CN1850617A - Method for producing titanium pigment using blast-furnace slag capable of recovering other resources - Google Patents
Method for producing titanium pigment using blast-furnace slag capable of recovering other resources Download PDFInfo
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- CN1850617A CN1850617A CNA2006100208382A CN200610020838A CN1850617A CN 1850617 A CN1850617 A CN 1850617A CN A2006100208382 A CNA2006100208382 A CN A2006100208382A CN 200610020838 A CN200610020838 A CN 200610020838A CN 1850617 A CN1850617 A CN 1850617A
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Abstract
The invention is a method for producing titanium dioxide with blast furnace slag, able to recover other resources, firstly using circulating acid to make selective primary acid hydrolysis on Al, Mg and other components in the blast furnace slag, then using sulphuric acid to make secondary acid hydrolysis on secondary slag, making solid-liquid separation, where solid phase is silicon-titanium plaster as building material, water is added to liquid phase to make hydrolytic crystallization reaction, and the crystallized phase is metatitanic acid. Before the procedure of hydrolytic crystallization reaction of the liquid acid, it can perform electromagnetic wave excited radiation on liquid phase pulp in the acid hydrolysis course or after the acid hydrolysis reaction. After dehydrolyzed, filtered and washed, the crystallized metatitanic acid is thermally refined with salt processing agent and then burnt at high temperature to make the pigment-level titanium oxide. By further processing, the liquid phase obtained by primary acid hydrolysis can recover aluminum resources in aluminium ammonium sulfate form, and recover magnesium resources in magnesium hydroxide form so that precious resources are completely recovered from the blast furnace slag.
Description
One, technical field
The present invention relates to smelting iron and steel blast furnace slag resource recovery technology, more particularly, relate to the processing method that titanium resource in a kind of smelting iron and steel titanium-containing blast furnace slag and other resource comprehensive are recycled.
Two, background technology
Titanium is one of main component of climbing western vanadium titano-magnetite, accounts for 86% of national total reserves.Titanium in the vanadium titano-magnetite about 50% enters iron ore concentrate by ore dressing, is enriched in the blast furnace slag behind blast furnace smelting and drains.Blast furnace slag contains CaO28.80%, SiO
224.16%, V
2O
50.25%, TiO
222.56%, S 0.49%, Al
2O
313.31%, MgO 7.49%, finds that through X-ray diffraction the titaniferous composition mainly is made up of uhligite and titanaugite.Climb the blast furnace slag of storing up steel thing slag field at present and reached more than 6,000 ten thousand tons, and increase with annual 3000000 tons speed.Because of the slag stockyard progressively enlarges, not only polluted Jinsha jiang River of Upper Yangtze River, injured the riverbed and the peripheral ecotope in Jinsha jiang River, become serious environmental problem.Titanium in the comprehensive reutilization Flos Bombacis Malabarici vanadium titano-magnetite and other precious resources are realized sustained economic development and are preserved the ecological environment, and have great economic benefit and social benefit.
Steel climbing high slag is mainly used to use as material of construction at present, and a large amount of noble elements that it is contained such as titanium etc. all fail to be fully used.Titanium-containing blast furnace slag generally contains TiO
2About 20-25% also contains essences such as silicon, calcium, vanadium, aluminium, sulphur in addition.The wherein existence of calcium, aluminium, magnesium has material impact to the recovery technology of titanium, but also is available valuable source simultaneously.Domestic more existing units have carried out a large amount of research work to extract titanium from blast furnace slag, and some achievements in research have been obtained, but achievement in research is owing to the Financial cost of extracting titanium from blast furnace slag is too high mostly, and in the blast furnace slag contained a large amount of other elements to extracting the restriction of titanium, cause the treating processes of from blast furnace slag, extracting titanium very difficult, thereby fail to realize industrialization.The present inventor has carried out going deep into systematic research to processes such as the composition of steel climbing high slag, acidolysis, hydrolysis, having finished on this basis is the processing method of the rich titanium material of raw material production with the steel climbing high slag, but obtained the breakthrough achievement of suitability for industrialized production, the technological achievement that the application's applicant finishes has at this point proposed application for a patent for invention to Patent Office of the People's Republic of China, and application number is 200510021390.1.But this application has only been recycled valuable titanium resource in the blast furnace slag and silicon, calcium resource, and other precious resources such as contained aluminium, magnesium do not obtain recycling in the blast furnace slag.
Three, content of the present invention:
Deficiency at the titanium-containing blast furnace slag resource recycling Technology of prior art, recyclable other resource of blast furnace slag that the present invention proposes be the method for raw material production titanium dioxide with the titanium-containing blast furnace slag, when producing titanium dioxide, can also distinguish or solve following technical problem simultaneously with titanium-containing blast furnace slag:
1, with the bauxite resource in the form recovery titanium-containing blast furnace slag of exsiccated ammonium alum, exsiccated ammonium alum can be used as flocculation agent and produces the material of aluminum products;
2, with the magnesium resource in the form recovery titanium-containing blast furnace slag of magnesium hydroxide, magnesium hydroxide can be used as fire retardant;
3, with silicon titanium gypsum form reclaim silicon, calcium and a spot of titanium in the titanium-containing blast furnace slag, as the raw material of novel wall material;
4, make the sulfur waste acid in the Cornstarch production process be able to recycling.
Main thought of the present invention is according to the composition of titanium-containing blast furnace slag and the difficulty or ease of reaction, by sulfuric acid blast furnace slag is carried out selective reaction and isolate aluminium, magnesium, titanium component one by one with different concns, the reaction residues that contains silicon and a little amount of titanium is a titanium silica cream, can use for material of construction.By implementing the electromagnetic wave excites radiation, promote the selective reaction and the enhanced hydrolysis process of blast furnace slag, thereby obtain higher titanium yield simultaneously, become rich titanium material or titanium dioxide through calcining.
The above-mentioned technical problem that the present invention will solve can be by having following technical scheme the titanium-containing blast furnace slag of recyclable other resource of the slag method of producing titanium dioxide realize:
The method with titanium-containing blast furnace slag production titanium dioxide of recyclable other resource of slag mainly comprises following processing step:
1, granularity is that 80-200 purpose titanium-containing blast furnace slag weight concentration is that 3%-25% sulfuric acid carries out optionally preliminary acidolysis reaction to aluminium, magnesium under 55~80 ℃ of conditions, fully behind the acidolysis reaction slip is carried out solid-liquid separation, enter next process respectively as the solid phase and the liquid phase of secondary slag;
2, the solid phase secondary slag concentration that preliminary hydrolysis procedure 1 solid-liquid separation is obtained is that 25%-60% sulfuric acid carries out the secondary acidolysis reaction under 80~120 ℃ of conditions, the acidolysis slip is through solid-liquid separation, the gained solid phase is titanium silica cream, and liquid phase enters down hydrolyzing process one;
3, in the liquid phase of secondary hydrolysis procedure 2 gained, add the entry crystallization reaction that under 100~115 ℃ condition, is hydrolyzed, the crystallization reaction precipitated phase is the hydrate metatitanic acid of titanium, fully behind the hydrolysis crystallization reaction metatitanic acid is separated, metatitanic acid enters next process;
4, the liquid phase slip that enters before the hydrolysis crystallization reaction operation is implemented the electromagnetic wave excites radiation;
5, hydrolysis crystallization reaction operation 3 is separated the metatitanic acid that obtains after the dehydration washing, carries out modifier treatment with the salt treatment agent.Described salt treatment agent can be selected from salt of wormwood, Tai-Ace S 150, TiO
2At least a in colloidal sol and the phosphoric acid etc.;
6, the metatitanic acid after salt is handled is calcined under 800~1100 ℃, makes the finished product titanium dioxide;
7, preliminary hydrolysis procedure 1 separating obtained liquid phase is successively implemented following treatment process respectively separately or jointly:
(1) adds aluminium and deviate from agent and the reactive aluminum generation aluminium ammonium sulfate that enters liquid phase, through solid-liquid separation, dry preparation exsiccated ammonium alum product; Aluminium is deviate from agent can be ammonium sulfate, ammonia etc.
(2) add entry and be warming up to the boiling point reaction that is hydrolyzed, the titanium crystallization that enters liquid phase is separated out, prepare rich titanium material product through solid-liquid separation, drying, calcining;
(3) add alkali and generate magnesium hydroxide, through solid-liquid separation, dry preparation magnesium hydroxide products with the reactive magnesium that enters liquid phase.Described alkali alkali can be selected from least a in sodium hydroxide, potassium hydroxide, the ammoniacal liquor etc.
In such scheme, operation 1 is for a procedure that reclaims components such as aluminium in the titanium-containing blast furnace slag, magnesium and design, and is preliminary acidolysis reaction operation.This operation vitriolic consumption depends on components contents and sulfuric acid concentrations such as aluminium in the blast furnace slag, magnesium.The vitriolic consumption at least should be able to be with the blast furnace slag submergence, makes components such as aluminium in the blast furnace slag, magnesium can be dissolved in sulfuric acid fully.Be generally 1~5 times of blast furnace slag consumption.The acidolysis reaction time is depended on the granularity and the processing requirement of the distribution of components such as vitriolic concentration, temperature of reaction, magnalium and content, blast furnace slag, so that components such as the aluminium in the blast furnace slag, magnesium are dissolved in sulfuric acid fully.The acidolysis reaction time is generally 20~90min.The granularity of blast furnace slag generally is controlled to be about 0.08~0.18mm (200~80 order), preferably wherein 80% granularity less than 180 orders.
In such scheme, acidolysis reaction operation 2 is basic working procedure of present method, be in order to reclaim the titanium component in the titanium-containing blast furnace slag, the vitriolic consumption depends on the content and the sulfuric acid concentration of the titanium component in the blast furnace slag, at least should be able to be with the isolated solid phase submergence of preliminary acidolysis reaction operation as the secondary slag, make titanium in the blast furnace slag etc. can be dissolved in sulfuric acid fully, be generally 1~5 times of blast furnace slag consumption.The acidolysis reaction time is depended on the distribution and the content of vitriolic concentration, temperature of reaction, titanium component, and processing requirement, so that the titanium component in the blast furnace slag is dissolved in sulfuric acid fully.The acidolysis reaction time is generally 60~120min.
In the hydrolysis reaction operation of such scheme, how many add-ons of water depends primarily on the concentration of titanium component in the liquid phase, separates out and is as the criterion so that titanium component is able to crystallization fully in the more rational time.The add-on of water can not produce very big influence to technology.The add-on of water by weight, is generally liquid phase 50%~400%.
In such scheme, the liquid phase slip is implemented the electromagnetic wave excites radiation, enter hydrolysis crystallization reaction operation from preliminary hydrolysis procedure 1 to the acidolysis slip before arbitrary to the radiation of titaniferous liquid phase slip enforcement electromagnetic wave excites, both can in the acidolysis reaction process, implement the electromagnetic wave excites radiation, as being to implement the electromagnetic wave excites radiation when 3%-25% sulfuric acid carries out preliminary acidolysis reaction to titanium-containing blast furnace slag under 55~80 ℃ of conditions with concentration, also can implement the electromagnetic wave excites radiation to the acidolysis slip behind the acidolysis reaction, as be 25%-60% sulfuric acid with concentration under 80~120 ℃ of conditions to the radiation of the enforcement of the slip behind secondary slag acidolysis reaction electromagnetic wave excites.The hertzian wave of being implemented, its frequency can be 0.1~7.0GH, and yield of radiation can be 1000~3200KW/cm
3
In such scheme, if the electromagnetic wave excites radiation is to implement when carrying out preliminary acidolysis reaction, because the electromagnetic wave excites radiation titanium component that can suppress in the blast furnace slag enters liquid phase, therefore to the separating obtained liquid phase of operation 1 can be respectively separately or successively implement following operation and further handle jointly:
A, adding ammonium sulfate generate aluminium ammonium sulfate with the reactive aluminum that enters liquid phase, prepare the exsiccated ammonium alum product through solid-liquid separation, drying;
B, adding sodium hydroxide generate magnesium hydroxide with the reactive magnesium that enters liquid phase, prepare magnesium hydroxide products through solid-liquid separation, drying.
Liquid phase is handled, also fewer when the magnesium component that enters liquid phase, when not reclaiming the magnesium component, can only implement treatment process a, on the contrary also fewer when the al composition that enters liquid phase, when not reclaiming al composition, can only implement treatment process b.To being the raw material production Cornstarch with the steel climbing high slag, normally two operations are all implemented, perhaps earlier liquid phase is implemented treatment process a, again the isolated liquid phase of treatment process a is executed treatment process b, perhaps earlier liquid phase is implemented treatment process b, the more isolated liquid phase of treatment process b is executed treatment process a.
If the electromagnetic wave excites radiation is to implement after preliminary acidolysis reaction finishes, before entering hydrolysis crystallization reaction operation, implement at the acidolysis slip, when blast furnace slag carries out preliminary acidolysis reaction, titanium component in the blast furnace slag is understood the liquid phase that enters of some, therefore, operation 1 separating obtained liquid phase is successively implemented treatment process a and the b except that distinguishing separately or jointly, also need the titanium that enters liquid phase is implemented recycling, promptly by adding entry to liquid phase and being warming up to boiling point, the titanium crystallization that enters liquid phase is separated out, through solid-liquid separation, dry, rich titanium material product is prepared in calcining.
In such scheme, the hydrate metatitanic acid of the titanium of the hydrolysis crystallization reaction being separated out with treatment agent carries out salt to be handled, to improve the product quality of titanium dioxide, the time of carrying out the salt processing is relevant with the product quality requirement of titanium dioxide, and the time that salt is handled generally is no less than 60min.
Hydrolysis crystallization reaction operation 3 at such scheme, the hydrolysis crystallization reaction be after the liquid phase of solid-liquid separation gained can turn back to it preliminary acidolysis reaction operation, or recycles as secondary acidolysis sulfuric acid after concentrating, this had both recycled the sulfuric acid resource, had avoided the pollution to environment again.
At the calcination process 6 of such scheme, will insert calcining furnace through the metatitanic acid after the salt treatment agent is handled and under 800~1100 ℃, calcine, the incinerating time is relevant with the incinerating temperature, generally all is no less than 60min.
The present invention has also taked some other technical measures.
Blast furnace slag generally contains the about 20-25% of TiO2, also contains essences such as silicon, calcium, vanadium, aluminium, sulphur in addition.The wherein existence of calcium, aluminium, magnesium, not only the recovery technology to titanium has material impact, and is available valuable source.Produce the method for titanium dioxide with titanium-containing blast furnace slag disclosed by the invention blast furnace slag is handled, its contained aluminium is reclaimed with the form of exsiccated ammonium alum, and exsiccated ammonium alum can be used as flocculation agent and produces the material of aluminum products; Contained magnesium is reclaimed with the form of magnesium hydroxide, and magnesium hydroxide can be used as fire retardant; Contained silicon, calcium are reclaimed with the form of titanium silica cream, and titanium silica cream can be used as the raw material of novel wall material; Contained titanium is then reclaimed with the form of rich titanium material, pigment-level titanium dioxide or non-pigment-level titanium dioxide, and titanium dioxide is a kind of industrial raw material of having many uses.Adopt method of the present invention that titanium-containing blast furnace slag is handled, make blast furnace slag obtain utilizing fully, realized the resource utilization of discarded blast furnace slag to greatest extent, protected environment simultaneously.The present invention reclaims calcium, aluminium, magnesium simultaneously comprehensively, has also realized useless vitriolic recycling, for better condition has been created in the extraction of titanium.
Project | Consumption (t) | Unit price (unit/t) | The amount of money (unit) |
1. titanium dioxide | |||
Sulfuric acid (98%) | 4.2 | 350 | 1470 |
Electricity | 247kWh | 0.45 | 111 |
Coal | 1.6 | 260 | 416 |
Labour cost | 108 | ||
Depreciation | 150 | ||
Expense | 50 | ||
Add up to | 2305 | ||
2. exsiccated ammonium alum | |||
Consume the sulphur ammonium | 1 | 800 | 800 |
The by-product exsiccated ammonium alum | 4.7 | 300 | -1410 |
3. magnesium hydroxide | |||
Consume sodium hydroxide | 0.1 | 2000 | 200 |
Coproduct hydrogen magnesium oxide | 0.16 | 4000 | -640 |
4. materials for wall | |||
Depreciation and expense | 150 | ||
The high strength walling | 4.7m 3 | 120 | -564 |
The comprehensive utilization total cost | 841 |
The present invention also has very high economic benefit except having the huge social benefit.Produce titanium dioxide with method of the present invention with blast furnace slag, its cost depends primarily on the vitriolic consumption, but sulfuric acid can be recycled, and maybe can adopt the spent acid of existing sulfuric acid method titanium pigment factory to produce.One ton of titanium dioxide of every production consumes 4.2 tons of sulfuric acid approximately, and its production cost estimation ginseng sees the above table.As seen from the above table, the cost of producing one ton of titanium white is about 841 RMB, and 9800 yuan/ton of anatase pigmentary titanium dioxide prices on the market, the benefit of one ton of anatase pigmentary titanium dioxide of every production is 8900 yuan.This shows that processing method disclosed by the invention by having formed a benign recycling economy system after fully utilizing, also has very big economic benefit except having very high social benefit.Set up one and produce 10000 tons the titanium dioxide and the ecological Industrial Area of multiple product per year, about 1,500 ten thousand yuan of facility investment, annual value of production reaches 1.22 hundred million yuan.Profits tax can reach 100,000,000 yuans.If do not consider comprehensive utilization, then the profits tax of pigment-level titanium dioxide also can reach 7,000 ten thousand yuans.
Four, description of drawings
Accompanying drawing 1 is one embodiment of the present of invention technical process schematic block diagram.
Accompanying drawing 1 is an alternative embodiment of the invention technical process schematic block diagram.
Five, embodiment
The present invention is further illustrated below in conjunction with embodiment.In following each present embodiment, except that specifying, concentration is weight concentration, and per-cent all is weight percentage, and umber is parts by weight.
Embodiment 1.
The technical process of present embodiment as shown in Figure 1.
(1) contains TiO
2Be about 100 parts of 22% steel climbing high slags, granularity is 0.08~0.18mm, inserts in No. 1 groove acidolysis reaction device, adds concentration and is about 220 parts in 12% sulfuric acid, carries out preliminary acidolysis reaction under about 65 ℃, reacts about 120min.In the reaction process, use the hertzian wave exciting radiation, about 5 minutes of radiated time, intensity is about 2500KW/m
3, frequency is about 5.45GH.
(2) preliminary acidolysis reaction is finished after behind the whizzer separating, washing, liquid phase enters reactive tank No. 2, adds ammonium sulfate and sloughs aluminium, and the add-on of sulphur ammonium is by the cubage decision of aluminium.Post precipitation is through the vacuum filter filtration washing, and drying is about 1 hour under about 70 ℃, obtains the exsiccated ammonium alum product.
(3) operation (2) filtration washing clear liquid enters reactive tank again No. 3, adjusts the pH value with sodium hydroxide and is about 9 (the pH setting range is 8~14), and crystalline deposit is after about 12 hours, after filtration, drying obtains industrial magnesium hydroxide, can be used as flame retardant products.
(4) the secondary slag that is obtained by the preliminary acidolysis reaction of operation (1) is sent into the acidolysis reaction groove again No. 4, is about 50% sulfuric acid with concentration, is about in temperature under 80 ℃ the condition to carry out the secondary acidolysis reaction, and the time is about 120min.Slip after the acidolysis after filtration and the washing, the residue obtained titanium silica cream that is can be made high-intensity building materials.
(5) operation (4) filtration washing clear liquid enters the hydrolysis reaction groove No. 5, adds 150 parts of entry, the crystallization reaction that under the condition about 108 ℃, is hydrolyzed, and the hydrate metatitanic acid of titanium is separated out in crystallization.About about 3 hours of hydrolysis crystallization reaction is dewatered and is washed by vacuum filter, sends into next process and handles.
(6) slip after dehydration washing is sent into the salt treatment trough and is carried out modifier treatment, and the salt treatment agent is salt of wormwood and phosphoric acid, successively adds salt of wormwood (K successively
2O) be about TiO
20.5% (scope all can) 0.2~1.5%, phosphoric acid (P
2O
5) be about TiO
20.1% (scope all can) 0.08~0.35%, the solid phase amount is controlled at about 260g/L (solid phase amount 250~320g/L scope all can), the about 120min of modifier treatment.
(7) calcined about 2 hours down about 840 ℃ with the metatitanic acid after the modifier treatment of salt treatment agent, promptly be prepared into the anatase pigmentary titanium dioxide.
Embodiment 2
The technical process of the technical process of present embodiment and embodiment 1 is basic identical, and different is the filtration washing clear liquid in the embodiment 1 hydrolysis crystallization reaction operation (5) to be turned back to preliminary hydrolysis procedure (1) recycle.
Embodiment 3
The technical process of the technical process of present embodiment and embodiment 1 is basic identical, the liquid phase that different is only obtains the preliminary acidolysis reaction operation (1) among the embodiment 1 is implemented the processing of operation (2), be about to liquid phase and send into reactive tank No. 2, add ammonium sulfate and slough aluminium, the add-on of sulphur ammonium is according to the cubage decision of aluminium.Post precipitation is through the vacuum filter filtration washing, and drying is about 1 hour under about 90 ℃, obtains the exsiccated ammonium alum product.
Embodiment 4
The technical process of the technical process of present embodiment and embodiment 1 is basic identical, the processing of the unreal construction preface of liquid phase (2) that different is only obtains the preliminary acidolysis reaction operation (1) among the embodiment 1, and directly implement the processing of operation (3), be about to liquid phase and send into reactive tank No. 3, adjust the pH value with sodium hydroxide and be about 12, (pH be adjusted into 8~14 between can), crystalline deposit is after about 12 hours, obtain industrial magnesium hydroxide after filtration, can be used as flame retardant products.
Embodiment 5
The technical process of present embodiment as shown in Figure 2
(1) contains TiO
2Be about 100 parts of 20% steel climbing high slags, granularity is 0.08~0.18mm, inserts in No. 1 groove acidolysis reaction device, adds concentration and is about 150 parts in 20% sulfuric acid, carries out preliminary acidolysis reaction under about 80 ℃, reacts about 60min.After filtering, obtain the secondary slag.
(2) liquid phase enters reactive tank No. 2, adds ammonium sulfate and sloughs aluminium.The add-on of sulphur ammonium is according to the cubage decision of aluminium in the liquid phase.Post precipitation is through the vacuum filter filtration washing, and following drying is 1.2 hours about 80 ℃, obtains the exsiccated ammonium alum product.
(3) clear liquid that obtains of operation (2) enters the successive reaction groove No. 6, and temperature is risen to boiling point, and by the elementary metatitanic acid that the continuous hydrolysis crystallization obtains, washing about 500 ℃ down after filtration, calcining obtained rich titanium material in about 1 hour.
(4) the filtration washing liquid in the operation (3) is sent into reactive tank No. 3, and adjusting the pH value with potassium hydroxide is about 12 (the pH setting range is 8~14), and post precipitation after filtration, drying obtains industrial magnesium hydroxide, can be used as the flame retardant grade product.
(5) the secondary slag that obtains of the preliminary acidolysis reaction of operation (1) is sent into No. 4 reactive tanks again and is carried out the secondary acidolysis reaction, sulfuric acid concentration is about 60%, temperature is 100 ℃, time is about 90min, the residue obtained after filtration titanium silica cream that is, the treated high-intensity building materials that obtains, liquid phase enters next process.
(6) liquid phase of operation (5) gained is implemented the electromagnetic wave excites radiation, yield of radiation is 1400KW/m
3, frequency is 4.25GH.
(7) liquid after the electromagnetic wave excites radiation enters hydrolysis crystallization reaction groove No. 5, is hydrolyzed under boiling temperature, and the crystallization reaction thing is the hydrate metatitanic acid of titanium.Add about 128 parts of boiling water, about 4 hours of time.The metatitanic acid slip enters next process through vacuum filtration, washing, bleaching.
(8) the metatitanic acid slip after dewatering after filtration, wash, bleaching is sent into the salt treatment trough and is carried out modifier treatment, and the salt treatment agent is salt of wormwood, Tai-Ace S 150, TiO
2Colloidal sol and phosphoric acid.Salt of wormwood K
2O is about TiO
20.2~0.8%, Tai-Ace S 150 Al
2O
3Be TiO
2Be about 0.7~1.1%, TiO
2Colloidal sol is TiO
21.5~2.2%, phosphoric acid P
2O
5Be TiO
20.05~0.1%, the about 120min of modifier treatment., the solid phase amount is controlled at that (scope of solid phase amount is 250~320g/L) about 300g/L.
(9) calcined about 2 hours down about 1050 ℃ with the metatitanic acid after the modifier treatment of salt treatment agent, promptly be prepared into the pigment-grade rutile type titanium dioxide.
Embodiment 6
The technical process of the technical process of present embodiment and embodiment 5 is basic identical, the liquid phase that different is only obtains the preliminary acidolysis reaction operation (1) among the embodiment 1 is only implemented the processing of operation (2) and operation (3), be about to liquid phase and send into reactive tank No. 2, add ammonium sulfate and slough aluminium, the add-on of sulphur ammonium is according to the cubage decision of aluminium.Post precipitation is through the vacuum filter filtration washing, drying is about 1 hour under about 90 ℃, obtain the exsiccated ammonium alum product, the clear liquid that operation (2) is obtained enters the hydrolysis reaction groove No. 6 again, temperature is risen to boiling point, by the elementary metatitanic acid that the continuous hydrolysis crystallization obtains, calcining obtained rich titanium material in about 1 hour under the vacuum filtration washing is about 500 ℃.
Embodiment 7
The technical process of the technical process of present embodiment and embodiment 5 is basic identical, the liquid phase that different is only obtains the preliminary acidolysis reaction operation (1) among the embodiment 1 is only implemented the processing of operation (3) and operation (4), the liquid phase that the preliminary acidolysis reaction separation of operation (1) soon obtains is sent into the hydrolysis reaction groove No. 6, temperature is risen to boiling point, the elementary metatitanic acid that obtains by the continuous hydrolysis crystallization, solid phase after the washing is calcined down about 600 ℃ and was obtained rich titanium material in about 1.5 hours after filtration, liquid phase is sent into reactive tank No. 3, adjusting the pH value with sodium hydroxide is about 10 (the pH setting range is 8~14), post precipitation after filtration, drying obtains industrial magnesium hydroxide, can be used as the flame retardant grade product.
Embodiment 8
The technical process of the technical process of present embodiment and embodiment 5 is basic identical, different is with the filtration washing clear liquid in the embodiment 5 hydrolysis crystallization reaction operations (7), and turning back to for the second time after concentrating, hydrolysis procedure (5) recycles as the acidolysis acid second time.
Claims (10)
1, a kind of using blast-furnace slag capable of recovering other resources is produced the method for titanium dioxide, it is characterized in that comprising following processing step:
(1) granularity is that the titanium-containing blast furnace slag concentration of 0.08~0.18mm is that 3%-25% sulfuric acid carries out preliminary acidolysis reaction under 55~80 ℃ of conditions, fully carries out solid-liquid separation after the reaction, and solid phase and liquid phase enter next process respectively;
(2) the solid phase secondary slag concentration that obtains of operation (1) solid-liquid separation is that 25%-60% sulfuric acid carries out the secondary acidolysis reaction under 80~120 ℃ of conditions, fully carry out solid-liquid separation after the reaction, solid phase is the titanium silica cream that can be used as materials for wall, and liquid phase enters next process;
(3) water that in the liquid phase of operation (2) gained, adds amount of liquid phase 50%~400% crystallization reaction that under 100~115 ℃ condition, is hydrolyzed, the crystallization reaction precipitated phase is a metatitanic acid, fully behind the hydrolysis crystallization reaction metatitanic acid is separated, metatitanic acid enters next process;
(4) the liquid phase slip that enters before the hydrolysis crystallization reaction operation is implemented the electromagnetic wave excites radiation;
(5) operation (3) is separated the solid phase metatitanic acid obtain after the dehydration washing, carries out modifier treatment with the salt treatment agent;
(6) metatitanic acid after salt is handled is calcined under 800~1100 ℃, makes the finished product titanium dioxide;
(7) the separating obtained liquid phase of operation (1) is successively implemented following operation respectively separately or jointly:
A, adding aluminium are deviate from agent and are generated exsiccated ammonium alum with the reactive aluminum that enters liquid phase, through solid-liquid separation, dry preparation exsiccated ammonium alum product;
B, add entry and be warming up to the boiling point reaction that is hydrolyzed, the titanium crystallization that enters liquid phase is separated out, prepare rich titanium material product through solid-liquid separation, drying, calcining;
C, adding alkali generate magnesium hydroxide with the reactive magnesium that enters liquid phase, through solid-liquid separation, dry preparation magnesium hydroxide products.
2, using blast-furnace slag capable of recovering other resources as claimed in claim 1 is produced the method for titanium dioxide, it is characterized in that the electromagnetic frequency of being implemented is 0.1~2.45GH, and yield of radiation is 1500~3200KW/cm
3
3, using blast-furnace slag capable of recovering other resources as claimed in claim 2 is produced the method for titanium dioxide, it is characterized in that with concentration being enforcement electromagnetic wave excites radiation when 3%-25% sulfuric acid carries out acidolysis reaction to titanium-containing blast furnace slag under 55~80 ℃ of conditions.
4, using blast-furnace slag capable of recovering other resources as claimed in claim 3 is produced the method for titanium dioxide, it is characterized in that the separating obtained liquid phase of operation (1) is successively implemented following operation separately or jointly respectively to be handled:
A, adding ammonium sulfate generate aluminium ammonium sulfate with the reactive aluminum that enters liquid phase, prepare the exsiccated ammonium alum product through solid-liquid separation, drying;
B, adding alkali generate magnesium hydroxide with the reactive magnesium that enters liquid phase, prepare magnesium hydroxide products through solid-liquid separation, drying.
5, using blast-furnace slag capable of recovering other resources as claimed in claim 1 is produced the method for titanium dioxide, it is characterized in that said salt treatment agent is selected from the salt treatment agent and is selected from salt of wormwood, Tai-Ace S 150, TiO
2At least a in colloidal sol and the phosphoric acid.
6, using blast-furnace slag capable of recovering other resources as claimed in claim 1 is produced the method for titanium dioxide, it is characterized in that and enters alkali that reactive magnesium in the liquid phase generates magnesium hydroxide and be selected from least a in sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
7, using blast-furnace slag capable of recovering other resources as claimed in claim 2 is produced the method for titanium dioxide, and it levies to be with concentration to be that 25%-60% sulfuric acid is implemented the electromagnetic wave excites radiation to secondary slag acidolysis reaction slip under 80~120 ℃ of conditions.
8, skill blast furnace slag capable of recovering other resources as claimed in claim 7 is produced the method for titanium dioxide, it is characterized in that to the separating obtained liquid phase of operation (1) respectively separately or successively implement following operation and handle jointly:
A, adding ammonium sulfate generate aluminium ammonium sulfate with the reactive aluminum that enters liquid phase, prepare the exsiccated ammonium alum product through solid-liquid separation, drying;
B, add entry and be warming up to boiling point, the reaction that is hydrolyzed is separated out the crystal of hydrate of the titanium that enters liquid phase, prepares rich titanium material product through solid-liquid separation, drying, calcining;
C, adding alkali generate magnesium hydroxide with the reactive magnesium that enters liquid phase, prepare magnesium hydroxide products through solid-liquid separation, drying.
9, the method for producing titanium dioxide as the described using blast-furnace slag capable of recovering other resources of each claim in the claim 1 to 8, it is characterized in that the hydrolysis crystallization reaction after the liquid phase of solid-liquid separation gained turns back to preliminary acidolysis reaction operation or turn back to secondary acidolysis reaction process after concentrating, recycle as acidolysis sulfuric acid.
10, produce the method for titanium dioxide as the described using blast-furnace slag capable of recovering other resources of each claim in the claim 1 to 8, it is characterized in that titanium-containing blast furnace slag grinding to particle diameter wherein is no less than 80% less than 180 purposes.
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