CN207361808U - A kind of titanium white waste acid utilization system - Google Patents
A kind of titanium white waste acid utilization system Download PDFInfo
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- CN207361808U CN207361808U CN201721404410.8U CN201721404410U CN207361808U CN 207361808 U CN207361808 U CN 207361808U CN 201721404410 U CN201721404410 U CN 201721404410U CN 207361808 U CN207361808 U CN 207361808U
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Abstract
The utility model discloses a kind of titanium white waste acid utilization system, belong to titanium white waste acid technical field of comprehensive utilization.The utility model includes spent acid storage tank, neutralization chamber, Ammonia vessel, Deironing mechanism, vacuum concentrating apparatus, main reactor and drying and crushing mechanism, spent acid storage tank connects neutralization chamber with the outlet pipe of Ammonia vessel, neutralization chamber connects Deironing mechanism through equipment for separating liquid from solid one, Deironing mechanism connects vacuum concentrating apparatus through equipment for separating liquid from solid three, vacuum concentrating apparatus is connected with main reactor, and barium sulphide storage tank is also connected with main reactor；Main reactor is connected through equipment for separating liquid from solid four with drying and crushing mechanism, and equipment for separating liquid from solid four is also connected with ammonium sulfide storage tank.The utility model is by after titanium white waste acid and ammonium hydroxide neutralization and purification and impurity removal, traditional saltcake solution is instead of to produce for blanc fixe, the positive metatitanic acid precipitation of recycling at the same time can be used for titanium white production, both resource has been saved, energy waste utilization again, reduces titanium powder plant spent acid processing cost and environmental protection pressure.
Description
Technical field
Titanium white waste acid technical field of comprehensive utilization is the utility model is related to, it is comprehensive more specifically to a kind of titanium white waste acid
Conjunction utilizes system.
Background technology
Barium sulfate is a kind of important basic chemical industry raw material, is widely used in coating, ink, rubber, plastics, insulating tape
Filler, the surface smears of impression paper and art paper, the sizing agent of weaving, the heavy weight additive of deep drilling exploration.Be additionally operable to pigment,
A variety of industries such as ceramics, storage battery, enamel, ore dressing, adhesive, medicine, glass and spices, while still produce other barium salts
Raw material.
The production technology of China's barium sulfate is mainly grey black-mirabilite method：Barite and coal are mixed in a certain ratio, through broken
It is broken to enter rotary kiln, under high temperature reduction roasting barium sulphide melt (grey black, BaS contents are 60% or so) is made, it is black with water extraction
The obtained barium sulfide solution of ash, the saltcake solution (Na with clarification2SO4Content 17% -20%) metathesis reaction in chemical combination tank, it is raw
Into barium sulfate precipitate and byproduct vulcanized sodium, reaction equation BaS+Na2SO4→BaSO4↓+Na2S.By reaction solution separation of solid and liquid, barium
Cake obtains barium sulfate finished product by washing, drying, crushing.This method is the main method of domestic production blanc fixe, has work
The advantages that skill is simple, mature technology, is used by most of producer.
China is the first big producer of titanium dioxide, and based on sulfuric acid process.Sulfuric acid process produces 1 ton of titanium white
Powder, about produces 3~4m3Titanium white waste acid, containing a large amount of unreacted free acids in titanium white waste acid, sulfuric acid content about 20~
25%, in addition also containing materials such as a certain amount of titanyl sulfate, ferrous sulfate.If spent acid does not handle direct discharge, can cause tight
The environmental pollution of weight, and serious waste resource.
Common process mode to spent acid is neutralized using alkaline matters such as lime, carbide slags, such a processing mode meeting
A large amount of calcium mud are produced, it is necessary to which place stacking, brings influence to environment, increase titanium dioxide environmental protection of enterprise pressure and processing cost.Such as
What scientifically handles spent acid, titanium white waste acid is had application value, or the valuable resource (such as titanyl sulfate) in recycling the inside,
Become an important technology problem of sulfate process titanium dioxide production, and mitigated titanium dioxide environmental protection of enterprise pressure, promote titanium white row
Industry sound development key subjects.
Current both economical environmentally friendly processing method, is that 98% concentrated sulfuric acid of technical grade is added in titanium white waste acid, is carried out
Complex acid concentrate.Lifted with the concentration of sulfuric acid, the impurity such as ferrous sulfate contained in spent acid can be separated out in a manner of crystallization, significantly
The iron content of spent acid is reduced, the production of sulfuric acid method titanium pigment can be reused for.But this method needs titanium white production device,
And complex acid concentrate needs the substantial amounts of technical grade concentrated sulfuric acid, and the spent acid prepared, the initiation acid of titanium dioxide acid hydrolysis link is only used for, is used
Way and dosage are limited, and cause the treating capacity of spent acid limited.Still an alternative is that titanium white waste acid is carried out vacuum concentration processing, make
Its concentration reaches 55%~60%, separates out errous sulfate crystal, is then back to titanium white production, forms spent acid and recycles.
But supporting graphite heat exchange enrichment facility is needed, cost of investment is big, and the errous sulfate crystal separated out easily scabs, and blocks graphite and changes
Hot device, causes concentrated effect to be deteriorated, fluctuation of service.Such a method spent acid processing cost is high, often dense far above technical grade
Sulfuric acid price, influences the economic benefit of titanium powder plant.
With reference to the production technology of blanc fixe industry, titanium white waste acid is produced for barium sulfate, carries out waste utilization, can
Effectively reduce the environmental protection pressure of titanium dioxide enterprise.Grey black-mirabilite method is prepared in blanc fixe technique, can use sulfuric acid H2SO4Replace
For saltcake solution (Na2SO4) reacted, obtain blanc fixe and byproduct hydrogen sulfide.But titanium white waste acid cannot be substituted directly
Saltcake solution because containing titanyl sulfate and ferrous sulfate in spent acid, can give production barium sulfate quality bring it is larger negative
Influence.Therefore, how titanium white waste acid is handled, blanc fixe production technology can be applied to, becoming needs to solve
Key technology difficulty.
It is through retrieval, patent announcement CN104118893B, patent name：One kind utilizes titanium white waste acid production technical grade sulphur
The method of sour magnesium, method of this application titanium white waste acid Jing Guo complex acid concentrate remove impurity, are reacted after concentrated with light-burning magnesium powder,
Purification adjusts pH using milk of lime or carbide slag, adds hydrogen peroxide in alkaline conditions, then the mode for adjusting pH is returned with the concentrated sulfuric acid, goes
Impurity in sulfuric acid magnesium, centrifuges after crystallisation by cooling, and drying obtains technical grade sulfuric acid magnesium finished product.This method is given up using titanium white
Acid prepares technical grade sulfuric acid magnesium, but to remove ferrous sulfate not thorough enough for the mode of complex acid concentrate, it is impossible to meets blanc fixe
Production requirement, and Adlerika is made in this method first, recycles pH control means to make contamination precipitation, and barium sulfate is inherently
It is precipitation, mixes, can not separate with contamination precipitation, do not have impurity-eliminating effect, thus the spent acid impurity removal process of this method is not
Produced suitable for blanc fixe.
China Patent No. ZL201120446027.5, patent name are：A kind of titanium white waste acid high level efficient utilization device, should
The titanium white waste acid high level efficient utilization device that application case provides is made of sulfuric acid mixture, nitration mixture purification, purification acid-utilising three parts,
The sulfuric acid blending device is made of spent acid pretreatment tank, spent acid pump, nitration mixture groove；The nitration mixture purifier is cooled down by acid
Device, cyclic acid pump, digester, press filtration acid pump, pressure filtration mechanism into；Acid-utilising device is purified by the sour storage tank of purification, phosphoric acid by wet process system
Phosphate device, by-product phosphorus titanium gypsum Sulphuric acid and cement plant, production of sulfur from pyrite acid device are formed.This application realize by
Titanium white waste acid phosphoric acid extraction producing phosphate, by-product phosphorus titanium gypsum Sulphuric acid and cement, filter residue and troilite mix firing sulfuric acid, break through
The problem of traditional waste acid concentration reclamation set high energy consumption, but this application does not solve to prepare precipitation using titanium white waste acid
The problem of barium sulfate is poor quality.
Utility model content
1. utility model technical problems to be solved
In order to overcome above-mentioned technical problem existing in the prior art, the utility model provides a kind of titanium white waste acid synthesis profit
With system, the purpose of this utility model is that preparing blanc fixe using a large amount of titanium white waste acids that titanium dioxide factory produces, give up
Thing utilizes, in view of containing titanyl sulfate and ferrous sulfate impurity in spent acid, if directly used, can give the barium sulfate quality of production
Larger negative effect is brought, the utility model has carried out efficient purified treatment to titanium white waste acid, is used further to prepare precipitated sulfur
Sour barium.
2. technical solution
To reach above-mentioned purpose, technical solution provided by the utility model is：
A kind of titanium white waste acid utilization system of the utility model, including spent acid storage tank, neutralization chamber, Ammonia vessel, remove
Iron mechanism, vacuum concentrating apparatus, barium sulphide storage tank, main reactor, ammonium sulfide storage tank and drying and crushing mechanism, spent acid storage
Groove connects neutralization chamber with the outlet pipe of Ammonia vessel, and neutralization chamber connects Deironing mechanism through equipment for separating liquid from solid one, and described removes
Iron mechanism connects vacuum concentrating apparatus through equipment for separating liquid from solid three, and vacuum concentrating apparatus is connected with main reactor, the vulcanization
Barium storage tank is also connected with main reactor；Main reactor is connected through equipment for separating liquid from solid four with drying and crushing mechanism, separation of solid and liquid dress
Put four and be also connected with ammonium sulfide storage tank.
Further improved as the utility model, the Deironing mechanism includes an iron removal trough, secondary iron removal trough
With hydrogen peroxide storage tank, equipment for separating liquid from solid one is connected with an iron removal trough, and another outlet pipe of Ammonia vessel connects one at the same time
Secondary iron removal trough, described iron removal trough connect secondary iron removal trough, secondary iron removal trough and separation of solid and liquid through equipment for separating liquid from solid two
Device three connects；The outlet pipe of the hydrogen peroxide storage tank connects secondary iron removal trough.
Further improved as the utility model, the drying and crushing mechanism includes type expansion drier and air-flow
Pulverizer, equipment for separating liquid from solid four connect type expansion drier, type expansion drier connection airslide disintegrating mill.
Further improved as the utility model, the exhaust emissions of the type expansion drier and airslide disintegrating mill
Guan Jun is passed through vacuum concentrating apparatus.
Further improved as the utility model, the neutralization chamber, an iron removal trough and secondary iron removal trough are all provided with
It is equipped with online pH probes.
Further improved as the utility model, the neutralization chamber, an iron removal trough, secondary iron removal trough and master are anti-
Answer and agitating device is both provided with inside groove.
Further improved as the utility model, the equipment for separating liquid from solid one, equipment for separating liquid from solid two and solid
Liquid separating apparatus three is frame filter press.
Further improved as the utility model, the equipment for separating liquid from solid four is filtering sheet frame.
3. beneficial effect
Using technical solution provided by the utility model, compared with existing known technology, there is following remarkable result：
(1) a kind of titanium white waste acid utilization system of the utility model, first in neutralization chamber add ammonium hydroxide in and titanium
Ammonium sulfate, and control system pH are generated after white spent acid, separates out positive metatitanic acid precipitation；Then proceed to add ammonia in an iron removal trough
Water, control pH separate out ferrous hydroxide precipitation；Hydrogen peroxide is added in secondary iron removal trough in proportion again, by residual F e2+It is oxidized to
Fe3+, pH is adjusted, separates out ferric hydroxide precipitate, after titanium white waste acid and ammonium hydroxide neutralization and purification and impurity removal, it is molten to instead of traditional saltcake
Liquid is produced for blanc fixe, while the positive metatitanic acid precipitation recycled can be used for titanium white production, not only save resource, but also energy
Waste utilization, reduces titanium powder plant spent acid processing cost and environmental protection pressure, obtains preferable economy, environmental benefit；
(2) a kind of titanium white waste acid utilization system of the utility model, it is contemplated that the titanyl sulfate in titanium white waste acid is
The titanium dioxide hydrolysis stage, non-complete hydrolysis left behind, and there may be in highly acid system, thus pass through online pH probe monitors
And pH is controlled, system acidity is reduced, brings it about hydrolysis, generates positive metatitanic acid precipitation, the positive metatitanic acid precipitation recycled can be used for
Titanium white production, is conducive to efficiently using for resource；
(3) a kind of titanium white waste acid utilization system of the utility model, in view of the ferrous sulfate content in titanium white waste acid
It is higher, in an iron removal trough, pH is raised by adjusting, it is generated ferrous hydroxide Fe (OH)2Precipitation, so as to remove big portion
The ferrous sulfate divided；But ferrous ion Fe after an iron removaling2+Content is for the production requirement of blanc fixe or higher,
Thus in secondary iron removal trough, using hydrogen peroxide by remaining a small amount of ferrous ions into iron ion, then pH is adjusted, generate hydrogen
Iron oxide precipitation removes, molten by setting an iron removal trough and secondary iron removal trough to ensure to obtain more pure ammonium sulfate
Liquid, ensures the barium sulfate quality of subsequent production；
(4) a kind of titanium white waste acid utilization system of the utility model, barium sulfate use temperature successively by plate-frame filtering
Water and acid water washing, after recycling ammonium sulfide washing lotion and removing foreign ion, through type expansion drier and airslide disintegrating mill it is dry,
After crushing, blanc fixe product is made, high-temperature tail gas that is dry and crushing can be additionally used in the concentration of ammonium sulfate, the system
Control is simple, effect is good, can greatly save the energy.
Brief description of the drawings
Fig. 1 is the flow chart that the utility model prepares blanc fixe using titanium white waste acid.
Embodiment
To further appreciate that the content of the utility model, the utility model is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
With reference to Fig. 1, a kind of titanium white waste acid utilization system of the present embodiment, including the storage of spent acid storage tank, neutralization chamber, ammonium hydroxide
Groove, Deironing mechanism, vacuum concentrating apparatus, barium sulphide storage tank, main reactor, ammonium sulfide storage tank and drying and crushing mechanism, it is described
Spent acid storage tank connects neutralization chamber with the outlet pipe of Ammonia vessel.Neutralization chamber connects Deironing mechanism, institute through equipment for separating liquid from solid one
The Deironing mechanism stated includes an iron removal trough, secondary iron removal trough and hydrogen peroxide storage tank, equipment for separating liquid from solid one and an iron removal trough
Connection, another outlet pipe of Ammonia vessel connect an iron removal trough at the same time, and described iron removal trough is through equipment for separating liquid from solid
The two secondary iron removal troughs of connection, secondary iron removal trough are connected with equipment for separating liquid from solid three；The outlet pipe of the hydrogen peroxide storage tank connects
Connect secondary iron removal trough.Equipment for separating liquid from solid three connects vacuum concentrating apparatus, and vacuum concentrating apparatus is connected with main reactor, described
Barium sulphide storage tank is also connected with main reactor；Main reactor is connected through equipment for separating liquid from solid four with drying and crushing mechanism, xeraphium
Broken mechanism includes type expansion drier and airslide disintegrating mill, and equipment for separating liquid from solid four connects type expansion drier, expansion drying dress
Put connection airslide disintegrating mill.The type expansion drier and the tail gas discharging pipe of airslide disintegrating mill are passed through vacuum concentration dress
Put.Equipment for separating liquid from solid four is also connected with ammonium sulfide storage tank.
Neutralization chamber, an iron removal trough and secondary iron removal trough are both provided with online pH probes, and neutralization chamber, one in the present embodiment
Agitating device is both provided with inside secondary iron removal trough, secondary iron removal trough and main reactor.The equipment for separating liquid from solid one, solid-liquid point
It is frame filter press from device two and equipment for separating liquid from solid three, equipment for separating liquid from solid four is filtering sheet frame.
The titanium white waste acid utilization system of the present embodiment, the spent acid produced using Titanium White Production By Sulfuric Acid Process, is added first
Enter after ammonium hydroxide neutralizes and generate ammonium sulfate, and control system pH, separate out positive metatitanic acid precipitation, recycling is used for titanium white production；Then after
It is continuous to add ammonium hydroxide, pH is controlled, ferrous hydroxide precipitation is separated out, is filtered to remove precipitation；Oxidant is proportionally added into again, by residue
Fe2+It is oxidized to Fe3+, pH is adjusted, ferric hydroxide precipitate is separated out, is filtered to remove to obtain pure ammonium sulfate；Ammonium sulfate is molten
After liquid concentration, the saltcake solution in traditional blanc fixe production technology is substituted, double decomposition occurs with barium sulfide solution in proportion
Reaction, is made barium sulfate precipitate and byproduct ammonium sulfide, after washed, dry and crushing, blanc fixe product is made.
For component referring to table 1, the utility model considers that the titanyl sulfate in titanium white waste acid is titanium dioxide hydrolysis in titanium white waste acid
Stage, non-complete hydrolysis left behind, and there may be in highly acid system.Thus by raising pH, system acidity is reduced, is made
It is hydrolyzed, and generates positive metatitanic acid precipitation, and positive metatitanic acid precipitation recycling can be used for titanium white production, be conducive to effective profit of resource
With.
Component data in 1 titanium white waste acid of table
In view of the ferrous sulfate content in titanium white waste acid is higher, rise pH can be equally adjusted, it is generated hydroxide
Iron Fe (OH)2Precipitation, so that remove most ferrous sulfate, i.e. an iron removaling；But ferrous ion Fe after an iron removaling2+Contain
Amount is for the production requirement of blanc fixe or higher, and due to iron hydroxide Fe (OH)3The solubility product constant of precipitation
Far below ferrous hydroxide Fe (OH)2Precipitation, thus by remaining a small amount of ferrous ions into iron ion, then pH is adjusted, it is raw
Removed into ferric hydroxide precipitate, i.e., secondary iron removaling.It can ensure to obtain more pure ammonium sulfate by iron removal twice molten
Liquid, ensures the barium sulfate quality of subsequent production.Hydrogen peroxide is best selection as oxidant, because oxidation effectiveness is good, and not
New foreign ion can be introduced.
Since the dedoping step of above titanyl sulfate, ferrous sulfate all uses rise system pH, generation hydroxide precipitation
To realize, and titanium white waste acid contains a large amount of free acids, and pH is very low, could be carried out after must carrying out titanium white waste acid neutralization.Spent acid
The product of neutralization should can participate in blanc fixe production, while cannot bring new foreign ion into.Consider, this practicality is new
Type utilizes in ammonia spirit and titanium white waste acid becomes best selection.Using in ammonia spirit and titanium white waste acid, neutralized reaction product sulphur
Sour ammonium (NH4)2SO4Saltcake Na can be substituted2SO4Metathesis reaction life occurs for solution, and black ash leaching solution barium sulphide BaS solution
Into blanc fixe, and other impurities ion will not be introduced.
And since ammonium hydroxide has paired electrons, there is stronger coordination, complex can be formed with ferrous ion,
So as to influence the effect of an iron removaling, ammonium hydroxide consumption can be also greatly increased, so it is particularly important that pH in an iron removaling is controlled,
It should ensure de-ferrous effect, can not cause to be coordinated, reduce de-ferrous effect, increase ammonium hydroxide consumes.
Technical solution provided in this embodiment is：
First by titanium white waste acid and ammonium hydroxide and generation ammonium sulfate, by controlling pH to separate out positive metatitanic acid first and precipitate 3.0,
Recycle in titanium white production；Be further continued for adding ammonium hydroxide, control pH as 8.0~9.0, make most of ferrous sulfate (95% with
On) ferrous hydroxide precipitation is separated out, precipitation is filtered to remove, and will not be with ferrous ion Fe in 8.0~9.0 scopes, ammonium hydroxide in pH2+
Form mating reaction；Hydrogen peroxide is proportionally added into again, by remaining ferrous ion Fe2+It is oxidized to iron ion Fe3+, pH is 4.0 for adjustment
Left and right, separates out ferric hydroxide precipitate, is filtered to remove to obtain more pure ammonium sulfate.Under the conditions of pH >=4.0, iron ion is several
Precipitation completely, residual iron content are less than 0.06g/L, meet the production requirement of blanc fixe；Ammonium sulfate is concentrated
Afterwards, metathesis reaction occurs with black ash leaching solution barium sulfide solution in proportion, blanc fixe and byproduct vulcanization ammonia is made.Sulphur
Sour barium uses warm water and acid water washing successively by plate-frame filtering, after recycling ammonium sulfide washing lotion and removing foreign ion, through dry
After dry and crushing (high-temperature tail gas that is dry and crushing can be used for the concentration of ammonium sulfate), blanc fixe product is made.
Related reaction equation：
2NH3·H2O+H2SO4→(NH4)2SO4+2H2O
TiO2—+2OH—→TiO(OH)2↓
Fe2++2OH—→Fe(OH)2↓
Fe3++3OH—→Fe(OH)3↓
BaS+(NH4)2SO4→BaSO4↓+(NH4)2S
Concretely comprising the following steps for blanc fixe is prepared using titanium white waste acid utilization system provided in this embodiment：
Step 1: being transferred to neutralization chamber from spent acid storage tank by a certain amount of titanium white waste acid, stirring is opened, by Ammonia vessel in
Ammonium hydroxide is uniformly added into groove, neutralizes titanium white waste acid generation ammonium sulfate, the detection data popped one's head according to online pH, control neutralizes
Groove body system pH stops adding ammonium hydroxide 3.0, and ammonia spirit concentration is 25%, and the titanyl sulfate generation in titanium white waste acid at this time is just
Metatitanic acid precipitates；
Step 2: the solution and being deposited in neutralization chamber after neutralizing stir 20 minutes, the positive metatitanic acid of titanyl sulfate generation is set to sink
Form sediment after reaction fully, pump to frame filter press, filtered, filtrate enters an iron removaling from frame filter press filtrate (liquid
Groove, titanic acidleach cake can be used for titanium white production after collecting；
Step 3: ammonium hydroxide is slowly added to an iron removal trough by Ammonia vessel, the detection data popped one's head according to online pH,
Control system pH rises to 8.0, stops adding ammonium hydroxide, during making this, most of ferrous ion Fe2+Hydroxide can be increasingly generated
Ferrous precipitation.
Step 4: being stirred in an iron removal trough after twenty minutes, make ferrous ion Fe2+Generate ferrous hydroxide precipitation reaction
After fully, the ferrous hydroxide precipitation and solution of generation are pumped to frame filter press, filtered, separation ferrous hydroxide sinks
Form sediment, the ammonium sulfate filtrate after an iron removaling enters secondary iron removal trough from frame filter press filtrate (liquid；
Step 5: hydrogen peroxide, hydrogen peroxide and ferrous ion Fe are proportionally added into secondary iron removal trough by hydrogen peroxide storage tank2+
Molar ratio be 1:2, by residual F e2+Ionic oxide formation is into Fe3+, according to the detection data of online pH probes, pH value 3.8 is adjusted,
Separate out ferric hydroxide precipitate；
Step 6: stirred in secondary iron removal trough after twenty minutes, after precipitation reaction is abundant, by the ferric hydroxide precipitate of generation
And solution is pumped to frame filter press, is filtered, separation ferric hydroxide precipitate filter, ammonium sulfate after secondary iron removaling from
Frame filter press filtrate (liquid enters vacuum concentrating apparatus, after ammonium sulfate is concentrated into 160g/l, is transferred to ammonium sulfate storage tank
It is spare.
Step 7: being transferred to main reactor from barium sulphide storage tank by a certain amount of barium sulfide solution, 1 is pressed from ammonium sulfate storage tank:1 rubs
Ammonium sulfate is added main reactor (the micro- excess of barium) by that ratio, and with ammonium sulfate metathesis reaction occurs for barium sulphide, generates sulphur
Sour precipitated barium and accessory substance ammonium sulfide solution.
Step 8: being stirred 20 minutes in main reactor, reaction is to terminal, molten by the barium sulfate precipitate of generation and ammonium sulfide
Liquid is pumped to filtering sheet frame, separation of solid and liquid, ammonium sulfide solution and collected to ammonium sulfide storage tank, and it is accurate that barium sulfate filter cake stays in filtering sheet frame
Standby washing.
Step 9: barium sulfate filter cake is first washed with deionized, washing lotion is recycled to ammonium sulfide storage tank, (NH4) in washing lotion2When S is less than 0.02%, stopping is recycled to ammonium sulfide storage tank；Afterwards with the acid rinsing that pH is 4；Pressure is washed in whole washing process
Power is 300KPa, and wash time is 60 minutes.
Step 10: the barium cake after washing is discharged into after type expansion drier is dried, crushes, precipitated into steam powder machine
Barium sulfate finished product；Dry tail gas and steam powder machine tail gas are through heat-exchanger rig, the concentration for ammonium sulfate.
Embodiment 2
Concretely comprising the following steps for blanc fixe is prepared using titanium white waste acid utilization system provided in this embodiment：
Step 1: being transferred to neutralization chamber from spent acid storage tank by a certain amount of titanium white waste acid, stirring is opened, in molar ratio example 2:1 is logical
Cross Ammonia vessel and be uniformly added into ammonium hydroxide to neutralization chamber, neutralize titanium white waste acid generation ammonium sulfate, the inspection popped one's head according to online pH
Data are surveyed, neutralization chamber system pH is 3.0 or so for control, stops adding ammonium hydroxide, ammonia spirit concentration is 27%, at this time titanium white waste acid
In titanyl sulfate generate positive metatitanic acid precipitation；
Step 2: the solution and being deposited in neutralization chamber after neutralizing stir 30 minutes, the positive metatitanic acid of titanyl sulfate generation is set to sink
Form sediment after reaction fully, pump to frame filter press, filtered, filtrate enters an iron removaling from frame filter press filtrate (liquid
Groove, titanic acidleach cake can be used for titanium white production after collecting；
Step 3: ammonium hydroxide is slowly added to an iron removal trough by Ammonia vessel, the detection data popped one's head according to online pH,
Control system pH rises to 8.5, stops adding ammonium hydroxide, during making this, most of ferrous ion Fe2+Hydroxide can be increasingly generated
Ferrous precipitation.
Step 4: after being stirred 30 minutes in an iron removal trough, make ferrous ion Fe2+Generate ferrous hydroxide precipitation reaction
After fully, the ferrous hydroxide precipitation and solution of generation are pumped to frame filter press, filtered, separation ferrous hydroxide sinks
Form sediment, the ammonium sulfate filtrate after an iron removaling enters secondary iron removal trough from frame filter press filtrate (liquid；
Step 5: hydrogen peroxide, hydrogen peroxide and ferrous ion Fe are proportionally added into secondary iron removal trough by hydrogen peroxide storage tank2+
Molar ratio be 1:2, by residual F e2+Ionic oxide formation is into Fe3+, according to the detection data of online pH probes, pH value 4.0 is adjusted,
Separate out ferric hydroxide precipitate；
Step 6: after being stirred 30 minutes in secondary iron removal trough, after precipitation reaction is abundant, by the ferric hydroxide precipitate of generation
And solution is pumped to frame filter press, is filtered, separation ferric hydroxide precipitate filter, ammonium sulfate after secondary iron removaling from
Frame filter press filtrate (liquid enters vacuum concentrating apparatus, after ammonium sulfate is concentrated into 180g/l, is transferred to ammonium sulfate storage tank
It is spare.
Step 7: being transferred to main reactor from barium sulphide storage tank by a certain amount of barium sulfide solution, barium sulfide solution concentration is
160g/l, the barium sulfide solution are refined with 90 DEG C of water extraction and obtained by the barium sulphide melt reduction after barite and carbon dust calcining
.1 is pressed from ammonium sulfate storage tank:Ammonium sulfate is added main reactor (the micro- excess of barium), barium sulphide and ammonium sulfate by 1 molar ratio
Generation metathesis reaction, generates barium sulfate precipitate and accessory substance ammonium sulfide solution.
Step 8: being stirred 30 minutes in main reactor, reaction is to terminal, molten by the barium sulfate precipitate of generation and ammonium sulfide
Liquid is pumped to filtering sheet frame, separation of solid and liquid, ammonium sulfide solution and collected to ammonium sulfide storage tank, and it is accurate that barium sulfate filter cake stays in filtering sheet frame
Standby washing.
Step 9: barium sulfate filter cake is first washed with deionized, washing lotion is recycled to ammonium sulfide storage tank, (NH4) in washing lotion2When S is less than 0.02%, stopping is recycled to ammonium sulfide storage tank；Afterwards with the acid rinsing that pH is 5；Pressure is washed in whole washing process
Power is 350KPa, and wash time is 90 minutes.
Step 10: the barium cake after washing is discharged into after type expansion drier is dried, crushes, precipitated into steam powder machine
Barium sulfate finished product；Dry tail gas and steam powder machine tail gas are through heat-exchanger rig, the concentration for ammonium sulfate.
Embodiment 3
Concretely comprising the following steps for blanc fixe is prepared using titanium white waste acid utilization system provided in this embodiment：
Step 1: being transferred to neutralization chamber from spent acid storage tank by a certain amount of titanium white waste acid, stirring is opened, in molar ratio example 2:1 is logical
Cross Ammonia vessel and be uniformly added into ammonium hydroxide to neutralization chamber, neutralize titanium white waste acid generation ammonium sulfate, the inspection popped one's head according to online pH
Data are surveyed, neutralization chamber system pH is 3.0 or so for control, stops adding ammonium hydroxide, ammonia spirit concentration is 28%, at this time titanium white waste acid
In titanyl sulfate generate positive metatitanic acid precipitation；
Step 2: the solution and being deposited in neutralization chamber after neutralizing stir 40 minutes, the positive metatitanic acid of titanyl sulfate generation is set to sink
Form sediment after reaction fully, pump to frame filter press, filtered, filtrate enters an iron removaling from frame filter press filtrate (liquid
Groove, titanic acidleach cake can be used for titanium white production after collecting；
Step 3: ammonium hydroxide is slowly added to an iron removal trough by Ammonia vessel, the detection data popped one's head according to online pH,
Control system pH rises to 9.0, stops adding ammonium hydroxide, during making this, most of ferrous ion Fe2+Hydroxide can be increasingly generated
Ferrous precipitation.
Step 4: being stirred in an iron removal trough after forty minutes, make ferrous ion Fe2+Generate ferrous hydroxide precipitation reaction
After fully, the ferrous hydroxide precipitation and solution of generation are pumped to frame filter press, filtered, separation ferrous hydroxide sinks
Form sediment, the ammonium sulfate filtrate after an iron removaling enters secondary iron removal trough from frame filter press filtrate (liquid；
Step 5: hydrogen peroxide, hydrogen peroxide and ferrous ion Fe are proportionally added into secondary iron removal trough by hydrogen peroxide storage tank2+
Molar ratio be 1:2, by residual F e2+Ionic oxide formation is into Fe3+, according to the detection data of online pH probes, pH value 4.2 is adjusted,
Separate out ferric hydroxide precipitate；
Step 6: stirred in secondary iron removal trough after forty minutes, after precipitation reaction is abundant, by the ferric hydroxide precipitate of generation
And solution is pumped to frame filter press, is filtered, ferric hydroxide precipitate is separated, ammonium sulfate after secondary iron removaling is from frame
The outlet of formula filter press filtrate enters vacuum concentrating apparatus, and after ammonium sulfate is concentrated into 220g/l, it is standby to be transferred to ammonium sulfate storage tank
With.
Step 7: being transferred to main reactor from barium sulphide storage tank by a certain amount of barium sulfide solution, barium sulfide solution concentration is
200g/l, 1 is pressed from ammonium sulfate storage tank:Ammonium sulfate is added main reactor (the micro- excess of barium), barium sulphide and sulphur by 1 molar ratio
Metathesis reaction occurs for sour ammonium, generates barium sulfate precipitate and accessory substance ammonium sulfide solution.
Step 8: being stirred 40 minutes in main reactor, reaction is to terminal, molten by the barium sulfate precipitate of generation and ammonium sulfide
Liquid is pumped to filtering sheet frame, separation of solid and liquid, ammonium sulfide solution and collected to ammonium sulfide storage tank, and it is accurate that barium sulfate filter cake stays in filtering sheet frame
Standby washing.
Step 9: barium sulfate filter cake is first washed with deionized, washing lotion is recycled to ammonium sulfide storage tank, (NH4) in washing lotion2When S is less than 0.02%, stopping is recycled to ammonium sulfide storage tank；Afterwards with the acid rinsing that pH is 5；Pressure is washed in whole washing process
Power is 400KPa, and wash time is 120 minutes.
Step 10: the barium cake after washing is discharged into after type expansion drier is dried, crushes, precipitated into steam powder machine
Barium sulfate finished product；Dry tail gas and steam powder machine tail gas are through heat-exchanger rig, the concentration for ammonium sulfate.
Schematically the utility model and embodiments thereof are described above, this describes no restricted, attached drawing
Shown in be also the utility model one of embodiment, actual structure is not limited thereto.So if this area
Those of ordinary skill enlightened by it, without deviating from the purpose of the present invention, not inventively design
The frame mode similar to the technical solution and embodiment, all should belong to the protection range of the utility model.
Claims (8)
- A kind of 1. titanium white waste acid utilization system, it is characterised in that：Including spent acid storage tank, neutralization chamber, Ammonia vessel, magnetic separator de-ironing Structure, vacuum concentrating apparatus, barium sulphide storage tank, main reactor, ammonium sulfide storage tank and drying and crushing mechanism, the spent acid storage tank and The outlet pipe connection neutralization chamber of Ammonia vessel, neutralization chamber connect Deironing mechanism, the magnetic separator de-ironing through equipment for separating liquid from solid one Structure connects vacuum concentrating apparatus through equipment for separating liquid from solid three, and vacuum concentrating apparatus is connected with main reactor, barium sulphide storage Groove is also connected with main reactor；Main reactor is connected through equipment for separating liquid from solid four with drying and crushing mechanism, equipment for separating liquid from solid four It is also connected with ammonium sulfide storage tank.
- A kind of 2. titanium white waste acid utilization system according to claim 1, it is characterised in that：The Deironing mechanism bag An iron removal trough, secondary iron removal trough and hydrogen peroxide storage tank are included, equipment for separating liquid from solid one is connected with an iron removal trough, Ammonia vessel Another outlet pipe connects an iron removal trough at the same time, and described one time iron removal trough connects secondary iron removaling through equipment for separating liquid from solid two Groove, secondary iron removal trough are connected with equipment for separating liquid from solid three；The outlet pipe of the hydrogen peroxide storage tank connects secondary iron removal trough.
- A kind of 3. titanium white waste acid utilization system according to claim 1 or 2, it is characterised in that：The xeraphium Broken mechanism includes type expansion drier and airslide disintegrating mill, and equipment for separating liquid from solid four connects type expansion drier, expansion drying dress Put connection airslide disintegrating mill.
- A kind of 4. titanium white waste acid utilization system according to claim 3, it is characterised in that：The expansion drying dress Put and be passed through vacuum concentrating apparatus with the tail gas discharging pipe of airslide disintegrating mill.
- A kind of 5. titanium white waste acid utilization system according to claim 4, it is characterised in that：The neutralization chamber, one Secondary iron removal trough and secondary iron removal trough are both provided with online pH probes.
- A kind of 6. titanium white waste acid utilization system according to claim 5, it is characterised in that：The neutralization chamber, one Agitating device is both provided with inside secondary iron removal trough, secondary iron removal trough and main reactor.
- A kind of 7. titanium white waste acid utilization system according to claim 6, it is characterised in that：The separation of solid and liquid dress It is frame filter press to put one, equipment for separating liquid from solid two and equipment for separating liquid from solid three.
- A kind of 8. titanium white waste acid utilization system according to claim 7, it is characterised in that：The separation of solid and liquid dress Four are put as filtering sheet frame.
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| CN201721404410.8U CN207361808U (en) | 2017-10-27 | 2017-10-27 | A kind of titanium white waste acid utilization system |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963510A (en) * | 2020-01-13 | 2020-04-07 | 山东齐创石化工程有限公司 | Recovery processing device and process for waste sulfuric acid |
| CN116177779A (en) * | 2022-12-09 | 2023-05-30 | 四川大学 | Recycling method of titanium white wastewater |
| CN118307023A (en) * | 2024-04-08 | 2024-07-09 | 广东尚宸环境科技有限公司 | Method and treatment system for recycling titanium dioxide waste acid by sulfuric acid process |
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2017
- 2017-10-27 CN CN201721404410.8U patent/CN207361808U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963510A (en) * | 2020-01-13 | 2020-04-07 | 山东齐创石化工程有限公司 | Recovery processing device and process for waste sulfuric acid |
| CN116177779A (en) * | 2022-12-09 | 2023-05-30 | 四川大学 | Recycling method of titanium white wastewater |
| CN116177779B (en) * | 2022-12-09 | 2024-04-19 | 四川大学 | Recycling method of titanium white wastewater |
| CN118307023A (en) * | 2024-04-08 | 2024-07-09 | 广东尚宸环境科技有限公司 | Method and treatment system for recycling titanium dioxide waste acid by sulfuric acid process |
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