FI92578B - Method for producing titanium dioxide - Google Patents
Method for producing titanium dioxide Download PDFInfo
- Publication number
- FI92578B FI92578B FI892392A FI892392A FI92578B FI 92578 B FI92578 B FI 92578B FI 892392 A FI892392 A FI 892392A FI 892392 A FI892392 A FI 892392A FI 92578 B FI92578 B FI 92578B
- Authority
- FI
- Finland
- Prior art keywords
- sulfuric acid
- titanium oxide
- titanium dioxide
- titanium
- exhaust gases
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Description
9257892578
Menetelmä titaanidioksidin valmistamiseksi Tämä keksintö koskee menetelmää titaanidioksidin valmistamiseksi saattamalla titaania sisältävät raaka-5 aineet liukenevaan muotoon rikkkihapon avulla, hydroly soimalla. näin muodostettu titanyylisulfaatti, erottamalla metallisulfaattipitoinen rikkihappo hydrolyvsissä muodostuneesta titaanioksidihydraatista, valkaisemalla titaanioksidihydraati pelkistyskäsittelyllä rikkihapon 10 ollessa läsnä, kalsinoimalla valkaistu titaanioksidi- hydraatti titaanidioksidiksi ja poistamalla rikki prosessin SC^-pitoisista poistokaasuista kostealla aktiivi-hiilellä, jolloin muodostuu 5 - 20-%:ista rikkihappoa.The present invention relates to a process for the production of titanium dioxide by solubilizing titanium-containing raw materials with sulfuric acid by hydrolysis. the titanyl sulphate thus formed, by separating the metal sulphate-containing sulfuric acid from the titanium oxide hydrate formed in the hydrolysis, bleaching the titanium oxide hydrate by a reduction treatment in the presence of sulfuric acid 10, desulfurizing the
Niin sanottua sulfaattimenetelmää käyttävien ti-15 taanidioksidin tuottajien ponnistelut menetelmien paran tamiseksi ekologiselta kannalta liittyvät ennen kaikkea jätevesipuoleen. Niin sanotun laimean jätehapon käsittelemiseen on ehdotettu monenlaisia menetelmiä (US-patenttijulkaisu 2 098 056, DE-patenttijulkaisu 20 1 173 074 ja EP-julkaisu 133 505). Näiden käsittelypro sessien kustannusten pitämiseksi mahdollisimman pieninä pyritään käsiteltäväksi ajateltu jae säilyttämään mahdollisimman väkevänä kierrättämällä laimeita metalli-sulfaattipitoisia rikkihappojakeita (DE-patenttijulkai-*.25 su 2 729 755 ja EP-julkaisu 133 505).The efforts of producers of titanium dioxide using the so-called sulphate method to improve the methods from an ecological point of view are primarily related to the waste water side. A variety of methods have been proposed for treating so-called dilute waste acid (U.S. Patent 2,098,056, DE 20,173,074, and EP 133,505). In order to keep the costs of these treatment processes to a minimum, the aim is to keep the fraction to be treated as concentrated as possible by recycling dilute metal sulphate-containing sulfuric acid fractions (DE patent publication * *. 25 su 2 729 755 and EP publication 133 505).
Titaanidioksidin kalsinoinnissa syntyvien poisto-kaasujen sisältämän SC^sn pelkistykseen tunnetaan menetelmiä, joissa SO2 muunnetaan kostealla aktiivihiilellä rikkihapoksi, joka pestään aktiivihiilestä vedellä 30 5 - 20-%:iseksi laimennettuna happona (Lurgi Scnellin- formation C1217/12, 76, s. 6 - 11).Methods are known for the reduction of SC® sn in the exhaust gases from the calcination of titanium dioxide, in which SO2 is converted with moist activated carbon into sulfuric acid, which is washed from the activated carbon with water as a dilute acid to 5-20% (Lurgi Scnell formation C1217 / 12, 76, p. 6 - 11).
Sellaiselle rikkihapolle, joka on kyllä puhdas mutta voimakkaasti laimennettu, on tähän saakka ollut tuskin lainkaan käyttömahdollisuuksia. Sen käyttäminen •3 5 TiC^m raaka-aineen liuotuksessa tai titanyylisulfaatin 2 92578 hydrolyysissä veden tilalla johtaa viimein siihen, että haihdutettava määrä kierrätettyjä, metallisulfaat-tipitoista, 20 - 25-%:ista jätehappoa kasvaa ja merkitsee siis huomattavaa rasitusta prosessille.So far, there has been hardly any use for sulfuric acid, which is pure but heavily diluted. Its use • 3 5 TiCl 2 in the dissolution of the raw material or in the hydrolysis of titanyl sulphate 2 92578 in place of water finally leads to an increase in the amount of recycled metal sulphate-containing 20-25% waste acid and thus places a considerable strain on the process.
5 Tämän keksinnön päämääränä on siksi tarjota käy tettäväksi menetelmä titaanidioksidin valmistamiseksi taloudellisesti ja ekologisesti edullisella tavalla, jossa menetelmässä titaanioksidihydraatin kalsinoinnista ja mahdollisesti titaaniraaka-aineen liuotuksesta peräi-10 sin olevista poistokaasuista poistetaan suurin osaIt is therefore an object of the present invention to provide a process for the production of titanium dioxide in an economically and ecologically advantageous manner, in which most of the exhaust gases from the calcination of titanium oxide hydrate and possibly from the dissolution of the titanium raw material are removed.
Seasta kostealla aktiivihiilellä, jolloin muodostuu 5 - 20-%:ista rikkihappoa, joka voidaan käyttää uudelleen titaanidioksidin tuottamisessa, jolloin se ei rasita jätehappo- tai jätevesitasetta.Sea with moist activated carbon to form 5 to 20% sulfuric acid, which can be reused to produce titanium dioxide without straining the waste acid or wastewater balance.
15 Tämä keksinnön mukainen päämäärä saavutetaan si ten, että rikin poistamisessa poistokaasuista syntyvää 5 - 20-%:ista rikkihappoa käytetään ilman edeltävää väkevöintiä yhdessä teknisesti puhtaan, noin 96-%:isen rikkihapon kanssa titaanioksidihydraatin pelkistyskä-20 sittelyssä raskasmetalli-ionien poistamiseen, jota kut sutaan myös valkaisuksi.This object of the invention is achieved in that, in the desulphurisation process, 5 to 20% sulfuric acid from the exhaust gases is used without prior concentration together with technically pure sulfuric acid of about 96% in a titanium oxide hydrate reduction treatment to remove heavy metal ions. also bleached.
Tämä keksintö koskee siis menetelmää titaanidioksidin valmistamiseksi saattamalla titaania sisältävät raaka-aineet liukenevaan muotoon rikkihapon avulla, hydroly-. 25 soimalla tällöin muodostunut titanyylisulfaatti, erotta- * maila metallisulfaattipitoinen rikkihappo hydrolyysis sä muodostuneesta titaanioksidihydraatista, valkaisema-la titaanioksidihydraatti pelkistyskäsittelyllä rikkihapon ollessa läsnä, kalsinoimalla valkaistu titaaniok-30 sidihydraatti titaanidioksidiksi ja poistamalla rikki prosessin S02-pitoisista poistokaasuista kostealla ak-tiivihiiellä, jolloin muodostuu 5 - 20-%:ista rikkihappoa, jolle menetelmälle on tunnusomaista, että valkaisussa käytetään rikkihappona rikin poistamisessa poisto-35 kaasuista muodostuvaa 5 - 20-%:ista rikkihappoa yhdessä teknisesti puhtaan väkevän rikkihapon kanssa.The present invention therefore relates to a process for the production of titanium dioxide by solubilizing titanium-containing raw materials with sulfuric acid, hydroly-. 25 by separating the titanyl sulphate thus formed from the titanium oxide hydrate formed in the hydrolysis of the metal sulphate, bleaching the titanium oxide hydrate by a reduction treatment with the diacidate in the presence of sulfuric acid and removing the sulfuric acid from the titanium oxide by calcining the titanium oxide with 20% sulfuric acid, which process is characterized in that 5 to 20% sulfuric acid, consisting of exhaust-35 gases, is used as sulfuric acid in bleaching to remove sulfur, together with technically pure concentrated sulfuric acid.
Il .Il.
3 925783,92578
On havaittu, että koko poistokaasujen rikinpoisto-käsittelyssä syntyvä rikkihappomäärä voidaan käyttää valkaisussa keksinnön mukaisesti. Sen mukaan sopivissa suodatuslaitteissa, esimerkiksi Moore-suodattimissa, 5 sulfaatista vapaaksi pesty titaanioksidihydraatti sus- pendoidaan käytettävissä olevaan 5 - 20-%:iseen rikkihappoon ja tähän suspensioon sekoitetaan sitten niin paljon väkevää rikkihappoa,että tuloksena on valkaisun vaatima rikkihappopitoisuus. Varsinainen valkaisu pelkis-10 timiä käyttäen tapahtuu sitten tunnetulla tavalla, esi merkiksi Ai tai Zn-jauheella tai natriumformaldehydisul-foksylaatilla.It has been found that the entire amount of sulfuric acid generated in the desulfurization treatment of the exhaust gases can be used in bleaching according to the invention. According to it, in suitable filtration equipment, for example Moore filters, the sulphate-free washed titanium oxide hydrate is suspended in the available 5 to 20% sulfuric acid and this suspension is then mixed with enough concentrated sulfuric acid to give the sulfuric acid content required for bleaching. The actual bleaching using reducing agents then takes place in a known manner, for example with Al or Zn powder or sodium formaldehyde sulfoxylate.
Eräässä erityisen edullisessa keksinnön mukaisen menetelmän toteutusmuodossa 10 - 50 % rikkihaposta lisä-15 tään 5 - 20-%sisen rikkihapon muodossa.In a particularly preferred embodiment of the process according to the invention, 10 to 50% of the sulfuric acid is added in the form of 5 to 20% of sulfuric acid.
Seuraavaksi keksintöä valaistaan esimerkein, joita ei pidä katsoa rajoittaviksi.The invention will now be illustrated by examples, which should not be construed as limiting.
Vertailuesimerkki 3.75 tonnin suodatuskakku, joka sisältää 1,31 t 20 kiintoainetta (SO^ -pitoista titaanioksidihydraattia) joka vastaa 1 t:a Ti02:ta, suspendoidaan metallisulfaat-tien poispesun jälkeen 524 litraan vettä, ja suspensioon sekoitetaan 253 kg teknisesti puhdasta 96-%:ista rikkihappoa. Sen jälkeen suoritetaan suodatuskakun val-25 kaisu pelkistimiä, esimerkiksi alumiinijauhetta, lisää- « • mällä.Comparative Example A 3.75 tonne filter cake containing 1.31 t of 20 solids (SO 2 -containing titanium oxide hydrate) corresponding to 1 t of TiO 2 is suspended in 524 liters of water after washing the metal sulphate roads, and 253 kg of technically pure 96% water are mixed into the suspension. sulfuric acid. The preparation of the filter cake is then carried out by adding reducing agents, for example aluminum powder.
Esimerkki 3.75 tonnin suodatuskakku (samanlainen kuin vertai-luesimerkissä) suspendoidaan 608 kg:aan 13,2-%:ista rikki- 30 happoa, suspensioon sekoitetaan 170 kg teknisesti puhdas ta 96-%:ista rikkihappoa, ja suodatuskakku valkaistaan kuten edellä.Example A 3.75 tonne filter cake (similar to the comparative example) is suspended in 608 kg of 13.2% sulfuric acid, 170 kg of technically pure 96% sulfuric acid are mixed into the suspension, and the filter cake is bleached as above.
96-%:ista rikkihappoa kuluu 33 % vähemmän kuin vertailuesimerkissä, vaikka suspension koostumus ennen 35 pelkistimen lisäystä on sama.The consumption of 96% sulfuric acid is 33% less than in the comparative example, although the composition of the suspension before the addition of the 35 reducing agents is the same.
• 1 » 4 92578 13,2-%:inen rikkihappo sisältää 80 kg I^SO^iä. Se vastaa sitä kokonaisrikkihappomäärää, joka enintään on saatavissa talteen poistamalla rikki kalsinointikaa-suista, jotka syntyvät kalsinoitaessa 1 t TiC>2:ta. Tä-5 mä rikkihappo muodostetaan siten, dttä titaanioksidihyd- raatin kalsinoinnissa syntyvät S02~pitoiset kalsinointi-kaasut johdetaan vesipesun jälkeen kosteata aktiivihiiltä sisältävän kerroksen läpi. Aktiivihiilikerroksessa S02 muunnetaan 02:lla ja H20:lla H2SO^:ksi. Hiiliker-10 ros suihkutetaan niin suurella määrällä vettä, että siitä valuu ulos 13,2-%:ista rikkihappoa.• 1 »4 92578 13.2% sulfuric acid contains 80 kg I ^ SO ^. It corresponds to the total amount of sulfuric acid that can be recovered at most by desulphurisation of the calcination gases produced by the calcination of 1 t of TiO 2. This sulfuric acid is formed in such a way that the SO2-containing calcination gases formed during the calcination of titanium oxide hydrate are passed through a bed containing moist activated carbon after washing with water. In the activated carbon layer, SO 2 is converted with H 2 O and H 2 O to H 2 SO 4. The carbon 10-ros is sprayed with such a large amount of water that 13.2% sulfuric acid flows out of it.
IIII
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Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3817445A DE3817445A1 (en) | 1988-05-21 | 1988-05-21 | METHOD FOR PRODUCING TITANIUM DIOXIDE |
| DE3817445 | 1988-05-21 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| FI892392A0 FI892392A0 (en) | 1989-05-18 |
| FI892392A FI892392A (en) | 1989-11-22 |
| FI92578B true FI92578B (en) | 1994-08-31 |
| FI92578C FI92578C (en) | 1994-12-12 |
Family
ID=6354921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI892392A FI92578C (en) | 1988-05-21 | 1989-05-18 | Method for producing titanium dioxide |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0343418B1 (en) |
| JP (1) | JPH0218324A (en) |
| DE (2) | DE3817445A1 (en) |
| ES (1) | ES2037322T3 (en) |
| FI (1) | FI92578C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006103999A (en) * | 2004-10-01 | 2006-04-20 | Murata Mfg Co Ltd | Method of manufacturing titanium oxide fine particle |
| EP2165974A1 (en) | 2008-09-17 | 2010-03-24 | L. Brüggemann Kommanditgesellschaft | Method for bleaching hydrolytically cut titanium hydroxide hydrate |
| JP2012028026A (en) * | 2010-07-20 | 2012-02-09 | Nippon Chem Ind Co Ltd | Negative electrode active material for lithium secondary battery, and method of manufacturing the same |
| DE102012017854A1 (en) * | 2012-09-08 | 2014-05-28 | Kronos International, Inc. | Infrared-reflecting pigment based on titanium dioxide and process for its preparation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1052188A (en) * | 1900-01-01 | |||
| US2999011A (en) * | 1959-12-31 | 1961-09-05 | Nat Lead Co | Method for bleaching hydrous titanium dioxide |
| US4113840A (en) * | 1974-09-19 | 1978-09-12 | Beamer/Wilkinson & Associates | Process for the removal of sulfur dioxide from exhaust flue gases |
| DE3826372A1 (en) * | 1988-08-03 | 1990-02-22 | Bayer Ag | METHOD FOR PRODUCING SULFURIC ACID AND DEVICE FOR CARRYING OUT THIS METHOD |
-
1988
- 1988-05-21 DE DE3817445A patent/DE3817445A1/en not_active Withdrawn
-
1989
- 1989-05-06 ES ES198989108213T patent/ES2037322T3/en not_active Expired - Lifetime
- 1989-05-06 EP EP89108213A patent/EP0343418B1/en not_active Expired - Lifetime
- 1989-05-06 DE DE8989108213T patent/DE58901456D1/en not_active Expired - Lifetime
- 1989-05-16 JP JP1120621A patent/JPH0218324A/en active Pending
- 1989-05-18 FI FI892392A patent/FI92578C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI892392A (en) | 1989-11-22 |
| JPH0218324A (en) | 1990-01-22 |
| DE3817445A1 (en) | 1989-11-23 |
| FI92578C (en) | 1994-12-12 |
| EP0343418A3 (en) | 1991-03-27 |
| EP0343418B1 (en) | 1992-05-20 |
| FI892392A0 (en) | 1989-05-18 |
| DE58901456D1 (en) | 1992-06-25 |
| ES2037322T3 (en) | 1993-06-16 |
| EP0343418A2 (en) | 1989-11-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| BB | Publication of examined application | ||
| MM | Patent lapsed | ||
| MM | Patent lapsed |
Owner name: BAYER AKTIENGESELLSCHAFT |