CA1303329C

CA1303329C - Process for preparing pigmentary titanium dioxide

Info

Publication number: CA1303329C
Application number: CA 556812
Authority: CA
Inventors: Henrik R. Heikel
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1986-01-21
Filing date: 1988-01-19
Publication date: 1992-06-16
Anticipated expiration: 2009-06-16
Also published as: AU585187B1

Abstract

ABSTRACT

A process for preparing pigmentary titanium dioxide by grinding and mixing a titanium-bearing material, such as sorelslag, with an alkali metal compound, such as sodium hydroxide, and roasting the mixture. The roasted material is sandmilled followed by washing and filtering. Thereafter, the solid residue is digested with hydrochloric acid. After removing the acid by filtration and washing, the solid residue is calcined to provide a titanium dioxide pigment. By employing the proper process conditions, the process of the invention is capable of producing either nodular or acicular titanium dioxide pigment.

30,371-B

Description

~3~

PROCESS FOR PREPARING PIGMENTARY
TITANIUM DIOXIDE

This lnvention relates to a process for preparing pigmentary titanium dioxide from titanium dioxide-bearing materials. More particularly, it is desired to provide a simplified and relatively less expensive process for preparing a TiO2 pigment whereby the titanium values in titanium dioxide-bearing materials or ores are not solubilized or converted to a vaporizable liquid compound, but are separated, through solid-liquid reactions, from the ore's impurities and mechanically comminuted to pigmentary size.
The process provides a means of obtaining a TiO2 pigment which has either a nodular or a~ acicular particle shape.
- Titanium dioxide (TiO2) is a well-known opacifying pigment useful in paint and coating compositions, in plastic materials and as a filler in paper and other materials. Various known processes for producing TiO2 include, for example/ conventional processes commonly referred to as the "sulphate"
process and the "chloride" process.

30,371B-F

~3V;~3~

The "sulphate" process involves solubilizing the titanium values in low grade titanium ores, such as ilmenite or sorelslag, with concentrated sulfuric acid and meticulously removing ferrous sulfate formed in the process. This is followed by precipitation, washing, and calcining to form pigmentary TiO2.
The "chloride" process involves volatilizing, as tetrahalide, the titanium values in high grade titanium ores, such as Australian rutile (containing about.95 percent TiO2) or highly beneficiated ilmenite.
This is followed by purification and oxidation.
The sulphate and chloride processes are very complex and capital intensive which accounts for the relatively costly product of TiO2 pigment made by such processes.
The present invention is therefore directed to a process for preparing a titanium dioxide pigment comprising the steps of:
(a) comminuting a titanium bearing material to a article size of less than 15 microns;
(b) mixing said titanium dioxide bearing material with an alkali metal compound selected from alkali metal hydroxide, alkali metal carbonate and alkali metal oxide prior to, during or after said comminuting, the ratio by weight of said titanium dioxide bearing material and said alkali metal compound being from 100:30 to 100:60;
(c) roasting the mixture of step (b) at a temperature of from 700C to 950C;

30,371B-F -2-3~P
2a-(d) digesting the roasted material of step (c) in hydrochloric acid for a period of time of from 10 to 120 min; and (e) calcining the solid product formed in the digesting step (d) at a temperature of from 800C to 1000C to form a titanium dioxide pigment.

;~
~ 30,371B-F -2a-.. . .

~3~

Figure 1 is a schematic flow diagram of one manner in which the process of the present invention can be carried out.
The starting material for the process of the 5 present invention is a titanium bearing material, for example, sorelslag. Various grades of sorelslag may be used in the present process. For example, the composition of one typical grade of sorelslag, expressed as oxides, may consist of approximately 70 weight percent TiO2 and approximately 11 weight pe~cent FeO as an impurity with the remainder being impurities including, for example, CaO, MgO, SiO2, Al2O, MnO~ V2O5, Cr2O3 and other oxides as trace impurities. Another grade of sorelslag useful in the present process may consist of approximately 78 weight percent TiO2, approximately 8 weight percent FeO as an impurity, and the remainder impurities such as those listed above.
It is to be understood that the present invention is not limited to sorelslag. Other titanium-bearing materi~ls or ores as starting materials for thepresent invention are within the scope thereof. For example, "chloride slag" may also be used in the process of the present invention. A typical chloride slag may consist of approximately 85 weight percent TiO2, approximately 10 weight percent FeO as an impurity and the remainder impurities such as those listed above.
Another suitable raw material for the process of ~he present invention can be an intermediate product --- 30,371B-F _3_ formed during a beneficiation process of ilmenite such as that described in U.S. Patent No. 3~825,41. A
typical raw material formed during the beneficiation process above may consist of approximately 95 weight percent TiO2, approximately 1 weight percent FeO as an impurity and the remainder impurities such as those listed above.
Examples of other titanium bearing materials which can be used in the process according to the present invention are any titanium-bearing materials which are so treated that the titanium dioxide portion thereof becomes reactive with an alkali metal compound when heated at to a temperature of from 700C to 950C.
An alkali metal compound, as used herein includes, for examplel an alkali metal hydroxide, an alkali metal carbonate, or an alkali metal oxide or mixtures thereof.
All of the equipment used in the process of the present invention for grinding, mixing, roasting, filtering and calcining and all other operations are carried out by conventional equipment suitable for the purpose of continuous or batch type operation. For comminuting the titanium bearing starting material to micron size it is preferred to use "sandmills" of the type described and illustrated, for example, in U.S.
Patent No. 2,581,414. A "sandmilling" process will refer herein to a process of grinding a material to micron particle size using the type of equipment ~ described and illustrated, for example, in U.S. Patent No. 2,581,414. However, the grinding media used in such equipment is not limited to sand, but can be 35. glass, steel, ceramic or any other suitable grinding 30,371B-F 4-p ~5--media having a spherical or bead shape, generally, in the range of from 0.5 to 3 millimeters in diameter.
The digesting step has to be carried out in vessels with inner surface portions or linings resistant, under normal operating conditions, to the acid utilized in the process. Suitable materials for such surface portions are, for example, glass, FRP
~glass fiber reinforced polymeric composites), polyester, vinylester, epoxy and other suitable plastics, Hasteloy (Ni/Mo alloy), rubber, refractory metals (Ta, Zr, Cb) or acid resistant brick.
~ccording to a preferred embodiment of the present invention, the particle size of the titanium bearing material should be small enough for all or substantially all of the material to react with an alkali metal compound. With reference to Fiyure 1, the titanium bearing starting material is first ground, for example, by hammermilling to a size suitable for sandmilling. Hereinafter, the process of the present invention will be described with reference to sorelslag as the titanium bearing material but, as afore-mentioned, the material is not limited to sorelslag.
After the hammermilling step, the sorelslag ispreferably sandmilled to an average particle size of about 15 microns , more preferably, a particle size of about 10 microns. Even more preferably, the startin~
material may be sandmilled to a maximum particle size of 10 mi¢ron or less.` Particles larger than about 15 microns may occlude impurities which may not be ` readily removed from the starting material in the subsequent process steps of the present invention.

30,371B-F -5-1 ~ ~3 After the sorelslag is ground to the preferred particle size, it is intimately mixed with an alkali metal compound such as, for example, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal oxide or mixtures thereof. Alkali metals such as sodium, potassium~ lithium, rubidium, cesium or mixtures thereof may be used. The preferred compound is an alkali metal hydroxide, and more preferably, sodium hydroxide because it is readily reactive with the finely ground sorelslag material. Hereinafter, the process of the present invention will be described with reference to sodium hydroxide as the preferred alkali metal compound but it is understood that the present invention is not limited thereto.
Sodium hydroxide may be mixed with the sorelslag material prior to roasting and preferably during the sandmilling step above or, alternatively, prior to the sandmilling step. The mixture of sorelslag and sodium hydroxide can contain about 30 parts by weight ~pbw) or above of sodium hydroxide to 100 pbw of sorelslag. Preferably, from 30 to 60 pbw of sodium hydroxide to about 100 pbw of sorelslag is used. - 25 More preferably, the ratio by weight of sorelslag to sodium hydroxide is from 100:35 to 100:45. Using a ratio of sorelslag to sodium hydroxide above or below the range of from 100:30 to 100:60 is operable, however, it may result in an unsatisfactory TiO2 3 pigmentary product. When a material bearing a higher than 70 weight percent Tio2 content is used, the hydroxide portion of the mixture is increased accordingly.
After the sandmilling step, the mixture of sorelslag and sodium hydroxide is heated or roasted at temperatures of from 700C to 950C for a length of time of from l to 3 hours. At roasting temperatures above 950C a hard material or clinker may result, and below 700C the reaction between the sodium hydroxide and sorelslag may not be complete. It is, therefore, preferred to roast the mixture at a temperature of from 800C to 870C for 12 to 2 hours. Preferably, the roasted mixture is subsequently ground to a particle size of from 0.5 to 2 microns. As mentioned above, fine particles will enhance the removal of impurities during subsequent treatment of the roasted material.
During the roasting step, it is believed that the Tio2 contained in the mixture reacts with the sodium hydroxide forming a sodium titanate. Some of the impurities in the material may also react with the particular hydroxide used to form an alkali metal salt, leaving them in an extractable form. For example, when sodium hydroxide is used, the impurities in their alkali metal salt form include sodium vanadate, sodium chromate, sodium aluminate and sodium silicate, which are readily soluble in water~ These impurities are therefore preferably at least partially dissolved in water by washing, after the roasting step, to reduce, or more preferably, substantially entirely remove deleterious amounts of the impuritiesO Other compounds present in the starting material such as iron oxide, magnesium oxide and calcium oxide are soluble in 3 mineral acids, such as hydrochloric acid (HCl), and are removed during the digestion step as discussed below.
After the water soluble impurities are washed off or dissolved from the roasted material, the remaining insoluble alkali metal titanate with additional insoluble oxides is digested in hydrochloric 30,371B-F -7-::~L3~33~

acid. It is preferred to use about 6 normal tN) HC1 acid because a much weaker acid is not as effective as about 6 N. A stronger acid may be effectively used in -a pressurized container but tends to approach 6 N when boiled in a vessel open to the atmosphere. It is therefore entirely within the scope of the present invention to use acid concentra-tions of from as low as 5 N to as high a concentration as 12 N. However, when the concentration exceeds 6 N (which is the HCl azeotrope boilin~ at 108C) a pressure vessel is required. It is therefore mo,re practical to operate at atmospheric pressure.
At standard atmospheric pressure, the digestion step can be carried out at 80C or above and preferably under reflux at a temperature of from 90C to 110C, and more preferably at 108C, for a length of time ranging from 10 to 120 minutes, preferably from 10 to 40 minutes. Higher temperatures can be used, however, pressurized equipment may be necessary. The digestion step above may be carried out one or more times, however, it is preferred to carry out the digestion step at least two times.
~A nodular or an acicular TiO2 particle shape is ` obtained depending on how long time the roasted material (sodium titanate) dwells in 6 N ~Cl at a temperature below about 90C. When the 6 N acidic suspension in the digestion step is heated slowly (less -than 5C/min) to its boiling point of 108C, the process yields an essentially nodular Tio2. An acicular particle shape results from raisin~ the temperature of the digestion mixture very fast or by using an acid concentration below 4 N in the heating step and 30,371B-F -8-.

p~3V33~
g increasing the acidity to 6 N when the temperature has exceeded 90C.
In a preferred embodiment of the present invention, the roasted material is mixed with HCl at room temperature (i.e., from 20C to 30C)~ The roasted material/acid mixture is then heated, slowly, up to the boiling point of the acid at a rate of about 5C/minute or less, preferably from 2C/min. to 3C/min., and more preferably at 2C/min~ or less. It is believed that the nodular sodium titanate material is formed during the digestion step.
In either case, for obtaining a nodular or an acicular particle shape, the suspension of the washed roasted material in the about ~ N HCl is boiled with reflux for a length of time to substantially complete the digestion step. The boiling point, which varies with prevailing pressure, is in the range of 90C to ~ 111C and preferably about 108C. The digestion is substantially complete in from lO to 15 minutes.
Digestion times of up to about 120 minutes can be used but preferably the digestion time is from lO to 40 minutes. Higher heating rates and time may be used, - however, pressurized equipment may be necessary.
During the digestion step, the alkali metal titanate formed is believed to hydrolyze into amorphous hydrous TiO2-nH2O and the iron oxides solubilize as ferrous and erric chloride. The iron chlorides and other impurities in the acid suspension are removed by, for example, centrifugation or filtration and, optionally, disposed of or further treated to recover unreacted acid. The insoluble amorphous titanium dioxide residue is washed with a fluid such as water to 30,371B-F -9-3~h..~l further remove soluble impurities. Thereafter, the Tio2 is recovered from the water by, for example, filtering or centrifuging. A white residual cake results after this step is carried out.

The iron impurities in the Tio2 pigment are believed to be the cause of a non-white pigment.
Preferably the TiO2 pigment contains less than 520 ppm Fe and more preferabIy less than 200 ppm.
The amorphous TiO2 is calcined, preferably, or 30 to 60 minutes at temperatures ranging from 800C to 1000C to convert the TiO2 to its crystalline rutile form. More preferably, a temperature of from 875C to 925C for 30 minutes to one hour is employed, because undesirable discoloration of the resulting pigment is minimized and lower temperatures are not as effective in converting the product into its desirable crystalline form.
If the crystalline rutile product, which is either acicular or nodular in shape, obtained after calcination is severely agglomerated, it may be pulverized or sandmilled. The final particle size for the acicular version is from 0.05 to 0.3 micron in thickness and from O.l to l.0 mic-ron in length, preferably of about 0.2 micron in thickness and about 0.7 micron in length. Its value as an opacifier is dlctated by a narrow optimum size range.
When the crystalline rutile product is nodular in shape, the TiO2 particle has an average particle size of less than about l micron and preferably about 0.3 micron.

30,371B-F -10-`` ~3~33~

The TiO2 product can be used as a pigment in any of the typical applications for which opacifying pigments are used. As an illustration only and not to limit the scope of the the present invention, the TiO2 pigment obtained from the process of the present invention can be used as an opacifier in paint, paper or plastics. The opacifying power and brightness of the product is determined by measuring its light scattering coefficient and reflectance. Pigment obtained by the process of this invention desirably has a light scattering coefficient of above 2000 cm2/g, preferably above 4000 cm2/g, and more preferably above 9000 cm2/g, and a brightness of above 80 percent and preferably from 85 percent to 93 percent when measured in accordance to the method described in Examples l and 12.
The examples which follow are illustrative of the present invention but the present invention ought not to be limited thereby.
Exa~ple l A 600 gram (g) sample of hammermilled sorelslag ore, about 75 micrometers (~um), with approximately 70 weight percent TiO2 and approximately 30 weight percent impurities was dispersed in 450 milliliters (ml) of water. The sorelslag in suspension was sandmilled 3~ with 800 ml of 1.5 millimeters ~mm) diameter steelshot for 120 minutes (min.) at lQ00 revolutions per minute (rpm)~ The sandmill used was a vertical water-cooled laboratory sandmill constructed of stainless steel having a cylindrical grinding vessel with an inside diameter of ll.5 centimeters (cm) and a height of 19 cm; a shaft, driven by an air turbine, and two 8.5 cm diameter 30,371B-F

3 ~ 3 polyurethane disc impellers 4 cm apart. The peripheral velocity of the impellers was 4.4 meters per second (m/s). Speed was controlled with an optical tachometer. At completion of the sandmilling, the top size of the sorelslag particles was about l0 ~m, the average size being about 5 ~um. After the steelshot was removed from the slag suspension by screening through a screen having openings of 0.5 mm, 240 g of anhydrous sodium hydroxide (NaOH) was added to the slag suspension and then thoroughly mixedO The mixture, having a sorelslag/NaOH ratio of l00/40, was then evaporated to dryness in air in a shallow dish at 120C.
To break up any agglomerates formed after drying and obtain a homogeneous mixture, the dried material was hammermilled using a Weber Brothers Lab Mill S-500.
The resulting fine powder was roasted in air in porcelain crucibles for 2 hours at a temperature of 820C. A 150 g sample of the roasted material was pulverized in a mortar to remove any lumps formed after roasting and dispersed in 350 ml water. The roasted material and water was sandmilled with 700 ml of l.2 mm diameter glass beads for 30 minutes at l000 rpm. Glass beads were used in this sandmilling step instead of steelshot to avoid discoloration of the material caused by steelshot.
After removing the beads by screeniny, the sandmilled roasted material and water dispersion was 3 centrifuged. The solid residue for~ed after centri-fugation ~solids) was washed by redispersing in water and recentrifuging. The washing was repeated twice.
The solids were then dispersed in l000 ml of (about 100C) 6 N HCl acid and boiled at a temperature of about 108C in an open beaker while agitating with a 30,371B-F ~12-~3~332 magnetic stirrer for 9o minutes. The acidic liquor containing the solids was centrifuged. The solids were washed with water twice and dried in air at 120C. The dried solids were then calcined for 1 hour at 900C
The density of the resulting white calcined product was 4.14 g/cm and X-ray diffraction analysis showed the calcined product had a rutile structure.
Electron transmission microscopy revealed pigmentary grade TiO2 particles with an acicular shape. The particle size of the acicular pigment ranged from 0.05 to 0.3 ym thick and from 0.1 to 1.0 ~m long.
The bri~htness (R~) of the pigment was 88.4 percent based on the measurement of light reflectance of a fumed magnesium oxide surface having a 100 percent reflectance, and its scattering coefficient (S) was 6,835 square centimeters per gram (cm2/g). The iron (Fe) content of the pigment was determined by X-ray fluorescence and found to be 520 parts per million (ppm).
Determininq Scatterinq Coefficient (S) and Briqhtness (R~) The primary function of a TiO2 pigment is to provide opacity to a material, such as paint, paper, plastics, etc., in which it is incorporated as a uniform dispersion. Of the many modes used for 3 expressing a pigment's opacifying power, the term scattering coefficient is particularly meaningful and.
can be easily determined accurately and reproducibly.
The principle of this test is to make a thin film of the pigment over a black plate glass so that the film is slightly translucent, i.e., has a 30,371B-F -13-3~ ~ 3 reflectance of about 80 to 90 percent of that of the reflectance of a thick, completely opaque film.
Another film of the same dispersion is applied on a white glass plate and made so thick that a further increase in thickness does not change its light reflectance. When the reflectances of these two films (R and R~), respectively, are measured and the weight ~W) of the film coating over the black plate is determined (weight of dry film per unit area, g/cm2), the scattering coefficient S (cm2/g) can be calculated using the Kubelka-Munk Theory of light scattering (Zeitschrift. fur Tech. Physik, 12, 593, 1931). The reflectance measurement of the film over the white ~lass, R~, is often referred to as brightness. Tables, based on Kubelka-Munk equations are found in an article by Mitton-Jacobsen, "New Graphs for Computing Scattering Coefficient and Hiding Power," Official Digest, September, 1963, pages 871-913. Using the tables of the above article, S can be easily computed knowing R, R~r and W. Example A, below, further illustrates a method of determining S.
Example A
A pigment is dispersed in water and a small amount of binder is added which as a film former makes a coherent film when the dispersion is cast on glass plates for reflectance measurements. Since the opacity of the film is very sensitive to the volume ratio of pigment to binder, this ratio must be kept accurately constant and at high enough level at which the opacifying power of the pigment is not appreciably depressed by the presence of binder. Tests are run at pigment volume concentration (pvc) of 70.00 percent (pigment's volume = 70.00 percent of total solids 30,371B-F -14-~3(~3;~ f~

volume and total solids volume = pigment volume +
binder volume) and at low enough solids content so that the film, when cast with a 37 ~m applicator on black glass will be slightly translucent (having a reflectance of about 80-90 percent of that of the reflectance of a thick, completely opaque film of the same dispersion). A solids volume of about 4 percent is a suitable level for TiO2 dispersions (pigment volume + binder volume = 4 percent of total volume of dispersion). An example of a film composition with TiO2 pigment for testing S and R~, is described in Table A below:
TABLE A
ml ml Grams gJml VolumeVolume Weiqht Density of of Solids Dispersicn TiO2 pi~ent sample 15.00 4.20 ~.57 3.57 Nalco 2324 Di~persantl0.50 1.00 0.50 Dispersant Binder (50.1~
solids by weight)2 3.06 1.04 1.53 3.11 Water 120.32- 1.00 120.32 138.88 5.10 127.50 An anionic polyacrylate disper.sant, sold under the trade name "Nalco~ 2324" by Nalco Chemical Company.
2A carboxylated styrene-butadiene latex sold under the trade name "Dow Latex 620A" by The Dow Chemical Company.

In the above composition the pvc.= 70.OG percent and solids volume of dispersion solids = 4.00 percent.
The pigment, water and dispersant is mixed for 5 minutes with a homogenizer sold under the trade name "PT 45!80 Brinkmann Homogenizer" by Brinkmann 30,371B-F -15-` ~ 3 ~ 3 Instruments Company, at speed setting 4. Then Dow Latex 620 is added and the mixture is stirred at speed setting 2 for s minutes.
A Bird Film Applicator, commercially available from Gardner Laboratory, a Division of Pacific Scientific Company, having a width of 15 cm and a gap of 0.037 mm is placed on the top edge of an 50 x 50 cm black glass plate (reflectance - 0) and about 3 ml of the dispersion is put in front of the applicator. The applicator is drawn down on a glass plate uniformly with an even speed. The film is allowed to dry at room temperature in a horizontal position. Using a Bird applicator with a gap of 75 ~m, the same dispersion is drawn down on a white glass plate (reflectance = 85.6).
After the films are allowed to dry For about 2 hours, a 5 x 6.25 cm rectangular template, having an area of 32 cm2, is placed over the film on the black ~ plate and the coating outside the template is removed with a razor blade leaving a 32 cm2 rectangular patch on the black plate. Next, a Photovolt reflectometer equipped with an external digital voltmeter and a search unit with a blue filter, having a wavelength of - 457 nanometers and sold under the trade name Wratten filter by Eastman Kodak Company, was used to measure the reflectances of the patch on the black plate and the coating on the white plate. Next, the patch on the black glass is removed with a razor blade and weighed on an analytical balance.
The following values represent an example:

30,371B-F -16-R - 79.5 R~ - 92.0 ~ = 0.0186 gram/32 cm2 or 0.000577 g/cm2 From Table 8, on page 895 of the article by Mitton-Jacobsen above, and given the above values for R and R~
the scattering power (SW) is found to equal 4.09. The scattering coefficient (S) can then be calculated as follows:

W 0.000577 g/cm2 = 7088 cm2/g Example 2 A 600 g sample of sorelslag with approximately 70 weight percent TIO2 and approximately 30 weight percent impurities was sandmilled as in Example l. The steelshot-ground suspension contained 57 percent slag.
175 g of this suspension (=lO0 g solid slag) was mixed with 67 g anhydrous Na2CO3, dried, hammermilled and roasted for 2 hours at 1050C. The hard, roasted material was broken into 3.6 mm bits in mortar and then hammermilled into fine powder which was further - sandmilled with glass beads as in Example l.
The roasted material was dispersed in water and separated centrlfugally and washed as in Example l, and 3 digested in 1000 ml of 6 N HCl for 90 minutes, followed by solids separation and washing as in Example 1.
After calcining for l hour at 900C, a white pigment having a rutile structure and a density of 4.l0 g/cm3 3~ was obtained. The pigment had a brightness of 78~3 percent and an S of 4,128 cm2/g.

30,371B-F -17-~ ~33~

Example 3 A 600 g sample of hammermilled sorelslag with approximately 70 weight percent Tio2 and approximately 30 weight percent impurities ~as sandmilled with steelshot as in Example 1. The screened steelshot was washed with water. The wash water was combined with ground slag suspension. With the added water the suspension had a solids content of 45.9 percent.
' 10 A 327 g sample of the slag suspension (=150 g solid slag) was mixed with 52.5 g anhydrous NaOH
resulting in a slag/NaOH ratio of 100:35. The mixture was evaporated to dryness at 120C, followed by hammermilling and then roasting for 2 hours at 800C.
Without further sandmilling, the roasted material was dispersed in water and centrifuged. The separated solids were washed with water twice by redispersing in water and recentrifuging. The washed roasted material was then boiled fo~ one hour in 1000 ml 6 N HCl in an open beaker. After digestion in the acid liquor the solids were separated and washed centrifugally two times. The solids were then redispersed in 300 ml water and sandmilled with 700 ml glass beads for 60 minutes at 1000 rpm. After the glass beads were screened out, the white, opaque suspension was mixed with an equal volume of 12 N HCl and boiled for lG
minutes in an open beaker (the final boiling point being about 108C). The solids were then separated and washed twice with water and dried at 120C~ The solids were then calcined for l hour at 900C. A pigmentary TiO2 having a density of 4.0 g/cm and an iron content of 150 ppm was obtained. The pigment had a brightness of 8B.9 percent and a~n S of 3~760 cm2/g.

30,371B-F -18-~ 3V ~

Example 4 A 327 9 sample of steelshot ground soxelslag suspension prepared in Example 3 ~=150 g solid slag) was mixed with 45 g anhydrous NaOH (the slag/NaOH ratio = 100/30). The mixture was evaporated to dryness at 120C, followed by hammermilling and roasting as in Example 3. The two digestion steps and other processing steps were also performed as in Example 3.
This example was carried out to determine the affect of reducing the amount of NaOH added to the sorelslag material of Example 3 on final pigment properties.
After calcination, the pigmentary Tio2 obtained was buff in color and had an iron content of 8300 ppm.
The pigment had a brightness of about 50 percent. The value of S was not determined.
Example 5 A 600 g sample of hammermilled sorelslag with approximately 70 weight percent TiO2 and approximately 30 weight percent impurities was dispersed in 480 g 50 percent NaOH solution (the slag/NaOH ratio = 100/40)~
~5 The suspension was sandmilled for 150 minutes at 900 rpm with 800 ml steelshot with the sandmill described in Example 1. The sandmilled suspension had solid particles up to about 13 ~m in size with the average size being about 7 ~m.
After the steelshot was screened from the suspension, the suspension was dried at 120C, hammer-milled and roasted for 2 hours at 850C.
A 150 9 sample of the roasted material was sandmilled with 700 ml glass beads and 350 ml water at .
30,371B-F -19-~3~3~
~20-1000 rpm for 10 minutes. After the glass beads were screened out, the solids were separated centrifugally and washed twice. The solids residue formed after centrifugation was then dispersed in 500 ml of 10.8 N
HCl and boiled with reflux at 107C for 25 minutes. The solids were separated from the acid liquor centri-fugally and washed once with water. The centrifuged solids were redispersed in 500 ml 7 N HCl and boiled with reflux at 108C for 30 minutes. The solids were 0 separated from the acid liquor centrifugally and washed three times. The centrifuged solids were dried at 120C
and calcined for 45 minutes at 900C. A pigmentary TiO2 was obtained with an iron content of 65 ppm. The pigment had a brightness of 90.5 percent and an S of 4,472 cm2/g.
Example 6 A 400 g sample of hammermilled sorelslag with approximately 70 weight percent TiO2 and approximately 30 weight percent impurities was dispersed in 2B0 ml water and 180 g anhydrous NaOH (the slag/NaOH ratio =
100/45). The suspension was sandmilled for 150 minutes at 1350 rpm with 600 ml of 1O5 mm steelshot with the sandmill described in Example 1.
After screening out the steelshot, the sand-milled suspension was dried at 120C, hammermilled and roasted for 2 hours at-840C. A 150 g sample of roasted material was dispersed in 350 ml water and sandmilled with 70~ ml of 1.2 mm diameter glass beads for 10 minutes at 1000 rpm. After screening, the glass beads, the suspension was centrifuged and washed twice. The washed centrifuge cake weighed 234 g and contained 96 g water, Thus, the yield of solid roasted material was 30,371B-F -20-~3~

138 ~. This cake was dispersed in 300 ml water and 605 ml 12 N HCl. The liquid portion resulted in a 7.3 N HCl which after neutralization of solids became 6 N. Digestion with reflux at 108C lasted 20 minutes.
The solids were separated from the acid liquor centri-fugally and washed twice, then redispersed in 600 ml 6 N HCl and digested another 20 minutes, followed by centrifugal solids separation and 2 washings. The solids were then dried at 120C and calcined for 1 hour at 300C. A TiO2 pigment was produced with an iron content of 30 ppm. The pigment had a brightness o 90.1 percent and an S of 6,170 cm2/g.
Example 7 In this example, the sorelslag/NaOH ratio was changed to 100/50 and processed as follows:
A 600 9 sample of hammermilled sorelslag with approximately 70 weight percent TiO2 and approximately 30 weight percent impurities was dispersed in 400 ml of water and sandmilled with 800 ml of 1.5 mm steelshot for 120 minutes at 1800 rpm with the sandmill described in Example 1. The steelshot was removed by screening.

Into 200 ~rams of this slag suspension, containing 120 g sorelslag, 60 g of anhydrous NaOH was solubilized and dried in a shallow dish in an oven at 120C. The dried material was hammermilled and roasted 3 for 2 hours at 840C. The roasted material was - dispersed in 350 ml of water and sandmilled with 700 ml of 1.2 mm diameter glass beads for 10 minutes at 1000 rpm. After screening the ylass beads, the sandmilled roasted material was vacuum filtered in a 15 cm diameter Buchner funnel with a filter paper 30,371B-F -21-33~

having a pore size of about 7 microns made by W&R
Bolton, Ltd., England, and sold under the trade name "Whatman Filter Paper No. 541" and washed with about 2 liters of water. The washed roasted material was then digested with reflux in 1000 ml 6 N HCl at 108C
for 20 minutes. Then 7 g of a 1 percent solution of a first flocculating agent was added. The first flocculating agent added was a cationic homopolymer manufactured by The Dow Chemical Company of the type generally described in U.S. Patent No. 3,719,748. The flocculated suspension was vacuum filtered and washed on the filter with 2 liters of water. The filter cake was dispersed in 1000 ml of 6 N HCl at about 30C and the temperature was gradually raised (within about 20 minutes) to the boiling point of 108C which was maintained for 20 minutes. Then 1000 ml of cold water and 7 g of a 1 percent solution of a second flocculating agent was added. The second flocculating agent, also manufactured by The Dow Chemical Company, was a slightly anionic homopolymex of acrylamide in solid form with a degree of hydrolysis of from 1 to 5 percent. Viscosity of a 0.5 percent solids in water solution at a pH of 3 and 25C of the second flocculating agent was in the range of from 31 to~5a - centipoise (cp). The flocculated suspension was vacuum filtered and washed with 2 liters of water followed by drying at 120C. The solids were calcined for 1 hour at 900C.
Electronmicrographs revealed a nodular or non-acicular shaped pigment. An X-ray diffraction analysis confirmed that the pigment had a rutile structure.
S-value was 2408 cm2/g and the brightness 83.9 percent.

30,371B-F -22-Example 8 In this example, a titanium bearing material, referred to as "chloride slag" with approximately 85 weight percent Tio2 and approximately 15 weight percènt impurities was used to produce a pigmentary TiO2. This material, in granular form, had a particle size of about 840 um.

0 A 400 g sample of this material was mixed with 200 9 anhydrous NaOH and 300 ml water. The mixture was sandmilled, using the sandmill described in Example 1, with 700 ml of 1.5 mm steelshot at 1500 rpm for 240 minutes to an average particle size below about 10 ~m. After the steelshot was screened from the sandmilled suspension, the suspension was dried at 120C, hammermilled and roasted for 2 hours at 840C.
A 150 g sample of the roasted material was dispersed in 350 ml of water and sandmilled at 1000 rpm with 700 ml glass beads for 10 minutes. The glass beads were screened out from the suspension and then the suspension was centrifuged. The centrifuge cake was washed 4 times. The centrifuged cake was digested in 1000 ml of 6 N HCl for 20 minutes with reflux at 108C. At the end of the digestion, S g~of a 1 percent solution of the first flocculating agent described in Example 7, was added to the digested material and the flocculated suspension was vacuum filtered. The filter cake was then washed on the filter with 1000 ml water.
- The washed filter cake was digested a second time- in 1000 ml of 6 N HCl for 20 minutes with reflux at 108C.
After digestion, 5 g of a 1 percent solution of the second flocculating agent described in Example 7, was added to the digested material. The flocculated 30,37lB-F -23-suspension was then vacuum filtered and washed with 2 liters of water on the filter. The filter cake was then dried at 120C. The solids were calcined for l hour at 900C. A pigmentary TiO~ was obtained having an S of 5,670 cm2/g and a brightness oE 89.0 percent.
Example 9 A 500 g sample of hammermilled sorelslag with approxlmately 78 weight percent TiO2 and approximately 22 weight percent impurities was dispersed in 350 ml water and sandmilled for 180 minutes at 1800 rpm with 800 ml of 1.5 mm steelshot with the sandmill described in Example 1. The peripheral velocity of impellers was 8 m/s.
The ground slag was screened through a 425 ~m screen to remove the steelshot. The steelshot was rinsed with water and the rinse water was combined into the slag grind resulting in a slag suspension having a solids content of 24.5 percent.
Into 612 g of this slag suspension (=150 g solid slag), 67.5 g anhydrous NaOH was added giving a sorelslag/NaOH ratio o 100/45. The mixture was evaporated to dryness at 120C in a shallow dish. The dried material was hammermilled to obtain a homogeneous fine powder. The powder was then heated or roasted in a porceIain crucible for 150 minutes at 840C. Upon 3 cooling, the roasted material was pulveri7ed in a mortar. The roasted matexial was then dispersed in 350 ml of water and sandmilled for 10 minutes at 1800 rpm in the laboratory sandmill above using 700 ml of 1.2 mm diameter glass beads as srinding media. The sandmilled roasted material was screened free of , 30 9 37lB-F ~24-3~

beads, diluted to 1500 ml with water and vacuum filtered through a 15 cm diameter Buchner funnel using No. 541 Whatman paper. The filter cake, being abou-t ? cm thick was washed on the filter with about 2 liters of water. Solids content of the filter cake was 62.6 percent.
The washed filter cake was dispersed in 300 ml of ~ater plus 200 ml 12 N HCl. The mixture having a normality of about 4.4 was put into a 2 liter, 4-necked glass flask equipped with a reflux condenser, a thermometer, an agitator and a funnel with a stopcock.
The dispersion was heated up to a temperature of 100C.
Thereafter, to raise the acidity to 6 N, 400 ml 12 N
HCl was added into the flask. The temperature dropped momentarily to 85C, however, within 5 minutes the temperature reached 108C, the boiling point of 6 N HCl.
The mixture was boiled for 20 minutes and then diluted with cold water to 2000 ml. Under continued agitation, 7 g of a l percent solution of the first flocculating agent, described in Example 7, was added to the mixture.

The mixture now beiny about 3 N was vacuum filtered. T~e filter cake was washed on the filter with 2 liters of water. The solids content of the ilter cake was 32.5 percent.
The filter cake, weiyhing 323 g (solids -105 g), was dispersed in a solution containing 280 ml of water plus 200 ml of 12 N HCl. This mixture was placed in the 4-necked glass flask and heated to 100C.
Thereafter 300 ml of 12 N HCl was added to the mixture.
The temperature was raised to 108C boiling point of 5 N
HCl and kept at this temperature for 20 minutes. The 30,371B-F -25- -~ 3~ 3 mixture was diluted to 2000 ml with cold water. Under continued agitation, 7 g of a 1 percent solution of the second flocculating agent described in Example 7, was added to the mixture. The mixture was filtered and washed the same as after the first digestion.
The filter cake, about 3 cm thick, was dried at 120C, and thereafter ground in a mortar. The ground cake was calcined for 1 hour at 900C. The calcined material was immediately placed in a large shallow porcelain dish and cooled at room temperature exposed to air. A pigmentary TiO2 was obtained.
An X-ray diffraction analysis identified the pigment as rutile which had a density of 4.1 g/cm3.
The pigment had an S of 6,900 cm2/g and a brightness of 92.2 percent. The crystal habit was acicular.
Example 10 A TiO2 pigment was produced as in Example 9, except that the sorelslag/NaOH ratio was changed to 100/40 and the NaOH was added to the sorelslag prior to sandmilling rather than after the slag was sandmilled.
The acicularly shaped pigment had an S of 8,900 cm2/g and a brightness of 31.0 percent.
Example ll 3 A titanium-bearing material made ~uring the Benilite Cyclic Process from ilmenite by reduction roasting and subsequent HCl acid leaching was used as starting material in this example. This black material had approximately 93 weight percent Tio2 and 30,371B-F -26-~3~332'~

approximately 7 weight percent impurities and a particle size of about 250 ~m.
A 400 g sample of the material was mixed with 200 g NaOH, and 350 ml H2O and sandmilled with the sandmill described in Example 1 with 600 ml of 1.5 mm ` steelshot for 90 minutes at 1600 rpm. The sandmilled material contained particles with an average size of below about 10,~m. After the steelshot was screened out, the ground material was dried at 120C, hammer~
milled and roasted for 2 hours at 840C. A 170 g sample of roasted material was dispersed in 350 ml of water and sandmilled with 700 ml of glass beads at 1600 rpm for 10 minutes. After the beads were screened out, the suspension was centrifuged and the centrifuged cake was washed 2 times with water.
The centrifuged cake was digested with reflux in 1000 ml 6 N HCl for 20 minutes. The solids were separated from the acid liquor and washed centri-fugally. A second digestion also in 1000 ml 6 N HCl was carried out followed by centrifugal separation and washing. The solids were dried at 120C and then calcined for 1 hour at 900C. An a,cicularly shaped~
pigmentary TiO2 was o~tained. The pigment had an S'of 4,260 cm2/g and a brightness of 90.0 percent.
Table I, below, summarizes the examples above excluding Examples 2, 8 and li.

30~371B-F ~27- ,, , ~3V~
-` --28--~ ~1 ~ ' o L~ ~ ~ N O
~ ~ 0 0 0 0 0 ~ ~ ~
S., C CO oo U~ 0 O~
m~

~ ~ o ~ o 0 o o ~ ~o ~ ~ o o o E~ D N

o o L~ o O ~
S . ~ ~ J N N N N N
~
H Z ~ ~

n ~ ~ z o = ~ O O n ~_ U~

n C ~ O O O O ~ O O O

o o U~ o o ~ o ~ o ~d ~ ~ t`~ J ~ ~ J
o z ~ ~ ~ ~ ~ ~ ~ ~
~ oooooooo ~ o o o o o o o o ~ V~ ~ ,_ ~ ,_ ~ ,_ ~ ,_ a~ O

30, 371B-F -28-3~

Example 12 A sorelslag sample with a particle size of about 74 microns was obtained from QIT-FER ET TITANEr INC., a Canadian company. A 1200 9 sample of the sorelslag and 480 g of sodium hydroxide (NaOH) were placed in a laboratory sandmiil containing one liter of 1.2 mm in diameter steel shot and about 1,000 ml of water. The mixture was then sandmilled until the maximum particle size (top size) of the sorelslag was 10 microns. The slag/NaO~ ratio of the mixture was 100~40 by weight. After the steel shot was screened out~ the mixture was dried in an oven at a temperature of 100C. The dried material was hammermilled to break up the agglomerates formed after drying.
The hammermilled material was then roasted at a temperature of 875C or two hours. The roasted material was run through a grinder to break up the 2Q agglomerates formed after roasting and then the roasted material was sandmilled for five minutes in about 700 ml of water and one liter of 1.2 mm in diameter zirconium oxide beadsO After the beads were scr~ened out, the suspension was vacuum filtered and the filter cake was washed with water two times, each wash using about one liter of waterO
A 194 g sample of the roasted material on a dry basis was digested in 1,0C0 ml of 6 N hydrochloric acid (HCl). The digestion step was carried out as follows:
The temperature of the 6 N solution (i.e. roasted material/acid mixture) was at room temperature (20C).
Then the temperature was increased slowly at a rate of about 5C/minute up to the boiling point of the 6 N acid solution and the solution was allowed to reflux for lS

30,371B-F 29-3~ 3 minutes. The amount of water in the wet filter cake was taken into account when the normality of the HCl acid was calculated. A flocculant, 3 g of a 1 percent solution of SEPARAN MG-205 ~a trademark of The Dow Chemical Company) was added to the digestion suspension. The suspension was filtered and washed two times with wat~r, each wash using about one llter of water. The filter cake was redispersed in water and digested a second time with 800 ml of 6 N HCl in the 0 same manner as ~he first digestion. The same amount of flocculant as in the first digestion was added to the suspension. The suspension was then vacuum filtered and washed as in the first digestion. A filter cake was dried at a temperature of 110C for about three hours. The dried material was then calcined for one hour at a temperature of 900C. The obtained rutile pigment had a distinctly nodular particle shape.

20The dry brightness of the calcined material was measured by packing a portion of the material into a sample vial cap which was about 1.3 cm deep by 2.5 cm inch in diameter and measuring the reflectance of the sample using a Photovolt equipped with a blue filter.
The instrument was first calibrated by using a white - standard chip of known brightness of 86.9 with the blue - filter. The dry brightness of the calcined material of this example was 88.0 percent.
.
30The scattering coefficient oE the calcined material was me~sured by the following procedureO
A 15 g sample of pigment and 1/2 g of sodium tripolyphosphate in 70 g of water was dispersed in a high speed disperser for 5 minutes. Then 3.1 g of a latex sold under the trade name Rhoplex ~100 by Rohm , 30,371B-F -30 -~ ~ 3 and Haas Co. and 1/2 g of a surfactant sold under -the ~- trade name Triton X-100 by Rohm and Haas Co. was added to the dispersion and stirred gently by hand for about 3 minutes. A drawdown coating of the dispersion was applied on a 50 um thick clear plastic sheet of Mylar (a trademark of E.I. DuPont de Nemours & Co.) with a 37 ,um Bird film applicator and placed in an oven and dried at a temperature of 100C for 3 minutes. A 5 cm by 5 cm square sample of the coated Mylar sheet was weighed and then placed on a 5 cm by 12.5 cm optically flat black glass plate which was coated with propylene glycol. The propylene glycol was used to ensure optical contact. Using a Photovolt the reElectance over the black glass, RBI was measured for the sample.
The coating on the 5 x 5 cm Mylar sheet was washed off and the Mylar sheet was dried and then weighed to find the coating weight per unit area, W. A practical approximation to an infinitely opaque coating, R~, was obtained as follows: A drawdown coating was applied on a sheet of 50 micron Mylar and dried and this step was repeated until a maximum reflectance was reached as measured by the Photovolt. Using the RB, R~, and W
values, a scattering power value~ SW, was found by using the Tables in the article Mitton Jacobsen, "New Graphs for Computing Scattering Coefficient and Hiding Power", Official Digest, September 1963, pages 871-913.
The scattering coefficient, Sj was then calculated using the formula:

SW

30,371B-F -31-:~3~3;~

In this example the scattering coefficient of the calcined material was 3,336 cm2/g.
The iron content of the calcined material was measured using ionic coupled plasma spectrometry. In this example the iron content of the calcined material was 200 ppm.

30,371B-F . -32-

Claims

1. A process for preparing a titanium dioxide pigment comprising the steps of:

(a) comminuting a titanium bearing material to a article size of less than 15 microns;

(b) mixing said titanium dioxide bearing material with an alkali metal compound selected from alkali metal hydroxide, alkali metal carbonate and alkali metal oxide prior to, during or after said comminuting, the ratio by weight of said titanium dioxide bearing material and said alkali metal compound being from 100:30 to 100:60;

(c) roasting the mixture of step (b) at a temperature of from 700°C to 950°C;

(d) digesting the roasted material of step (c) in hydrochloric acid for a period of time of from 10 to 120 min; and 30,371B-F -33-(e) calcining the solid product formed in the digesting step (d) at a temperature of from 800°C to 1000°C to form a titanium dioxide pigment.

2. The process of Claim 1, wherein said titanium dioxide bearing material is selected from sorelslag, beneficiated ilmenite, and chloride slag, and wherein said alkali metal compound is an alkali metal hydroxide.

3. The process of Claim 1, wherein the titanium dioxide bearing material is sorelslag and the alkali metal hydroxide is sodium hydroxide, and wherein the comminuting takes place in a sandmill to a particle size of less than 10 microns.

4. The process of Claim 1, 2 or 3 wherein the roasted mixture of step (c) is washed with water for removal of water-soluble impurities and wherein the titanium dioxide obtained in step (d) is washed with water and recovered from the water by filtering or centrifuging.

5. The process of Claim 1, 2 or 3, wherein the roasted mixture of step (c) is digested in hydrochloric acid in step (d) at a temperature of from 90°C to 110°C to form a hydrated, amorphous titanium dioxide material, and washing said titanium dioxide material prior to calcining in step (e).

6. The process of Claim 5, wherein the digestion of the roasted material in step (d) is carried out for a time of from 10 to 40 minutes.

7. The process of Claim 1 or 2, wherein the titanium dioxide pigment from step (e) is micronized to 30,371B-F -34-form particles of a size of about 3 microns when the titanium dioxide pigment is nodularly shaped.

8. The process of Claim 1 or 2, wherein the titanium dioxide pigment of step (e) is micronized to form particles of a size of 0.1 to 1.0 microns in length and 0.05 to 0.3 microns in thickness when the titanium dioxide pigment is acicularly shaped.

9. The process of Claim 1, wherein the titanium oxide pigment produced has an iron content of from 30 to 600 ppm.

10. The process of Claim 1 or 2, wherein the roasted material/acid mixture in step (d) is heated to its boiling point at a rate sufficient to form a nodularly shaped material.

11. The process of Claim 10, wherein the roasted material/acid mixture in step (d) is heated up to its boiling point temperature of from 90°C to 110°C
at a rate of less than 5°C/minute.

12. The process of Claim 1, wherein the roasted material/acid mixture in step (d) is heated up to its boiling point temperature at a rate and an acidity sufficient to form an acicularly shaped material.

13. The process of Claim 12, wherein the acidity of the roasted material/acid mixture in step (d) is maintained below 4 N during the heating and increased to 6 N when the temperature has exceeded 90°C.

14. The process of Claim 1, wherein the digestion step (d) is carried out at least two times.

30,371B-F -35-