CN104649279A - Process for preparing white carbon black from pulverized fuel ash as raw material - Google Patents
Process for preparing white carbon black from pulverized fuel ash as raw material Download PDFInfo
- Publication number
- CN104649279A CN104649279A CN201510078402.8A CN201510078402A CN104649279A CN 104649279 A CN104649279 A CN 104649279A CN 201510078402 A CN201510078402 A CN 201510078402A CN 104649279 A CN104649279 A CN 104649279A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- white carbon
- flyash
- technique
- waste white
- 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.)
- Pending
Links
Abstract
The invention provides a process for preparing white carbon black from pulverized fuel ash which serves as a raw material. The process comprises the following steps: soaking the pulverized fuel ash in an acid; filtering and separating; calcining; dissolving with water; decomposing carbon dioxide; filtering and separating; washing and drying. The adopted auxiliary raw materials can be recycled, and the secondary pollution to environment due to the comprehensive utilization of the pulverized fuel ash can be solved. Compared with the existing processes for preparing white carbon black, the process provided by the invention is simple and has the advantages of short circular reaction cycle, high production capacity and stable product quality. In addition, no waste liquid and residue can be discharged, the pollution to environment can be avoided, and the environment-friendly production can be realized. Moreover, the three wastes can be recycled, and the production cost and the production energy consumption can be reduced.
Description
Technical field
The present invention relates to solid waste comprehensive utilization technique, specifically belonging to a kind of take flyash as the technique of waste white carbon black.
Background technology
White carbon black also known as hydrated SiO 2, active silica and precipitated silica, chemical formula SiO2nH2O.It is the inorganic silicon compound of a kind of white, nontoxic, amorphous fine powdery, have porousness, polymolecularity, light weight, chemical stability good, high temperature resistant, do not burn, the excellent properties such as electrical insulating property is good, be widely used in the numerous areas such as plastics, rubber, papermaking, coating, dyestuff and ink.
The production of white carbon black has physics and chemistry two kinds of methods, and usual activity is good and reinforcing property is high amorphous white carbon black all adopts chemical method to produce.Chemical method is produced and is mainly adopted vapor phase process, hydrochloric acid precipitation method, sulfuric acid precipitation method, vapor phase process produce due to energy consumption and cost of material higher thus development be subject to certain restrictions, sulfuric acid precipitation method technical maturity and development very fast, but the specific surface being not so good as the white carbon black that vapor phase process is produced is large, purity is high, can not be applicable to special dimension.
The rise in price raw materials used due to the high speed development of automobile and transport trade thereof in recent years, white carbon black production and the requirement of energy-saving and emission-reduction, make again white carbon black become the outstanding person of rubber industry supporting material.As far back as 2007, the production capacity of China's precipitated silica was 800,000 tons, and output is 630,000 tons, ranks first in the world.Calendar year 2001 ~ within 2007, increase by 18.2% every year.The market intelligence done according to Na Chi consulting firm of the U.S. claims, the market demand of world's precipitated silica estimate by with annual 4% speed increase, within 2015, precipitated silica demand will reach 2,100,000 tons, and market value will be increased to 2,500,000,000 dollars the same period.
A kind of method utilizing coal gangue to carry waste slag of aluminum to prepare white carbon black mentioned in patent 201310337070.1.First coal gangue is carried waste slag of aluminum and make SiO by the method for mixing quartz sand
2content is more than or equal to 90%, Al
2o
3content is less than 6%, then according to SiO
2add sodium carbonate with the mol ratio 1: 0.3 ~ 1 of sodium carbonate, after mixed grinding becomes the particle of 50 ~ 200 μm, be placed in converter frit reaction 1 ~ 5 hour, the thick water glass particle obtained dissolves to obtain sodium silicate solution in autoclave; Sodium silicate solution is diluted to 5 ~ 15B é, passes into the CO produced in process
2carry out carbon and divide obtained white carbon black.Patent 201010266645.1 provides a kind of coal gangue combustion lime-ash and extracts aluminum oxide, the method of silicon oxide and ferric oxide, acid system is adopted to carry aluminium to coal gangue coal blending calcining lime-ash, alkaline process carries silicon, patent 201310062888.7 provides a kind of by the method for coal ash for manufacturing for rubber grade white carbon black, by the sodium silicate solution of aluminous fly-ash by 98% caustic soda 80-100 DEG C of alkali leaching 50-60min filtering separation, again sodium silicate solution is injected the interchanger that Zeo-karb is housed, sodium ion in liquor can be replaced by the hydrogen ion in exchanged resin, reduce sodium ions content, the sodium silicate solution that the silicon sodium ratio obtained is very high flows out from interchanger bottom, carry out direct carbon to divide, obtain rubber grade white carbon black.
Above patent ubiquity cumbersome, silicon extraction yield are lower, and are difficult to eliminate the problems such as three-waste pollution.Mention adding quartz sand in its Patent 201310337070.1 and improve SiO
2content and melting calcining 5h, add material consumption and the energy consumption of suitability for industrialized production; The acid system mentioned in patent 201010266645.1 carries aluminium, alkaline process carries silicon, production unit is required to the defects such as high, complex process; The aluminous fly-ash used in patent 201310062888.7 limits raw material sources.
The present invention with flyash be raw material by acidleach, filtering separation, calcining, water-soluble, carbon divides, filtering separation, washing drying and other steps production of silica white, first the environmental pollutions such as the stacking of flyash solid waste, floor space be large are solved, secondly the present invention is that the comprehensive utilization of flyash opens a new research and development direction, finally for avoiding the secondary pollution in utilization of fly ash, adopt auxiliary material to achieve recycle in the present invention, solve the secondary pollution of total utilization of PCA to environment.The present invention simultaneously has the advantages such as reasonable in design, energy consumption is low, less investment, flow process are simple, easy and simple to handle.
Summary of the invention
The object of the present invention is to provide a kind of less energy-consumption, low material consumption, free of contamination take flyash as the technique of waste white carbon black.
In order to reach above object, the technical scheme that the present invention takes is:
Take flyash as a technique for waste white carbon black, specifically comprise the following steps:
1) pre-treatment of flyash: by levigate for flyash ball mill;
2) acid leaching residue is produced in preliminary acidleach: levigate flyash and mixed in hydrochloric acid, and wherein concentration of hydrochloric acid is 20-22%, and the liquid-solid ratio of hydrochloric acid and flyash is acidleach at 3-4: 1,100-110 DEG C, obtains pickling liquor and acid leaching residue, and the chemical reaction that this step occurs is:
Al
2O
3+6HCl→2AlCl
3+3H
2O；Fe
2O
3+6HCl→2FeCl
3+3H
2O
3) solid water glass is produced: acid leaching residue and sodium carbonate are carried out batching mixing (modulus refers to the mol ratio of silicon-dioxide and sodium oxide in mixture) by required modulus of water glass 2.3, mixture is at retort furnace 780-850 DEG C of calcining 3h, shrend obtains solid water glass, and the chemical reaction that this step occurs is:
Na
2CO
3+SiO
2→Na
2SiO
3+CO
2↑
4) liquid soluble glass is produced: the solid water glass produced and soft water put into high pressure vessel, and solid-to-liquid ratio adds by 1: 3-4, is warming up to 200 DEG C, and insulation 2h dissolves, and obtains liquid soluble glass.
5) carbon divides production of silica white: the liquid soluble glass obtained adds soft water and is diluted to 10-12 degree Beaume, and the water glass after dilution is put into when carbon divides reactor to be heated to 50-90 DEG C and started to pass into CO
2carry out carbon and divide reaction, when monitoring solution PH reaches 8-9, stop ventilation, filtering separation, filter cake obtains white carbon black product through washing, drying, and the chemical reaction that this step occurs is:
Na
2SiO
3+CO
2+2H
2O→Na
2CO
3+H
4SiO
4；H
4SiO
4→SiO
2+2H
2O
The carbon sodium carbonate solution that middle filtration, washing process produce step by step is prepared sodium carbonate through condensing crystal drying and is carried out recycle, and crystallization also can be used for the shrend link of solid water glass.
Pickling liquor acidleach obtained is placed in polymerization reaction kettle, adds after calcium aluminate powder carries out polyreaction 2h, filtered by material, obtain polymeric aluminum chlorides solution and filter residue when 80-85 DEG C.Filter residue is used for the material of construction such as brickmaking.The chemical reaction that this step occurs is:
2AlCl
3+12H
2O＝Al
2(OH)
nCl
6-n+(12-n)H
2O
2FeCl
3+12H
2O＝Fe
2(OH)
nCl
6-n+(12-n)H
2O
mAl
2(OH)
nCl
6-n+
mxH
2O＝[Al
2(OH)
nCl
6-nx’H
2O]
m
mFe
2(OH)
nCl
6-n+mxH
2O＝[Fe
2(OH)
nCl
6-nx’H
2O]
m
{1≤n≤5；m≤10；x＜12}
Compared with prior art, advantage of the present invention and effect:
The present invention is that white carbon black prepared by raw material with flyash, and saying from raw material, take fine coal as the exploitation that raw material decreases to occurring in nature mineral substance, and the present invention simultaneously also plays refuse second stage employ, reduces flyash to the pollution of environment.Technique of the present invention designs with the thinking of zero release, and first present invention process is relative to white carbon black production technique was simple, the reaction cycle cycle is short, throughput is high, constant product quality in the past.Secondly empty waste liquid of the present invention, waste sludge discharge, avoid environmental pollution, reaches the pattern that environmental protection is produced.Simultaneously the recycling of the three wastes of the present invention, reduces production cost and production energy consumption.
Accompanying drawing explanation
Fig. 1 is that flyash carbon method prepares white carbon black technique schema;
Fig. 2 is chemical composition analysis result (WB%) table of somewhere, Shanxi aluminous fly-ash;
Fig. 3 is the indices table of white carbon black product;
Fig. 4 is the chemical composition analysis result table of polymerize aluminum chloride product.
Embodiment
Embodiment 1
1, somewhere, Shanxi chemical composition of PCA analytical results is shown in Fig. 2, by levigate for flyash to 80 orders
2, be the hydrochloric acid of 22% by the flyash after levigate and massfraction, be to mix at 1: 3 in mass ratio, be heated to 110 DEG C, react 2h at this temperature, reaction terminates rear filtering separation, and filter cake is dealuminzation flyash, and filtrate is used for making aluminium polychloride.
3, get 100g dealuminzation flyash and 40.15g sodium carbonate Homogeneous phase mixing, mixed 150g material is through retort furnace 780 DEG C of low temperature calcination 3h, and shrend cooling obtains solid water glass 128.4g.
4, the 128.4g solid water glass that step (3) obtains is put into high pressure vessel, add soft water 386ml, be heated to 200 DEG C of insulation 2h, obtain liquid soluble glass 455ml.
5, put into carburizing reagent still after the 455ml water glass that step (4) obtains being diluted to 12 degree Beaume, when being heated to 50 DEG C, pass into CO
2gas, gas flow is 40ml/min, carry out carburizing reagent, monitor the pH value in carbonization process at any time, the stopped reaction when pH value reaches 9, filtering separation, filter cake washing 3 times, obtain white carbon black product (indices the results are shown in Figure 3) at 105 DEG C of oven dryings, the washings filtering filtrate and the washing generation produced is used for recycling through condensing crystal preparing soda.
6, the filtrate in step (2) is put into polymerization reaction kettle and be heated to 80-85 DEG C, add calcium aluminate powder, carry out polyreaction 2h, the filtrate obtained after filtration is product polymeric aluminum chlorides solution (chemical analysis results is shown in Fig. 4), and the filter residue obtained is for brickmaking.
Claims (8)
1. be a technique for waste white carbon black with flyash, it is characterized in that, specifically comprise the following steps:
1) flyash is levigate;
2) by levigate flyash and mixed in hydrochloric acid, described concentration of hydrochloric acid is 20-22%, and the liquid-solid ratio of hydrochloric acid and flyash is acidleach at 3-4: 1,100-110 DEG C, obtains pickling liquor and acid leaching residue;
3) acid leaching residue and sodium carbonate are carried out batching mixing by required modulus of water glass 2.3, mixture is at retort furnace 780-850 DEG C of calcining 3h, and shrend obtains solid water glass;
4) by solid-to-liquid ratio 1: 3-4, solid water glass and soft water are added high pressure vessel, be warming up to 200 DEG C, 2h is dissolved in insulation, obtains liquid soluble glass;
5) liquid soluble glass obtained adds soft water and is diluted to 10-12 degree Beaume, puts into when carbon divides reactor to be heated to 50-90 DEG C and starts to pass into CO
2carry out carbon and divide reaction, when monitoring solution PH reaches 8-9, stop ventilation, filtering separation, filter cake obtains white carbon black product through washing, drying.
2. a kind of as claimed in claim 1 take flyash as the technique of waste white carbon black, it is characterized in that, described step 2) in acidleach temperature be 110 DEG C.
3. a kind of as claimed in claim 1 take flyash as the technique of waste white carbon black, it is characterized in that, described step 3) in calcining temperature be 780 DEG C.
4. a kind of as claimed in claim 1 take flyash as the technique of waste white carbon black, it is characterized in that, described step 5) mesosilicic acid sodium solution is diluted to 12 degree Beaume, and be placed in carburizing reagent still, under 50 DEG C of conditions, pass into CO
2, termination reaction when being reduced to 9 to pH value.
5. a kind of as described in claim 1-4 take flyash as the technique of waste white carbon black, it is characterized in that, described step 2) pickling liquor that obtains is placed in polymerization reaction kettle, add calcium aluminate powder when 80-85 DEG C and carry out polyreaction, after reaction 2h, filtered by material, obtain polymeric aluminum chlorides solution and filter residue, polymeric aluminum chlorides solution is prepared into polymerize aluminum chloride further.
6. a kind of as claimed in claim 5 take flyash as the technique of waste white carbon black, and it is characterized in that, described filter residue is used for brickmaking.
7. a kind of as described in claim 1-4 take flyash as the technique of waste white carbon black, it is characterized in that, described step 5) in filter, sodium carbonate solution that washing process produces prepares sodium carbonate through condensing crystal drying.
8. a kind of as described in claim 1-4 take flyash as the technique of waste white carbon black, it is characterized in that, described step 5) in filter, sodium carbonate solution that washing process produces is through the calcining link of condensing crystal for the preparation of solid water glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510078402.8A CN104649279A (en) | 2015-02-10 | 2015-02-10 | Process for preparing white carbon black from pulverized fuel ash as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510078402.8A CN104649279A (en) | 2015-02-10 | 2015-02-10 | Process for preparing white carbon black from pulverized fuel ash as raw material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104649279A true CN104649279A (en) | 2015-05-27 |
Family
ID=53240997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510078402.8A Pending CN104649279A (en) | 2015-02-10 | 2015-02-10 | Process for preparing white carbon black from pulverized fuel ash as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104649279A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836864A (en) * | 2016-05-30 | 2016-08-10 | 江西旭锂矿业有限公司 | Method of using lithium-extracted waste residue to prepare polymerized aluminum calcium chloride water purifying agent |
| CN109516466A (en) * | 2017-09-18 | 2019-03-26 | 湖南行者环保科技有限公司 | A method of high-purity white carbon is prepared by silicon-containing material |
| CN111592001A (en) * | 2020-05-31 | 2020-08-28 | 佛山经纬纳科环境科技有限公司 | Method for preparing layered double hydroxide and white carbon black from fly ash |
| CN113277821A (en) * | 2021-06-28 | 2021-08-20 | 山西瑞恩泽科技有限公司 | Solid-phase foaming fly ash calcium-silicon slag non-sintered ceramsite and preparation method thereof |
| CN113484209A (en) * | 2021-05-24 | 2021-10-08 | 浦林成山（山东）轮胎有限公司 | Method for identifying white carbon black in vulcanized rubber and application thereof |
-
2015
- 2015-02-10 CN CN201510078402.8A patent/CN104649279A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836864A (en) * | 2016-05-30 | 2016-08-10 | 江西旭锂矿业有限公司 | Method of using lithium-extracted waste residue to prepare polymerized aluminum calcium chloride water purifying agent |
| CN109516466A (en) * | 2017-09-18 | 2019-03-26 | 湖南行者环保科技有限公司 | A method of high-purity white carbon is prepared by silicon-containing material |
| CN111592001A (en) * | 2020-05-31 | 2020-08-28 | 佛山经纬纳科环境科技有限公司 | Method for preparing layered double hydroxide and white carbon black from fly ash |
| CN113484209A (en) * | 2021-05-24 | 2021-10-08 | 浦林成山（山东）轮胎有限公司 | Method for identifying white carbon black in vulcanized rubber and application thereof |
| CN113484209B (en) * | 2021-05-24 | 2023-08-18 | 浦林成山（山东）轮胎有限公司 | Identification method of white carbon black in vulcanized rubber and application thereof |
| CN113277821A (en) * | 2021-06-28 | 2021-08-20 | 山西瑞恩泽科技有限公司 | Solid-phase foaming fly ash calcium-silicon slag non-sintered ceramsite and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101306826B (en) | Process for extracting metallurgy-level aluminum oxide from fly ash or slag | |
| CN101306926B (en) | Process for abstracting floating air ball from fly ash or slag | |
| CN102515279B (en) | Comprehensive extraction method of ferro-silico-aluminum in gangue | |
| CN101913632B (en) | Method for extracting aluminum oxide, monox and ferric oxide from gangue combustion ashes | |
| CN101041450B (en) | Clean production technique for preparation of aluminium oxide and white carbon black by using high-alumina coal ash | |
| CN102424394B (en) | Process for preparing water glass from silicon micropowder by using wet method | |
| CN104649279A (en) | Process for preparing white carbon black from pulverized fuel ash as raw material | |
| CN103121700B (en) | Method for preparing ultrafine alumina and coproducing and white carbon black by utilizing coal series kaolin | |
| CN103979584B (en) | A kind of boric sludge is for Magnesium Carbonate Light 41-45 technique | |
| CN100582009C (en) | Combined method for producing aluminum-hydrate by lime-sintering-Bayer method | |
| CN102897810B (en) | Method for producing aluminum oxide by using fly ash | |
| CN101306426A (en) | Method for extracting iron washed ore from fly ash or slag | |
| CN101913637A (en) | Process method for producing fluorine compounds and silicon compounds by cleanly utilizing fluosilicic acid | |
| CN103145161A (en) | Method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue | |
| CN102838147B (en) | Method for preparing mixed solution of sodium aluminate and potassium aluminate from alkaline syenite | |
| CN101306819B (en) | Process for abstracting white carbon black from fly ash or slag | |
| CN110040753A (en) | A method of sodium aluminate solution is prepared using Bayer process red mud dry sintering | |
| CN103420386A (en) | Method for preparing silica through coal gangue aluminum extraction waste slag | |
| CN105483816A (en) | Method for preparing calcium sulfate whiskers from acetylene sludge and waste sulfuric acid | |
| CN103663516B (en) | A kind of method utilizing aluminous fly-ash to prepare aluminium hydroxide | |
| CN105060326B (en) | The technique that AZS solid wastes prepare sodium metaaluminate | |
| CN103663505A (en) | Method for treating potassium feldspar according to sub-molten salt method to prepare potassium carbonate | |
| CN102838299A (en) | Method for producing cement by electrolytic manganese residue and red mud | |
| CN102180498B (en) | Method for extracting alumina from bauxite | |
| CN101913633B (en) | Extraction technology of alumina and potassium sulfate from alunite by using hot-pressing leaching process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150527 |
|
| RJ01 | Rejection of invention patent application after publication |