CN102616842A - Method for preparing titanium white - Google Patents

Abstract

The invention provides a method for preparing titanium white. The method comprises the following steps of: preparing titanium solution from high titanium hydrochloric acid leaching residue, which is prepared from a titanium iron material through a hydrochloric acid leaching method, serving as a raw material or one of raw materials through acidolysis by using sulfuric acid; oxidizing the titanium solution, performing organic extraction and purification, and hydrolyzing to obtain metatitanic acid; and performing washing, salt treatment, calcination and surface treatment on the metatitanic acid to prepare the titanium white. According to the method, hydrochloric acid composite system solution containing chlorate is subjected to diffluent disposal and is recycled after the titanium iron material is leached, and is organically matched with a cyclic process of an organic extraction and purification and sulfuric acid system of the titanium solution, so that the titanium solution treatment process and the cost are reduced; and since the used hydrochloric acid, sulfuric acid and organic extraction agent can be recycled, ferrous sulfate (green vitriol) is not produced; and thus, the discharge of dilute sulfuric acid and acidic wastewater is effectively reduced, and the quality of the titanium white is obviously improved. According to the method provided by the invention, high efficiency, cleanness, low cost, low energy consumption and low waste discharge effects of an entire flow are realized; a novel process technology is provided for producing the titanium white by a sulfuric acid method; and fine grained rock type ilmenite with high calcium and magnesium content at the Panxi area can be effectively utilized.

Description

A kind of method for preparing white titanium pigment

Technical field

The invention belongs to the titanium white production field, be specifically related to a kind of method that adopts the ferrotianium material to prepare white titanium pigment.

Background technology

The titanium resource reserves of China's Panxi Diqu account for more than 90% of national reserves; The ilmenite of this area mainly is symbiosis rock ore deposit; Grade of titanium dioxide is low; Calcium magnesium addition content is high, and generally about 46-47wt%, quicklime and Natural manganese dioxide amount to generally about 5-7% the grade of titanium dioxide of its choosing back ilmenite concentrate.In addition, fine size is the another characteristic in this ore deposit, and its granularity accounts for more than 50% greatly less than 200 purposes, and along with the exploitation of deep ore, ilmenite will be more and more thinner.This miningly will be produced acid of a large amount of sulfur waste and green vitriol waste residue in Titanium White Production By Sulfuric Acid Process, and this ore deposit is inappropriate for and makes the chloride process titanium dioxide powder raw material.Developing a kind of efficient, the cleaning of Panxi Diqu ilmenite, high-grade titanium white production technology and technology that environmental protection utilizes of being suitable for, is China's titanium white collar territory researcher wish in decades, also is the basic outlet that solves the titanium powder industry in China Sustainable development.Yet even to this day, still none otherwise effective technique titanium resource that can make full use of Panxi Diqu is produced high-grade white titanium pigment, to such an extent as to the huge titanium resource in this area is not fully utilized.

Chlorination and sulfuric acid process are two main technique flow processs of producing white titanium pigment in the world today.

Sulfuric acid process comprises and adopts primary ilmenite or solubility in acid titanium slag to carry out acidolysis, dissolving, (condensing crystal), hydrolysis, washing, bleaches, adds step such as crystal seed burning, finally makes white titanium pigment.Wherein, Used solubility in acid titanium slag is the pyrometallurgical smelting gained, promptly adopts ilmenite and reductive agent in electric furnace, to heat approximately to 1600-1800 ℃, and high melt makes that ferriferous oxide is reduced into metallic iron in the ilmenite; Flow out with molten iron; Remove most of iron composition thereby separate, and the titanium in the ilmenite is stayed in the slag of melting with other impurity, formed the solubility in acid titanium slag.Although it is bigger that sulfuric acid process is polluted, its technical maturity is low to ingredient requirement, and cost is lower, so Panxi Diqu and even China mainly still are the main white titanium pigment of producing with the sulfuric acid process.With the ilmenite is that raw material adopts Titanium White Production By Sulfuric Acid Process, with producing a large amount of ferrous sulfate (green vitriol) wastes, has greater environmental impacts.Though and select for use titanium slag can reduce the generation of ferrous sulfate (green vitriol) as the raw material of Titanium White Production By Sulfuric Acid Process; But the sulfuric acid that needs higher concentration during the acidolysis titanium slag; Limit the dilute sulphuric acid reuse that produces in the technology, discharged contaminate environment with aftertreatment during a large amount of dilute sulphuric acids can only pass through.Simultaneously, need and will wear into negative 325 orders than the titanium slag of difficult mill, it is also higher to consume energy.

The environmental pollution that chlorination caused is than sulfuric acid process much less, but the chloride slag waste toxic action that produces is bigger, needs through the deep-well landfill disposal.Chlorination is higher to ingredient requirement, general requirement raw material content of titanium dioxide more than 92%, granularity must be more than 200 orders, foreign matter content is low, so the chlorination raw material is main with rutile.The reserves of natural rutile are extremely low, only account for the 0.3-1% of titanium total reserves, so the used raw material of chlorination mainly is an artificial rutile.The ilmenite of Panxi Diqu is low because of grade, impurity is many, fine size; Many critical technological points are arranged, " the hydrochloric acid normal pressure directly leaches the Panxi Diqu ilmenite and prepares artificial rutile " (non-ferrous metal, in November, 2007 with its preparation artificial rutile; The 59th the 4th phase of volume; P108-111) literary composition has compared the relative merits of each technology, and combines the characteristics of Panxi Diqu ilmenite, points out that the salt acid leaching process is the preferable scheme of the rich titanium material artificial rutile of preparation.Salt acid leaching process two big technical process commonly used at present are respectively preoxidation-fluidization normal pressure lixiviation process and selecting smelting combination pressure leaching process.Preoxidation-fluidization normal pressure lixiviation process has solved the refinement problem of raw ore in leaching process through the preoxidation measure; But this method still has refinement rate (" the hydrochloric acid legal system is got the artificial rutile technical study ", steel vanadium titanium, in June, 2006 about 15%; The 27th the 2nd phase of volume; P1-6), add raw ore more than 50% less than 200 orders, cause the artificial rutile granularity that has at least about 60% less than 200 orders; And this part artificial rutile can't be used for chloride process titanium dioxide because of its granularity is meticulous, and it is insoluble to acid can not be used for sulfuric acid legal system white titanium pigment.Therefore with state-of-the art, the economic implications that is applied to prepare white titanium pigment with the ilmenite production artificial rutile of Panxi Diqu is little.

In decades; Comprehensive utilization mainly concentrates on production artificial rutile aspect to the Panxi Diqu titanium resource in China; Especially be devoted to solve the problem such as granularity refinement and leaching effect of salt acid leaching process; All be that the result is unsatisfactory for the quality that improves artificial rutile is beneficial to produce white titanium pigment with chlorination.Its reason does not lie in the technology of producing artificial metal and stone and does not pass a test, but is that the characteristics of Panxi Diqu titanium resource are inappropriate for the rutile of producing as the chlorination raw material.There are not the intermediate product with the salt acid leaching process, the titanium slag that promptly obtains (being called high titanium salt acidleach slags tap) to be used for the report that sulfate process titanium dioxide is produced at present both at home and abroad as yet through acidleach, solid-liquid separation, washing.The one Chinese patent application CN201010270577.6 (publication number CN101935063A) that the inventor submits to; Require a kind of high titanium salt acidleach of protection to slag tap and uses thereof; Wherein disclose the intermediate product with the salt acid leaching process, promptly high titanium salt acidleach is slagged tap and is prepared white titanium pigment as raw material through sulfuric acid process.The denomination of invention that the inventor submits to is the one Chinese patent application CN200910311886.0 (publication number CN102102149A) of " being used to leach the application of leaching liquid, salt acid leaching process and the leached mud of ilmenite "; Disclose a kind of ilmenite hydrochloric acid leaching liquid that contains solubility chlorination salt, its hydrochloric acid leaching that is used for ilmenite can significantly improve its leaching efficiency.The denomination of invention that the inventor submits to is the one Chinese patent application CN201010119318.3 of " method of purification of titanium liquid "; A kind of method of purification of titanium liquid extraction deironing has been proposed; This method is applied in the sulfuric acid solution technology that high titanium salt acidleach slags tap titanium liquid purified.But still not having at present the employing sulfuric acid process utilizes high titanium salt acidleach to slag tap to prepare the maturation method of white titanium pigment.

Summary of the invention

The purpose of this invention is to provide a kind of novel method for preparing white titanium pigment, this method adopts the high titanium salt acidleach of salt acid leaching process preparation to slag tap as one of raw material or raw material, and utilizes sulfuric acid solution to produce white titanium pigment.The organic extraction that said method has combined to contain the reuse of shunting cycle of treatment, the titanium liquid of the hydrochloric acid leaching liquid of chlorate is purified and technology such as sulfuric acid system circulation; Realized full-range organic supporting, the technology of a kind of novel, cleaning of Titanium White Production By Sulfuric Acid Process, efficient, low cost, less energy-consumption are provided, hanging down waste discharge.Simultaneously; Said method has realized effective utilization of the particulate lithotype ilmenite of high contents of calcium and magnesium content, reduces titanium liquid treatment process and cost, and owing to used hydrochloric acid and sulfuric acid recycles; Do not produce ferrous sulfate (green vitriol); Also can convert iron to can fully utilize brown iron oxide, thereby effectively reduce dilute sulphuric acid and acid waste water discharging, significantly improve the quality of white titanium pigment.

Technical scheme of the present invention is following:

The invention provides a kind of method for preparing white titanium pigment, said method comprises the steps:

A. with the ferrotianium material or through pretreated ferrotianium material with carry out hydrochloric acid leaching after hydrochloric acid leaching liquid mixes, obtain to leach slurry;

B. the leaching slurry that obtains through steps A is carried out solid-liquid separation; The gained solid is slagged tap for high titanium salt acidleach after washing, drying; Said liquid is for leaching mother liquor, after shunting, gets into mother liquor burning operation and regeneration of hydrochloric acid operation respectively and is regenerated as hydrochloric acid leaching liquid, thereby return steps A;

C. will slag tap and carry out acidolysis and be incubated slaking after aqueous sulfuric acid mixes through the high titanium salt acidleach that step B obtains;

D. will obtain slip through acidolysis thing water and/or the dilute sulphuric acid dissolving that step C obtains, obtain low impurity titanium liquid through solid-liquid separation;

E. randomly will handle through oxidation and organic extraction, to obtain high purity titanium liquid through the low impurity titanium liquid that step D obtains; Wherein the organic phase after organic extraction is carried out back extraction, and the anti-raffinate that obtains gets into the regeneration of hydrochloric acid operation of step B, thereby returns steps A through being regenerated as hydrochloric acid leaching liquid;

The low impurity titanium liquid that F. will obtain through step D or randomly be hydrolyzed through the high purity titanium liquid after evaporation concentration that step e obtains, thus the metatitanic acid slurry obtained; Wherein the Hydrogen chloride of evaporation concentration operation acquisition gets into the regeneration of hydrochloric acid operation of step B, thereby returns steps A through being regenerated as hydrochloric acid leaching liquid;

G. filter the metatitanic acid slurry that obtains through step F, the solid that washing and filtering obtains is low impurity metatitanic acid, and filtrating is dilution heat of sulfuric acid, after the said dilution heat of sulfuric acid partial equilibrium discharging, thereby returns step C through the evaporation concentration operation;

H. will handle and calcining through salt through the low impurity metatitanic acid that step G obtains, thereby obtain white titanium pigment.

In this Production Flow Chart, steps A, step B, step e, step F form salt acid circulation system, hydrochloric acid recycle; Step C, step D, step e, step F, step G form the sulfuric acid recycle system, sulfuric acid recycle; Step e forms organic extraction cycle system, the organic extractant recycle, and this is the present invention and one of difference of disclosed CN101935063A and CN102102149A patented claim.In addition, in the above-mentioned steps, the anti-raffinate of step e gets into the regeneration of hydrochloric acid operation of step B; The regeneration of hydrochloric acid operation that the Hydrogen chloride that the evaporation concentration operation obtains in the step F gets into step B; After the said dilution heat of sulfuric acid partial equilibrium discharging of step G, thereby return step C through the evaporation concentration operation.These are also different with the CN102102149A patented claim with disclosed CN101935063A; Because complementing one another and organic linking between the flow process of the present invention; Its materials inside proportioning is different with above-mentioned prior art with balance; And those of ordinary skill in the art can not draw through simple technological reasoning, more can not simply just draw the mutual configuration of each link in the technological process of the present invention.

Above-mentioned preparation method provided by the invention will describe in detail as follows to each step:

In the steps A, said ferrotianium material comprises the ferrotianium oxide compound, for example ilmenite, ilmenite concentrate, modification ilmenite concentrate, titanium slag; Preferably, the titanium oxide mass percentage content is 30%～80% in the said ferrotianium material;

Ferrotianium material described in the steps A can randomly be done pre-treatment, comprising: the ferrotianium material through first weak oxide restore, earlier reduction reoxidizes, an oxidation is not reduced and one or more modes of only reducing in the not oxidation are carried out pre-treatment;

And the hydrochloric acid leaching liquid that adopts in the steps A is hydrochloric acid or the hydrochloric acid compound system solution that contains chlorate, and said chlorate is aluminum chloride, magnesium chloride, calcium chloride, iron(ic)chloride, Manganous chloride tetrahydrate for example, and its free concentration of hydrochloric acid is 15%～25%, the Fe in the leaching liquid ²⁺+ Fe ³⁺Concentration is 30～100g/l.Chlorate in the said leaching liquid can add preparation, also can be by the raffinate cyclically utilizing that contains chlorate in the leaching mother liquor that contains chlorate in the said hydrochloric acid leaching of step B and wash filtrate and the said organic extraction of step e, preferred cycle reuse.The raffinate cyclically utilizing is different with the CN102102149A patented claim with disclosed CN101935063A.

In steps A, adopt hydrochloric acid directly to leach in method, BCA hydrochloric acid leaching method, preoxidation-fluidization normal pressure leaching method and preoxidation-selecting smelting combination pressurization leaching method one or more and carry out hydrochloric acid leaching, preferably adopt hydrochloric acid directly to leach method; Directly leaching method of said hydrochloric acid comprises: preheat hydrochloric acid leaching liquid to 70 ℃～100 ℃; Then with 1g: the mass volume ratio of 2.5ml～5ml makes the ferrotianium material or mixes with hydrochloric acid leaching liquid through pretreated ferrotianium material, under 70 ℃～150 ℃ temperature, carries out hydrochloric acid and directly leaches 1～8 hour.

Among the step B; Can randomly will carry out stage treatment through the leaching slurry that steps A obtains earlier; Make and leach the fine granules solid-liquid separation after evaporation concentration below 200 orders in the slurry, the above direct solid-liquid separation of Coarse Aggregate of 200 orders is used to prepare artificial rutile in the leaching slurry;

During solid-liquid separation in carrying out step B, adopt concentrate, spinning and filter in one or more, the preferred employing filtered; When adopting filtration, will be cooled to 80 ℃～90 ℃ through the leaching slurry that steps A obtains earlier;

When the solid that washing obtains after the solid-liquid separation; Adopt the sour water washing gained solid of water or pH＜1, the preferred Hydrogen chloride of said sour water, its HCl concentration is greater than 0.1mol/L or pH＜1; Wash filtrate gets into the regeneration of hydrochloric acid operation, returns steps A through being regenerated as hydrochloric acid leaching liquid;

Particulate slurry below said 200 orders carries out solid-liquid separation after evaporation concentration, and washing gained solid, during its drying operation, the solid after the washing is carried out drying 2～8 hours being lower than under 600 ℃ the temperature, slags tap thereby obtain high titanium salt acidleach; Said drying temperature preferably is lower than 250 ℃, further preferred 150 ℃～250 ℃; Coarse grain slurry more than said 200 orders is through solid-liquid separation and wash the gained solid, and its calcining temperature should be higher than 900 ℃, preferred 950 ℃ to 1100 ℃.

The high titanium salt acidleach of the said ferrotianium material of step B behind the hydrochloric acid leaching liquid leaching slagged tap and is porosity and looseness shape residue and metatitanic acid aggregate, and contains a spot of rutile, titanaugite, anosovite and quartz, wherein TiO ₂Composition mainly exists with non-crystal state, it is characterized in that this high titanium salt acidleach is slagged tap to contain chlorion, and its content is lower than 5%, and preferred content is 1%～3%, and these are also different with the CN102102149A patented claim with disclosed CN101935063A.

Acidolysis described in the step C also is incubated slaking and comprises: be that 1.4～1.9: 1 acid sludge is slagged tap than mix sulphur aqueous acid and high titanium salt acidleach by weight; Be heated to 150～240 ℃; Carry out obtaining thick solid mixt behind the acidolysis reaction slaking 1～4 hour under uniform temp afterwards; And said acidolysis reaction preferably carried out 5～240 minutes;

And the aqueous sulfuric acid weight percent concentration of employing is 55～98%, is preferably 85～91%

Wherein, before acidolysis, can earlier the high titanium salt acidleach that obtains through step B be slagged tap is ground to negative 325 orders;

Among the step C, high titanium salt acidleach is slagged tap to mix with one or more of ilmenite concentrate, modification ilmenite concentrate, solubility in acid titanium slag or other ferrotianium material and is carried out sulfuric acid solution;

Preferably, high titanium salt acidleach is slagged tap and can also be carried out sulfuric acid solution respectively with ilmenite concentrate, modification ilmenite concentrate, solubility in acid titanium slag or other ferrotianium material and prepare titanium liquid, and the titanium liquid that will prepare respectively then is by TFe/TiO ₂Be to produce mixed with titanium liquid after 0.25～0.35 standard is mixed, this titanium liquid is without the organic extraction direct hydrolysis, and this also is the present invention and one of difference of disclosed CN101935063A and CN102102149A patented claim.

Comprise the steps: among the step D

D-1) first cooling reaction system is to being lower than 80 ℃, adds the acidolysis thing after the water dissolution slaking that is lower than 60 ℃ then, 40～70 ℃ of dissolvings 1～8 hour down, simultaneously with TiO in the solution ₂Amount be controlled at 180g/L～260g/L; Perhaps

Elder generation's cooling reaction system is to being lower than 80 ℃; Add earlier then that to be lower than 60 ℃, weight percent concentration be 20% dilution heat of sulfuric acid, its add-on is controlled by the titanium hydrolysis F value of required control, adds entry again; Dissolved 1～8 hour down at 40～70 ℃, simultaneously with TiO in the solution ₂Amount be controlled at 180g/L～260g/L;

D-2) to through D-1) before the slip that obtains carries out solid-liquid separation, in slip, add flocculation agent, the optimization polypropylene amide solution.Its add-on depends on impurities in raw materials amount content; Be generally the polyacrylamide solution of weight percent concentration 0.05%～0.15%; Its additional proportion is every cubic metre of slurry titanium liquid 10L～30L flocculant solution, after deposition, filtration or press filtration, obtains low impurity titanium liquid then.

The described low impurity titanium liquid of step D contains 180g/l～260g/l TiO ₂, TFe/TiO ₂Be lower than 0.1, other foreign matter content≤10g/l such as Ca, Mg, Al.

In step e, said oxidation and organic extraction comprise the steps:

E-1) add the oxidation of divalent iron ion that oxygenant will hang down in the impurity titanium liquid and become ferric ion; Wherein said oxygenant is one or more in chlorine, oxygen, ozone and the hydrogen peroxide, preferred ozone; Preferably, add oxygenant and make the amount of hanging down ferrous ion in the impurity titanium liquid less than 0.5g/L, the amount that further preferably makes ferrous ion is less than 100ppm;

E-2) to through step e-1) add complexing agent in the titanium liquid that obtains, with the ferric ion in the complexing titanium liquid; Wherein said complexing agent is hydrochloric acid or hydrogenchloride, and the volumetric molar concentration that preferably makes cl ions in the titanium liquid is at least 4 times of ferric ion volumetric molar concentration, and concentration of hydrochloric acid is 1～5mol/L;

E-3) to through step e-2) mixture that adds extraction agent and thinner in the titanium liquid that obtains is as organic phase, to extract the ferric ion in the titanium liquid; Wherein said extraction agent is one or more of acid organo phosphorous compounds, carboxylic acid, sulfonic acid hydroxyoxime, oxine, beta-diketon, neutral phosphate, phosphorus oxide, ketone, alcohols, ethers and amine, preferable methyl isobutyl ketone and tributyl phosphate; Said thinner is one or more in benzene, trichloromethane, toluene, kerosene, sulfonated kerosene and the normal hexane, preferred sulfonated kerosene; The volumetric mixture ratio 0～4.5: 1 of thinner and extraction agent, preferred 3: 1; The volume ratio of organic phase and titanium liquid is 0.2～1.5: 1, preferred 1: 1, normal temperature to 50 ℃ extraction 1～20 minute, preferred 10 minutes;

Said back extraction operation in the step e comprises:

Adopt water or Hydrogen chloride or NaCl solution to come the ferric ion in the back extraction organic phase, and make the anti-raffinate that obtains get into the regeneration of hydrochloric acid operation of step B, thereby return steps A through being regenerated as hydrochloric acid leaching liquid as strip liquor; Wherein the volume ratio of organic phase and strip liquor is 1: 0.5～1: 3, preferred 1: 2.

High purity titanium liquid through evaporation concentration in the step F contains TiO ₂Be 180～260g/l, TFe＜100ppm, other impurity＜10g/l;

Said hydrolysis comprises: in titanium liquid, add an amount of reductive agent, like aluminium powder, its add-on makes Ti in the titanium liquid ³⁺Concentration get final product at 1～3g/L, and add and to account for TiO in the titanium liquid ₂Weight percent is 1.5%～5% rutilization nuclei or anatase titanium dioxide crystal seed, hydrolysis 2～8 hours under 90 ℃～boiling point then.

The metatitanic acid slurry that filters among the step G through step F obtains should carry out under acid and reduced state, and said acidity refers to pH＜1, and reduced state requires Ti ³⁺Concentration in 1～3g/L scope.The impure TFe＜30ppm of low impurity metatitanic acid after the said washing, impurity such as iron, magnesium equal size≤10g/l in the said dilution heat of sulfuric acid;

Step H comprises the steps:

H-1) in the low impurity metatitanic acid that obtains through step G, add granularity and crystal formation control agent, be sintered into the white titanium pigment particle then; Said granularity and crystal formation control agent are selected from one or more in hydroxide agent, phosphoric acid, zinc oxide, the White tin oxide;

H-2) will be through step H-1) the white titanium pigment particle that obtains grinds, one or more processing in broken of surface-coating, filtration washing, the gentle abrasive dust of spraying drying, to obtain the white titanium pigment finished product.

The supporting flow process that the high titanium salt acidleach of the present invention is slagged tap between sulfuric acid solution, the organic extraction of titanium liquid, the titanium hydrolysis is all different with the CN102102149A patented claim with disclosed CN101935063A with reaction conditions and sulfuric acid Recycle design.

In method provided by the invention; Described mother liquor shunting of step B and regeneration of hydrochloric acid comprise: will leach mother liquor and split into two portions; A part gets into mother liquor burning operation and in incinerator, burns through spraying, owing to hydrolysis and decomposition reaction take place high temperature, generates MOX and hydrogen chloride gas; Most of metal oxide solid particle can be deposited to the incinerator bottom and be excluded, and few part metals oxide compound and hydrogen chloride gas and waste gas get into the regeneration of hydrochloric acid operation; Another part leaches mother liquor and through diluting after, gets into the regeneration of hydrochloric acid operation and the hydrogen chloride gas of burning operation eliminating is absorbed obtain regenerating hydrochloric acid leaching liquid, returns the leaching steps A;

Said leaching mother liquor shunting is the differentiation standard with its iron concentration; Be that 100～160g/l, preferred 140～150g/l are as the shunting standard wherein with iron concentration; Iron concentration gets into spraying burning operation greater than the leaching mother liquor of this shunting standard, and iron concentration gets into the regeneration of hydrochloric acid operation less than leaching mother liquor of this shunting standard; As with the iron concentration be 140g/L as the shunting standard, it is worth between 100g/L 160g/L, iron concentration gets into mother liquor greater than the mother liquor of 140g/L and burns operation, iron concentration gets into the regeneration of hydrochloric acid operation less than 140g/L;

The regeneration of hydrochloric acid operation of said step B is carried out in the absorption tower, the hydrogen chloride in gas that adopts hydrochloric acid adsorption liquid counter-current absorption to get into the absorption tower; The gas on said entering absorption tower is that mother liquor burns the gas that operation is got rid of; The part that distributes from step B of comprising said hydrochloric acid adsorption liquid leaches the wash filtrate of mother liquor, wash solids and from the anti-raffinate of step e, and the Hydrogen chloride of water or pH＜1.

The present invention is based on characteristic and the existing hydrometallurgy and the technical defective of titanium white production of Panxi Diqu titanium resource, integrated optimization aforementioned three patented claims of the inventor, and make technical process organic supporting, creatively produce new function and effect.This method is through the intermediate product with the salt acid leaching process; The high titanium salt acidleach that promptly obtains through hydrochloric acid acidleach, solid-liquid separation, hydrochloric acid cyclically utilizing, washing is slagged tap as one of raw material or raw material; Through obtaining the titanium liquid of low impurity after the sulfuric acid solution dissolving; Obtain high purity titanium liquid through organic extraction again, said high purity titanium liquid makes high-grade white titanium pigment after hydrolysis, washing, calcining, surface treatment.Its whole production flow process is organic supporting; Technological process is coordinated each other; Material proportion and material trend are more optimized; And the circulation of formation hydrochloric acid system, sulfate system and organic extraction system, make material consumption, energy consumption, the discharging wastes of whole production system all be different from CN101935063A and CN102102149A patented claim.

Do further refinement explanation below in conjunction with 1 pair of Technology of the present invention of schema and flow process, but do not limit the present invention.Comprise the steps:

1, leaches

Ferrotianium material according to the invention comprises ferrotianium oxide compounds such as ilmenite (rock ore deposit and placer), ilmenite concentrate, modification ilmenite concentrate, titanium slag, and is not limited to above-mentioned ferrotianium material.Steps A is mixed ferrotianium material and hydrochloric acid leaching liquid, can adopt hydrochloric acid directly to leach, or the BCA hydrochloric acid leaching; Or preoxidation-fluidization normal pressure leaching, or preoxidation-selecting smelting combination pressurization leaching, preferred hydrochloric acid directly leaches; The titanium oxide mass percentage content that it is characterized in that the ferrotianium material is 30% to 80%; And steps A ferrotianium material also can carry out pre-treatment through one or more modes of preoxidation reductive, be about to ferrotianium material elder generation weak oxide and restore, or reduction reoxidizes earlier; Or only oxidation is not reduced, or only reduces not oxidation.

Get ferrotianium material and leaching liquid and in reaction vessel-1., mix, prepare high titanium salt acidleach with the salt acid leaching process and slag tap.Its processing condition are the processing condition of the salt acid leaching process of existing preparation artificial rutile; Specifically can adopt (1) hydrochloric acid directly to leach method, promptly directly leach the ferrotianium material, be high titanium salt acidleach and slag tap (referring to " the hydrochloric acid normal pressure directly leaches the Panxi Diqu ilmenite and prepares artificial rutile " through filtration, washing gained solid with hydrochloric acid; Non-ferrous metal; In November, 2007, the 59th the 4th phase of volume, P108-111; " artificial rutile process mineralogy and ore dressing Study on Purification ", rare metal, 1984, the 4 phases, P16-23 is that the hydrochloric acid pressurization is leached); Or adopt (2) BCA hydrochloric acid leaching method, the reductive agent (coal, refinery coke) that is about to ilmenite or ilmenite concentrate and 3%～6% adds in the rotary kiln continuously, about 870 ℃ with the Fe in the ore deposit ³⁺Be reduced to Fe ²⁺, then with 18～20% hydrochloric acid 90～120 ℃ of leachings 4 hours down, leaching is filtered the gained solid and is high titanium salt acidleach slag tap (referring to " titanium white production and utilisation technology ", Chen Chaohua, Liu Changhe write, Chemical Industry Press, 162 pages of P); Or adopt (3) preoxidation-fluidization normal pressure lixiviation process, promptly ilmenite or ilmenite concentrate sieve through preoxidation; The gained solid is high titanium salt acidleach and slags tap behind the hydrochloric acid leaching; Process method is referring to " dynamics research that Flos Bombacis Malabarici ilmenite fluidization hydrochloric acid leaches " (Liu Ziwei, Huang Zhuoshu, Wang Kanghai, mining metallurgical engineering, 1991; The 11st the 2nd phase of volume, P48-52); Or adopt (4) preoxidation-selecting smelting combination pressure leaching process, promptly ilmenite or ilmenite concentrate be through preoxidation, magnetic separation; The gained solid is high titanium salt acidleach and slags tap behind the hydrochloric acid leaching; Technology is referring to " the hydrochloric acid legal system is got the artificial rutile technical study " (Fu Zibi, Huang Beiwei, Wang Xuefei, steel vanadium titanium, in June, 2006; The 27th the 2nd phase of volume, P1-6).In above-mentioned four kinds of methods; It is the most convenient directly to leach the ferrotianium material with hydrochloric acid; Because slagging tap, the high titanium salt acidleach of sulfuric acid solution need not to consider ferrotianium material refinement and the low problem of leaching grade in the acidleach process; Can directly be used for existing sulfuric acid solution after the acidleach and prepare white titanium pigment, can effectively utilize Panxi Diqu fine fraction lithotype ilmenite.

Steps A of the present invention leaches preferably stage treatment of slurry; Classification is to utilize ore pulp particulate natural subsidence to realize; Contain upper strata slurry that most particulates soak slag (200 orders below) self pressure in the leaching container from flowing to evaporization process, after evaporation, carry out solid-liquid separation, the gained solid is slagged tap for high titanium salt acidleach through washing, drying; Get into the sulfuric acid solution operation, be used for sulfuric acid legal system white titanium pigment; Lower coarse grade (more than 200 orders) is soaked slag and is directly carried out solid-liquid separation, and the gained solid is artificial rutile through washing, drying, calcining, is one of sub product of the present invention, is used for the production of chloride process titanium dioxide powder.It is characterized in that the high titanium salt acidleach of the coarse fraction calcining temperature of slagging tap should be higher than 900 ℃, preferred 950 ℃～1100 ℃.

The described leaching liquid of steps A of the present invention is the hydrochloric acid of different concns or is the different concns hydrochloric acid compound system solution that contains chlorate; Its chlorate is a kind of of solubility chlorination salt such as iron(ic)chloride, magnesium chloride, calcium chloride, aluminum chloride, Manganous chloride tetrahydrate or is multiple mixing; It is characterized in that this leaching liquid chlorate can add preparation separately; Also can carry leaching mother liquor and the wash filtrate of chlorate and the raffinate cyclically utilizing that the organic extraction system contains solubility chlorination salt, preferred cycle reuse by the leaching system.Hydrochloric acid in the leaching liquid is master to reclaim hydrochloric acid mainly, add hydrochloric acid is auxilliary, add hydrochloric acid mainly be used for balance hydrochloric acid in technological process loss and regulate the concentration of hydrochloric acid of leaching liquid, recovery hydrochloric acid comes from the regeneration of hydrochloric acid operation.Leaching liquid preferably leaches mother liquor and wash filtrate and organic raffinate cyclically utilizing; At least contain part in the preferred leaching liquid and leach mother liquor; Contain a certain amount of iron(ic)chloride (ferrous iron and ferric iron) and other leaching impurity chlorides (like calcium chloride, magnesium chloride, aluminum chloride, Manganous chloride tetrahydrate etc.) in the mother liquor recovery because of leaching, can significantly improve the leaching speed and the efficient of ferrotianium material.

Dyeing elements such as Fe, Ni, Cr, Mn, V, Nb are the major impurities that influences its quality product in the white titanium pigment, and content is high more, and the whiteness of white titanium pigment and luminance index are low more.Removing these impurity in the production of tradition sulfate process titanium dioxide mainly is to be accomplished by rinsing process, thereby the staining impurity content in the raw material is low more, and the rinsing removal of impurities is just easy more.The present invention adopts the hydrochloric acid leaching method can effectively remove the dyeing element in the ferrotianium material; It is characterized in that hydrochloric acid leaches respectively the dye leaching yield of element of ferrotianium material and all is higher than more than 50%; The leaching yield of Fe, Mn, Mg is higher than more than 90%; Thereby a kind of raw material of low impurity content is provided for the downstream sulfuric acid process; Table 1 has been listed the chemical composition of several kinds of sulfate process titanium dioxide powder raw materials, from table, can find out that Fe, Mn, V, Nb equal size during the high titanium salt acidleach of the present invention is slagged tap are obviously low than solubility in acid titanium slag and ilmenite concentrate.Since the ferrotianium material under certain temperature and pressure by hydrochloric acid compound system liquid leaching; Impurity major parts such as Fe, Al, Mn, V, Nb, Ca, Mg are dissolved in the hydrochloric acid compound system and are removed through liquid phase; Formed slag phase staining impurity content obviously reduces; Table 2 has been listed hydrochloric acid and has been leached respectively the dye leaching yield of element of ilmenite concentrate, explains that the leaching effect of staining impurity is very good, and especially the iron major part is leached.Thereby by the white titanium pigment that the high titanium salt acidleach of this low impurity content is slagged tap and produced, its whiteness and luminance index are all apparently higher than the white titanium pigment of being produced by acid-dissolved titanium slag.

Table 1 sulfuric acid legal system titanium white material component is analyzed

Annotate: N/D representes that its content can't measure, and N/A representes its content undetermined

Table 2 hydrochloric acid leaches each element leaching yield of ilmenite concentrate

Element

Fe

Mn

V

Al

Nb

Ca

Mg

Leaching yield %

＞90

＞98

＞50

＞60

＞50

＞85

＞90

2, solid-liquid separation and washing I

After hydrochloric acid leached the ferrotianium material, impurity such as iron, magnesium, calcium got into solution and TiO ₂Stay in the solid phase.Solid-liquid separation-2. be used for separating after the leaching solid phase prod (high titanium salt acidleach is slagged tap) with leach mother liquor.Solid-liquid separation method is concentrated, spinning, filtration etc.Filtration is the most frequently used solid-liquid separation method, is called the leaching mother liquor by the liquid that filters gained, and the leaching mother liquor contains higher iron(ic)chloride and can all or part of entering burn, and redundance gets into regeneration of hydrochloric acid.The burning by-product is a red oxide of iron, is two of sub product of the present invention, though it contains higher Ca, Mg, Ca, Mg are that blast furnace ironmaking must add auxiliary material, can be mixed and made into pelletizing with iron ore concentrate, are used for blast furnace ironmaking raw material.

In filtering filter cake, more or less mechanically or chemical mode carrying impurity secretly, like FeCl ₂, FeCl ₃, CaCl ₂, MgCl ₂Deng.Washing-3. be one of effective ways that reduce impurity in the filter cake, the washing used water, but Hydrogen chloride is more effective.The liquid of washing gained is referred to as wash filtrate, returns leaching behind the low directly entering of its contained ferric chloride concn regeneration of hydrochloric acid.Filter cake after the washing is high titanium salt acidleach and slags tap.

Step B directly leaches through hydrochloric acid in the main-process stream of the present invention; Or the BCA hydrochloric acid leaching, or preoxidation-fluidization normal pressure leaching, or after preoxidation-selecting smelting combination pressurization leaching; The high titanium salt acidleach of leaching is slagged tap after solid-liquid separation; Need not high temperature drying or calcining, its drying temperature should be controlled and be lower than 600 ℃, preferred 150 ℃～250 ℃.Slagging tap because of the high titanium salt acidleach of leaching is with armorphous TiO ₂Be main residue, contain a small amount of rutile, if high temperature drying (such as being higher than 900 ℃) can make leached mud be converted into rutile in a large number, rutile is insoluble to sulfuric acid, makes leached mud lose solubility in acid, can't be used for next step sulfuric acid solution.But as aforementioned when taking the classification measure, the coarse grain that classification goes out soaks slag, then needs high-temperature calcination, makes it to be converted into rutile, just can be used for chloride process titanium dioxide production.Therefore the present invention can produce rich titanium material that is used for sulfuric acid process and the rutile that is used for chlorination simultaneously through the classification measure, makes the effective titanium in the Panxi Diqu ilmenite obtain hundred-percent utilization.

The high titanium salt acidleach of ferrotianium material of the present invention behind the hydrochloric acid leaching liquid leaching slagged tap and is porosity and looseness shape residue and metatitanic acid aggregate, and contains a spot of rutile, titanaugite, anosovite and quartz, wherein TiO ₂Composition mainly exists with non-crystal state, armorphous TiO ₂Content is 65～97%, it is characterized in that this high titanium salt acidleach is slagged tap to contain chlorion, and chlorion content is lower than 5%, and preferred content is 1%～3%.This is that the high titanium salt acidleach of the present invention is slagged tap and other sulfate process titanium dioxide raw material different character, and chlorine (Cl) is with FeCl ₃, FeCl ₂, CaCl ₂, MgCl ₂, AlCl ₃Exist etc. form; Its reason is the solid-liquid separation of ilmenite concentrate leaching slurry and washs and can not remove mother liquor fully; And the impurity in the mother liquor exists with the form of chlorate, and the height of its content depends on that ilmenite concentrate leaches the solid-liquid separation of slurry, the solid-liquid separation process of washing and selecting for use.The small amounts of chlorine radical ion does not only influence technical process of the present invention and quality product in next step sulfate process titanium dioxide production, on the contrary the organic extraction of titanium liquid being purified has suitablely, in the acidolysis process, meets sulfuric acid because of it and can produce following reaction:

MCl ₂+H ₂SO ₄-→2HCl+MSO ₄

Wherein M is metallic cations such as Fe, Ca, Mg, Al; HCl can volatilize at 120 ℃; So most of chlorine is removed with steam and acid mist, gets into titanium liquid on a small quantity, in titanium liquid purification by liquid extraction process, also need add HCl simultaneously as complexing agent in the acidolysis process; The existence of chlorion has suitable on the contrary to titanium liquid organic extraction purification, can help the complexing ferric iron.Chlorion gets into the recycle of hydrochloric acid recovery system through subsequent evaporation operation (evaporation concentration I-10.), does not produce the chlorate waste.

3, acidolysis

High titanium salt acidleach slagged tap carry out acidolysis in acidolysis container-4., mixing under certain temperature and the solid-liquid proportioning, and the insulation certain hour lets reaction be able to fully carry out with certain density sulfuric acid.High titanium salt acidleach after acidolysis slag tap generate titanyl sulfate or (with) titanium sulfate sosoloid.In this acidolysis process, high titanium salt acidleach is slagged tap also to join with one or more of ilmenite, ilmenite concentrate, modification ilmenite concentrate, solubility in acid titanium slag or other ferrotianium material and is carried out mixing acid behind ore deposit and separate.In addition, high titanium salt acidleach is slagged tap and can also be carried out sulfuric acid solution respectively with ilmenite concentrate, modification ilmenite concentrate, solubility in acid titanium slag or other ferrotianium material and prepare titanium liquid, and the titanium liquid that will prepare respectively then is by TFe/Ti0 ₂Be to produce mixed with titanium liquid after 0.25～0.35 standard is mixed, this mixed with titanium liquid without following organic extraction-8. directly be hydrolyzed- Obtain metatitanic acid.

Under usual conditions, the high titanium salt acidleach directly acidolysis of slagging tap need not to grind, but its acidolysis is more complete after being ground to-325 orders.The used sulfuric acid of the present invention, part comes from cyclic regeneration sulfuric acid.98% vitriol oil is directly added in acidolysis container-4., and 98% vitriol oil of adding is used for the loss of balance flow process vitriolic and regulates the sulfuric acid concentration of acidolysis.

4, dissolving

After the acidolysis, in acidolysis container-4., inject water or dilute sulphuric acid and make titanyl sulfate/titanium sulfate sosoloid process water-soluble or dilute sulphuric acid be referred to as that dissolving-5., titanyl sulfate/titanium sulfate gets into solution, residue is not referred to as slag by the solids of sulfuric acid solution.The major ingredient of slag is quartz, titanaugite, calcium sulfate etc., and this part slag is the same with traditional sulfuric acid process, can be used for making cement or slag brick.The main chemical constitution of its typical case is as shown in table 3 below.

Table 3, the main chemical constitution of typical acidolysis slag

In titanyl sulfate/titanium sulfate sosoloid dissolution process, in order to prevent the hydrolysis of titanyl sulfate, tackle the solid-to-liquid ratio in the dissolution process, free vitriolic concentration and temperature etc. are carried out process control.

5, solid-liquid separation

After dissolving, the titanium liquid and the slag that contain titanyl sulfate/titanium sulfate form slurry.In solid-liquid separation-6., add suitable flocculation agent, optimization polypropylene acid amides (PAM) after deposition, filtration or press filtration, can obtain pure low impurity titanium liquid, and this titanium liquid contains 180～260g/l TiO ₂, TFe/TiO ₂Be lower than 0.1, other foreign matter content≤10g/l such as calcium magnalium, this low impurity titanium liquid get into oxidation-7. and organic extraction-8. further purified, but also can without purification by liquid extraction directly get into hydrolysis- Isolated solid part is exactly to be the clean filter residue of staple with quartz, titanaugite, calcium sulfate, is three of sub product of the present invention.

6, oxidation and extraction

Produce white titanium pigment by high purity titanium liquid, not only can improve white titanium pigment quality and reclaim(ed) sulfuric acid concentration and also can reduce the discharging of acid waste water.The purpose of oxidation-7. and organic extraction-8. is exactly further to improve the purity of low impurity titanium liquid, generates high purity titanium liquid.The method of purification of described titanium liquid oxidation of abovementioned steps E and organic extraction specifically comprises the steps:

(1), adds oxygenant and become ferric ion to the oxidation of divalent iron ion in the titanium liquid;

Fe ²⁺-----→Fe ³⁺+e

(2), add complexing agent and make the ferric ion complexing in the titanium liquid, generally hydrochloric acid or hydrogen chloride gas are added (leading to) and go into titanium liquid complexing ferric ion, make it to generate the complexing body, help to combine with organic phase;

Fe ³⁺+4HCl-----→4H ⁺+FeCl ₄ ^-

(3), add extraction agent and the thinner ferric ion after with complexing and be extracted to organic phase, extraction agent generally adopts tbp (TBP);

H ⁺+FeCl ₄ ^-+2TBP-----→HFeCl ₄?2TBP

(4), separate organic phase and titanium liquid, liquid phase is the high purity titanium liquid after the purification;

(5) load organic phases is gone organic extractant regeneration-9., add water or Hydrogen chloride or NaCl solution and realize extraction agent, the reuse of thinner reprocessing cycle through multistage back extraction.

The invention is characterized in that leaching mother liquor and wash filtrate that anti-raffinate and step B distribute mix the hydrogenchloride adsorption liquid entering hydrochloric acid recovery system as the salt acid recovery, need not the spent acid treatment system, also no acidic discharge of wastewater.

Above-mentioned steps can be used the different oxidation agent in (1); Adopt one or more methods in chlorine oxidation, dioxygen oxidation, ozone oxidation, hydrogen peroxide oxidation or the electrolytic oxidation to mix; Oxidation of divalent iron ion is become ferric ion, preferably adopt ozone oxidation, its chemical principle is following:

● with chlorine oxidation: 2Fe ²++ Cl ₂→ 2Fe ³⁺+ 2Cl ^-

● with dioxygen oxidation: 2Fe ²⁺+ 1/2O ₂+ H ₂O → 2Fe ³⁺+ 2OH ^-

● with ozone oxidation: 2Fe ²⁺+ O ₃+ H ₂O → 2Fe ³⁺+ 2OH ^-+ O ₂

● with hydrogen peroxide oxidation: 2Fe ²⁺+ H ₂O ₂→ 2Fe ³⁺+ 2OH ^-

● with electrolytic process oxidation: Fe ²⁺→ Fe ³⁺+ e.

For matching step (2) forms complex compound HFeCl ₄And do not mix other impurity, and preferred chlorine, oxygen, ozone, hydrogen peroxide are used for the oxidation ferrous ion in the step (1), or adopt electrolytic process to make ferrous ion change into ferric ion, and each oxidation style can select one or mix and use.

After titanium liquid handled according to method of purification of the present invention, titanium liquid was pure, foreign matter content is few, does not have the impurity crystallization during sulphuric acid concentration reuse, sulfuric acid is most of to concentrate reuse, had reduced the discharging of spent acid, waste water, had improved the quality product of white titanium pigment.

Because of the volumetric molar concentration of free ferric ion in the high more titanium liquid of volumetric molar concentration of cl ions in the titanium liquid is just low more, the titanium liquid after the extraction is just pure more.In order to impel complex reaction to carry out, form more complex compound, feed hydrochloric acid or hydrogen chloride gas in the step (2) as complexing agent, the volumetric molar concentration that makes cl ions in the titanium liquid is 4 times of volumetric molar concentration of ferric ion at least.

For ferric ion is extracted to organic phase, extraction agent is one or more mixtures of acid organo phosphorous compounds, carboxylic acid, sulfonic acid hydroxyoxime, oxine, beta-diketon, neutral phosphate, phosphorus oxide, ketone, alcohols, ethers and amine.In order to regulate extraction agent viscosity, the emulsion of control in the extraction process, can also add the suitable dilution agent, as adopting a kind of or any mixing in benzene, trichloromethane, toluene, kerosene, sulfonated kerosene, the normal hexane etc. as thinner.When thinner was used, those skilled in the art can allocate according to practical situation, and the blending ratio of thinner and extraction agent (volume ratio) is (0～4.5): 1, and preferred 3: 1.

During extraction, the adding proportion of organic phase (O) and titanium liquid (A), promptly (adding proportion that is organic phase and titanium liquid is 0.2～1.5 to the O/A volume ratio: 1) between 0.2: 1 and 1.5: 1.The O/A ratio is looked ferric iron concentration and extraction agent Fe in the titanium liquid ³⁺Loading capacity and changing, the ferric iron concentration in the titanium liquid is high, preferred high O/A ratio.

7, extractant regeneration circulation

Ferric iron is with HFeCl ₄Form get into organic phase, the water-washable mode of load organic phases makes extractant regeneration-9. return extraction, forms closed cycle.Collection machine agent regeneration (or claiming to strip) used water, Hydrogen chloride or NaCl solution are to being loaded with FeCl ₃Load organic phases mix, separate, in order to obtain more purified organic phase, can adopt what reextraction.The impurity iron of extraction is mainly with FeCl ₃Form exist, through the liquor ferri trichloridi (anti-raffinate) of washing back extraction because of FeCl ₃Concentration is lower, directly get into the regeneration of hydrochloric acid of ferrotianium material hydrochloric acid leaching part- Recovery system.This point also is the difference that the present invention is different from CN101935063A and CN102102149A; Acid regeneration--leaching--leaches mother liquor and burns operation because anti-raffinate desalts; The residual organic extractant of anti-raffinate is realized qualified discharging behind high temperature incineration, this technical process does not have the organic extractant discharge of wastewater.

8, evaporation concentration I

According to the hydrolysis process parameter request, to the high purity titanium liquid after the extraction carry out high purity titanium liquid after 10. evaporation concentration I-maybe will extract directly get into next step hydrolysis-

Because in extraction process, added the complexing agent HCl of iron, the high purity titanium liquid after the extraction contains a certain amount of hydrochloric acid, can adopt heating evaporation to concentrate I-and 10. reclaim hydrochloric acid, meanwhile also adjusted the TiO in the titanium liquid ₂Concentration.The general direct entering regeneration of hydrochloric acid of Hydrogen chloride-

recovery system that reclaims also can be collected the back as washing I-washing water 3..The high purity titanium liquid of evaporation concentration contains TiO after extraction ₂180～260g/l, (conversion is TFe/TiO to TFe＜100ppm ₂Be lower than 10 ^-3), other impurity＜10g/l.

9, hydrolysis

Hydrolysis-

is the process that titanium sulfate or titanyl sulfate hydrolytic precipitation under the condition that certain temperature, acidity, ionic strength and crystal seed exist become metatitanic acid.Concrete chemical equation is as follows:

TiOSO ₄+2H ₂O----→TiO(OH) ₂+H ₂SO ₄

Or Ti (SO ₄) ₂+ 3H ₂O----→ TiO (OH) ₂+ 2H ₂SO ₄

In order to prevent ferric hydrolysis, the hydrolysis of titanium liquid is under reduced state, to carry out.Before hydrolysis, an amount of reductive agent (like aluminium powder) need be added in the titanium liquid, and its add-on makes Ti in the titanium liquid ³⁺Concentration get final product at 1～3g/L, also need add and account for TiO in the titanium liquid ₂Weight percent is 1.5%～5% rutilization nuclei or anatase titanium dioxide crystal seed, decides according to product needed, and the former produces Rutile type Titanium Dioxide, and the latter produces anatase thpe white powder.90 ℃～boiling point of hydrolysis temperature, hydrolysis time 2～8 hours.

Solid-liquid mixed pulp after the hydrolysis gets into solid-liquid separation-

10, solid-liquid separation

Titanium liquid is after hydrolysis, and titanium is with TiO (OH) ₂Deposition be mixed in the dilution heat of sulfuric acid, solid-liquid separation- Be from dilution heat of sulfuric acid, to separate TiO (OH) ₂Deposition.Filtration adds washing and is not only the solid-liquid separation process, and is metatitanic acid (TiO (OH) ₂) the removal of impurities purification process.For fear of ferric deposition, filter with washing and must carry out at acid and reduced state, prevent ferric existence as far as possible.Filter cake was calcined low impurity enters metatitanic -

The filtrate is dilute sulfuric acid solution into the solution called evaporation II-

The present invention is characterised in that the impure TFe＜30ppm of the said low impurity metatitanic acid of step G.

The present invention is characterised in that dilution heat of sulfuric acid impurity (Fe, the Mg etc.) content≤10g/l after the said solid-liquid separation of step G; The low impurity titanium liquid of step D gained directly gets into the dilution heat of sulfuric acid foreign matter content≤36g/l after the hydrolysis without purification by liquid extraction.

11, calcining

Calcining-

Be not only metatitanic acid and convert the TiO that specifies crystal formation to ₂The process of (like rutile-type, anatase titanium dioxide) also is the control process of finished product white titanium pigment globule size and distribution, and in this process, some granularities and crystal formation control agent can be added in this process, and promptly salt is handled, for example KOH, H ₃PO ₄, ZnO, SnO etc.

12, surface treatment

White titanium pigment particle agglomeration after calcining can produce crystal growth and connect together in calcination process between the particle.Connect because of crystal growth through grinding white titanium pigment to be reunited break up but also can interrupt between the particle.

Different according to the purposes of white titanium pigment, carry out different surface treatment method-

surface treatment and comprise that the steps such as grinding, surface-coating, filtration washing, spraying drying and gas abrasive dust be broken gather.For example, silicon and aluminium coating are prevailing.

13, hydrochloric acid leaches the mother liquor burning

The part or all of hydrochloric acid of solid-liquid separation-2. leaches mother liquor and gets into mother liquor and burn-and to leach that mother liquor burns is in incinerator, to carry out ; Leach mother liquor from furnace roof by sour rifle nozzle with the vaporific entering stove; And coal gas and air mixed burning back get in the stove with tangential direction at the stove middle part; Leach mother liquor at the stove middle part because high temperature generation hydrolysis and decomposition reaction, generate hydrogen chloride gas and be the particle of leading and contain Natural manganese dioxide, quicklime etc. with ferric oxide particle.Most of solid particulate is fallen the stove bottom because of action of gravity, and discharges from the stove bottom, and the waste gas that the small portion solid particulate produces after along with hydrogen chloride gas, water vapour and gas-fired is extracted out from furnace roof portion by blower fan, and major part is returned in the stove after dedusting.Waste gas gets into next regeneration of hydrochloric acid- operation that absorbs hydrochloric acid gas.The burning of leaching mother liquor is the process that a muriate hydrolysis and metal hydroxides decompose:

2FeCl ₂+2H ₂O+1/2O ₂-----→Fe ₂O ₃+4HCl

2FeCl ₃+3H ₂O-----→Fe ₂O ₃+6HCl

CaCl ₂+H ₂O----→CaO+2HCl

MgCl ₂+H ₂O----→MgO+2HCl

2AlCl ₃+3H ₂O-----→Al ₂O ₃+6HCl

The red oxide of iron that comes out from incinerator is a sub product of the present invention, can be used for producing the pelletizing or the iron powder of blast furnace ironmaking.

14, regeneration of hydrochloric acid

The waste gas that is come by mother liquor burning-

contains hydrochloric acid gas, and waste gas separates hydrochloric acid through secondary or three grades of absorption towers from waste gas.At first get into the bottom on first step absorption tower from the next waste gas that contains hydrogen chloride gas of incinerator; Through supporting the screen of filler, the circuitous rising in the space of packing layer is discharged by the top on first step absorption tower again; Then; Get into the hydrogen chloride gas in the further absorbing waste gas in bottom on absorption tower, the second stage again, last, discharge by the top on absorption tower, the second stage again.Directly be disposed to atmosphere behind the absorption tower, the second stage or after third stage absorption tower (neutralizing tower) handled, be disposed to atmosphere again according to environmental requirement decision waste gas.

Opposite with the waste gas traffic direction; Hydrochloric acid gas adsorption liquid from the top spray on third stage absorption tower and under be collected in the bottom; Hydrogen chloride gas in the further absorbing waste gas of pump to the top spray on absorption tower, the second stage again; Get into first step absorption tower with same connecting mode, reclaim hydrochloric acid and discharge by bottom, first step absorption tower.

Hydrochloric acid gas adsorption liquid can be clear water or diluted acid or contain rare leaching mother liquor of solubility chlorination salt by wash filtrate and extractant regeneration-anti-raffinate blended 9. that part leaches mother liquor and washing-3..These three kinds of hydrochloric acid gas adsorption liquids can use separately also and can mix use.Rare leaching mother liquor of the preferred independent reuse in first step absorption tower, third stage absorption tower and absorption tower, the second stage are connected into one water or Hydrogen chloride absorption.

All regenerated hydrochloric acid comprise that extractant regeneration-9. and evaporation concentration I-hydrochloric acid 10. all return leaching-1. realize closed cycle.

15, rare sulfur waste acid concentrates reuse.

The metatitanic acid wash filtrate of solid-liquid separation-

is dilution heat of sulfuric acid (being called dilute acid soln); Partial equilibrium discharging back gets into evaporation concentration II-

operation, returns the operation cyclically utilizing of acidolysis-4. and dissolving-5. through evaporation concentration.According to material balance, dilution heat of sulfuric acid balance quantity discharged is slagged tap by used high titanium salt acidleach or the impurity content and the acidolysis process parameter of its mixture are confirmed; The concrete treatment process process of evaporation concentration adopts the spent acid concentration technology of traditional sulfate process titanium dioxide, comprises that negative pressure heating concentrates, crystallisation by cooling and solid-liquid separation etc.

In the traditional process, dilute sulphuric acid concentrates and reclaims is the process of a vaporize water, and in this process, impurity concentrates 3～5 times, and too high like impurity concentration in the dilution heat of sulfuric acid, in concentration process, impurity can be with vitriol (like FeSO ₄NH ₂O, Al ₂(SO ₄) ₃) the form crystallization, this crystallization often occurs in heat exchanger surface, influences vitriolic and further concentrates.The low impurity titanium liquid of solid-liquid separation of the present invention-6. is through organic extraction-8. further after the removal of impurities; Very low through hydrolysis-

solid-liquid separation- and the dilute acid soln impurities that produced of washing (being step G); Its total impurities should be in the ppm rank; The most very much not can surpass 10g/l; Can not produce crystallization in the sulphuric acid concentration process; Can reclaim by 100% ground warp evaporation concentration II- ; Can reach the required sulfuric acid concentration of acidolysis (more than 85%) after the evaporation concentration, recycle.And the dilute sulphuric acid amount that traditional sulfuric acid process is handled because of needs is too big, and impurity content is very high, after multistage concentrating, also can only reach the concentration about 50%, can't all concentrate reuse, realizes the sulfuric acid circulation.In the present invention; Another selection of technical process be solid-liquid separation-6. low impurity titanium liquid without purification by liquid extraction directly get into hydrolysis-

thus titanium hydrolysis and dilution heat of sulfuric acid, its total impurities should be smaller or equal to the rank of 36g/l.Behind evaporation concentration II-

, also can reach the required sulfuric acid concentration of acidolysis (more than 65%), recycle.

After the said dilution heat of sulfuric acid partial equilibrium discharging of step G of the present invention, return acidolysis through evaporation concentration again, according to material balance, dilution heat of sulfuric acid balance quantity discharged is slagged tap by used high titanium salt acidleach or the impurity content and the acidolysis process parameter of its mixture are confirmed.Because sulfuric acid uses at system's internal recycle; The ion that makes some lower concentrations and be not excluded (like aluminium, magnesium, vanadium plasma) is constantly accumulation in system; For these ions of balance need to carry out an amount of balance discharging in that evaporation concentration II-

is preceding; Quantity discharged depends on impurity content and the acidolysis process parameter that used high titanium salt acidleach is slagged tap; Therefore, the discarded dilute sulphuric acid quantity discharged in the technical process of the present invention is significantly less than the spent acid quantity discharged of traditional sulfuric acid process.The dilute acid soln of balance discharging is with lime neutralizations such as (CaO).

Compared with prior art, the present invention has the following advantages:

1, the present invention adopts salt acid system pre-processing titanium iron material; The high titanium salt acidleach of salt acid leaching process gained slagged tap be used for method for producing gtitanium dioxide with sulphuric acid; Can effectively utilize fine-grained Panxi Diqu ilmenite; Utilization ratio almost 100% obviously is superior to preoxidation-fluidization hydrochloric acid and leaches ilmenite system artificial rutile (have because of this technology 10%～15% refinement product can't utilize).Simultaneously, hydrochloric acid leaching of the present invention adopts the classification measure, and coarse fraction is produced artificial rutile, and fine-graded production is used for the rich titanium material of sulfuric acid process, can satisfy sulfuric acid process and chloride process titanium dioxide production needs simultaneously, and this also can 100% utilizes the Panxi Diqu ilmenite.

2, the present invention slags tap the high titanium salt acidleach of ferrotianium material hydrochloric acid leaching generation and is applied to sulfuric acid method titanium pigment production; Make sulfuric acid process raw material impurity content low; Staining impurities such as especially most of iron, magnesium, calcium and vanadium, chromium, manganese are removed (leaching yield of iron, magnesium, calcium, manganese, vanadium can reach 90%, 90%, 85%, 98%, 50% respectively) in the hydrochloric acid leaching process, gained titanium liquid foreign matter content is few behind the sulfuric acid solution, and further through the organic extraction deironing; The high purity titanium liquid quality that obtains obviously is superior to traditional sulfuric acid process; The metatitanic acid impurity content is low after hydrolysis, and quality is good, can significantly improve the white titanium pigment quality.

3, the present invention produces the rich titanium material of salt acid leaching process and sulfuric acid method titanium pigment production technique and titanium liquid organic extraction technology close fit; The particularly anti-raffinate of titanium liquid organic extraction and hydrochloric acid extract technology UNICOM; Realized three closed cycles of hydrochloric acid solution system and sulphuric acid soln system and extraction organic agent, the whole cyclically utilizing of hydrochloric acid, sulfuric acid only have the partial equilibrium discharging; There is not extraction organic agent discharge of wastewater; And do not produce ferrous sulfate (green vitriol), its waste discharge is superior to traditional sulfuric acid method titanium pigment greatly, is a kind of cleaning, environmental protection, production technique efficiently

4, the present invention takes the shunting measure because ferrotianium material hydrochloric acid leaches mother liquor, and part is burned, the part cyclically utilizing, and the burning amount that leaches mother liquor is reduced greatly, and the energy consumption of hydrochloric acid recovery system reduces more than 30%.In the sulfuric acid solution technology since in the titanium liquid iron and other foreign matter contents low; Can save bigger freezing deironing of power consumption and titanium liquid enrichment process; Simultaneously, titanium liquid is through the further removal of impurities posthydrolysis of organic extraction, and impurity content is very low in the rare sulfur waste acid after its metatitanic acid separates; Greatly reduce the process energy consumption of sulphuric acid concentration, make the entire system energy consumption reduce about 15%.In addition, ferrotianium material of the present invention need not fine grinding, saves the Grinding procedure high energy consumption, is superior to the solubility in acid titanium slag greatly and produces white titanium pigment technology (titanium slag needs fine grinding just can be used for sulfate process titanium dioxide production to-325 orders).

5, the present invention slags tap with the high titanium salt acidleach of low impurity content and carries out sulfuric acid solution system titanium white owing to adopt salt acid system pretreating raw material, and the acidolysis sulfuric acid concentration is low, can make the sulfuric acid consumption reduce about 50%.The rare sulfur waste acid of the present invention impurity content is very low, except that a small amount of balance discharging, does not produce sulphate crystal when concentrated, can obviously be superior to traditional sulfuric acid process all through evaporation concentration 100% ground cyclically utilizing.Particularly compare, have clear superiority, because of the titanium slag sulfate process titanium dioxide needs the high-concentration sulfuric acid acidolysis with titanium slag sulfate process titanium dioxide technology; It is big to need to concentrate the rare useless sulfuric acid amount that reclaims, and it is high to concentrate cost, and receives the sulphuric acid concentration process technology limit; The crystallization in concentrating of a large amount of impurity is separated out in the spent acid, produces congee shape thing, can't further concentrate; Spent acid can not all reclaim, and needs discharging in a large number.

6, utilize part to leach mother liquor in the hydrochloric acid leaching technology of the present invention and wash filtrate removes to adsorb the HCl gas in the incinerator waste gas, reduced the consumption of adding water.Titanium liquid in the sulfuric acid solution technology contains ferrous iron and ferric iron is extremely low, has significantly reduced the metatitanic acid washing times, thereby reduced the discharging of acid waste water.Thereby the total system water consumption reduces about 40%.Simultaneously, because of the high titanium salt acidleach iron-holder of slagging tap is low, acidolysis reaction is gentle, helps acidolysis vent gas treatment qualified discharge.

7, the present invention adopts high titanium salt acidleach to slag tap and the acidolysis that is mixed of other ferrotianium material; Particularly high titanium salt acidleach is slagged tap and the solubility in acid titanium slag sulfate process titanium dioxide that the prepared low impurity titanium liquid of acidolysis is used to produce that is mixed; Its quality product obviously is superior to the sulfate process titanium dioxide that the solubility in acid titanium slag is produced separately; Its whiteness, brightness are high, and acidolysis do not emit pot, do not produce ferrous sulfate.Adopt high titanium salt acidleach to slag tap and the acidolysis respectively of other ferrotianium material; Produce mixed with titanium liquid after the titanium liquid of the preparation of acidolysis respectively is mixed; Particularly high titanium salt acidleach slag tap with ilmenite or ilmenite concentrate respectively acidolysis produce titanium liquid, with the titanium liquid of producing the respectively white titanium pigment that back gained mixed with titanium liquid produces that is mixed, its quality product obviously is superior to the sulfate process titanium dioxide that ilmenite concentrate is produced separately again; And the production cost first mate reduces, and does not produce ferrous sulfate.

Description of drawings

Fig. 1: titanium white production process flow sheet of the present invention;

Fig. 2: the SEM-X10000 photo (ESEM) of the embodiment of the invention one gained white titanium pigment;

Fig. 3: the SEM-X50000 photo (ESEM) of the embodiment of the invention one gained white titanium pigment;

Fig. 4: the XRD of the embodiment of the invention one gained white titanium pigment (X-ray diffraction) figure, its used instrument, condition determination and parameter are: DX-2700 type X diffractometer; SSC 40KV/25mA; Slit:1deg&1 deg&0.2m; Monochromator:On; TS-Td.

Fig. 5: the embodiment of the invention three schemas.

Embodiment

Salt acid leaching process and sulfuric acid solution all can use existing technology in the inventive method; Can adopt in the example hydrochloric acid lixiviation process that hydrochloric acid directly leaches, BCA hydrochloric acid leaching method, preoxidation-fluidization normal pressure lixiviation process or preoxidation-selecting smelting combination pressure leaching process, as adopt easy hydrochloric acid directly to leach ilmenite technology.Concrete extract technology is following:

1, hydrochloric acid directly leaches method

Ferrotianium material hydrochloric acid of the present invention directly leaches step and is:

The preparation of a, leaching liquid is formed by recovery hydrochloric acid that contains iron ion and the mixed in hydrochloric acid of newly adding, and the free concentration of hydrochloric acid in the leaching liquid is 15%-25%, the Fe in the leaching liquid ²⁺+ Fe ³⁺Concentration is 30～100g/l, and with a little whiles, leaching liquid contains calcium, magnesium, aluminium, manganese plasma.

B, mixed with titanium iron ore and hydrochloric acid leaching liquid, ilmenite quality (gram) is 1g: 2.5ml～5ml with volume (milliliter) ratio of leaching liquid.Preheat leaching liquid to 70 ℃～100 ℃ and get into and leach reactor drums, then, adopt the mode that directly feeds steam or indirect heating will leach the temperature of reacting and be controlled at 70 ℃～150 ℃, and kept its temperature of reaction 1-8 hour;

C, reaction paste are through solid-liquid separation (filtration), and filter cake is acid soluble high titanium salt acidleach and slags tap through washing, dry gained solid.

D, leaching mother liquor get into according to iron ion equilibrium concentration shunting back and burn and hydrochloric acid recovery system cyclic regeneration.

It is characterized in that the said leaching mother liquor of steps d shunts according to the iron ion equilibrium concentration; The leaching mother liquor that iron concentration is high gets into and burns; The leaching mother liquor that iron concentration is low advances the hydrochloric acid recovery system; Keep the iron of ferrotianium material leaching entering hydrochloric acid system and the iron that the organic extraction raffinate is brought system into to equal to shunt the iron that burns the eliminating hydrochloric acid system, the iron concentration branch is defined as 100～160g/l, preferred 140～150g/l.

Wherein, the hydrochloric acid in the step a leaching liquid mainly comes from regeneration of hydrochloric acid, the Fe in the leaching liquid ²⁺And Fe ³⁺Preferably come from the circulation of leaching mother liquor and return, so the concentration of other impurity (calcium, magnesium, aluminium etc.) in leaching liquid depends on the foreign matter content of institute's processing ilmenite.

Wherein, step b leaching liquid with need preheat leaching liquid to 70～100 ℃ before ilmenite mixes, the preheating purpose is to shorten heat-up time as far as possible, reduces the diluted possibility of leaching liquid.It is in the reaction vessel of a sealing, to carry out that leaching liquid mixes with ilmenite.

When step c filters, need reaction solution be cooled to 80-90 ℃ earlier and filter, filtration can be adopted any form, all can like vacuum filtration or press filtration.Washing is one of effective means of foreign ion during the high titanium salt acidleach of removing is slagged tap, the washing used water, and the sour water of preferred pH＜1, like diluted hydrochloric acid aqueous solution, its HCl concentration is greater than 0.1mol/L or pH＜1.

When step c was dry, controlled temperature was lower than 600 ℃, and 2～8 hours time of drying, temperature is too high, possibly produce artificial rutile or anatase titanium dioxide TiO ₂And can not be by sulfuric acid dissolution.Preferred controlled temperature is lower than 250 ℃, more preferably 150 ℃～250 ℃.

When steps d filtration and washing filter cakes, the leaching mother liquor of gained is collected in respectively in two different containers by the ionic concn difference, and iron concentration is the differentiation standard in the mother liquor to leach, and is generally 100～160g/l, preferred 140～150g/l.Go mother liquor to burn greater than the leaching mother liquor of this concentration, less than leaching mother liquor/rare leaching mother liquor of this concentration HCl gas that acid regeneration absorption mother liquor burns that desalts.As being example with the 140g/L mother liquor, it is worth between 100g/L～160g/L, and the mother liquor entering mother liquor burning operation greater than 140g/L gets into the regeneration of hydrochloric acid operation less than 140g/L.

2, acidolysis and dissolving

Get high titanium salt acidleach and slag tap and sulfuric acid mixing acidolysis and dissolving, concrete steps are following:

A, mix sulfuric acid and slag tap with high titanium salt acidleach, be heated to 150～240 ℃ after, the control heating lets react to be carried out and keeps its temperature of reaction; Wherein acid sludge is 1.4～1.9: 1 than by weight;

Obtain thick solid mixt after b, the reaction;

C, this mixture is placed 150～240 ℃ of slakings 1～4 hour, be cooled to and be lower than 80 ℃, add and be lower than 60 ℃ warm water, amount of water contains TiO with control titanium liquid ₂Be as the criterion at 180～260g/L, adding water is in order titanyl sulfate and titanium sulfate to be dissolved in the water, to dissolve 1～8 hour down at 40～70 ℃;

Wherein, slaking promptly is with acid hydrolysate--thick solid mixt further carries out acidolysis reaction;

D, be stirred to solid mixt dissolving, cross and filter low impurity titanium liquid.This titanium liquid is the mixture of titanyl sulfate and titanium sulfate, uses this titanium liquid and can further purify or adopt existing method to prepare white titanium pigment through organic extraction and get final product.

It is characterized in that the described low impurity titanium liquid of steps d contains TiO ₂180～260g/l, TFe/TiO ₂Be lower than 0.1, other foreign matter content≤10g/l such as Ca, Mg, Al.

Wherein, the used sulfuric acid concentration of step a is 55～98%, and preferred sulfuric acid concentration is 85～91%.Because receive the restriction of dilute sulphuric acid concentrate recovery process and equipment, the traditional technology reclaim(ed) sulfuric acid has a threshold concentration, so the acidolysis sulfuric acid concentration has determined dilute sulphuric acid to concentrate the recovery, promptly the low more available dilute sulphuric acid of acidolysis sulfuric acid concentration is many more.Acidolysis sulfuric acid concentration that the high titanium salt acidleach of the present invention is slagged tap and ilmenite concentrate (about 85～89%) are suitable, and be lower than solubility in acid titanium slag acidolysis sulfuric acid concentration 91～93%, thereby help the concentrated reuse of next step dilute sulphuric acid.Let reaction carry out and keep 150～240 ℃ of its temperature of reaction, restir to be beneficial to react completely in 5～240 minutes carrying out in step a control heating.The purpose that stirs is to let reaction carry through to the end and consolidates sour thorough mixing; If do not stir, adopt lower concentration acid will produce the solid-liquid layering.Traditional technology is with in ilmenite concentrate and the solubility in acid titanium slag sulfuric acid legal system titanium white production; Acidolysis reaction is paid strong very much, within 3～5 minutes, accomplishes acidolysis, in abrupt release in a large number with the water vapor of acid mist; Making the water pouring remove acid system can't bear, so that discharging can't be up to standard.Because the high titanium salt acidleach of the present invention contains Fe in slagging tap ₂O ₃Lower, acidolysis reaction is gentle, within 15～20 minutes, accomplishes acidolysis, helps water and drenches except that the acid system works better.

Step c is except adding warm water, can add also that to be lower than 60 ℃ of weight percent concentration in right amount be that 20% dilute sulphuric acid is dissolved in all solid compounds in the dilute sulphuric acid.And then adding water, the water yield is by 180～260g/L TiO ₂Calculate.It leaches solvent temperature is 40～70 ℃ of the bests, leach solvent temperature and be higher than 85 ℃ and titanium sulfate might take place be hydrolyzed into the metatitanic acid deposition with titanyl sulfate and be lost in and soak in the slag, and that the leaching solvent temperature is lower than 40 ℃ of its dissolution raties is too casual.Leaching dissolution time is 1～8 hour.Wherein, be cooled to add again after being lower than 80 ℃ its major cause of warm water be sulfuric acid to meet water be thermopositive reaction, might local temperature be higher than 85 ℃ and the generation titanium hydrolysis influences dissolution rate as not cooling off.The too low meeting of the too high or local acidity of water and reactant mixing temperature causes titanium hydrolysis, should be lower than 60 ℃ so institute adds warm water temperature, is about 40～60 ℃.Amount of water contains TiO with control titanium liquid ₂Be as the criterion at 180～260g/L.

Using high titanium salt acidleach slags tap and can adopt existing any sulfuric acid process to be used to produce white titanium pigment.Existing sulfuric acid process is different according to the sulfuric acid concentration of acidolysis and the state that forms final product, can be divided into liquid phase method, two phase process and solid phase method.But with high titanium salt acidleach slag tap carry out acidolysis and ilmenite concentrate acidolysis process with form difference to some extent on the final product, be embodied in:

Liquid phase method is to adopt 55%～65% sulfuric acid that high titanium salt acidleach is slagged tap to carry out acidolysis; Acidolysis is carried out in liquid phase; 130～140 ℃ of temperature of reaction in 1.5～8.0 hours reaction times, get thick water solid mixture after the reaction; After 140～220 ℃ of slakings, get block solid mixt, need with getting titanium liquid after the water dissolution.

Two phase process is to adopt 65%～75% sulfuric acid that high titanium salt acidleach is slagged tap to carry out acidolysis; Acidolysis is carried out in liquid phase, 160～180 ℃ of temperature of reaction, 20～60 minutes reaction times; Get thick water solid mixture after the reaction, after 140～220 ℃ of slakings, get block solid mixt.

Solid phase method is to adopt sulfuric acid more than 80% that high titanium salt acidleach is slagged tap to carry out acidolysis; Acidolysis is carried out in liquid phase, 160～200 ℃ of temperature of reaction, 5～20 minutes reaction times; Get thick solid mixture after the reaction, after 140～220 ℃ of slakings, get block solid mixt.

The high titanium salt acidleach of the inventive method sulfuric acid solution is slagged tap and all should be solid phase method in fact on final formation product, just its acidolysis reaction temperature and the difference in reaction times.Used sulfuric acid concentration is low, and then temperature of reaction is low, long reaction time, and it is finer and close than imitating to form lurid final product.Opposite used sulfuric acid concentration is high, and then temperature of reaction is high, and reaction is fast, and it is big to form tawny final product porosity.

3, oxidation and extraction

The concrete steps of extraction are following:

(1), oxidation of divalent becomes ferric iron

Can come the feeding amount or the oxidising process of controlled oxidation agent when the present invention is characterised in that oxidation with ferrous content in the titanium liquid, during preferred ozone oxidation in the titanium liquid ferrous content at Fe ²⁺＜0.5g/l controls the feeding amount of ozone, more preferably Fe ²⁺＜100ppm.Iron in the titanium liquid at first becomes ferric ion to the oxidation of divalent iron ion in the titanium liquid with ferrous iron and ferric iron coexistence.Most preferred scheme is to use the ozone oxidation ferrous iron, and the ozone that comes from ozonizer will directly be blasted the titanium liquid, controls the feeding amount of ozone with ferrous content in the titanium liquid, generally is controlled in the above-mentioned scope to good.Its reaction formula is following:

2Fe ²⁺+2H ⁺+O ₃-----→2Fe ³⁺+O ₂+H ₂O

(2), ferric ion and HCl complexing

Hydrochloric acid or hydrogen chloride gas are added (leading to) go into complexing ferric ion in the titanium liquid; Its reaction formula is following:

Fe ³⁺+4HCl-----→4H ⁺+FeCl ₄ ^-

Every mole of ferric ion needs 4 moles of HCl to come complexing, and adding the hydrochloric acid minimum concentration is the concentration of 4 times iron ion, and the concentration of hydrochloric acid in titanium liquid is generally 1～5mol/L.

(3), the ferric ion after the complexing is extracted to organic phase

The ferric ion of extraction after the complexing be to organic phase, its extraction agent preferable methyl isobutyl ketone and tributyl phosphate (TBP), and tributyl phosphate (TBP) extraction process is following:

H ⁺+FeCl ₄ ^-+2TBP-----→HFeCl ₄?2TBP

Extraction process is relevant with extraction agent TBP concentration and acidity.Extraction agent TBP and thinner are made into organic phase by a certain percentage, and preferable absorbent has kerosene, sulfonated kerosene, benzene, toluene etc., and more preferably thinner is a sulfonated kerosene.Thinner (like sulfonated kerosene) is 0～4.5: 1 with the volumetric mixture ratio of extraction agent (like TBP), preferred 3: 1.

Organic phase (O) is called the O/A ratio with the volume ratio of titanium liquid (A), and O/A is generally 0.2～1.5: 1, and preferred 1: 1.The extraction time was generally 1～20 minute, preferred 10 minutes.Extraction temperature is generally normal temperature to 50 ℃, the natural temperature of preferred titanium liquid, more specifically, the temperature of not regulating titanium liquid in the preferred extraction process.

(4), separating load organic phase and titanium liquid

Separating load organic phase and titanium liquid can be through the modes of deposition or spinning, preferred precipitate and separate.Load organic phases after the extraction and titanium liquid mixed solution separate upper strata load organic phases and bottom titanium liquid after staticly settling.

(5), Fe ³⁺Strip

Fe ³⁺Stripping and also claim extractant regeneration, is with being loaded with Fe ³⁺Load organic phases mix and separating process with strip liquor.The preferred pure water of strip liquor, Hydrogen chloride or NaCl solution.Or select for use pure water and Hydrogen chloride to intersect and use and carry out multistage back extraction as strip liquor.The O/A ratio was generally 1: 0.5～1: 3, preferred 1: 2.

4, mother liquor burns and regeneration of hydrochloric acid

The burning main purpose that leaches mother liquor is to reclaim hydrochloric acid, and the concentration that gets into iron in the incinerator leaching mother liquor is controlled at as in table 4 scope.The practical implementation way is that the leaching mother liquor in the process of solid-liquid separation-is 2. collected by the concentration shunting of iron.The burning amount that leaches mother liquor is determined by the balance that leaches the major impurity component iron in the mother liquor, is promptly equaled to leach the iron that mother liquor is got rid of by burning by the iron that gets into system in the ilmenite concentrate leaching process, and the remaining mother liquor that leaches directly or indirectly returns the leaching operation.Iron concentration is inversely proportional in the volume of burning leaching mother liquor and the leaching mother liquor, and the volume that leaches the high more leaching mother liquor burning of iron concentration in the mother liquor is few more.Leaching the mother liquor incineration temperature is 500～820 ℃, and furnace roof portion roaster gas temperature out is 370～450 ℃

Table 4, the chemical constitution that gets into incinerator leaching mother liquor

The hydrogen chloride gas bulk absorption: the absorption of hydrochloric acid gas is that hydrochloric acid gas is separated from waste gas, makes the process of regeneration of hydrochloric acid.Whole process is accomplished in two-level absorption tower.At first get into the bottom of first grade absorption tower from the next waste gas that contains hydrogen chloride gas of incinerator; Through supporting the screen of filler, the circuitous rising in the space of packing layer is discharged by the top of first grade absorption tower again; Then; Get into the hydrogen chloride gas in the further absorbing waste gas in bottom of two-level absorption tower again, last, discharge by the top of two-level absorption tower again.Directly be disposed to atmosphere behind the two-level absorption tower or after three grades of off gas treatments, be disposed to atmosphere again according to environmental requirement decision waste gas.

The solution (being called rare leaching mother liquor) that absorbs hydrochloric acid gas by part leach wash filtrate, the extraction process of mother liquor, washing procedure anti-raffinate, add water or Hydrogen chloride is formed.Rare leaching mother liquor typical case chemical constitution is as shown in table 5.

The chemical constitution of table 5, rare leaching mother liquor

Rare leaching mother liquor at first evenly sprays the packing layer upper surface from the top of two-level absorption tower; And flow downward to the bottom of two-level absorption tower along filling surface; Then; The top of pump to first grade absorption tower is behind spray again, the solution that is collected in the bottom of first grade absorption tower rare leaching mother liquor that is referred to as to circulate, and pump to leaching liquid preparation process is realized Recycling again.Rare leaching mother liquor typical case chemical constitution that circulates is as shown in table 6.

The chemical constitution of table 6, the rare leaching mother liquor of circulation

Off gas treatment: environmental requirement and processing condition are depended in the further processing of waste gas; Can behind two-level absorption tower, directly be disposed to atmosphere; Also can be again after third stage neutralizing tower is handled, be disposed to atmosphere, off gas treatment can adopt water or basic soln as absorption agent to reach waste gas emission standard.

The concrete embodiment of following reference explains the present invention, it will be appreciated by those skilled in the art that these embodiment only are used to explain the present invention, the scope that it does not limit the present invention in any way.As do not have a specified otherwise, below experimental technique among each embodiment, be ordinary method, used test materials is to buy from conventional suppliers and obtains.

Embodiment 1

A, hydrochloric acid directly leach ilmenite concentrate and prepare high titanium salt acidleach and slag tap

1, takes by weighing 7.2 tons of ilmenite concentrates, pour in the retort, sealing.

2, pump into 25 cubic metres of weight percent concentration be 19% hydrochloric acid leaching liquid in retort, hydrochloric acid leaching liquid contains TFe 42g/L; Ca ²⁺1.2g/L; Mg ²⁺6.7g/L; Al ³⁺0.8g/L; Mn ²⁺2.0g/L leaching liquid is preheated to 100 ℃ through heat exchanger of graphite.

3, rotational response jar makes leaching liquid and ilmenite concentrate thorough mixing in the retort.

4, feed steam in retort, heat rapidly about leaching liquid to 120 ℃, stop steam.

5, reaction heat can make retort be warming up to about 135 ℃, and the insulation leaching liquid is after 3 hours, and the stopped reaction jar directly discharges reaction paste in the flashing tower internal cooling.

5, wash with slurries filtration and with Hydrogen chloride.

6, filter cake promptly makes high titanium salt acidleach and slags tap behind 250 ℃ of rotary kiln dryings.

To the high titanium salt acidleach chemical ingredients analysis of slagging tap, the result sees table 7.

The main chemical constitution (wt.%) that table 7, Flos Bombacis Malabarici ilmenite concentrate and high titanium salt acidleach are slagged tap

	Al 2O 3	CaO	Fe 2O 3	MgO	SiO 2	TiO 2	V 2O 5
								Raw ore (ilmenite concentrate)	0.9	1.1	44.0	4.0	3.0	46.1	0.1
High titanium salt acidleach is slagged tap	0.4	0.5	4.7	0.45	4.8	86.7	0.1

B, the high titanium salt acidleach sulfuric acid solution of slagging tap

Get the high titanium salt acidleach of steps A and slag tap and 89% sulfuric acid (89% sulfuric acid being amounted to into 100% sulfuric acid) like the sulfuric acid of sulfuric acid=89g 100% of 100g 89%, by high titanium salt acidleach slag tap weight ratio with 100% vitriol oil be 1: 1.65 in the acidolysis pot.After air agitation is even, begin heating with superheated vapour.Under agitation condition, be heated to let about 150 ℃ and react spontaneous carrying out.Continue 40 minutes afterreaction things of stir about and form thick solid mixt, the reaction top temperature is 220 ℃.Insulation acidolysis pot added 60 ℃ of 20% dilute sulphuric acid and water after 2 hours, was stirred to till the whole dispersions of resultant of reaction.Pump to flocculation sedimentation tank carries out solid-liquid separation then, and more after filtering, the filter residue oven dry is also carried out chemical composition analysis such as table 8, its TiO ₂The sulfuric acid solution rate be 97.1%.Filtering filtrating is low impurity titanium liquid, and its compositional analysis result lists in table 9.

Table 8, the main chemical constitution of acidolysis slag

Compositional analysis is learned in table 9, low impurity titanium liquefaction

TFe(g/L)	TiO 2(g/L)	Iron titanium ratio	The F value
				8.2	188	0.044	1.95

Wherein, F value representation acidity quotient is effective acid amount and TIO ₂The ratio of total content.

The purification of C, titanium liquid

The titanium liquid of B preparation set by step carries out oxidation with the ozone with ozonizer in the container of 30 liters/wheel cylinder to 3000 liter.

The chemical constitution of titanium liquid after table 10, the oxidation

In the titanium liquid after oxidation (its component is seen table 10), to 2mol/L, the chemical constitution of titanium liquid is as shown in table 11 with the HCl concentration in 31% the hydrochloric acid adjustment titanium liquid.

The chemical constitution of titanium liquid behind table 11, the adding hydrochloric acid

Titanium liquid carries out the extraction of three stage countercurrents after will adding hydrochloric acid, and organic phase is to be mixed by 30% tributyl phosphate (TBP) and 70% sulfonated kerosene.It is 1: 1 that O/A is selected in extraction for use, and ferric ion optionally is extracted into organic phase and removes.Extraction back titanium liquid, its chemical constitution is as shown in table 12.

The chemical constitution of table 12, extraction back titanium liquid

To extract back titanium liquid under 80 ℃ of constant temperatures, and get high purity titanium liquid after negative pressure spray demineralizing acid concentrates, its chemical constitution is as shown in table 13.

The chemical constitution of table 13, deacidification back high purity titanium liquid

The hydrolysis of D, titanium liquid

Get the high purity titanium liquid after step C deacidifies, add an amount of aluminium powder and make Ti in the titanium liquid ³⁺For about 2g/L.Stir in the containers with outer heating with 4000 liters of bands of 30 liters/wheel cylinder to 3 series connection, the control hydrolysis temperature is 95 ℃, with 1.5%～5% (with TiO ₂Be radix) rutilization nuclei add in first container and be hydrolyzed, the slurry after the hydrolysis is after barrier film press filtration and washing, through 0.5%K ₂O and 0.1%P ₂O ₅After salt is handled, calcined 2 hours the SEM of its white titanium pigment (scanning electron microscope) photo such as Fig. 2, Fig. 3 down at 900 ℃; XRD (X-ray diffraction) is like Fig. 4.

Embodiment 2

Steps A, B, D are identical with embodiment 1, and the step C titanium liquid used extraction agent of purifying is different,

Specific as follows:

Titanium liquid behind the embodiment 1 step C adding hydrochloric acid is carried out the extraction of three stage countercurrents, and organic phase is to be mixed by 30% mibk (TBP) and 70% sulfonated kerosene.It is 1: 1 that O/A is selected in extraction for use, and ferric ion optionally is extracted into organic phase and removes.Extraction back titanium liquid, its chemical constitution is as shown in table 14.

The chemical constitution of table 14, extraction back titanium liquid

To extract back titanium liquid under 80 ℃ of constant temperatures, and get high purity titanium liquid after negative pressure spray demineralizing acid concentrates, its chemical constitution is as shown in Tble 15.

The chemical constitution of table 15, deacidification back high purity titanium liquid

Embodiment 3

Referring to Fig. 4, in embodiment 1 steps A, increase reaction paste classification operation, retort upper strata particulate slurry Artesian Drainage is put in the flashing tower internal cooling, filter then and wash with Hydrogen chloride, filter cake promptly makes high titanium salt acidleach and slags tap behind rotary kiln drying.Retort lower floor coarse grain slurry cooling back direct filtration is carried out solid-liquid separation, and filter cake with after 950 ℃ of calcinings of rotary kiln promptly get artificial rutile, can be used for chloride process titanium dioxide production with Hydrogen chloride washing back seasoning.

The prepared high titanium salt acidleach of embodiment 1 steps A is slagged tap further according to implementing with embodiment 1 step B, C, method that D is identical.

Embodiment 4

Make low impurity titanium liquid according to embodiment 1 steps A, B, this low impurity titanium liquid directly be hydrolyzed without organic extraction, according to the slurry after the embodiment one step C hydrolysis after barrier film press filtration and washing, through 0.5% K ₂O and 0.1% P ₂O ₅After salt was handled, calcining promptly got Rutile type Titanium Dioxide in 2 hours under 900 ℃.Through foreign matter content≤18g/l such as the dilution heat of sulfuric acid Ca of barrier film press filtration, Mg, Al, a part of balance discharging, the major part of determining is used for the sulphuric acid concentration reuse.

Embodiment 5

Prepare high titanium salt acidleach according to embodiment 1 steps A and slag tap, high titanium salt acidleach is slagged tap and carried out the industriallization acidolysis after market solubility in acid titanium slag mixes.High titanium salt acidleach slag tap composition such as table 16, market solubility in acid titanium slag composition such as table 17.

The high titanium salt acidleach of table 16. composition of slagging tap

Composition

TiO 2

TFe

H 2O

Content (%)

78.68

4.07

2.25

Table 17. market solubility in acid titanium slag composition

Composition	TiO 2	TFe	H 2O
				Content (%)	75.58	8.44	-

A, acidolysis reaction condition

Acidolysis reaction is at 60m ³Carry out in the acidolysis pot.The high titanium salt acidleach charging capacity of slagging tap: 3.3 tons, market solubility in acid titanium slag charging capacity: 12.64 tons.Acid ore deposit ratio: 1.7, concentration 98% sulfuric acid: 27.00 tons.

B, reaction process

Earlier in acid hydrolysis tank, send into 98% sulfuric acid that measures, add rich titanium material and titanium slag, mixed 30 minutes with pressurized air, feed saturation steam, about 2 ℃/minute of heat-up rate stops to heat up to 120 ℃, and temperature rises voluntarily, but lift velocity is very slow; 180 ℃ of afterreactions quicken, and rate of rise in temperature is accelerated, and reach maximum temperature to 229 ℃, and temperature begins to descend after about 5 minutes, to about 205 ℃, reduces compressed air require.Maturation time 160 minutes, leaching time 240 minutes.

C, acidolysis detected result

After leaching, titanium liquid and acidolysis result such as following table 18.

Table 18. titanium liquid and acidolysis result

Total TiO 2(g/l)	The F value	Fe/TiO 2	Acidolysis rate (%)
				233.09	1.87	0.12	93.09

Embodiment 6

Prepare high titanium salt acidleach according to embodiment 1 steps A and slag tap, high titanium salt acidleach is slagged tap and carried out the industriallization acidolysis after market solubility in acid titanium slag mixes.High titanium salt acidleach slag tap composition such as table 19, market solubility in acid titanium slag composition such as table 17.

The high titanium salt acidleach of table 19. composition of slagging tap

Composition	TiO 2	TFe	H 2O
				Content (%)	74.38	4.70	1.40

A, acidolysis reaction condition

Acidolysis reaction is at 60m ³Carry out in the acidolysis pot.The high titanium salt acidleach charging capacity of slagging tap: 4.6 tons, market solubility in acid titanium slag charging capacity: 10.46 tons.Acid ore deposit ratio: 1.7, concentration 98% sulfuric acid: 25.50 tons.

B, reaction process

Earlier in acid hydrolysis tank, send into 98% sulfuric acid that measures, add rich titanium material and titanium slag, mixed 30 minutes with pressurized air; Feed saturation steam, about 4 ℃/minute of heat-up rate stops to heat up to 130 ℃; Temperature rises voluntarily, and 180 ℃ of afterreactions quicken, and rate of rise in temperature is accelerated; Reach maximum temperature to 220 ℃, temperature begins to descend after about 5 minutes, to about 205 ℃, reduces compressed air require.Maturation time 210 minutes, leaching time 240 minutes.

C, acidolysis detected result

After leaching, titanium liquid and acidolysis result such as following table 20.

Table 20. titanium liquid and acidolysis result

Total TiO 2(g/l)	The F value	Fe/TiO 2	Acidolysis rate (%)
				217.68	2.14	0.15	91.95

Embodiment 7

Prepare high titanium salt acidleach according to embodiment 1 steps A and slag tap, high titanium salt acidleach is slagged tap and carried out the industriallization acidolysis after market solubility in acid titanium slag mixes.High titanium salt acidleach slag tap composition such as table 21, market solubility in acid titanium slag composition such as table 17.

The high titanium salt acidleach of table 21. composition of slagging tap

Composition	TiO 2	TFe	H 2O
				Content (%)	72.86	5.22	1.56

A, acidolysis reaction condition

Acidolysis reaction is at 60m ³Carry out in the acidolysis pot.The high titanium salt acidleach charging capacity of slagging tap: 7.70 tons, market solubility in acid titanium slag charging capacity: 7.50 tons.Acid ore deposit ratio: 1.65, concentration 98% sulfuric acid: 24.88 tons.

B, reaction process

Earlier in acid hydrolysis tank, send into 98% sulfuric acid that measures, add rich titanium material and titanium slag, mixed 30 minutes with pressurized air; Feed saturation steam, about 3 ℃/minute of heat-up rate stops to heat up to 135 ℃; Temperature rises voluntarily, and lift velocity is than first obvious quickening; 180 ℃ of afterreactions quicken, and rate of rise in temperature is accelerated, and reach maximum temperature to 230 ℃, are about that temperature begins to descend after 10 minutes the main reaction time, to about 205 ℃, reduce compressed air require.Maturation time 218 minutes, leaching time 240 minutes.

C, acidolysis detected result

After leaching, titanium liquid and acidolysis result such as following table 22.

Table 22. titanium liquid and acidolysis result

Total TiO 2(g/l)	The F value	Fe/TiO 2	Acidolysis rate (%)
				195.30	2.24	0.10	89.69

Embodiment 8

Prepare high titanium salt acidleach according to embodiment 1 steps A and slag tap, adopt liquid phase method with 55%～65% sulfuric acid high titanium salt acidleach to be slagged tap and carry out acidolysis, acidolysis is carried out in liquid phase; 150～160 ℃ of temperature of reaction; 1.5～8.0 hours reaction times got thick water solid mixture after the reaction, after 140～220 ℃ of slakings, get block solid mixt; Need with getting titanium liquid after the water dissolution, subsequent technique carries out according to embodiment 1 step C, D.

Embodiment 9

Prepare high titanium salt acidleach according to embodiment 1 steps A and slag tap, adopt two phase process with 65%～75% sulfuric acid high titanium salt acidleach to be slagged tap and carry out acidolysis, acidolysis is carried out in liquid phase; 160～180 ℃ of temperature of reaction; 20～60 minutes reaction times got thick water solid mixture after the reaction, after 140～220 ℃ of slakings, get block solid mixt; With getting titanium liquid after the water dissolution, subsequent technique carries out according to embodiment 1 step C, D.

Embodiment 10

With high titanium salt acidleach slag tap with pulverize after ilmenite concentrate in acid hydrolysis tank, carry out acidolysis respectively; Gained titanium liquid mixes at subsider; The mixed with titanium liquid that obtains is handled, calcines, is pulverized through sedimentation, filtration, hydrolysis, washing, bleaching, rinsing, salt, prepares the Rutile type Titanium Dioxide first product.The high titanium salt acidleach composition of slagging tap is seen table 23, and the ilmenite concentrate composition is seen table 24.

The high titanium salt acidleach of table 23 Chemical Composition of slagging tap

Composition	TiO 2	TFe	Cl	H 2O
					Content (%)	79.76	7.21	1.78	2.01

Table 24 ilmenite concentrate chemical ingredients

Composition	TiO 2	TFe	CaO	MgO
					Content (%)	46.55	31.26	2.43	5.89

1, acidolysis

Volume is 60m ³Totally 5 of acid hydrolysis tanks, wherein 3 acid hydrolysis tanks are used for the high titanium salt acidleach acidolysis of slagging tap, 2 are used for the ilmenite concentrate acidolysis.

A, the high titanium salt acidleach acidolysis of slagging tap.High titanium salt acidleach about 14 tons of the charging capacity of slagging tap, acid sludge is than 1.70.Earlier in acid hydrolysis tank, import 98% sulfuric acid, add high titanium salt acidleach again and slag tap, mixed 30 minutes with pressurized air with pump; Feed steam, make the acid sludge mixture temperature reach 140 ℃ to 150 ℃, stop to feed steam; The acid sludge mixture temperature rises voluntarily, to about 210 ℃, reaches maximum temperature, about 10～12 minutes of main reaction time; Temperature drops to 190 ℃ of closes compression air afterwards, ripe 2.5 hours, adds 30m ³Water leaches, and leaching time 5～6 hours adds 400 kilograms of iron powder reducings.

B, ilmenite concentrate acidolysis.About 15 tons of ilmenite concentrate charging capacity, sour ore deposit is than 1.50.Earlier in acid hydrolysis tank, import 93% sulfuric acid, add ilmenite concentrate again, mixed 30 minutes with pressurized air with pump; Add spent acid, utilize Dilution of sulphuric acid heat that sour ore deposit mixture temperature is risen voluntarily, to about 205 ℃, reach maximum temperature; About 3～5 minutes of main reaction time; Temperature drops to 190 ℃ of closes compression air afterwards, ripe 2.5 hours, adds 30m ³Water leaches, about 4 hours of leaching time.

2, sedimentation

3 jars high titanium salt acidleach that obtain according to the steps A acidolysis titanium liquid that 2 jars of ilmenite concentrates that titanium liquid and the step B of preparation obtain prepare of slagging tap adds 1.5m respectively ³Concentration is 0.1% flocculation agent, mixes, and is discharged to subsider, in subsider, mixes sedimentation, and gained mixed with titanium liquid index is seen table 25:

Table 25 mixed with titanium liquid index

3, filter

Through Plate Filtration, control titanium fluid solid content obtains the qualified titanium liquid of clarity less than 30mg/l with mixed with titanium liquid.

4, hydrolysis

Hydrolysis titanium liquid is long-pending to be 65m ³, crystal seed titanium liquid is long-pending to be 1.4m ³, in the crystal seed preparation vessel, add 41.5 kilograms of sheet alkali, add 445 liters in water, rising temperature for dissolving; Crystal seed titanium liquid and liquid caustic soda are heated to 85 ℃ simultaneously, in 3 minutes, crystal seed titanium liquid are put into liquid caustic soda, be rapidly heated, be incubated 3～5 minutes to 96 ℃.

Fast crystal seed is put into dense titanium liquid fore-warmer tank, dense titanium liquid has been warming up to 96 ℃ before this, stirs 20 minutes, mixes.

Titanium liquid is put into hydrolytic tank, in 30 minutes, titanium liquid is heated to first boiling point, continue heating and keep boiling, occur, stopped to heat 30 minutes until becoming the ash point.; Then at 20 minutes internal heating to second boiling point, continue heating and keep boiling 240 minutes, in this process, evenly add dilution water continuously.

Hydrolysis finishes, and detects metatitanic acid and obtains like table 26 index:

Table 26 metatitanic acid index

Percent hydrolysis (%)	Total titanium (g/l)	Filtration velocity (s)	Ti 3+(g/l)
				95.88％	170.66	?148	2.27

5, washing

Metatitanic acid is cooled to 60 ℃,,, unloads the sheet making beating and be delivered to bleaching tank with water washing 3 hours with leaf-type vacuum filter suction filtration last slice.

6, bleaching

In bleaching tank, in metatitanic acid, add sulfuric acid and Ti ³⁺Solution is warming up to 60 ℃ with steam, is incubated 2 hours, adds rutilization nuclei by 4% dosage, stirs to mix in 1 hour.Ti in the bleaching detection of end metatitanic acid ³⁺Content is 0.7g/l.

7, rinsing

Metatitanic acid with leaf-type vacuum filter suction filtration last slice, with de-mineralized water washing 3 hours, is unloaded the sheet making beating and is delivered to the salt treatment tank.

8, salt is handled

Metatitanic acid in the salt treatment tank is 23ppm through detecting iron level.Add Pottasium Hydroxide by 0.6% dosage, add phosphoric acid, add zinc oxide, mixed 1 hour by 0.23% dosage by 0.2% dosage.

9, calcining, pulverizing

Metatitanic acid after the salt processing is carried out filter dehydration with the diaphragm pressing machine, send into rotary kiln with worm conveyor again and calcine.920～930 ℃ of rotary kiln end temperature, temperature is 680～700 ℃ in the kiln. 270～280 ℃ of kiln end temperatures. and 9～10 hours residence time.The kiln article that fall are pulverized with Raymond mill, the product quality indicator such as the table 27 that obtain:

Table 27 Rutile type Titanium Dioxide final product quality index

Embodiment 11: comparison example

Ilmenite concentrate after pulverizing is carried out acidolysis in acid hydrolysis tank, through sedimentation, filtration, ferrous sulfate crystallization filter, concentrate, hydrolysis, washing, bleaching, rinsing, salt are handled, calcining, pulverize, and prepare the Rutile type Titanium Dioxide first product.The ilmenite concentrate chemical ingredients is seen table 28:

Table 28 ilmenite concentrate chemical ingredients

Composition	TiO 2	TFe	CaO	MgO
					Content (%)	46.55	31.26	2.43	5.89

1, acidolysis

At volume is 60m ³Acid hydrolysis tank in carry out the ilmenite concentrate acidolysis.Ilmenite concentrate is crushed to 325 mesh screen residues less than 5%, 15.1 tons of charging capacitys, and sour ore deposit is than 1.50.Earlier in acid hydrolysis tank, import 93% sulfuric acid, add ilmenite concentrate again, mixed 30 minutes with pressurized air with pump; Add spent acid, utilize Dilution of sulphuric acid heat that sour ore deposit mixture temperature is risen voluntarily, to about 207 ℃, reach maximum temperature; About 3～5 minutes of main reaction time; Temperature drops to 190 ℃ of closes compression air afterwards, ripe 2.5 hours, adds 30m ³Water leaches, about 4 hours of leaching time.

2, sedimentation

Add 1m to titanium liquid ³Flocculation agent mixes, and is discharged to subsider, sedimentation in subsider, and gained titanium liquid index is seen table 29:

Table 29 sedimentation titanium liquid index

3, filter

Through Plate Filtration, control titanium fluid solid content obtains the qualified titanium liquid of clarity less than 30mg/l with titanium liquid.

4, the ferrous sulfate crystallization is filtered

Titanium liquid is sent into the vacuum crystallization jar, and crystallization is 2 hours under vacuum tightness 0.088MPa, and the ferrous sulfate crystallization is separated out, and filters through disk filter, and ferrous sulfate is separated.The titanium liquid index such as the table 30 that obtain:

Titanium liquid index after table 30 crystallization

5, concentrate

Titanium liquid is carried out vacuum concentration through thin-film evaporator, the titanium liquid index such as the table 31 that obtain after concentrating:

Titanium liquid index after table 31 crystallization

6, hydrolysis

Hydrolysis titanium liquid is long-pending to be 65m ³, crystal seed titanium liquid is long-pending to be 1.4m ³, in the crystal seed preparation vessel, add 45.6 kilograms of sheet alkali, add 465 liters in water, rising temperature for dissolving; Crystal seed titanium liquid and liquid caustic soda are heated to 85 ℃ simultaneously, in 3 minutes, crystal seed titanium liquid are put into liquid caustic soda, be rapidly heated, be incubated 3～5 minutes to 96 ℃.

Fast crystal seed is put into dense titanium liquid fore-warmer tank, dense titanium liquid has been warming up to 96 ℃ before this, stirs 20 minutes, mixes.

Titanium liquid is put into hydrolytic tank, in 30 minutes, titanium liquid is heated to first boiling point, continue heating and keep boiling, occur, stopped to heat 30 minutes until becoming the ash point.; Then at 20 minutes internal heating to second boiling point, continue heating and keep boiling 240 minutes, in this process, evenly add dilution water continuously.

Hydrolysis finishes, and detects metatitanic acid and obtains like table 32 index:

Table 32 metatitanic acid index

Percent hydrolysis (%)	Total titanium (g/l)	Filtration velocity (s)	Ti 3+(g/l)
				96.22％	170.66	?139	1.20

7, washing

Metatitanic acid is cooled to 60 ℃,,, unloads the sheet making beating and be delivered to bleaching tank with water washing 3 hours with leaf-type vacuum filter suction filtration last slice.

8, bleaching

In bleaching tank, in metatitanic acid, add sulfuric acid and Ti ³⁺Solution is warming up to 60 ℃ with steam, is incubated 2 hours, adds rutilization nuclei by 4% dosage, stirs to mix in 1 hour.Ti in the bleaching detection of end metatitanic acid ³⁺Content is 0.8g/l.

9, rinsing

Metatitanic acid with leaf-type vacuum filter suction filtration last slice, with de-mineralized water washing 3 hours, is unloaded the sheet making beating and is delivered to the salt treatment tank.

10, salt is handled

Metatitanic acid in the salt treatment tank is 25ppm through detecting iron level.Add Pottasium Hydroxide by 0.6% dosage, add phosphoric acid, add zinc oxide, mixed 1 hour by 0.23% dosage by 0.2% dosage.

11, calcining, pulverizing

Metatitanic acid after the salt processing is carried out filter dehydration with the diaphragm pressing machine, send into rotary kiln with worm conveyor again and calcine.920～930 ℃ of rotary kiln end temperature, temperature is 680～700 ℃ in the kiln. 270～280 ℃ of kiln end temperatures. and 9～10 hours residence time.The kiln article that fall are pulverized with Raymond mill, the product quality indicator such as the table 33 that obtain:

Table 33 Rutile type Titanium Dioxide final product quality index

Claims (15)

1. method for preparing white titanium pigment, said method comprises the steps:

A. with the ferrotianium material or through pretreated ferrotianium material with carry out hydrochloric acid leaching after hydrochloric acid leaching liquid mixes, obtain to leach slurry;

B. the leaching slurry that obtains through steps A is carried out solid-liquid separation; The gained solid is slagged tap for high titanium salt acidleach after washing, drying; Said liquid is for leaching mother liquor, after shunting, gets into mother liquor burning operation and regeneration of hydrochloric acid operation respectively and is regenerated as hydrochloric acid leaching liquid, thereby return steps A;

C. will slag tap and carry out acidolysis and be incubated slaking after aqueous sulfuric acid mixes through the high titanium salt acidleach that step B obtains;

D. will obtain slip through acidolysis thing water and/or the dilute sulphuric acid dissolving that step C obtains, obtain low impurity titanium liquid through solid-liquid separation;

E. randomly will handle through oxidation and organic extraction, to obtain high purity titanium liquid through the low impurity titanium liquid that step D obtains; Wherein the organic phase after organic extraction is carried out back extraction, and the anti-raffinate that obtains gets into the regeneration of hydrochloric acid operation of step B, thereby returns steps A through being regenerated as hydrochloric acid leaching liquid;

The low impurity titanium liquid that F. will obtain through step D or randomly be hydrolyzed through the high purity titanium liquid after evaporation concentration that step e obtains, thus the metatitanic acid slurry obtained; Wherein the Hydrogen chloride of evaporation concentration operation acquisition gets into the regeneration of hydrochloric acid operation of step B, thereby returns steps A through being regenerated as hydrochloric acid leaching liquid;

G. filter the metatitanic acid slurry that obtains through step F, the solid that washing and filtering obtains is low impurity metatitanic acid, and filtrating is dilution heat of sulfuric acid, after the said dilution heat of sulfuric acid partial equilibrium discharging, thereby returns step C through the evaporation concentration operation;

H. will handle and calcining through salt through the low impurity metatitanic acid that step G obtains, thereby obtain white titanium pigment.

2. method according to claim 1 is characterized in that, the ferrotianium material in the said steps A comprises the ferrotianium oxide compound, for example ilmenite, ilmenite concentrate, modification ilmenite concentrate, titanium slag; Preferably, the titanium oxide mass percentage content is 30%～80% in the said ferrotianium material;

Randomly, said ferrotianium material through first weak oxide restore, earlier reduction reoxidizes, an oxidation is not reduced and one or more modes of only reducing in the not oxidation are carried out pre-treatment;

Said hydrochloric acid leaching liquid is hydrochloric acid or the hydrochloric acid compound system solution that contains chlorate, and said chlorate is aluminum chloride, magnesium chloride, calcium chloride, iron(ic)chloride, Manganous chloride tetrahydrate for example, and its free concentration of hydrochloric acid is 15%～25%, the Fe in the leaching liquid ²⁺+ Fe ³⁺Concentration is 30～100g/l;

Chlorate in the said leaching liquid is formulated, perhaps by the raffinate cyclically utilizing that contains chlorate in the leaching mother liquor that contains chlorate in the said hydrochloric acid leaching of step B and wash filtrate and the said organic extraction of step e, preferred cycle reuse.

3. method according to claim 1 and 2; It is characterized in that; Adopt hydrochloric acid directly to leach in method, BCA hydrochloric acid leaching method, preoxidation-fluidization normal pressure leaching method and preoxidation-selecting smelting combination pressurization leaching method one or more in the said steps A and carry out hydrochloric acid leaching, preferably adopt hydrochloric acid directly to leach method;

Directly leaching method of said hydrochloric acid comprises: preheat hydrochloric acid leaching liquid to 70 ℃～100 ℃; Then with 1g: the mass volume ratio of 2.5ml～5ml makes the ferrotianium material or mixes with hydrochloric acid leaching liquid through pretreated ferrotianium material, under 70 ℃～150 ℃ temperature, carries out hydrochloric acid and directly leaches 1～8 hour.

4. method according to claim 1; It is characterized in that; Randomly; Said step B also comprises earlier will carry out stage treatment through the leaching slurry that steps A obtains, and make to leach the fine granules solid-liquid separation after evaporation concentration below 200 orders in the slurry, and the above direct solid-liquid separation of Coarse Aggregate of 200 orders is used to prepare artificial rutile in the leaching slurry;

Said solid-liquid separation comprises: adopt to concentrate, spinning and filter in one or more carry out, the preferred employing filtered; Adopt when filtering, will be cooled to 80 ℃～90 ℃ through the leaching slurry that steps A obtains earlier;

Said washing comprises: the sour water washing gained solid of water or pH＜1, and the preferred HCl concentration of said sour water is greater than the Hydrogen chloride of 0.1mol/L or pH＜1, and the liquid after the washing gets into the regeneration of hydrochloric acid operation, returns steps A through being regenerated as hydrochloric acid leaching liquid;

Fine granules drying below said 200 orders comprises: the solid after the washing was carried out drying 2～8 hours being lower than under 600 ℃ the temperature, slag tap thereby obtain high titanium salt acidleach; Said temperature preferably is lower than 250 ℃, further 150 ℃～250 ℃;

The above Coarse Aggregate calcining temperature of said 200 orders should be higher than 900 ℃, preferred 950 ℃ to 1100 ℃.

5. according to the described method of claim 1 to 4, the high titanium salt acidleach of ferrotianium material behind the hydrochloric acid leaching liquid leaching slagged tap and is porosity and looseness shape residue and metatitanic acid aggregate, and contains a spot of rutile, titanaugite, anosovite and quartz, wherein TiO ₂Composition mainly exists with non-crystal state, it is characterized in that this high titanium salt acidleach is slagged tap to contain chlorion, and its content is lower than 5%, and preferred content is 1%～3%.

6. method according to claim 1; It is characterized in that; Said acidolysis also is incubated slaking and comprises: be that 1.4～1.9: 1 acid sludge is slagged tap than mix sulphur aqueous acid and high titanium salt acidleach by weight; Be heated to 150～240 ℃, carry out obtaining thick solid mixt behind the acidolysis reaction, slaking 1～4 hour under uniform temp afterwards; Preferably, said acidolysis reaction carried out 5～240 minutes;

Said aqueous sulfuric acid concentration is 55～98%, is preferably 85～91%;

Preferably, said step C, can earlier the high titanium salt acidleach that obtains through step B be slagged tap before the acidolysis is ground to negative 325 orders.

7. according to claim 1 and 6 said methods, it is characterized in that high titanium salt acidleach is slagged tap to mix with one or more of ilmenite concentrate, modification ilmenite concentrate, solubility in acid titanium slag or other ferrotianium material and carried out sulfuric acid solution among the said step C;

Preferably, high titanium salt acidleach is slagged tap and is carried out sulfuric acid solution respectively with ilmenite concentrate, modification ilmenite concentrate, solubility in acid titanium slag or other ferrotianium material and prepare titanium liquid, and the titanium liquid that will prepare respectively then is by TFe/TiO ₂Be to produce mixed with titanium liquid after 0.25～0.35 standard is mixed, this titanium liquid is without the organic extraction direct hydrolysis.

8. method according to claim 1 is characterized in that said step D comprises the steps:

D-1) cooling reaction system is to being lower than 80 ℃, adds the acidolysis thing after the water dissolution slaking that is lower than 60 ℃, 40～70 ℃ of dissolvings 1～8 hour down, simultaneously with TiO in the solution ₂Amount be controlled at 180g/L～260g/L; Perhaps

Cooling reaction system is to being lower than 80 ℃, and adding earlier is lower than 60 ℃ 20% dilute sulphuric acid, adds entry again, dissolves 1～8 hour down at 40～70 ℃, simultaneously with TiO in the solution ₂Amount be controlled at 180g/L～260g/L;

D-2) to through D-1) before the slip that obtains carries out solid-liquid separation, in slip, add flocculation agent, the optimization polypropylene amide solution obtains low impurity titanium liquid then after deposition, filtration or press filtration; Wherein, the concentration of said polyacrylamide solution is preferably 0.05%～0.15%, and add-on is every cubic metre of slurry titanium liquid 10L～30L.

9. according to claim 1 and 8 described methods, it is characterized in that the described low impurity titanium liquid of step D contains 180g/l～260g/l TiO ₂, TFe/TiO ₂Be lower than 0.1, other foreign matter content≤10g/l such as Ca, Mg, Al.

10. method according to claim 1 is characterized in that, oxidation and organic extraction in the said step e comprise the steps:

E-1) add the oxidation of divalent iron ion that oxygenant will hang down in the impurity titanium liquid and become ferric ion; Wherein said oxygenant is one or more in chlorine, oxygen, ozone and the hydrogen peroxide, preferred ozone; Preferably, add oxygenant and make the amount of hanging down ferrous ion in the impurity titanium liquid less than 0.5g/L, the amount that further preferably makes ferrous ion is less than 100ppm;

E-2) ferric ion in the adding complexing agent complexing titanium liquid; Wherein said complexing agent is hydrochloric acid or hydrogenchloride, and the volumetric molar concentration that preferably makes cl ions in the titanium liquid is at least 4 times of ferric ion volumetric molar concentration, and concentration of hydrochloric acid is 1～5mol/L;

E-3) mixture that adds extraction agent and thinner is as the ferric ion in the organic extractant phase titanium liquid; Wherein said extraction agent is one or more of acid organo phosphorous compounds, carboxylic acid, sulfonic acid hydroxyoxime, oxine, beta-diketon, neutral phosphate, phosphorus oxide, ketone, alcohols, ethers and amine, preferable methyl isobutyl ketone and tributyl phosphate; Said thinner is one or more in benzene, trichloromethane, toluene, kerosene, sulfonated kerosene and the normal hexane, preferred sulfonated kerosene; The volumetric mixture ratio 0～4.5: 1 of thinner and extraction agent, preferred 3: 1; The volume ratio of organic phase and titanium liquid is 0.2～1.5: 1, preferred 1: 1, and normal temperature to 50 ℃ extraction 1～20 minute, preferred 10 minutes.

11. method according to claim 1 is characterized in that, the back extraction in the said step e comprises:

Adopt water or Hydrogen chloride or NaCl solution as the ferric ion in the strip liquor back extraction organic phase, and make the anti-raffinate that obtains get into the regeneration of hydrochloric acid operation of step B, thereby return steps A through being regenerated as hydrochloric acid leaching liquid; Wherein the volume ratio of organic phase and strip liquor is 1: 0.5～1: 3, preferred 1: 2.

12. method according to claim 1 is characterized in that, the high purity titanium liquid through evaporation concentration in the said step F contains TiO ₂Be 180～260g/l, TFe＜100ppm, other impurity＜10g/l;

Said hydrolysis comprises: in titanium liquid, add an amount of reductive agent such as aluminium powder, its add-on makes Ti in the titanium liquid ³⁺Concentration at 1～3g/L, and add and to account for TiO in the titanium liquid ₂Weight percent is 1.5%～5% rutilization nuclei or anatase titanium dioxide crystal seed, then 90 ℃ of hydrolysis 2～8 hours to the boiling point.

13. method according to claim 1 is characterized in that, filtering the metatitanic acid slurry that obtains through step F among the said step G should be at the acidity and the Ti of pH＜1 ³⁺Concentration is carried out under the reduced state of 1～3g/L scope, the impure TFe＜30ppm of low impurity metatitanic acid after the said washing, foreign matter content≤10g/l in the said dilution heat of sulfuric acid.

14. method according to claim 1 is characterized in that, said step H comprises the steps:

H-1) in the low impurity metatitanic acid that obtains through step G, add granularity and crystal formation control agent, be sintered into the white titanium pigment particle then; Said granularity and crystal formation control agent are selected from one or more in Pottasium Hydroxide, phosphoric acid, zinc oxide, the White tin oxide;

H-2) will be through step H-1) the white titanium pigment particle that obtains grinds, one or more processing in broken of surface-coating, filtration washing, the gentle abrasive dust of spraying drying, to obtain the white titanium pigment finished product.

15. method according to claim 1 is characterized in that, described mother liquor shunting of step B and regeneration of hydrochloric acid comprise:

To leach mother liquor and split into two portions, part entering mother liquor burns operation and in incinerator, burns generation MOX and hydrogen chloride gas through spraying; Another part gets into the regeneration of hydrochloric acid operation and the hydrogen chloride gas that burns operation and get rid of is absorbed obtains regenerating hydrochloric acid leaching liquid after diluting, return the leaching steps A;

Said leaching mother liquor shunting is the differentiation standard with its iron concentration; Be that 100～160g/l, preferred 140～150g/l are as the shunting standard wherein with iron concentration; Iron concentration gets into spraying burning operation greater than the leaching mother liquor of this shunting standard, and iron concentration gets into the regeneration of hydrochloric acid operation less than leaching mother liquor of this shunting standard;

Said regeneration of hydrochloric acid operation is carried out in the absorption tower, the hydrogen chloride in gas that adopts hydrochloric acid adsorption liquid counter-current absorption to get into the absorption tower; The gas on said entering absorption tower is that mother liquor burns the gas that operation is got rid of; The part that distributes from step B of comprising said hydrochloric acid adsorption liquid leaches the wash filtrate of mother liquor, wash solids and from the anti-raffinate of step e, and water or Hydrogen chloride.

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