CN1090553A

CN1090553A - With the titanium ore is the method for raw material enrichment titanium dioxide

Info

Publication number: CN1090553A
Application number: CN 93101040
Authority: CN
Inventors: 宁甲保
Original assignee: Individual
Current assignee: Individual
Priority date: 1993-02-06
Filing date: 1993-02-06
Publication date: 1994-08-10
Anticipated expiration: 2013-02-06
Also published as: CN1038324C

Abstract

The method that with the titanium ore is raw material enrichment titanium dioxide is to provide rich titanium material---the novel method of hydrated titanium dioxide for Titanium White Production By Sulfuric Acid Process.This method adopts the infrastructure and the flow process of Production By Sulfuric Acid Process, by the introducing of new acid hydrolysis method, and needn't deironing, needn't cooling concentration, greatly reduce the processing parameter and the technological standard of sulfuric acid process, thereby equipment is simple, power consumption is low, less investment, cost are low, can increase economic efficiency more than 2 times.

Description

With the titanium ore is the method for raw material enrichment titanium dioxide

The present invention is to be the method for raw material enrichment titanium dioxide with the titanium ore, and the titanium dioxide of this method enrichment is particularly suitable for mixed acid process and produces titanium dioxide.

Be the method for raw material enrichment titanium dioxide with the titanium ore in the world at present, from essence, can be divided into pyrogenic process and wet method two classes.Pyrogenic process generally is with titanium ore process high temperature reduction, and electrometallurgy and rapid cooling obtain hydrated titanium dioxide to remove impurity, and this kind enriching method technical difficulty is high, has only the company of a handful of countries to grasp in the world.Wet method is more common in placer, still among constantly improving, and the Xin Hafa (Sinha) of example hydrochloric acid leaching, Ou Xin (Ocean) method etc. of iron salt solutions leaching all can obtain TiO ₂79% artificial rutile is produced titanium dioxide but the product of this kind method only is applicable to chlorination process, can't be used for Titanium White Production By Sulfuric Acid Process.

The object of the present invention is to provide a kind of is the method for raw material enrichment titanium dioxide with the titanium ore, its product hydrated titanium dioxide can be produced titanium dioxide behind the catalyzer and adopted by sulfuric acid process adds, and process of enriching is simple, operation is short, acidolysis rate is high, the rate of recovery is big, cost is low, can carry out on the production line of Titanium White Production By Sulfuric Acid Process.

The present invention is the method for raw material enrichment titanium dioxide with the titanium ore, follows these steps to carry out:

A, titanium ore oven dry is milled down to 200～320 orders,

B, than 1: 1.5～1: 1.7 the vitriol oil is added in the acidolysis groove by material acid,

C, under agitation adding 0.3～3%(and account for the ore weight percent) fluorochemical is as catalyzer, then

D, add entry or water and useless diluted acid and make sulfuric acid concentration reach 80～90%(weight percent), initiation reaction,

E, question response thing till the solid shape, carry out slaking and cooling by rare retrogradation,

F, under 60～65 ℃ of stirrings, add iron reduction, make CTi in the new titanium liquid ³⁺=0.0221CTiO ₂Till,

G, add crystal seed hydrolysis, filtration washing routinely, last

H, dewater, be milled down to 60～100 orders 300～500 ℃ of following dryings.

Titanium ore is selected concentrated sulfuric acid dissolution for use, and sulfuric acid concentration adopts 93～98%.

The present invention adds fluorochemical and makes catalyzer when acidolysis, speed of response thousandfold ground is increased, and catalyzer is selected for use and met NaF, the CaF that acid can discharge HF ₂, Na ₂TiF ₆Or HF all can, certainly, do not introduce other impurity in the reaction in order to make, catalyzer is generally selected Na ₂TiF ₆Be the best.The optimum amount of catalyzer is controlled at 0.3～1%.

When the sulfuric acid dissolution titanium ore is fastest be concentration 80～90%, so, in the vitriol oil, to add entry or water and useless diluted acid and be diluted to 80～90%, the dilution liberated heat be enough to make acidolysis reaction acutely to cause.

Slaking and process for cooling and Titanium White Production By Sulfuric Acid Process are identical, leave standstill slaking in 2～12 hours after promptly solidifying, and blast pressurized air and are cooled to 90～120 ℃.

To reduce, leach, add crystal seed hydrolysis, filtration, washing all identical with the Titanium White Production By Sulfuric Acid Process process conditions for the iron that adds in the enriching method of the present invention.Here needn't comment one by one.

At last, the hydrated titanium dioxide of clean paste is dry under 300～500 ℃, be milled down to 60～100 orders, promptly become the enrichment material of titanium dioxide, it can be by the acid hydrolyzation dissolving of inventor's invention, to prepare titanium dioxide.

The present invention adopts sulfuric acid process to make the master operation of hydrated titanium dioxide, equipment and facility, but technological standard requirement, and working method slightly changes, and it needn't deironing (the band molten iron is separated), only pursues high acidolysis rate, and extraction yield is big, TiO ₂Content greater than 90%; To adding metatitanic acid granularity after crystal seed, the hydrolysis before the hydrolysis when titanium concentration, hydrolysis, making hydrated titanium dioxide, quality does not have technical requirements, thereby produces than sulfuric acid process that the hydrated titanium dioxide technical requirements is low, technology is short, facility investment is little.The hydrated titanium dioxide that adopts the present invention to make, content by this enrichment material, is used the Rutile type Titanium Dioxide of " Rutile type Titanium Dioxide preparation method " preparation of the inventor all greater than 90% after dewatering, through the test of national coatings industry institute, its quality has been caught up with advanced international standard.

Accompanying drawing is a process flow sheet of the present invention.

Embodiment 1:

Sichuan Flos Bombacis Malabarici ilmenite concentrate (is contained TiO ₂47%) oven dry, levigate (200 order), again by ore deposit acid than 1: 1.53 under the pressurized air stirring, adding 0.5%Na in the 3.7598% sulfuric acid adding acid hydrolysis tank ₂TiF ₆Spent acid after (referring to HF content) and 2.41 tons of ilmenite concentrate powder stir after the certain water gaging of adding or water and the hydrolysis, make vitriolic concentration reach 85%, but initiation reaction under case without heating, internal reaction finished in 30 minutes, began to solidify about 0.3～1 hour, and then slaking is 4～12 hours, recompression air cooling to 90～120 ℃ about 1～2 hour, 3 times of water that add breeze weight leach under compression is stirred, and then reduce by adding 25～40 kilograms of iron filings powder in the breeze per ton, make titanium liquid CTi ³⁺=0.0221CTiO ₂, add down sinking agent at 50～55 ℃ then and carry out sedimentation and filter and make titanium liquid, add spontaneous kind 1% band molten iron at last and separate, after filtration, washing makes hydrated titanium dioxide.

Washed hydrated titanium dioxide will be through 500 ℃ of oven dry (if require TiO ₂The content height can be removed the SO in the hydrated titanium dioxide earlier ₃, oven dry then) can make and contain TiO ₂The titanium dioxide of 95%1.2 tons of enrichments is milled down to 60 orders at last, just can make the enrichment titanium dioxide about 1 ton.

Embodiment 2:

Ilmenite (is contained TiO ₂52%) oven dry, levigate (320 order) add 3.65 ton of 93% sulfuric acid in the acid hydrolysis tank than 1: 1.5 by ore deposit acid and add 1%Na under the pressurized air stirrings ₂TiF ₆Spent acid after (referring to HF content) and 2.26 tons of ilmenite concentrate powder stir after the certain water gaging of adding or water and the hydrolysis, make vitriolic concentration reach 78%, initiation reaction, internal reaction finished in 40 minutes, begin curing, slaking, leach, reduce, purify (not deironing) again until make till the hydrated titanium dioxide.Substantially same sulfuric acid process.Different is the not deironing of titanium liquid and concentrates, with the pursuit extraction yield that spontaneous kind is directly separated with molten iron, TiO ₂Content reaches more than 90%, does not all require for purity, foreign matter content, fineness, and washed hydrated titanium dioxide is (if require to contain TiO ₂Gao Kexian removes wherein SO ₃) 500 ℃ of oven dry down, be crushed to 100 orders then, just make the titanium dioxide of the enrichment about 1 ton.

Claims

1, a kind of is the method for raw material enrichment titanium dioxide with the titanium ore, it is characterized in that carrying out according to the following steps:

A, titanium ore oven dry is milled down to 200～320 orders;

B, than 1: 1.5～1.7 the vitriol oil is added in the acidolysis groove by material acid;

C, under agitation add 0.3～3% fluorine cpd as catalyzer, then

D, add entry or useless diluted acid makes sulfuric acid concentration reach 80～90%, initiation reaction;

E, question response thing till the solid shape, carry out slaking and cooling by rare retrogradation;

F, under 60～65 ℃ of stirrings, add iron filings, make CTi in the new titanium liquid ³⁺=0.0221CTiO ₂Till;

G, add crystal seed, hydrolysis, filtration washing routinely.

H, oven dry under 300～500 ℃ are milled down to 60～100 orders.

2, the method for enrichment titanium dioxide according to claim 1, the concentration that it is characterized in that adding the vitriol oil is 93～98%.

3, the method for enrichment titanium dioxide according to claim 1 is characterized in that as catalyzer be NaF, CaF ₂, Na ₂TiF ₆In any.

4,, it is characterized in that catalyzer adopts Na according to the method for claim 1 or 3 described enrichment titanium dioxide ₂TiF ₆

5, the method for enrichment titanium dioxide according to claim 1 is characterized in that catalyst consumption is 0.3～1%.