CN109052608A - Sulfuric acid method titanium pigment waste water treating agent and preparation method thereof - Google Patents
Sulfuric acid method titanium pigment waste water treating agent and preparation method thereof Download PDFInfo
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- CN109052608A CN109052608A CN201810891715.9A CN201810891715A CN109052608A CN 109052608 A CN109052608 A CN 109052608A CN 201810891715 A CN201810891715 A CN 201810891715A CN 109052608 A CN109052608 A CN 109052608A
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The present invention discloses a kind of sulfuric acid method titanium pigment waste water treating agent and preparation method thereof, react by control lime with the digestive pharmaceutical mixed containing water and hydroxyl organic matter, CaO of the preparation with mobility and high-ratio surfacex(OH)(2‑2x)Powder, CaOx(OH)(2‑2x)Powder can be well-dispersed in formation Ca (OH) in water2Fine colloid, makes itself and spent acid and FeSO4Sufficiently reaction, overcomes Fe (OH)2/Fe(OH)3At Ca (OH)2Surface deposition and with package phenomenon, greatly reduce the dosage of neutralizer, to reduce the yield of sulfuric acid method titanium pigment solid waste GYPSUM RUBRUM, provide new, better raw material for method for producing gtitanium dioxide with sulphuric acid production wastewater treatment and select.
Description
Technical field
The present invention relates to field of waste water treatment more particularly to a kind of wastewater from TiO2 factory inorganic agent and preparation method thereof.
Background technique
Sulfuric acid method titanium pigment industry is all made of titaniferous material and sulfuric acid reaction, and sulfuric acid is process substance, plays intermediation, removes
Waste acid concentration, waste acid concentration ferrous sulfate monohydrate, ferrous sulfate heptahydrate, which crystallize three links, with reuse or to take away a part of sulphur
It is sour outer, remaining sulfuric acid overwhelming majority with free sulfuric acid and sulphate form by acid waste water, spent acid enter Sewage Disposal into
Titanium white production system is finally discharged in row acid-base neutralization in the form of calcium sulfate slag.In sulfuric acid method titanium pigment production, every production 1
Ton titanium dioxide will generate 10 tons of the spent acid, 5% acid below that 3 tons of green vitriol, 0.5 ton of acid waste residue, concentration are about 15~20%
20 tons of waste water of property.Table 1 is sulfuric acid method titanium pigment manufacturing enterprise lime, lime stone unit consumption and gypsum specific yield.
1 sulfuric acid method titanium pigment of table produces lime, lime stone unit consumption and gypsum specific yield
| Project | Lime t/t.TiO2 | Lime stone t/t.TiO2 | Transport outward gypsum t/t.TiO2 |
| Creation data | 1.8 | 1.8 | 15.3 |
The waste water generated in Titanium White Production By Sulfuric Acid Process technique mainly has hydrolysis spent acid, bleaching spent acid and acid waste water.It is right
In the high hydrolysis spent acid of acid concentration and bleaching spent acid, a part can return to hydrolysis procedure directly to adjust the acidity coefficient of titanium liquid,
It is most of that high-concentration sulfuric acid is made using concentration, it is used further to the production of other chemical products.China's sulfuric acid method titanium pigment row
Industry all carries out acid waste water processing using milk of lime neutralization/aeration and sedimentation group technology substantially.Its antalkali is lime
Stone and lime are usually used in the spent acid of one section of processing 15~20% since lime stone is cheap, and lime stone is beaten laggard through ball milling
Enter processing pond, but lime stone can not obtain sufficiently high pH to precipitate and be similar to FeSO4Salt.Two sections of processing need quick lime,
Quick lime (CaO) is usually digested to white lime Ca (OH) in application2.General quicklime slaking system include lime bin,
Belt conveyor, calcium hydroxide machine etc..Quick lime enters belt conveyor by hopper, then is transported in calcium hydroxide machine, passes through
Collision crashing and with clear water mixture slaking, it is most of formed it is microgranular is suspended in solution, form lime slurry.Due to low-quality original
Expect that active oxidation calcium content is low, impurity is more, causes conventional lime digestion process there are low efficiency, lime slurry particle is big, reacts
Slowly, easily by Fe (OH)2/Fe(OH)3There are problems for wrap up and lose activity etc., cause limestone/lime utilization rate not
Phenomena such as high, waste is seriously, severe operational environment, operating cost are high, the secondary quantity of slag is big and seriously polluted.And ultra-fine, Gao Bibiao
Face and the lime easily dispersed are the key that solve the problems, such as this.
United States Patent (USP) US8480018B2 discloses a kind of particulate calcium hydroxide dry-forming method and device (Method
And Apparatus for the Preparation of Finely Divided Calcium Hydroxide), at this
Then the water that digestion lime needed for one third is added in patent equipment first in quenching process adds remaining three points
Two water.
European patent EP 2366666A1 discloses a kind of preparation method (the Process for Producing of calcium hydroxide
A Calcium Hydroxide Compound), silicon base compound, al-based compound, phosphoric acid based compound, organic acid or
Under the conditions of inorganic acid single or multiple compounds are existing, calcium chloride solution is mixed with sodium hydroxide solution and generates calcium hydroxide
Precipitating, up to calcium hydroxide after filtration drying.
The system of a kind of high-purity and high activity calcium hydroxide as disclosed in Chinese patent application discloses No. 101254935A
Preparation Method includes following preparation step using the preparation method of common quick lime preparation high-purity and high activity calcium hydroxide:
(1) digestion of quick lime；(2) dissolving with hydrochloric acid；(3) separation of foreign ion；(4) precipitate C a2+；(5) high-temperature roasting；(6) it digests,
Obtain high-purity and high activity calcium hydroxide.The advantages of patent application, is: selected raw material quick lime contain Si, Fe,
The impurity such as Mg, Al are applicable in, CaO and Ca (OH)2Purity is high；Plurality of impurities can be removed simultaneously by adjusting pH value with ammonium hydroxide, only be needed
Solution ph is controlled greater than 11, can achieve the purpose that clean completely；Obtained calcium carbonate whiteness reaches 100 or more,
Calcium oxide activity obtained reaches 400ml or more after roasting.However, the patent application prepares the method for calcium hydroxide with ammonium hydroxide tune
PH value is saved, is difficult to control, easily causes calcium hydroxide low output, containing miscellaneous height.
For another example Chinese patent application discloses a kind of high adsorption activity calcium hydroxide nanometer of No. 104069793A announcement
The preparation method of grain, comprising the following steps: CaCl2It is put into three-necked bottle, deionized water dissolving is added, is stirred using magnetic stirring apparatus
It mixes；SDS or PEG is weighed, they and CaCl2Mass ratio are as follows: CaCl2: SDS=22.2: (0.47~2.34) or CaCl2∶PEG
=22.2: (2.65~14.44) are added to stirring and dissolving in three-necked bottle；NaOH is dissolved in deionized water, CaCl2: NaOH mass
Than=22.2: 8, is then instilled in three-necked bottle with the rate of 40ml/h, be stirred to react 0.5h~2.5h and obtain slurry；Slurry is taken out
It is dry after washing after filter.The present invention prepare particle uniformly, in dispersed nano Ca (OH)2Powder, grain graininess 200nm
~300nm；Specific surface area is up to 88m2/g.To N2Maximal absorptive capacity can reach 80mL/g；It is reachable to NOx removal rate simultaneously
98%.However, the high adsorption activity calcium hydroxide nano particle of patent application preparation is mainly used in space launching site liquid
Propellant N2O4Leakage processing, the problem of not can solve for sulfuric acid method titanium pigment production wastewater treatment.
For another example Chinese patent application discloses a kind of high surface calcium hydroxide particle of No. 105502457A announcement
Preparation method includes the following steps: that quick lime and glass fibre are mixed in a certain ratio uniformly by (1)；It (2) will be in step (1)
Obtained mixture, organic solvent and deionized water is configured to suspension by a certain percentage；(3) it will be hanged obtained in step (2)
It is uniform that turbid is placed in ultrasonic disperse in ultrasonic reactor；(4) suspension after ultrasonic disperse in step (3) is depressurized and is filtered, then
Obtained solid substance is dried in vacuo, the high surface Strong oxdiative calcium particle is obtained.However, the system of the patent application publication
For Preparation Method for obtaining pure calcium hydroxide product, production process requirement is stringenter, is not suitable for largely handling waste water.
Therefore it provides a kind of simple process, the ultra-fine, high-ratio surface that reduces cost, reduce environmental pollution and easily dispersing
Sulfuric acid method titanium pigment waste water treating agent and preparation method thereof becomes urgent problem in the industry.
Summary of the invention
The object of the present invention is to provide a kind of simple process, the sulfuric acid method titanium pigment for reducing cost, reducing environmental pollution are useless
Water treatment agent and preparation method thereof, the easy environmental protection of this method, the waste water treating agent (CaO which obtainsx(OH)(2-2x))
Have the characteristics that mobility and high-ratio surface.
According to an aspect of the invention, there is provided a kind of sulfuric acid method titanium pigment waste water treating agent, the sulfuric acid method titanium pigment
The chemical formula of waste water treating agent is CaOx(OH)(2-2x), wherein X=0.03~0.17.
According to another aspect of the present invention, it provides and a kind of mix and disappear with water and hydroxyl organic matter is contained using control lime
Agent reaction sulfuric acid method titanium pigment waste water treating agent preparation method, specifically include: (1), include: (1), prepare quick lime
Grain and digestive pharmaceutical, quicklime particles are that quick lime is broken into granularity is particle less than 10~20 millimeters, digestive pharmaceutical by water and
One or more are mixed with the organic matters of hydroxyl, wherein organic matter with hydroxyl and water in digestive pharmaceutical
Weight ratio is 1:5~20；(2), quicklime particles are placed in closed mixing slot, spray digestion to being mixed in slot
Agent generates midbody product to be sufficiently mixed with quicklime particles, wherein the temperature in control stirred tank is 40~70 Celsius
It spends, the additional amount of the water in digestive pharmaceutical is the 25%~31% of the weight of quicklime particles；(3), friction-stir midbody product,
Precursors product is isolated, the granularity of precursors product is less than 200 mesh, bulk density less than 0.5 gram/cc；
(4), precursors product is placed in stirred tank, is reacted 30~60 minutes under conditions of 65~95 degrees Celsius, generate sulphur
Acid system wastewater from TiO2 factory inorganic agent first product；(5), in stirred tank under conditions of stirring, heating ventilation is adsorbed in sulphur to be desorbed
The hydroxyl organic matter on acid system wastewater from TiO2 factory inorganic agent first product surface generates hydroxyl organic gas, wherein desorption temperature 85
~115 DEG C, desorption time is 10~20 minutes；And (6), the sulfuric acid that hydroxyl organic matter has been desorbed that will obtain in step (5)
Method wastewater from TiO2 factory inorganic agent first product carries out classification removal of impurities, to obtain sulfuric acid method titanium pigment.
Wherein, in step (1), quick lime (CaO) is fractured into fritter of the granularity less than 10~20mm, is stored in feed bin
It is interior.
Selectively, the organic matter (R-OH) with hydroxyl (- OH) in digestive pharmaceutical is that alcohol type organic, phenols are organic
Object or other hydroxyl organic matters.
Preferably, alcohol type organic can be one of methanol, ethyl alcohol, propyl alcohol or a variety of mixtures.
It is highly preferred that the boiling point of selected alcohol type organic or mixture is lower than 115 DEG C.
Wherein, in step (2), the digestion reaction of quick lime is that quick lime reacts as follows with water generation:
CaO+2H2O→CaO·2H2O→Ca(OH)2+H2O-64.8KJ/mol
Digestion reaction is exothermic reaction.The digestion process of quick lime is digestion water elder generation and quick lime appearance face contact
It learns reaction generation calcium hydroxide and is covered in unreacted quick lime surface, when digesting water excess, digestion water passes through calcium hydroxide
After capillary channel, continues and the contact of quick lime kernel generates the 2nd layer of calcium hydroxide, repeatedly.But the first layer surface
Calcium hydroxide not only prevents the contact of the quick lime of kernel with digestion water, but also can occur with newly generated calcium hydroxide solidifying
Poly-, reunion and the growth of crystal grain, to reduce the activity of calcium hydroxide, the dispersibility in water and the ratio for increasing calcium hydroxide
Surface area.
So controlling the specific surface of calcium hydroxide in digestion process, quicklime slaking speed should be not only controlled, and
And it should also be prevented from generated calcium hydroxide and participate in further digestion reaction.Using digestive pharmaceutical to inbound traffics and in digestive pharmaceutical
The middle method that hydroxyl organic matter is added controls the digestion rate of quick lime and uses the method for big cycle volume by generated hydrogen
Calcium oxide leaves mixing channel in time, removes the Ca (OH) on quick lime surface2And Ca (OH) is separated from quick lime2, to prevent
Calcium hydroxide is further contacted with digestive pharmaceutical.
In the present invention, digestive pharmaceutical is made of water and hydroxyl organic matter (R-OH), and main function is control water and life
The reaction of the lime ,-OH in hydroxyl organic matter can occur hydrogen bond with the oxygen in quick lime and react such as:
Wherein ,-the OH in hydroxyl organic matter and the oxygen in quick lime form hydrogen bond, and the oxygen in quick lime is made to lose absorption
Hydrone (H2O activity), so that quick lime and water reaction speed are reduced, the crystal grain of the calcium hydroxide generated with this condition
More carefully, specific surface area is bigger.
In step (2), the temperature control that slot is mixed is determined by digestive pharmaceutical spray flow, in certain life stone
When grey feeding coal, digestive pharmaceutical spray flow is bigger, and the temperature that slot is mixed is higher, otherwise lower.Slot heating is mixed
Digestion reaction heat of the heat from quick lime.The additional amount of total water is the 25~31% of quick lime weight.
Selectively, between step (3) and step (4) further include: return part remaining after separation quicklime particles
It is back in step (2) that the reaction was continued with digestive pharmaceutical.
In order to remove the hydroxide calcium layer in quick lime Surface Creation in time, using mixture operation (i.e. step 2) with separate
Operation (i.e. the two steps of step 3).Mixture operation is digestive pharmaceutical and quick lime adsorption, and is realized raw on quick lime surface
At one layer of thin calcium hydroxide.Volume will increase simultaneously swelling fracture after quick lime meets water, occur on fine and close quick lime surface
The upper loose calcium hydroxide for generating one layer thin.Detached job is the side by the calcium hydroxide on quick lime surface by stirring friction
Formula dissociates quick lime and calcium hydroxide, utilizes the small physical characteristic of calcium hydroxide fine size, bulk density and coarse size, bulk density
Big lime stone separation.Remaining part quick lime after separation returns to mixture operation and further reacts production hydrogen-oxygen with digestive pharmaceutical
Change calcium, and light fine-precursors product enters next reaction operation, i.e. step 4.
Selectively, the amount of solid (hereinafter referred to as discharge) and return that internal circulating load of the invention is discharged after being reacted by step (2)
The quicklime particles (hereinafter referred to as coarse fodder CaO return) reacted in step (2) are back to control, discharge or coarse fodder CaO are returned
It returns and is known as recycle ratio with the ratio of CaO feed (carrying out the quicklime particles of initial reaction in step (2)).Recycle ratio is higher, newly
The faster of calcium hydroxide exclusion of generation, quick lime surface are cleaner, and calcium hydroxide specific surface area generated is also bigger.
Selectively, discharge: CaO feed is 2~4, and coarse fodder CaO is returned: CaO feed is 1~3.Discharge is returned with coarse fodder CaO
It returns there is interrelated relationship, relational expression is as follows:
WCoarse fodder CaO is returned=WDischarge-K
WCoarse fodder CaO is returnedFor coarse fodder CaO return flow, unit is ton/hour (t/h)；
K depends on the constant of CaO feeding coal and quick lime property, and unit is ton/hour (t/h)；
WDischargeFor discharge flow, unit is ton/hour (t/h)；
Wherein, CaO feeding coal is bigger, and K value is bigger；For quick lime containing miscellaneous more, K value is smaller, fixed raw material raw material with
Under working condition, K is constant.
The particle size after cracking for the quick lime (CaO) that the present invention uses is less than 10~20mm.Lime stone is raw after high-temperature calcination
At quick lime, still containing the lime stone and impurity aluminum, silicon mineral etc. for not completing reaction in quick lime.The granularity shadow of quick lime
The absorption of digestive pharmaceutical is rung, the deslagging of mixture operation is mainly influenced.As the digestion granularity of quick lime is tapered, and it is therein
Impurity also gradually becomes clean, and impurity (lime stone and aluminium, silicon mineral) is in the form of slag periodically from the bottom that slot is mixed
Portion's discharge.
Selectively, the reaction process of step (4) is from CaO after detached job removingx(OH)(2-2x)Precursors
Product further changes into CaOx(OH)(2-2x), X of the invention is 0.03~0.17.Wherein, CaOx(OH)(2-2x)It can be considered as raw
Lime is not completely converted into Ca (OH)2A midbody compound, air can be adsorbed in air by putting as quick lime
In moisture, still, not with when contact with moisture it be a stable compound.Products C aOx(OH)(2-2x)It is to lack digestive pharmaceutical
It is formed under conditions of water, its purpose is to products C aOx(OH)(2-2x)With good mobility and dispersibility, in and
It can make CaO when sulfuric acid method titanium pigment waste waterx(OH)(2-2x)With SO4 2-Ion is sufficiently reacted and is prevented Fe (OH)2/Fe(OH)3?
Calcium hydroxide surface covers and loses activity, to play the discharge saved neutralizer and reduce GYPSUM RUBRUM waste residue.It is optional
Select ground, CaOx(OH)(2-2x)X value speed is added by digestive pharmaceutical and amount determines, that is to say, that the temperature of mixed process and mix
Conjunction/separation internal circulating load is determined.The temperature that the more fast namely mixed process of speed is added in digestive pharmaceutical is higher, and X value is smaller；Circulation
Amount is bigger, and X value is bigger.Relative to quick lime weight, the additional amount of water is more, that is to say, that digestion dosage is more, and X value is smaller.
Selectively, the reaction operation of step (4) is completed in stirred tank, since precursors product has well
Mobility and lesser bulk density, the optional spiral agitator of stirred tank or common paddle stirred tank or it is other it is general stirring set
It is standby.
Preferably, reaction operation needs Hot-blast Heating.
Compared to Ca (OH)2, CaO of the inventionx(OH)(2-2x)Heat can be generated into the water increases the temperature of water, this
One phenomenon illustrates CaOx(OH)(2-2x)It is further digested in water and generates Ca (OH)2, and Ca (OH)2It will not generate heat, be put into the water
Fever phenomenon is inorganic agent and Ca (OH) of the invention in water2One of essential difference.
Wherein, the step of step (5) is recycling hydroxyl organic matter, under stirring conditions, is passed through a certain amount of hot-air
It will be by Hydrogen Binding Adsorption in CaOx(OH)(2-2x)The hydroxyl organic matter on surface is desorbed, and is brought by hydroxyl organic gas to condensation and is made
Industry.Wherein, the factor for influencing to recycle operation is desorption temperature, time and gas flow.
Preferably, the heating of operation is recycled using hot-air.
Selectively, further include the steps that the hydroxyl organic gas in condensing recovery step (5).Heat in step (5)
Wind has carried hydroxyl organic matter secretly, since the boiling point of hydroxyl organic matter lower than 115 DEG C and is dissolved in water.Condensation operation is added using water cooling
The i.e. recyclable hydroxyl organic matter of water spray.The temperature for recycling operation is lower than 40 DEG C.The ratio of water spray and quick lime should be less than
0.25.In order to reach water balance, water spray should be less than mixture operation digestion water.Condense operation recycling hydroxyl organic matter and
The mixed liquor of water returns to mixture operation after being added adjustment water and hydroxyl organic matter by requirement of the mixture operation to digestive pharmaceutical.
Selectively, the main purpose of the graded operation of step (6) is removal of impurities, is typically contained in quick lime unreacted
Lime stone, silica be the quartz of free shape, aluminium oxide with silica synthetic aluminium silicate, iron compound in the form of bloodstone etc.
In the presence of.These mineral will not generate granularity variation, but meeting and CaO during detached jobx(OH)(2-2x)Separation, finally
The impure mineral of monomer dissociation is formed, granularity keeps original state, and typically greater than 38 μm, specific gravity is both greater than 2.65g/cm3。
Preferably, graded operation uses cyclone separator, and partition size is equivalent to specific gravity (2.65g/cm3) mineral 30~
38μm.The underflow of cyclone separator is impurity, overflow CaOx(OH)(2-2x)。
The beneficial effects of the present invention are: (1), waste water treating agent CaO prepared by the present inventionx(OH)(2-2x)It is with mobility
With the powder of high-ratio surface, formation Ca (OH) in water can be well-dispersed in2Fine colloid, with spent acid and FeSO4Sufficiently reaction,
Overcome Fe (OH)2/Fe(OH)3At Ca (OH)2Surface deposition and with package phenomenon, greatly reduce the dosage of neutralizer, to drop
The low yield of sulfuric acid method titanium pigment solid waste GYPSUM RUBRUM；(2), powdery CaO of the inventionx(OH)(2-2x)Product is transported with tank car
It is closed to be pumped into feed bin after lime storehouse, through screw conveyor it is closed send to milk of lime pulp pond adjust concentration after, then with waste water,
Spent acid neutralization reaction, whole process are run in closed system, compared to traditional ashing technique, reduce loading machine feeding
4 sections of process, ashing process, lime-ash Secondary Transport, secondary pulping processes, and closed-loop operation has very clean operating environment；
(3), it is starched compared to quick lime ashing, CaO prepared by the present inventionx(OH)(2-2x)With the low characteristic of fine size, impurity content, add
Upper pulp concentration adjust in secondary agitation dispersion further increase dispersibility, in spent acid and when react fast, calcareous by hydrogen
The reaction of iron oxide wrapped up less, given full play to calcium and acid；(4), waste water treating agent CaO prepared by the present inventionx(OH)(2-2x),
In the content and quantity for handling same spent acid, compared to 87%, CaO of market quick limex(OH)(2-2x's)Dosage can at least save
About 35%；(5), present invention preparation CaOx(OH)(2-2x)Product is containing miscellaneous low, in the content and quantity for handling same process spent acid
In the case of, the waste residue amount of corresponding process can be made to reduce by 22% or more using product of the present invention, be produced for method for producing gtitanium dioxide with sulphuric acid
Wastewater treatment provides new, better raw material selection.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of sulfuric acid method titanium pigment waste water treating agent of the invention.
Fig. 2 is that calcium hydroxide reacts generation solid product with titanium white waste acid water progress solid-liquid and is adsorbed in solid reaction
The process schematic on object surface.
Specific embodiment
Please refer to Fig. 1, a kind of non-limiting embodiment according to the present invention provides at a kind of acid system wastewater from TiO2 factory
The preparation method of agent is managed, this approach includes the following steps.
(1), quicklime particles and digestive pharmaceutical are prepared, quicklime particles are that quick lime is broken into granularity for less than 10~20
The particle of millimeter, digestive pharmaceutical are mixed by water and one or more kinds of organic matters with hydroxyl, wherein in digestive pharmaceutical
The weight ratio of organic matter and water with hydroxyl is 1:5~20.
(2), quicklime particles are placed in closed mixing slot, to be mixed slot in spray digestive pharmaceutical with life
Lime particle is sufficiently mixed, and generates midbody product, wherein the temperature in control stirred tank is 40~70 degrees Celsius, digestive pharmaceutical
Additional amount be quicklime particles weight 25%~31%.
(3), friction-stir midbody product, isolates precursors product, and the granularity of precursors product is less than
200 mesh, bulk density are less than 0.5 gram/cc.
(4), precursors product is placed in stirred tank, 30~60 points is reacted under conditions of 65~95 degrees Celsius
Clock generates sulfuric acid method titanium pigment waste water treating agent first product.
(5), in stirred tank under conditions of stirring, heating ventilation is adsorbed in sulfuric acid method titanium pigment wastewater treatment to be desorbed
The hydroxyl organic matter on agent first product surface generates hydroxyl organic gas, wherein desorption temperature is 85~115 DEG C, and desorption time is
10~20 minutes.
(6), the sulfuric acid method titanium pigment waste water treating agent first product that hydroxyl organic matter has been desorbed obtained in step (5) is carried out
Classification removal of impurities, to obtain sulfuric acid method titanium pigment.
In sulfuric acid method titanium pigment technique waste water treatment process, pH is removed in 1 or so titanium white waste acid water containing H2SO4Except it is main
To contain a large amount of FeSO4With a small amount of Fe2(SO4)3CCa(OH)2It is the neutralizer of waste water and the precipitating reagent of sulfate radical, at waste water
It is main during reason that following reaction occurs:
Ca(OH)2(s)+H2SO4→CaSO4(s)+2H2O
Ca(OH)2(s)+FeSO4→CaSO4(s)+Fe(OH)2(s)
3Ca(OH)2(s)+Fe2(SO4)→CaSO4(s)+2Fe(OH)3(s)
2Fe2+1/2O2+H2O→2Fe3+2OH-
2Fe(OH)2(s)+1/2O2+H2O→2Fe(OH)3(s)
Due to Ca (OH)2Very low in the solubility of water, entire neutralization reaction process is a solid reactant Ca (OH)2With
Contain Fe2+, Fe3+, SO4 2-Liquid phase reactor object reacted, generate solid phase product Fe (OH)3And CaSO4, solid phase product
It is covered in solid reactant Ca (OH)2Surface, prevent contact of the liquid phase reactor object further with solid reactant, solid is anti-
Object is answered to lose reactivity in a manner of residual core and be not fully utilized.Fig. 2 illustrate calcium hydroxide and titanium white waste acid water into
The process that the reaction of row solid-liquid generates solid product and is adsorbed in solid reactant surface.
It can be seen that reducing Ca (OH)2Residual core size and number are to increase Ca (OH)2The most effectual way of utilization rate.Using
The method production of miniaturization has the powdery CaO of mobilityx(OH)(2-2x)Increase Ca (OH) to reach2The purpose of utilization rate.
The quick lime of the embodiment of the present invention is derived from the limekiln discharge of Panzhihua Region, Chemical bath deposition such as table 2.
The quick lime chemical analysis of 2 embodiment of the present invention of table
| Chemical analysis | CaO | SiO2 | Fe2O3 | Al2O3 | MgO |
| Content % | 89.89 | 3.08 | 0.32 | 0.70 | 0.34 |
Titanium white waste acid water of the embodiment of the present invention is derived from Panzhihua Region titanium dioxide enterprise, analysis indexes such as table 3.
3 titanium white waste acid water analysis indexes of table
| Project | pH | ss(mg/l) | COD(mg/l) |
| Titanium white waste acid water | 1.03 | 725 | 840 |
The present invention is made combined with specific embodiments below and being further elaborated on, but embodiment and comparative example should not be understood
For limiting the scope of the invention.
Comparative example quick lime handles titanium white waste acid water
Embodiment 1 selects quick lime (table 2) to be used as in inorganic agent and titanium white waste acid water (table 3).The preparation present invention is derived to produce
For quick lime (table 2) raw material of product as water treatment agent, quick lime sample is directly derived from the finished product calcium oxide of limekiln production, through broken
It is spare after broken, sample preparation, chemical examination.The calcium oxide of quick lime is 89.89%, activity 290.
Mixing time determines
Test takes titanium dioxide wastewater (table 3) 1000ml, is put into 3000ml beaker, is placed on blender and starts turning stirring.According to
The acidity of waste water estimates required quality, first its quality is referred to as 11g (accounting for 95% under 120 meshes) calcium oxide 100ml
The quick pulp of tap water, is slowly added to stirring cup.It is added in waste water, is stirred continuously under room temperature, mixing speed 75r/min,
Investigate the influence for neutralizing the time to pH.Experiment, which is selected, neutralizes the time as 9min.The pH and time relationship of titanium dioxide wastewater are listed in table 4.
The pH and time relationship of 4 embodiment of table, 1 titanium dioxide wastewater
| Time (min.) | 0 | 1 | 2 | 3 | 4 | 5 |
| pH | 1.03 | 6.0 | 7.0 | 7.5 | 8.2 | 8.5 |
Therefore pH kept stable after the discovery of table 4 4min neutralizes experiment and is determined as stirring at 75r/min
4min。
Neutralize experiment
Titanium dioxide wastewater (table 3) 1000ml is taken, 3000ml beaker is put into and 11g quick lime (table 2) is put into 100ml water, it will
After 100ml lime white and titanium dioxide wastewater stir 4min, start to filter.Obtaining wet (filter cake) weight of slag is 81g.Wet slag is put into baking oven to exist
After constant temperature is placed 5 hours in 105 DEG C of temperature, obtaining dry weight is 25g.Filtered fluid detects Fe2+, pH, COD and SS (suspended matter), through examining
Measuring result is in water containing Fe2+Mass fraction < 0.05%, water colorless is transparent, and pH reaches 7.8, COD≤95mg/L, and SS is (outstanding
Floating object)≤100mg/L, the index of water reaches the second level emission request of " national sewage comprehensive emission standard " GB8978-2002.
1 powdery CaO of embodimentx(OH)(2-2x)Preparation
Using the process flow of Fig. 1 of the present invention and the technological parameter of table 5, quick lime (table 2) is used as raw material and prepares this hair
Bright products C aOx(OH)(2-2x)。
The CaO of the preparation embodiment 1 of table 5x(OH)(2-2x)Technological parameter
The CaO of 6 embodiment of the present invention 1 of tablex(OH)(2-2x)Chemical analysis.
| Chemical analysis | CaO | SiO2 | Fe2O3 | Al2O3 | MgO |
| Content % | 69.14 | 0.21 | 0.05 | 0.19 | 0.77 |
The powdery CaO of embodiment 1x(OH)(2-2x)Neutralize the test of titanium white waste acid water
Mixing time determines
Test takes titanium dioxide wastewater (table 3) 1000ml, is put into 3000ml beaker, is placed on blender and starts turning stirring.According to
1 powdery CaO of embodiment required for the acidity of waste water estimatesx(OH)(2-2x)Quality, first its quality is referred to as 8.0g, use
The quick pulp of 100ml tap water, is slowly added to stirring cup.It is added in waste water, is stirred continuously under room temperature, mixing speed 75r/
Min investigates the influence for neutralizing the time to pH.Experiment, which is selected, neutralizes the time as 9min.The pH of titanium dioxide wastewater is listed in time relationship
Table 7.
7 embodiment of table, 2 powdery CaOx(OH)(2-2x)Neutralize the pH and time relationship of titanium dioxide wastewater
| Time (min.) | 0 | 1 | 2 | 3 | 4 | 5 |
| pH | 1.03 | 6.5 | 7.3 | 8.2 | 8.5 | 8.7 |
Therefore pH kept stable after the discovery of table 7 3min neutralizes experiment and is determined as stirring at 75r/min
3min。
Neutralize experiment
Titanium dioxide wastewater (table 3) 1000ml is taken, 1 powdery CaO of 3000ml beaker and embodiment is put intox(OH)(2-2x)7.6g being put into
In 100ml water, by 100mlCa (OH)2Slurry starts to filter with after titanium dioxide wastewater stirring 3min.After obtaining slag wet (filter cake) weighing, put
Enter baking oven to be saved 5 hours with 105 DEG C of constant temperature, the results are shown in tables 8.Filtered fluid detects Fe2+, pH, COD and SS (suspended matter), warp
Detect that result is in water containing Fe2+Mass fraction < 0.05%, water colorless is transparent, and pH reaches 7.8, COD≤95mg/L, SS
(suspended matter)≤100mg/L, the second level discharge that the index of water reaches " national sewage comprehensive emission standard " GB8978-2002 are wanted
It asks.
8. embodiment of table, 2 powdery CaOx(OH)(2-2x)Performance indicator and neutralization titanium dioxide wastewater result
2 powdery CaO of embodimentx(OH)(2-2x)Preparation
Using the process flow of Fig. 1 of the present invention and the technological parameter of table 9, quick lime (table 2) is used as raw material and prepares this hair
Bright products C aOx(OH)(2-2x)。
The CaO of the preparation embodiment 2 of table 9.x(OH)(2-2x)Technological parameter
The CaO of 10 embodiment of the present invention 2 of tablex(OH)(2-2x)Chemical analysis.
| Chemical analysis | CaO | SiO2 | Fe2O3 | Al2O3 | MgO |
| Content % | 70.65 | 0.25 | 0.07 | 0.20 | 0.75 |
The powdery CaO of embodiment 2x(OH)(2-2x)Neutralize the test of titanium white waste acid water
Mixing time determines
Test takes titanium dioxide wastewater (table 3) 1000ml, is put into 3000ml beaker, is placed on blender and starts turning stirring.According to
2 powdery CaO of embodiment required for the acidity of waste water estimatesx(OH)(2-2x)Quality, first its quality is referred to as 7.7g, use
The quick pulp of 100ml tap water, is slowly added to stirring cup.It is added in waste water, is stirred continuously under room temperature, mixing speed 75r/
Min investigates the influence for neutralizing the time to pH.Experiment, which is selected, neutralizes the time as 9min.The pH of titanium dioxide wastewater is listed in time relationship
Table 11.
11. embodiment of table, 2 powdery CaOx(OH)(2-2x)Neutralize the pH and time relationship of titanium dioxide wastewater
| Time (min.) | 0 | 1 | 2 | 3 | 4 | 5 |
| pH | 1.03 | 6.7 | 7.3 | 8.1 | 8.7 | 9.1 |
Therefore pH kept stable after the discovery of table 11 3min neutralizes experiment and is determined as stirring at 75r/min
3min。
Neutralize experiment
Titanium dioxide wastewater (table 3) 1000ml is taken, 2 powdery CaO of 3000ml beaker and embodiment is put intox(OH)(2-2x)7.3g being put into
In 100ml water, by 100mlCa (OH)2Slurry starts to filter with after titanium dioxide wastewater stirring 3min.After obtaining slag wet (filter cake) weighing, put
Enter baking oven with 105 DEG C constant temperature 5 hours.The results are shown in tables 12.Filtered fluid detects Fe2+, pH, COD and SS (suspended matter), through detecting
Result is to contain Fe in water out2+Mass fraction < 0.05%, water colorless is transparent, and pH reaches 7.8, COD≤95mg/L, and SS (suspends
Object)≤100mg/L, the index of water reaches the second level emission request of " national sewage comprehensive emission standard " GB8978-2002.
12. embodiment of table, 2 powdery CaOx(OH)(2-2x)) performance indicator and neutralize titanium dioxide wastewater result
3 powdery CaO of embodimentx(OH)(2-2x)Preparation
Using the process flow of Fig. 1 of the present invention and the technological parameter of table 13, quick lime (table 2) is used as raw material and prepares this hair
Bright products C aOx(OH)(2-2x)。
The CaO of the preparation embodiment 3 of table 13.x(OH)(2-2x)Technological parameter
The chemical analysis of the CaOx (OH) (2-2x) of 14. embodiment of the present invention 3 of table
| Chemical analysis | CaO | SiO2 | Fe2O3 | Al2O3 | MgO |
| Content % | 71.15 | 0.29 | 0.09 | 0.24 | 0.74 |
The powdery CaO of embodiment 3x(OH)(2-2x)Neutralize the test of titanium white waste acid water
Mixing time determines
Test takes titanium dioxide wastewater (table 3) 1000ml, is put into 3000ml beaker, is placed on blender and starts turning stirring.According to
3 powdery CaO of embodiment required for the acidity of waste water estimatesx(OH)(2-2x)Quality, first its quality is referred to as 7.5g, use
The quick pulp of 100ml tap water, is slowly added to stirring cup.It is added in waste water, is stirred continuously under room temperature, mixing speed 75r/
Min investigates the influence for neutralizing the time to pH.Experiment, which is selected, neutralizes the time as 9min.The pH of titanium dioxide wastewater is listed in time relationship
Table 15.
The powdery CaO of 15. embodiment 3 of tablex(OH)(2-2x)Neutralize the pH and time relationship of titanium dioxide wastewater
| Time (min.) | 0 | 1 | 2 | 3 | 4 | 5 |
| pH | 1.03 | 6.9 | 7.7 | 8.3 | 8.8 | 9.2 |
Therefore pH kept stable after the discovery of table 15 3min neutralizes experiment and is determined as stirring at 75r/min
3min。
Neutralize experiment
Titanium dioxide wastewater (table 3) 1000ml is taken, 3 powdery CaO of 3000ml beaker and embodiment is put intox(OH)(2-2x)7.15g putting
Enter in 100ml water, by 100mlCa (OH)2Slurry starts to filter with after titanium dioxide wastewater stirring 3min.After obtaining slag wet (filter cake) weighing,
Baking oven is put into be saved 5 hours with 105 DEG C of constant temperature.The results are shown in tables 16.Filtered fluid detects Fe2+, pH, COD and SS (suspended matter),
Detected that result is in water containing Fe2+Mass fraction < 0.05%, water colorless is transparent, and pH reaches 7.8, COD≤95mg/L, SS
(suspended matter)≤100mg/L, the second level discharge that the index of water reaches " national sewage comprehensive emission standard " GB8978-2002 are wanted
It asks.
The powdery CaO of 16. embodiment 3 of tablex(OH)(2-2x)Performance indicator and neutralization titanium dioxide wastewater result
Although detailed description of the present invention preferred embodiment herein, it is to be understood that the invention is not limited to this
In the specific structure being described in detail and show and step, without departing from the spirit and scope of the present invention can be by this field
Technical staff realize other modifications and variant.In addition, the parameters such as temperature, concentration or time in the present invention can be according to tool
Body use condition is suitably chosen within the scope of the present disclosure.
Claims (10)
1. a kind of sulfuric acid method titanium pigment waste water treating agent, which is characterized in that the chemistry of the sulfuric acid method titanium pigment waste water treating agent
Formula is CaOx(OH)(2-2x), wherein X=0.03~0.17.
2. a kind of preparation method of sulfuric acid method titanium pigment waste water treating agent as described in claim 1 characterized by comprising
(1), quicklime particles and digestive pharmaceutical are prepared, the quicklime particles are that quick lime is broken into granularity for less than 10~20
The particle of millimeter, the digestive pharmaceutical are mixed by water and one or more kinds of organic matters with hydroxyl, wherein described to disappear
The weight ratio of the organic matter and water with hydroxyl in agent is 1:5~20；
(2), the quicklime particles are placed in closed mixing slot, spray the digestion into the mixing slot
Agent generates midbody product to be sufficiently mixed with the quicklime particles, wherein control temperature in the stirred tank be 40~
70 degrees Celsius, the additional amount of the water in the digestive pharmaceutical is the 25%~31% of the weight of the quicklime particles；
(3), midbody product described in friction-stir isolates precursors product, the granularity of the precursors product
Less than 200 mesh, bulk density less than 0.5 gram/cc；
(4), the precursors product is placed in stirred tank, 30~60 points is reacted under conditions of 65~95 degrees Celsius
Clock generates the sulfuric acid method titanium pigment waste water treating agent first product；
(5), in the stirred tank under conditions of stirring, heating ventilation is adsorbed in the sulfuric acid method titanium pigment waste water to be desorbed
The hydroxyl organic matter on inorganic agent first product surface generates hydroxyl organic gas, wherein desorption temperature is 85~115 DEG C, when desorption
Between be 10~20 minutes；And
(6), the sulfuric acid method titanium pigment waste water treating agent first product that hydroxyl organic matter has been desorbed obtained in step (5) is carried out
Classification removal of impurities, to obtain the sulfuric acid method titanium pigment.
3. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 2, which is characterized in that described to have hydroxyl
The organic matter of base is alcohol type organic, phenol organic matter or other hydroxyl organic matters.
4. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 3, which is characterized in that the alcohols has
Machine object is one of methanol, ethyl alcohol, propyl alcohol or a variety of above mixtures.
5. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 4, which is characterized in that the alcohols has
The boiling point of machine object is lower than 115 DEG C.
6. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 2, which is characterized in that in step (3)
Between step (4) further include: by part remaining after separation quicklime particles be back in step (2) with the digestive pharmaceutical after
Continuous reaction.
7. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 6, which is characterized in that be back to step
(2) quicklime particles reacted in are 1:1~3 with the weight ratio for being initiated at the quicklime particles that step (2) is reacted,
It is initiated at the weight ratio of the midbody product generated after the quicklime particles that step (2) is reacted are reacted with step (2)
For 1:2~4.
8. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 7, which is characterized in that be back to step
(2) pass of the flow for the midbody product that the flow for the quicklime particles reacted in generates after reacting with step (2)
System are as follows:
WIt returns=WIt is intermediate-K
Wherein, WIt returnsFor the flow for being back to the quicklime particles reacted in step (2), WIt is intermediateIt is raw after step (2) reaction
At the midbody product flow, K is depending on the flow and the life that are initiated at the quicklime particles that step (2) is reacted
The constant of lime property.
9. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 2, which is characterized in that further include condensation
The step of recycling the hydroxyl organic gas in the step (5), using water cooling and water spray, in the environment for being lower than 40 degrees Celsius
Hydroxyl organic matter in lower condensation hydroxyl organic gas, water spray are less than the water in the digestive pharmaceutical in step (2), condensation
The hydroxyl organic matter of acquisition and the mixed liquor of water are passed through by the requirement in step (2) to digestive pharmaceutical, after adjusting water and hydroxyl organic matter
It is used in return step (2).
10. the preparation method of sulfuric acid method titanium pigment waste water treating agent as claimed in claim 2, which is characterized in that in step (6)
In, classification removal of impurities is carried out using cyclone separator, the air classification granularity of the cyclone separator is equivalent to specific gravity 2.65g/cm3
30~38 microns of mineral.
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| CN109879304A (en) * | 2019-03-29 | 2019-06-14 | 桂林理工大学 | A kind of nano/submicron efficient calcium carbonate carbonization technique |
| CN111116061A (en) * | 2019-12-31 | 2020-05-08 | 米易东立矿业有限公司 | Dry preparation method of nano calcium hydroxide |
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