AU2020101888A4

AU2020101888A4 - A process for recovering aluminium and silicon from clay rock and enriching niobium and titanium

Info

Publication number: AU2020101888A4
Application number: AU2020101888A
Authority: AU
Inventors: Hannian Gu; Chongguang Luo; Ning Wang; Hanjie Wen
Original assignee: Institute of Geochemistry of CAS
Current assignee: Institute of Geochemistry of CAS
Priority date: 2020-08-19
Filing date: 2020-08-19
Publication date: 2020-09-24
Anticipated expiration: 2028-08-19

Abstract

The invention discloses a method for recovering aluminium and silicon from clay rock and enriching niobium and titanium, in particular, the method is high-temperature roasting activation, separating and recovering the aluminium and the silicon respectively, and then the niobium and the titanium enriched material is finally obtained. The method comprises the following steps: Crushing clay rock, grinding and high-temperature roasting activation at 550 900°C, treating and recovering aluminium therein with hydrochloric acid, reacting and recovering silicon therein with sodium hydroxide solution, and washing with dilute sodium hydroxide. In the obtained Nb-rich and Ti-rich materials, the recovery rate of Nb and Ti is more than 80%, the content of Nb in the material can reach 4280 [g/g. The content of TiO2 can reach 81%, which is an important Nb and Ti resource and can be further processed. -1/1 Claystorie Hvdrochkzicacid High ter~tzatuie maibkzidcla Filterng nd pro dixt Fig.1I

Description

-1/1

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AUSTRALIA

PATENTS ACT 1990

PATENT SPECIFICATION FOR THE INVENTION ENTITLED: A PROCESS FOR RECOVERING ALUMINIUM AND SILICON FROM CLAY ROCK AND ENRICHING NIOBIUM AND TITANIUM

The invention is described in the following statement:-

A PROCESS FOR RECOVERING ALUMINIUM AND SILICON FROM CLAY ROCK AND ENRICHING NIOBIUM AND TITANIUM TECHNICAL FIELD

[0001] The present invention relates to the enrichment of the rare element niobium, and in

particular to a method for enrichment of niobium and titanium in clay rock.

BACKGROUND

[0002] Niobium (niobium), Nb) is a kind of rare metal widely used, which has the

characteristics of high melting point, corrosion resistance, fatigue resistance, deformation

resistance, good thermoelectric conductivity and excellent superconducting performance,

especially in the modern iron and steel industry, it plays a very important role. The clark

value of Nb in the crust is 24x10-6, and there are many independent Nb deposits in the

earth, but the distribution of Nb deposits is very concentrated (Guo Qingwei and Wang

Zhaoxin, 2009; Gibson et al., 2015). It is mainly distributed in Brazil and Canada, and

Brazil alone accounts for 95% of the world's niobium reserves (USGS, 2016). China has

only 18,500 tons of niobium ore reserves, all of which are polymetallic paragenetic deposits

with low Nb grade (Guo Qingwei and Wang Zhaoxin, 2009). The dependence of niobium

ore and niobium products is as high as 90%. It is not difficult to see that Nb resources have

become a more and more important resource which is, scarce and strategic in China.

[0003] Nb mineralization has been found in the basaltic paleoclimate-type sedimentary

rocks (clay rocks at the bottom of Xuanwei Formation) at the border of Sichuan-Guizhou-

Yunnan, and the content is generally several hundred g / g. According to the Standard of

Geological Prospecting Code for Rare Metal Minerals (DZ / T0203-2002), the industrial

grade required for the weathering crust Nb deposit is 160 ~ 200 [g/g. It is predicted that

only the potential Nb2 05 resources in western Guizhou are more than 1 million tons. This

kind of Nb resource is mainly located in clay stone, which is closely associated with

titanium and may belongs to a new type of deposit (Dai et al., 2010). However, little

research has been done on this kind of Nb resources.

[0004] The Nb ore resources of this type are characterized by the small particle size of the

constituent minerals, and the average particle diameter of the minerals is less than 1-2

microns. In addition, in general, if the separation particle size is less than 30 micron or the

sludge content (less than 20 microns) exceeds 25%, the separation effect of the

conventional physical separation method and equipment is extremely poor. It is difficult to

separate the target minerals and gangue minerals therein. Therefore, it is of great

significance to develop a new method to enrich Nb and Ti from clay rock and to utilize Al

and Si in it comprehensively.

SUMMARY

[0005] The object of the present invention is to provide a method for enriching niobium

and titanium while comprehensively utilizing other valuable components therein.

[0006] The technical scheme adopted by the present invention is as below:

[0007] The invention relates to a method for recovering aluminium and silicon from clay

rock and enriching niobium and titanium at the same time, in particular, the method is high

temperature roasting and activation, and the aluminium and the silicon are separated and

recovered respectively, so that the niobium and the titanium enriched material is finally

obtained. Comprising the steps: Crushing the clay rock,

[0008] Grinding and high-temperature roasting at 550 ~ 900°C for activation, treatment

with hydrochloric acid to recover aluminium and silicon respectively, and finally the

enriched materials of niobium and titanium are obtained The steps are as follows: crushing

and grinding clay rock, calcining and activating at 550-900 °C, recovering aluminium in it

by hydrochloric acid treatment, recovering silicon in it by reaction with sodium hydroxide

solution, and washing with dilute sodium hydroxide. Finally, the residue is niobium

titanium enriched material. The specific steps are as follows:

[0009] In the first step, a sample is prepared, a clay rock sample containing Nb is crushed,

and the clay rock sample is crushed by a general crusher to about 100 mesh.

[0010] In the second step, the crushed clay rock sample is placed in a muffle furnace, which

is subjected to calcination treatment, and kept for a period of time.

[0011] In the third step, weigh a certain amount of roast sample, and taking a certain

volume of hydrochloric acid solution, hydrochloric acid and calcined clay rock samples are

put into a reactor with a cover, and the reactor is gradually heated to boiling, and the water

is not lost during heating. Stirring for 30-60 minutes, filtering separation residue and

washing 2-3 times, the filtrate is aluminium chloride by-product.

[0012] In the fourth step, a sodium hydroxide solution is added to that residue and stirred

completely. After reaction for 1 h, the residue was separated by filtration.

[0013] And washed with dilute sodium hydroxide solution for 2-3 times, the filtrate is

sodium silicate by-product, and the residue is a material rich in Nb and Ti.

[0014] Preferably, the main constituent mineral phases of the niobium-containing clay rock

are kaolinite clay minerals, titaniferous and ferruginous minerals, in which the content of

A1203 is about 35-40%, that of SiO2 is about 40-45%, TiO2 > 3-9%, Nb content is about

200-500 g /g.

[0015] Preferably, the high temperature baking temperature is 550 to 900 °C.

[0016] Preferably, when the aluminium is recovered by hydrochloric acid, the amount of

hydrochloric acid is twice the theoretical amount of the hydrochloric acid required for

A1203 in the clay sample, the reaction conditions are boiling conditions, and the reaction

time is 20 to 60 minutes.

[0017] Preferably, when recovering silicon from sodium hydroxide solution, the reaction

is stirred for 1 hour at normal temperature to 75 °C, the solution concentration is 20%, the

solid-liquid ratio is 1 g: 5 mL, and the silicon is separated by filtration after the reaction.

The residue is washed 2-3 times with dilute sodium hydroxide solution and the silicon

therein is sufficiently washed.

[0018] Alternatively, in the process of extracting aluminium with hydrochloric acid

solution and silicon with sodium hydroxide solution, aluminium chloride solution and

sodium silicate solution are produced respectively; aluminium chloride can be recycled.

The aluminium can also be recovered by precipitation; the sodium silicate can be used as

a by-product.

[0019] Preferably, the titanium dioxide content in the obtained residue can reach 81%, and

the Nb content can reach 4280 [g/g; compared with the original residue, the content of Ti

and Nb in the residue is enriched by about 8 times, which can act as a Nb-rich material.

[0020] Advantageous effects: The present invention has the following advantages

compared with the prior art:

[0021] 1, providing a method for enriching Nb and Ti from clays contain extremely low

Nb, which is an important method for enriching Nb and Ti, in which corrosive acid such

as hydrofluoric acid and the like are not used, so there is not environmental pollution, and

Al and Si in the obtained solution can be taken as important by-products.

[0022] Product recycling.

[0023] 2, the recovery of Nb and Ti in the Nb-rich and Ti-rich materials is over 80%, the

content of Nb in the materials can reach 4,280 [g/g, and the TiO2 content can reach 81%,

which is an important resource of Nb, Ti that can be further developed.

BRIEF DESCRIPTION OF THE FIGURES

[0024] Figure 1 shows the process flow diagram of recovering Al and Si products from

clay rock and enriching Nb and Ti.

DESCRIPTION OF THE INVENTION

[0025] In the following, the present invention is further described with reference to the

follow examples:

[0026] Example 1

[0027] In the first step, about 200 g/g of Nb, about 37% of A1203 about 45% of SiO2

and about 3% of TiO2 in clay rock samples were crushed to about 100 mesh.

[0028] In the second step, the crushed clay rock samples were placed in a muffle furnace,

heated to 650 °C for calcination and keep for 2 hours.

[0029] In the third step, 10 g of roasted sample is weighed, 100 mL of 10% hydrochloric

acid solution is taken, hydrochloric acid and roast clay rock sample are put into a covered

reactor for reaction, and the reactor is gradually heated to boiling, The reaction was stirred

for 30-60 minutes, the residue was separated by filtration and washed 2-3 times, and the

filtrate was aluminium chloride by-product.

[0030] In the fourth step, adding 20% sodium hydroxide solution to the residue at a solid

liquid ratio of 1 g: 5 mL, and sufficiently stirring the mixture. React for 1 h at 50°C, filter

and separate the residue, and wash it with dilute sodium hydroxide solution for 2-3 times.

The filtrate is a by-product of sodium silicate solution. After washing, the content of Nb in

the residue is 1150 [g/g, and that of TiO2 is 22.8%, which are enriched by 5-6 times

respectively.

[0031] Example 2

[0032] In the first step, about 491-534 g/g of Nb, about 35% of A1203 about 40% of SiO2

and about 8.8% of TiO2 clay rock samples were crushed to about 100 mesh.

[0033] In the second step, the crushed clay rock samples were placed in a muffle oven,

which are heated to 850°C for calcination and keep for 2 hours.

[0034] In the third step, weighing 10 g of roasted sample, taking 100 mL of 10%

hydrochloric acid solution, putting hydrochloric acid and calcined clay rock sample into a

covered reactor for reaction, gradually heating the reactor to boiling, stirring for reaction

for 30-60 minutes, filtering to separate the residue, and washing for 2-3 times, the filtrate

was aluminium chloride by-product.

[0035] In the fourth step, adding 20% sodium hydroxide solution to the residue at a solid

liquid ratio of 1 g: 5 mL, and the mixture was sufficiently stirred. React for 1h at room

temperature at 25°C, filter and separate the residue, and wash 2-3 times with dilute sodium

hydroxide solution, and the filtrate is sodium silicate side.After washing, the residue

contained 2160 g/g of Nb and 39.67% of TiO2.

[0036] Example 3

[0037] In the first step, about 491-534 g/g of Nb, about 35% of A1203, about 40% of

SiO2 and about 8.8% of TiO2 clay rock samples were crushed to about 100 mesh.

[0038] In the second step, the crushed clay rock samples were placed in a muffle oven,

heated to 850°C for calcination and held for 2 hours.

[0039] In the third step, weighing 10 g of roasted sample, taking 100 mL of 10%

hydrochloric acid solution, hydrochloric acid and roast clay rock sample are put into a

covered reactor for reaction, and the reactor is gradually heated to boiling. Stirring for 30

minutes, the residue was separated by filtration and washed 2-3 times, and the filtrate

was aluminium chloride by-product.

[0040] In the fourth step, 20% sodium hydroxide solution was added to the residue at a

solid-liquid ratio of 1 g: 5 mL, and the mixture was sufficiently stirred at 50°C for 1h, filter

The filtrate is the by-product of sodium silicate, after washing, the content of Nb in the

residue is 4000g / g, that of TiO2 is 7 5 .17%, and the concentration is more than 8 times.

[0041] Example 4

[0042] In the first step, about 491-534 g / g of Nb, about 35% of A1203 about 40% of

SiO2 and about 8.8% of TiO2 clay rock samples were crushed to about 100 mesh.

[0043] In the second step, the crushed clay rock samples were placed in a muffle oven,

heated to 850°C for calcination and held for 2 hours.

[0044] In the third step, weighing 10 g of roasted sample, taking 100 mL of 10%

was aluminium chloride by-product.

[0045] In the fourth step, adding 20% sodium hydroxide solution to the residue at a solid

liquid ratio of 1 g: 5 mL, and the mixture was sufficiently stirred. React at 75°C for 1h,

filter and separate the residue, and wash it with dilute sodium hydroxide solution for 2-3

times. The filtrate is a by-product of sodium silicate, and after washing, the residue contains

4280 g/g of Nb, 80.5% of TiO2, which are about 9 times of enrichment.

[0046] Example 5

[0047] In the first step, about 491-534 g/g of Nb, about 35% of A1203, about 40% of

SiO2 and about 8.8% of TiO2 clay rock samples were crushed to about 100 mesh.

[0048] In the second step, the crushed clay rock samples were placed in a muffle oven,

which is heated to 850°C for calcination and held for 2 hours.

[0049] In the third step, weighing 10 g of roasted sample, taking 100 mL of 10%

covered reactor for reaction, and the reactor is gradually heated to boiling, The reaction

was stirred for 30-60 minutes, the residue was separated by filtration and washed 2-3 times,

and the filtrate was aluminium chloride by-product.

[0050] In the fourth step, adding 20% sodium hydroxide solution to the residue at a solid

liquid ratio of 1 g: 5 mL, and the mixture was sufficiently stirred. Carrying out the reaction

for 1h at 100°C, the residue was separated by filtration and washed 2-3 times with dilute

sodium hydroxide solution, and the filtrate was by-product of sodium silicate.

[0051] After washing, the content of Nb in the residue was 3760 [g/g, and that of TiO2

was 69.17%.

[0052] Example 6

[0053] In the first step, about 491-534 g/g of Nb, about 35% of A1203 about 40% of SiO2

and about 8.8% of TiO2 clay rock samples were crushed to about 100 mesh.

[0054] In the second step, the crushed clay rock samples were placed in a muffle furnace,

heated to 550°C for calcination and keep for 2 hours.

[0055] In the third step, weighing 10 g of roasted sample, taking 100 mL of 10%

and the filtrate was aluminium chloride by-product.

[0056] In the fourth step, 20% sodium hydroxide solution was added to the residue at a

solid-liquid ratio of 1 g: 5 mL, and the mixture was sufficiently stirred. The reaction is

carried out for 1 h at 50°C, the residue is separated by filtration and washed 2-3 times with

dilute sodium hydroxide solution, and the filtrate is sodium silicate by-product and washed.

[0057] The residue contains 1750 g/g of Nb and 33% of TiO2.

[0058] Example 7

[0059] In the first step, about 491-534g / g of Nb, about 35% of A1203, about 40% of

SiO2 and about 8.8% of TiO2 clay rock samples were crushed to about 100 mesh.

[0060] In the second step, the crushed clay rock samples were placed in a muffle furnace,

heated to 900°C for calcination, and kept for 2 hours.

[0061] In the third step, 10 g of roasted sample is weighed, 100 mL of 10% hydrochloric

acid solution is taken, and the hydrochloric acid is roast.

[0062] Placing the subsequent clay rock sample in a covered reactor for reaction, the

reactor was gradually heated to boiling and the reaction was stirred for 20 minutes.

[0063] The residue was separated by filtration and washed 2-3 times. The filtrate was

aluminium chloride by-product.

[0064] In the fourth step, adding 20% sodium hydroxide solution to the residue at a solid

liquid ratio of 1 g: 5 mL, and the mixture was sufficiently stirred. The reaction is carried

out for 1 h at 50°C, the residue is separated by filtration and washed 2-3 times with dilute

sodium hydroxide solution, and the filtrate is sodium silicate by-product and washed

[0065] The residue contained 3020 g/g of Nb and 56.7% of TiO2.

[0066] The above is only a better specific implementation mode of the invention, but the

protection scope of the invention is not limited to this. Any technical personnel familiar

with the technical field shall be included in the scope of protection of the invention if they replace or change the same according to the technical scheme and the invention concept of the invention within the technical scope disclosed by the invention.

Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

1. A process for recovering aluminium and silicon from clay rock and enriching

niobium and titanium, comprising the following steps:

(1) Sample preparation: The clay rock samples containing Nb 491-534 [g/g, A1203

%, SiO2 40%, TiO28.8% were crushed to 100 mesh with a crusher, for future use;

(2) High-temperature roasting and activation: Put the clay rock sample crushed in step

(1) into a muffle furnace, heat it to 850°C for roasting, and keep warm for 2 hours;

(3) In this method, weigh 10 g of roasted sample, measure 100 mL of 10%

hydrochloric acid solution, hydrochloric acid and the calcined clay rock sample are put into

a covered reactor for reaction, the reactor is gradually heated to boiling, and stirring for 30

minutes, the residue is filtered and washed 2-3 times, and the filtrate is aluminium

chloride by-product;

(4) Put 20% sodium hydroxide solution to the residue of the above step (3) by a solid

liquid ratio of Ig: 5mL, and stirring thoroughly; after reacting for 1 h at 75°C, the residue

was separated by filtration and washed with dilute sodium oxyhydroxide solution for 2-3

times. The filtrate was sodium silicate by-product and the residue was Nb and Ti rich

material.

2. The process for recovering aluminium and silicon from clay rock and enriching

niobium and titanium, according to claim 1 wherein, in the step (1), the clay rock mainly

consists of clay minerals of kaolinite group, titanium and iron bearing minerals.

-1/1-

Fig. 1