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Title:
A METHOD OF PROCESSING AND TREATMENT OF ALUNITE ORES
Document Type and Number:
WIPO Patent Application WO/2019/149293
Kind Code:
A1
Abstract:
The alunite ore processing method consists of crushing, grinding and flotation of raw alunite ore. The enriched alunite ore is roasted at 520 to 620 °C, the roasting time is 1 to 3 hours. The roasted alunite is leached with 5 to 20 % sodium carbonate solution, which is in 100 to 110 % of the stoichiometric amount required to bond the SO3 aluminum sulfate in the alunite with leaching conditions of 70 - 100 °C for 0.5 - 2.0 hours. The obtained slurry contains all of the potassium sulfate from the alunite and all of the sodium sulfate obtained from sodium carbonate. In the insoluble residue remains all aluminium oxide and residual rock. The sulfate solution is separated from the insoluble residue and is converted with potassium chloride to potassium sulphate (fertilizer) and kitchen salt. The insoluble residue is treated by the Bayer method without the use of an autoclave and results in aluminium oxide (alumina) and quartz sand.

Inventors:
TAGIJEV ELŠAD (CZ)
TAGHIYEV ELDAR (CZ)
AGAJEVA LALE (CZ)
Application Number:
CZ2019/000004
Publication Date:
August 08, 2019
Filing Date:
January 22, 2019
Export Citation:
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Assignee:
TAGIJEV ELSAD (CZ)
International Classes:
C01F7/06; C01D3/08; C01D5/00; C22B3/12; C22B21/00
Foreign References:
GB1375996A1974-12-04
US1338428A1920-04-27
CA271816A1927-06-21
CN103130254A2013-06-05
Attorney, Agent or Firm:
DANĚK, Vilém (CZ)
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Claims:
PATENT CLAIMS

1. Process for the treatment of alunite ores comprises of the following steps:

- crushing of alunite ore,

- grinding,

- enrichment of the ore by flotation to the content of at least 50 % of alunite by weight.

- roasting at 520 to 620 °C, roasting time is 1 to 3 hours,

- preparation of a sodium salt solution, characterized in that in the next step of leaching Na2C03 sodium carbonate is used in the first phase of the leaching,

1.e. leaching with 5 to 20 % sodium carbonate solution, which is added in the quantity of 100 to 110 % of the stoichiometric amount required to bond the S03 aluminum sulphate in the alunite ,

separation of the sulphate solution from the insoluble residue ,

- conversion of sodium sulphate by the conversion method with KC1 to potassium sulphate and sodium chloride,

- filtration and washing of the suspension,

- evaporation of the filtrate and of the washing water,

- the insoluble residue is treated by the Bayer method without the use of an autoclave with production of aluminium oxide (alumina) and quartz sand.

2. The process of the treatment of alunite ores according to claim 1, characterized in that the solution of Na2C03 is prepared in a 5 % excess over the stoichiometric balance of the K2S04 equation. A12(S04)3. 2A1203 + waste rock + 3Na2C03 =

K2S04 + 3Na2S04 + 3A1203 + waste rock + 3C02, where 3A1203 + waste rock is an insoluble residue containing silica, silica sand (Si02) and aluminosilicate.

3. The process of the treatment of alunite ores according to claim 1, characterized in that the leaching is carried out at a temperature of 70 to 100 °C for 0.5 to 2.0 hours during the course of the reaction from the equation according to claim 2.

4. The process of the treatment of alunite ores according to claim 1 or/and claim 2, characterized in that the Bayer method without autoclaving takes place at a temperature below 100 °C, with NaOH and the working solution entering the reaction and forming alimunium oxide (g-A1203) with silica sand (Si02) and aluminosilicate remaining.

5. The process of the treatment of alunite ores according to claim 4 , characterized in that the products from the Bayer method are processed by hydroseparation to a sand fraction and a clay fraction, that is aluminosilicate and y-Al203 accordingly.

6. The process of the treatment of alunite ores according to claim 5, characterized in that the clay fraction is precipitated including the filtration cake flush, to form sludge in the sediment and the supernatant.

7. The process of the treatment of alunite ores according to claim 5, characterized in that the sand fraction formed by the hydroseparation is washed and filtered to produce the silica sand and the filtrate.

8. The process of the treatment of alunite ores according to claims 6 and 7, characterized in that the filtrate after the filtration of the sand and the supernatant after the precipitation of the clay fraction are combined and this solution undergoes desilication to form the white sludge (sediment) and the aluminate solution (supernatant) .

9. The process of the treatment of alunite ores according to claim 8, characterized in that the reaction of the white sludge with sulfuric acid results in the formation of a coagulant .

10. The process of the treatment of alunite ores according to claims 4 and 8, characterized in that the supernatant formed from desilication is decomposed to form A1 (OH) 3 and the mother liquor, which is further evaporated to form the working solution which is repeatedly used in the Bayer method (reconcentration and recycling of water) .

11. The process of the treatment of alunite ores according to claim 10, characterized in that metallurgical g-Aΐ203 is formed by the calcination of Al(OH)3.

12. The use of sodium carbonate Na2C03 in the leaching phase according to claim 1 for the treatment of alunite ores and the production of aluminium oxides such as y-Al203 and other products such as potassium sulphate, quartz sand, coagulant for the purification of utility and potable water and kitchen salt as a by-product.

AMENDED CLAIMS

received by the International Bureau on

28 June 2019 (28.06.2018)

1. Process for the treatment of alunite ores comprises of the following steps:

- crushing of alunite ore,

- grinding,

- enrichment of the ore by flotation to the content of at least 50 % of alunite by weight.

- roasting at 520 to 620 °C, roasting time is 1 to 3 hours,

- preparation of a sodium salt solution Na2C03, which is later used for the first phase of the leaching,

characterized in that in the next step of leaching Na2C03 sodium carbonate is used in the first phase of the leaching, i.e. leaching with 5 to 20 % sodium carbonate solution, which is added in the quantity of 100 to 110 % of the stoichiometric amount required to bond the S03 aluminum sulphate in the alunite ,

- separation of the sulphate solution from the insoluble residue,

- conversion of sodium sulphate by the conversion method with KC1 to potassium sulphate and sodium chloride,

- filtration and washing of the suspension,

- evaporation of the filtrate and of the washing water,

- the insoluble residue is treated by the Bayer method without the use of an autoclave with production of aluminium oxide (alumina) and quartz sand.

2. The process of the treatment of alunite ores according to claim 1, characterized in that the solution of Na2C03 is prepared in a 5 % excess over the stoichiometric balance of the K2SO4 equation. A12(S04)3. 2A1203 + waste rock + 3Na2CC>3 = K2SO4 + 3Na2S04 + 3A1203 + waste rock + 3C02, where 3A1203 + waste rock is an insoluble residue containing silica, silica sand (Si02) and aluminosilicate .

3. The process of the treatment of alunite ores according to claim 1, characterized in that the leaching is carried out at a temperature of 70 to 100 °C for 0.5 to 2.0 hours during the course of the reaction from the equation according to claim 2.

4. The process of the treatment of alunite ores according to claim 1 or/and claim 2, characterized in that the Bayer method without autoclaving takes place at a temperature below 100 °C, with NaOH and the working solution entering the reaction and forming alimunium oxide (Y-AI2O3) with silica sand (Si02) and aluminosilicate remaining.

5. The process of the treatment of alunite ores according to claim 4, characterized in that the products from the Bayer method are processed by hydroseparation to a sand fraction and a clay fraction, that is aluminosilicate and Y-AI2O3 accordingly.

6. The process of the treatment of alunite ores according to claim 5, characterized in that the clay fraction is precipitated including the filtration cake flush, to form sludge in the sediment and the supernatant.

7. The process of the treatment of alunite ores according to claim 5, characterized in that the sand fraction formed by the hydroseparation is washed and filtered to produce the silica sand and the filtrate.

8. The process of the treatment of alunite ores according to claims 6 and 7, characterized in that the filtrate after the filtration of the sand and the supernatant after the precipitation of the clay fraction are combined and this solution undergoes desilication to form the white sludge (sediment) and the alu inate solution (supernatant) .

9. The process of the treatment of alunite ores according to claim 8, characterized in that the reaction of the white sludge with sulfuric acid results in the formation of a coagulant.

10. The process of the treatment of alunite ores according to claims 4 and 8, characterized in that the supernatant formed from desilication is decomposed to form Al(OH)3 and the mother liquor, which is further evaporated to form the working solution which is repeatedly used in the Bayer method (re-concentration and recycling of water) .

11. The process of the treatment of alunite ores according to claim 10, characterized in that metallurgical g-Aΐ2q3 is formed by the calcination of A1(0H)3.

12. The use of sodium carbonate Na2C03 in the leaching phase according to claim 1 for the treatment of alunite ores and the production of aluminium oxides such as Y-AI2O3 and other products such as potassium sulphate, quartz sand, coagulant for the purification of utility and potable water and kitchen salt as a by-product .

Description:
A method of processing and treatment of alunite ores

Technical field

This invention relates to/concerns technology of alunite ore processing resulting in the production of g-Aΐ 2 0 3 with the production of fertilizer potassium sulfate, kitchen salt, metallurgical aluminum oxide and quartz sand.

Background art

Alunite is a raw material for the aluminum and chemical industries. Industrial alunite ore deposits are common in the USA, China, Azerbaijan, Iran, Mexico, Kazakhstan, Ukraine, Russia and other countries. The presented invention concerns the processing of alunite ore with the production of fertilizer potassium sulphate, kitchen salt, metallurgical alumina and quartz sand.

An alkaline reduction method for processing alunite ore [1] is known. This method was used in the Ganja Aluminum Combine (GGC) . Due to significant technological drawbacks (such as low alumina yield of less than 70 %, pollution of the environment by dust and gas, a need for rare and expensive raw materials, large quantities of solid waste from 5 tons per 1 ton of alumina and an undesirable by-product sulfuric acid) GGC ceased its operations in 1992 and to this date does not operate .

A method for processing of alunite ore was developed for the production of potassium fertilizers (SOP) , sulfuric acid, alumina and quartz sand in Utah (USA) [2] . In this method, the alunite ore is roasted at 600 °C or lower with the release of S0 2 , which leads to the production of sulfuric acid, and the roasted alunite is extracted with hot water to produce K 2 S0 4 (SOP) . A reducing agent (excess oil or elemental sulfur vapors) should be introduced during roasting in order to acquire entire S0 2 aluminium sulphate. The combustion temperature of 600 °C allows to preserve g-A1 2 0 3 in an active form. However, leaching (in hot water at 80 to 99 °C) of the alunite T £ 600 °C results in the loss of SOPs due to the formation of water- insoluble basic salts. The yield of SOP in the solution does not exceed 65 to

70 %. Roasting of the alunite at 800 to 900 °C improves SOP yield to almost 100 %, while y-Al 2 0 3 is converted into an insoluble form of a- A1 2 0 3 . There is no floatation method that can divide a- A1 2 0 3 and quartz the insoluble residue in order to obtain metallurgical alumina.

The drawbacks were eliminated by the potash-alkaline method (Liner-Taghiyev) [3, 4, 5, 7], where the alunite roasted at the temperature of T £ 550 °C was leached with potassium carbonate solution according to the reaction:

K 2 S0 4 . Al 2 (S0 4 ) 3 . 2A1 2 0 3 + nn + 3K 2 C0 3 = 4K 2 S0 4 + 3A1 2 0 3 + nn +

3C0 2 (nn-waste rock) .

Up to 4 times more SOP and alumina (g-A10 3 ) is transferred into the solution, the metallurgical-Al 2 0 3 remains in the insoluble residue. The SOP is obtained from the solution and the insoluble residue is processed by the Bayer method by means of leaching with the recycled solution of aluminate at T = 80 - 90 °C to obtain metallurgical alumina and quartz sand. The disadvantage of this method is the use of a rare and expensive (including USA) potassium carbonate.

The foregoing drawbacks are addressed by the invention below.

The state of the art is further described in the following literature : 1. G.V. Labutin Recovery method for the processing of alunite. Autor. Svid. USSR No. 9911 a No. 108947 from year 1948,

2. Internet. Potash Ridge Corp. Technical report. Dated 24.

April 2017 Project No. 17M16.

3. A. I. Liner, V.I. Zakharova, Yu.A. Layner, El Taghiyev, Z. Pevzner Autor. Svid. SSSR No. 460709 d. 21.10.1974.

4. E.I.Tagijev, patent of the Republic of Azerbaijan I 2001 0142 dated 02.10.2001.

5. E.I.Tagijev, patent of the Republic of Azerbaijan I 2003 0210 dated 30.10.2003.

6. E.I. Tagijev, I.S. Babayev, S.B. Rajabli, A.T. Khudiev, T.B. Aliyev Autofi. Svid. SSSR 5 No. 872456 dated 15.06.1981.

7. E.I. Tagijev, Technology Of Complex Waste-fee Processing

Of Alunite Ores. Baku, Elm, 2006, 504 pages (research monograph in Russian) .

Summary of the invention

The processing of the alunite ore (alunite) consists first of the known steps: crushing, grinding and flotation of alunite ore. Flotation of the alunite ore proceeds with a flotoreagent and is proposed in the method according to the state of the art, point 2. The enriched alunite ore containing 25-95 % preferably 60 % of mineral alunite is further roasted at a temperature of 520 to 620 °C, the roasting time is 1 to 3 hours. The roasted alunite, in accordance with the present invention, is further leached with 5 to 20% sodium carbonate solution, which is added in an amount of 100 to 110% of the stoichiometric amount required to bond the S0 3 aluminium sulphate in the alunite, that is Na 2 C0 3 is added in an excess of 0 to 10 % over the calculated stoichiometric coefficients of the reaction equation 1, at 70-100 °C for 0.5 to 2.0 hours. The obtained slurry solution contains all potassium sulphate from alunite and sodium sulphate obtained from sodium carbonate. In the insoluble residue remains all of aluminium oxide from alunite and waste rock, where the waste rock is silica-Si0 2 and clay (aluminum) aluminosilicate. The sulfate solution is further separated by either filtration or precipitation from an insoluble residue and is converted with potassium chloride to potassium sulphate (fertilizer) and kitchen salt. The insoluble residue is processed by the Bayer method without autoclaving and at a temperature of less than 100 °C to form aluminium oxide (alumina) and quartz sand.

In order to overcome the disadvantages of the prior art, it is proposed to replace the solution of potassium carbonate with a solution of calcined soda (1) and then to convert right after the first leaching the obtained sodium sulphate by the conversion method with KC1 to potassium sulphate (fertilizer) and sodium chloride NaCl (2) , which is the basic/fundamental inventive idea of this invention.

Reaction (1) :

K2SO4 · Al 2 ( SO4 ) 3 . ΆI2O3 + nn + 3Na 2 C0 3 = K2SO4 + 3Na 2 S04 +

3AI2O3 + nn + 3CC>2

Reaction (2) :

K2SO4 + 3Na 2 S0 4 + 6KC1 = 4K 2 S0 4 + 6NaCl,

3A1 2 0 3 + nn is the insoluble residue, which is processed by the Bayer method without autoclaving to form aluminium oxide (alumina) and quartz sand. Alunite is roasted at 520 to 620 °C, the time of roasting is 1 to 3 hours. The roasted alunite is leached with 5 to 20% sodium carbonate solution in an amount of 100 to 110% of the stoichiometric amount required to bond the S0 3 aluminium sulphate in the alunite, that is Na 2 C0 3 is added in an excess of 0 to 10 % over the calculated stoichiometric coefficients of the reaction equation at 70 to 100 °C for 0.5 to 2.0 hours.

The products of this process are: K 2 S0 4 - fertilizer, NaCl - kitchen salt, A10 3 - metallurgical, Si0 2 - quartz sand and coagulant for water purification [6] .

Note: The United States is the second largest producer of sodium carbonate in the world, and Canada is the world's largest producer of potassium chloride (KC1) .

Examples of embodiments of the invention

Example 1

We take an alunite ore with an alunite content of 60% by weight, with the following composition, % by weight:

100 g of alunite (alumina) is crushed. Alunite (alunite ore) is further grinded, after the flotation enrichment it is roasted in an oven at T = 550 °C for 1 hour and then leached in the solution of Na 2 C0 3 .

A sodium salt solution is prepared: 22.2 g of Na 2C03 is dissolved in 350 ml of water, the amount of soda is 105% wt . from stoichiometric. The leaching time is 1.5 hours at Ti each 90 °C.

Into solution are transferred: K 2 0 - 99% by weight; Na 2 C0 3 -

100% by weight; A1 2 0 3 - 0.5% wt . ; S03 - 9 8% wt. or K 2 0 = 6.8 g, Na 2 0 = 13 g, S0 3 = 2.3 g, A1 2 0 3 = 0.1 g.

In the insoluble residue remains 62.2 g. C0 2 gas is formed.

The suspension is filtered and washed.

The filtrate with the washing water is evaporated.

We obtain a mixture of sulphates K, Na, where the sulphate K is 12.5 g, Na sulphate - 29.8 g, the total of 42.3 g of the mixture. This is a mixture of sulphates obtained from the evaporated mixture of the filtrate and washed water.

It is required 23.7 g of KC1 to produce 29.8 g of NaS0 4 . This is reaction number 2: K 2 S0 4 + 3Na 2 S0 4 + 6KC1 = 4K 2 S0 4 + 6NaCl, with K 2 S0 4 already present in the alunite in the amount of 12.5 g·

The result is 36.6 g of K 2 S0 4 plus 12.5 g of K 2 S0 4 from alunite. Total of 49 g of K 2 S0 4 and NaCl of 16.8 g.

Example 2

The method of treating the alunite ore consists of the following steps:

1. The alunite ore from the mine is crushed resulting in particles of 10 to 20 mm in size. 2. Followed by wet milling with a resulting particle size of the resulting powder under 0.074 micron (passed through a 200 mesh) .

3. Enrichment of the ground alunite ore by means of flotation. The resulting weight of the enriched ore containing 60% of alunite is 5.02 t.

4. Drying and roasting of the enriched alunite ore from step

3 at 530 to 550 °C for one hour.

After drying and roasting, the weight of alunite ore is 4.63 tons.

5. A solution from 1.12 t of Na 2 C0 3 (100%) is prepared, the solution is prepared in a 5% excess over the stoichiometric balance of equation (1) .

(1) K 2 S0 4 . Al 2 ( S04 ) 3 . 2A1 2 0 3 + waste rock + 3Na 2 C0 3 = K 2 S0 4

+ 3Na 2 S0 4 + 3A1 2 0 3 + waste rock + 3C0 , where 3A1 2 0 3 + waste rock is the insoluble residue. The waste rock contains silica, silica sand (Si0 2 ) and aluminosilicate (alumosilicate) .

6. The enriched alunite ore, after drying and roasting from step 4, is leached in a solution of Na 2 C0 3 prepared according to step 5 for 1.5 hours at 90 °C in the course of the reaction (1) .

The slurry suspension from leaching (step 6) is filtered and the filter cake is washed. 2.133 t of solution for evaporation is formed (mother liquors containing Na 2 S0 4 and K 2 S0 4 and an insoluble residue) .

The water after the washing of the cake can be used to prepare the solution of Na 2 C0 3 . The mother liquors from step 7 are evaporated/concentrated and converted according to the reaction (2) to K 2 S0 4 fertilizer (2.47 t) and kitchen salt NaCl (0.845 t) .

(2) K 2 S0 4 + 3Na 2 S0 4 + 6KC1 = 4K 2 S0 4 + 6NaCl The insoluble residue from step 5 (3A1 2 0 3 + waste rock) is processed by the Bayer method according to the reaction (3) without using an autoclave at a temperature below 100 °C. 0.05 t of NaOH and the working solution are introduced into the reaction.

(3) A1 2 0 3 + 2NaOH = 2NaA10 2 + H 2 0.

Aluminium oxide (alumina) is formed and remains unchanged "waste rock", i.e. silica sand (Si0 2 ) and aluminosilicate.. The products from step 9 are hydroseparated into the sand fraction and the clay fraction (aluminosilicate and alumina) .

. The clay fraction from step 10 is precipitated and the filter cake is rinsed, with the formation of sludge in the sediment and the supernatant.

. The sand fraction is washed and filtered to form the silica sand (2.0 t) and the filtrate.

. The filtrate after filtration of the sand from step 12 and the supernatant after precipitation of the clay fraction from step 11 are combined. Thusly formed solution undergoes desilication to form a white sludge and aluminate solution (supernatant) .

. A reaction of the white sludge with H 2 S0 4 (0.05 t) gives the coagulant from the white sludge (0.33 t) .

. The solution of aluminates resulting from the desilication from step 13 is further decomposed to form A1 (OH) 3 and the mother liquor. The mother liquor may be further evaporated to form a working solution which may enter step 9 (re concentration and recycling of water) .

. One ton of y-Al 2 0 3 is formed by calcination of A1(0H) 3 . Brief description of drawings

Diagram in Fig. 1 shows the method for processing and treating of alunite ores .

Advantages of the invention over the prior art

- Production of metallurgical aluminium oxide (alumina, A1 2 0 3) reaches 90 %

- The amount of SOP produced is increased 4 times, with a yield of 90 %.

- Procedures that pollute the environment with dust and gas (S0 2 ) are eliminated.

There is no need to use precious and expensive raw materials .

- This method is in fact free of solid waste.

- In addition to the efficient production of metallurgical aluminite and SOP, this method allows to simultaneously produce other products: kitchen salt, quartz sand and coagulant for cleaning potable and industrial water.

Industrial applicability

According to the present invention, the method for the treatment of alunite is used to treat alunite ores with the production of Al0 3 , as well as potassium sulphate, quartz sand, utility and potable water purification coagulant and kitchen salt as a by-product .