CN104528834A - Novel method for recycling synthetic rutile mother liquor - Google Patents
Novel method for recycling synthetic rutile mother liquor Download PDFInfo
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- CN104528834A CN104528834A CN201410770095.5A CN201410770095A CN104528834A CN 104528834 A CN104528834 A CN 104528834A CN 201410770095 A CN201410770095 A CN 201410770095A CN 104528834 A CN104528834 A CN 104528834A
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Abstract
The invention discloses a novel method for recycling synthetic rutile mother liquor. The method comprises the following steps: treating TiO2 colloid, mechanical impurities and a part of residual metal ions in the mother liquor, concentrating and crystallizing the pretreated mother liquor to obtain a ferrous crystal, re-dissolving the ferrous crystal in deionized water, adding iron powder to reduce, and adsorbing with modified activated carbon to obtain the purified solution of ferrous oxide; preparing the solution of sodium carbonate, adding a certain amount of a heavy-metal precipitating agent, and adding activated charcoal to purify; carrying out coprecipitation reaction on the purified solution of ferrous oxide and the purified solution of sodium carbonate under a certain condition, and introducing air to oxidize at the same time; filtering the product of reaction after reaction, and separating to obtain a filter cake; calcining the filter cake at a certain temperature, cooling, and grinding to obtain primary iron oxide red; and coating the primary iron oxide red, and pulverizing by gas flow to finally obtain the finished iron oxide red. By adopting the method provided by the invention, high-quality rutile mother liquor can be obtained, and the problem of poor economic benefit of the existing technology for treating synthetic rutile mother liquor can be solved.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of novel method of artificial rutile mether liquor recycling, be specifically related to a kind of method utilizing artificial rutile mether liquor to prepare pigment-level iron oxide red.
Background technology
Artificial rutile is the rich titanium material in a kind of important centre, the outstanding substitute products of natural rutile, in the production process route that they are different, hydrochloric acid method Production of Artificial Rutile has that leaching velocity is fast, purification capacity is strong, product grade is high, be applicable to the advantages such as process all kinds mineral resources and become prevailing technology route, achieve suitability for industrialized production very early.
In hydrochloric acid method Production of Artificial Rutile technique, the iron in the general hydrochloric acid Selectively leaching ilmenite concentrate adopting about 20% and most of CaO, MgO, Al
2o
3deng impurity, more finally obtained containing TiO by operations such as washing, calcining, magnetic separation
2content is the high-grade artificial rutile of 88% ~ 96%.But hydrochloric acid leaching ilmenite concentrate manufactures in artificial rutile process, artificial rutile product per ton can form the artificial rutile mether liquor of 5 ~ 7t, this mother liquor contains various metals muriate, main lower containing quantity of material iron protochloride concentration, in addition also have the unreacted hydrochloric acid of part, make it be difficult to by recycling.The typical case of its mother liquor forms as shown in the table:
Country " six or five ", " the Seventh Five-Year Plan " had once carried out large quantity research to the comprehensive utilization that artificial rutile leaches mother liquor, lead to oxychlorination as utilized acidleach mother liquor to prepare liquid ferrous trichloride, produce iron oxide red and bittern etc. by salting-out crystallization legal system for iron powder, integrated process process mother liquor, but due to factors such as its technology, economy, market capacitys, fail to realize large-scale industrial production always.
Be disclose a kind of method for recovery and treatment components from mother liquid of artificial rutile in the application for a patent for invention specification sheets of CN 1657426A at publication number.The method is after artificial rutile mether liquor heating being concentrated, ferric chloride concn is wherein improved, then roasting kiln roasting is sprayed into, iron(ic) chloride generation pyrolysis under high temperature oxidative atmosphere, form hydrogen chloride gas and the soild oxide based on ferric oxide, hydrogen chloride gas then absorbs with water and obtains regenerating hydrochloric acid.Although the method achieves the recycle of chlorion, energy consumption is very high, often processes the heat of about 6,400,000 kilocalories of mother liquor needs that one ton of artificial rutile produces, needs Sweet natural gas and 800Nm
3left and right, and the heat of this processing mode 70% all consumes on evaporation of water latent heat, under country advocates energy-conservation policies and regulations for a long time always, this method does not obviously have sustainability; What is more important, the method, owing to not carrying out purification & isolation to the iron(ic) chloride in mother liquor, makes its product of roasting Fe
2o
3in containing the more impurity such as chlorion, MgO and CaO, Fe
2o
3purity only can arrive about 90%, and its density is only 500kg/m
3left and right, causes its packaging, stacks, transportation cost is high, be difficult to directly serve as iron-smelting raw material.
The Belgian CMI company in Europe proposes fluidized bed calcination method process artificial rutile mether liquor recently, while calcining, adopt micron-sized ferric oxide powder to be induced crystallization center, greatly improve the density of ferric oxide and reduce chloride ion content, this byproduct can be directly used in pig iron smelting.But this kind of method exists that energy consumption is large, the high deficiency of facility investment, the area be difficult to energy prices are higher is promoted.
The patent No. is that the patent of invention of ZL 90105886.6 discloses a kind of method of obtaining through refining ultrafine iron oxide from dilute hydrochloric acid rutile mether liquor.The method is in rutile waste liquor, add the swarf that particle diameter is 2 ~ 25 millimeters, process when being about 3.8 to PH at 30 ~ 100 DEG C of temperature, add polyacrylamide precipitation again, after clear liquid leads to chlorine oxidation, by the solution of chloride containing iron when to add ammoniacal liquor be 5 ~ 8 to PH to 25 ~ 70 DEG C of temperature strong mixing hollow grassland formulas, generate amorphous ferric hydroxide colloidal precipitation, making containing Fe by this precipitation is the slurry of 0.5 ~ 15%, add iron filings successively, trivalent iron salt, tensio-active agent and positively charged mass treatment, filter, the obtained ultrafine iron oxide of filter cake drying grinding is yellow, gained iron oxide yellow is calcined in calcining furnace, can brown iron oxide be obtained.Although the method can obtain iron oxide yellow or the iron oxide red of high-quality, but technical process is tediously long, complicated, operation control overflow is high, and poisonous ammonia, chlorine will be used, chlorine element fails to be recycled utilization, and the waste liquid of a large amount of chloride ion-containing of by-product brings severe contamination to environment.
The patent No. is that the patent of invention of ZL 89105794.3 discloses a kind of process for continuous production of high-purity iron oxide from ferrous salt, the method is to contain the waste material (or waste liquid) of ferrous salt for raw material, join in one group of mechanical stirring aeration tank of connecting together with the crystal seed of preparation after purifying treatment, adding ammonia adjustment pH value is between 2.5 ~ 6, and maintain solution temperature 75 ~ 90 DEG C, make in ferrous ions and form crystalloid α-Fe
2o
3product, the isolated ammonium solution that contains reacts with lime or magnesia in ammonia still process groove, reclaims during ammonia returns and recycles with oxidation trough.Although the method obtains ferric oxide, ammonia is also regenerated, and technical process is very complicated, and chlorine element is not still recycled utilization, and the waste liquid of a large amount of chloride containing calcium of by-product, magnesium chloride, brings pollution to environment.
Publication number is the treatment process that the patent of invention of CN 103159263A discloses a kind of artificial rutile mether liquor, and artificial rutile mether liquor is first carried out heating pre-concentration by it, makes Fe in mother liquor
3+after concentration brings up to more than 150g/L, mixing source of iron is reacted in the fluidized-bed reactor of logical HCl gas, and improve the concentration of iron of mother liquor, then filter acid hydrolysis solution, freezing and crystallizing obtains iron trichloride crystal, and last roasting crystal obtains higher-grade iron oxide red.This inventive method technical process is simple, easy to operate, use the method process mother liquor energy consumption low, achieve the recycle and reuse of chlorine element in mother liquor, all substances in mother liquor are recycled, by product is few, energy-conserving and environment-protective, and the mother liquor after this inventive method adopts sulfate slag or other iron-containing tailings and prevapourising reacts, solve the problem that acidity in mother liquor is excessive, improve the concentration of iron in artificial rutile mether liquor, sulfate slag or other iron-containing tailings is make use of while obtaining a large amount of iron protochloride, this inventive method has carried out purification & isolation to the iron(ic) chloride in mother liquor simultaneously, roasting can obtain high-grade iron oxide red for answering the market requirement.Although but the method has carried out purification & isolation by re-crystallization step to iron(ic) chloride, still there is the problem that in the iron protochloride obtained, foreign matter content is high, fire decompose when preparing iron oxide red large to the corrosion of equipment.
Similar patent also has a lot, early stage artificial rutile mether liquor process is nearly all just reclaimed iron and is not considered the recycling of chlorine element, the chlorate of a large amount of calcic of by-product, magnesium brings pollution to environment, although and ripe by the method for spray roasting regeneration hydrochloric acid, but equipment is perishable, energy consumption is high, the ferric oxide grade obtained is very low, by-product value is low, can not offset processing cost far away.
Summary of the invention
At present, wastes reduction, harmless treatment stage are rested on substantially to the research of artificial rutile mether liquor process, seldom Resource analysis is carried out to it.Industrial more ripe technique uses for reference the technology of Steel Plant's process spent pickle liquor, direct employing Lu Sina stove carries out torch firing to mother liquor, achieve minimizing, harmless treatment, but gained by-product value is limited, can not processing cost be offset far away, without the cheap energy if the area of blast furnace tail gas is without promotional value.
Object of the present invention is just the deficiency for existing production technology, solve the problem of existing artificial rutile mether liquor treatment technology deficiency in economic performance, a kind of novel method of artificial rutile mether liquor recycling is provided, utilize the method can obtain pigment-level high-quality red iron oxide, improve the value of byproduct.
To achieve these goals, the technical solution used in the present invention is such:
A kind of artificial rutile mether liquor recycling novel method, comprises the following steps:
(1) mother liquor purification: artificial rutile mether liquor is left standstill 48h separation and obtain colloidal precipitation thing and clarified mother liquor, again colloidal precipitation thing is added in clarified mother liquor to stir and be warming up to boiling state, the add-on of colloidal precipitation thing is 0.1% ~ 0.5% of clarified mother liquor volume, maintain boiling state 30 ~ 50min, be cooled to room temperature and be separated;
(2) mother liquor concentrations: the liquid evaporation after step (1) being separated concentrates, cooling, crystallization are separated and obtain iron protochloride crystal and filtrate;
(3) pure solution of ferrous chloride is prepared: it is the solution of ferrous chloride of 15% ~ 25% that the iron protochloride dissolution of crystals of step (2) is obtained concentration in deionized water, add the iron powder reaction that mass ratio is 0.5 ~ 5% wherein, the modified activated carbon that mass ratio is 0.1 ~ 10% is added after reaction terminates, absorption 10 ~ 120min filtering separation obtains pure solution of ferrous chloride, and the quality of iron powder and modified activated carbon is in iron protochloride quality;
(4) prepare pure sodium carbonate solution: be the sodium carbonate solution of 30 ~ 50% with deionized water and technical grade sodium carbonate configuration concentration, add wherein mass ratio be 0.5 ~ 5% containing S
2-heavy metal precipitator reacts, and adds the modified activated carbon that mass ratio is 3 ~ 5% after reaction terminates, and absorption 30 ~ 120min filtering separation obtains pure sodium carbonate solution, containing S
2-the quality of heavy metal precipitator and modified activated carbon is in technical grade sodium carbonate quality;
(5) ferric oxide is prepared: join in reactor by step (3) gained solution of ferrous chloride and step (5) gained sodium carbonate solution according to solute mol ratio 1:1 ~ 3, controlling reactor temperature is 20 ~ 50 DEG C, reaction 1 ~ 6h under the condition of mechanical stirring and blowing air;
(6) step (5) gained reaction slurry is filtered obtain filter cake and filtrate, filter cake is dried at 50 ~ 120 DEG C of temperature, pulverize, calcine and obtain red iron oxide;
Artificial rutile mether liquor described in above-mentioned steps be Fe content lower than 0.8% ilmenite concentrate prepare the mother liquor produced in artificial rutile process.
The present invention adopts the precipitator method to the TiO in mother liquor
2colloid, mechanical impurity, part remaining metal ions processes, again by pretreated mother liquor concentrations crystallization, control moisture and evaporate rate, obtain comparatively pure ferrous crystal, it is heavy molten with deionized water, add iron powder reducing, add modified activated carbon again and carry out adsorption treatment, after separation, obtain pure iron protoxide solution; Configure certain density sodium carbonate solution, add a certain amount of heavy metal precipitator wherein, then add active carbon purifying process.Pure ferrous iron solution and sodium carbonate solution are carried out coprecipitation reaction under certain condition, pass into atmospheric oxidation simultaneously, filtering separation obtains filter cake after completion of the reaction, it is calcined at a certain temperature, after cooling, grinding obtains red iron oxide first product, again to its coating, comminution by gas stream process, finally obtains the red finished product of grade ferric oxide.
Owing to adopting multistep control techniques, it is high-quality pigment-level iron oxide red that the present invention obtains red iron oxide, and its Testing index is suitable with domestic iron sheet method iron oxide red quality product, greatly improves the marketable value of mother liquid disposal byproduct, reduce mother liquid disposal cost, there is good market popularization value.And the filtrate after above-mentioned steps (2) iron protochloride crystal separation be mainly concentrated after artificial rutile mether liquor, available limestone vegetation process, residue obtained is low-grade ferric oxide, can making cement raw material or stacking; After the Waste water concentrating of chloride containing calcium, mist projection granulating can manufacture level Calcium Chloride Powder Anhydrous.The main component of above-mentioned steps (6) filtrate is sodium-chlor, can chlor-alkali enterprises be sent to do electrolysis bittern after impurity and purification process.
The present invention's artificial rutile mether liquor used be derived from Fe content lower than 0.8% ilmenite concentrate prepare and produce in artificial rutile process, it solves ferrous ion and is difficult to be separated with bivalent manganese thus causes the problem of red iron oxide hue difference from source; Artificial rutile mether liquor complicated component, its principal constituent iron protochloride can pass through the technique means separating-purifyings such as condensing crystal, adjustment pH value precipitation, selective adsorption, but manganese and ferro element character very close, means of common techniques cannot effectively be isolated, and pigment-level iron oxide red is comparatively responsive to manganese element, small amounts manganese just can obviously affect its pigment performance, therefore the present invention adopts low manganese raw material (rock ore deposit, placer type ilmenite concentrate), the technical barrier avoiding ferromanganese to be separated from source, ensure that the quality of red iron oxide product.
First the present invention adds volume ratio in artificial rutile mether liquor is that the colloid of 0.1% ~ 0.5% is as precipitation seed, this colloid comes from artificial rutile mether liquor and leaves standstill separating obtained throw out after 48 hours, under agitation above-mentioned artificial rutile mether liquor is warming up to boiling, refrigerated separation after maintenance boiling state 30 ~ 50min.In this step, a certain amount of crystal seed colloid is added and control temperature in mother liquor, titanic ion wherein and part heavy metal ion hydrolytic precipitation can be made to get off, and the hydrocolloid of nascent state has extremely strong adsorptivity, can active adsorption part heavy metal ion, finally reach the object of purification mother liquor.Further, the modified polyacrylamide adding clarified mother liquor volume ratio 0.1% ~ 1% after the clarified mother liquor adding precipitation seed is cooled to room temperature again makees flocculation agent, leaves standstill 48h and is separated, can remove the heavy metal ion in mother liquor further, purification mother liquor.
Mother liquid evaporation after purification concentrates by above-mentioned steps (2), and the quality controlling vaporize water in evaporating concentration process accounts for 0.3 ~ 0.9 of the rear mother liquor total mass of purification.Control water evaporation rate index very important, too small rate of evaporation can cause the ferrous crystal yield of gained less than normal, and economic target is unreasonable; And excessive moisture evaporation can cause, and ferrous Crystal impurity content is higher, quality sharply worsens.
And step (3) is prepared in pure solution of ferrous chloride, iron powder adds makes Fe a small amount of in ferrous iron solution
3+be reduced to Fe
2+, and replace heavy metal ion further, finally reach the object of purifying ferrous iron solution, the object adding modified activated carbon carries out adsorbing the colloid in ferrous iron solution and part heavy metal ion.
Step (4) is prepared in pure sodium carbonate solution, because general industry level sodium carbonate all contains the heavy metals such as a small amount of iron, manganese, chromium, can end product quality be affected as directly used, adopting step (4) control techniques effectively can remove heavy metal ion in technical grade sodium carbonate and insoluble mechanical impurity and colloid.Wherein containing S
2-the preferred sodium sulphite of heavy metal precipitator.
Step (5) iron protochloride and sodium carbonate carry out the two hydrolysis reaction of co-precipitation under the condition of mechanical stirring and blowing air, and reaction mechanism is as follows:
FeCl
2+Na
2CO
3→FeCO
3↓+2NaCl
FeCO
3+2H
2O→4FeOOH+4CO
2↑
4FeCO
3+O
2→2α-Fe
2O
3+4CO
2↑
2FeOOH+O
2→2α-Fe
2O
3+H
2O
In this step, the mol ratio controlling solution of ferrous chloride and sodium carbonate solution can better control sedimentary particle diameter and pattern, and control temperature of reaction and air flow quantity can make throw out be converted into α-Fe as far as possible
2o
3, finally obtain the iron oxide product of pigment performance excellence.
Step (6) is carried out drying by filter cake and the object pulverized prevents filter cake from sintering in calcination process, affect particle morphology, thus finally affect iron oxide red quality product, and according to the calcinating system of the thermogravimetric test result formulation filter cake of filter cake be: thermograde is 120 ~ 240 DEG C, heating-up time is greater than 30min, insulation 1 ~ 8h; 300 ~ 600 DEG C, the heating-up time is greater than 30min, insulation 1 ~ 8h.Filter cake oven dry, pulverizing, calcining can be obtained high-quality iron oxide red.
Further, by the pulverizing of step (6) gained red iron oxide, making beating, dispersion treatment, the coating agent of Silicified breccias is added, hierarchy of control pH completes sial coating, reacted rear separation, the laggard row comminution by gas stream of gained filtration cakes torrefaction, finally obtains the red product of high-quality grade ferric oxide.Iron oxide red is carried out sial coating can make the weathering resistance of ferric oxide red colorant, chemical stability all improves, there is tint permanence, dispersed strong, have the permanent yellowing resistance of excellent photostabilization and open air.
At present, ripe, the industrialized artificial rutile mether liquor treatment technology of energy be Spray calcination method, this method have clean, without the advantage such as secondary useless producing, byproduct all reclaims, but this method equipment corrosion is serious, energy consumption is excessive, according to related data introduction, mother liquor that 1 ton of artificial rutile produces needs 800m to adopt this method to process completely
3sweet natural gas, and its by-product value is well below energy consumption, and therefore this method only has industrial value in the region that energy prices are lower.All there are some defects that cannot overcome in other artificial rutile treatment technologies, does not all carry out industrialization.
Advantage of the present invention and positively effect are:
(1) multiple control techniques is adopted to improve the purity of iron protochloride and technical grade sodium carbonate, adopt advanced hydrolysis process controlled hydrolysis thing particle morphology and grain size, effective calcinating system is adopted to ensure the unicity of ferric oxide crystal formation conversion, effective coating process is adopted to ensure dispersiveness and the weathering resistance of the finished product, finally obtain high-quality pigment-level iron oxide red, the significant increase marketable value of byproduct, counteract environmental protection treatment cost and even can also produce economic benefit, therefore there is promotional value.
(2) this inventive method does not relate to special process and equipment, and facility investment and operational requirement are not high, and flow process adds medicament is in addition customary commercial, and market can be purchased, and consumes few in addition, increases cost limited.
(3) other secondary the giving up produced in this invention production technique are all useful products, can form upstream and downstream industry chain of circular economy with cement and chlor-alkali enterprises.
(4) secondary waste product zero release has been accomplished in this invention substantially, has good environmental benefit, has also accomplished that chemical industry gives up secondary recycling.
Accompanying drawing explanation
Fig. 1 is the inventive method process flow diagram.
Embodiment
In order to the object of the present invention of understanding clearly, technical scheme and beneficial effect, below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention do not limited in the examples below.
Following embodiment artificial rutile mether liquor used composed as follows described in:
Free hydrochloric acid 116.7g/L, Fe
3+97.2g/L, Fe
2+4.2g/L, AL
3+4.2g/L, Al
3+0.22g/L, Ca
2+0.41g/L, Mg
2+3.16g/L, Si
4+0.03g/L, Ti
4+1.6g/L, Mn
2+0.63g/L, V
5+0.05g/L.
Embodiment 1:
(1) mother liquor is left standstill 48h separation and obtain colloidal precipitation thing and clarified mother liquor, in clarified mother liquor, add volume ratio 0.1% colloidal precipitation thing again stir, it is heated in 30min boiling, maintain slight boiling condition 30min, be cooled to room temperature, add the modified polyacrylamide of volume ratio 0.5%, normal temperature filters after leaving standstill 48h;
(2) concentrated by the mother liquid evaporation after above-mentioned filtration, the quality of vaporize water accounts for 0.3 of mother liquor total mass, is cooled to crystallization under 5 DEG C of conditions, filters to isolate crystal;
(3) above-mentioned gained crystal is configured to the ferrous iron solution of 15%, the iron powder adding mass percent 0.5% carries out replacement(metathesis)reaction, and add the modified activated carbon absorption of 3% after reaction terminates, adsorption time is 30min, filtering separation;
(4) configure the sodium carbonate solution of 30%, add the sodium sulphite precipitation heavy metal ion wherein of mass percent 0.5%, add the charcoal absorption of 3% after having reacted, adsorption time 30min, filtering separation;
(5) coprecipitation reaction is carried out according to the flow velocity of solute mol ratio 1:1 in above-mentioned (3) and (4) step gained solution, it is 30 DEG C in churned mechanically condition hierarchy of control temperature, pass into a certain amount of air with pneumatic pump simultaneously, after precipitin reaction terminates, continue to react 60min under these conditions, be cooled to normal temperature and filter;
(6) dried under the condition of 50 DEG C by filter cake, be ground to pulverulence, then calcined, calcinating system is: thermograde is 180 ~ 300 DEG C, heats up and is greater than min, insulation 4h; 200 ~ 600 DEG C, heat up and be greater than min, insulation is greater than 1h, and after cooling, grinding is stand-by.
(7) above-mentioned gained croci being pulled an oar under certain solid-to-liquid ratio condition, carrying out sand mill, adding dispersant, add water glass again and regulate PH, adding aluminum chloride, finally complete coating reaction, by filtration cakes torrefaction, comminution by gas stream after filtration, finally obtain the red product of grade ferric oxide.Analyzing and testing is carried out to it, the results are shown in following table 1.
Embodiment 2:
(1) mother liquor is left standstill 48h separation and obtain colloidal precipitation thing and clarified mother liquor, in clarified mother liquor, add volume ratio 0.5% colloidal precipitation thing again stir, it is heated in 30min boiling, maintain slight boiling condition 50min, be cooled to room temperature, add the modified polyacrylamide of volume ratio 0.1%, normal temperature filters after leaving standstill 48h;
(2) concentrated by the mother liquid evaporation after above-mentioned filtration, the quality of vaporize water accounts for 0.6 of mother liquor total mass, is cooled to crystallization under 5 DEG C of conditions, filters to isolate crystal;
(3) above-mentioned gained crystal is configured to the ferrous iron solution of 25%, the iron powder adding mass percent 1% carries out replacement(metathesis)reaction, and add the modified activated carbon absorption of 5% after reaction terminates, adsorption time is 60min, filtering separation;
(4) configure the sodium carbonate solution of 50%, add the sodium sulphite precipitation heavy metal ion wherein of mass percent 1%, add the charcoal absorption of 5% after having reacted, adsorption time 60min, filtering separation;
(5) coprecipitation reaction is carried out according to the flow velocity of solute mol ratio 1:1 in above-mentioned (3) and (4) step gained solution, it is 50 DEG C in churned mechanically condition hierarchy of control temperature, pass into a certain amount of air with pneumatic pump simultaneously, after precipitin reaction terminates, continue to react 120min under these conditions, be cooled to normal temperature and filter;
(6) dried under the condition of 80 DEG C by filter cake, be ground to pulverulence, then calcined, calcinating system is: thermograde is 180 ~ 210 DEG C, and heat up 30 ~ 60min, insulation 4h; 240 ~ 300 DEG C, heat up 30 ~ 60min, and insulation 2 ~ 4h, after cooling, grinding is stand-by.
(7) above-mentioned gained croci being pulled an oar under certain solid-to-liquid ratio condition, carrying out sand mill, adding dispersant, add water glass again and regulate PH, adding aluminum chloride, finally complete coating reaction, by filtration cakes torrefaction, comminution by gas stream after filtration, finally obtain the red product of grade ferric oxide.Analyzing and testing is carried out to it, the results are shown in following table 1.
Embodiment 3:
(1) mother liquor is left standstill 48h separation and obtain colloidal precipitation thing and clarified mother liquor, in clarified mother liquor, add volume ratio 0.4% colloidal precipitation thing again stir, it is heated in 30min boiling, maintain slight boiling condition 50min, be cooled to room temperature, add the modified polyacrylamide of volume ratio 1%, normal temperature filters after leaving standstill 48h;
(2) concentrated by the mother liquid evaporation after above-mentioned filtration, the quality of vaporize water accounts for 0.9 of mother liquor total mass, is cooled to crystallization under 10 DEG C of conditions, filters to isolate crystal;
(3) above-mentioned gained crystal is configured to the ferrous iron solution of 22%, the iron powder adding mass percent 1% carries out replacement(metathesis)reaction, and add the modified activated carbon absorption of 5% after reaction terminates, adsorption time is 120min, filtering separation;
(4) configure the sodium carbonate solution of 50%, add the sodium sulphite precipitation heavy metal ion wherein of mass percent 1%, add the charcoal absorption of 5% after having reacted, adsorption time 60min, filtering separation;
(5) coprecipitation reaction is carried out according to the flow velocity of solute mol ratio 1:1 in above-mentioned (3) and (4) step gained solution, it is 45 DEG C in churned mechanically condition hierarchy of control temperature, pass into a certain amount of air with pneumatic pump simultaneously, after precipitin reaction terminates, continue to react 120min under these conditions, be cooled to normal temperature and filter;
(6) dried under the condition of 80 DEG C by filter cake, be ground to pulverulence, then calcined, calcinating system is: thermograde is 180 ~ 210 DEG C, and heat up 30 ~ 60min, insulation 4h; 240 ~ 300 DEG C, heat up 30 ~ 60min, and insulation 2 ~ 4h, after cooling, grinding is stand-by.
(7) above-mentioned gained croci being pulled an oar under certain solid-to-liquid ratio condition, carrying out sand mill, adding dispersant, add water glass again and regulate PH, adding aluminum chloride, finally complete coating reaction, by filtration cakes torrefaction, comminution by gas stream after filtration, finally obtain the red product of grade ferric oxide.Analyzing and testing is carried out to it, the results are shown in following table 1.
The red iron oxide of embodiment 1,2,3 is carried out sreen analysis and electron-microscope scanning, finds that its particle morphology is spherical, centralized particle diameter is at 1 ~ 5 μm, and 5 ~ 10 μm of two intervals, size distribution is good.
Above-mentioned three embodiment gained red iron oxides are carried out composition analysis (after coating), and its result is:
Basic demand index for grade ferric oxide product in standard GB/T 1863-2008 is as follows:
Therefore, the red iron oxide prepared through the inventive method has that purity is high, size distribution good, particle morphology is spherical, the feature such as transformation of crystal is thorough.Pigment performance detects and shows, the iron oxide red performance that this iron oxide red product pigment performance index and domestic conventional iron sheet method prepare is suitable, reaches the red A grade standard in GB/T 1863-2008 completely.
Claims (8)
1. an artificial rutile mether liquor recycling novel method, is characterized in that: comprise the following steps:
(1) mother liquor purification: artificial rutile mether liquor is left standstill 48h separation and obtain colloidal precipitation thing and clarified mother liquor, again colloidal precipitation thing is added in clarified mother liquor to stir and be warming up to boiling state, the add-on of colloidal precipitation thing is 0.1% ~ 0.5% of clarified mother liquor volume, maintain boiling state 30 ~ 50min, be cooled to room temperature and be separated;
(2) mother liquor concentrations: the liquid evaporation after step (1) being separated concentrates, cooling, crystallization are separated and obtain iron protochloride crystal and filtrate;
(3) pure solution of ferrous chloride is prepared: it is the solution of ferrous chloride of 15% ~ 25% that the iron protochloride dissolution of crystals of step (2) is obtained concentration in deionized water, add the iron powder reaction that mass ratio is 0.5 ~ 5% wherein, the modified activated carbon that mass ratio is 0.1 ~ 10% is added after reaction terminates, absorption 10 ~ 120min filtering separation obtains pure solution of ferrous chloride, and the quality of iron powder and modified activated carbon is in iron protochloride quality;
(4) prepare pure sodium carbonate solution: be the sodium carbonate solution of 30 ~ 50% with deionized water and technical grade sodium carbonate configuration concentration, add wherein mass ratio be 0.5 ~ 5% containing S
2-heavy metal precipitator reacts, and adds the modified activated carbon that mass ratio is 3 ~ 5% after reaction terminates, and absorption 30 ~ 120min filtering separation obtains pure sodium carbonate solution, containing S
2-the quality of heavy metal precipitator and modified activated carbon is in technical grade sodium carbonate quality;
(5) ferric oxide is prepared: join in reactor by step (3) gained solution of ferrous chloride and step (5) gained sodium carbonate solution according to solute mol ratio 1:1 ~ 3, controlling reactor temperature is 20 ~ 50 DEG C, reaction 1 ~ 6h under the condition of mechanical stirring and blowing air;
(6) step (5) gained reaction slurry is filtered obtain filter cake and filtrate, filter cake is dried at 50 ~ 120 DEG C of temperature, pulverize, calcine and obtain red iron oxide;
Artificial rutile mether liquor described in above-mentioned steps be Fe content lower than 0.8% ilmenite concentrate prepare the mother liquor produced in artificial rutile process.
2. a kind of artificial rutile mether liquor recycling novel method according to claim 1, it is characterized in that: the flocculation agent adding clarified mother liquor volume ratio 0.1% ~ 1% after the clarified mother liquor adding colloidal precipitation thing in described step (1) is cooled to room temperature, leave standstill 48h and be separated.
3. a kind of artificial rutile mether liquor recycling novel method according to claim 2, is characterized in that: described flocculation agent is modified polyacrylamide.
4. a kind of artificial rutile mether liquor recycling novel method according to claim 1, is characterized in that: the quality controlling vaporize water in described step (2) evaporating concentration process accounts for 0.3 ~ 0.9 of the rear liquid total mass of step (1) separation.
5. a kind of artificial rutile mether liquor recycling novel method according to claim 1, is characterized in that: with limestone vegetation treatment step (2) gained filtrate.
6. a kind of artificial rutile mether liquor recycling novel method according to claim 1, is characterized in that: containing S in described step (4)
2-heavy metal precipitator is sodium sulphite.
7. a kind of artificial rutile mether liquor recycling novel method according to claim 1, is characterized in that: in described step (6), the calcinating system of filter cake calcining is: thermograde is 120 ~ 240 DEG C, heats up and is greater than 30min, insulation 1 ~ 8h; 300 ~ 600 DEG C, heat up and be greater than 30min, insulation 1 ~ 8h.
8. a kind of artificial rutile mether liquor recycling novel method according to claim 1, is characterized in that: step (6) gained red iron oxide is carried out sial coating.
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Cited By (8)
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| CN105110784A (en) * | 2015-08-03 | 2015-12-02 | 宜宾天原集团股份有限公司 | Method for preparing manganese zinc ferrite by using artificial rutile mother liquor |
| CN105692716A (en) * | 2016-01-18 | 2016-06-22 | 宜宾天原集团股份有限公司 | Method for preparing high-purity ferrous chloride from synthetic rutile mother liquor |
| CN108439483A (en) * | 2018-06-01 | 2018-08-24 | 茂名粤桥集团矿业有限公司 | A kind of production method of ferric oxide red colorant |
| CN108863875A (en) * | 2018-07-23 | 2018-11-23 | 贵州红星发展股份有限公司 | The method of purification and thiocarbamide of thiocarbamide |
| CN109467123A (en) * | 2018-11-23 | 2019-03-15 | 宜宾天原集团股份有限公司 | A kind of artificial rutile mether liquor comprehensive resource utilizes method |
| CN111439771A (en) * | 2020-03-31 | 2020-07-24 | 广西金茂钛业有限公司 | Method for preparing barium sulfate from titanium white waste acid |
| CN111825123A (en) * | 2020-08-06 | 2020-10-27 | 华东理工大学 | Preparation method of iron oxides with different crystal forms |
| CN113912130A (en) * | 2021-11-29 | 2022-01-11 | 龙佰集团股份有限公司 | Iron oxide red and preparation method thereof |
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| CN105110784B (en) * | 2015-08-03 | 2017-04-12 | 宜宾天原集团股份有限公司 | Method for preparing manganese zinc ferrite by using artificial rutile mother liquor |
| CN105692716A (en) * | 2016-01-18 | 2016-06-22 | 宜宾天原集团股份有限公司 | Method for preparing high-purity ferrous chloride from synthetic rutile mother liquor |
| CN108439483A (en) * | 2018-06-01 | 2018-08-24 | 茂名粤桥集团矿业有限公司 | A kind of production method of ferric oxide red colorant |
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| CN111439771A (en) * | 2020-03-31 | 2020-07-24 | 广西金茂钛业有限公司 | Method for preparing barium sulfate from titanium white waste acid |
| CN111439771B (en) * | 2020-03-31 | 2022-09-20 | 广西金茂钛业有限公司 | Method for preparing barium sulfate from titanium white waste acid |
| CN111825123A (en) * | 2020-08-06 | 2020-10-27 | 华东理工大学 | Preparation method of iron oxides with different crystal forms |
| CN113912130A (en) * | 2021-11-29 | 2022-01-11 | 龙佰集团股份有限公司 | Iron oxide red and preparation method thereof |
| CN113912130B (en) * | 2021-11-29 | 2023-07-07 | 龙佰集团股份有限公司 | Iron oxide red and preparation method thereof |
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