CN106744721A - The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid - Google Patents

The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid Download PDF

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CN106744721A
CN106744721A CN201611187549.1A CN201611187549A CN106744721A CN 106744721 A CN106744721 A CN 106744721A CN 201611187549 A CN201611187549 A CN 201611187549A CN 106744721 A CN106744721 A CN 106744721A
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acid
titanium
dissolubility
less salt
sulfuric acid
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梅涛
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PANZHIHUA JINGYAN TECHNOLOGY Co Ltd
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PANZHIHUA JINGYAN TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
    • C01B17/904—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/324—Preparation from a reaction solution obtained by acidifying with an acid other than orthophosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/40—Magnesium sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/0475—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
    • C05B1/04—Double-superphosphate; Triple-superphosphate; Other fertilisers based essentially on monocalcium phosphate
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The invention belongs to hydrometallurgy, field of fine chemical, and in particular to the recovery separation method and application of sulfuric acid and dissolubility titanium in a kind of titanium white waste acid.The technical problems to be solved by the invention are to provide the recovery separation method of a kind of titanium white waste acid sulfuric acid and dissolubility titanium, comprise the following steps：Titanium white waste acid is adsorbed by resin chromatography post, and efflux is high-salt wastewater；With the above-mentioned resin chromatography post of water wash, efflux is less salt spent acid.Contained acid is high in less salt spent acid obtained by the method separation and recovery, and other impurity are few, high containing sour low, titanium dioxide containing dissolubility in high-salt wastewater, and two kinds of materials can obtain recycle and reuse well.

Description

The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid
Technical field
The invention belongs to hydrometallurgy, field of fine chemical, and in particular to sulfuric acid and dissolubility titanium in a kind of titanium white waste acid Recovery separation method and application.
Background technology
The production meeting substantial amounts of spent acid of output of sulfuric acid method titanium pigment, due to the sulfuric acid containing higher concentration in this part spent acid With the metallic salt such as dissolubility titanium, larger threat is caused to environment.Simultaneously because substantial amounts of free sulfuric acid and metal in spent acid Salt and deposit, cause the difficulty of the direct recycling of the metallic salt such as sulfuric acid and dissolubility titanium in spent acid larger.
The treating method of current titanium white waste acid comparative maturity has two kinds：1) neutralisation：Acid pickle addition alkaline matter is entered Row acid-base neutralization, liquid pH 6~9 after regulation neutralization, air can be passed through if necessary carries out forced aeration, improves neutralization precipitation thing Cohesion speed and structure, neutralizing disposed slurry carries out separation of solid and liquid, and filter residue slag input is stacked, discharge after filtrate is up to standard；2) spent acid is dense Contracting method：Using traditional heating evaporation technique, acid pickle is concentrated, with the raising of acid-spending strength and temperature, in spent acid The reduction of solubility of the substantial amounts of metallic salt in acid can crystallize precipitation, divide by necessary solid-liquid after being concentrated into finite concentration From, except the metallic salt of precipitation of decrystallizing, certain density gelled acid being obtained, metallic salt major part is removed in acid, and this is dense Contracting acid can return to factory and fresh acid collocation is used.
The handling process of above two spent acid is in sides such as the utilization of resources, investment, operating cost, environmentally friendly secondary pollution, safety Face there are problems that larger：1) neutralisation treatment industrial waste acid, largely there is the free acid and metallic salt of economic worth in spent acid It is not utilized completely, while adding substantial amounts of alkaline matter to neutralize, the filter residue of output several times volume causes the secondary dirt of environment Dye；2) waste acid concentration method treatment spent acid, plays a positive role to the solution pollution of industrial waste acid and recycling, but existing useless Sour device directly uses the titanium white waste acid without desalination, substantial amounts of metallic salt to be separated out in concentration link consumption of calorie, crystallization stifled Plug heat-exchanger rig simultaneously causes the abrasion to cause the expenses such as plant running, maintenance high to pump apparatus；Reclaimed using the technique simultaneously Spent acid, valuable dissolubility titanium does not obtain any using and into concentration waste residue, wastes serious.
In recent years, the acid such as resin adsorption method and UF membrane/salt isolation technics processed ring in the industry such as stainless steel, aluminium foil spent acid Section is studied and small-scale application, achieves a certain degree of effect；But because titanium white waste acid total amount is huge, complicated component, It is simultaneously salt acidic to a large amount of less salt spent acid and height that are produced after the acid such as application resin adsorption method and UF membrane/salt separation technical finesse The subsequent applications aspect of waste water, does not make the research of further practicality, so as to cause the acid/salinity such as resin adsorption method and UF membrane From technology before the application deterioration not in the comprehensive regulation field of titanium white waste acid.
The content of the invention
It is contemplated that overcoming the shortcomings of existing titanium dioxide waste acid by sulfuric acid process Processing tecchnics technology, there is provided a kind of adaptability compared with Good, the economy titanium white waste acid comprehensive utilization technique for being available for industrial scale high, using this technology, can to greatest extent by Substantial amounts of sulfuric acid and dissolubility titanium are for recycling and reuse in titanium white waste acid.Titanium white waste acid of the present invention refers in titanium white The hydrolysis link of production procedure carries out separation of solid and liquid after hydrolysis process separates out solid phase metatitanic acid and a kind of composition of output is answered Industrial waste acid miscellaneous, containing the metallic salt such as a large amount of sulfuric acid and dissolubility titanium, containing 220~340g/L free sulfuric acids, 35~65g/L Fe, 4~9g/L dissolubility titaniums.
First technical problem to be solved by this invention is to provide the sour recovery side of separation with salt in a kind of titanium white waste acid Method.The method is comprised the following steps：Titanium white waste acid is adsorbed by resin chromatography post, and trickle is high-salt wastewater；With The above-mentioned resin chromatography post of water wash is desorbed, and efflux is less salt spent acid.
Specifically, in above-mentioned titanium white waste acid in the recovery separation method of acid and salt, the titanium white waste acid is Producing Titanium Dioxide stream The hydrolysis link of journey carries out separation of solid and liquid and a kind of complicated component of output, contains after hydrolysis process separates out solid phase metatitanic acid The industrial waste acid of a large amount of metallic salts such as sulfuric acid and dissolubility titanium.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, the titanium white waste acid contains 220~340g/L free sulfuric acids, 35~65g/L Fe, 4~9g/L dissolubility titaniums.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, the resin is band quaternary amine At least one in strong basic type anion-exchange resin, the strongly acidic cation-exchange of functional group.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, described band quaternary amine official The strong basic type anion-exchange resin that can be rolled into a ball is Du's sheng, a reed pipe wind instrumentA-32, described strongly acidic cation-exchange is D101 Macroporous absorbent resin.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, gained less salt spent acid contains 200 ~300g/L free sulfuric acids, 5~15g/L Fe, 0.5~2g/L dissolubility titaniums；Gained high-salt wastewater free sulphur containing 20~80g/L Acid, 15~40g/L Fe, 3~8g/L dissolubility titaniums.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, the resin filling of chromatographic column Amount is 1 ︰ 0.1~1 with the volume ratio of single treatment titanium white waste acid.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, the diameter of the chromatographic column It is 0.15~5 ︰ 1 with height ratio.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, the column diameter It is 100~3000mm, is highly 300~25000mm.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, titanium white gives up during the absorption The trend of acid is bottom in and top out, and the trend of water is upper entering and lower leaving during desorption；The flow velocity of absorption and parsing is 0.002~0.02 Meter per second.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, control is by chromatographic column The ratio of titanium white waste acid and water is 0.5~3 ︰ 1.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, control passes through chromatographic column Titanium white waste acid and water ratio be 1~3 ︰ 1.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, according to less salt spent acid Requirement, repeat resin adsorption desorption or UF membrane, number of repetition is for more than once.
Preferably, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, gained less salt spent acid is carried out Second adsorption, desorption, second Adsorption and desorption mode are any one in resin chromatography or UF membrane.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, second absorption, Desorb to repeat above-mentioned resin chromatography.
Further, in above-mentioned titanium white waste acid in the recovery separation method of sulfuric acid and dissolubility titanium, second absorption, Desorption gained less salt spent acid composition is 150~280g/L free sulfuric acids, 0.5~5g/L Fe, 0.05~0.5g/L dissolubility titaniums； Gained high-salt wastewater composition is 10~50g/L free sulfuric acids, 3~8g/L Fe, 0.3~1.5g/L dissolubility titaniums.
The inventive method can be dense with titanium white production (link such as acidolysis leaching, bleaching, concentrated sulfuric acid mixed preparing), spent acid The industry technique such as contracting, concentrated sulfuric acid mixed preparing, ore deposit/acid production with sulphur, phosphate fertilizer, hydrometallurgy mineral floating and leaching is combined, will The less salt spent acid and high-salt wastewater that titanium white waste acid of the present invention is obtained through peracid/salt separating treatment are selectively applied directly to State industry, link or by less salt spent acid using returning to above-mentioned link, OK after waste acid concentration, concentrated sulfuric acid mixed preparing PROCESS FOR TREATMENT Industry is used, and reclaim simultaneously free sulfuric acid and dissolubility titanium in titanium white waste acid to reach, and then titanium white waste acid entered to greatest extent Row is comprehensive, the purpose of economic treatment.Concrete application method is as follows：
Present invention also offers the application method of above-mentioned gained less salt spent acid.
Application method one：Less salt spent acid is comprised the following steps in the application method of titanium dioxide acid hydrolysis link：By less salt spent acid and The concentrated sulfuric acid is deployed into the sulfuric acid that mass concentration is 90~95%, used as reaction acid；Or less salt spent acid and the concentrated sulfuric acid are deployed into quality Concentration is 45~55% sulfuric acid, sour as triggering；Or directly as leaching acid.
Application method two：Less salt spent acid bleaches the application method of link in titanium white, comprises the following steps：Less salt spent acid is added Free acid content is 40~80g/L in entering to bleach control in slurry slurry, for lower one washing procedure.Preferably 50~60g/ L。
Application method three：Less salt spent acid is comprised the following steps in the application method of phosphate fertilizer industry：By less salt spent acid and dense sulphur Acid is hybridly prepared into the sulfuric acid that mass concentration is 35~55% and phosphorus ore and carries out reaction production coarse whiting phosphate fertilizer.
Application method four：Less salt spent acid is comprised the following steps in the application method of hydrometallurgy industry mineral floating link： During less salt spent acid and the concentrated sulfuric acid added into ore pulp, the acidity required for being modulated into mineral floating.
Application method five：Less salt spent acid leaches the application method of link in hydrometallurgy industry, comprises the following steps：Will be low Salt spent acid and miberal powder are mixed, and according to the requirement of leaching technology, concentrated sulfuric acid adjustment acidity are added, in situation about stirring and heat The lower sulfuric acid to leach completed to mineral.
Application method six：Less salt spent acid is comprised the following steps in magnesium sulfate industry application method：By less salt spent acid and magnesium ore deposit Powder is mixed, and adds concentrated sulfuric acid adjustment acidity, and the synthesis of magnesium sulfate is carried out in stirring or in the case of stirring heat tracing.
Present invention also offers the application method of above-mentioned gained high-salt wastewater.
Application method seven：High-salt wastewater is comprised the following steps in the application method of titanium dioxide acid hydrolysis link：To titanium dioxide acid hydrolysis work Skill is adjusted, and traditional acid/ore deposit proportioning is adjusted to 1.44~1.50 by 1.52~1.56, after acidolysis main reaction, by high salt Waste water is added in acid hydrolysate after proportionally measuring；The ratio is the weight ratio of free acid amount and titanium ore in high-salt wastewater It is 0.06~0.12.
Application method eight：High-salt wastewater washs the application method of link in titanium white ferrous sulfate crystallization, comprises the following steps： High-salt wastewater is uniformly sprayed at ferrous sulfate surface carries out drip washing to it, collects leacheate and repeats to carry out drip washing to ferrous sulfate Dissolubility titanium reaches 30~80g/L into leacheate.
Present invention also offers second application method of separating obtained less salt spent acid.The application method is removed and first time point From the application method one, two, three, four, five, six of gained less salt spent acid it is identical beyond, also including application method nine, ten.
Application method nine：Second separating obtained less salt spent acid is comprised the following steps in the application method of sulphur dioxide of phosphor chemical industry： Sulfuric acid and phosphorus ore that secondary less salt spent acid and the concentrated sulfuric acid are hybridly prepared into mass concentration 35~55% are carried out into reaction production phosphoric acid Hydrogen calcium.
Application method ten：Second separating obtained less salt spent acid does the application method for inhaling link in ore deposit/acid production with sulphur, including Following steps：The traditional absorption water of secondary less salt spent acid replacement and the concentrated sulfuric acid are configured to 98.0%~98.5% absorption acid, To SO3Carry out absorption production sulfuric acid.
Present invention also offers another application method for the first time with separating obtained less salt spent acid for the second time, application method 11：Comprise the following steps：By for the first time and for the second time, separating obtained less salt spent acid carries out waste acid concentration treatment, is concentrated to sulfuric acid After concentration reaches 40~65%, concentrate spent acid is obtained by simple being separated by filtration, concentrate spent acid reapplies above-mentioned user Industry and link described in method one, two, three, four, five, six, nine, ten.The usage quantity of spent acid was so both increased, while also subtracting Few use for even preventing the fresh concentrated sulfuric acid.
The inventive method can be according to the industry and link described in application method one, two, three, four, five, six, nine, ten to less salt The spent acid component content requirement different with high-salt wastewater, reasonably chooses whether to need to carry out separating for several times or concentration.
Less salt spent acid metal salt concentration of the inventive method as obtained by control is reasonably apart from condition recovery is low, purity It is high such that it is able to fine to be used for other operations；Acid content is low in gained high-salt wastewater simultaneously, containing substantial amounts of dissolubility titanium, Also can recycle well, it is to avoid secondary pollution.
Brief description of the drawings
Fig. 1 the inventive method is separated and recovered and technique for applying flow chart
Specific embodiment
The recovery separation method of sulfuric acid and dissolubility titanium, comprises the following steps in titanium white waste acid：By titanium white waste acid by tree Fat chromatographic column adsorbs free sulfuric acid, and trickle is high-salt wastewater after sulfuric acid is adsorbed, and the part contains a small amount of sulfuric acid, more Iron ion, dissolubility titanium；Again with the chromatographic column after the above-mentioned absorption free sulfuric acid of water wash, adsorbed free sulfuric acid is eluted Desorption outflow, as less salt spent acid, the part contains substantial amounts of sulfuric acid, a small amount of iron ion, dissolubility titanium.
The resin is the acid such as the strong basic type anion-exchange resin with quarternary amine functional group, strongly acidic cation-exchange At least one in retardance resinoid.Further, the strong basic type anion-exchange resin of described band quarternary amine functional group is Du Sheng, a reed pipe wind instrumentA-32, described strongly acidic cation-exchange is D101 macroporous absorbent resins.
It will be understood by those skilled in the art that：As adsorption treatment, the acid of gained waste water are carried out after resin adsorption saturation again Content is high and acid can not be reclaimed fully, so, when resin adsorption reaches saturation, drip washing need to be carried out to resin with water, drench Wash gained and be restored acid；Then the resin after the cleaning is recycled to be adsorbed again or inhaled using new resin It is attached, the suction that those skilled in the art can carry out next time according to actual conditions selection using the resin after new resin or drip washing It is attached.In order to ensure the abundant absorption of acid, the waste water after absorption also can again be carried out second adsorption and desorption ensures that acid recovery is more thorough Bottom.So, in order to ensure to be no more than the absorption maximum saturation value of resin, it is necessary to control the ratio of resin and industrial waste acid, control The resin loading of chromatographic column is 1 ︰ 0.1~1 with the volume ratio of single treatment industrial waste acid.Further, in order to ensure absorption Quality, it is that diameter and height ratio are 0.15~5 ︰ 1 with height relationships also to need to control the diameter of chromatographic column.Preferably, the color Spectrum column diameter is 100~3000mm, is highly 300~25000mm.
In order to ensure fully absorption, the trend of titanium white waste acid is bottom in and top out during the absorption, and flow velocity is 0.002~0.02 Meter per second.
In order to ensure fully desorption, it is 1 ︰ 0.5~3 to control by the titanium white waste acid of chromatographic column and the volume ratio of water.Enter One step, it is 1 ︰ 1~3 to control by the titanium white waste acid of chromatographic column and the volume ratio of water.On the trend of water is during the desorption Go out under entering, desorption flow velocity is 0.002~0.02 meter per second.
During by the once absorption of the inventive method and desorption, gained acid recovering rate is the removal of 60~90%, slaine Rate is 60~90%.Gained less salt spent acid contains 200~300g/L free sulfuric acids, 5~15g/L Fe, 0.5~2g/L dissolubility titaniums； Gained high-salt wastewater contains 20~80g/L free sulfuric acids, 15~40g/L Fe, 3~8g/L dissolubility titaniums.
Further, according to the different demands to titanium white waste acid purification and impurity removal degree, removal slaine as much as possible is right Gained less salt spent acid is separated again, can use resin or UF membrane.Resin mode is such as used, then control condition and above Cause.Gained less salt spent acid contains 200~300g/L free sulfuric acids, 5~15g/L Fe, 0.5~2g/L dissolubilities after separating for second Titanium；Gained high-salt wastewater contains 20~80g/L free sulfuric acids, 15~40g/L Fe, 3~8g/L dissolubility titaniums.Inhaled by second Attached desorption, acid recovering rate is that the clearance of 60~80%, slaine is 88~99%.
Chromatographic column can singly cover operation during absorption, can also cover series operation more.When two sets or many sets are used in series, per one-level Spent acid charging can both be directly connected to the spent acid discharging of previous stage, can also connect the spent acid discharging medial launder of previous stage；And it is each Production water/the pure water feed of level can be used alone production water/pure water, it is possible to use the brine waste after rear stage treatment；In control On the basis of the different production water of system/pure water consumption and different brine waste quantums of output, the place that spent acid depth acid/salt is separate is reached Reason effect.
Acid of the invention/salt isolation technics can be with the titanium white production (ring such as acidolysis leaching, bleaching, concentrated sulfuric acid mixed preparing Section), waste acid concentration, concentrated sulfuric acid mixed preparing, ore deposit/acid production with sulphur, phosphate fertilizer, the industry technique such as mineral floating be combined, by titanium white The less salt spent acid and high salt acid waste water that spent acid is obtained through peracid/salt separating treatment are selectively applied directly to above-mentioned row Industry, link make less salt spent acid using returning to above-mentioned link, industry after waste acid concentration, concentrated sulfuric acid mixed preparing PROCESS FOR TREATMENT With to reach the purpose of free sulfuric acid and dissolubility titanium in recovery titanium white waste acid simultaneously.
The inventive method is further illustrated with reference to the accompanying drawings and examples, and is given up with gained less salt spent acid, high salt Aquatic products titanium dioxide acidolysis, complex acid, bleaching, ferrous sulfate washing, ore deposit/acid production with sulphur, phosphate fertilizer, hydrometallurgy mineral floating and The utilization ways of industry and the links such as leaching are typical case, but protection scope of the present invention therefore are not limited in into typical case and show Among example.
Embodiment 1
It is all 8m to use disposal ability3The resin adsorption system and film separation system of/hr, take respectively resin adsorption method, Three kinds of processing modes such as resin adsorption method+resin adsorption method, resin adsorption method+UF membrane, give up to certain sulfate process titanium dioxide enterprise Acid carries out acid/salt and separates, and after continuously running 8 hours, material sampling after before processing is dissociated using chemical method detection is therein The change in concentration of the representative composition such as acid, iron and dissolubility titanium, examines treatment effeciency and product quality index such as table 1 below：(wherein Membrane separation process uses NF membrane)
Table 1
Find out from upper table, under the operating condition for controlling acid/water volume ratio to be 1 ︰ 1.5, single hop resin adsorption method point It is free acid recovering rate 78%, metallic salt clearance (in terms of iron) 81% from efficiency；Two sections of separative efficiencies of resin adsorption method It is the accumulative rate of recovery 64% of free acid, metallic salt adds up clearance (in terms of iron) 95%；Using resin adsorption method and NF membrane Separate combined treatment process, separative efficiency is the accumulative rate of recovery 67% of free acid, and metallic salt adds up clearance (in terms of iron) 96%, slightly better than two sections resin adsorption method handling process.
Embodiment 2
Certain sulfate process titanium dioxide enterprise is using single hop resin adsorption method, two sections of resin adsorption method treatment titanium white sulfuric acid, before processing Index such as table 2 below afterwards：(acid/water ratio is 1 ︰ 1.6)
Table 2
By improving desorption water, during acid/salt is separated, free acid recovering rate slightly has reduction, and metallic salt is removed Rate slightly rises.
Embodiment 3
In Producing Titanium Dioxide acidolysis link, the less salt spent acid and 98% produced using single hop resin adsorption method in embodiment 2 are dense The concentrated sulfuric acid of degree, is configured to the sulfuric acid of 93% concentration and the sulfuric acid of 48% concentration respectively, and the mixing apparatus of use is Venturi tube spray Emitter, equipment is continuously run 3 months, and it is diluent that contrast uses production water, prepares link machine operation, see the table below 3：
Table 3
It follows that by the way that using sour hybrid technique and equipment, less salt spent acid and the concentrated sulfuric acid after acid/salt is separated are prepared Into the reaction acid and initiation acid that meet acidolysis main reaction technological requirement, compounding system equipment normal operation, due to using containing big The less salt spent acid of free acid is measured as diluting concentrated sulfuric acid agent, is prepared compared to using production water, reduce the caloric value for preparing link, Acid yield is prepared to have been lifted, and acidolysis main reaction is normal；Using this technique, free acid in spent acid is reclaimed, reduced acidolysis new Fresh sulfuric acid consumption, saves cost.
Embodiment 4
Certain sulfate process titanium dioxide enterprise bleaching process：Bleaching adds aluminium powder to prepare after titanous in metatitanic acid using 98% concentrated sulfuric acid According to 0.2% than row add, heating-up temperature 700C, be incubated 240 minutes.Washed after the completion of bleaching.
Using less salt spent acid (free sulfuric acid content 270g/L, Fe content 9g/L, dissolubility titanium 1.5g/L), operation 3 is investigated Individual month, two kinds of methods of operation of Integrated comparative see the table below 4：
Table 4
As can be known from the above table, the former traditional handicraft of bleaching of metatitanic acid carries out the preparation and partially of reducing agent using the substantial amounts of concentrated sulfuric acid The bleaching of metatitanic acid, the link is the second largest sulfuric acid consumption point of sulfate process titanium dioxide.Traditional handicraft can be substituted using less salt spent acid 60% fresh sulfuric acid, i.e., titanium white per ton can save the fresh concentrated sulfuric acid of the concentration of 100kg 98%, whitening procedure and bleaching effect Without influence.
Embodiment 5
Certain original acidolysis process of sulfate process titanium dioxide enterprise：Acid/ore deposit proportioning 1.54；After ilmenite concentrate and strong sulfuric acid response, adopt Leached with production water；
Adjusted Option：Acid/ore deposit proportioning is adjusted to 1.48 by 1.54, after acidolysis main reaction, using the tree described in embodiment 2 Fat absorption method technique, the high-salt wastewater (free sulfuric acid content 50g/L, Fe content 30g/L, dissolubility titanium 6g/L) of output, according to After sulfuric acid amount contained by high-salt wastewater calculates volume according to 0.06 coefficient, added in acidolysis pot to acidolysis in the acidolysis main reaction later stage Reactant is leached, and in the case of the total sulfuric acid amount for ensureing traditional handicraft is immovable, can be consumed close to 7M3High salt give up Water, so as to reclaim the dissolubility titanium of 42kg in high-salt wastewater；It is shown in Table 5：
Table 5
Therefore, on the basis of maintaining the original total sulfuric acid amount of titanium dioxide acid hydrolysis immovable, the adjustment matched by sour ore deposit, largely Leaching operation is carried out through the high-salt wastewater that acid/salt treatment is obtained using titanium white waste acid, acidolysis intermediate product quality has both been ensure that, together When also reclaimed valuable dissolubility titanium and free acid in high-salt wastewater in large quantities, reduce acidolysis cost；
Remarks：Using the process bands come the metallic salt total amount such as iron increase, can be removed in postorder crystallization link, but dissolving Property titanium reclaimed completely utilize.
Embodiment 6
Ferrous crystallizing and washing link in certain sulfate process titanium dioxide enterprise production procedure：Original technique is using substantial amounts of production water pair Ferrous sulfate crystallization is rinsed, and washes returns to acidolysis flow as small degree water (titanium powder industry is commonly called as)；Using high salt Waste water (free sulfuric acid content 50g/L, Fe content 30g/L, dissolubility titanium 6g/L) replaces production water to wash ferrous sulfate, It is same to produce washes, both washes constituent analysis such as table 6 below：
Table 6
As seen from the above table, high-salt wastewater replaces production water to wash ferrous iron, and the redissolution quantity of ferrous sulfate is reduced, and is washed The stability for washing waste water is greatly improved, the effluent part can refer to embodiment 5 described in mode return to acidolysis flow, in high-salt wastewater Dissolubility titanium is recycled utilization.
Embodiment 7
The attached 300,000 tons/sulphur-burning sulphuric acid system of certain sulfate process titanium dioxide enterprise：Original technique next month consumption 3750 tons of water of production, Month 25000 ton of 98% sulfuric acid of output.
Using resin adsorption method acid twice/salt separating technology in embodiment 2, output less salt spent acid (free sulfuric acid content 190g/L, Fe content 1.1g/L, dissolubility titanium 0.06g/L), substitute production water and enter dry matter translocation, investigate operation 3 months：Often 5400 tons of less salt spent acid of moon consumption, 730 tons of moon sulfuric acid volume increase is done and inhales link production water without supplement, the big storage tank acid mud increase of sulfuric acid 7%, reduce by 580 tons of lime in sewage disposal with spent acid, outer bed drain purge reduces 2000 tons.
Remarks：1) for using after less salt spent acid, iron content is increased slightly (3ppm increases to 8ppm) in finished product sulfuric acid, should Titanium dioxide acid hydrolysis production is used, titanium white product quality is unchanged.
2) it is increased slightly using finished product concentrated sulfuric acid acid mud after less salt spent acid, can periodically extracts bottom using small-sized filter press is set up Portion's acid mud, the mode of solid-liquid separation acid sludge solves the problems, such as sour mud deposition.
Embodiment 8
Certain sulfate process titanium dioxide enterprise pigment waste acid concentrator：Spent acid treating capacity 2*12m3/ hour, one or two effect forced circulation amounts 1400m3/ hour, 1800m3/ hour, the water of output one is ferrous 2.4 tons per hour, amount containing free acid 15%.
Using less salt spent acid (free sulfuric acid content 290g/L, Fe content 11g/L, dissolubility titanium 1.8g/L), operation 6 is investigated Individual month, two kinds of methods of operation of Integrated comparative see the table below 7：
Table 7
Learnt from upper table, carried out at waste acid concentration using the less salt spent acid obtained after the inventive method acid/salt separating treatment Reason, can effectively solve concentration systems normal operation, simultaneously because a large amount of metallic salt materials are deviate from advance in spent acid, reduce spent acid Viscosity, brings moisture evaporation improved efficiency under equal evaporating temperature, and waste acid concentration maximum concentration improves 8 percentage points, while Improve the quantity that spent acid returns to titanium white system；Acid recovering rate of dissociating in waste acid concentration system concentration link spent acid significantly increases Plus, significantly reduce and cause to administer the work difficulty of secondary pollution due to ferrous iron entrainment sulfuric acid.
Calculate according to field practice, less salt spent acid is by after waste acid concentration, free acid concentration brings up to 57%, you can with by titanium The spent acid of white device is all consumed in acidolysis link, to realize the full recovery of the total free acid of spent acid.
General principle of the invention, principal character and advantage has been shown and described above.The technical staff of the industry should Understand, the present invention is not limited to the above embodiments.Simply original of the invention is illustrated described in above-described embodiment and specification Reason, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes and improvements Each fall within scope of the claimed invention.The claimed scope of the invention is by appending claims and its equivalent circle. It is fixed.

Claims (11)

1. in titanium white waste acid sulfuric acid and dissolubility titanium recovery separation method, it is characterised in that：Comprise the following steps：Titanium white waste acid Adsorbed by resin chromatography post, efflux is high-salt wastewater；Desorbed with the above-mentioned resin chromatography post of water wash, flowed out Liquid is less salt spent acid.
2. in titanium white waste acid according to claim 1 sulfuric acid and dissolubility titanium recovery separation method, it is characterised in that：Institute State hydrolysis link of the titanium white waste acid for Producing Titanium Dioxide flow carry out separation of solid and liquid after hydrolysis process separates out solid phase metatitanic acid and A kind of complicated component of output, the industrial waste acid containing the metallic salt such as a large amount of free sulfuric acids and dissolubility titanium；Further, institute Titanium white waste acid is stated containing 220~340g/L free sulfuric acids, 35~55g/L Fe, 4~9g/L dissolubility titaniums.
3. in titanium white waste acid according to claim 1 sulfuric acid and dissolubility titanium recovery separation method, it is characterised in that：Institute It is the strong basic type anion-exchange resin with quarternary amine functional group, at least one in strongly acidic cation-exchange to state resin； Further, the strong basic type anion-exchange resin of described band quarternary amine functional group is Du's sheng, a reed pipe wind instrumentA-32, described is strong Acid type cationic ion-exchange resin is D101 macroporous absorbent resins.
4. in the titanium white waste acid according to any one of claims 1 to 3 sulfuric acid and dissolubility titanium recovery separation method, it is special Levy and be：Gained less salt spent acid contains 200~300g/L free sulfuric acids, 5~15g/L Fe, 0.5~2g/L dissolubility titaniums；Gained is high Salt waste water contains 20~80g/L free sulfuric acids, 15~40g/L Fe, 3~8g/L dissolubility titaniums.
5. in the titanium white waste acid according to any one of Claims 1 to 4 sulfuric acid and dissolubility titanium recovery separation method, it is special Levy and be：The resin loading of chromatographic column is 1 ︰ 0.1~1 with the volume ratio of single treatment titanium white waste acid.
6. in the titanium white waste acid according to any one of Claims 1 to 4 sulfuric acid and dissolubility titanium recovery separation method, it is special Levy and be：The diameter and height ratio of the chromatographic column are 0.15~5 ︰ 1；Further, the column diameter be 100~ 3000mm, is highly 300~25000mm.
7. in the titanium white waste acid according to any one of Claims 1 to 4 sulfuric acid and dissolubility titanium recovery separation method, it is special Levy and be：The trend of titanium white waste acid is bottom in and top out during the absorption, and the trend of water is upper entering and lower leaving during desorption；Absorption and desorption Flow velocity be 0.002~0.02 meter per second.
8. in the titanium white waste acid according to any one of Claims 1 to 4 sulfuric acid and dissolubility titanium recovery separation method, it is special Levy and be：It is 1 ︰ 0.5~3 to control by the titanium white waste acid of chromatographic column and the volume ratio of water；Further, control passes through chromatogram The titanium white waste acid of post and the volume ratio of water are 1 ︰ 1~3.
9. in the titanium white waste acid according to any one of Claims 1 to 4 sulfuric acid and dissolubility titanium recovery separation method, it is special Levy and be：According to the requirement to less salt spent acid, resin adsorption desorption or UF membrane are repeated, number of repetition is for more than once；Enter one Step, second Adsorption and desorption is repetition resin chromatography；Further, gained after second Adsorption and desorption Less salt spent acid composition is 150~280g/L free sulfuric acids, 0.5~5g/L Fe, 0.05~0.5g/L dissolubility titaniums；Gained high salt Waste component is 10~50g/L free sulfuric acids, 3~8g/L Fe, 0.3~1.5g/L dissolubility titaniums.
10. the recovery separation method of sulfuric acid and dissolubility titanium is isolated in the titanium white waste acid described in any one of claim 1~9 Less salt spent acid and high-salt wastewater in titanium white production, waste acid concentration, ore deposit/acid production with sulphur, phosphorous chemical industry, magnesium sulfate, hydrometallurgy The application of mineral floating and acid leaching extraction industry；
Wherein, the application of less salt spent acid is as follows：
Application method one：Less salt spent acid is comprised the following steps in the application method of titanium dioxide acid hydrolysis link：By less salt spent acid and dense sulphur Acid is deployed into the sulfuric acid that mass concentration is 90~95%, used as reaction acid；Or less salt spent acid and the concentrated sulfuric acid are deployed into mass concentration It is 45~55% sulfuric acid, it is sour as triggering；Or directly as leaching acid；
Application method two：Less salt spent acid bleaches the application method of link in titanium white, comprises the following steps：Less salt spent acid is added and is floated Free acid content is 40~80g/L during slurry is controlled in white slurry；Preferably 50~60g/L；
Application method three：Less salt spent acid is comprised the following steps in the application method of phosphate fertilizer industry：Less salt spent acid and the concentrated sulfuric acid are mixed Conjunction is configured to the sulfuric acid that mass concentration is 35~55% and phosphorus ore and carries out reaction production coarse whiting phosphate fertilizer；
Application method four：Less salt spent acid is comprised the following steps in the application method of hydrometallurgy industry mineral floating link：Will be low Salt spent acid and the concentrated sulfuric acid are added in ore pulp, the acidity required for being modulated into mineral floating；
Application method five：Less salt spent acid leaches the application method of link in hydrometallurgy industry, comprises the following steps：Less salt is given up Acid and miberal powder are mixed, and according to the requirement of leaching technology, add concentrated sulfuric acid adjustment acidity, complete in the case of stirring and heating The sulfuric acid to leach of paired mineral；
Application method six：Less salt spent acid is comprised the following steps in magnesium sulfate industry application method：Less salt spent acid and magnesium slag are mixed Stirring is closed, concentrated sulfuric acid adjustment acidity is added, the synthesis of magnesium sulfate is carried out in stirring or in the case of stirring heat tracing；
Wherein, the application of high-salt wastewater is as follows：
Application method seven：High-salt wastewater is comprised the following steps in the application method of titanium dioxide acid hydrolysis link：Titanium dioxide acid hydrolysis technique is entered Row adjustment, traditional acid/ore deposit proportioning is adjusted to 1.44~1.50 by 1.52~1.56, after acidolysis main reaction, by high-salt wastewater After proportionally measuring in addition acid hydrolysate；The ratio is that the weight ratio of free acid amount and titanium ore in high-salt wastewater is 0.06~0.12；
Application method eight：High-salt wastewater washs the application method of link in titanium white ferrous sulfate crystallization, comprises the following steps：By height Salt waste water is uniformly sprayed at ferrous sulfate surface and drip washing is carried out to it, collects leacheate and repeats to carry out ferrous sulfate drip washing to pouring Dissolubility titanium reaches 30~80g/L in washing lotion；
Wherein, the application of second less salt spent acid is as follows：With the application method one of separating obtained less salt spent acid for the first time, two, three, 4th, five, six it is identical beyond, also including application method nine, ten；
Application method nine：Second separating obtained less salt spent acid is comprised the following steps in the application method of sulphur dioxide of phosphor chemical industry：By two The sulfuric acid and phosphorus ore that secondary less salt spent acid and the concentrated sulfuric acid are hybridly prepared into mass concentration 35~55% carry out reaction production calcium monohydrogen phosphate；
Application method ten：Second less salt spent acid does the application method for inhaling link in ore deposit/acid production with sulphur, comprises the following steps：Will The traditional absorption water of secondary less salt spent acid replacement and the concentrated sulfuric acid are configured to 98.0%~98.5% absorption acid, to SO3Inhaled Grow nonparasitically upon another plant product sulfuric acid；
Wherein, less salt spent acid or second application of less salt spent acid also includes application method 11：By less salt spent acid or second After separating obtained less salt waste acid concentration reaches 40~65% to sulfuric acid concentration, concentrate spent acid is obtained by being separated by filtration, concentrate is given up Acid reapplies the industry and link described in above-mentioned application method one, two, three, four, five, six, nine, ten.
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CN109865599A (en) * 2019-03-28 2019-06-11 中国矿业大学 A kind of resource utilization method of chemical industry carnallite
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CN107346670A (en) * 2017-06-16 2017-11-14 中国原子能科学研究院 Removed in a kind of high-salt wastewater90Sr intermediate processing
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CN113171881A (en) * 2021-04-28 2021-07-27 郑州大学 Method for recycling metal ions in sulfuric acid process titanium dioxide waste acid
CN113337737A (en) * 2021-06-01 2021-09-03 贵州威顿催化技术有限公司 Method for recovering waste vanadium catalyst by using chromatographic technique

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