CN107857297A - The recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment - Google Patents
The recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment Download PDFInfo
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- CN107857297A CN107857297A CN201711209903.0A CN201711209903A CN107857297A CN 107857297 A CN107857297 A CN 107857297A CN 201711209903 A CN201711209903 A CN 201711209903A CN 107857297 A CN107857297 A CN 107857297A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The present invention relates to a kind of sulfuric acid method titanium pigment production technology, specifically discloses a kind of recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment, comprises the following steps：A, small degree water is collected, filters off and removes wherein suspension；B, the small degree water of concentrating clarifying, makes wherein TiO2Concentration >=140g/L；C, crystallization treatment is carried out to concentrating small degree water, separates ferrous crystallization therein；D, the hydrolysis workshop section in enamel level titanium white production technique is sent to be recycled as raw material titanium liquid in small degree water after crystallization treatment.It is an advantage of the invention that：1) caused small degree water is effectively reclaimed in sulfuric acid method titanium pigment production process, avoid small degree Water circulation to titanium white production line hydrolysis procedure simultaneously, so that the titanium liquid index of titanium dioxide especially rutile titanium white powder production line is more stable, the titanium dioxide better quality produced is more stable；The efficient coproduction of rutile type titanium white and enamel level titanium dioxide can be achieved；2) scheme is easy, is easy to industrially promote.
Description
Technical field
It is secondary in especially a kind of sulfuric acid method titanium pigment production process the present invention relates to a kind of sulfuric acid method titanium pigment production technology
The processing method of product.
Background technology
Titanium dioxide property is stable, is not reacted with most of material in general.Have in nature
Three kinds of crystallizations：Plate titanium-type, rutile titania and rutile-type.Plate titanium-type is unstable crystal formation, no industrial utility value.
Anatase titanium dioxide (Anatase) abbreviation A types, and rutile-type (Rutile) abbreviation R types, all there is stable lattice, be
Important Chinese white and porcelain glaze, with other Chinese whites relatively have superior whiteness, tinting strength, tinting power, covering power, weatherability,
Heat resistance and chemical stability, particularly no toxicity, it is a kind of current best Chinese white of performance in the world, extensively should
For industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, cosmetics.
Enamel level titanium dioxide is a subdivision species of one of two big principal items of titanium dioxide " anatase titanium dioxide " titanium dioxide, is had
Have purity is high, whiteness is good, color is fresh, uniform particle sizes, very strong refractive index and higher reducing power, there is very strong opacity and not
The transparency, makes that coating is thin after the application of slip, smooth and acid resistance is strong, can be well mixed in enamel manufacturing process with other materials, no
The advantages that luming, being easy to found.
The production of titanium dioxide is broadly divided into chloridising and sulfuric acid process at present, and based on sulfuric acid process, it produces work in China at present
Skill can be summarized as follows：
(1) preparation of titanyl sulfate solution：Acidolysis reaction is carried out with sulfuric acid with ilmenite concentrate or acid-dissolved titanium slag, obtains sulfuric acid
Oxygen titanium solution；
(2) hydrolyze：Hydrolysing titanyl sulfate solution obtains thick metatitanic acid slurry；
(3) thick metatitanic acid slurry is washed, salt treatment, obtains pretreatment metatitanic acid；
(4) calcine：Pre-process metatitanic acid and be sent into rotary kiln calcining output crude product；
(5) post-process：Crude product is post-treated to obtain titanium dioxide product.
Generally in the hydrolyzing process of step (2), the hydrolysising condition of titanyl sulfate solution controls what is be strict, not only
Need to carry out under suitable acid-base value, and react and also rely on suitable temperature, concentration, the effective acid (sulphur combined with titanium
Acid and its free sulfuric acid sum) etc. condition, could hydrolyze, generation metatitanic acid.
In above-mentioned steps, the preparation of titanyl sulfate solution specifically comprises the following steps：
(1) acidolysis：Acidolysis reaction is carried out with sulfuric acid with ilmenite concentrate or acid-dissolved titanium slag, obtains acidolysis slurry；
(2) settle：Settlement treatment is carried out to acidolysis slurry, obtains acidolysis slag and clarification titanium liquid；
(3) crystallize：Clarification titanium liquid removes ferrous sulfate heptahydrate therein by vacuum crystallization, titanium liquid and Asia after being handled
Scum；
(4) concentrate：Titanium liquid is concentrated after processing further improves concentration, adds alkali to neutralize, obtains titanyl sulfate solution.
For rutile titanium white powder as high-grade pigment, its production process requires strict technology controlling and process, per ton in actual production
The rutile titanium dioxide yield about 82~84% of product, the main loss point of yield have acidolysis, ferrous residual titanium, hydrolysis, trivalent
Caused acidolysis slag and acidolysis slag eat influence of the liquid to yield close to 10% in titanium and waste water, wherein acid hemolysis process, therefore portion
For man of subsidiary factory by using water to be beaten after acidolysis slag press filtration, magnetic separator reclaims unreacted titanium ore, while will be obtained after magnetic separation
Waste residue slurry carries out separation of solid and liquid and obtains small degree water and waste residue after magnetic separation；Similarly influence of the ferrous residual titanium to titanium dioxide total recovery be about
2.0%, part producer produces the ferrous small degree water of centrifugation by starching ferrous slag, centrifuging the wherein residual titanium of recovery again.Above two
The solution of the titanium containing low concentration is referred to as small degree water, 50~100g/l of its titanium dioxide concentration, produces titanium dioxide per ton and produces small degree water
About 1.5~2.0 sides.
As the disposal of small degree water, small degree water is returned to hydrolysis procedure as leaching water and used by most producers, specific method
Referring to Fig. 1.But due to the stability extreme difference of small degree water, and ton product yield is big, therefore small degree water exists in use
Following subject matter:1st, small degree water yield is big, and process uses before returning, process such as acidolysis, sedimentation, crystallization work before having a strong impact on
The equipment capacity of sequence；2nd, small degree water stability is poor, returns hydrolysis procedure and is imitated using the stability and sedimentation for having a strong impact on normal titanium liquid
Fruit；3rd, the early stage hydrolysis of small degree water exists on the hydrolysis of rear process and TiO 2 pigment performance and influenceed, especially with science and technology
Development, requirement of the modern every profession and trade to pigment performance is more and more stricter, in the production technology of rutile titanium white powder, this influence
It is particularly evident.
How the scientific and reasonable small degree water of recovery, reduce production cost, while do not influence product quality again and turn into a need
The problem to be studied.
The content of the invention
To solve the problems, such as the recycling of small degree water, while prevent that the small degree anti-hydrolysis procedure reuse of water is outstanding to titanium dioxide product
It is the influence of rutile titanium white powder product quality, and the invention provides a kind of recycling side of the small degree water of sulfuric acid method titanium pigment
Method.
The technical solution adopted in the present invention is：The recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment, including following step
Suddenly：
A, small degree water is collected, filters off and removes wherein suspension, obtain clarifying small degree water；
B, the small degree water of concentrating clarifying, makes wherein TiO2Concentration >=140g/L, obtain concentrating small degree water；
C, crystallization treatment is carried out to concentrating small degree water, separates ferrous crystallization therein, obtain small degree water after crystallization treatment；
D, the hydrolysis workshop section in enamel level titanium white production technique is sent to be returned as raw material titanium liquid in small degree water after crystallization treatment
Receive and utilize.
Inventor proposes, in enamel level titanium white production technique, the titanyl sulfate solution concentration before it is hydrolyzed is relatively low, real
Verify bright, hydrolysis titanium concentration >=140g/l can reach technological requirement, and also have not strong to titanium liquid stability dependency
The characteristics of.Therefore inventor proposes to possess is used for enamel grade titanium dioxide powder water by caused small degree water in sulfate process titanium dioxide powder preparation technique
Solve workshop section, the possibility used as Hydrolysis of Titanium liquid.The method that inventor devises the present invention accordingly.Experiment demonstrates, and uses
The method of the present invention handles small degree water, and enters the small degree water after processing as the raw material titanium liquid of enamel level titanium dioxide hydrolysis workshop section
Row recycles, and will not cause any harmful effect to the quality of enamel level titanium dioxide.
It should be noted that the present invention must first carry out concentration step, crystallisation step is carried out afterwards, because small degree water concentration
Low, direct crystallization is (or energy consumption is high) having no way, so need to first be concentrated into close to normal acidolysis blowing titanium concentration, so
After crystallize, iron titanium ratio could be controlled.
As a further improvement on the present invention, the iron titanium ratio of small degree water is after the crystallization treatment that step C is obtained：0.3~
0.4:1, it is in order to control ionic strength total in solution, beneficial to metatitanic acid grain in hydrolytic process the reason for titanium hydraulic control iron titanium ratio
The particle diameter and distributed controll of son, rutile production is strict to iron titanium ratio requirement to be controlled, and rutile titania and the enamel relative range of control are wider,
Can be by the iron titanium ratio control of raw material titanium liquid within the above range in enamel grade titanium dioxide powder hydrolytic process.
" iron titanium ratio " of the present invention refers to the mass fraction (being calculated with fe) of iron ion total in solution in molten
The ratio of the mass fraction (being calculated with titanium dioxide) of total titanium in liquid.
As a further improvement on the present invention, small degree water is in sulfuric acid process rutile titanium white powder production process described in step A
Small degree water and/or the ferrous small degree water of centrifugation after caused magnetic separation.Small degree water of the present invention includes all sulfuric acid method titanium pigments
Caused small degree water in (rutile, rutile titania and enamel level) production process, it can be reclaimed in the way of the present invention, so as to anti-
Only small degree water, which returns hydrolysis procedure, influences hydrolysis particle and product pigment performance, and rutile titanium white powder product quality requires highest,
Therefore it is also maximum to handle small degree water meaning in the present inventive method.
The beneficial effects of the invention are as follows：1) caused small degree water is effectively reclaimed in sulfuric acid method titanium pigment production process,
Avoid small degree Water circulation to titanium white production line hydrolysis procedure simultaneously so that titanium dioxide especially rutile titanium white powder production line
Titanium liquid index it is more stable, the titanium dioxide better quality produced is more stable；Rutile type titanium white and enamel level can be achieved
The efficient coproduction of titanium dioxide；2) scheme is easy, is easy to industrially promote.
Brief description of the drawings
Fig. 1 is small degree process of reusing water figure of the prior art.
Fig. 2 is the small degree process of reusing water figure of the present invention.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment one：
According to the rutile titanium white powder production procedure shown in Fig. 1, rutile titanium is carried out in same standardized production line
White powder continuous production, 6 batches of continuous production, each batch output are 30 tons.Be recorded as respectively batch A, batch B, batch C,
Batch D, batch E, batch F.
Small degree water (titanium dioxide concentration 87g/L) caused by batch A, batch B, batch F is collected, not returned
With.And by caused small degree water in batch C, batch D, batch E productions, (titanium dioxide concentration is respectively 86g/L, 86g/L, 87g/
L) collected respectively, and reuse leaches water as the acidolysis of adjacent next batch respectively.
After production terminates, product quality indicator detection, detection knot are carried out to the rutile titanium white powder product of 6 batches respectively
Fruit is shown in Table 1.
Embodiment two：
Small degree water caused by the batch A collected in embodiment one, batch B, batch F is warded off for production in accordance with the following methods
Porcelain level Cornstarch：
(1) the above-mentioned small degree side of water 100 is taken, it is 87g/L to measure its titanium dioxide concentration.Filtered off by control except wherein outstanding
Float, obtain clarifying small degree water.
(2) concentration is evaporated to clarifying small degree water, makes wherein TiO2Concentration=165g/L, obtain concentrating small degree water.
(3) vacuum crystallization is carried out to concentrating small degree water, is then demultiplex out ferrous crystallization, the iron of the small degree water after crystallization treatment
Titanium ratio is 0.32:1.
(4) small degree water after crystallization treatment is sent to the hydrolysis workshop section in enamel level titanium white production technique, as raw material titanium liquid
Directly it is hydrolyzed, hydrolytic process no abnormality seen.
(5) after hydrolysis is completed, the production of enamel level titanium dioxide, gained are continued according to normal process set in advance
Every product index of enamel level titanium dioxide product is shown in Table 2.
Embodiment three：
Small degree water caused by the batch A collected in embodiment one, batch B, batch F is warded off for production in accordance with the following methods
Porcelain level Cornstarch：
(1) the above-mentioned small degree side of water 100 is taken, it is 87g/L to measure its titanium dioxide concentration.Filtered off by control except wherein outstanding
Float, obtain clarifying small degree water.
(2) concentration is evaporated to clarifying small degree water, makes wherein TiO2Concentration=140g/L, obtain concentrating small degree water.
(3) vacuum crystallization is carried out to concentrating small degree water, is then demultiplex out ferrous crystallization, the iron of the small degree water after crystallization treatment
Titanium ratio is 0.36:1.
(4) small degree water after crystallization treatment is sent to hydrolysis workshop section in enamel level titanium white production technique, and by titanyl sulfate
The TiO that solution preparation section obtains2Concentration=140g/L titanyl sulfate solution is according to 1:1 mass ratio mixing is hydrolyzed,
Hydrolytic process no abnormality seen.
(5) after hydrolysis is completed, according to the life for continuing enamel level titanium dioxide with the identical normal process of embodiment one
Production, every product index of gained enamel level titanium dioxide product are shown in Table 2.
Example IV：
According to the production that enamel level titanium dioxide is carried out with the identical normal process of embodiment one, wherein former used in hydrolysis workshop section
Expect all TiO obtained by titanyl sulfate solution preparation section of titanium liquid2Concentration=165g/L titanyl sulfate solution, gained are warded off
Every product index of porcelain level titanium dioxide product is shown in Table 2.
Table 1：Rutile titanium white powder product quality indicator testing result table
Table 2：Enamel level titanium dioxide product quality indicator testing result table
| Product index | |
| Embodiment two | It is qualified |
| Embodiment three | It is qualified |
| Example IV | It is qualified |
Claims (3)
1. the recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment, comprises the following steps：
A, small degree water is collected, filters off and removes wherein suspension, obtain clarifying small degree water；
B, the small degree water of concentrating clarifying, makes wherein TiO2Concentration >=140g/L, obtain concentrating small degree water；
C, crystallization treatment is carried out to concentrating small degree water, separates ferrous crystallization therein, obtain small degree water after crystallization treatment；
D, the hydrolysis workshop section in enamel level titanium white production technique is sent to reclaim profit as raw material titanium liquid in small degree water after crystallization treatment
With.
2. the recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment according to claim 1, it is characterised in that：Step C is obtained
To crystallization treatment after it is small degree water iron titanium ratio be：0.3~0.4:1.
3. the recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment according to claim 1 or 2, it is characterised in that：Step A
The small degree water is that small degree water and/or ferrous iron centrifuge small degree after caused magnetic separation in sulfuric acid process rutile titanium white powder production process
Water.
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| CN201711209903.0A CN107857297A (en) | 2017-11-28 | 2017-11-28 | The recoverying and utilizing method of the small degree water of sulfuric acid method titanium pigment |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441613A (en) * | 2019-08-29 | 2021-03-05 | 攀枝花大互通钛业有限公司 | Method for recycling titanium liquid in titanium dioxide acidolysis sludge |
| CN115321592A (en) * | 2022-09-21 | 2022-11-11 | 中国有色集团（广西）平桂飞碟股份有限公司 | Pretreatment method capable of improving quality of titanium acidolysis solution in continuous acidolysis reaction |
-
2017
- 2017-11-28 CN CN201711209903.0A patent/CN107857297A/en active Pending
Non-Patent Citations (2)
| Title |
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| 唐振宁: "《钛白粉的生产与环境治理》", 31 May 2000, 化学工业出版社 * |
| 黄小芳等: ""基于投入产出模型的钛白粉生产企业经济效益研究"", 《工业工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441613A (en) * | 2019-08-29 | 2021-03-05 | 攀枝花大互通钛业有限公司 | Method for recycling titanium liquid in titanium dioxide acidolysis sludge |
| CN112441613B (en) * | 2019-08-29 | 2023-05-12 | 攀枝花大互通钛业有限公司 | Recycling method of titanium liquid in titanium dioxide acidolysis sludge |
| CN115321592A (en) * | 2022-09-21 | 2022-11-11 | 中国有色集团（广西）平桂飞碟股份有限公司 | Pretreatment method capable of improving quality of titanium acidolysis solution in continuous acidolysis reaction |
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Application publication date: 20180330 |