CN111362301A - Preparation method of sulfuric acid process titanium dioxide hydrolysis seed crystal - Google Patents

Preparation method of sulfuric acid process titanium dioxide hydrolysis seed crystal Download PDF

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Publication number
CN111362301A
CN111362301A CN202010246316.4A CN202010246316A CN111362301A CN 111362301 A CN111362301 A CN 111362301A CN 202010246316 A CN202010246316 A CN 202010246316A CN 111362301 A CN111362301 A CN 111362301A
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seed crystal
titanium dioxide
hydrolysis
sulfuric acid
liquor
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Inventor
熊怀忠
何俊
周春勇
钟晓英
吴彭森
和奔流
谢鑫伟
谢浩
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Longbai Sichuan Titanium Co ltd
Sichuan Lomon Titanium Industry Co Ltd
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Longbai Sichuan Titanium Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • C01G23/053Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • C01G23/0534Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts in the presence of seeds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/51Particles with a specific particle size distribution
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
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  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention belongs to the technical field of sulfate process titanium dioxide production, and discloses a preparation method of sulfate process titanium dioxide hydrolysis seed crystal, which comprises the following steps: and (3) adding preheated alkali liquor and titanium liquor into a tubular mixer in a concurrent flow mode according to the volume ratio of 1: 2-1: 5 for reaction, and allowing the reacted mixture to flow into a seed crystal ageing tank for ageing to obtain the sulfuric acid process titanium dioxide hydrolysis seed crystal. The method ensures that the nucleation speed of the seed crystal is consistent, the prepared seed crystal has uniform particle size and high hydrolytic activity, the particle size distribution of the produced hydrolyzed metatitanic acid is greatly improved, the impurity removal efficiency of the subsequent washing of metatitanic acid is improved, and the particle size distribution of titanium dioxide is also greatly improved.

Description

Preparation method of sulfuric acid process titanium dioxide hydrolysis seed crystal
Technical Field
The invention belongs to the technical field of sulfuric acid process titanium dioxide production, and particularly relates to a preparation method of a sulfuric acid process titanium dioxide hydrolysis seed crystal.
Background
The production of titanium dioxide by a sulfuric acid method roughly comprises the following process steps: crushing raw ores, mixing, acidolysis, precipitation, heat filtration, vacuum crystallization, crystallization separation, controlled filtration, concentration, hydrolysis, primary washing, bleaching, secondary washing, salt treatment, calcination, pre-crushing, wet grinding, classification, surface treatment, tertiary washing, rotary flash evaporation drying and airflow crushing to obtain a finished product of titanium dioxide.
The titanium solution is produced by a concentration process, and the main components of the titanium solution are titanyl sulfate and ferrous sulfate. The hydrolysis of titanium liquid, namely the hydrolysis of titanium dioxide by a sulfuric acid method, needs three stages, namely a first stage: formation of hydrolyzed seeds; and a second stage: titanium is precipitated on the surface of the formed seed crystal in the form of hydrated titanium dioxide, so that crystal nuclei are promoted to grow gradually; and a third stage: as the hydrolysis proceeds, the titanium dioxide particles gradually agglomerate and grow to precipitate. Adding hydrolysis seed crystals, on one hand, the hydrolysis speed is accelerated, higher hydrolysis rate is obtained, and the water washing is accelerated and the titanium white with excellent pigment performance is obtained; on the other hand, the hydrated titanium dioxide which ensures that the prepared hydrolysate has proper and uniform particle size and a certain structure. The particle size and distribution of the hydrolysis seed crystal directly determine the particle size and uniformity of the hydrolysis product.
There are two general methods for preparing hydrolysis seeds by alkali neutralization: 1. adding alkali liquor into titanium liquor for neutralization; 2. adding the titanium liquid into alkali liquor for neutralization. The acidity or alkalinity of the two preparation methods in the seed crystal forming stage is not constant, and the formed seed crystal has uneven granularity due to the fact that the nucleation speed in the seed crystal forming process is in a constantly changing state, so that the uniformity of subsequent hydrolysis particles is influenced.
Disclosure of Invention
In order to overcome the difficulties, the invention aims to provide a method for preparing titanium dioxide hydrolysis seed crystals by a sulfuric acid method, which solves the problem of poor uniformity of the particle size of the seed crystals.
The invention provides a method for preparing a sulfuric acid process titanium dioxide hydrolysis crystal seed, which comprises the following steps: and (3) adding preheated alkali liquor and titanium liquor into a tubular mixer in a concurrent flow mode according to the volume ratio of 1: 2-1: 5 for reaction, and allowing the reacted mixture to flow into a seed crystal ageing tank for ageing to obtain the sulfuric acid process titanium dioxide hydrolysis seed crystal.
Preferably, the volume ratio of the concurrent flow of the alkali liquor and the titanium liquor is 1: 3-1: 4.
In the invention, the concentration of the alkali liquor can be 75-100 g/L. Preferably, the concentration of the alkali liquor is 85-95 g/L.
In the invention, the preheating temperature of the alkali liquor and the titanium liquor can be 50-80 ℃. Preferably, the preheating temperature of the alkali liquor and the titanium liquor is 60-75 ℃.
Preferably, the curing temperature is 60-90 ℃ and the curing time is 5-60 min. Further preferably, the curing temperature is 70-80 ℃ and the curing time is 15-25 min.
The process parameters not defined in the present invention are carried out in a conventional manner in the art.
Compared with the prior art, the invention has the following beneficial effects:
the hydrolysis crystal seeds are prepared by carrying out parallel flow reaction on the alkali liquor and the titanium liquor according to a specific proportion, the stable acidity ensures that the nucleation speed of the crystal seeds is consistent, the prepared crystal seeds have uniform particle size and high hydrolysis activity, the particle size distribution of the produced hydrolysis metatitanic acid is greatly improved, the subsequent washing impurity removal efficiency of metatitanic acid is improved, and the particle size distribution of titanium dioxide is also greatly improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Examples 1 to 3 are intended to illustrate the method for producing seed crystals for hydrolysis of titanium dioxide by the sulfuric acid process of the present invention.
Example 1
Preparing 75g/L alkali liquor, and respectively preheating the alkali liquor and the titanium liquor to 70 ℃; allowing alkali liquor and titanium liquor to flow into a tubular mixer in a volume ratio of 1: 4 in a parallel flow manner for reaction, and then flowing into a seed crystal ageing tank; the seed crystal curing temperature is 80 ℃, and the curing time is 20 min.
Example 2
Preparing 85g/L alkali liquor, and respectively preheating the alkali liquor and the titanium liquor to 60 ℃; allowing alkali liquor and titanium liquor to flow into a tubular mixer in a volume ratio of 1: 3 in a parallel flow manner for reaction, and then flowing into a seed crystal ageing tank; the seed crystal curing temperature is 70 ℃, and the curing time is 20 min.
Example 3
Preparing 95g/L alkali liquor, and respectively preheating the alkali liquor and the titanium liquor to 50 ℃; allowing alkali liquor and titanium liquor to flow into a tubular mixer in a volume ratio of 1: 2 in a parallel flow manner for reaction, and then flowing into a seed crystal ageing tank; the seed crystal curing temperature is 60 ℃, and the curing time is 20 min.
Comparative example 1
Adding titanium liquid preheated to 50 ℃ into a seed crystal preparation tank, adding alkali liquor preheated to 50 ℃ and with the concentration of 95g/L into the seed crystal preparation tank, wherein the mixing volume ratio of the alkali liquor to the titanium liquid is 1: 2, and then carrying out constant-temperature curing; the seed crystal curing temperature is 60 ℃, and the curing time is 20 min.
Comparative example 2
Adding alkali liquor preheated to 50 ℃ and with the concentration of 95g/L into a seed crystal preparation tank, adding titanium liquid preheated to 50 ℃ into the seed crystal preparation tank for reaction, wherein the mixing volume ratio of the alkali liquor to the titanium liquid is 1: 2, and then carrying out constant-temperature curing; the seed crystal curing temperature is 60 ℃, and the curing time is 20 min.
The sulfuric acid process titanium dioxide hydrolysis seed crystals prepared in the examples and the comparative examples are used for preparing the hydrolysis metatitanic acid, the preparation method and the adopted materials are the same, the prepared hydrolysis metatitanic acid is subjected to subsequent titanium dioxide preparation, the preparation method is the same, the conventional test method is adopted to characterize the hydrolysis seed crystals, the hydrolysis metatitanic acid, the titanium dioxide and other parameters, and the specific table is shown in table 1.
TABLE 1
Figure DEST_PATH_IMAGE002
As can be seen from the data in Table 1, compared with the conventional method of the comparative example, the hydrolysis seed crystal prepared by the method of the application has uniform particle size and high hydrolysis activity, the particle size and the uniformity of the hydrolysis product are directly determined due to the particle size and the distribution of the hydrolysis seed crystal, and the particle size distribution of the hydrolysis metatitanic acid can be greatly improved, so that the impurity removal efficiency of the subsequent washing of metatitanic acid is improved, and the particle size distribution of titanium dioxide is also greatly improved.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.

Claims (5)

1. A method for preparing sulfuric acid process titanium dioxide hydrolysis seed crystal is characterized by comprising the following steps: and (3) adding preheated alkali liquor and titanium liquor into a tubular mixer in a concurrent flow mode according to the volume ratio of 1: 2-1: 5 for reaction, and allowing the reacted mixture to flow into a seed crystal ageing tank for ageing to obtain the sulfuric acid process titanium dioxide hydrolysis seed crystal.
2. The method for preparing seed crystal for hydrolysis of titanium dioxide by sulfuric acid process according to claim 1, characterized in that: the volume ratio of the concurrent flow of the alkali liquor and the titanium liquor is 1: 3-1: 4.
3. The method for preparing seed crystal for hydrolysis of titanium dioxide by sulfuric acid process according to claim 1, characterized in that: the concentration of the alkali liquor is 75-100 g/L.
4. The method for preparing seed crystal for hydrolysis of titanium dioxide by sulfuric acid process according to claim 1, characterized in that: the preheating temperature of the alkali liquor and the titanium liquor is 50-80 ℃.
5. The method for preparing seed crystal for hydrolysis of titanium dioxide by sulfuric acid process according to claim 1, characterized in that: the curing temperature is 60-90 deg.C, and the curing time is 5-60 min.
CN202010246316.4A 2020-03-31 2020-03-31 Preparation method of sulfuric acid process titanium dioxide hydrolysis seed crystal Pending CN111362301A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113155687A (en) * 2021-04-25 2021-07-23 龙佰四川钛业有限公司 Method for evaluating hydrolytic activity of high-concentration external seed crystal
CN113155687B (en) * 2021-04-25 2024-05-31 龙佰四川钛业有限公司 Evaluation method for hydrolytic activity of high-concentration additional seed crystal

Citations (5)

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CN1834019A (en) * 2006-04-05 2006-09-20 江苏太白集团有限公司 Prepn. method of hydrolytic crystal seeds for producing titanium pigment
CN103964494A (en) * 2014-05-27 2014-08-06 贵州东华工程股份有限公司 Normal-pressure hydrolysis method for autogenous seed crystal of sulfuric-acid-process titanium dioxide production
CN106430300A (en) * 2016-08-30 2017-02-22 襄阳龙蟒钛业有限公司 Alkali-neutralization seed crystal external addition method for producing titanium dioxide
CN107857298A (en) * 2017-11-30 2018-03-30 河北麦森钛白粉有限公司 A kind of preparation method of sulfuric acid titanium hydrolysis high-activity crystal seed
CN109205663A (en) * 2018-10-19 2019-01-15 攀枝花学院 Automatic growing crystal species and preparation method thereof are hydrolyzed in Producing Titanium Dioxide

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Publication number Priority date Publication date Assignee Title
CN1834019A (en) * 2006-04-05 2006-09-20 江苏太白集团有限公司 Prepn. method of hydrolytic crystal seeds for producing titanium pigment
CN103964494A (en) * 2014-05-27 2014-08-06 贵州东华工程股份有限公司 Normal-pressure hydrolysis method for autogenous seed crystal of sulfuric-acid-process titanium dioxide production
CN106430300A (en) * 2016-08-30 2017-02-22 襄阳龙蟒钛业有限公司 Alkali-neutralization seed crystal external addition method for producing titanium dioxide
CN107857298A (en) * 2017-11-30 2018-03-30 河北麦森钛白粉有限公司 A kind of preparation method of sulfuric acid titanium hydrolysis high-activity crystal seed
CN109205663A (en) * 2018-10-19 2019-01-15 攀枝花学院 Automatic growing crystal species and preparation method thereof are hydrolyzed in Producing Titanium Dioxide

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113155687A (en) * 2021-04-25 2021-07-23 龙佰四川钛业有限公司 Method for evaluating hydrolytic activity of high-concentration external seed crystal
CN113155687B (en) * 2021-04-25 2024-05-31 龙佰四川钛业有限公司 Evaluation method for hydrolytic activity of high-concentration additional seed crystal

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