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    • 专利摘要:
    Solar electricity and salt from seawater are used to produce a solution of soda, and hydrochloric acid. This known Chlor-Alkali process is implemented here while adapting well to the variability of solar energy, because the production of soda and acid are adjustable depending on the sun. In times of plenty of sunshine the surplus chemicals are stored, to be used in times of energy deficit. In addition, the continuous photovoltaic current generated can be used directly by electrolysers without expensive inverters. The resulting economy allows to obtain in abundance, economically and insitu, the chemicals necessary for the production of TiO2 according to the methods described. These chemicals also serve to neutralize the effluents to obtain valuable hydroxides. If Ilmenite was first transformed into Ti slag, the process is also able to extract TiO2 from these slags.
    公开号:BE1025151B1
    申请号:E2017/0162
    申请日:2017-11-21
    公开日:2018-11-13
    发明作者:Ngoc Ngan Phan；NGOC Hien PHAN
    申请人:Ngoc Ngan Phan；NGOC Hien PHAN；
    IPC主号:
    专利说明:


    economy
    1025151 Bl
    FPS Economy, SMEs, Middle Classes & Energy Intellectual Property Office
    Date of issue: 13/11/2018
    PATENT
    Priority date:
    International classification: C22B 3/12, C01G 23/053, C09C 1/36, C22B 3/44, C22B 34/12
    Filing number: BE2017 / 0162
    Filing date: 11/21/2017
    Holder:
    PHAN NGOC Ngan
    1410, WATERLOO
    Belgium
    PHAN NGOC Hien
    14600, GENNEVILLE
    France
    Inventor:
    PHAN NGOC Ngan 1410 WATERLOO Belgium
    PHAN NGOC Hien 14600 GENNEVILLE France
    Process for the production of titanium dioxide (TiO2), from Ilmenite using solar energy and sea water
    Solar electricity and salt from seawater are used to produce a solution of soda, and hydrochloric acid. This known Chlor-Alkali process is implemented here while adapting well to the variability of solar energy, since the production of soda and acid are adjustable depending on the amount of sunshine. In times of plenty of sunshine, excess chemicals are stored to be used in times of energy deficit. In addition, the direct photovoltaic current generated can be used directly by electrolysers without expensive inverters. The resulting economy makes it possible to obtain in abundance, economically and insitu, the chemicals necessary for the production of TiO2 according to the methods described. These chemicals also serve to neutralize effluents in order to obtain recoverable hydroxides. If the Ilmenite was first transformed into Ti slag, the process is also capable of extracting TiO2 from these slag.
    BELGIAN INVENTION PATENT
    FPS Economy, SMEs, Middle Classes & Energy Publication Number: 1025151Filing number: BE2017 / 0162 Intellectual Property Office International Classification: C22B 3/12 C01G 23/053 C09C 1/36C22B 3/44 C22B 34/12Date of issue: 13/11/2018
    The Minister of the Economy,
    Having regard to the Paris Convention of March 20, 1883 for the Protection of Industrial Property;
    Considering the law of March 28, 1984 on patents for invention, article 22, for patent applications introduced before September 22, 2014;
    Given Title 1 “Patents for invention” of Book XI of the Code of Economic Law, article XI.24, for patent applications introduced from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 relating to the request, the issue and the maintenance in force of invention patents, article 28;
    Given the patent application received by the Intellectual Property Office on November 21, 2017.
    Whereas for patent applications falling within the scope of Title 1, Book XI of the Code of Economic Law (hereinafter CDE), in accordance with article XI. 19, §4, paragraph 2, of the CDE, if the patent application has been the subject of a search report mentioning a lack of unity of invention within the meaning of the §ler of article XI.19 cited above and in the event that the applicant does not limit or file a divisional application in accordance with the results of the search report, the granted patent will be limited to the claims for which the search report has been drawn up.
    Stopped :
    First article. - It is issued to
    PHAN NGOC Ngan, Chaussée de Tervuren 104.1410 WATERLOO Belgium;
    PHAN NGOC Hien, Route du Lavoir 132, 14600 GENNEVILLE France;
    represented by a Belgian invention patent with a duration of 20 years, subject to payment of the annual fees referred to in article XI.48, §1 of the Code of Economic Law, for: Process for the manufacture of titanium dioxide ( T1O2), from Ilmenite using solar energy and sea water.
    INVENTOR (S):
    PHAN NGOC Ngan, Chaussée de Tervuren 104, 1410, WATERLOO;
    PHAN NGOC Hien, Route du Lavoir 132, 14600, GENNEVILLE;
    PRIORITY (S):
    DIVISION:
    divided from the basic request:
    filing date of the basic application:
    Article 2. - This patent is granted without prior examination of the patentability of the invention, without guarantee of the merit of the invention or of the accuracy of the description thereof and at the risk and peril of the applicant (s) ( s).
    Brussels, 11/13/2018,
    By special delegation:

    BE2017 / 0162
    Process for the manufacture of Titanium dioxide (TXO2), from Ilmenite using solar energy and sea water
    Description of the process
    Ilmenite, a mixed oxide with the formula FeTiCh mixed with other oxides and compounds with a T1O2 content of between 35 (if magnetite is present) and 59% or more (if rutile is present), is the main ore titanium.
    Currently to produce T1O2 from Ilmenite the sulfuric process and the chlorine process are used, with drawbacks linked to pollution and costs. The process which is the subject of this patent application uses solar electricity and the salt extracted from sea water to produce a solution of soda (or potash), known process Chlor-Alkali. The Hydrogen and Chlorine produced by electrolysis will be combined to produce hydrochloric acid.
    Always with solar energy, soda (or potash) and hydrochloric acid are used to produce a red mud by caustic digestion and then T1O2 hydrated by hydrolysis. No other chemicals are used in this production process.
    Wensheng Zhang et al. in "A literature review of titanium metallurgical processes", Hydrometallurgy, Elsevier Scientific Publishing Cy, Amsterdam, NL, vol. 108, no. 3, April 10, 2011, pages 177-188, already mentioned the use of soda or potash and hydrochloric acid in the treatment of ilmenite to produce T1O2. The process which is the subject of this patent is different because it starts with seawater for the manufacture of NaCl / KCl and HCl by photovoltaic means in order to improve the efficiency of the manufacture of T1O2.
    Tennakone et al. in “Hydrogen from brine electrolysis: A new approach”, International Journal of Hydrogen Energy, Elsevier Science Publisher B.V., Barking, GB, vol. 14, no. 9, January 1, 1989, pages 681-682, already described a process for the production of NaCl / KCl and HCl from sea water by photovoltaic route. The process which is the subject of this patent is different because it relates to the manufacture of T1O2, starting from sea water for the manufacture of NaCl / KCl and HCl by photovoltaic route in order to improve the efficiency of this manufacture.
    Edgar Klein et al. in US Patent 3,549,322 "Process for the
    Manufacture of Acicular rutile pigments from hydrochloric acid titanium chloride solutions "already described a process for
    BE2017 / 0162 production of acicular T1O2 rutile using acid digestion of titaniferous ore and seeds made from T1CI4. The process which is the subject of this patent is different because it uses the caustic digestion of titaniferous ore, starting from sea water for the manufacture of NaCl / KCl and HCl by photovoltaic way in order to improve the efficiency of the manufacture of T1O2. .
    Detailed description of the process
    Solar energy is an economic renewable resource often criticized for its variability linked to the solar cycle. However, the Chlor-Alkali process accommodates this variability well, because the production of NaOH (or KOH), CI2 and info can be modulated according to the sunshine.
    The NaCl (or KC1) used for the electrolysis is obtained from sea water by filtration, evaporation and progressive precipitation with solar energy to collect only NaCl (or KC1) at a purity of 95%.
    The use of the known Chlor-Alkali process makes it possible to obtain NaOH (or KOH) liquid at 30% (this concentration is not critical because the caustic digestion allows the vaporization, to increase it if necessary), of ΙΉ2 and of CI2 gas.
    The two gaseous compounds CI2 and H 2 are recombined to produce hydrochloric acid (at 22% -37% - this concentration is not critical because the hydrolysis in acid medium of the process accommodates a wide range of variation in acid concentration), an acid which is used to extract TiO2 from red mud obtained by caustic digestion of Ilmenite. In times of energy surplus these chemical compounds can be produced and stored, to be used in times of energy deficit. In addition, the direct current generated by the solar panels can be used directly by the electrolysers without having to go through expensive inverters. The resulting economy makes it possible to obtain, economically and in situ, soda (potash) and hydrochloric acid in abundance for the production of TiCh.
    The solar panels (frequently mono or poly crystalline) economic and available in abundance make solar energy very competitive in the regions with strong sunning, in particular the tropical regions. Between 2012 and 2017 alone, the price of these panels fell by more than 62%, making solar energy the most competitive currently.
    A direct current of 12, 24 or 48 V, supplied by a solar panel installation is sufficient to supply rows of electrolysers composed of 4, 8 or 16 membrane cells, each typically needing around 3 V to electrolyze the salt. The available current of these panels being variable, the number of rows in parallel connected to the panels must be modulated according to the sunshine through
    BE2017 / 0162 of charge regulators based on Industrial Programmable Logic Controllers in order to avoid overloading the electrolysers during periods of strong sunshine, and by the use of diodes preventing reverse current in solar panels.
    During this period the production of soda (or potash) and acid will be high allowing the storage of surpluses in tanks. In periods of little or no sunshine, these surpluses will make it possible to maintain the production of T1O2 (with ancillary equipment operating on the conventional electrical network. Alternatively or may consider providing for the storage of a small part of solar electricity on batteries , and the use of inverters for these stations).
    The savings obtained on inverters and batteries make it possible to maintain a very low cost per kWh produced. The abundance of NaOH (or KOH) and HCl obtained at low cost makes it possible to avoid any constraint on the use of these products to produce pure T1O2 and to treat the effluents to retain the hydroxides to be valorized, thus not loosening than neutral effluents.
    Also, the liquid soda (or potash) obtained from in-situ electrolysers is used directly for the caustic digestion of Ilmenite, avoiding the stage of production of solid soda (or potash) and its transport, and thus constituting a factor in reducing manufacturing costs.
    The Ilmenite is first mixed with the liquid sodium hydroxide (or potash) produced by the electrolysers, at a rate of 0.5 - 1 kg of NaOH (or 0.7 - 1.4 kg of KOH) per kg d 'Ilmenite, this mixture is brought to 250-450 ° C for 1 to 5 hr, making it possible to dissolve the compounds other than those of Ti and Fe contained in the Ilmenite.
    The diluted HCl acid (pH 0.2 then diluted to pH 2 at 60 ° C when adding demineralized water during the hydrolysis phase) then dissolves the cooled red mud resulting from caustic digestion. Cathodic reduction is used to reduce the Ti 4+ and Fe 3+ ions present in the acid solution of red mud to Ti 3+ and Fe 2+ . This solution is heated to 6080 ° C, then demineralized water is added at the same temperature, all brought to 100 ° C for 1 - 4 hr. The hydrated TiCh precipitates by hydrolysis. It will be recovered by filtration, then by washing with demineralized water. After calcination at 450-950 ° C for 0.5-2 hr, ÜO2 is obtained.
    Examples
    1) 4 solar panels marketed under the name of “Parallel Energie® of 15 W / 7A with multiple output voltages: 3V, 6V and 12V are used to supply electricity to a Fumatech® FT-EC 500 electrolyser. The panels are arranged in two rows in parallel each row comprising two panels in series.
    BE2017 / 0162
    The Fumatech® FT-EC 500 chlorinator operates on direct current 24 - 25 V, and its membrane can be selected. To produce soda (or potash) an ASAHI membrane is used.
    The soda (or potash) obtained is used for the caustic digestion of Ilmenite.
    2) Production of T1O2 from Ilmenite:
    Caustic digestion of Ilmenite: 1000 gr of Ilmenite are mixed with 1500 ml of NaOH (or KOH) at 30% obtained by electrolysis of NaCl (or KC1). This mixture is brought to a sufficient temperature in order to evaporate the excess water in the soda (or potash), then at a temperature of 450 ° C. for one hour. The process uses NaCl (or KC1) to produce NaOH (or KOH) in order to carry out the caustic digestion of Ilmenite.
    - Recovery of the compound (FeO, T1O2) - red mud, then T1O2: after caustic digestion the Ilmenite + Soda (or Potash) mixture at the outlet of the oven is cooled to room temperature, then leached in order to recover the red mud and Ilmenite not digested by decantation. This red mud is then washed to remove the soda (or potash), filtered and mixed with an HCl acid solution to obtain a clear solution, in which a cathodic reduction is carried out, to reduce the Fe 3+ to Fe 2+ and Ti 4+ to Ti 3+ . This solution is brought to a temperature of 5060 ° C., then demineralized water at the same temperature is added in order to obtain a pH of 2. The whole, possibly supplemented with seeds of crystallization, brought to a temperature of 100 ° C for 4 hours makes it possible to recover the hydrated T1O2 in the form of a suspension in the liquid. The T1O2 hydrate is recovered by filtration, then undergoes washing with demineralized water and calcination.
    - Recycling of Ilmenite not having been digested with sodium hydroxide (potash): washed and neutralized with a dilute HCl solution, the Ilmenite can be digested again with NaOH (or KOH) in order to extract the remaining T1O2.
    3) Production of T1O2 if the ilmenite has been previously transformed into Ti slag (or Ti slag):
    Caustic digestion: Ti Slag is ground and then mixed with soda (potash) in order to undergo the same treatment as the previous example.
    Recovery of the compound (Fe, TiCb) - red mud, and
    TiOï, recycling of Ti Slag not digested with soda (or potash): the same process as that of the previous example is applied.
    BE2017 / 0162
    J)
    ΒΕ2017 / 0162
    权利要求:
    Claims (9)
    [1]
    Claims
    1- T1O2 manufacturing process using combined NaOH soda (or KOH potash) and HCl acid produced with solar energy and seawater, solar energy being produced electricity by photovoltaic panels supplying the electrolysers with membranes in direct current, and the sea water used to produce NaCl salt (or KC1), following the steps below:
    (a) The NaCl (or KC1) used is obtained from sea water by filtration, evaporation and progressive precipitation with solar energy to collect only NaCl (or KC1) at a purity of 95%;
    (b) Use of the known Chlor-Alkali process to produce NaOH (or KOH) liquid at 30% (this concentration is not critical because the caustic digestion makes it possible to vaporize the water and to increase this concentration if necessary), ΙΉ2 and CI2 gas;
    (c) Recombination of ΙΉ2 and CI2 in the presence of water to obtain 22% -37% HCl acid (this concentration is not critical since the hydrolysis in an acid medium of the process accommodates a wide range of variation in acid concentration);
    (d) Chlor-Alkali membrane electrolysers are powered by solar panels providing direct current of 12, 24 or 48 V, electrolysers which are arranged in series / parallel rows, each typically needing about 3 V to electrolyze the salt ;
    (e) Caustic digestion at 250 - 450 ° C for 1 to 5 hr of Ilmenite (or Ti Slag) mixed with a solution of NaOH (or KOH) at about 30% obtained by electrolysis of NaCl (or KC1) , mixture produced in a ratio of approximately 0.5: 1.0 mass of NaOH: mass of ore (0.7: 1.4 mass of KOH: mass of ore);
    (f) After the caustic digestion, the Ilmenite + Soda (or Potash) mixture is cooled to room temperature, then leached in order to recover a red mud and the undigested Ilmenite by decantation;
    (g) This red mud is washed to remove the soda (or potash), filtered and mixed with an HCl acid solution (pH 0.2) to obtain a solution of 80 - 250 g / 1 T1O2 in which one performs a discount
    BE2017 / 0162 cathodic, to reduce Fe 3+ to Fe 2+ and Ti 4+ to
    Ti 3+ ;
    (h) This solution is brought to a temperature of 5060 ° C., then demineralized water (0.5 to 10 times the volume of solution) at the same temperature is added in order to obtain a pH of 2, all then brought to a temperature of 100 ° C for 1 to 4 hours in order to recover the hydrated TiC> 2;
    (i) The T1O2 hydrate is recovered by filtration, then undergoes washing with demineralized water and calcination at 450-950 ° C for 0.5-2 hr;
    (j) Recycling of Ilmenite not having been digested with sodium hydroxide (potash): washed and neutralized with a dilute HCl solution, the Ilmenite can be digested again with NaOH (or KOH) in order to d 'extract the remaining TiO2.
    [2]
    2- The method of claim 1, by which, in periods of strong sunlight the excess production of soda (or potash) and acid is stored in reservoirs, and in periods of low or no sunshine, these surpluses are used to continuously maintain T1O2 production.
    [3]
    3- A method according to claim 1, by which the direct current of the voltaic panels is used without the intermediary of an inverter for the production of NaOH (or KOH) and HCl, and the combination of the solar panels and the number of rows of electrolysers in service can be adjusted according to the intensity of the sunshine.
    [4]
    4- A method according to claim 1, wherein the excess production of soda (or potash) and acid is stored in storage tanks instead of the use of storage battery of solar energy.
    [5]
    5- A method according to claim 1, by which the NaOH soda (or KOH potash) liquid obtained is used directly in the caustic digestion of Ilmenite without having to go through a step of vaporization of the soda (or potash) liquid.
    [6]
    6- The method of claim 5, wherein the red mud obtained from caustic digestion is dissolved in hydrochloric acid, for hydrolysis to obtain a precipitate of hydrated T1O2, which after calcination gives T1O2.
    BE2017 / 0162
    [7]
    7- Process according to claim 6, by which a cathodic reduction is carried out to reduce the Ti 4+ and Fe 3+ ions to Ti 3+ and Fe 2+ respectively just before the hydrolysis.
    [8]
    8- The method of claim 7, whereby, due to the abundance of NaOH (or KOH) and HCl produced at low cost, it is possible to renew the caustic digestion of the hydrated T1O2 to produce a clear mud, dissolve it using HCl, then hydrolyze it to obtain a pure T1O2 at 99.3% or more after calcination.
    [9]
    9- The method of claim 8, wherein, due to the abundance of NaOH (or KOH) and HCl produced at low cost, it is possible to neutralize the effluents with HCl and NaOH (or the KOH) to precipitate the hydroxides to be recovered, and to reject only neutral effluents.
    Wocj
    BE2017 / 0162
    Process for the manufacture of Titanium dioxide (TXO2), from Ilmenite using solar energy and sea water
    summary
    Solar electricity and salt from seawater are used to produce a solution of soda, and hydrochloric acid. This known Chlor-Alkali process is implemented here while accommodating the variability of solar energy well, since the production of soda and acid are adjustable according to the amount of sunshine. In times of plenty of sunshine, excess chemicals are stored to be used in times of energy deficit. In addition, the direct photovoltaic current generated can be used directly by electrolysers without expensive inverters. The resulting economy makes it possible to obtain in abundance, economically and insitu, the chemicals necessary for the production of T1O2 according to the methods described. These chemicals also serve to neutralize effluents in order to obtain recoverable hydroxides. If the Ilmenite was first transformed into Ti slag, the process is also capable of extracting T1O2 from these slag.
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    同族专利:
    公开号 | 公开日
    BE1025151B9|2019-01-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3549322A|1968-02-17|1970-12-22|Titan Gmbh|Process for the manufacture of acicular rutile pigments from hydrochloric acid titanium chloride solutions|
    法律状态:
    2018-12-13| FG| Patent granted|Effective date: 20181113 |
    优先权:
    申请号 | 申请日 | 专利标题
    BE20170162A|BE1025151B9|2017-11-21|2017-11-21|Manufacturing process for Titanium dioxide , from Ilmenite using solar energy and seawater|BE20170162A| BE1025151B9|2017-11-21|2017-11-21|Manufacturing process for Titanium dioxide , from Ilmenite using solar energy and seawater|
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