Untitled record

RESUME

ES NON-STECHIOMETRIC OXIDE DISPLAYING PROPERTIES

PHOTOCATALYTICS AND ANTI-BACTERIALS, PROCESS FOR

YOUR PREPARATION AND USE

The present invention relates to non-stoichiometric titanium oxide having improved antibacterial photocatalytic properties.

non-stoichiometric titanium oxide range of 10 has a m².g^_1, a rutile surface area content in the mean particle size range in the range of 100 specific

400 at one nm.

The oxide invention further relates to the process of producing said non-stoichiometric titanium. Titanium oxide obtained according to the process of the invention can be used in the ceramic and paint industries.

DESCRIPTION

ΤΙΤΑΝΙΟ NON-STECHIOMETRIC OXIDE DISPLAYING IMPROVED PHOTOCATALYTIC AND IAN — BACTERIAL PROPERTIES, PROCESS FOR THEIR PREPARATION AND USE OF THEREOF

FIELD OF INVENTION

The present invention relates to non-stoichiometric titanium oxide exhibiting improved photocatalytic and antibacterial properties, as well as its production process and the use of the resulting material.

BACKGROUND OF THE INVENTION Titanium dioxide is the most important white pigment used as such in the production of pigments, paper and ceramics. He is also involved in the production technologies of rubbers, plastics and various creams and cosmetics, including UV-protective preparations.

It is known that titanium dioxide can be prepared by hydrolysis of titanium chloride or sulfate at low temperature or by hydrolysis of titanium chloride at high temperature, with water required for hydrolysis from reaction between an oxygen-containing gas (eg. ar) and hydrogen according to equation (1):

TiCl₄ + 2H₂ + 0₂ -> Uncle₂ + 4 HCl (1) resulting titanium dioxide is generally present in the anatase and rutile crystalline forms.

Simultaneously with reaction (1) another reaction may occur, described by equation (2):

HCl + 0₂ -> 2 H₂0 + 2 Cl₂ (2)

Reactions (1) and (2) are responsible for the presence of acid gases adsorbed on the titanium dioxide particles.

Patent application WO 2008141891A1 relates to a process for the production of TiO₂ with sintering activity, where the TiCl flow rates₄, air and H₂ are selected so that in the equation:

A = 10⁵{[(TiCl₄ x H₂) / (amount of air x total gas)] / BET]}, where:

-TiCl molar flow units₄, H₂, air and total gas are kmol.kT¹;

-the BET unit, the specific surface area of ​​the TiO particles₂, in².g^_1; and

-A unit is 10⁵ g.irf²,

A is between 6 and 12.

According to said process, titanium tetrachloride is evaporated at a temperature below 200 ° C, fed into a mixing chamber and separately hydrogen and air preheated to a temperature in the range of 50 to 500 ° C are also fed to the mixing chamber; the vapor mixture of titanium tetrachloride, hydrogen and air is subsequently ignited in a burner and the flame is burned in a reaction chamber.

The obtained TiO 2 particles are then treated with water vapor at a temperature in the range of 450 to 550 ° C.

The resulting product has a specific surface area of ​​30 to 65 m². g^_1 and a rutile content of 50 to 70%.

The main disadvantage of the above process is the reduced photocatalytic and antibacterial activity of the resulting product.

Furthermore, when this product is calcined at a temperature above 800 ° C, as, for example, in the ceramic industry, said photocatalytic and antibacterial properties will be further reduced.

WO 2008076308A1 relates to a process for obtaining a titanium oxide exhibiting photocatalytic activity by reacting a titanium chloride (eg, titanium tetrachloride) with gas containing oxygen (eg, air) and hydrogen (H₂) .

Hydrogen is present in excess of the amount stegiometrically necessary to react with oxygen (molar ratio H₂:O₂ between 2.02: 1 and 2.61: 1), and in relation to the steguiometrically necessary amount to react with titanium chloride (TiCl molar ratio₄:H₂ between 1: 4 and 1: 2).

Oxygen-containing gas is dried, heated to 70-100 ° C, and saturated with TiCl vapor₄. Hydrogen is then added and the

<td>resulting mixture</td><td>is fed to</td><td>a device</td><td>in</td><td>burn,</td>

<td>the reaction taking place</td><td>from hydrolysis to</td><td>a temperature</td><td>at</td><td>gamma of</td>

<td>700 to 1100 ° C.</td><td></td><td></td><td></td><td></td>

<td colspan="2">The resulting titanium oxide</td><td>is then</td><td colspan="2">treated with</td>

steam at 150-200 ° C to remove residual amounts of HCl and Cl 2 produced in the reaction.

The final product comprises particles of 0,01-0,04 μιη with a specific surface area of ​​45 to 75 m². g^_1 and a photocatalytic activity of 1.4 to 3.0 mg. mLá¹. min^-1. m ~²(determined by methylene blue reduction reaction).

The main disadvantages of the above process are the low antibacterial activity of the product, which does not meet the requirements of ISO 27447: 2009 (E) as the results are less than 93%, insufficient sintering activity due to a low rutile content (45-55% rutile, the rest being anatase) and the high specific surface area of ​​TiCq particles.

In addition, due to the small particle size, the product may undergo aggregation when preparing an aqueous suspension, such as for application to ceramic materials, resulting in uneven distribution of titanium oxide on the surface of the ceramic material.

Accordingly, there is a need for an improved product which combines high levels of photocatalytic and antibacterial activity with high sintering activity. Such a product is particularly interesting in the ceramic industry, but can also be used in the paint industry.

SUMMARY OF THE INVENTION

The present invention relates to non-stoichiometric titanium oxide, comprising a mixture of rutile and anatase crystalline forms in the form of agglomerated particles having:

• a specific surface area in the range of 10 to 29 m²g^_1;

• a rutile content ranging from 71 to 85% by weight; and • an average particle size in the range 100 to 400 nm.

In one aspect of the invention, the titanium oxide further comprises HCl and CI2 present in a mass ratio in the range of 0.30% to 0.60%.

In one embodiment, titanium oxide has:

• a specific surface area in the range of 15 to 25 m²g^_1;

• a rutile content ranging from 75 to 82% by weight; and • an average particle size in the range of 200 to

300 nm.

In another preferred embodiment, titanium oxide has:

• a specific surface area in the range of 18 to 20 m²g^_1;

• a rutile content ranging from 77 to 80% by weight; and • an average particle size in the range of 240 to

275 nm.

The invention further relates to a process for producing said non-stoichiometric titanium oxide comprising the steps of:

• mix titanium tetrachloride, dry air and hydrogen, wherein the molar ratio of titanium tetrachloride to oxygen is between 1.0: 0.9 and 1.0: 0.99 and the molar ratio of hydrogen to oxygen is from 4.14: 1.0 to 5.56: 1.0;

Hydrolyzing titanium tetrachloride by igniting said mixture in a reaction chamber at a temperature in the range of 1110 ° C to 1200 ° C to produce titanium oxide particles;

• agglomerate the titanium oxide particles obtained in the previous step in a coagulator with a residence time of 20 to 30 s to produce agglomerated titanium oxide particles; and • separate solids from the gas stream.

In one embodiment, the process comprises the steps of mixing titanium tetrachloride, dry air and hydrogen, wherein the molar ratio of titanium tetrachloride to oxygen is between 1.0: 0.92 and 1.0: 0. 97 and the molar ratio of hydrogen to oxygen is from 4.52: 1.0 to 5.24: 1.0;

Hydrolyzing titanium tetrachloride by igniting said mixture in a reaction chamber at a temperature in the range of 1130 ° C to 1180 ° C to produce titanium oxide particles;

• agglomerate the titanium oxide particles obtained in the previous step in a coagulator with a residence time of 24 to 27 s to produce agglomerated titanium oxide particles.

In another preferred embodiment, the process comprises the steps of:

• mix titanium tetrachloride, dry air and hydrogen, wherein the molar ratio of titanium tetrachloride to oxygen is between 1.0: 0.93 and 1.0: 0.95 and the molar ratio of hydrogen to oxygen from 4.75: 1.0 to 4.83: 1.0;

• hydrolyzing titanium tetrachloride by igniting said mixture in a reaction chamber at a temperature of 1150 ° C to produce titanium oxide particles.

In one aspect of the invention the process further comprises a step of preheating the reagents to a temperature in the range of 25 to 50 ° C prior to the mixing step.

In one embodiment of the invention, the reagents are preheated to a temperature of 40 to 50 ° C prior to the mixing step.

In another embodiment of the invention, the reagents are preheated to a temperature of 50 ° C prior to the mixing step.

The invention also relates to the use of titanium oxide obtained according to the process of the present invention for the coating of ceramic articles, the titanium oxide being applied to the surface of the ceramic article at a deposition rate of 0.5 to 4 µm. .0 g titanium oxide per square meter surface of the ceramic article.

In one embodiment, the deposition rate of titanium oxide on the surface of the ceramic article is from 0.9 to 2.0 g of titanium oxide per square meter of surface of the ceramic article.

In another possible use, titanium oxide is incorporated into the paint production, the concentration of titanium oxide in the paint being between 5 and 20% by weight.

The use of the titanium oxide of the present invention results in ceramic articles and paints having substantially improved photocatalytic and antibacterial properties.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a titanium oxide exhibiting enhanced photocatalytic and antibacterial properties; the process of producing said titanium oxide by hydrolysis of titanium tetrachloride (T1CI4) in an oxygen-deficient air-hydrogen flame; and the use of the resulting material in the ceramic and paint industries.

<td>THE</td><td>activity</td><td>photocatalytic</td><td>particles is</td><td colspan="2">measured by</td>

<td>time</td><td>required</td><td>for reduction</td><td>from the blue of</td><td>methylene</td><td>The</td>

<td colspan="3">room temperature (300 K) as</td><td>described in</td><td>page 7</td><td>of</td>

<td>request</td><td>patent</td><td>international WO 200</td><td> 8/076308.</td><td></td><td></td>

<td>THE</td><td>definition</td><td>previous one requires</td><td>determination</td><td>of the area</td><td>in</td>

specific surface. The specific surface area, measured m².g^_1, is obtained by gas adsorption measurements according to the Brunauer-Emmett-Teller theory and is referred to as specific surface area BET or S_Bet ·

The average particle size is obtained from the particle size distribution measured with a sedigraph instrument where x-rays are used to determine the particle deposition velocity, from which the particle size is calculated using Stokes law.

Antibacterial activity is measured according to ISO 27447: 2009 (E) (Fine ceramics (Advanced ceramics, advanced technical ceramics) - Test method for antibacterial activity of semiconducting photocatalytic materials).

Unless otherwise stated, the percentages used in the present description refer to percentages by weight.

Regardless of the explicit presentation of a quantitative expression about X, any X value presented during the present description should be interpreted as an approximate value of the actual X value, as such approximation to the actual value would be reasonably expected by one skilled in the art due to experimental and / or measurement conditions that introduce deviations from the actual value.

Surprisingly it was found that when the hydrolysis reaction of TiCl₄ is carried out under non-stoichiometric conditions with oxygen deficit, particularly when the molar ratio of titanium oxygen tetrachloride is between 1: 0,90 and

1: 0.99, a non-stoichiometric titanium oxide is obtained which combines high levels of photocatalytic and antibacterial activity with high sintering activity.

In the present description, the term titanium oxide refers to a non-stoichiometric titanium oxide having the general formula TiO₍₂-_x)where x, related to oxygen deficit, is in the range 0.02 to 0.2.

According to the present invention, the process for the production of titanium oxide comprises the steps of:

a) Preparation of reagents

Titanium tetrachloride, air and hydrogen reagents are previously dried, heated to a temperature in the range 25 to 50 ° C, preferably 40 to 50 ° C, more preferably 50 ° C and homogenized in a mixture.

b) High temperature hydrolysis

The main physico-chemical transformation of the process is the hydrolysis of titanium tetrachloride in an oxygen deficient hydrogen flame as above.

The reaction temperature ranges from 1110 to 1200 ° C, preferably 1130-1180 ° C, more preferably 1150 ° C, and the molar ratios of the reactants are:

-N (TiCl₄) :AT THE₂) = 1.0: 0.9 to 1.0: 0.99, preferably N (TiCl₄) :AT THE₂) = 1.0: 0.92 to 1.0: 0.97; more preferably N (TiCl₄) :AT THE₂) = 1.0: 0.93 to 1.0: 0.95; and,

-N (H₂):AT THE₂) = 4.14: 1.0 to 5.56: 1.0, preferably N (H₂) :AT THE₂) = 4.52: 1.0 to 5.24: 1.0; more preferably N (H₂):AT THE₂) = 4.75: 1.0 to 4.83: 1.0.

As a result of the reaction intermediate titanium oxide particles ranging in size from 5 to 40 nm are obtained.

c) Agglomeration

The products obtained in the previous step are cooled from 1110 - 1200 ° C to 150 - 250 ° C (preferably 170 - 200 ° C) and fed to the coagulator with a gas velocity of 2 to 4 ms.^-1. The residence time of the reaction products within the coagulator is from 20 to 30 s (preferably from 24 to 27 s), allowing agglomeration of the intermediate particles to agglomerated particles with an average size in the range of 100 to 400 µm. nm, and a specific surface area BET, Sbet, in the range 10 - 2 9 m². g^_1.

d) Separation of agglomerated solid particles from the gas stream.

It should be noted that, unlike prior art processes, the titanium oxide resulting from the process of the present invention is not subjected to additional water vapor treatment to remove acidic gases (HCl and Cl₂) formed

<td>at</td><td colspan="2">reaction than</td><td>results a</td><td colspan="3">shorter cycle time,</td><td>costs</td>

<td>in</td><td>production</td><td>more</td><td>reduced</td><td>and improvement</td><td>at</td><td>activity</td><td>anti-</td>

<td colspan="2">bacterial</td><td>oxide</td><td>titanium</td><td>resulting.</td><td></td><td></td><td></td>

<td></td><td>0 oxide</td><td colspan="3">titanium obtained according to</td><td>with</td><td>the process</td><td>above</td>

described has the following characteristics:

Average particle size in the range 100 - 400 nm, preferably in the range 200 - 300 nm, more preferably in the range 240 - 275 nm;

- Specific surface area, S_Bet = 10-29 m²g^_1preferably SBet = 15-25 m²g^_1, more preferably SBet - 18 ^— 20 mg;

Rutile to anatase ratio between 71: 29% and 85: 15%, preferably between 75: 25% and 82: 18%, more preferably between 77: 23% and 80: 20%;

- Acid gas mass ratio (HC1 and Cl₂) adsorbed in the range of 0.30 - 0.60%.

In one embodiment of the invention, titanium tetrachloride may be substituted for a material known as distillation residue or unrefined titanium tetrachloride obtained as a by-product of the production of metallic titanium. Said distillation residue comprises titanium tetrachloride and chlorides of other metals such as silicon, iron, and / or vanadium. Typical distillation residue composition comprises 99.9% TiCl₄,

0.002% FeCl₃0.005% SiCl₄ and 0.002% CV1₃.

Titanium oxide obtained according to the process described above can be used in the ceramic and paint industries.

In order to obtain ceramic products exhibiting the desired antibacterial activity, an aqueous suspension comprising the titanium oxide obtained according to the process of the present invention and an adhesive is sprayed onto the surface of the ceramic material previously heated to 120-150 °. C, such that the deposition rate of titanium oxide on the surface of the ceramic article is in the range 0.5 to 4.0 g.²preferably in the range from 0.9 to 2.0 g.².

The ceramic articles are then heat treated in accordance with a temperature profile known to those skilled in the art.

The antibacterial activity of the resulting ceramic articles, measured according to ISO 27447: 2009 (E) within 4 hours against Escherichia coli ATCC 25922, is over 95%, which is a surprisingly high value never achieved in the products of the ceramic. prior art.

EXAMPLES

The following examples illustrate the process of producing titanium oxide according to the present invention.

Example 1

6.95 m³.re² dry (252.05 kmol.h ¹ O 2) at 45 ° C were placed in contact with titanium tetrachloride vapor, passing the dry air over

0.03 0 m³.re² (272.99 kmol.ré¹) in

Preheated to 45 ° C, and then mixed with

25, 72 m³.re² of hydrogen (1148.21 kmol.ré¹), homogenized in a mixing chamber and fed to a burner, where the reaction at a temperature of 1170 ° C is ignited and made in a reaction chamber.

Titanium oxide intermediate particles were agglomerated with a coagulator residence time of 24 s, and then cooled.

Titanium oxide thus obtained has the following properties:

-Specific photocatalytic activity = 3.2 mg.mL^-1 .min^-1 .m^-2; -Specific Surface Area, S_Bet = 24 m²g^-1;

Proportion between rutile and anatase = 75:25;

- average particle size = 218 nm;

Chlorine mass ratio = 0.45%.

Example 2

7.73 m³.H^-1 (259.34 kmol .h ¹ O 2) at 50 ° C were placed in contact with titanium tetrachloride vapor, passing dry air over

0.03 0 m³.H^-1 (272.99 kmol.h^-1) in

TiCl₄ preheated to 50 ° C, and then mixed with 27.88 m³.H¹ (PTN) of hydrogen (1244.83 kmol.h¹), homogenized in a mixing chamber and fed to a burner, where the mixture is ignited and reacted at a temperature of 1150 ° C in a reaction chamber.

The intermediate titanium oxide particles were agglomerated with a coagulator residence time of 27 s, and then cooled.

The titanium oxide thus obtained has the following properties:

-Specific photocatalytic activity = 3.3 mg.mLh¹ .mir® .m ~²;

-Specific Surface Area, S_Bet = 20 m²g^_1;

Proportion between rutile and anatase = 78:22;

- average particle size = 247 nm;

Chlorine mass ratio = 0.50%.

Example 3

28.86 m³.H^_1 (PTN) dry air (269, 91 kmol.iT¹ O2), preheated to 50 ° C, 0.030 m³.H^_1 of unrefined titanium tetrachloride (272, 72 kmol.h^-1) and 31.80 m³.H^_1 (PTN) of hydrogen (1419.73 kmol.h^-1) were fed to a burner as described in example 1 and the mixture reacted at a temperature of 1125 ° C in a reaction chamber.

The intermediate titanium oxide particles were agglomerated with a coagulator residence time of 20 s, and then cooled.

The titanium oxide thus obtained has the following properties:

-Specific photocatalytic activity = 3.5 mg.mLh¹.min^-1.naked²;

-Specific Surface Area, S_Bet = 28 m²g^_1;

Proportion between rutile and anatase = 73:27;

-Average particle size = 152 nm;

Chlorine mass ratio = 0.59%.

The following examples illustrate the use of titanium oxide obtained according to the process of the present invention in the ceramic and paint industries.

Example 4 (ceramic industry)

An aqueous suspension containing 63% solids was prepared by mixing 37 parts water, 6.3 parts titanium oxide obtained according to example 1 and 56.7 parts of an inorganic adhesive having the following chemical composition: 45.3- 49.0% S1O2;

15.2-18.7% A1₂O₃; 23.0-24.9% BaO; 4.6-6.8% CaO; 5.8-7.5% Na₂O.

The above suspension was spray-applied onto the surface of a ceramic article, previously heated to 150 ° C, at a deposition rate of 11.8 g of solids (1.18 g of TiO₂) per square meter of surface.

The ceramic article thus coated was then heat treated according to the following temperature profile:

<td>Warm</td><td>since</td><td> 150</td><td>° C to 880 ° C</td><td>in 17 min</td><td>0 2 s;</td>

<td>Warm</td><td>since</td><td> 880</td><td>° C to 1010 ⁰</td><td>C in 13 min</td><td>0 5 s;</td>

<td>Warm</td><td>since</td><td> 1010</td><td>° C to 1175</td><td>° C in 2 min</td><td>37 s;</td>

<td>Warm</td><td>since</td><td> 1175</td><td>° C to 1205</td><td>° C in 2 min</td><td>37 s;</td>

• Maintain temperature at 1205 ° C for 2 min 37s;

• Cool from 1205 ° C to 1110 ° C in 2 min 37s;

• Cool from 1110 ° C to 550 ° C in 4 min37 s;

• Maintain temperature at 550 ° C for 19 min 48s.

The antibacterial activity of the resulting ceramic article, measured according to ISO 27447: 2009 (E) at 4 hours against Escherichia coli ATCC 25922, was 98%.

Example 5 (paint industry)

An acrylic paint was prepared by mixing 39 parts water, 9.15 parts titanium oxide obtained according to example 1 and 51.85 parts of an acrylic base mixture.

The acrylic paint thus obtained has the following composition:

Polymeric acrylic emulsion (50% in water) as binder 49.4%;

Titanium Oxide - 15.0%

Calcium carbonate with an average particle size of 5 pm as inert - 15,0%;

Argilite as gelling material - 3,0%;

2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, commercially available as Texanol ™, from Eastman Chemical Company, as coalescent - 0.8%;

Water -14.3%;

Dispersing agent to facilitate mixing of components and stabilize dispersion of solids in water - 0.5%;

Ethylene glycol as antifreeze - 1.5%;

Viscosity modifier, to favor uniform application of paint - 0.4%; and,

NH₄OH-0.1% to adjust the pH in the range of 7 to 8.

The acrylic paint described above, incorporating 15% titanium oxide obtained according to example 1, was mixed with water and the resulting suspension sprayed onto the surface of a metal article to obtain a homogeneous paint layer. coating the entire surface of the article.

article thus obtained was dried during

The antibacterial activity of the article according to ISO 27447: 2009 (E) Escherichia coli ATCC 25922 was 97%.

September 2012

H.

measured in 4 hours against