CN103145161B - Method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue - Google Patents

Method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue Download PDF

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CN103145161B
CN103145161B CN201310006059.7A CN201310006059A CN103145161B CN 103145161 B CN103145161 B CN 103145161B CN 201310006059 A CN201310006059 A CN 201310006059A CN 103145161 B CN103145161 B CN 103145161B
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solution
boehmite
naalo
white carbon
time
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CN103145161A (en
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孙俊民
苏杰
伍泽广
张战军
高志军
张生
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High Aluminum Coal Resources Development and Utilization R&D Center of Datang International Power Generation Co Ltd
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High Aluminum Coal Resources Development and Utilization R&D Center of Datang International Power Generation Co Ltd
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    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention provides a method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue. The method comprises the steps: the coal gangue is ground, roasted, alkaline-leached and filtered so that sodium silicate solution and alkaline leaching dregs are obtained, a dispersing agent is added to the sodium silicate solution and after gas containing CO2 is fed into the solution, a white carbon black product is prepared; lime and sodium carbonate are added into the alkaline leaching dregs for sintering, clinker obtained by the sintering is water-quenched to obtain NaAlO2 solution, the gas containing CO2 is added to the NaAlO2 solution for carbonation to form glue, ageing treatment is performed to seriflux after glue forming and powder-shaped pseudo-boehmite is obtained after the aged seriflux is washed, filtered, dried and smashed. The coal gangue serves as a raw material for preparation of the pseudo-boehmite and the white carbon black so that high-valued comprehensive utilization of industry solid wastes is achieved and an additional value of a product is high; all by-products can be recovered and recycled so that zero release, low energy consumption, economy and environment protection are achieved; and a requirement for a device is low, the while coal black prepared and the pseudo-boehmite prepared are high in purity, fine and even in granularity and high in specific surface area.

Description

A kind of method utilizing gangue to prepare pseudo-boehmite co-preparation white carbon black
Technical field
The present invention relates to a kind of method being prepared pseudo-boehmite co-preparation white carbon black by gangue, particularly relate to a kind of coal gangue alkaline legal system that utilizes for the method for pseudo-boehmite co-preparation white carbon black.
Background technology
Gangue composes the main intergrowth mineral thing being stored in coal measure strata, they are generally positioned at roof or base plate, or be present in coal seam with the form of dirt band, often abandoned by as solid waste in progress of coal mining, not only cause the waste of resource, and accumulation earth's surface, occupy good farmland, cause serious environmental pollution.Based on comprehensive utilization of resources, environmental protection and the requirement of developing a circular economy, carrying out with gangue is raw material, produces the chemical products with high added-value such as boehmite and white carbon and has very important economic implications and social effect.
At present, the boehmite production method of report has been had to have a variety of.Representative method comprise disclosed in CN 1247773 with the slurries of aluminium hydroxide for raw material (these slurries by a kind of aluminum contained compound solution and a kind of precipitant solution temperature at least 50 DEG C with keep pH value 7.5 ~ 8.8 condition under contact and make), at the temperature of at least 50 DEG C, acid reagent and alkaline reagent is added successively in these slurries, the pH value of slurries is first made to drop to less than 5, slurry pH value is made to go back up to 9.4 ~ 10.4 again, filtration, washing, drying, obtain boehmite, roasting again, obtains gama-alumina.And preparation process of pseudoboehmite disclosed in CN100999328, comprising: a) under the acid condition being enough to make aluminum precipitation, the aluminium in the aqueous solution of precipitation aluminum contained compound, is isolated to a kind of unbodied hydrated alumina; B) by the mixing of water miscible to unbodied hydrated alumina, water and at least one alkali, pulp, slurries are aging 0.2 little of 6 hours in 20 DEG C to 90 DEG C, and wherein, the consumption of described alkali makes the pH value of slurries be 6-11.The preparation method of boehmite disclosed in CN101172631, sodium aluminate solution is carried out carbonating plastic, aging, separating, washing and drying, after it is characterized in that sodium aluminate solution carbonating plastic, first carry out slurries separation, then it is aging to carry out temperature raising after filter cake being added wash water mixing making beating.The preparation method of boehmite disclosed in CN101665262, comprise, sodium aluminate solution carbonation is become slurries, slurries is warmed up to aging temperature, slurries are aging, isolated by filtration, washing and drying step, wherein, also comprise in described method and add seed precipitation solution or kind point washing lotion in described slurries.Adding described seed precipitation solution or planting time of point washing lotion is that described slurries are when being warmed up to aging temperature or in described slurries ageing process.
In a word, the preparation method of existing boehmite mainly with aluminium hydroxide and industrial sodium metaaluminate for raw material is produced, the cost of material of production is higher, and when containing siliceous composition in raw material, the overwhelming majority is arranged outward by as residue, and resource utilization is low, damages environment.
Gangue contains abundant aluminium oxide and silica resource, is splendid production boehmite and the raw material of white carbon black product.If how gangue is that the preparation that raw material carries out pseudo-boehmite co-preparation white carbon black becomes the problem needing to be solved.
Summary of the invention
The invention provides a kind of method that coal gangue alkaline legal system obtains pseudo-boehmite co-preparation white carbon black; solve defect of the prior art, realize reducing cost of material, resource utilization is provided; while protection of the environment, obtain boehmite and the white carbon with good quality.
A kind of method utilizing gangue to prepare pseudo-boehmite co-preparation white carbon black provided by the invention, comprises the following steps:
1) the gangue powder of preparation activation: cool after gangue fragmentation, abrasive dust, removal of impurities, roasting, obtain the gangue powder activated;
2) alkali leaching desiliconization: leached by the gangue powder sodium hydroxide solution of above-mentioned activation, filters and obtains sodium silicate solution and alkali leaching slag;
3) prepare white carbon, comprising:
A, in described sodium silicate solution, add dispersant, and pass into containing CO 2gas carry out carbonating process, when the pH of solution is 4 ~ 7, carbonation reaction terminates, filter, obtain orthosilicic acid precipitated filter cakes and filtrate;
B, described orthosilicic acid precipitated filter cakes is carried out ageing, roasting, pulverize and obtain white carbon;
4) prepare boehmite, comprising:
A, by step 2) obtained alkali leaching slag sinters after mix with sodium carbonate and lime stone, acquisition grog, what produce in sintering process contains CO 2gas reclaim do carbonating use;
B, cool described grog, then through shrend, filter and obtain NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2naAlO is obtained after thick liquid lime milk solution deep desilication 2seminal fluid;
NaAlO described in c, use distilled water diluting 2seminal fluid obtains NaAlO 2solution, to NaAlO 2pass into containing CO in solution 2gas carry out carbonating plastic, after plastic has been reacted, reacting slurry is carried out burin-in process, then filter and obtain glue and filtrate, glue obtains pulverous boehmite through washing, dry, pulverization process.
In method provided by the invention, adopt alkaline process desiliconization and soda lime sintering process, little to the corrosion of equipment, the accessory substance produced in method is (as contained CO 2gas, filtrate and a small amount of calcium silicate slag) all recycling uses, such as: produce in sintering process containing CO 2gas can pass into sodium silicate solution and/or NaAlO 2carry out carbonating process in solution, after filtration, obtain orthosilicic acid precipitated filter cakes and filtrate, glue and filtrate (being generally dilute sodium carbonate solution), feedstock circulation can be made use after evaporation and concentration; Step 4-b) in produce a small amount of calcium silicate slag can be made into high standard cement, make whole process achieve zero-emission.
In the solution of the present invention, step 1) to prepare in the gangue powder process of activation: gangue being broken into granularity is 50-300 object powder, and the temperature range of roasting can be 700-1050 DEG C, and the time of roasting can be 30 ~ 60 minutes.To the roasting of Coal gangue powder be in order to make wherein kaolinite activation, rational grinding particle size can further improve the efficiency of activation, when the temperature of roasting is 700-1050 DEG C, the SiO in kaolinite 2change the amorphous Si O be easy to alkali reaction into 2, the amorphous Al in kaolinite 2o 3be converted into the γ-Al of crystalline state 2o 3, the γ-Al of crystalline state 2o 3stable chemical nature, thus aluminium is stayed in desiliconization under the effect of alkali leaching; When being heated to 950-1050 DEG C, SiO 2can be stable exist with amorphous state, Al 2o 3can stably with γ-Al 2o 3crystalline state exists, thus improves desiliconization rate further.
In a specific embodiment of the present invention, step 2) to may be controlled in alkali leaching desiliconization process under 80 ~ 100 DEG C of conditions with mass fraction be that 5-25% sodium hydroxide solution leaches described gangue powder 30 ~ 90 minutes, total consumption of NaOH is according to Na 2o:SiO 2the mol ratio of=1.0 ~ 1.2 calculates.Further, step 2) in can leach described gangue powder 50 ~ 70 minutes with the sodium hydroxide solution that mass fraction is 10% ~ 20%.Further, step 2) in can leach described gangue powder 60 minutes with the sodium hydroxide solution that mass fraction is 15%.Carry out the alumina silica ratio that alkali leaching greatly can improve alkali leaching slag under these conditions, not only meet the requirement of soda lime sintering process to raw material, also drastically increase Al 2o 3actual dissolution rate, decrease the consumption of lime stone, and the side reaction in soda lime sintering process can be reduced, reduce the amount of accessory substance calcium silicate slag.
In a specific embodiment of the present invention, preparing the process of white carbon, rate-determining steps 3-a) condition of acidification can be: the quality of the dispersant added is 0.5 ~ 5% of sodium silicate solution, add containing CO 2gas in CO 2volumetric concentration be not less than 15%, the initial temperature of carbonation reaction 50 ~ 95 DEG C, pressure is 0.25 ~ 0.4Mpa, and outlet temperature is 40 ~ 60 DEG C, and when the pH of solution is 6, carbonation reaction terminates.Further, step 3-a) in pass into containing CO 2volumetric concentration be 30 ~ 60% gas carry out carbonating process.Further, the quality of the dispersant added is sodium silicate solution or NaAlO 2solution quality is 0.6 ~ 1%.Further, step 3-a) in dispersant be selected from calgon, polyethylene glycol, lauryl sodium sulfate, polyvinyl alcohol and triethanolamine one or more.Further, dispersant is made up of by the mass ratio of 1:1 calgon and polyethylene glycol.
Step 3-b) in orthosilicic acid precipitated filter cakes is carried out ageing in the ageing tank of temperature 75 DEG C, the time is 6 ~ 9 hours, dewaters under 200 ~ 250 DEG C of conditions, then 500 ~ 650 DEG C of roastings 1 hour, pulverizes and obtains white carbon.
In a specific embodiment of the present invention, can be ageing 6 ~ 9 hours under the condition of 5 ~ 7 in pH value by orthosilicic acid precipitated filter cakes, the silica of particle fine uniform more can be obtained, in 200 ~ 250 DEG C of dehydrations, then 500 ~ 650 DEG C of roastings 1 hour.
The particle diameter of the white carbon that the inventive method obtains at 15 ~ 50nm, and can have 250-350m 2the specific area of/g, and the purity of about 98%.
In a specific embodiment of the present invention, prepare the process of boehmite, step 4-a) may be controlled to alkali be soaked slag and sodium carbonate and lime stone according to mol ratio: Ca/Si=2 ~ 3, Na/Al=1 ~ 1.2 mix, sinter at 1000 ~ 1350 DEG C, obtain grog, it is 0.5 ~ 1 hour that sintering time controls.Preferably, step 4-a) in: alkali is soaked slag, sodium carbonate and lime stone according to mass ratio: Ca/Si=2, Na/Al=1 mix, at 1200 ~ 1300 DEG C, carry out sintering processes, time controling was at 50 minutes.Above-mentioned mixed proportion and sintering time both can ensure that each material can fully react in sintering process, and again because silicone content is few in alkali leaching slag, the consumption of the lime stone allocated into is few, adds Al 2o 3with Na 2cO 3contact, thus greatly improve Al 2o 3leaching rate.
Further, clinker cooling to 600 ~ 700 of sintering DEG C can be taken out from sintering equipment (such as: alkali melts device), the β-2CaOSiO in grog 2change γ-2CaOSiO rapidly into 2, volumetric expansion, proportion reduces, and causes crystal to become fine powder, and grog is produced from efflorescence.Thus make soda lime sintering process technique have more excellent economy.
Further, step 4-b) in the temperature of shrend can control at 20 DEG C-30 DEG C, the time can control at 30 ~ 60min, and the condition of deep desilication is: lime milk solution concentration is 5 ~ 25wt%, and total consumption of calcium hydroxide is according to Ca 2o:SiO 2the mol ratio of=0.8 ~ 1.2 calculates, and the deep desilication time is 3 ~ 10 minutes.
Step 4-c) in NaAlO 2pass into containing CO in solution 2volumetric concentration be 30 ~ 50% gas carry out carbonating plastic, plastic reaction condition is temperature: 20 ~ 45 DEG C, the time: 45 ~ 90 minutes.Further, step 4-c) middle NaAlO 2solution is the Al making to be diluted with distilled water into 2o 3concentration is rare NaAlO of 30 ~ 65g/L 2solution.
Further, in step 4-c) in NaAlO 2after adding the expanding agent of 0.1 ~ 0.5wt% in solution, under the mixing speed of 800-2000r/min, pass into containing CO 2volumetric concentration be 30 ~ 50% gas carry out carbonating plastic, plastic reaction condition is temperature: 20 ~ 45 DEG C, the time: 45 ~ 90 minutes, and described expanding agent is one or more in active carbon, polyvinyl alcohol, polyacrylamide, cellulose, urea and starch.
Step 4-c) in after plastic reacted, described reacting slurry is warmed up to 60 ~ 100 DEG C, carries out insulation aging 2 ~ 6 hours.
In another detailed description of the invention of the present invention, step 2) alkali leaching desiliconization process in sodium hydroxide solution divide can add for twice leaching described gangue powder, the mass fraction of the sodium hydroxide solution added is 15 ~ 20%, the quality adding NaOH is for the first time the 50-80% of NaOH total amount, and the time of alkali leaching first time is 30 ~ 40 minutes; Second time adds the NaOH of residual mass, and the time of second time alkali leaching is 20 ~ 30 minutes.
Due in the process with alkali leaching desiliconization, along with the continuation of alkali leaching time, the viscosity of sodium silicate solution constantly increases, desilication efficiency is more and more lower, alkali leaching weak effect, in prior art, in order to improve desiliconization speed and desiliconization rate, adopt two sections of stripping desiliconizations, namely after desiliconization a period of time, Separation of Solid and Liquid is carried out, and filter cake is reentered into continuation stirring stripping in new alkali lye, but two sections of stripping desiliconizations add processing step and cost, extend total operating time, increase aluminium loss amount, simultaneously, co-producing white carbon black is abandoned because aluminum content in the sodium silicate solution after alkali leaching is high, make a low multiple use, value-added content of product is low.
What the present invention adopted adds sodium hydroxide solution leaching powder for twice, the mass fraction of sodium hydroxide solution is 15 ~ 20%, the amount adding NaOH is for the first time the 50-80% of NaOH total amount, under this condition, desilication reaction can carry out with reaction rate faster in the early stage, when reaction proceeds to certain degree, the viscosity of reactant liquor becomes large, at this moment remaining sodium hydroxide solution is added, both the amount of sodium hydroxide in reactant liquor had been supplemented, again diluting effect is played to reactant liquor, reduce the viscosity of reactant liquor, desilication reaction can be gone on speed faster, improve the efficiency of desiliconization.Add sodium hydroxide solution leaching powder for twice, one is the efficiency that improve desiliconization, thus improve the utilization rate of silicon and increase alumina silica ratio, be conducive to the carrying out of follow-up white lime sintering process, two is the aluminium loss amounts significantly reducing the dipped journey of alkali, be conducive to the utilization rate improving aluminium, reduce the aluminium content in alkali immersion liquid simultaneously, be conducive to the purification in subsequent production white carbon process.
The particle diameter of the boehmite that the inventive method obtains at 35 ~ 100nm, and can have 300-350m 2the specific area of/g, the pore volume of 1.2-2.0ml/g, is better than existing macropore boehmite specific area (250m 2/ g) and the performance indications of pore volume (0.3-1.0ml/g).
Scheme provided by the invention has the following advantages:
1. the present invention adopts gangue as the raw material producing boehmite and white carbon, and achieve the high-valued comprehensive utilization of industrial solid castoff, value-added content of product is high;
2. accessory substances all in the present invention is all recyclable, achieves zero-emission, and energy consumption is low, economic environmental protection;
3. the present invention utilizes alkaline process desiliconization and soda lime sintering process, low to the requirement of equipment;
4. produce white carbon and boehmite purity is high, uniform particles, fine size.
Accompanying drawing explanation
The X-ray diffractogram of boehmite powder prepared by Fig. 1 embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail; but it is not thereby limiting the invention; under the prerequisite not departing from design philosophy of the present invention, the various changes and modifications that those skilled in the art make technical scheme of the present invention, all belong to protection scope of the present invention.
Embodiment 1
Main mineral constituent in the present embodiment in gangue is kaolinite, and impure mineral content is extremely low; Aluminium oxide, silica, loss on ignition account for 40.08%, 37.65% and 17.32% respectively.
1) preparation activation gangue powder: take gangue 50 grams, be broken for 50-300 order, after abrasive dust, removal of impurities, roasting through naturally cooling obtain activate gangue powder;
2) alkali leaching desiliconization: be placed in leacher by the gangue powder of above-mentioned activation, be that 20% diluted sodium hydroxide solution leaches 30 minutes under 90 DEG C of conditions with mass fraction, total consumption of NaOH is according to Na 2o:SiO 2the mass ratio of=1.0 calculates, and after completion of the reaction, filters, and obtains sodium silicate solution and alkali leaching slag;
3) white carbon is prepared:
A, in above-mentioned sodium silicate solution, add calgon, the quality of calgon is 0.5% of sodium silicate solution quality, passes into containing CO 2gas carry out carbonating process, when the pH of solution is 4, carbonation reaction terminates, filter, obtain orthosilicic acid precipitated filter cakes and sodium carbonate filtrate; Described containing CO 2gas in CO 2volumetric concentration be not less than 15%;
B, described orthosilicic acid precipitated filter cakes carried out ageing, roasting, pulverizing i.e. obtained white carbon;
4) boehmite is prepared:
A, by step 2) obtained alkali leaching slag and sodium carbonate and lime stone be according to mass ratio: Ca/Si=2, Na/Al=1 put into alkali after mix and melt device, sintering 1 hour acquisition grog at 1350 DEG C; What produce in sintering process contains CO 2gas reclaim do carbonating use;
B, this grog to be melted device from alkali and takes out being cooled to 600 DEG C, achieve from efflorescence, the powder from efflorescence is carried out shrend, filtration, obtains NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2thick liquid obtains NaAlO after lime milk solution deep desilication 2seminal fluid;
C, described seminal fluid are for become Al by distilled water diluting 2o 3concentration is rare NaAlO of 60g/L 2solution, by above-mentioned rare NaAlO 2solution passes into containing CO after being heated to 30 DEG C 2volumetric concentration be 35% gas carry out carbonating plastic 1 hour, then reacting slurry is continued to be warming up to 80 DEG C, be incubated aging 4 hours, then filter and obtain glue and filtrate, glue is gained powder after washing, drying, pulverizing, be boehmite through X-ray powder diffraction analysis, X-ray powder diffraction analysis chart as shown in Figure 1.
After testing, the aluminium oxide in gangue and silica utilization rate are respectively 97.3%, 95.1%, and the rate that recycles of sodium carbonate, carbon dioxide, water is all more than 95%.The particle diameter obtaining boehmite powder is 50 ~ 100nm, and specific area is 302m 2/ g, pore volume is 1.2ml/g; White carbon particle diameter is 20 ~ 50nm, and the purity of white carbon is 98.0%, and specific area is 267m 2/ g, reaches the product quality requirement of boehmite and white carbon.
Embodiment 2
In the gangue adopted in the present embodiment, aluminium oxide, silica, loss on ignition account for 37.36%, 42.79%, 15.60% respectively.
1) preparation activation gangue powder: take gangue 50 grams, be broken for 50-300 order, abrasive dust, removal of impurities, after 800 DEG C of roastings through naturally cooling obtain activate gangue powder.
2) alkali leaching desiliconization: the gangue powder of above-mentioned activation is placed in leacher, add at twice mass fraction be 18% sodium hydroxide solution carry out alkali leaching: first time adds the 50-80% of total amount, and the alkali leaching time is 30 ~ 40 minutes; Second time adds remaining sodium hydroxide solution, and the alkali leaching time is 20 ~ 30 minutes; Total consumption of NaOH is according to Na 2o:SiO 2the mass ratio of=1.1 calculates, and after completion of the reaction, filters, and obtains sodium silicate solution and alkali leaching slag.
3) white carbon is prepared:
A, in above-mentioned sodium silicate solution, add calgon, the quality of calgon is 0.6% of sodium silicate solution quality, passes into containing CO 2gas carry out carbonating process, when the pH of solution is 6, carbonation reaction terminates, filter, obtain orthosilicic acid precipitated filter cakes and sodium carbonate filtrate.Described containing CO 2gas in CO 2volumetric concentration be not less than 15%, the initial temperature of carbonation reaction 50 ~ 80 DEG C, pressure is 0.25 ~ 0.4Mpa, and outlet temperature is 40 ~ 50 DEG C.
B, the ageing in ageing tank of orthosilicic acid precipitated filter cakes to be filtered after 6 ~ 9 hours, and dewater under 200 ~ 250 DEG C of conditions, then 500 ~ 650 DEG C of roastings 1 hour, pulverize and obtain white carbon.
4) boehmite is prepared:
A, by step 2) obtained alkali leaching slag and sodium carbonate and lime stone be according to mass ratio: Ca/Si=3, Na/Al=1.2 put into alkali after mix and melt device, sintering 50 minutes acquisition grogs at 1000 DEG C; What produce in sintering process contains CO 2gas reclaim do carbonating use.
B, this clinker cooling to 600 DEG C melted device from alkali and takes out, achieve from efflorescence, the powder from efflorescence is carried out shrend, filtration, obtains NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2thick liquid obtains NaAlO after rare lime milk solution deep desilication 2seminal fluid.The temperature of shrend controls at 20 DEG C, and time controling is at 30 ~ 60min, and the condition of deep desilication is: lime milk solution concentration is 5%, and total consumption of calcium hydroxide is according to Ca 2o:SiO 2the mol ratio of=0.8 calculates, and the deep desilication time is 3min.
C, described seminal fluid are the Al become by distilled water diluting 2o 3concentration is rare NaAlO of 75g/L 2solution, by above-mentioned rare NaAlO 2solution passes into containing CO after being heated to 30 DEG C 2volumetric concentration be 45% gas carry out after carbonating plastic reacts 70 minutes, then reacting slurry is continued to be warming up to 100 DEG C, be incubated aging 5 hours, filtration obtains glue and filtrate, glue is gained powder after washing, drying, pulverizing, be detected as boehmite powder through X-ray diffraction analysis, X-ray diffraction analysis figure and Fig. 1 is similar.
After testing, the aluminium oxide in gangue and silica utilization rate are respectively 97.3%, 95.1%, and the rate that recycles of sodium carbonate, carbon dioxide, water is all more than 95%.The particle diameter obtaining boehmite powder is 45 ~ 70nm, and specific area is 325m 2/ g, pore volume is 1.6ml/g; White carbon particle diameter is 20 ~ 50nm, and the purity of white carbon is 98.0%, and specific area is 267m 2/ g.
Embodiment 3
In the gangue adopted in the present embodiment, aluminium oxide, silica, loss on ignition account for 40.08%, 37.65%, 17.32% respectively.
1) preparation activation gangue powder: take gangue 50 grams, be broken for 50-300 order, abrasive dust, removal of impurities, after 1000 DEG C of roastings through naturally cooling obtain activate gangue powder;
2) alkali leaching desiliconization: the gangue powder of above-mentioned activation is placed in leacher, add at twice mass fraction be 15% sodium hydroxide solution carry out alkali leaching: first time adds the 50-80% of total amount, and the alkali leaching time is 30 ~ 40 minutes; Second time adds remaining sodium hydroxide solution, and the alkali leaching time is 20 ~ 30 minutes; Total consumption of NaOH is according to Na 2o:SiO 2the mass ratio of=1.1 calculates, and after completion of the reaction, filters, and obtains sodium silicate solution and alkali leaching slag.
3) white carbon is prepared:
A, in above-mentioned sodium silicate solution, add polyethylene glycol, addition is 1% of sodium silicate solution quality, passes into containing CO 2gas carry out carbonating process, when the pH of solution is 4, carbonation reaction terminates, filter, obtain orthosilicic acid precipitated filter cakes and sodium carbonate filtrate.Described containing CO 2gas in CO 2volumetric concentration be 30-60%, the initial temperature of carbonation reaction 50 ~ 80 DEG C, pressure is 0.25 ~ 0.4Mpa, and outlet temperature is 40 ~ 50 DEG C.
B, the ageing in the ageing tank of 75 DEG C of orthosilicic acid precipitated filter cakes to be filtered after 6 ~ 9 hours, and dewater under 200 ~ 250 DEG C of conditions, then 500 ~ 650 DEG C of roastings 1 hour, pulverize and obtain white carbon.
4) boehmite is prepared:
A, by step 2) obtained alkali leaching slag and sodium carbonate and lime stone be according to mass ratio: Ca/Si=2, Na/Al=1 put into alkali after mixing and melt device, sintering processes 1 hour acquisition grog at 1350 DEG C; What produce in sintering process contains CO 2gas reclaim do carbonating use.
B, this sintered clinker is cooled to 600 DEG C and melts device from alkali and take out, achieve from efflorescence, the powder from efflorescence is carried out shrend, filtration, obtains NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2thick liquid obtains NaAlO after rare lime milk solution deep desilication 2seminal fluid.
C, described seminal fluid become Al by distilled water diluting 2o 3concentration is rare NaAlO of 80g/L 2solution, by above-mentioned rare NaAlO 2solution passes into containing CO after being heated to 40 DEG C 2volumetric concentration be 35% gas carry out carbonating plastic 1 hour, then reacting slurry is continued to be warming up to 90 DEG C, be incubated aging 4.5 hours, filtration obtains glue and filtrate, glue is gained powder after washing, drying, pulverizing, be detected as boehmite powder through X-ray diffraction analysis, X-ray diffraction analysis figure and Fig. 1 is similar.
After testing, the aluminium oxide in gangue and silica utilization rate are respectively 97.3%, 95.1%, and the rate that recycles of sodium carbonate, carbon dioxide, water is all more than 95%.The particle diameter obtaining boehmite powder is 45 ~ 70nm, and specific area is 325m 2/ g, pore volume is 1.6ml/g; White carbon particle diameter is 15 ~ 40nm, and the purity of white carbon is 98.0%, and specific area is 314m 2/ g.
Embodiment 4
In the gangue adopted in the present embodiment, aluminium oxide, silica, loss on ignition account for 40.08%, 37.65%, 17.32% respectively.
1) preparation activation gangue powder: take gangue 50 grams, be broken for 50-300 order, abrasive dust, removal of impurities, after 700 DEG C of roastings through naturally cooling obtain activate gangue powder;
2) alkali leaching desiliconization: be placed in leacher by the gangue powder of above-mentioned activation, be that 15% diluted sodium hydroxide solution leaches 85 minutes under 80 DEG C of conditions with mass fraction, total consumption of NaOH is according to Na 2o:SiO 2the mass ratio of=1.1 calculates, and after completion of the reaction, filters, and obtains sodium silicate solution and alkali leaching slag;
3) white carbon is prepared:
A, in above-mentioned sodium silicate solution, add polyethylene glycol and the calgon mixed solution according to 1:1 proportional arrangement, addition is 0.5% of sodium silicate solution quality, passes into containing CO 2gas carry out carbonating process, when the pH of solution is 4, carbonation reaction terminates, and filters to obtain orthosilicic acid precipitated filter cakes and sodium carbonate filtrate; Described containing CO 2gas in CO 2volumetric concentration be 30-50%, the initial temperature of carbonation reaction 50 ~ 80 DEG C, pressure is 0.25 ~ 0.4Mpa, and outlet temperature is 40 ~ 50 DEG C.
B, silicic acid precipitated filter cakes carried out ageing, namely drying, pulverizing obtain white carbon;
4) boehmite is prepared:
A, by step 2) obtained alkali leaching slag and sodium carbonate and lime stone be according to mass ratio: Ca/Si=2, Na/Al=1 put into alkali and melt device and at 1350 DEG C, sinter 1 hour obtain grog after mixing; What produce in sintering process contains CO 2gas reclaim do carbonating use;
B, this clinker cooling to 600 DEG C melted device from alkali and takes out, achieve from efflorescence, the powder from efflorescence is carried out shrend, filtration, obtains NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2thick liquid obtains NaAlO after rare lime milk solution deep desilication 2seminal fluid; The temperature of shrend controls at 30 DEG C, and time controling is at 30 ~ 60min, and the condition of deep desilication is: lime milk solution concentration is 10wt%, and total consumption of calcium hydroxide is according to Ca 2o:SiO 2the mol ratio of=1.0 calculates, and the deep desilication time is 5 minutes.
C, described seminal fluid become Al by distilled water diluting 2o 3concentration is rare NaAlO of 65g/L 2solution, by above-mentioned rare NaAlO 2solution passes into containing CO after being heated to 35 DEG C 2volumetric concentration be 50% gas carry out carbonating plastic 75 minutes, then reacting slurry is continued to be warming up to 90 DEG C, be incubated aging 3.5 hours, filtration obtains glue and filtrate, glue is gained powder after washing, drying, pulverizing, be detected as boehmite powder through X-ray diffraction analysis, X-ray diffraction analysis figure and Fig. 1 is similar.
After testing, the aluminium oxide in gangue and silica utilization rate are respectively 97.3%, 95.1%, and the rate that recycles of sodium carbonate, carbon dioxide, water is all more than 95%.The particle diameter obtaining boehmite powder is 45 ~ 70nm, and specific area is 325m 2/ g, pore volume is 1.6ml/g; White carbon particle diameter is 15 ~ 25nm, and the purity of white carbon is 98.0%, and specific area is 346m 2/ g.
Embodiment 5
In the gangue adopted in the present embodiment, aluminium oxide, silica, loss on ignition account for 40.08%, 37.65%, 17.32% respectively.
1) preparation activation gangue powder: take gangue 50 grams, be broken for 50-300 order, abrasive dust, removal of impurities, after 1000 DEG C of roastings through naturally cooling obtain activate gangue powder;
2) alkali leaching desiliconization: the gangue powder of above-mentioned activation is placed in leacher, add at twice mass fraction be 22% sodium hydroxide solution carry out alkali leaching, first time adds the 50-80% of total amount, and the alkali leaching time is 30 ~ 40 minutes; Second time adds remaining sodium hydroxide solution, and the alkali leaching time is 20 ~ 30 minutes.Total consumption of NaOH is according to Na 2o:SiO 2the mass ratio of=1.1 calculates, and after completion of the reaction, filters, and obtains sodium silicate solution and alkali leaching slag.
3) white carbon is prepared:
A, in above-mentioned sodium silicate solution, add polyethylene glycol and the calgon mixed solution according to 1:1 proportional arrangement, addition is 0.7% of sodium silicate solution quality, passes into containing CO 2gas carry out carbonating process, when the pH of solution is 6.5, carbonation reaction terminates, and filters to obtain orthosilicic acid precipitated filter cakes and sodium carbonate filtrate; Described containing CO 2gas in CO 2volumetric concentration be 30-60%, the initial temperature of carbonation reaction 50 ~ 80 DEG C, pressure is 0.25 ~ 0.4Mpa, and outlet temperature is 40 ~ 50 DEG C.
B, orthosilicic acid precipitated filter cakes carried out ageing, roasting, pulverizing obtain white carbon.
4) boehmite is prepared:
A, by step 2) obtained alkali leaching slag and sodium carbonate and lime stone be according to mass ratio: Ca/Si=2, Na/Al=1 put into alkali after mix and melt device, sintering 1 hour acquisition grog at 1350 DEG C; What produce in sintering process contains CO 2gas reclaim do carbonating use;
B, the clinker cooling to 600 of sintering processes DEG C melted device from alkali and takes out, achieve from efflorescence, the powder from efflorescence is carried out shrend, filtration, obtains NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2thick liquid obtains NaAlO after rare lime milk solution deep desilication 2seminal fluid; The temperature of shrend controls at 20 DEG C, and time controling is at 30 ~ 60min, and the condition of deep desilication is: lime milk solution concentration is 10%, and total consumption of calcium hydroxide is according to Ca 2o:SiO 2the mol ratio of=1.0 calculates, and the deep desilication time is 5 minutes.
C, described seminal fluid become Al by distilled water diluting 2o 3concentration is /rare NaAlO of L 2solution, by above-mentioned rare NaAlO 2after solution is heated to, add the expanding agent accounting for solution total amount 0.2wt%, described expanding agent be in active carbon, polyvinyl alcohol, polyacrylamide, cellulose, urea and starch one or more, and to pass into containing CO 2volumetric concentration is the gas of 35%, under the mixing speed of 800-2000r/min, carry out carbonating plastic react 75 minutes, then reacting slurry is continued to be warming up to 90 DEG C, insulation is carried out aging 6 hours to glue, filtration obtains glue and filtrate, glue is through washing, dry, pulverizing gained powder, and be detected as boehmite powder through X-ray diffraction analysis, X-ray diffraction analysis figure and Fig. 1 is similar.
After testing, the aluminium oxide in gangue and silica utilization rate are respectively 97.3%, 95.1%, and the rate that recycles of sodium carbonate, carbon dioxide, water is all more than 94%.The particle diameter obtaining boehmite powder is 35 ~ 50nm, and specific area is 341m 2/ g, pore volume is 1.84ml/g; White carbon particle diameter is 15 ~ 25nm, and the purity of white carbon is 98.0%, and specific area is 346m 2/ g.

Claims (11)

1. utilize gangue to prepare a method for pseudo-boehmite co-preparation white carbon black, it is characterized in that, comprise the following steps:
1) the gangue powder of preparation activation: cool after gangue fragmentation, abrasive dust, roasting, obtain the gangue powder activated;
2) alkali leaching desiliconization: the gangue powder sodium hydroxide solution of above-mentioned activation is leached, filtration obtains sodium silicate solution and alkali leaching slag, 80 ~ 100 DEG C of conditions, sodium hydroxide solution is added at twice the described gangue powder of leaching, the mass fraction of sodium hydroxide solution is 15 ~ 20%, the quality adding NaOH is for the first time the 50-80% of NaOH total amount, and the time of alkali leaching first time is 30 ~ 40 minutes; Second time adds the NaOH of residual mass, and the time of second time alkali leaching is 20 ~ 30 minutes, and total consumption of NaOH is according to Na 2o:SiO 2the mol ratio of=1.0 ~ 1.2 calculates;
3) prepare white carbon, comprising:
A, in described sodium silicate solution, add dispersant, and pass into containing CO 2gas carry out carbonating process, when the pH of solution is 4 ~ 7, carbonation reaction terminates, filter, obtain orthosilicic acid precipitated filter cakes and filtrate;
B, described orthosilicic acid precipitated filter cakes is carried out ageing, roasting, pulverize and obtain white carbon;
4) prepare boehmite, comprising:
A, by step 2) obtained alkali leaching slag sinters after mix with sodium carbonate and lime stone, acquisition grog, what produce in sintering process contains CO 2gas reclaim do carbonating use;
B, cool described grog, then through shrend, filter after obtain NaAlO 2thick liquid and calcium silicate slag, described NaAlO 2naAlO is obtained after thick liquid lime milk solution deep desilication 2seminal fluid;
NaAlO described in c, use distilled water diluting 2seminal fluid obtains NaAlO 2solution, to NaAlO 2pass into containing CO in solution 2gas carry out the reaction of carbonating plastic, after plastic has been reacted, reacting slurry is carried out burin-in process, then filter and obtain glue and filtrate, glue obtains pulverous boehmite through washing, dry, pulverization process.
2. method according to claim 1, step 1) in the granularity of powder be 50-300 order, the temperature range of roasting is 700-1050 DEG C, and the time of roasting is 30 ~ 60 minutes.
3. method according to claim 1, step 3-a) in dispersant be selected from calgon, polyethylene glycol, lauryl sodium sulfate, polyvinyl alcohol and triethanolamine one or more.
4. the method according to claim 1 or 3, step 3-a) in the quality of dispersant that adds be 0.5 ~ 5% of sodium silicate solution, described containing CO 2gas in CO 2volumetric concentration be not less than 15%, the initial temperature of carbonation reaction 50 ~ 95 DEG C, pressure is 0.25 ~ 0.4Mpa, and outlet temperature is 40 ~ 60 DEG C, and when the pH of solution is 6, carbonation reaction terminates.
5. method according to claim 4, step 3-a) in pass into containing CO 2volumetric concentration be 30 ~ 60% gas carry out carbonating process.
6. method according to claim 1, step 3-b) in the ageing in ageing tank of orthosilicic acid precipitated filter cakes was filtered after 6 ~ 9 hours, and to dewater under 200 ~ 250 DEG C of conditions, then 500 ~ 650 DEG C of roastings 1 hour, pulverize and obtain white carbon.
7. method according to claim 1, step 4-a) in alkali is soaked slag and sodium carbonate and lime stone according to mol ratio: Ca/Si=2 ~ 3, Na/Al=1 ~ 1.2 mix, and sinter at 1000 ~ 1350 DEG C, and it is 0.5 ~ 1 hour that sintering time controls.
8. method according to claim 1, step 4-b) in the temperature of shrend control at 20 DEG C-30 DEG C, time controling is at 30 ~ 60min, and the condition of deep desilication is: lime milk solution concentration is 5 ~ 25wt%, and total consumption of calcium hydroxide is according to Ca 2o:SiO 2the mol ratio of=0.8 ~ 1.2 calculates, and the deep desilication time is 3 ~ 10 minutes.
9. method according to claim 1, step 4-c) in NaAlO 2pass into containing CO in solution 2volumetric concentration be 30 ~ 50% gas carry out carbonating plastic, plastic reaction condition is temperature: 20 ~ 45 DEG C, the time: 45 ~ 90 minutes.
10. the method according to claim 1 or 9, step 4-c) in, to NaAlO 2after adding the expanding agent accounting for described solution total amount 0.1-0.5wt% in solution, under the mixing speed of 800-2000r/min, pass into containing CO 2volumetric concentration be 30 ~ 50% gas carry out carbonating plastic, plastic reaction condition is temperature: 20 ~ 45 DEG C, time: 45 ~ 90 minutes, described expanding agent is one or more in active carbon, polyvinyl alcohol, polyacrylamide, cellulose, urea and starch.
11. methods according to claim 1 or 9, step 4-c) in after plastic reacted, described reacting slurry is warmed up to 60 ~ 100 DEG C, carries out insulation aging 2 ~ 6 hours.
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