Lightweight materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/1305—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/131—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The present invention is a kind of composite scrap tailing porous material and its preparation method and application.The material is spherical porous ceramsite material, and diameter is 5~8mm, porosity 43%~52%；Its raw material components mass percent are as follows: discarded copper tailing: 58%~65%；Discarded iron tailings: 9%~18%；Sodium bicarbonate: 4%~12%；Waterglass: 5%~10%；Cornstarch: 3%~14% and active powdered carbon: 3%~9%.This method is using discarded copper tailing and iron tailings as primary raw material, material ratio needed for calculating target haydite, is aided with waterglass as binder, processed, is formed with certain mechanical strength, high porosity, the repeatedly used porous carrier materials for wastewater treatment.The carrier material can be used for loading the catalyst of cyanide catalytic ozonation, and the degradation efficiency of cyanide reaches as high as 92.11%.

Description

A kind of composite scrap tailing porous material and its preparation method and application
Technical field
The invention belongs to mineral resources comprehensive utilization and the dirty water decontamination handles field, specially a kind of composite scrap tailing is more Porous materials and its preparation method and application.
Background technique
Industrial wastewater containing cyanide is known as cyanide wastewater, and cyanide wastewater mostlys come from Metallurgical Factory, chemical fertilizer factory, coking Factory, electroplate factory etc..Cyanide belongs to hypertoxicity substance, it is necessary to its concentration of emission is controlled according to national standards, if cannot be appropriate Processing will seriously affect the efficient stable operation of biochemical processing process, while can also generate to people's lives and natural environment huge Big harm.It under normal circumstances, can be using recovery processing, for the cyanide wastewater of low concentration, then for the cyanide wastewater of high concentration The method that Oxidative demage can be taken, high-level oxidation technology include catalytic ozonation, catalytic oxidation of hydrogen peroxide, photocatalytic-oxidation Change, electrocatalytic oxidation, photoelectrocatalysioxidization oxidization etc..
Hydrogen peroxide has oxidisability, and cyanide can be under alkaline condition cyanate CNO by hydrogen peroxide oxidation-, so Afterwards cyanate will continue to be hydrolyzed into carbonic acid by or bicarbonate by.Since hydrogen peroxide and cyanide reaction rate are slower, Metal ion catalyst, such as copper, cobalt, nickel, iron can be added during the reaction, for accelerating reaction rate.The reaction is known as Catalyzing hydrogen peroxide chemical oxidization method.Ozone can be reacted by direct with indirect mode with target substance, wherein indirect ozone Oxidation reaction is free radical type reaction, and ozone is decomposed to form-OH free radical, can non-selectivity in conjunction with organic matter, according to institute With the difference of catalyst, it is divided into using the homogeneous catalysis of free metal in solution and with solid metal, solid metal oxide With the metal being supported on carrier, the heterogeneous catalysis that metal oxide is catalyst.The catalyst master of heterogeneous catalytic oxidation Have: MnO2、Al2O3、CeO/Al2O3、TiO2And MnO2/ active carbon etc..
The application range of metallic copper and metallic iron is very wide, and demand is growing day by day with the development of the global economy, with This is opposite, and in order to meet the needs of people are to metallic copper and steel, the yield of copper mine and iron ore also increasingly increases.It produces as a result, A large amount of nominal group process and iron tailings are given birth to, the geological environment on discarded tailing periphery is complicated, easily the ground such as generation landslide, mud-rock flow Matter disaster, it is destructive very big；In addition, the accumulation on tailing mountain is even more to cause seriously to pollute to surrounding enviroment, harmful substance is in vegetation Middle enrichment simultaneously enters living nature food chain, so that bigger harm is constantly caused, finally by human consumption.China's copper tailing and iron The comprehensive reutilization of tailing includes: filling mine or Reclaimed Land, is used for production of construction materials raw material, for firing devitrified glass, For firing ceramics.In addition, the novel research utilized to copper tailings comprehensive further include: carry out copper tail using Microorganism Leaching technology The nonmetallic recycling such as the metals such as copper, iron, zinc, bismuth and sulphur in mine；The sand mold of resistance to copper tailing plant is screened, realizes and copper tailing is polluted The improvement of soil and the reparation of Pollution Plant.Novel research to the comprehensive utilization of iron tailings include: as soil conditioner and Trace-element fertilizer and land reclamation in mining area vegetation.
A kind of porous material of the iron tailings as microorganism ceramic grain filter is disclosed in Chinese invention patent CN105693277A The preparation method and applications of material, raw materials used is tailings of high silicon iron, clay, pore creating material, calcium carbonate, due to silicon high in raw material Iron tailings content is higher, and in tailings of high silicon iron, SiO2Content is very high, and the firing of haydite is caused to need compared with high sintering temperature, institute It not can guarantee with prepared haydite while iron tailings utilization rate with higher and higher porosity, the content liter of iron tailings Height, porosity is inevitable greatly to be reduced；Fe content is lower simultaneously, and under 1100 DEG C of hot conditions, Fe is oxidized to Fe2O3, therefore Its application, which is only to ceramic grain filter, sprays the bacterium solution handled through course of cultivating the microorganism, is obtained later as microorganism ceramic grain filter Porous material, and this method technique is more demanding, time-consuming for course of cultivating the microorganism.It is disclosed in Chinese invention patent CN108440013A A kind of biological aerated filter ceramic grain filter and preparation method thereof, raw materials used is iron tailings, flyash, binder, the party Method equally uses tailings of high silicon iron, but is not related to the addition of cosolvent in raw material proportioning, this make this preparation method energy consumption compared with Greatly, and this method is not related to the utilization of discarded copper tailing.It is disclosed in Chinese invention patent CN105669157A a kind of as garden Woods greening copper tailing haydite preparation method, will pass through pretreated copper tailing, with sludge, red mud, gangue, flyash, The raw materials such as silicon ash, alumina solution handle through overmolding, steam curing, are finally made target haydite, are not related to giving up in this method The utilization of iron tailings is abandoned, and raw material complicated composition, additive is more, is not that a kind of ideal copper tailing utilizes method.
Summary of the invention
The object of the invention is to provide a kind of composite scrap tailing porous material and its system for deficiency existing for current techniques Preparation Method and application.This method is using discarded copper tailing and iron tailings as primary raw material, material ratio needed for accurately calculating target haydite, It is aided with waterglass as binder, it is processed, it is formed with certain mechanical strength, high porosity, repeatedly used for waste water The porous carrier materials of processing.The carrier material can be used for loading the catalyst of cyanide catalytic ozonation, the drop of cyanide Solution efficiency reaches as high as 92.11%.
Technical solution of the present invention are as follows:
A kind of composite scrap tailing porous material, the material are spherical porous ceramsite materials, and diameter is 5~8mm, porosity 43%~52%；Its raw material components mass percent are as follows:
Discarded copper tailing: 58%~65%；
Discarded iron tailings: 9%~18%；
Sodium bicarbonate: 4%~12%；
Waterglass: 5%~10%；
Cornstarch: 3%~14%；
Active powdered carbon: 3%~9%.
The quality percentage composition of the discarded copper tailing, main chemical compositions includes: SiO2: 55.6%~60.3%, (Al2O3+Fe2O3): 15.7%~22.5%, Cu:0.04%~0.10%；
The quality percentage composition of the discarded iron tailings, main chemical compositions includes: SiO2: 33.4%~38.7%； (Al2O3+Fe2O3): 13.6~14.9%；Fe:17.1%~18.5%.
The composite scrap tailing porous material the preparation method comprises the following steps:
(1) pretreatment of raw material: copper, the iron tailings after drying are subjected to ball milling respectively, cross 200 meshes, extracting screen underflow obtains Copper, iron tailings powder；
(2) ingredient: discarded copper tailing powder, discarded iron tailings powder, calcium carbonate, corn are weighed respectively by above-mentioned mass percent Starch, active powdered carbon；
(3) mixing: above-mentioned load weighted raw material is mixed, progress ball mill mixing, 20~40min of Ball-milling Time, later mistake 60 meshes, extracting screen underflow are the raw material that mixing is completed.
(4) form: the raw material that above-mentioned mixing is completed is added to the waterglass of the proportion, after mixing, using rub with the hands ball plate at Type method is granulated；Particle size range is 5~8mm；
(5) aging and dry: above-mentioned gained haydite to be stood into aging 12h~15h at room temperature, then in 100~110 DEG C of items Dry 3h~5h under part.
(6) it roasts: the haydite after drying is put into sintering furnace 150 DEG C of preheating 30min, in 900 DEG C~1000 DEG C conditions 20~30min of lower roasting, sintering furnace heating rate are 10~15 DEG C/min, obtain porous material.
The application of the composite scrap tailing porous material, for loading the catalyst of cyanide catalysis oxidation.
The application of the composite scrap tailing porous material, comprising the following steps:
Under conditions of room temperature and ultrasound, glycol water is added drop-wise in mixed solution, TiO is obtained2Presoma is molten Liquid；Haydite is added to TiO2In precursor solution, 3~5h of lower submergence is stirred, is later taken out haydite, and in 90~100 degree 3~5h of lower drying, 600~700 DEG C of 1.5~2.5h of calcining are after taking-up to get the catalysis loaded for cyanide catalysis oxidation The haydite of agent；
Wherein, the group of mixed solution becomes butyl titanate, ethylene glycol and citric acid, and molar ratio is butyl titanate: ethylene glycol: Citric acid=4~5:20~25:5.5~6.5；In glycol water, volume ratio is ethylene glycol: water=7:5, and with ammonium hydroxide tune Save ph=6~7；The volume ratio of the mixed solution and glycol water is 4~5:1；The mixing speed be 50~ 100rad/min。
Substantive distinguishing features of the invention are as follows:
Using discarded copper tailing and iron tailings as primary raw material, it is aided with waterglass as binder, it is processed, it is formed with centainly Mechanical strength, high porosity, the repeatedly used porous carrier materials for wastewater treatment, feature are as follows: auxiliary agent type is few； Silica ratios are lower, are 35.25%~46.16%, sintering temperature is low, energy conservation and environmental protection；Contain a small amount of copper simple substance in raw material With more iron simple substance, after sintering, respectively with CuO and FeO or Fe3O4Form be present in ceramsite carrier, in urging for cyanide Changing copper ion and ferrous ion in oxidation has catalyst action, this haydite is loaded TiO2, copper ion, ferrous ion and TiO2 Synergy, the highest degradation rate of cyanide are a kind of efficient catalyst up to 92.11%.
Invention beneficial effect
The present invention it has the advantage that:
(1) it uses discarded copper tailing and iron tailings for primary raw material, is processed through pretreatment of raw material, compounding, mixing, molding etc. Target haydite is made in process, in haydite surface, load will can be obtained using the titanium dichloride load of sol-gel method preparation The haydite is used for the catalytic ozonation of cyanide under alkaline condition by the haydite of cyanide catalysis oxidation used catalyst, Its broken cyanide efficiency is up to 80% or more.Have that raw material sources are extensive, availability is high, preparation process is simple, the features such as being easily recycled.
(2) according to obtained by mercury injection apparatus test result and haydite SEM result, prepared haydite has compared with high porosity and a large amount of connection Venthole, infusion method learn that haydite water absorption rate is higher, reach as high as 10%, are used in combination and calculate according to infusion method and fractal theory Haydite surface roughness with higher out, these characteristics enable haydite load target catalyst as much as possible, And the haydite after supported catalyst and the contact of target waste water are more extensive, deeper into experiment gained: after supported catalyst Haydite, carry out cyanide catalysis oxidation, the degradation efficiency of cyanide reaches as high as 92.11%, so being good catalyst Carrier.
Detailed description of the invention
For the clearer elaboration purpose of the present invention, technical solution and feature, with reference to the accompanying drawing to the present invention make into The detailed description of one step.
Fig. 1 is ceramsite sintering heating curve described in embodiment 1
Fig. 2 is 1000 times of SEM figure of haydite described in embodiment 2
Fig. 3 is 4000 times of SEM figure of haydite described in embodiment 2
Fig. 4 is that cyanide surplus described in embodiment 2 changes over time figure
Specific embodiment
The present invention is further detailed below in conjunction with specific embodiment:
The main composition of the copper, iron tailings are as follows:
(1) the quality percentage composition of the main chemical compositions of copper tailing includes: SiO2: 55.6%~60.3%, (Al2O3+ Fe2O3):
15.7%~22.5%, Cu:0.04%~0.10%；
(2) the quality percentage composition of the main chemical compositions of iron tailings includes: SiO2: 33.4%~38.7%；(Al2O3+ Fe2O3):
13.6~14.9%；Fe:17.1%~18.5%；
Embodiment 1
Copper, iron tailings after drying is subjected to ball milling respectively, crosses 200 meshes, extracting screen underflow obtains copper, iron tailings powder；Claim Take: discarded copper tailing powder 60g discards iron tailings powder 15g, calcium carbonate 11g, cornstarch 7.5g, active powdered carbon 7.5g.It will weigh Good raw material mixing, carries out ball mill mixing, crosses 60 meshes later, and extracting screen underflow is the raw material that mixing is completed；Measure 8.5g water glass Glass is added the raw material that mixing is completed, carries out molding granulation, partial size 6mm with plate of chopping the chop after mixing as binder；Molding haydite exists At room temperature after aging 12h, it is put into 100 DEG C of oven drying 3h；Put the haydite raw material after drying into sintering furnace 150 DEG C of preheatings 30min is sintered at a temperature of 1000 DEG C, and sintering furnace heating rate is 10 DEG C/min.Ceramsite sintering temperature increasing schedule as shown in Figure 1, It is taken out from furnace after being cooled to 150 DEG C or so in air after the completion of sintering, and continues cool to room temperature.
By test, gained haydite clinker uses mercury injection apparatus to measure its porosity as 49%, and electronic universal tester measures Its radial crushing force 146.13N, infusion method measure its water absorption rate 8.7%, and infusion method and fractal theory, which are used in combination, calculates to obtain it Fractional dimension value is 2.65 (fractional dimension value is greater than 1 constant less than 3, and theoretically fractional dimension value is bigger, and degree of roughness is higher), ICP-AES is analyzed: the Cu of haydite in water2+The amount of dissolution is 0.01mg/L, Fe2+The amount of dissolution is 0.2mg/L.
Embodiment 2
Copper, iron tailings after drying is subjected to ball milling respectively, crosses 200 meshes, extracting screen underflow obtains copper, iron tailings powder；Claim Take: discarded copper tailing powder 65g discards iron tailings powder 10g, sodium bicarbonate 11g, cornstarch 11.25g, active powdered carbon 3.75g. Load weighted raw material is mixed, ball mill mixing is carried out, crosses 60 meshes later, extracting screen underflow is the raw material that mixing is completed；Measure 10g Waterglass is added the raw material that mixing is completed, carries out molding granulation with plate of chopping the chop after mixing as binder；Haydite is formed in room temperature Under after aging 12h, be put into 100 DEG C of oven drying 4h；Put the haydite raw material after drying into sintering furnace 150 DEG C of preheating 30min, It is sintered at a temperature of 1000 DEG C, sintering furnace heating rate is 10 DEG C/min, obtains haydite clinker.
By test, gained haydite clinker uses mercury injection apparatus to measure its porosity as 53%, and electronic universal tester measures Its radial crushing force 133.52N, infusion method measure its water absorption rate 9.6%, using ICP-AES method, measure haydite Cu in water2+It is molten Output is 0.01mg/L, Fe2+The amount of dissolution is 0.03mg/L.The section SEM figure of gained haydite is as shown in Figure 2 and Figure 3, aperture 5 ~60 μm, accidental aperture is more than 100 μm of macroscopic super big holes, and internal aperture is flourishing, and linked hole is in the majority, and macropore set is small Hole, this pore structure pole is conducive to the transmission of gas and liquid inside ceramsite carrier, and increases contact of the gas with liquid Area, to improve carrier to the removal efficiency of cyanide.
According to molar ratio butyl titanate: ethylene glycol: citric acid=4.3:23.2:5.8 weighs butyl titanate (C16H36O4Ti, Molecular weight 340.30) 29.24g；Ethylene glycol ((CH2OH)2, molecular weight 62.07) and 28.76g；Citric acid (C6H8O7, molecular weight 192.14) 22.27g prepares the mixed solution 55mL of butyl titanate；Ethylene glycol 7mL, deionized water 5mL are measured, ammonium hydroxide tune is added dropwise Ph=6~7 are saved, the mixed solution of ethylene glycol and water is obtained, by this mixed solution with 1mL/min's under conditions of room temperature and ultrasound Speed is added drop-wise to dropwise in the mixed solution of butyl titanate, obtains TiO2Precursor solution；The haydite clinker being previously obtained is soaked Bubble is in TiO2In precursor solution, while 80rad/min revolving speed stirs 5h, later takes out haydite, and in 100 DEG C of items in baking oven Dry 4h under part, 650 DEG C of calcining 1.5h are after taking-up to get the catalyst TiO loaded for cyanide catalysis oxidation2Pottery Grain.
This TiO has been loaded into2Haydite be placed in preparation cyanide (potassium cyanide) concentration be 7mg/L solution conical flask In, solution ph control carries out catalytic ozonation 9~10.Ozone is passed through from conical flask bottom, ozone concentration 45mg/L, Exhaust gas is absorbed by connected KI absorption bottle, and cyanide surplus changes over time as shown in figure 4, as seen from the figure, reaction carries out After 30min, using remaining total cyanogen concentration in spectrophotometry measurement solution, cyanide removal rate is up to 82.67%；Reaction carries out After 60min, cyanide removal rate is up to 88.36%；Reaction carry out 90min after, cyanide removal rate up to 91.11%, at this point, Total cyanogen concentration in solution is 0.62mg/L, has reached the dirt of two classes specified in " integrated wastewater discharge standard " GB8978-1996 Contaminate object three-level discharge standard.
Unaccomplished matter of the present invention is well-known technique.

Claims (5)

1. a kind of composite scrap tailing porous material, it is characterized in that the material is spherical porous ceramsite material, diameter is 5 ~ 8mm, Porosity 43% ~ 52%；Its raw material components mass percent are as follows:
Discarded copper tailing: 58% ~ 65%；
Discarded iron tailings: 9% ~ 18%；
Sodium bicarbonate: 4% ~ 12%；
Waterglass: 5% ~ 10%；
Cornstarch: 3 % ~ 14%；
Active powdered carbon: 3% ~ 9%.
2. composite scrap tailing porous material as described in claim 1, it is characterized in that the discarded copper tailing, primary chemical The quality percentage composition of ingredient includes: SiO2: 55.6% ~ 60.3%, (Al2O3+Fe2O3): 15.7% ~ 22.5%, Cu:0.04% ~ 0.10%；
The quality percentage composition of the discarded iron tailings, main chemical compositions includes: SiO2: 33.4% ~ 38.7%；(Al2O3+ Fe2O3): 13.6 ~ 14.9%；Fe:17.1% ~ 18.5%.
3. the preparation method of composite scrap tailing porous material as described in claim 1, method includes the following steps:
(1) pretreatment of raw material: carrying out ball milling for copper, the iron tailings after drying respectively, crosses 200 meshes, extracting screen underflow, obtain copper, Iron tailings powder；
(2) ingredient: discarded copper tailing powder, discarded iron tailings powder, calcium carbonate, corn are weighed respectively by above-mentioned mass percent and is formed sediment Powder, active powdered carbon；
(3) mixing: by above-mentioned load weighted raw material, ball mill mixing is carried out, 20 ~ 40min of Ball-milling Time crosses 60 meshes later, takes Screenings is the raw material that mixing is completed；
(4) it forms: the raw material that above-mentioned mixing is completed is added to the waterglass of the proportion, after mixing, using stranding ball sheet metal forming method It is granulated；Particle size range is 5 ~ 8mm；
(5) aging and dry: above-mentioned gained haydite to be stood into aging 12h ~ 15h at room temperature, then under the conditions of 100 ~ 110 DEG C Dry 3h ~ 5h；
(6) it roasts: the haydite after drying being put into 150 DEG C of preheating 30min in sintering furnace, is roasted under the conditions of 900 DEG C ~ 1000 DEG C 20 ~ 30min is burnt, sintering furnace heating rate is 10 ~ 15 DEG C/min, obtains porous material.
4. the application of composite scrap tailing porous material as described in claim 1, it is characterized in that for loading cyanide catalysis The catalyst of oxidation.
5. the application of composite scrap tailing porous material as described in claim 1, it is characterized in that the following steps are included:
Under conditions of room temperature and ultrasound, glycol water is added drop-wise in butyl titanate mixed solution, TiO is obtained2Presoma Solution；Haydite is added to TiO2In precursor solution, 3 ~ 5h of lower dipping is stirred, is later taken out haydite, and in 90 ~ 100 DEG C 3 ~ 5h of lower drying, 600 ~ 700 DEG C of 1.5 ~ 2.5h of calcining after taking-up can be prepared by having loaded the catalysis for cyanide catalysis oxidation The haydite of agent；
Wherein, the group of mixed solution becomes butyl titanate, ethylene glycol and citric acid, and molar ratio is butyl titanate: ethylene glycol: lemon Acid=4 ~ 5:20 ~ 25:5.5 ~ 6.5；In glycol water, volume ratio is ethylene glycol: water=7:5, and adjusts ph=6 ~ 7 with ammonium hydroxide； The volume ratio of the mixed solution and glycol water is 4 ~ 5:1；The mixing speed is 50 ~ 100r/min.
CN201811465905.0A 2018-12-03 2018-12-03 Composite waste tailing porous material and preparation method and application thereof Active CN109437629B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811465905.0A CN109437629B (en) 2018-12-03 2018-12-03 Composite waste tailing porous material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811465905.0A CN109437629B (en) 2018-12-03 2018-12-03 Composite waste tailing porous material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109437629A true CN109437629A (en) 2019-03-08
CN109437629B CN109437629B (en) 2021-06-08

Family

ID=65555405

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811465905.0A Active CN109437629B (en) 2018-12-03 2018-12-03 Composite waste tailing porous material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109437629B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110294626A (en) * 2019-07-17 2019-10-01 于克福 Using waste materials such as red muds as ecological sandstone aggregate of raw material and preparation method thereof
CN111807814A (en) * 2020-06-16 2020-10-23 日昌升建筑新材料设计研究院有限公司 Process for preparing sintered heat-insulation building block from filter cake
CN112850858A (en) * 2021-01-12 2021-05-28 山东中侨启迪环保装备有限公司 A integrative electric ammonia nitrogen removal device for waste water treatment
CN115160015A (en) * 2022-06-30 2022-10-11 武钢资源集团程潮矿业有限公司 Low-silicon iron tailing high-strength ceramsite and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU657000A1 (en) * 1977-10-20 1979-04-15 Уральский научно-исследовательский и проектный институт строительных материалов Raw mix for making light concrete
JPH06116057A (en) * 1992-09-30 1994-04-26 Ehime Pref Gov Porous ceramic and its production
CN101747077A (en) * 2009-12-30 2010-06-23 南京鑫翔新型建筑材料有限责任公司 Sintered product of rejects and shale modular cellular bricks and preparing method thereof
CN103537272A (en) * 2013-09-24 2014-01-29 苏磊 Modified TiO2 loaded photocatalytic ceramsite and preparation method thereof
CN103980001A (en) * 2014-05-19 2014-08-13 河北工业大学 Porous ceramic material of iron tailings and preparation method thereof
CN105126760A (en) * 2015-09-28 2015-12-09 福州大学 Heavy metal poly-hole adsorption material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU657000A1 (en) * 1977-10-20 1979-04-15 Уральский научно-исследовательский и проектный институт строительных материалов Raw mix for making light concrete
JPH06116057A (en) * 1992-09-30 1994-04-26 Ehime Pref Gov Porous ceramic and its production
CN101747077A (en) * 2009-12-30 2010-06-23 南京鑫翔新型建筑材料有限责任公司 Sintered product of rejects and shale modular cellular bricks and preparing method thereof
CN103537272A (en) * 2013-09-24 2014-01-29 苏磊 Modified TiO2 loaded photocatalytic ceramsite and preparation method thereof
CN103980001A (en) * 2014-05-19 2014-08-13 河北工业大学 Porous ceramic material of iron tailings and preparation method thereof
CN105126760A (en) * 2015-09-28 2015-12-09 福州大学 Heavy metal poly-hole adsorption material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
兰阳等: "尾矿回收的研究与应用", 《2017 年中国非金属矿科技与市场交流大会》 *
张宏泉等: "铜尾矿资源的利用现状及展望", 《现代矿业》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110294626A (en) * 2019-07-17 2019-10-01 于克福 Using waste materials such as red muds as ecological sandstone aggregate of raw material and preparation method thereof
CN111807814A (en) * 2020-06-16 2020-10-23 日昌升建筑新材料设计研究院有限公司 Process for preparing sintered heat-insulation building block from filter cake
CN112850858A (en) * 2021-01-12 2021-05-28 山东中侨启迪环保装备有限公司 A integrative electric ammonia nitrogen removal device for waste water treatment
CN112850858B (en) * 2021-01-12 2023-04-07 山东中侨启迪环保装备有限公司 A integrative electric ammonia nitrogen removal device for waste water treatment
CN115160015A (en) * 2022-06-30 2022-10-11 武钢资源集团程潮矿业有限公司 Low-silicon iron tailing high-strength ceramsite and preparation method thereof
CN115160015B (en) * 2022-06-30 2023-09-29 武钢资源集团程潮矿业有限公司 Low-silicon iron tailing high-strength ceramsite and preparation method thereof

Also Published As

Publication number Publication date
CN109437629B (en) 2021-06-08

Similar Documents

Publication Publication Date Title
CN109437629A (en) A kind of composite scrap tailing porous material and its preparation method and application
CN103145442B (en) Method for preparing non-sintered ceramisites by using chemical sludge
CN101708499B (en) Method for jointly stabilizing fly ash and arsenic-containing waste
CN103334007B (en) The method of liquid recycling more than baking acid immersion extraction process output extraction copper
CN104069690B (en) A kind of utilize coal gangue to prepare zeolite ceramsite filtrate and its preparation method
Ji et al. Nitrogen and phosphorus adsorption behavior of ceramsite material made from coal ash and metallic iron
CN108203760A (en) A kind of granulation-biological dump leaching process suitable for low-grade oxygen-sulfur mixed copper ore
CN105772483A (en) Incineration fly ash synchronous solidification/stabilization method based on geo-polymerization
CN111116224B (en) Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof
CN114804797A (en) Gold tailing non-sintered light ceramsite and preparation method thereof
CN102603359A (en) Coal ash biological filter material and preparation method of coal ash biological filter material
CN105801150B (en) A kind of preparation method of manganese ore tailing ceramic wafer
CN114394800A (en) Method for resource utilization of sludge biochar
CN104060092A (en) Biochemical sludge processing method
CN103910481A (en) Method for carrying out curing treatment on landfill leachate membrane concentration solution sludge by using novel curing agent
CN103848495A (en) Application of copper-adsorbed fly ash ceramsite
CN102910631A (en) Preparation method of silica micropowder-carbon composite raw material used for smelting industrial silicon
CN113501679B (en) Method for preparing high-strength brick by synergistically utilizing waste incineration fly ash and steel slag
CN108745358A (en) It is electrolysed preparation method and its electrolysis unit of the landfill leachate except the catalyst of ammonia nitrogen
CN108525644A (en) The preparation method of complex ore granule adsorbent
CN111378831B (en) Use method of pore-forming composite additive for dephosphorization of high-phosphorus iron ore pellets
CN107721373A (en) The production method of light concrete product based on red mud desulphurization denitration
CN104402354B (en) With micro-nano CeO2powder is that the Pb-Zn tailings of heavy metal ion fixative is non-burning brick
CN106944040A (en) Utilize the method that catalyst for purification of nitrogen oxides is prepared containing Titanium slag and containing manganese mud
CN106498157A (en) A kind of large-scale kiln-burning extracts vanadium from high-calcium type Rock coal containing alum

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
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Liang Jinsheng

Inventor after: Du Yi

Inventor after: Ding Yan

Inventor after: Gao Guiyang

Inventor before: Ding Yan

Inventor before: Du Yi

Inventor before: Liang Jinsheng

Inventor before: Gao Guiyang

GR01 Patent grant
GR01 Patent grant