CN106335921A - Recycling method of sulfate process titanium dioxide alkali dissolution filtrate - Google Patents
Recycling method of sulfate process titanium dioxide alkali dissolution filtrate Download PDFInfo
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- CN106335921A CN106335921A CN201610688056.XA CN201610688056A CN106335921A CN 106335921 A CN106335921 A CN 106335921A CN 201610688056 A CN201610688056 A CN 201610688056A CN 106335921 A CN106335921 A CN 106335921A
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- Prior art keywords
- filtrate
- alkali
- alkali soluble
- soluble
- barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
- C01G23/0534—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts in the presence of seeds
Abstract
The invention relates to a processing method of a by-product from sulfate process titanium dioxide production process and specifically discloses a recycling method of a sulfate process titanium dioxide alkali dissolution filtrate. The method comprises the following steps: (1) carrying out solid-liquid separation on an alkali dissolution filtrate to obtain a clear filtrate; (2) adding soluble barium salt into the clear filtrate, uniformly mixing and filtering to obtain regenerated alkali lye; and (3) recycling the regenerated alkali lye as a liquid alkali raw material for the alkali dissolution step in a calcining seeds preparation technology. The invention has the following advantages: 1) recycling of the alkali dissolution filtrate used as the liquid alkali raw material for the alkali dissolution step in the calcining seeds preparation technology is realized; and 2) the technology is simple and easy to implement.
Description
Technical field
The present invention relates to a kind of sulfuric acid method titanium pigment production technology, secondary in especially a kind of sulfuric acid method titanium pigment production process
The processing method of product.
Background technology
Titanium White Production By Sulfuric Acid Process is ilmenite concentrate and the concentrated sulfuric acid to be carried out acidolysis reaction generate titanium sesquisulfate, generates through hydrolysis
Metatitanic acid, obtain titanium dioxide product through calcining, pulverizing.This method can produce anatase titanium dioxide and rutile type titanium white.Sulfuric acid process
Advantage be can be with the low ilmenite being easy to get of valency and sulfuric acid as raw material, technology is more ripe, and equipment is simple, and requirement for anticorrosion is low.It lacks
Point is long flow path, and accessory substance is many, big for environment pollution.The recycling of therefore accessory substance is the major technique of sulfuric acid method titanium pigment
Problem.
In the production process that sulfuric acid process prepares rutile titanium dioxide, need during metatitanic acid calcining to add calcining brilliant
Kind, so-called calcining seeds are usually the metatitanic acid using titanium liquid to be obtained through hydrolysis, then obtain after washing twice pure partially
Metatitanic acid slurry and concentrated base react, wash after obtain sodium titanate (this process is commonly called as alkali soluble), sodium titanate is obtained with hydrochloric acid reaction again
Calcining seeds.The preparation of calcining seeds comprises the following steps:
A, alkali soluble: two are washed qualified metatitanic acid and liquid caustic soda (naoh) boils alkali soluble at high temperature, obtain sodium titanate；
B, the sodium titanate generating send into the temperature that cooling bath is cooled to technological requirement, send Filter Press, washing；
C, acid are molten: add hydrochloric acid reaction that calcining seeds are obtained under agitation.
In b step, sodium titanate washes press filtration with water, and during press filtration, part alkali flows out with pressing filtering liquid, and this pressing filtering liquid is commonly referred to
Alkali soluble filtrate.The logical naoh containing mass concentration 15～20% for the product in alkali soluble filtrate.
Due to containing more impurity in alkali soluble filtrate, it is difficult to recycle, therefore usually as byproduct emission, but alkali
The yield of lixiviation liquid very big (one ton of sodium titanate will produce 15 tons about of alkali soluble filtrate after washing press filtration), if not in addition
Recycle and directly arrange outward, not only result in the loss of alkali and increase production cost, but also sewage disposal difficulty can be increased,
If deal with improperly easily causing environmental pollution.
In the prior art, some producers by alkali soluble filtrate carry out sedimentation separation go out carry out after most of impurity reclaim profit
With the application documents of such as Publication No. cn104098135a disclose a kind of recoverying and utilizing method of alkali soluble filtrate, and it is
Supernatant liquor and lower floor's thick slurry are obtained using thickener sedimentation；Coating operation ph that supernatant liquor is used for titanium dioxide controls, lower floor
Thick slurry is circulated sedimentation.But inventor finds, even if having carried out sufficient settlement treatment, alkali soluble filtrate yet suffers from can not
The soluble impurity filtering, the alkali soluble filtrate supernatant liquor containing impurity is used for coating operation will make coating effect and three wash effect
Fruit is under some influence.
Therefore inventor proposes, if can return alkali soluble filtrate in the step a alkali soluble operation of calcining seeds preparation technology
Recycle as liquid caustic soda, it will solution alkali soluble filtrate discharge and the wherein Utilizing question of naoh.But in alkali soluble filtrate due to
The soluble impurity that presence cannot be filtered, even if having carried out sufficient settlement treatment, also can make when it recycles as liquid caustic soda
Become alkali soluble washing difficult or time lengthening, the molten rutile content of rear operation acid can be led to when serious cannot to be lifted, have a strong impact on and forge
Burn the activity of crystal seed, and the defect that can make problem more serious is recycled for multiple times for a long time.Just because of this, industry many factories
Alkali soluble filtrate just is used for calcining the purposes such as tail gas spray, the control of coating operation ph by family, and is recycled as alkali soluble material liquid
Alkali using method never carry out correlative study and be not affected by pay attention to.
Content of the invention
Recycle problem for solve alkali soluble filtrate in prior art, the invention provides a kind of sulfuric acid method titanium pigment alkali
The recoverying and utilizing method of lixiviation liquid.
The technical solution adopted in the present invention is: the recoverying and utilizing method of sulfuric acid method titanium pigment alkali soluble filtrate, including following
Step:
(1) alkali soluble filtrate is carried out separation of solid and liquid, obtain clear filtrate；
It is characterized in that, also include step (2) and step (3), specific as follows:
(2) add soluble barium salt toward in clear filtrate, filter after mixing, obtain regenerating alkali lye；
(3) regeneration alkali lye is used as the alkali soluble step in calcining seeds preparation technology with liquid caustic soda feedstock circulation.
The preparation principle of rutile calcining seeds is: the metatitanic acid that first will have like sharp titanium structural arrangement adopts highly basic,
High temperature is cracked so that the metatitanic acid of indentation molecules align occurs chain rupture, dissociation, obtain having positive metatitanic acid unimolecule or
In random chemistry crystal formation arrangement in the alkali soluble product of its oligomer, positive metatitanic acid unimolecule or its oligomer molecules.Washing is closed
The positive metatitanic acid of lattice occurs acid molten in the presence of hcl, re-starts intermolecular, intramolecular dehydration, positive metatitanic acid or its oligomer it
Between be connected with each other by dehydration, because reaction environment is in acid condition, only there is the hydroxyl of octahedra red plane in titanic acid molecule
Dehydration, polycondensation, obtain the predecessor with the arrangement of rutile characteristic molecular, then pass through curing, there is rutile feature crystal face
The molecule of structure carries out regularly arranged obtaining rutile crystal.
Inventor is found through experiments, if adding a small amount of sulfate ion, sulphur in the acid dissolution of above-mentioned positive metatitanic acid
Acid group is directly coordinated by force with an octahedra summit of titanic acid molecule and a red plane summit, thus seriously hindering titanic
Acid or its oligomer are dehydrated by red plane and form rutile feature predecessor, and the compound therefore obtaining cannot smoothly, fully
Rutilization, have a strong impact on the activity of calcining seeds.
And in the preparation process of titanium dioxide, metatitanic acid is that titanium liquid forces reaction to obtain through hydrolysis, and hydrolyze end slip
Sulfuric acid concentration be higher than 20%, only have metatitanic acid and 10% about through once washing the metatitanic acid obtaining therefore under this acidity
Absorption sulfuric acid, 0.03% ferrous sulfate residual, remaining 0.02% alundum (Al2O3)；The metatitanic acid once washed is again in sulphur
After carrying out in the case of sour (50～90g/l) bleaching, reducing, wash with water again, obtain pure metatitanic acid, this metatitanic acid is used
In alkali soluble raw material.The mass percent of its butt main component is: tio2=88～92%, fe=10ppm, h2so4=8～
12%.H therein after processing through alkali soluble2so4React just generation na with naoh2so4So that after Filter Press, washing
There is more soluble impurity na in alkali soluble filtrate2so4Exist.In conjunction with above it will be appreciated that, sulfate radical will seriously suppress rutile to turn
Change, and cannot be removed by sedimentation, this exactly alkali soluble filtrate has a strong impact on calcining seeds when using as the liquid caustic soda of alkali soluble operation
Activity main cause.
Therefore, inventor proposes, and the liquid caustic soda that will realize the recovery of alkali soluble filtrate as alkali soluble operation uses, actually mainly
It is that desulfurization process are carried out to alkali soluble filtrate.
As a further improvement on the present invention, described soluble barium salt's addition and sulfate ion in described clear filtrate
The mol ratio of amount be 1:1.00～1.01 it is therefore intended that to prevent soluble barium salt from adding excessive, regeneration alkali lye is polluted.
As a further improvement on the present invention, described soluble barium salt is selected from barium chloride, barium nitrate, barium monoxide, hydroxide
One of which in barium.During from these soluble barium salts, the anion brought into toward in clear filtrate will not be to follow-up rutile
Conversion produce inhibitory action.More preferably, described soluble barium salt is barium hydroxide, and barium hydroxide can be with the sulphur in clear filtrate
Sour sodium generates NaOH, improves concentration and the purity that final gained regenerates alkali lye.
The invention has the beneficial effects as follows: 1) realize using alkali soluble filtrate as the alkali soluble step in calcining seeds preparation technology
Liquid caustic soda feedstock circulation uses；2) process is simple is it is easy to implement.
Specific embodiment
With reference to embodiment, the present invention is further described.
Embodiment:
(1) measure the alkali soluble filtrate that in 1000ml sulfuric acid method titanium pigment production technology, alkali soluble operation produces, through being filtrated to get
Clear filtrate.
(2) after testing, the mass concentration of clear filtrate main component is: naoh:20%, na2so4: 11%.
(3) add and the wherein equimolar barium hydroxide solution of sulfate ion, be sufficiently stirred for, filter, obtain regenerating alkali
Liquid, recording naoh mass concentration in regeneration alkali lye is 24% (remarks: because adopting barium hydroxide, therefore obtain concentration of lye meeting suitably
Improve), using icp analyze data, meet liquid caustic soda Grade A requirement, analysis result is shown in Table one:
Table one: regeneration alkali lye component list
| Project | Naoh% | Fe% | so42-% | al2o3% | Outward appearance |
| Regeneration liquid caustic soda | 24 | 0.001 | Do not detect | 0.001 | Water white transparency |
This regeneration alkali lye can use as the alkali soluble step liquid caustic soda feedstock circulation in calcining seeds preparation technology, also can be straight
Connect each operation for titanium white production, such as coating or chemical water station etc..
Claims (4)
1. the recoverying and utilizing method of sulfuric acid method titanium pigment alkali soluble filtrate, comprises the following steps:
(1) alkali soluble filtrate is carried out separation of solid and liquid, obtain clear filtrate；
It is characterized in that, also include step (2) and step (3), specific as follows:
(2) add soluble barium salt toward in clear filtrate, filter after mixing, obtain regenerating alkali lye；
(3) regeneration alkali lye is used as the alkali soluble step in calcining seeds preparation technology with liquid caustic soda feedstock circulation.
2. alkali soluble filtrate according to claim 1 recoverying and utilizing method it is characterised in that: described soluble barium salt plus
The mol ratio entering amount with the amount of sulfate ion in described clear filtrate is 1:1.00～1.01.
3. alkali soluble filtrate according to claim 1 recoverying and utilizing method it is characterised in that: described soluble barium salt is selected from
One of which in barium chloride, barium nitrate, barium monoxide.
4. alkali soluble filtrate according to claim 1 recoverying and utilizing method it is characterised in that: described soluble barium salt be hydrogen
Barium monoxide.
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| CN201610688056.XA CN106335921B (en) | 2016-08-18 | 2016-08-18 | The recoverying and utilizing method of sulfuric acid method titanium pigment alkali soluble filtrate |
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| CN201610688056.XA CN106335921B (en) | 2016-08-18 | 2016-08-18 | The recoverying and utilizing method of sulfuric acid method titanium pigment alkali soluble filtrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904645A (en) * | 2017-03-30 | 2017-06-30 | 四川龙蟒钛业股份有限公司 | Sodium aluminate solution is prepared for the method for titanium dioxide coating using alkali soluble filtrate |
| CN106966428A (en) * | 2017-03-30 | 2017-07-21 | 四川龙蟒钛业股份有限公司 | The method that calcining seeds are prepared using alkali soluble filtrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130313199A1 (en) * | 2012-05-23 | 2013-11-28 | High Sierra Energy, LP | System and method for treatment of produced waters |
| CN104098135A (en) * | 2014-07-22 | 2014-10-15 | 四川龙蟒钛业股份有限公司 | Recycling method of alkali-soluble filtrate |
| CN104532292A (en) * | 2014-12-20 | 2015-04-22 | 六盘水中联工贸实业有限公司 | Method for removing sulfate radical from lead sulfate alkaline electrolyte |
-
2016
- 2016-08-18 CN CN201610688056.XA patent/CN106335921B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130313199A1 (en) * | 2012-05-23 | 2013-11-28 | High Sierra Energy, LP | System and method for treatment of produced waters |
| CN104098135A (en) * | 2014-07-22 | 2014-10-15 | 四川龙蟒钛业股份有限公司 | Recycling method of alkali-soluble filtrate |
| CN104532292A (en) * | 2014-12-20 | 2015-04-22 | 六盘水中联工贸实业有限公司 | Method for removing sulfate radical from lead sulfate alkaline electrolyte |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904645A (en) * | 2017-03-30 | 2017-06-30 | 四川龙蟒钛业股份有限公司 | Sodium aluminate solution is prepared for the method for titanium dioxide coating using alkali soluble filtrate |
| CN106966428A (en) * | 2017-03-30 | 2017-07-21 | 四川龙蟒钛业股份有限公司 | The method that calcining seeds are prepared using alkali soluble filtrate |
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| CN106335921B (en) | 2018-01-12 |
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Address after: 618200 longmang chemical industry zone, industrial concentration zone, Mianzhu new city, Sichuan Province Patentee after: Longbai Sichuan Titanium Co., Ltd Address before: 618200 Sichuan city of Deyang province Sichuan Mianzhu new industrial zone longmang Chemical Industrial Zone Patentee before: SICHUAN LOMON TITANIUM Co.,Ltd. |