CN103193238A

CN103193238A - Method for producing superfine white carbon black, ferric hydroxide and aluminum oxide by using coal ash

Info

Publication number: CN103193238A
Application number: CN2013101373654A
Authority: CN
Inventors: 宫毅; 吴岩博; 宫雪莲
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-04-19
Filing date: 2013-04-19
Publication date: 2013-07-10
Anticipated expiration: 2033-04-19
Also published as: CN103193238B

Abstract

The invention belongs to a resourceful, economic and fine utilization method of coal ash, and relates to a method for producing superfine white carbon black, ferric hydroxide and aluminum oxide by using coal ash. The method comprises the following steps of: with the coal ash as a raw material and a sulfuric acid and caustic soda solution as a solvent, grinding the coal ash, heating to assist in dissolving the coal ash, carrying out acid leaching on the coal ash, and then, filtering and cleaning the coal ash to obtain a filtrate, wherein the filtrate is used for preparing the ferric hydroxide and the aluminum oxide, a filter cake obtained through leaching and filtering is used for preparing the superfine white carbon black, and a fluoride-contained gas generated through leaching is used for absorbing and preparing an AlF3 product. By using the method, the problem that the industrial application can not be realized because the traditional coal ash leaching way is low in useful substance leaching rate is better solved fundamentally, and the total useful substance dissolution rate of the coal ash can be increased from 15-20% to 75-85%, so that resourceful utilization, economic and fine utilization, product diversification and higher additional value of the coal ash can be realized.

Description

Produce the method for superfine white carbon black, ironic hydroxide and aluminum oxide with flyash

Technical field

The invention belongs to the method that Ash Utilization, economy become more meticulous and utilize; Particularly a kind of take thermal power generation, heat supply produce in the flyash that produced be raw material, produce the method for ultrafine hydrous silicon-dioxide (being superfine white carbon black), ironic hydroxide, aluminum oxide and aluminum trifluoride product.

Background technology

Flyash is the product after pulverized coal friring during thermal power generation, heat supply are produced.It mainly can utilize material that Al, Fe, Si are arranged.SiO wherein ₂content is up to 40%～60%, aluminum oxide 20%～30% also, ferric oxide 4%～20%.According to a tree name detected result, be not difficult to find out: it can be used as good products resource.China is a thermal power generation and heat supply big country, and along with the develop rapidly of thermal power generation and heat supply industry, the year generation of flyash is also increasing day by day; According to incompletely statistics: China's annual production breaks through hundred million tons already; Each firepower heat supply and power-generating industry prevent for solving environmental issue the amount that flyash environmental pollution waste pit has stored in addition, and the existing owning amount of flyash is very huge.And the increase day by day of flyash brings that floor space is large, environmental influence, fly ash scientific utilization problem become increasingly conspicuous.In recent years, along with the raising that day by day improve and fly ash development utilized cognition degree of people to the flyash attention rate, to its exploitation dynamics also in rapid raising.However, though obtain certain effect, its development of exploitation level only limits the use of in building material industry, and the utilization of flyash is very low, less than 5%, the only primary stage in developing; Compare and differ greatly with U.S. that flyash is higher as the resources development and utilization level.With regard to its major cause, key is to lack starts with and is fully utilized from its chemical constitution.Though recent year occurs less from the start with achievement of the exploitation of carrying out aluminium, iron of flyash chemical constitution, it,, due to aluminium, the low inferior problem of iron substance leaching yield, causes the propagation and employment of its comprehensive utilization technique to be taken a step as difficult.For example; The domestic pickling process of utilizing prepares water conditioner.Because Al～Fe～Si key in leaching such as can't open at the problem, cause water conditioner to yield poorly down, product cost is too high and product that develop is single, causes carrying out suitability for industrialized production.Hence one can see that: Al in utilization of fly ash, Fe material leaching yield is low and material single cost that develop is too high, is to cause that flyash chemical constitution comprehensive utilization technique is promoted, application is obstructed and is become crucial difficulties.

The industry personnel is known, and flyash has following characteristics from its chemical composition analysis: one, and silicon, aluminium, iron level is higher and quantum of output is huge, can be used as and enriches products resource; Its two, affected by the factors such as himself vitreum indissoluble, conventional liquid phase Leaching way useful matter leaching yield lowly becomes crucial difficulties.So improving the leaching yield problem is the key point of dealing with problems.Therefore how to solve a crucial difficult problem, further scientific and reasonable, economy becomes more meticulous and takes full advantage of flyash self Characteristics of Chemical Constituents, collection is existing relevant classical, mature technology advantage both at home and abroad, innovation solves key issue, develop flyash as resource and utilize, make that it becomes that technique is simple, economical rationality, polynary, the effective strong production technology of product, just seem very important and significant; Also the key that solves the flyash Problems Existing simultaneously.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of method of producing superfine white carbon black and ironic hydroxide, aluminum oxide with flyash; The method useful matter leaching yield is high, and cost of manufacture is low.

It is as follows that the present invention solves the problems of the technologies described above taked technical scheme: a kind of method of producing superfine white carbon black and ironic hydroxide, aluminum oxide with flyash is characterized in that: take flyash as raw material, take sulfuric acid, caustic soda soln is solvent; By flyash through grinding, the acidleach of one section heating hydrotropy, filter and wash; Gained filtrate is for the preparation of ironic hydroxide and aluminum oxide; One soaks the rear gained filter cake of filtration for the preparation of superfine white carbon black; Concrete steps comprise:

A. grind: flyash is ground to powder below 200 microns through shredder;

B. the extraction of aluminium-iron: the flyash after grinding adopts hydrotropy hot acid-leaching mode to carry out aluminium-iron and extracts;

B.1 one section heating hydrotropy acidleach (be called for short and soak): leach first by acidleach solvent strength 2～4Mol water distribution quantity by 60 ℃ of hot water to leaching kettle, under heated and stirred again by flyash: acidleach solvent solid-to-liquid ratio is after 1:8～10 add flyash, joining sulfuric acid amount by acidleach solvent strength 2～4Mol again adds the vitriol oil to after in leaching kettle, again by flyash: the hydrotropy medicament is solid: Gu, after weight ratio 100:16～22 add hydrotropy medicament NaF, continuous heating stirs after 4～6 hours and store up 1 to insulation;

All adopt afterwards circulating leaching, in being about in the discharge of storage 1 or B5 crystallization and overflow operation overflowing liquid add the vitriol oil to be mixed with and leach first isoconcentration acidleach solvent and heated the hydrotropy leaching; Its operation steps: first overflowing liquid after middle storage 1 precipitation, to reactor, add solubility promoter and flyash under heated and stirred after, then is added and the vitriol oil that last time leached isoconcentration acidleach solvent ingredients consumption; Other condition with last time leached identical; Processing condition: 200～250 rev/mins of stirring velocitys, one soaks Heating temperature 95 ^.C～120 ^。C；

B.2 insulation stores in the 1(abbreviation and stores up 1): by the mixed solution after acidleach, to the taper insulation hold-up vessel that is provided with overflow, B.3 the underflow after settlement on storage to step is filtered and is washed; After precipitation, the overflow clear liquid adds the vitriol oil and is mixed with one and soaks isoconcentration acidleach solvent and return to step and B.1 one soak;

B.3 filter and washing: the underflow after settlement on storage to filtering system is carried out to solid-liquid separation and washing; Filter cake to step D.1.1 two sections add thermokalite and soak operation and extract SiO2; Filtrate is to B.5 crystallization and overflow of step; B.4, the filter cake washing water cycle is incubated and stores 2 to step after using;

B.4 insulation stores 2(and stores up 2 in being called for short): the washing water after the filter cake circulation cleaning to insulated tank is stored, is respectively used to a B.1 supplementary water soaked after middle immersion liquid evaporation of step, when aluminium-iron level higher up to step C.1.1 xln dissolve water;

B.5 crystallization and overflow: by step B.3 circulating leaching filtrate to this operation after filtering carry out crystallization, B.6 the crystallization underflow after crystallization to step is filtered and is separated; After crystallization, overflowing liquid returns to step and B.1 one soaks, and soaks the solvent isoconcentration by a pickling and adds the vitriol oil to be mixed with the acidleach solvent;

B.6 filter and separate: by step B.5 gained crystallization underflow to this operation filter and separate, filter the post crystallization body to step C.1 aluminium-iron separate, filtrate is to B.5 crystallization and overflow of step; Store up 2 after equipment and the recycle of facility washing water in B.4;

C. aluminium-iron separation and aluminium, iron product preparation;

C.1 aluminium-iron separates: the aluminium in xln is separated with iron;

C.1.1 xln dissolves: B.6 step is filtered to post crystallization body to heated and stirred and disclose, add the washing water in middle storage 2 by xln and aqueous solvent solid-to-liquid ratio 1:2～5 afterwards, under agitation be heated to 25 ^.c obtains solution after xln is dissolved; 200～250 rev/mins of stirring velocitys;

C.1.2 depickling: solution is stirred and discloses to neutralization, slowly add afterwards white lime, pH value of solution is adjusted to 2.8～3.0 and obtains the depickling mixed solution;

C.1.3 filter and washing: by the depickling mixed solution, to filtration and washing system and carry out the solid-liquid separation washing, C.1.4 filtrate to step precipitates and overflow; Filter cake is by-produced gypsum; The filter cake washing water cycle is used rear to middle storage 2;

C.1.4 the precipitation and overflow: by step C.1.3 gained filtrate precipitated, after precipitation, the overflow clear liquid is to lower step C.1.5 oxidation and pH regulator, after precipitation, underflow carries out liquid-solid the separation to C.1.3 filtering with washing on step, filtrate and filter cake trend and C.1.3 identical;

C.1.5 oxidation and pH regulator: by the overflow clear liquid to reactor, be warming up to 60～70 ℃ under heated and stirred, by preparing liquid and oxygenant volume ratio 100:6～10 to after adding the oxygenant clorox in still, continuous heating insulation 60～70 ℃, stir 20 minutes, adding mass percent concentration is that 10%NaOH solution (as follows) is regulated pH value of solution to 4.0 in still, keep 30 minutes after solution temperature is risen to 80 ℃, obtain mixed solution;

C.1.6 precipitation and overflow: after mixed solution to this operation is precipitated, C.1.7, underflow to lower step is filtered and is washed, the overflow clear liquid divides two-way: a road is to aluminium product preparation section, and middle produced fluoro-gas absorption system absorbent preparation aluminum trifluoride product is soaked as one in another road;

C.1.7 filter and washing: underflow to filtering system after upper step C1.6 precipitation is carried out to solid-liquid separation and washing; Filter cake is to C.2.1 ageing of step, and filtrate is returned to step and C.1.6 precipitated and overflow; Filter cake washing water is extremely middle storage 2 after recycling; Filtrate is for containing aluminum solutions, and filter cake is iron cake;

C.2 ironic hydroxide product preparation: with iron cake, prepare the ironic hydroxide product;

C.2.1 ageing: by step C.1.7 the gained filter cake after 24 hours, obtain the precipitation underflow to ageing in the ageing pond that 10%NaOH solution is housed;

C.2.2 filter and washing: will precipitate underflow to filtering system and carry out solid-liquid separation and washing; Filter cake is that the ironic hydroxide work in-process are C.2.3 dry to step, and filtrate is returned to step ageing pond C.2.1; Filter cake washing water is extremely middle storage 2 after recycling;

C.2.3 dry: by upper step, C.2.2 the gained filter cake is dry under 100～200 ℃ of temperature, 60～120 minutes time condition, obtains dried material;

C.2.4 grind: dried material to shredder is ground to obtain to the ironic hydroxide product;

C.3 aluminium product preparation: with containing aluminum solutions, preparing solid oxide aluminium product;

C.3.1 pH regulator: by step, overflow clear liquid C.1.6 is to reactor, under agitation by preparing liquid in still, rise to 60～70 ℃, and add 10%NaOH solution in backward still, regulate pH value of solution to 5.3 in still, solution temperature is risen to 80 ℃ again, must regulate mixed solution after being incubated 30 minutes;

C.3.2 precipitation and overflow: will regulate mixed solution to this operation and be precipitated and overflow, C.3.3, the precipitation underflow filters and washing procedure to lower step, and after precipitation, the overflow clear liquid is mixed with step by it and D.2.1 disperses after the dispersion agent with the desired isoconcentration salt of gel amount to D.2.1 disperseing and gel;

C.3.3 filter and washing: by upper step C.3.2 gained precipitation underflow to filtering system carry out solid-liquid separation and washing; After washing, filter cake is for containing the aluminium filter cake to the C.3.4 ageing of lower step; Filtrate is returned to step and is C.3.2 precipitated and overflow; Filter cake washing water stores up 2 to step is B.4 middle after recycling;

C.3.4 evaporate brine and overflow: will C.3.2 precipitate with the overflow operation in the overflow clear liquid to this operation, obtain the sodium sulfate crystal byproduct through moisture content spontaneous evaporation to full crystallization, after its crystallization, the overflow clear liquid is to D.2.7 crystallization and overflow operation;

C.3.5 ageing: after C.3.3 step is washed containing the aluminium filter cake to ageing in the ageing pond that 10%NaOH solution is housed after 24 hours, must precipitate underflow extremely lower step C.3.5 filter and wash;

C.3.6 filter and washing: will precipitate underflow to filtering system and carry out solid-liquid separation and washing; After washing, filter cake is that the aluminium hydroxide work in-process are C.3.7 dry to step, and filtrate is returned to step ageing pond C.3.5; Filter cake washing water is extremely middle storage 2 after recycling;

C.3.7 dry: by upper step C.3.5 the gained washing leaching cake in temperature 100～200 ^.dry under C, 60～120 minutes time condition, obtain dried material;

C.3.8 grind: after dried material to shredder is ground, be alumina product;

D. silicon extracts and the preparation of silicon product: contained silicon-dioxide stripping in a leaching cake is extracted and the ultrafine hydrous silicon-dioxide of preparation

D.1 the silicon stripping is extracted

D.1.1 two sections add thermokalite and soak (being called for short two soaks): the filter cake that this operation is used comes from step and B.3 filters and wash; During leaching by filter cake (weight): alkali soak solvent (volume) than for 1:3～8 to reactor; It is concentration 12%～16%NaOH that alkali soaks solvent; Alkali soaks the solvent compound method two kinds, and corresponding, two leaching methods are: one; With the commodity liquid caustic soda, prepare: the NaOH liquid caustic soda by 32% or 42% adds water and is mixed with 12%～16%NaOH, after the alkali prepared soaks solvent and is heated to 90 ℃, under heated and stirred, filter cake is added to reactor, after being heated to 95 ℃～120 ℃, continuous heating stirs 2.5 hours, to in its still, two soak that mixed solution is hot stores up 3,200～250 rev/mins of stirring velocitys in D.1.2 lower step is incubated afterwards; (before leaching, the alkali prepared is soaked to solvent temperature and be heated to 90 ^.after C, enter reactor and leached; Purpose be reduce two soak to reach leach design temperature heat-up time used) its two; With the commodity solid caustic soda, prepare: by filter cake: alkali soaks its weight of solvent: the water yield that the alkali that volume ratio is 1:3～8 soaks the required use of solvent by 60 ℃ of hot water to reactor, under heated and stirred, filter cake is added to reactor, after the solid caustic soda amount of soaking the required use of solvent 12%～16%NaOH by preparation alkali again adds solid state N aOH, after being heated to 95 ℃～120 ℃, continuous heating stirs 2.5 hours, to in its still, two soak that mixed solution is hot stores up 3,200～250 rev/mins of stirring velocitys in D.1.2 lower step is incubated afterwards; Weight: volume ratio is g:ml or Kg:L or t:m ³;

D.1.2 in the insulation, storage 3(stores up 3 in being called for short): by upper step D.1.1 two soak mixed solution to middle storage 3 be incubated store after extremely lower step D.1.3 filter and wash; Soak reactor and leached rear holding time to shorten two, improve its operational use time and eliminate that to form the filtration that colloidal state causes not smooth due to temperature drop fast;

D.1.3 filter and washing: two after storing soak mixed solution after filtration system carry out solid-liquid separation and washing; D.2.1, two lixiviums disperse and gel to the step of silicon product preparation section, hot 1～3%NaOH alkaline solution repetitive scrubbing for filter cake; The extremely middle storage 4 of alkaline solution after circulation cleaning, reusable heat water cycle washing leaching cake, the filter cake after washing with water is discarded landfill, extremely middle storage 4 after washing water store and recycle;

D.1.4 storage 4 in: by upper step D.1.3 filter with cycles of washing washing after the higher alkali lye of silicone content and washing water to this operation store after to D.1.1 two soaking operation, soak operation alkali as two and soak solvent ingredients water;

D.2 silicon product preparation

D.2.1 disperse and gel: D.1.3 two lixiviums are to reactor, under agitation by prepare liquid and dispersion agent volume ratio 1:2～3 add mass percent concentration be 8%～14%NaCl solution as a dispersion agent, afterwards temperature is risen to 60 ℃ after lower step extremely;

Prepare first silicon product NaCl as a dispersion agent, D.2.4 all the other available subsequent steps are isolated overflow clear liquid with aging precipitation and are mixed with isoconcentration salts contg solution and make a dispersion agent;

D.2.2 heat up and pH regulator: upper step is prepared to liquid at heat tracing 60 ^.adding mass percent concentration under C, stirring is that 10% sulphuric acid soln adjusting prepares the rear extremely lower step of liquid pH to 7.0;

D.2.3 disperse and heat up: by prepare liquid with twice dispersing agent volume ratio 100:2.5～10 add twice dispersing agent ethanol, will prepare liquid be warming up to 80 ℃ after to isolating and aging process;

D.2.4 isolation is with aging: by preparing liquid and separant volume ratio 100:2.5～10 add the separant glycerol, 80 ℃ of temperature, continue to stir 15 minutes after, be incubated 80 ℃ and within aging 20 minutes, obtain aging mixed solution;

D.2.5 precipitation and overflow: aging mixed solution to this operation is precipitated to overflow, and the overflow clear liquid is to D.2.7 crystallization and overflow of step; The precipitation underflow is to lower step;

D.2.6 filter and washing: upper step precipitation underflow is carried out to solid-liquid separation and washing to filtering with washing system; Filtrate is returned to step precipitation and overflow; Washing leaching cake is D.2.8 dry to step; The filter cake washing water cycle is used rear to middle storage 4;

D.2.7 crystallization and overflow: by step, overflow clear liquid D.2.5 is to this operation; Its most of overflowing liquid to D.2.1 disperse with the gel operation in as a dispersion agent, another part overflow clear liquid is to C.3.4 evaporating brine and overflow; This operation overflow clear liquid recycles in after-bay as dispersion agent that sodium sulphate content can constantly increase through multifrequency time until saturated crystallization, and the gained crystal salt is the byproduct sodium sulfate crystal;

D.2.8 dry: by upper step D.2.6 the gained washing leaching cake in temperature 80 ^.dry under C, 60～120 minutes time condition, obtain dried material;

D.2.9 grind: by dried material, to shredder, after grinding, material is ultrafine hydrous silica product.

Further, the present invention also is used to the fluoro-gas produced in one section heating hydrotropy acidleach process, so the present invention also comprises the steps:

E. fluoro-gas absorbs and its product preparation: a fluoro-gas that soaks generation is absorbed and prepare AlF ₃product

E.1 fluoro-gas absorbs: B.1 step one is soaked to produced fluoro-gas and is introduced the absorption tower bottom air inlet by still top exhaust facility and absorbed, absorption agent be aluminium hydroxide solution through absorption tower top spray facility spray, obtain extremely lower step of absorption liquid;

E.2 precipitation and overflow: by absorption liquid, to this operation, the rear overflow clear liquid continuation of precipitation absorbs as absorption agent to lower step e .3 circulation, precipitates underflow to step e .4 filtration and separates;

E.3 circulation absorbs: after using the overflow clear liquid after upper step precipitation to circulation groove, spray the absorption that circulates as absorption agent to absorption tower top spray facility; Close this recycle system when clear liquid is low containing the Al amount after precipitation, start another standby recycle system; Simultaneously after the low aluminium absorption liquid of circulation groove to storage facility stores as B.1 one soaking in process the supplementary water after the immersion liquid evaporation and return to step and B.1 one soak operation, to the supplementary equivalent of circulation groove, C.1.6 precipitating with overflow operation overflow clear liquid afterwards is new aluminium hydroxide solution;

E.4 filter and separate: by step e .2 precipitation and overflow gained precipitation underflow after filtration system carry out solid-liquid separation and washing; Filter cake is aluminum trifluoride AlF ₃to step e .5 drying, filtrate is returned to the circulation groove that E.3 circulation absorbs; Filter cake washing water after circulation cleaning stores together with the low aluminum solutions of circulation groove, as one, seals and fills water;

E.5 dry: by upper step e .4 gained filter cake in temperature 80 ^.dry under C, 60～120 minutes time condition, obtain dried material;

E.6 grind: after material to shredder after upper step drying is ground, be AlF ₃product.

Production process route of the present invention has two, article one, production technique is comprised of two-step approach: by pretreated flyash to the first step: by adoption of innovation flyash hydrotropy leaching-out technique, that is: one section heating is leached Al, Fe is extracted and combine with its product preparation process, produces ironic hydroxide, alumina product; Second step: adopt absorption process: by one section leaching the fluoro-gas that produces by the deironing of Al-Fe separation circuit after the aluminium hydroxide clear liquid make the absorbent preparation aluminium fluoride product; The second production technique is comprised of single stage method: i.e. the 3rd step: two sections are leached silicon and extract the production superfine white carbon black product that combines with the silicon product preparation process.

Technical essential of the present invention is as follows:

1. the steps A grinding step remains on the granularity of flyash below 200 microns, to guarantee the extraction yield of Al, Fe, Si;

2. step one section hot acid-leaching B.1, by immersion liquid, circulate reach Al in immersion liquid, the Fe ionic concn increases to saturated crystallization, the add-on of the vitriol oil with the preparation rate that improves Al, Fe product and while reducing preparation acidleach solvent, thus the purpose of the preparation cost of product reduced;

Step B.2 in storage 1 and step D.1.2 in storage 3 be mainly to establish for improving reactor and filter plant operating rate; In order to reduce solution temperature drop in storage tank, this device should be set up thermal insulation layer at outside surface, with avoid because of solution sharply temperature drop form the silica type material and affect its lower step and filter smooth and easy;

4. B.5 crystallization and overflow of step: add the vitriol oil by liquid after a leaching and be mixed with and last time leached isoconcentration acidleach solvent and carry out soaking circulating leaching and reach the purpose that it soaks rear filtrate crystallization;

5. C.1.1 xln dissolving of step, should note after xln fully dissolves being allowed for access next operation;

Step C.1.2 depickling be to reduce NaOH to consume, thereby in reducing and cost and establishing, white lime should be made to the powder state during depickling and can add in deacidification tank and carry out depickling, otherwise can affect because the white lime piece is large stirring and deacidification effect;

Step C.1.5 oxidation with pH regulator, be the critical process that realizes that iron aluminium separates.This operation is mainly to prepare in the liquid iron ion ferrous iron by with chlor-alkali production system tail chlorine absorption liquid clorox, as oxygenant, carrying out oxidation, ferrous iron is transformed into to ferric iron, through pH regulator, ferric iron is transformed into to ironic hydroxide again, thereby realizes the purpose that ferro-aluminum separates;

8., after B.6 step is filtered and filtered with separation circuit, equipment and facility should clean in time.Avoid because of solution Crystallization Plugging installations and facilities again, impact is filtered next time;

9. C.1.5 step in oxidation and the oxidation of pH regulator operation, should add oxygenant pipe to stretch to the reactor bottom, prepares the oxidation efficiency of liquid with raising;

10. C.1.5 step can produce a certain amount of chlorine when oxidation and the oxidation of pH regulator operation, therefore to its chloride tail gas, must set up absorption system.Chloride tail gas absorbs the sodium hydroxide solution of selecting 10% and makes absorption agent.After absorbing, nearly saturated absorption liquid returns to step C.1.5 oxidation and pH regulator operation;

11. step C.1.3 with step D.1.3 filter with washing procedure in the washing of filter cake be very important link, so must strive that in filter cake, the enrichment of soluble substance minimizes with the boiling water repetitive scrubbing during filter cake washing;

12. it need, through twice dispersion, be to realize that hydrated SiO 2 reaches the key link of ultra-fine level, therefore must operate in accordance with regulations that step e .4.1 and step e .4.3 prepare liquid;

13. the washing application boiling water of each product preparation section filter cake is washed, the washing water after washing should recycle.Washing water after recycling return to separately storage tank in washing water, and for production technique separately, to save the usage quantitys of a large amount of new water.

Beneficial effect of the present invention mainly is:

1, adoption of innovation flyash hydrotropy soaks the extraction yield that technology has further improved useful matter

Fundamentally solve better traditional flyash Leaching way useful matter leaching yield and lowly can't realize the difficult problem of industrialized utilization.Flyash hydrotropy leaching-out technique, by add fluorochemical in leaching, disconnects Al～Si key, has greatly improved the dissolution rate of Al, Fe.In addition, be also that the two leachings dissolving raising extraction yields that soak silicon are laid a good foundation.Therefore adopt flyash hydrotropy leaching-out technique can become the flyash chemical composition and utilize resource utilization, industrialization sound assurance;

2, collect domestic and international related products technology of preparing advantage exploitation meeting the market requirement product

According to the produce market demand by flyash hydrotropy lixiviation process and classical, ripe Al, Fe, Si related products production technology is combined is large characteristics of this technical innovation.Thus the utilization of fly ash product is polynary, highizationer of added value realize, thoroughly solved the fine coal tradition utilize in single, the difficulties such as added value is low of product development;

3, will clean, environmental protection, recycling economy, synergy theory be in whole production technique

3.1 the fluoro-gas produced during one section hydrotropy is leached adopts absorption process to prepare aluminium fluoride product.Utilize the aluminium hydroxide clear liquid after ferro-aluminum separates to make absorption agent, utilize one to soak middle produced fluoro-gas for fluorine raw material production aluminium fluoride product;

3.2 soak and adopt the circulating leaching mode one, can save acidleach solvent vitriol oil at least 50% for ingredients.Thereby save a large amount of acidleach costs;

3.3 the washing water reuse after filter cake circulation cleaning in production technique, in production technique, is saved to new water consumption greatly;

3.4 the saliferous sodium sulfate clear liquid after the preparation of aluminium, silicon product is disperseed in the preparation of silicon product with the gel operation in a dispersion agent for wherein, not only can save in a large number dispersion agent NaCl, and can save a large amount of new water;

3.5 deacidification process selects dry hydrate to carry out depickling, not only can save a large amount of NaOH solid caustic soda or liquid caustic soda, but and output by-product gypsum, further increased economic benefit;

4, focusing on the process detail processing fulfills increasing the benefit

The present invention organically combines flyash hydrotropy leaching-out technique and the domestic and international related products technology of preparing advantage of collection, and is improved on this basis and innovation, by great many of experiments proved, summary, concludes to optimize and combine and forms; It is for above-mentioned total utilization of PCA problem, the innovation and the improvement that adopt are: at first, adopt two sections to leach i.e. one section hydrotropy circulating-heating acidleach and add the thermokalite mode of soaking and combine with two sections, with this, the total dissolution rate of flyash useful matter can be increased to 75%～85% by 15%～20%; Secondly, when after one section hot acid-leaching, in ironic hydroxide preparation technology, oxidation and pH regulator operation adopt oxidation, chlorine-containing gas absorbs with sig water, and the absorption liquid after circulation absorbs returns to oxidation and the pH regulator operation is made oxygenant, reduced widely the outer input of oxygenant; The 3rd, adopt flyash Al～Fe separating technology in the metal hydroxides product preparation process, for Al, the diversification of Fe Chemicals, seriation are laid a good foundation; The 4th, adopt twice dispersion, an isolation technology in the preparation of silicon product, in pH regulator, regular hydrochloric acid solution is regulated and changed the sulphuric acid soln adjusting into simultaneously, in the improving product grade, further reduced the product preparation cost; The 5th, in the preparation of silicon product, contains sodium sulfate overflow clear liquid after silicon product preparation precipitation is used for to gel and pH regulator operation as a dispersion agent, greatly reduce the consumption of NaCl, further save a large amount of process costs.

Embodiment

Each experimental example raw material sources used are as follows:

Flyash: from the Jinchang City thermoelectric power station, its main chemical constitution is in Table 1.

The main chemical constitution of table 1 Jinchang City thermoelectric power station flyash

Sulfuric acid: from certain group company's metallurgical off-gas acid-making chemical plant;

Sodium hydroxide: from certain group company's chemical plant chlor-alkali production system 42% liquid caustic soda;

The oxygenant clorox is from tail chlorine absorption system in certain group company's chemical plant chlor-alkali production system;

NaCl: from certain chemical agent factory; Ethanol: from certain chemical reagent factory; Glycerol: from certain chemical reagent factory.

experiment embodiment 1

1. grind: flyash to shredder is ground to 200 microns down to one, to soak operation;

2. ferro-aluminum extracts:

2.1 one soaks: after 100g is ground, flyash is to beaker, after the consumption that is 1:8 solid-to-liquid ratio water by flyash and 2Mol acidleach solvent ratio again adds 60 ℃ of hot water 700ml, to fill the immigration of liquid beaker is equipped with in the water-bath of water again, add again 100ml 93% vitriol oil under heated and stirred after, in beaker, solution temperature rises rapidly, now by flyash and hydrotropy medicament than after adding 22g anhydrous Na F for the 100:22 weight ratio, under agitation heating leaching is to middle storage 1 operation after 6 hours, and stirring velocity is: 200 rev/mins; The water-bath set temperature is 95 ℃,

2.2 middle storage 1: upper step is equipped with and soaks rear mixed solution beaker and be placed in water-bath after outer standing 10 minutes, can see glass interior lime-ash and clear liquid layering; After its precipitation, clear liquid is placed in another beaker to carry out circulating leaching stand-by in order to soaking operation next time one; After precipitation, underflow to lower step is filtered and washing procedure; After one leaching, the schedule of operation of liquid circulating leaching is: after first middle storage 1 being precipitated to rear clear liquid and a leaching, liquid is as for beaker, add again flyash and solubility promoter under heated and stirred, calculate the required vitriol oil amount of 2Mol acidleach solvent and add the vitriol oil by this amount by immersion liquid spent acid acidometer afterwards; Other condition with last time leached identical;

2.3 filter and washing: underflow to strainer after in upper step 2.1, storage 1 beaker is equipped with precipitation is carried out to solid-liquid separation.Filtrate pack into another beaker to 2.3 crystallization and overflow operation; The rear filter cake of washing is concentrated to 6.1. bis-and soaks operation; Filter cake washing water after repetitive scrubbing is packed another beaker into as xln dissolving water to 2.5 xln dissolution process;

2.4 crystallization and overflow: by one, soak in 2.1 and store up 1 overflowing liquid after six circulating leachings, by upper step 2.2 filtrate to another beaker, after cooling, standing 16 hours, see inner bottom of beaker section have certain thickness crystallization and with the clear liquid layering after, clear liquid is placed in to the beaker that the rear clear liquid of storage 1 precipitation is housed, return to one and soak operation as its acidleach solvent continuation circulating leaching, its working method is identical with the circulating leaching working method.Crystallization underflow in beaker to lower step is filtered and separation circuit;

2.5 filter and separate: upper step precipitation post crystallization body underflow is filtered to strainer, and the filtrate upper step of packing into is equipped with the beaker of clear liquid after crystallization for step 2.4 crystallization and overflow operation; The filter cake xln is to the xln dissolution process;

2.6 xln dissolves: after the crystallization after upper step is filtered is packed in beaker, then by solid-to-liquid ratio 1:3: weight and volume ratio add the washing water after 2.2 filtrations and washing; Continue stirring 20 minutes post crystallization bodies is dissolved in after liquid to 3.1 deacidification process in lower step 3. ironic hydroxide product preparation process;

3. ironic hydroxide product preparation: be that an iron ion soaked in rear solution is prepared into to the ironic hydroxide product;

3. 1 depickling: the solution that upper step 2.5 xln the are dissolved beaker of packing into, under agitation add dry hydrate, after preparing liquid pH and being adjusted to 3.0 to filtering and washing procedures;

3.2 filter and washing: mixed solution to strainer after upper step depickling is carried out to solid-liquid separation.Filtrate is to lower step 3.3 precipitations and overflow operations, and after washing, filter cake is gypsum, the washing water after the filter cake circulation cleaning pack into soak filter after the beaker of filter cake washing water for 2.5 xln dissolution process solvent ingredients waters;

3.3 precipitation and overflow: the liquid beaker of packing into after upper step is filtered has the throw out of one deck white fine particle at the bottom of can seeing after standing 3 hours glass; By clear liquid in cup pack into beaker to 3.4 oxidation and pH regulator operation, underflow to 2.2 filtration and washing procedure after precipitation;

3.4 oxidation and pH regulator: after upper step is filtered, filtrate is packed into after beaker, beaker is moved into and is equipped with in the water-bath of water, after under agitation preparing liquid temp and being heated to 60C, by preparing liquid and oxygenant clorox 100:4 volume ratio adds the oxygenant chlorine bleach liquor, carry out oxidation after 20 minutes, add again 10%NaOH solution, to prepare liquid pH regulator to 4.0, after preparing liquid and taking on a red color, to prepare liquid temp and rise to 80 ℃, and keep temperature to continue to stir after 30 minutes to precipitation and overflow operation;

3.5 precipitation and overflow: by the beaker of packing into of the solution after upper step oxidation and pH regulator, after staticly settling 2 hours, after cup end red precipitate occurring, pour the supernatant liquor after precipitation into another beaker to 4.1 heating up and the pH regulator operations in alumina product preparation technology, after precipitation, underflow to lower step is filtered and washing procedure;

3.6 filter and washing: solid-liquid separation is carried out to strainer in the end after upper step precipitation, and filtrate upper 3.5 steps of packing into are equipped with the beaker of clear liquid, and the rear filter cake of washing is to the ageing operation; Another beaker of packing into after filter cake washing liquid recycles, stand-by in order to next 2.5 xln dissolution process;

3.7 ageing: filter cake after upper step filtration washing is packed into and is equipped with in the beaker of 10%NaOH solution, and after standing 24 hours, extremely lower step is filtered and washing procedure;

3.8 filter and washing: the mixed solution after upper step ageing to strainer is carried out to solid-liquid separation; Filtrate is packed into and is treated next ageing use for the beaker of ageing; After washing, filter cake is packed in container to drying process;

3.9 dry: the container that filter cake will be housed is placed in loft drier and carries out drying, and dried material is to grinding step; The loft drier set temperature is 150 ℃, 1.5 hours time of drying;

3.10 grind: dried material is ground, and after grinding, material is the ironic hydroxide product.

4. alumina product preparation: utilize beaker to be equipped with after step 3.6 precipitations after supernatant liquor carries out the aluminium hydroxide preparation, then prepare alumina product according to the aluminium hydroxide characteristic;

4.1 heat up and pH regulator: the beaker that the rear supernatant liquor of step 3.6 precipitation will be housed is placed in the water-bath that water is housed, under agitation and by after preparing liquid in beaker and being warming up to 60 ℃, add 10%NaOH solution, after preparing liquid pH regulator to 5.3, be heated to 80 ℃, stir after 30 minutes to lower step 4.2 precipitations and overflow operation;

4.2 precipitation and overflow: upper step is equipped with to the beaker for preparing liquid after standing 3 hours, can see in glass interior solution and have throw out to occur, using supernatant liquor after its precipitation pour into another beaker in the silicon product preparation process 6.2 disperse with the gel operation stand-by as a dispersion agent, end liquid to 4.3 filtration and washing procedure after precipitation;

4.3 filter and washing: underflow to strainer after upper step precipitation is carried out to solid-liquid separation. the filtrate upper step of packing into is equipped with the beaker of supernatant liquor; After washing, filter cake is aluminium hydroxide; The filter cake washing water cycle after using extremely; Upper step 2.5 xln dissolves stand-by;

4.4 ageing: by after upper step washing, filter cake is to the beaker that 10%NaOH solution is housed, after standing 24 hours, extremely lower step is filtered and washing procedure;

4.5 filter and washing: underflow to this operation after upper step ageing is carried out to liquid-solid the separation; Filtrate is returned to the beaker of step for ageing; After washing, filter cake is to drying process; Supreme step 2.5 xln of washing water after the filter cake circulation cleaning dissolves stand-by;

4.6 dry: after the container that filter cake will be housed is placed in the loft drier inner drying, material is to grinding step; Drying temperature is 150 ℃, approximately 1.5 hours time of drying;

4.7 grind: dried material is ground, and after grinding, material is alumina product.

5. aluminium fluoride product preparation: the fluoro-gas that utilizes step 2. one to soak middle discharge prepares aluminium fluoride product by the circulation absorption pattern;

5.1 absorb: supernatant liquor 100ml after step 3.5 precipitation and overflow is packed into after absorption bottle, again a vapor pipe soaked on middle beaker top tapered extraction hood is connected with the absorption bottle inlet mouth with silicone tube, one of recycle silicon sebific duct and the absorption bottle mouth of pipe of giving vent to anger is connected, and the pipe connecting other end is connected with the absorption pump inlet mouth.One beginning of night sweating synchronizeed with end and absorption pump start-stop.After absorb finishing, after absorption liquid is carried out soaking and repeats absorption repeatedly next time one, after absorption liquid in absorption bottle to another beaker is carried out after cooling, standing crystallization occurring, by its absorption liquid to 5.2 precipitation and overflow operation;

5.2 precipitation and overflow: by absorption liquid to another beaker in upper step absorption bottle carry out cooling, standing crystallization appears after, pour standing rear supernatant liquor into another beaker and make a supplementary water soaked after middle immersion liquid evaporation, by standing post crystallization underflow to filtering and separation circuit;

5.3 filter and separate: the standing rear underflow of upper step to strainer is carried out to solid-liquid separation. the filtrate upper step of packing into is equipped with the beaker of clear liquid; The filter cake xln is aluminium fluoride product.

6. silicon product preparation: utilize to soak rear siliceous filter residue and prepare the silicon product;

6.1 the silicon stripping is extracted

6.1.1 two soak: after embathing filter cake 100g after washing and put into beaker one, then, after adding 12% NaOH alkali to soak solvent 500ml by solid-to-liquid ratio 1:5, dress liquid beaker is moved in the water-soluble pot that water is housed, under agitation solution in beaker is heated to 95 ^.after C, after leaching 2.5 hours, to lower step;

6.1.2 filter and washing: soak by two that mixed solution is hot carries out solid-liquid separation and filter cake washing down to strainer; Filter cake is first used the hot alkali lye repetitive scrubbing of 500ml, 3%NaOH, and the buck after circulation cleaning stores and continues on for next filter cake washing, and after washing, alkali lye is containing the higher use of solvent ingredients of soaking in order to next two caustic dips up to middle storage 4 beakers of silica concentration; Filter cake reusable heat water repetitive scrubbing after alkali cleaning, the filter cake after circulation cleaning stores discarded; It is identical with alkaline wash that washing water after the circulation cleaning filter cake to middle storage 4 is stored in its beaker effect; After two leachings liquid pack into after beaker to 6.2.1 and disperse and the gel operation;

6.1.3 middle storage 4: the washing water after upper step filter washing water cycle washing are soaked as alkali and soak solvent ingredients water to two after 6.7 filtrations store together with washing water after filter cake circulation in washing procedure;

6.2 silicon product preparation;

6.2.1 disperse and gel: upper step is packed into and two soaked rear filtrate beaker and be placed in water-bath, under agitation in preparing liquid and dispersion agent volume ratio 1:2 ratio adds 8%NaCl dispersion agent 1000ml, its solution is translucent after colloidal solution, after preparing liquid temp and being heated to 60 ℃, heats up and the pH regulator operation to lower step;

6.2.2 heat up and pH regulator: after upper step is prepared to liquid and is heated to 60 ℃, then add 10% sulphuric acid soln, after preparing liquid pH regulator to 7.0 and presenting white emulsus, disperse and heating process to lower step;

6.2.3 disperse and heat up: by the liquid for preparing of upper step, by after preparing liquid and dispersion agent volume ratio 100:8 and adding dispersion agent ethanol 120ml, then isolate and aging process to lower step after preparing liquid temp and rising to 80 ℃;

6.2.4 isolation is with aging: by after preparing liquid and separant volume ratio 100:8 and adding separant glycerol 120ml, continue to stir after 20 minutes to lower step precipitation and overflow operation after upper step is prepared to liquid and is heated to 80 ℃;

6.2.5 precipitation and overflow: after upper step is aging, the beaker of mixed solution is housed from water-bath shifts out, standing 6 hours, after can seeing the throw out of white fine particles, its supernatant liquor is poured another beaker into, as step 6.2.1 dispersion and the dispersion agent in the gel operation, recycle, the underflow after its precipitation to lower step is filtered and washing procedure;

6.2.6 filter and washing: after upper step beaker is equipped with precipitation, underflow to this operation is carried out solid-liquid separation and filter cake washing. filtrate packing into is equipped with after the beaker of clear liquid after precipitation to step 6.2.1 and disperses and the use of gel operation as a dispersion agent ingredients; After washing, filter cake is to drying process; Soak the use of solvent ingredients after the use of filter cake washing water cycle as two caustic dips;

6.2.7 dry: by after upper step washing, filter cake is to Vacuumdrier, set temperature is 80 ℃, and vacuum tightness is :-50pa;

6.2.8 grind: dried material to mill is ground, and its particle diameter of the material after grinding is the superfine white carbon black product lower than 20 microns.

experiment embodiment 2

1. grind: with identical in experiment embodiment 1;

2. ferro-aluminum extracts:

2.1 one soaks: after 100g is ground, flyash is to beaker, after the consumption that is 1:9 solid-to-liquid ratio water by flyash and 3Mol acidleach solvent ratio again adds 60 ℃ of hot water 730ml, again by flyash and hydrotropy medicament than after adding 16g anhydrous Na F for the 100:16 weight ratio, dress liquid beaker is moved into and is equipped with in oily water-bath, add 170ml 93% vitriol oil by aforementioned solid-to-liquid ratio vitriol oil consumption again under heated and stirred after, in reactor, solution temperature rises rapidly, stirring, heating will prepare liquid temp under leaching and be controlled at approximately 120 ℃, continue to leach after 6 hours to middle storage 1 operation, stirring velocity is: 250 rev/mins, in leaching every 1 hour moisturizing 50ml,

2.2 middle storage 1: with identical in experiment embodiment 1;

2.3 filter and washing: with identical in experiment embodiment 1;

2.4 crystallization and overflow: with identical in experiment embodiment 1;

2.5 filter and separate: with identical in experiment embodiment 1;

2.6 xln dissolves: with identical in experiment embodiment 1;

3. ironic hydroxide product preparation a: iron ion soaked in rear solution is prepared into to the ironic hydroxide product;

3. 1 depickling: the solution that upper step 2.6 xln the are dissolved beaker of packing into, under agitation add dry hydrate, after preparing liquid pH and being adjusted to 2.9 to filtering and washing procedures;

3.2 filter and washing: with identical in experiment embodiment 1; After washing, filter cake is that calcium sulfate is gypsum;

3.3 precipitation and overflow: with identical in experiment embodiment 1; After its precipitation, the supreme step 3.2 of underflow is filtered and washing procedure;

3.4 oxidation and pH regulator: after upper step is filtered, filtrate is packed into after beaker, beaker is moved into and is equipped with in the water-bath of water, after under agitation preparing liquid temp and being heated to 60 ℃, by preparing liquid and oxygenant clorox 100:10 volume ratio adds the oxygenant chlorine bleach liquor, carry out oxidation after 20 minutes, then add 10%NaOH solution, after preparing liquid pH regulator to 4.0, after preparing liquid and taking on a red color, will prepare liquid temp and rise to 80 ^.c, keep temperature to continue to stir after 20 minutes to precipitation and overflow operation;

3.5 precipitation and overflow: with identical in experiment embodiment 1;

3.6 filter and washing: with identical in experiment embodiment 1;

3.7 ageing: with identical in experiment embodiment 1;

3.8 filter and washing: with identical in experiment embodiment 1;

3.9 dry: the container that filter cake will be housed is placed in loft drier and carries out drying, and dried material is to grinding step; The loft drier set temperature is 100 ^.c, approximately 2.0 hours time of drying;

3.10 grind: dried material is ground, and after grinding, material is the ironic hydroxide product;

4. alumina product preparation: with identical in experiment embodiment 1;

4.1 heat up and pH regulator: the beaker that the rear supernatant liquor of step 3.6 precipitation will be housed is placed in the water-bath that water is housed, under agitation and by after preparing liquid in beaker and being warming up to 65 ℃, add 10%NaOH solution, after preparing liquid pH regulator to 5.3, continuous heating to 80 ℃ stirs after 20 minutes to lower step precipitation and overflow operation;

4.2 precipitation and overflow: with identical in experiment embodiment 1;

4.3 filter and washing: with identical in experiment embodiment 1;

4.4 ageing: with identical in experiment embodiment 1;

4.5 filter and washing: with identical in experiment embodiment 1;

4.6 dry: after the beaker that filter cake will be housed is placed in the loft drier inner drying, material is to grinding step; Drying temperature is 100 ℃, 2.0 hours time of drying;

4.7 grind: with identical in experiment embodiment 1.

5. aluminium fluoride product preparation: with identical in experiment embodiment 1; The filter cake xln is aluminium fluoride product;

6.1 the silicon stripping is extracted

6.1.1 two soak: after embathing filter cake 100g after washing and put into beaker one, then, after adding 12% NaOH alkali to soak solvent 400ml by solid-to-liquid ratio 1:4, will fill the liquid beaker and move on hot plate, and under agitation solution heating in beaker will be controlled at approximately to 100 ^.after C, after leaching 2.0 hours, to lower step filtration and washing procedure; Supplemented hot water 50ml every 1 hour to immersion liquid;

6.1.2 filter and washing: carry out solid-liquid separation and filter cake washing down to strainer by liquid after two leachings is hot.Filter cake is first used the hot alkali lye repetitive scrubbing of 500ml, 1%NaOH, and the buck after circulation cleaning stores and continues on for next filter cake washing, soaks the use of solvent ingredients when alkali lye is higher containing silica concentration after washing in order to next two caustic dips; Filter cake reusable heat water repetitive scrubbing after alkali cleaning, after circulation cleaning, filter cake stores discarded; It is identical with alkaline wash that washing water after the circulation cleaning filter cake are stored in another beaker effect; After two leachings liquid pack into after beaker to 6.2.1 and disperse and the gel operation;

6.1.3 middle storage 4: with identical in experiment embodiment 1;

6.2 silicon product preparation;

6.2.1 disperse and gel: upper step is packed into and two soaked rear filtrate beaker and be placed in water-bath, under agitation in preparing liquid and dispersion agent volume ratio 1:3 ratio, add in experiment embodiment 1 in step 6.2.5 precipitation and overflow operation supernatant liquor 1200ml after precipitation, now solution is translucent after colloidal solution, after under agitation preparing liquid temp and being heated to 65 ℃ to heating up and the pH regulator operation;

6.2.2 heat up and pH regulator: with identical in experiment embodiment 1;

6.2.3 disperse and heat up: completing steps 6.3 heat up with pH regulator after again by after preparing liquid and dispersion agent volume ratio 100:8 and adding dispersion agent ethanol 128ml, then will prepare liquid temp and rise to after 80C to isolating and aging process;

6.2.4 isolation is with aging: upper step is prepared to liquid and be heated to 80 ^.after C, by after preparing liquid and separant volume ratio 100:8 and adding separant glycerol 128ml, continue to stir after 20 minutes to precipitation and overflow operation;

6.2.5 precipitation and overflow: with identical in experiment embodiment 1;

6.2.6 filter and washing: with identical in experiment embodiment 1; After washing, filter cake is to drying process; Soak the use of solvent ingredients after the use of filter cake washing water cycle as two caustic dips;

6.2.7 dry: by after upper step washing, filter cake is to Vacuumdrier, set temperature is 80 ^.c, vacuum tightness is :-100pa;

6.2.8 grind: with identical in experiment embodiment 1.

experiment embodiment 3

1. grind: with identical in experiment embodiment 1;

2. ferro-aluminum extracts:

2.1 one soaks: 100g is ground to rear flyash to beaker, then the consumption that is 1:10 solid-to-liquid ratio water by flyash and 4Mol acidleach solvent ratio adds 60 ^.after C hot water 770ml, to fill the immigration of liquid beaker is equipped with in oily water-bath again, add 230ml 93% vitriol oil under heated and stirred after, in beaker, solution temperature rises rapidly, now by flyash and hydrotropy medicament than after adding 22g anhydrous Na F for the 100:22 weight ratio, under agitation heating leaching is to middle storage 1 operation after 6 hours, and stirring velocity is: 230 rev/mins; The water-bath set temperature is 120 ℃;

2.2 middle storage 1: with identical in experiment embodiment 1;

2.3 filter and washing: with identical in experiment embodiment 1;

2.4 crystallization and overflow: with identical in experiment embodiment 1;

2.5 filter and separate: with identical in experiment embodiment 1;

2.6 xln dissolves: after the crystallization after upper step is filtered is packed in beaker, again by solid-to-liquid ratio 1:5: weight and volume ratio, add step 2.3 filter with washing after washing water, continue to stir 20 minutes post crystallization bodies and be dissolved in after liquid to step 3.1 deacidification process in lower step 3. ironic hydroxide product preparation process;

3.1 depickling: the solution that upper step 2.6 xln the is dissolved beaker of packing into, under agitation add dry hydrate, after preparing liquid pH and being adjusted to 2.8 to filtering and washing procedures;

3.2 filter and washing: with identical in experiment embodiment 1;

3.3 precipitation and overflow: with identical in experiment embodiment 1;

3.4 oxidation and pH regulator: after upper step is filtered, filtrate is packed into after beaker, beaker is moved into and is equipped with in the water-bath of water, after under agitation preparing liquid temp and being heated to 70 ℃, by preparing liquid and oxygenant clorox 100:6 volume ratio adds the oxygenant chlorine bleach liquor, carry out oxidation after 20 minutes, add again 10%NaOH solution, after preparing liquid pH regulator to 4.0, after preparing liquid and taking on a red color, to prepare liquid temp and rise to 80 ℃, and keep temperature to continue to stir after 20 minutes to precipitation and overflow operation;

3.5 precipitation and overflow: with identical in experiment embodiment 1;

3.6 filter and washing: with identical in experiment embodiment 1;

3.7 ageing: with identical in experiment embodiment 1;

3.8 filter and washing: with identical in experiment embodiment 1;

3.9 dry: the container that filter cake will be housed is placed in loft drier and carries out drying, and dried material is to grinding step; The loft drier set temperature is 200 ℃, approximately 1.0 hours time of drying;

3.10 grind: with identical in experiment embodiment 1.

4.1 heat up and pH regulator: the beaker that the rear supernatant liquor of step 3.6 precipitation will be housed is placed in the water-bath that water is housed, under agitation and by after preparing liquid in beaker and being warming up to 70 ℃, add 10%NaOH solution, after preparing liquid pH regulator to 5.3, continuous heating to 80 ℃ stirs after 20 minutes to lower step 4.2 precipitations and overflow operation;

4.2 precipitation and overflow: identical with experiment embodiment 1;

4.3 filter and washing: with identical in experiment embodiment 1;

4.4 ageing: with identical in experiment embodiment 1;

4.5 filter and washing: with identical in experiment embodiment 1;

4.6 dry: after the beaker that filter cake will be housed is placed in the loft drier inner drying, material is to grinding step; Drying temperature is 200 ℃, approximately 1.0 hours time of drying;

4.7 grind: with identical in experiment embodiment 1.

5. aluminium fluoride product preparation: with identical in experiment embodiment 1;

6. silicon product preparation: utilize one to soak rear siliceous filter residue and prepare the silicon product,

6.1 the silicon stripping is extracted

6.1.1 two soak: after embathing filter cake 100g after washing and put into beaker one, after adding 12% NaOH alkali to soak solvent 800ml by solid-to-liquid ratio 1:8 again, dress liquid beaker is moved into and is equipped with in oily water-bath, after under agitation solution in beaker being heated to 120 ℃, leach after 2.0 hours, to lower step filtration and washing procedure;

6.1.2 filter and washing: carry out solid-liquid separation and filter cake washing down to strainer by liquid after two leachings is hot.Filter cake is first used the hot alkali lye repetitive scrubbing of 500ml, 2%NaOH, and the buck after circulation cleaning stores and continues on for next filter cake washing, soaks the use of solvent ingredients when alkali lye is higher containing silica concentration after washing in order to next two caustic dips; Filter cake reusable heat water repetitive scrubbing after alkali cleaning, follow the rear filter cake of washing and store discarded; It is identical with alkaline wash that washing water after the circulation cleaning filter cake to middle storage 4 is stored in another beaker effect; After two leachings liquid pack into after beaker to 6.2 dispersions and gel operation;

6.2 silicon product preparation;

6.2.1 disperse and gel: upper step is packed into and two soaked rear filtrate beaker and be placed in oil bath pan, under agitation in preparing liquid and dispersion agent volume ratio 1:2.5 ratio, add step 6.2.5 precipitation to make dispersion agent 2000ml with overflow operation supernatant liquor, its solution is translucent after colloidal solution, after preparing liquid temp and being heated to 70 ℃, heats up and the pH regulator operation to lower step;

6.2.2 heat up and pH regulator: with identical in experiment embodiment 1;

6.2.3 disperse and heat up: by the liquid for preparing of upper step, by after preparing liquid and dispersion agent volume ratio 100:2.5 and adding dispersion agent ethanol 70ml, then will prepare liquid temp and rise to 80 ^.after C, extremely isolate and aging process;

6.2.4 isolation is with aging: upper step is prepared to liquid and be heated to 80 ^.after C, by after preparing liquid and separant volume ratio 100:4 and adding separant glycerol 100ml, continue to stir after 20 minutes to precipitation and overflow operation;

6.2.5 precipitation and overflow: after upper step is aging, the beaker of mixed solution is housed from water-bath shifts out, standing 6 hours, after can seeing the throw out of white fine particles, pour supernatant liquor into another beaker, as step 6.2.1 dispersion and the dispersion agent in the gel operation, recycle, the underflow after its precipitation to lower step is filtered and washing procedure;

6.2.6 filter and washing: after upper step beaker is equipped with to precipitation, underflow to this operation is carried out solid-liquid separation and filter cake washing. filtrate packing into is equipped with after the beaker of clear liquid after precipitation to step 6.2.1 and disperses the use with a dispersion agent ingredients of gel operation; After washing, filter cake is to drying process; The use that the filter cake washing water cycle is soaked solvent as two caustic dips after using;

6.2.7 dry: by after upper step washing, filter cake is to Vacuumdrier, set temperature is 80 ℃, and vacuum tightness is :～-50pa;

Claims

1. a method of producing superfine white carbon black and ironic hydroxide, aluminum oxide with flyash is characterized in that: take flyash as raw material, take sulfuric acid, caustic soda soln is solvent; By flyash through grinding, the acidleach of one section heating hydrotropy, filter and wash; Gained filtrate is for the preparation of ironic hydroxide and aluminum oxide; One soaks the rear gained filter cake of filtration for the preparation of superfine white carbon black; Concrete steps comprise:

A. grind: flyash is ground to powder below 200 microns through shredder;

B.1 one section heating hydrotropy acidleach: leach first by acidleach solvent strength 2～4Mol water distribution quantity by 60 ℃ of hot water to leaching kettle, under heated and stirred again by flyash: acidleach solvent solid-to-liquid ratio is after 1:8～10 add flyash, joining sulfuric acid amount by acidleach solvent strength 2～4Mol again adds the vitriol oil to after in leaching kettle, again by flyash: the hydrotropy medicament is solid: Gu, after weight ratio 100:16～22 add hydrotropy medicament NaF, continuous heating stirs after 4～6 hours and store up 1 to insulation;

All adopt afterwards circulating leaching, in being about in the discharge of storage 1 or B5 crystallization and overflow operation overflowing liquid add the vitriol oil to be mixed with and leach first isoconcentration acidleach solvent and heated the hydrotropy leaching; Its operation steps: first overflowing liquid after middle storage 1 precipitation, to reactor, add solubility promoter and flyash under heated and stirred after, then is added and the vitriol oil that last time leached isoconcentration acidleach solvent ingredients consumption; Other condition with last time leached identical; Processing condition: 200～250 rev/mins of stirring velocitys, one soaks 95～120 ℃ of Heating temperatures;

B.2 insulation stores 1: by the mixed solution after acidleach, to the taper insulation hold-up vessel that is provided with overflow, B.3 the underflow after settlement on storage to step is filtered and is washed; After precipitation, the overflow clear liquid adds the vitriol oil and is mixed with one and soaks isoconcentration acidleach solvent and return to step and B.1 one soak;

B.4 insulation stores 2: the washing water after the filter cake circulation cleaning to insulated tank is stored, is respectively used to a B.1 supplementary water soaked after middle immersion liquid evaporation of step, when aluminium-iron level higher up to step C.1.1 xln dissolve water;

B.6 filter and separate: by step B.6 gained crystallization underflow to this operation filter and separate, filter the post crystallization body to step C.1 aluminium-iron separate, filtrate is to B.5 crystallization and overflow of step; Store up 2 after equipment and the recycle of facility washing water in B.4;

C. aluminium-iron separation and aluminium, iron product preparation;

C.1 aluminium-iron separates: the aluminium in xln is separated with iron;

C.1.1 xln dissolves: B.6 step is filtered to post crystallization body to heated and stirred and disclose, add the washing water in middle storage 2 by xln and aqueous solvent solid-to-liquid ratio 1:2～5 afterwards, under agitation be heated to 25 ℃ and make to obtain solution after the xln dissolving; 200～250 rev/mins of stirring velocitys;

C.3.7 dry: by upper step, C.3.5 the gained washing leaching cake is dry under 100～200 ℃ of temperature, 60～120 minutes time condition, obtains dried material;

C.3.8 grind: after dried material to shredder is ground, be alumina product;

D.1 the silicon stripping is extracted

D.1.1 two sections add thermokalite and soak: the filter cake that this operation is used comes from step and B.3 filters and wash; Soak weight of solvent by filter cake and alkali during leaching: volume ratio is that 1:3～8 are to reactor; It is concentration 12%～16%NaOH that alkali soaks solvent; Alkali soaks the solvent compound method two kinds, and corresponding, two leaching methods are: one; With the commodity liquid caustic soda, prepare: the NaOH liquid caustic soda by 32% or 42% adds water and is mixed with 12%～16%NaOH, after the alkali prepared soaks solvent and is heated to 90 ℃, under heated and stirred, filter cake is added to reactor, after being heated to 95 ℃～120 ℃, continuous heating stirs 2.5 hours, to in its still, two soak that mixed solution is hot stores up 3,200～250 rev/mins of stirring velocitys in D.1.2 lower step is incubated afterwards; They are two years old; With the commodity solid caustic soda, prepare: by filter cake: alkali soaks its weight of solvent: the water yield that the alkali that volume ratio is 1:3～8 soaks the required use of solvent by 60 ℃ of hot water to reactor, under heated and stirred, filter cake is added to reactor, after the solid caustic soda amount of soaking the required use of solvent 12%～16%NaOH by preparation alkali again adds solid state N aOH, after being heated to 95 ℃～120 ℃, continuous heating stirs 2.5 hours, to in its still, two soak that mixed solution is hot stores up 3,200～250 rev/mins of stirring velocitys in D.1.2 lower step is incubated afterwards; Weight: volume ratio is g:ml or Kg:L or t:m ³;

D.1.2 in the insulation, storage 3(stores up 3 in being called for short): by upper step D.1.1 two soak mixed solution to middle storage 3 be incubated store after extremely lower step D.1.3 filter and wash;

D.2 silicon product preparation

D.2.2 heat up and pH regulator: by upper step prepare liquid 60 ℃ of heat tracings, under stirring, add mass percent concentration be 10% sulphuric acid soln regulate prepare liquid pH to 7.0 after to lower step;

D.2.8 dry: by upper step, D.2.6 the gained washing leaching cake is dry under 80 ℃ of temperature, 60～120 minutes time condition, obtains dried material;

2. a kind of method of producing superfine white carbon black and ironic hydroxide, aluminum oxide with flyash as claimed in claim 1 characterized by further comprising following step:

E.5 dry: upper step e .4 gained filter cake is dry under 80 ℃ of temperature, 60～120 minutes time condition, obtain dried material;