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US 2013 0283703A1

(19) United States


(12) Patent Application Publication (10) Pub. No.: US 2013/0283703 A1
SAMA et al. (43) Pub. Date: Oct. 31, 2013
(54) TIO2 BASED SCRUBBING GRANULES, AND Publication Classification
METHODS OF MAKING AND USING SUCH
TO2 BASED SCRUBBING GRANULES (51) Int. Cl.
C09K3/14 (2006.01)
(71) Applicant: CRISTAL, USA INC. Hunt Valley, MD (52) U.S. Cl.
(US) CPC .................................... C09K3/1409 (2013.01)
USPC ............................................... 51/308; 51/309
(72) Inventors: Venkata Ramana Reddy SAMA,
Parkville, MD (US); Kit Stacey (57) ABSTRACT
EREMCHUK, Catonsville, MD (US); TiO based scrubbing granules, and methods of making and
Mark D. POMPONI, Ellicott City, MD using Such TiO, based scrubbing granules are described.
(US); Gabor FEHER, Glen Burnie, MD TiO-based scrubbing granules include granulated TiO, and
(US); Alexandre Jean FINES, Ellicott about 0.5% to about 20% dry weight inorganic salt binder.
City, MD (US) Other TiO, based scrubbing granules include unsintered
granulated TiO, and about 0.5% to about 20% dry weight
(73) Assignee: CRISTAL, USA Inc., Hunt Valley, MD inorganic salt binder. Inorganic salt binder include Sodium
(US) aluminate. Methods of making TiO, based scrubbing gran
ules include i) combining TiO particles with inorganic salt
binder to form TiO-binder mixture comprising from about
(21) Appl. No.: 13/871,278 0.5% to about 20% dry weight binder; ii) granulating the
TiO-binder mixture; and drying the granulated TiO-binder
(22) Filed: Apr. 26, 2013 mixture to form TiO-based scrubbing granules. Methods of
using such TiO-based scrubbing granules include introduc
Related U.S. Application Data ing TiO-based scrubbing granules to remove adherent
deposits on an inner Surface of a reactor or heat exchanger
(60) Provisional application No. 61/639.624, filed on Apr. during processes of forming TiO particles and finishing the
27, 2012. formed TiO particles into finished pigment products.
Patent Application Publication Oct. 31, 2013 Sheet 1 of 12 US 2013/0283703 A1

Fig. Prior Art

Step {}
Combining TiO, particles with binder to form a TiO,
binder mixture

Step 20
Compacting and/or granulating and drying the
TiO2-inder sixture

Step 130
Sintering or calcining the TiO2-binder mixture
Patent Application Publication Oct. 31, 2013 Sheet 2 of 12 US 2013/0283703 A1
Patent Application Publication Oct. 31, 2013 Sheet 3 of 12 US 2013/0283703 A1

waxws.sys

?~.ó
Patent Application Publication Oct. 31, 2013 Sheet 4 of 12 US 2013/0283703 A1

0.7

0.6

0.5

0.4

O.

A. NaCl (0.5%) NaCl (5%) B


FG, 4.
Patent Application Publication Oct. 31, 2013 Sheet 5 of 12 US 2013/0283703 A1

().7

0.6

0.5 -

O. 3

O. 2

0.

A SA (%) SA (2%) B
FG. 5
Patent Application Publication Oct. 31, 2013 Sheet 6 of 12 US 2013/0283703 A1

18 -

16 -

0. 6
82
0.4

A. SA (0.5%) SA (2.5%) B
FIG. 6
Patent Application Publication Oct. 31, 2013 Sheet 7 of 12 US 2013/0283703 A1

8 -

6 -

.4 -

0. 8

O. 6

0.4 –

OOC
RP69

FIG 7
Patent Application Publication Oct. 31, 2013 Sheet 8 of 12 US 2013/0283703 A1

OOC 300 C S00 C 700 C


P3.8 P3.8 Pi38 P3.8

FG. 8
Patent Application Publication Oct. 31, 2013 Sheet 9 of 12 US 2013/0283703 A1

2.5 -

00C 300 C SOOC 700 C


P34.5 P345 P345 P345

FIG. 9
Patent Application Publication Oct. 31, 2013 Sheet 10 of 12 US 2013/0283703 A1

6 2
24
.4

S.
e
i ().8
t 0.69
0.6

0.4 0.38

0.2

0 - f I l
OOC 300 C 500C 700 C
P69 P69 P69 P69

F.G. O.
Patent Application Publication Oct. 31, 2013 Sheet 11 of 12 US 2013/0283703 A1

A % Na2SiO3 2% Na2SiO3 39 Na2SiO3 B

F.G. 1.
Patent Application Publication Oct. 31, 2013 Sheet 12 of 12 US 2013/0283703 A1

-
A 9 NaAO2 296 NaAO2 3% NaAO2 B

FG. 12
US 2013/0283703 A1 Oct. 31, 2013

TIO2 BASED SCRUBBING GRANULES, AND or sintered TiO, scrubs can affect the dispersion and/or effec
METHODS OF MAKING AND USING SUCH tiveness of TiO, finishing processes.
TO2 BASED SCRUBBING GRANULES 0008 Thus, a need still exists for improved scrubbing
mediums, and method of making and using such improved
CROSS-REFERENCE TO RELATED scrubbing mediums.
APPLICATIONS
BRIEF SUMMARY
0001. This application claims priority to provisional appli
cation 61/639,624 filed Apr. 27, 2012 titled METHOD OF 0009 Embodiments of the present invention meet these
PRODUCING TO, SCRUBS AND THEIR USE IN TIO, and other needs by providingTiO-based scrubbing granules,
MANUFACTURING PROCESSES and methods of making and using such TiO-based scrubbing
granules.
BACKGROUND 0010. Accordingly, one aspect of the invention provides
TiO-based scrubbing granules. The TiO-based scrubbing
0002 1. Field of the Presently Disclosed and/or Claimed granules include granulated TiO, and about 0.5% to about
Inventive Concept(s) 20% dry weight sodium aluminate binder.
0003. This invention includes embodiments relating to 0011. A second aspect of the invention provides TiO
titanium dioxide (TiO) based scrubbing granules, and meth based scrubbing granules. The TiO-based scrubbing gran
ods of making and using Such TiO, Scrubbing granules. Par ules include granulated TiO, and about 0.5% to about 20%
ticularly, the invention includes embodiments relating to dry weight binder. The binder is selected from a group con
TiO based scrubbing granules with sodium aluminate binder sisting of Sodium aluminate, sodium sulfate, Sodium phos
and various methods of using such TiO, based scrubbing phate, Sodium silicate, sodium chloride, sodium hexameta
granules duringTiO production; and embodiments relating phosphate, and aluminum Sulfate, and combinations thereof.
to unsintered TiO, based scrubbing granules with inorganic 0012. A third aspect of the invention provides TiO-based
metal binder and various methods of using Such TiO, based scrubbing granules. The TiO-based scrubbing granules
scrubbing granules during TiO production include granulated TiO, and about 0.5% to about 20% dry
0004 2. Background of the Presently Disclosed and/or weight binder and wherein the TiO-based scrubbing gran
Claimed Inventive Concept(s) ules are unsintered.
0005 Generally, TiO, particles are produced by a chloride 0013. A fourth aspect of the invention provides a method
or a sulfate process. In the chloride process, titanium tetra of making TiO-based scrubbing granules. The method
chloride (TiCl) undergoes vapor phase oxidation to form includes: i) combiningTiO particles with sodium aluminate
TiO particles as part of a hot gaseous suspension. The hot binder to formaTiO-binder mixture comprising from about
TiO particles, along with other gaseous by-products in the 0.5% to about 20% dry weight binder; ii) granulating the
hot gaseous Suspension, are passed from a reactor to a heat TiO-binder mixture; and iii) drying the granulated TiO
exchanger. The hot gaseous Suspensions are cooled by con binder mixture to form TiO-based scrubbing granules.
tact with the inner surface walls of the heat exchanger which 0014. A fifth aspect of the invention provides a method of
have temperatures less than that of the hot gaseous Suspen making TiO-based scrubbing granules. The method
sion. As the hot TiO, particles are cooled, the TiO, particles includes: i) combining TiO, particles with binder to form a
may deposit on the inner walls of the heat exchanger or TiO-binder mixture comprising from about 0.5% to about
reactor and form adherent layer deposits. The adherent layer 20% dry weight binder; ii) granulating the TiO-binder mix
deposits lower heat transfer efficiency through the inner walls ture; and iii) drying the granulated TiO-binder mixture to
of the heat exchanger and thus reduce cooling efficiencies. form TiO-based scrubbing granules. The binder is selected
Such inefficiencies affect the quality of the formed TiO, from a group consisting of sodium aluminate, Sodium sulfate,
particles and the efficiency of the downstream finishing and Sodium phosphate, Sodium silicate, sodium chloride, sodium
Surface treatment steps. hexametaphosphate.
0006. In attempts to remove adherent layers, “scrubs' 0015. A sixth aspect of the invention provides a method of
such as sodium chloride (NaCl), silica sand, calcined TiO, making TiO-based scrubbing granules. The method
particles, sintered TiO, particles have been added to the hot includes: i) combiningTiO particles with a binder to form a
TiO2 pigment particles flowing through the reactor and heat TiO-binder mixture; ii) granulating the TiO-binder mix
exchanger. For example, NaCl scrubs such as U.S. Pat. No. ture; and iii) drying the granulated TiO-binder mixture to
3.511,308 increase viscosity of TiO, slurry, thereby lowering formTiO-based scrubbing granules without sintering the
the throughput rate in the finishing step. Silica sand Scrubs TiO-based scrubbing granules. The binder comprises from
introduce contaminants into the process and may also about 0.5% to about 20% by dry weight of the TiO-based
increase reactor wear and downtime of the process equip scrubbing granules.
ment, e.g., the reactor, the heat exchanger, etc. 0016 A seventh aspect of the invention provides a method
0007 U.S. Pat. No. 5,266,108 discloses calcined TiO, of using TiO-based scrubbing granules. The method
scrubs typically prepared by heating the TiO particles to a includes:
maximum temperature of approximately 1000°C. Unfortu 0017 i. introducing TiClinto a TiO reaction Zone of a
nately, such high temperatures decrease the Surface area of reactor to form TiO, particles;
most known TiO, scrubs and makes size of scrubs difficult to 0.018 ii. introducing TiO-based scrubbing granules
control. Calcined or sintered TiO, scrubs also have one or into the reactor or a heat exchanger, thereby resulting in
more of the following disadvantages. Calcined or sintered aTiO product stream comprising the TiO-based scrub
TiO, Scrubs contaminate the finished TiO, pigments, thus bing granules and formed TiO particles; and
requiring additional processes. Calcined or sintered TiO2 0.019 iii. cooling the TiO product stream via the heat
scrubs are difficult to reduce to pigmentary size; and calcined exchanger, wherein the TiO-based scrubbing granules
US 2013/0283703 A1 Oct. 31, 2013

in the TiO product stream removes deposits on an inner 0033 FIG. 6 compares crush strengths of the same com
Surface of the heat exchanger as the TiO product stream parative examples calcined TiO, scrubs A and B with TiO,
comprising the TiO-based scrubbing granules passes based scrub granules with sodium aluminate as binder with
through the heat exchanger. The TiO-based scrubbing multiple recycle in accordance with an embodiment of the
granules include granulated TiO, and about 0.5% to invention;
about 20% dry weight sodium aluminate binder. 0034 FIG. 7 compares crush strengths of TiO, based
0020. An eighth aspect of the invention provides a method scrub granules with sodium aluminate binder compressed
of using TiO-based scrubbing granules. The method respectively under 13.8 barg, 34.5 barg, and 69 barg roll
includes: pressures in accordance with embodiments of the invention;
0021 i. introducing TiClinto a TiO reaction Zone of a 0035 FIG. 8 compares crush strengths of TiO, based
reactor to form TiO, particles; scrub granules with sodium aluminate binder compressed
0022 ii. introducing TiO-based scrubbing granules under 13.8 barg and dried at respective temperature condi
into the reactor or a heat exchanger, thereby resulting in tions in accordance with embodiments of the invention;
aTiO product stream comprising the TiO-based scrub 0036 FIG. 9 compares crush strengths of TiO, based
bing granules and formed TiO particles; and scrub granules with sodium aluminate binder compressed
0023 iii. cooling the TiO product stream via a heat under 34.5 barg and dried at respective temperature condi
exchanger, wherein the TiO-based scrubbing granules tions in accordance with embodiments of the invention;
in the TiO product stream removes deposits on an inner 0037 FIG. 10 compares crush strengths of TiO, based
Surface of the heat exchanger as the TiO product stream scrub granules with sodium aluminate binder compressed
comprising the TiO-based scrubbing granules passes under 69 barg dried at respective temperature conditions in
through the heat exchanger. The TiO-based scrubbing accordance with embodiments of the invention;
granules include granulated TiO particles and about 0038 FIG. 11 is a boxplot comparison of crush strengths
0.5% to about 20% dry weight binder. The binder is of same comparative examples calcined TiO, Scrubs A and B
Selected from a group consisting of sodium aluminate, versus TiO, based scrubbing granules with sodium silicate
Sodium Sulfate, Sodium phosphate, sodium silicate, binder, not pressure rolled and dried at 100° C. overnight in
Sodium chloride, sodium hexametaphosphate, and alu accordance with embodiments of the invention; and
minum sulfate, and combinations thereof. 0039 FIG. 12 is a boxplot comparison of crush strengths
0024. A ninth aspect of the invention provides a method of same comparative examples calcined TiO, Scrubs A and B
making TiO, particles. The method includes: versus TiO, based scrubbing granules with sodium aluminate
0025 i. introducing TiClinto a TiO reaction Zone of a binder, not pressure rolled and dried at 100° C. overnight in
reactor to form TiO, particles; accordance with an embodiment of the invention
0026 ii. introducing unsintered TiO-based scrubbing
granules into the reactor or a heat exchanger, thereby DETAILED DESCRIPTION
resulting in a TiO product stream comprising the TiO 0040. In the following description, it is understood that
based scrubbing granules and formed TiO particles; terms such as “top,” “bottom.” “outward,” “inward, and the
and like are words of convenience and are not to be construed as
0027 iii. cooling the TiO, product stream via a heat limiting terms. Reference will now be made in detail to exem
exchanger, wherein the TiO-based scrubbing granules plary embodiments of the invention, which are illustrated in
in the TiO product stream removes deposits on an inner the accompanying figures and examples. Referring to the
Surface of the heat exchanger as the TiO product stream drawings in general, it will be understood that the illustrations
comprising the TiO-based scrubbing granules passes are for describing a particular embodiment of the invention
through the heat exchanger. The unsintered TiO-based and are not intended to limit the invention thereto.
Scrubbing granules include granulated and about 0.5% 0041. Whenever a particular embodiment of the invention
to about 20% dry weight binder. is said to comprise or consist of at least one element of a group
BRIEF DESCRIPTION OF THE DRAWINGS and combinations thereof, it is understood that the embodi
ment may comprise or consist of any of the elements of the
0028 FIG. 1 is a flow chart of a conventional method of group, individually or in combination with any of the other
making TiO-based scrubbing granules; elements of that group. Furthermore, when any variable
0029 FIG. 2 is a flow chart of a method of makingTiO occurs more than one time in any constituent or informula, its
based scrubbing granules in accordance with an embodiment definition on each occurrence is independent of its definition
of the invention; at every other occurrence. Also, combinations of substituents
0030 FIG. 3 is a flow chart of a method of using TiO and/or variables are permissible only if such combinations
based scrubbing granules in accordance with an embodiment result in stable compounds.
of the invention; and DEFINITIONS
0031 FIG. 4 compares crush strengths of comparative
examples calcined TiO, scrubs A and B and TiO, bases scrub 0042. The term calcining refers to the heating up of solids
granules with NaCl binder in accordance with an embodi to a high temperature, but below the incipient fusion or melt
ment of the invention; ing point temperature of the Solids. Calcination can result in
0032 FIG. 5 compares crush strengths of the same com thermal transition, Solids phase transition, and/or removal of
parative examples calcined TiO, scrubs A and B with TiO, volatile fraction(s) from the solids. The volatile fraction(s)
based scrub granules with sodium aluminate as binder with that is removed is bound with the solids, and exclude surface
out recycle in accordance with an embodiment of the inven Volatiles, such as Surface water or Surface moisture. The
tion; chemical composition of the product is typically different
US 2013/0283703 A1 Oct. 31, 2013

from that of the reactant. One example of calcination includes of pressure applied, either individually and or in combination
the thermal decomposition of limestone via the following of two or more thereofas discussed below.
reaction:
CaCO (solids)+Heat->CaO(solids)+CO(gas) Embodiment 2

0043. The term sintering refers to the “welding together 0049. In an embodiment of the invention, TiO-based
and growth of contact area between solid particles attempera scrubbing granules include granulated TiO, and about 0.5%
tures near the melting point of the solids. The solids are heated to about 20% dry weight binder. The binder includes one or
up to their incipient fusion temperature (or eutectic point more inorganic salts such as but not limited to Sodium alumi
temperature if the Solids contain more than one species of nate, sodium Sulfate, sodium phosphate, Sodium silicate,
compounds). In this heating process, there is a gradual clos Sodium chloride, Sodium hexametaphosphate, and aluminum
ing of the Voids between the particles and densification typi sulfate, either individually or in combinations of two or more
cally occurs. The Solid particles stick together due to partial thereof. In a particular embodiment, the binder comprises
melting, and form a solid porous mass. Chemical reaction is Sodium aluminate. In a particular embodiment, inorganic
not taking place, and the chemical composition of the product metal salt includes Substantially sodium aluminate. Similar to
(s) is substantially the same as the reactant. Examples of as described above, in a particular embodiment, the TiO
sintering include eutectic phase diagrams published in the based scrubbing granules are dispersible in finished TiO,
literature. pigment during a process of making such finished TiO2 pig
0044 Free flowing solids refers to solids capable of flow ment. In yet another embodiment, the TiO-based scrubbing
ing out of containers orbins without the aid offlow enhancers, granules are free flowing.
Such as bin vibrators, bin inserts, or special flow-enhancing 0050. In an embodiment, the TiO-based scrubbing gran
liners on the bin wall. Free flowing solids also refers to the ules are unsintered. An embodiment includes TiO, based
flow of material from the bin, sticky solids and dry powders scrubbing granules having an average size in a range of from
that tend to adhere strongly to the Surface of bins resulting in about 1 mm to about 25 mm. An embodiment includes TiO,
poor control of material flow. Whereas, with granular solids based scrubbing granules having a bulk density in a range of
that do not stick to the walls, the flow is consistent, controlled from about 800 to about 1800 kg/m.
and hence, called as free flowing.
Embodiment 3
TiO-Based Scrubbing Granules
0051. An embodiment of TiO-based scrubbing granules
Embodiment 1 include granulated TiO, and about 0.5% to about 20% dry
weight binder and wherein the TiO-based scrubbing gran
0045 An embodiment of the invention includes TiO ules are unsintered. In an embodiment, the binder comprises
based scrubbing granules. The TiO-based scrubbing gran Sodium aluminate. In another embodiment, the binder
ules include granulated TiO, and about 0.5% to about 20% includes one or more inorganic salts such as but not limited to
dry weight sodium aluminate binder. In another embodiment, Sodium aluminate, sodium Sulfate, Sodium phosphate,
the TiO-based scrubbing granules further include one or Sodium silicate, sodium chloride, Sodium hexametaphos
more inorganic salts. Non-limiting examples of inorganic phate, and aluminum sulfate, either individually or in combi
metal salts include Sodium aluminate, sodium sulfate, sodium nations of two or more thereof. In a particular embodiment,
phosphate, sodium silicate, Sodium chloride, Sodium hexam the binder comprises Substantially sodium aluminate. In a
etaphosphate, aluminum sulfate, either individually or in particular embodiment, the binder comprises greater than
combinations of two or more thereof. 90% by weight sodium aluminate based on total weight of the
0046. In a particular embodiment, the TiO-based scrub binder in the TiO-based scrubbing granules.
bing granules are dispersible in finished TiO, pigment during 0.052 Similar to as described above, in a particular
a process of making such finished TiO, pigment. In yet embodiment, the TiO-based scrubbing granules are dispers
another embodiment, the TiO-based scrubbing granules are ible infinished TiO2 pigment during a process of making Such
free flowing. An advantage of free flowingTiO-based scrub finished TiO, pigment. In yet another embodiment, the TiO
bing granules includes ease of introducingTiO-based scrub based scrubbing granules are free flowing. An embodiment
bing granules to a location or place Such a reactor or heat includes TiO, based scrubbing granules having an average
exchanger. size in a range of from about 1 mm to about 25 mm. An
0047. In an embodiment, the TiO-based scrubbing gran embodiment includes TiO, based scrubbing granules having
ules are unsintered. In another embodiment, the TiO-based a bulk density in a range of from about 800 to about 1800
scrubbing granules are uncalcined. An embodiment includes kg/m.
TiO based scrubbing granules having an average size in a 0053 Method of MakingTiO-Based Scrubbing Granules
range of from about 1 mm to about 25 mm. An embodiment 0054 Embodiment of the invention provide methods of
includes TiO, based scrubbing granules having a bulk density making TiO-based scrubbing granules as described above.
in a range of from about 800 to about 1800 kg/m. For illustration and not limitation, an embodiment of making
0048. It should be appreciated that embodiments of the TiO-based scrubbing granules is compared to conventional
invention include pre-determined and preselected choice of methods as depicted in FIG. 1. A conventional method of
mean size, size distribution, and hardness to provide adequate making TiO-based scrubbing granules includes Step 110 is
scrubbing action tailored for specific processes and method combining TiO, particles with binder to form a TiO-binder
ologies. Embodiments of the invention include varying non mixture. The binder does not include sodium aluminate as
limiting parameters such as drying conditions, type of bind shown in FIG. 1. Step 120 is compacting, and or granulating
ers, amount of binder, the type of pressure rolls, and amount and drying the TiO-binder mixture. Step 130 is sintering or
US 2013/0283703 A1 Oct. 31, 2013

calcining the TiO-binder mixture. In some conventional sure rolls can have depressions on the surface of the rolls to
methods, TiO-binder mixture is sintered or calcined, either facilitate compaction. Non-limiting examples of the form of
individually or both. compacted briquettes include Sticks, almonds, bricks, blocks,
0055. In contrast to conventional FIG. 1, FIG. 2 describes etc. either individually or in a combination of two or more
embodiments of the invention of making TiO-based scrub forms. Furthermore, properties of each compacted briquettes
bing granules. FIG. 2 is a flow chart of an embodiment of a are also independent of other compacted briquettes. For
method of making TiO-based scrubbing granules; and the example, the size or shape of the compacted briquettes may
method is not limited by the order or frequency of the steps have varying dimensions of depth, width, length and may
unless expressly noted. independently vary from embodiment to embodiment.
0056. The method includes Step 210 combiningTiO par 0064. The compacted briquettes can be used as is, if the
ticles with binder to form a TiO-binder mixture comprising particle size of the compacted briquettes is as desired. If the
from about 0.5% to about 20% dry weight binder. size of the compacted TiO binder briquettes is too large,
0057 The method is not limited by the shape, size and optimally, Step 230 includes breaking the compacted TiO,
kind of TiO, particles. Non-limiting examples of TiO, par binder briquettes into TiO, binder granules.
ticles used to make TiO, based scrubbing granules include 0065 Compacted TiO binder briquettes can be broken
rutile, anatase, and brookite, either individually or in a com into Smaller size by flake breaker or similar equipment to
bination of two or more thereof. In an embodiment, the TiO, form TiO bindergranules. In an embodiment, the compacted
particles include rutile phase or anatase phase, either indi briquettes are broken into TiO-binder granules having aver
vidually or in a combination of two or more thereof. Further age size in a range of from about 1 mm to about 25 mm. It
more, the TiO, particles used to make TiO, based scrubbing should be appreciated that the method includes repeating Step
granules may be produced from the chloride or Sulfate pro 220 compacting the TiO-binder mixture into compacted bri
cess, either individually or in combination. quettes and Step 230 breaking the compacted TiO into TiO
0058. In an embodiment, TiO, particles are pigmentary binder granules as desired.
sized particles having an average size greater than 0.20 0066 Step 240 optimally includes screening the TiO
micron. Furthermore. Such TiO2 pigment particles may be in binder granules. The TiO binder-granules may be screened
the form of a finished or intermediate product, either indi based on one or more desired specifications such as size
vidually or in combinations. specification and reprocessed. For example, TiO-binder
0059 Non-limiting embodiments of binders include as granules may be selected by an average size in a range of from
described above. A particular embodiment of making TiO about 1 mm to about 25 mm. Step 242 optionally includes
based scrubbing granules includes providing sodium alumi recycling the TiO binder granules. Oversized TiO2 granules
nate (NaAlO) as binder. Using sodium aluminate binder may Such as about >25 mm in size may be passed through milling
have unexpected advantage of TiO-based scrubbing gran equipment and undersized granules Such as about <1 mm may
ules dispersing in TiO2 slurry and minimizing contamination be recycled to a compaction unit to recompact into compacted
in downstream processes. briquettes. Upon screening, TiO-binder granules of desired
0060. In an embodiment, TiO, pigment particles are pre size range from about 1 mm to about 25 mm are collected and
mixed with sodium aluminate binder and water such that the passed on to be part of the TiO, based scrubbing granules.
binder comprises from about 0.5% to about 5% NaAlO dry 0067 Step 260 includes drying the TiO bindergranules to
weight of the TiO, sodium aluminate binder mixture and less than 1% water content to form TiO, based scrubbing
moisture content is about 4%-8%. Approximate mixing granules. In a particular embodiment, Step 260 includes dry
equipment Such as a pin mixer or turbulizer may be used to ing the TiO binder granules that have been screened for a
mix TiO, and binder to make the TiO2-binder mixture. It desired specification Such as size to less than 1% water con
should be appreciated that embodiments of the invention tent to form TiO, based scrubbing granules. Any Suitable
include introducing and adjusting the type and amount of drying unit may be used to dry the TiO binder granules and
binder to achieve a desired strength. invention is not restricted by how the TiO binder granules are
0061. It should be also appreciated that embodiments of dried. In an embodiment, TiO binder granules are dried to
the invention include introducing a plurality of binders which achieve <1% moisture thereby improving the strength of the
differ from each other. Furthermore, the plurality of binders TiO granules. For example the TiO-binder mixture may be
may independently have various characteristics which differ dried by to heating at a temperature in a range of from about
from each other. 90° C. to about 700° C. In an embodiment, drying tempera
0062 Optimally, Step 220 includes compacting the TiO ture may be in a range. Such as but not limited to from about
binder mixture under pressure to form the TiO-binder mix 90°C. to about 200°C. Additionally, the temperature may be
ture into compacted briquettes. For illustration and not limi varied and/or selected in a range or value to achieve a desired
tation, TiO2-binder mixture may be passed through a strength.
compacting apparatus Such as standard compactors or pres 0068 Method of making TiO-based scrubbing granules
sure rolls available in the market optionally, includes Step 250 introducing at least some source
0063 Embodiments of the invention are not limited by of nucleating agent to the TiO-binder mixture before step
how the TiO-binder mixture is compacted or by the form, 260 drying the TiO-binder mixture into TiO, based scrub
size or shape of the compacted briquettes. The compacted bing granules. An embodiment includes introducing nucleat
briquettes can beformed by any suitable method. An embodi ing agents from 1 A metals of the periodic table, either indi
ment includes subjecting TiO-binder mixture to sufficient vidually or in a combination of two or more thereof. Example
pressure to compact. The TiO-binder mixture can be com of group 1A metals include salts and halides of cesium, either
pacted by pressure by any suitable means such as, but not individually or combinations of two or more thereof. The
limited to, pressure rolls and presses. A specific embodiment method is not limited by the sequential order or frequency of
includes counter-rotating pressure rolls. If desired, the pres the steps unless expressly as shown in FIG. 2. An embodiment
US 2013/0283703 A1 Oct. 31, 2013

includes Step 250 introducing nucleating agent simulta pigment. FIG.3 is a flow chart of an embodiment of a method
neously with step 210 or 220. Another embodiment includes of removing adherent deposits and making finished TiO2
Step 260 introducing nucleating agent sequentially before or pigment using one or more of the above described TiO-based
after step 220 compacting the TiO-binder mixture. An scrubbing granules. Step 310 includes introducing TiClinto
embodiment includes Step 250 introducing nucleating agent a TiO reaction Zone of a reactor to form TiO, particles. It is
before step 220 compacting the TiO-binder mixture. It understood to one of ordinary skill in the art that TiCl, is
should also be appreciated that embodiments of the invention oxidized in the reaction Zone of the reactor to form TiO,
include introducing a plurality of nucleating agents which particles. Step 320 includes introducing TiO-based scrub
differ from each other. Furthermore, the plurality of nucleat bing granules into the reactor or a heat exchanger resulting in
ing agents may independently have various characteristics. A a TiO product stream comprising the TiO-based scrubbing
particular embodiment includes introducing a plurality of granules and formed TiO, particles.
nucleating agents simultaneously or sequentially before Step 0074 The method is not limited by the order or frequency
260 drying. of the steps unless expressly noted. As shown in FIG. 3, the
method is not limited by sequential order or frequency of Step
Embodiment 1 310 and 320. An embodiment of the method includes intro
0069. As shown in FIG. 2, a particular embodiment of ducing TiCl, and TiO-based scrubbing granules into the
making TiO-based scrubbing granules includes: i) combin reactor simultaneously. Another embodiment includes intro
ing TiO particles with sodium aluminate binder to form a ducing TiCl, and TiO-based scrubbing granules into the
TiO-binder mixture comprising from about 0.5% to about reactor sequentially.
20% dry weight binder; ii) granulating the TiO-binder mix (0075 Embodiments of the invention include Step 320
ture; and iii) drying the granulated TiO-binder mixture to introducing TiO-based scrubbing granules into the reactor
form TiO-based scrubbing granules. before, during or after Step 310 introducing TiClinto a TiO,
reaction Zone. In a particular embodiment, a plurality of TiO,
Embodiment 2 based scrubbing granules which differ from each other are
introduced into the reactor before, or after introducing TiCl,
0070. As shown in FIG. 2, another particular embodiment into the TiO reaction Zone.
of making TiO-based scrubbing granules includes: i) com 0076. In a sequential embodiment, the method include
biningTiO particles with binder to form a TiO-binder mix Step 320 introducingTiO-based scrubbing granules into the
ture comprising from about 0.5% to about 20% dry weight reactor before Step 310 introducing TiClinto the TiO reac
binder; ii) granulating the TiO-binder mixture; and iii) dry tion Zone. Another embodiment includes Step 320 introduc
ing the granulated TiO-binder mixture to form TiO-based ing TiO-based scrubbing granules into the reactor during
scrubbing granules. The binder is selected from a group con Step 310 introducing TiClinto TiO, reaction Zone. Another
sisting of Sodium aluminate, sodium Sulfate, sodium phos embodiment includes Step 320 introducing TiO-based
phate, Sodium silicate, sodium chloride, sodium hexameta scrubbing granules into the reactor after Step 310 introducing
phosphate. TiClinto the TiO reaction Zone.
Embodiment 3
0077. An embodiment includes introducing TiO-based
scrubbing granules having about 0.5% to about 20% dry
0071. In contrast to conventional method as shown in FIG. weight binder, and the binder includes sodium aluminate,
1, embodiments of the invention include makingTiO-based Sodium sulfate, sodium phosphate, sodium silicate, Sodium
scrubbing granules without sintering or calcining the TiO chloride, sodium hexametaphosphate, and aluminum sulfate,
based scrubbing granules. A particular embodiment includes: either individually or in a combination of two or more thereof.
i) combining TiO, particles with a binder to form a TiO In a particular embodiment, the method includes introducing
binder mixture; ii) granulating the TiO-binder mixture; and TiO-based scrubbing granules having about 0.5% to about
iii) drying the granulated TiO-binder mixture to form TiO 20% dry weight sodium aluminate binder.
based scrubbing granules without sintering the TiO-based 0078. It should be appreciated embodiments of the inven
scrubbing granules as shown in FIG. 2. The binder comprises tion include methods of removing adherent deposits by intro
of from about 0.5% to about 20% by dry weight of the TiO,- ducing embodiments of the TiO-based scrubbing granules
based scrubbing granules. described above to one or more locations such as a reactor and
0072 Similar to the embodiments of TiO-based scrub or a heat exchanger.
bing granules described above, in an embodiment, the bulk 0079. In an embodiment, a plurality of TiO, based scrub
density of the unsintered TiO, Scrubbing granules formed is bing granules which differ from each other are introduced
in the range of from about 800 to about 1800 kg/m. In a into the reactor or heat exchanger. Furthermore, the plurality
particular embodiment, the unsintered TiO-based scrubbing of TiO, based scrubbing granules may have various charac
granules are dispersible in TiO2 slurry during a process of teristics.
making finished TiO, pigment. In another embodiment, the
unsintered TiO-based scrubbing granules are mixed with Embodiment 1
finished TiO, pigment during a process of making Such fin 0080. An embodiment includes introducing unsintered
ished TiO, pigment. In yet another embodiment, the unsin TiO-based scrubbing granules into the reactor. In an embodi
tered TiO-based scrubbing granules are free flowing. ment, the unsintered TiO-based scrubbing granules have
Method of UsingTiO-Based Scrubbing Granules from about 0.5% to about 20% dry weight binder; and the
binder includes one or more Sodium aluminate, Sodium Sul
0.073 Embodiments of the invention also include methods fate, Sodium phosphate, sodium silicate, sodium chloride,
of using the TiO, based scrubbing granules described above Sodium hexametaphosphate, and aluminum sulfate, either
Such as to remove adherent deposits and make finished TiO2 individually or in a combination of two or more thereof. In a
US 2013/0283703 A1 Oct. 31, 2013

particular embodiment, the unsintered TiO-based scrubbing depending upon particular processing conditions, proce
granules have from about 0.5% to about 20% dry weight dures, functional limitations, etc. within the scope and skills
Sodium aluminate binder. of one of ordinary skill in the art given. An embodiment
0081. In an embodiment of the invention, the introduced includes introducing one or more combinations of TiO, based
unsintered TiO, Scrubbing granules have an average size in a scrubbing granules with selected characteristics to provide a
range from about 1 mm to about 25 mm. It should be appre predetermined scrubbing efficiency. Furthermore, the intro
ciated that embodiments of the invention include pre-deter duced TiO-based scrubbing granules with the selected char
mined and preselected choice of size, distribution, and hard acteristics may be altered or changed in response to a change
ness to provide adequate Scrubbing action tailored for specific in the predetermined scrubbing efficiency. An embodiment
process and/or methodology. Embodiments of the invention includes increasing or decreasing the amount of introduced
include varying non-limiting parameters such as drying con TiO based scrubbing granules in response to one or more
ditions, binder, amount of binder, type of pressure rolls, and change in a scrubbing efficiency, either individually or com
amount of pressure applied, either individually and or in binations thereof. For example, an embodiment includes
combination of two or more thereofas discussed below. decreasing the amount of introduced TiO, based scrubbing
0082 In one embodiment, the bulk density of the unsin granules as accumulated adherent deposits on the inner wall
tered TiO, based scrubbing granules introduced into the reac of the heat exchanger or reactor decrease or vice versa.
tor or heat exchanger is in a range of from about 800 to about Amount of Scrubbing granule introduced may also be
1800 kg/m. In a particular embodiment, the TiO, based adjusted based upon the temperature limit of downstream
scrubbing granules are generally free flowing to simplify equipment i.e. filter inlet temperatures controls feeding rate
introduction of such TiO, based scrubbing granules into reac of scrubs.
tor and/or the heat exchanger. I0088. In an embodiments, TiO, based scrubbing granules
are introduced into the reactor and/or heat exchanger in the
Embodiment 2 range from about 0.5 to about 20 wt.% based on total TiO,
0083. In an embodiment of the invention, the introduced particle production rate in the reactor. In another embodi
TiO-based scrubbing granules include granulated TiO, and ments, TiO-based scrubbing granules are introduced in a
about 0.5% to about 20% dry weight binder. The binder range from about 1 to about 10 wt.% based on total TiO,
includes one or more inorganic salts such as but not limited to particle production rate in the reactor, to remove accumulated
Sodium aluminate, Sodium Sulfate, Sodium phosphate, adherent layers and thereby improves heat transfer efficiency.
sodium silicate, sodium chloride, sodium hexametaphos In yet another embodiment, TiO, Scrubbing granules are
phate, and aluminum sulfate, either individually or in combi introduced in a range from about 1 to about 5 wt.%, based on
nations of two or more thereof. In a particular embodiment, total TiO2 particle production rate in the reactor. In an
the binder comprises sodium aluminate. embodiment, TiO, based scrubbing granules are introduced
0084. Similar to as described above, in an embodiment, in an amount Such that the reaction mass exiting the heat
the TiO-based scrubbing granules are unsintered. In another exchanger will be at a temperature compatible with down
embodiment, the TiO2-based scrubbing granules further stream process equipment such as cyclones, filters, and screw
include one or more inorganic salts. Examples of inorganic conveyers.
metal salt include Sodium aluminate, sodium sulfate, sodium I0089. Furthermore, embodiments of the invention option
phosphate, sodium silicate, Sodium chloride, Sodium hexam ally include Step 350 introducing a nucleating agent, such as
etaphosphate, aluminum sulfate, either individually or in from 1A metals of the periodic table, either individually or in
combinations of two or more thereof. a combination of two or more thereof. Non-limiting examples
I0085. In an embodiment of the invention, the TiO-based of nucleating agents include salts and halides of cesium,
scrubbing granules have an average size in a range of from either individually or in combinations of two or more thereof
about 1 mm to about 25 mm. In one embodiment, the bulk of. The method is not limited by the order or frequency of the
density of the TiO-based scrubbing granules is in a range of steps unless expressly noted. As shown in FIG. 3, the method
from about 800 to about 1800 kg/m. The TiO.-based scrub is not limited by sequential order or frequency of Step 350.
bing granules are generally but without limitation, free flow (0090. Optionally, embodiments include Step 350 intro
ing which facilitates feeding of TiO-based scrubbing gran ducing nucleating agent before, during or after step 320 intro
ules into process equipments such as reactors and heat ducing TiO-based scrubbing granules into the reactor. An
exchangers. embodiment of the method includes Step 350 introducing
I0086 Step 330 includes cooling the TiO product stream nucleating agent and step 320 introducingTiO-based scrub
via a heat exchanger. The TiO-based scrubbing granules in bing granules into the reactor simultaneously. An embodi
the TiO product stream removes deposits from an inner wall ment of the method includes Step 350 introducing nucleating
of the heat exchanger as the TiO product stream comprising agent and step 320 introducing TiO-based scrubbing gran
the TiO-based scrubbing granules passes through the heat ules into the reactor sequentially.
exchanger. The TiO, based scrubbing granules remove 0091. A sequential embodiment includes Step 350 intro
deposits or residues within apparatus Such as reactors and ducing nucleating agent before Step 320 introducing TiO
heat exchangers used in the production of TiO, pigment par based scrubbing granules into the reactor. Another sequential
ticles via a chloride process as described here. In addition to embodiment includes Step 350 introducing nucleating agent
removing deposits, TiO, based scrubbing granules also after Step 320 introducing TiO-based scrubbing granules
increase and/or maintaining heat transfer efficiencies through into the TiO, reaction Zone. It should be appreciated that the
the inner walls of the heat exchanger. method includes repeating Step 350 as desired, simulta
0087 Embodiments of the invention include adjusting and neously or sequentially.
varying the amount of TiO, based scrubbing granules that is 0092 An embodiment includes introducing nucleating
introduced (Step 320) to remove adherent layer deposits agents from 1A metals of the periodic table, either individu
US 2013/0283703 A1 Oct. 31, 2013

ally or in a combination of two or more thereof. Example of Embodiments of TiO, based scrubbing granules are not as
group 1A metals includes salts and halides of cesium. Salts or hard as conventional silica sand or sintered TiO, as shown in
halides of cesium may control or reduce the particle size FIG. 1 which tends to abrade the walls of process equipments
distribution of the TiO, finished product. It should be appre Such as reactors and heat exchangers and result in metal pick
ciated that one or more group 1A metal nucleating agents can affecting the quality of finished TiO product.
also be used instead of, or as a mixture with KCl as nucleating
agents. EXAMPLES
0093 Step 340 optionally includes recovering the cooled 0099. The following examples illustrate the features of
TiO, particles and TiO-based scrubbing granules from the embodiments of the invention and are not intended to limit the
TiO product stream after having passed through the heat invention thereto.
exchanger. The recovered cooled TiO, particles and TiO 0100 Experimental Results and Analysis
based scrubbing granules may be recovered Such as via a bag 0101 TiO, pigment particles and binder were mixed to
filter which separates solid TiO, particles from gas. Embodi form a TiO-binder mixture; and TiO-binder mixture was
ments of the invention also include various finishing pro compacted to form various types of TiO-based scrubbing
cesses to form the recovered TiO, particles and TiO-based granules in studies.
scrubbing granules into finished TiO, pigment. 0102 Lab studies were conducted on two compaction pro
0094. A finishing process includes Step 360 forming some cesses, pressure roll compaction using an L-83 compactor
of the recovered TiO, particles and TiO-based scrubbing from Fitzpatrick Company and compaction using a lab scale
granules into finished TiO, pigment via dry finishing process. DISPERMATR) from VMA-Getzmann. Binders such as
0095. Another finishing process includes Step 370 intro Sodium aluminate (NaAlO), Sodium silicate (Na2SiO), and
ducing some of the recovered TiO, particles and TiO-based sodium chloride (NaCl) were selected for study. Crush
scrubbing granules into a slurry tank to form finished TiO2 strength tests were used to qualitatively compareTiO2-based
pigment via wet finishing process. Unexpected advantages of scrubbing granules in accordance with embodiments of the
using TiO, based scrubbing granules include one or more of invention with comparative calcined TiO, Scrubs examples A
the following. In an embodiment, the TiO-based scrubbing and B. Comparative calcined TiO, scrubs examples A and B
granules are dispersible in the aqueous slurry and disperse are calcined sulfate TiO, scrub materials with different addi
into TiO particles such that the TiO-based scrubbing gran tives and at calcination temperature of 970° C. to 1020° C.
ules do not need to be removed. The TiO, scrubbing granules Such calcined TiO, scrub materials were manufactured by
are capable of being dispersed within the aqueous slurry sulfate TiO, manufacturing process. Pressure compaction
without introducing foreign contaminants or oversized TiO. with the L-83 compactor showed that TiO-based scrubbing
The TiO-based scrubbing granules may also be interspersed granules in accordance with embodiments of the invention
within the finished TiO, pigment. Thus, embodiments include exhibited similar or higher strength than comparative
finished TiO, pigment with interdispersed TiO-based scrub examples A and B calcined TiO, Scrubs. Lab Studies demon
bing granules. strate that characteristics and quality of the TiO-based scrub
0096. Furthermore, the TiO-based scrubbing granules bing granules in accordance with embodiments of the inven
may be interspersed within the finished TiO, pigment without tion described above may be affected by, for example, the
affecting the quality of the finished TiO, pigment. As the choice of binder, binder concentration, roll pressure, pre
TiO-based scrubbing granules do not significantly degrade mixing of binder and pigment prior to pressure rolling, initial
or change the physical and or chemical functionality of fin moisture content, drying temperature, recycling of fines,
ished TiO2 pigment, the TiO-based scrubbing granules have either individually or combinations thereof.
the unexpected advantages of not needing to be separated (0103 Pressure Compaction
from the finished TiO, pigment, not needing to be recycled, 0104 Pressure compaction was performed using a Pilot
and not needing further processing. An embodiment of the scale pressure roller (L-83 compactor from The Fitzpatrick
invention includes not separatingTiO-based scrubbing gran Company). In a test procedure, an appropriate amount of
ules from the finished TiO, pigment and the finished TiO, binder and TiO particles were premixed to form TiO-binder
pigment may be sold and/or used with the TiO-based scrub mixture in accordance with embodiments of the invention
bing granules as a component thereof. described above. TiO-binder mixture was placed on a roller
0097. Furthermore, Applicant has also unexpectedly dis mill for about 45 minutes to achieve uniform mixing of the
covered that NaCl or silica sand scrub may be reduced or binder and TiO, pigment. The TiO-binder mixture was then
replaced with one or more embodiments of TiO, based scrub compacted via a pressure roller at 69 barg roll pressure and at
bing granules of the present inventions. NaCl Scrubs increase 5 rpm roll speed to form compacted briquettes. The com
viscosity of TiO2 slurry, thereby lowering the throughput rate pacted briquettes were then dried in lab oven at 100 C over
in the finishing step. Silica sand Scrubs introduce contami night. The compacted briquettes were dried such that it con
nants into the process and may also increase reactor wear and tains <1% moisture. The dried compacted briquettes were
downtime of the process equipments such as reactors and heat then sieved and briquettes greater than 3 mm were selected
exchangers. An embodiment includes TiO, based scrubbing for crush strength analysis. Compacted briquettes of 3 mm
granules substantially free of NaCl. An embodiment includes and above were chosen so that a qualitative comparison of
TiO based scrubbing granules substantially free of silica crush strength analysis can be done with Cristal A and Cristal
sand. Unexpected advantages include improved throughput B calcined scrubs. Results from the screening experiments
rate in the finishing step and increased operating life of pro are discussed below.
cess equipment the reactor, the heat exchanger, etc. 0105 Sodium Chloride as Binder
0098. Another unexpected advantage of embodiments of 0106 FIG. 4 shows the crush strength values for com
TiO based scrubbing granules of the present invention pacted briquettes formed with respectively 0.5% and 5%
includes minimizing trace metal pick-up by TiO particles. NaCl binder compared to the comparative example A and B
US 2013/0283703 A1 Oct. 31, 2013

calcined TiO, Scrubs. An increase in strength of the com moisture content of about 6% to 8%. Mixing was continued
pacted briquettes was observed with increase in binder con for about 10-15 minutes or until TiO-binder mixture sticking
centration from 0.5% to 5%. However, the average crush to the mixer was observed. TiO-bindergranules formed were
strength in both cases was lower than the crush strength of then dried in an oven at 100° C. overnight. The dried TiO,
comparative example A calcined TiO, Scrub. based scrubbing granules was then sieved into different mass
0107 Sodium Aluminate as Binder fractions. TiO, based scrubbing granules larger than 3 mm in
0108 FIG. 5 shows the crush strength values compacted size were taken and analyzed for crush strength.
briquettes formed with respectively 1% and 2% sodium alu 0120 Sodium Silicate as Binder
minate ("SA) binder compared to the comparative A and B I0121 TiO-binder mixture with respectively 1%, 2%, and
calcined TiO, Scrubs. Again, an increase in strength of the 3% sodium silicate binder and TiO2 pigment in accordance
compacted briquettes was observed with increase in binder with embodiments of the invention were mixed as described
concentration. above. FIG. 11 shows comparison of crush strength values of
0109 Effect of Premixing TiO-based scrubbing granules with respectively 1%, 2%,
0110 Binder and TiO, pigment particles were premixed in and 3% sodium silicate binder compared to comparative
batches using a mixer DISPERMATTM. During mixing, water examples A and B calcined TiO, scrubs.
was added to attain an initial moisture content of about 7%. I0122 Crush strength values of TiO-based scrubbing
With 2.5% sodium aluminate as binder, the average crush granules with 1%, and 2% sodium silicate binder are similar
strength of compacted briquettes was about three times of the to comparative example A calcined TiO, Scrub, whereas,
comparative A calcined TiO, scrubs as shown in FIG. 6. The TiO based scrubbing granules with 3% sodium silicate
term "compacts' as used herein and in the figures refers to binder have a lower average crush strength value than the
briquettes produced by pressure rolling. The briquettes are comparative example A calcined TiO, Scrub, but a higher
broken down to granules of required specification. Compari value than comparative example B calcined TiO, scrub.
son of FIGS. 5 and 6 shows significant increase in the crush (0123 Sodium Aluminate as Binder
strength of compacted briquettes formed by pre-mixing of I0124 TiO-binder mixture with respectively 1%, 2%, and
sodium aluminate (“SA) binder and TiO, pigment prior to 3% sodium aluminate binder and TiO, pigment were mixed
pressure rolling. as described above. FIG. 12 compares of crush strength val
0111) Effect of Roll Pressure and Recycle ues of TiO-based scrubbing with respectively 1%, 2%, and
0112 The effect of roll pressure and recycling of fines on 3% sodium aluminate binder. Average crush strength values
the quality of briquettes that are formed was studied. 2.5% of TiO-based scrubbing granules with 1%, 2% and 3%
Sodium aluminate binder (based on previous results with Sodium aluminate binder are higher than comparative
higher crush strength) and TiO, pigment particles were pre examples A and B calcined TiO, scrubs.
mixed and an initial moisture content of about 7% was 0.125. In general, with all tested binders, the crush strength
achieved. Effect of roll pressures of 13.8 barg, 34.5 barg, and of the granulated TiO2-based scrubbing granules increased as
69 barg and recycle offines or briquettes smaller than 3.3 mm binder concentration increased from about 0.5% to about 3%.
were studied. TiO-based scrubbing granules formed with sodium alumi
0113 FIG. 7 shows pressure rolling and recycling signifi nate as a binder had higher crush strength values when com
cantly affect the quality of briquettes that are formed. Average pared to Sodium silicate or sodium chloride as binders. Also,
crush strength of briquettes formed at roll pressure of 13.8 granulated TiO-based scrubbing granules with sodium alu
barg is higher than at roll pressure of 69 barg with or without minate showed an increased crush strength as (1) binder
recycling. However, crush strength for a roll pressure of 34.5 concentration increased from 0.5% to 2.5%, (2) drying tem
barg is slightly higher than those values obtained at 13.8 barg. perature increased from 100° C. to 700° C., (3) granules or
0114) Effect of Drying Temperature briquettes of less than 3.0 mm in size were recycled, and (4)
0115 The effect of drying temperature on the quality and initial moisture content was increased from 3% to 7%.
strength of compacted briquettes in accordance with embodi 0.126 Pilot Scale Studies
ments of the invention described above were also studied. The I0127 Pilot scale studies were performed at a vendor facil
compacted briquettes discharged from the pressure roll was ity to corroborate the laboratory results described above.
dried at 100° C. (overnight),300° C. (1 hour),500°C. (1 hour) 0.128 Sodium aluminate was used as the binder for the
and 700° C. (1 hour). TiO,-binder mixture included 2.5% pilot studies. Two experiments with binder levels of 2.5% and
sodium aluminate binder premixed with TiO, pigment with 4% sodium aluminate inaccordance with embodiments of the
an initial moisture content of about 7%. The TiO-binder invention described above were conducted. As in Step 210
mixture were compacted into briquettes via pressure roll and FIG. 2, sodium aluminate binder was mixed with TiO, spray
respectively dried at 100° C. (overnight), 300° C. (1 hour), dryer discharge using a mixer TurbulizerTM (model TCJS-8)
500° C. (1 hour) and 700° C. (1 hour). to form a TiO2-binder mixture. As in Step 220, the TiO
0116 FIGS. 8-10 crush data show that, independent of the binder mixture was compacted using a pilot scale MS-75
compacting roll pressure, an increase in drying temperature compaction system at 454kg/hour feed rate.
increases crush strength of the compacted briquettes. I0129. As in Step 230, the compacted briquettes were bro
0117 Granulation Studies Using Lab Scale Mixer ken into granules via passing through a flake breaker, Sweco
0118. In these studies, TiO, Spray Dryer Discharge pig 60" screener and a FrewittTM granulator produce TiO, binder
ment particles, binder, and water were combined. A mixer granules of desired size (e.g., 3.36 mmx1 mm or 2 mmX1
DISPERMATTM fitted with a 50mm high-shear impeller, was mm). As in Step 240 screening, TiO binder granules Smaller
used for mixing. than 1 mm were recycled to the feed hopper whereas granules
0119. In the test procedure, amounts of binder and TiO, greater than 3.36 mm or 2 mm were recycled to the granulator.
pigment were placed in the mixer and mixed at about 300 rpm The TiO-based binder granules meeting the above-noted
speed. During mixing, water was added to obtain an initial specifications was collected and dried as in Step 260 to less
US 2013/0283703 A1 Oct. 31, 2013

than 1% moisture by to form TiO, based scrubbing granules. TABLE 1


TiO-based binder granules were dried passing through a 1
m fluid bed dryer. The strength of the TiO.-based binder Results of pilot study using compactor
granules produced was tested using an attrition method as Test if 1 2
described below.
0130. Attrition Test Method: TiO2 Feed Rate (1b/hr) 1,000 1,000
Sodium Aluminate 2.50% 4.00%
0131 TiO-based binder granules s in accordance with MS75 Roll Face
MS75 Roll (psi)
Stick
500
Stick
500
embodiments of the invention were compared to comparative MS75 Roll (rpm) 3.5 3.5
calcined TiO, Scrubs examples A and Busing attrition tests. MS75 screw type Straight Straight
(0132) The attrition test was run by screening TiO, based Screw Speed (rpm) 118 100
Product Attrition Fresh 29.20% 26.80%
scrubbing granules using a Ro-Tap(R) sieve shaker, fitted with Product Attrition Cured 1.30% 1.50%
screens the same size as or slightly finer than the desired
product, for five minutes typically. All fines (smaller than 20
mesh) were discarded. Fifty grams of the product larger than 0.134 Laboratory finishing process evaluation was con
20 mesh were placed on the 20 m mesh screen with (50) 3/8" ducted using the TiO, based scrubbing granule produced
steel balls (171.18 g). The Ro-Tap(R) sieve shaker was run for through a MS75TM compaction system as described above. As
five minutes without tapper. The percentage of fines (<20 described in FIG. 3, TiO-based binder granules were intro
mesh) found in the panas a result of the attrition from the steel duced into Oxidizer TiO, slurry and processed through sand
balls is the attrition number. A lower number indicates harder mills, treatment, drying and milling processes as is typically
granules. performed to produce commercially acceptable finished TiO,
product such as finished TiO, pigment. The effect of TiO,
0133. The average attrition number of TiO binder gran based scrubbing granules on finished TiO2 pigment was
ules (undried) and the TiO, based scrubbing granule (dried evaluated for performance in a paint application. Table 2 is a
TiO, binder granules) at 165° C. were respectively 20% and Laboratory Investigation result of Performance Prototype
1.5%, indicating the desirability of drying to form harder Samples prepared in Lab; Micronized at Pilot Plant using air
granules. The average attrition value of Comparative example at 290° C. and TiO, 0.227 kg/min
A calcined TiO, scrub was 6.7% compared to the 1.5% 0.135 Unexpected results show that finished TiO, pigment
achieved through an embodiment of the present invention; with some of the of TiO, based scrubbing granule were sub
thus, embodiments of methods of the invention formed harder stantially identical when compared to finished product
granules than the comparative example A calcined TiO2 TiONAR 595 that did not include the TiO, based scrubbing
scrub. The attrition numbers did not change significantly granule. Lab finishing process compatibility studies in Table
(1.3% vs. 1.5% seen in Table 1 below) when the binder level 2 with TiONAR 595 oxidizer basemixed with 5%TiO, based
was increased from 2.5% to 4%, thereby confirming labora scrubbing granules show that there was no difference in the
tory results described above. Increasing binder levels from quality of finished TiO2 pigment formed when compared to
0.5% to 2.5% formed harder TiO, based scrubbing granules: TiONAR 595 without the TiO, based scrubbing granules.
but, significant impact was not observed when binder level Such results indicate that the TiO-based binder granules do
was increased above 2.5%. In addition, at 4% binder level, not need to be removed from the finished TiO, pigment.
processing issues related to caking in the compaction feed Furthermore, results indicate that using sodium aluminate
hopper was observed. The drying temperature in the fluidbed binder does not appear to introduce contamination and/or
dryer was varied from about 121° C. to about 165° C. impart undesirable properties into finished TiO, pigment.
TABLE 2

Lab Investigation - Effect of TiO2-based scrubbing granules on Product


Performance

Interior Interior
high-gloss high-gloss
latex paint latex paint Exterior
Sample Mean IEP Brightness Gloss Tint base

Description GSD pH 9.6 L Ab 2O 60° 96 L Ab

TONA595 TM 0.28O1424 7.3 100 O 5 5 100.2 -0.1


Oxidizer base +
5% Scrubs, then
Sandmilled,
Surface treated,
dried in lab
TONA595 TM O.277.1.409 7.5 1OO O.15 4 5 100.2 -0.11
Oxidizer base +
5% Scrubs, then
Sandmilled,
Surface treated,
dried in lab
Baseline
US 2013/0283703 A1 Oct. 31, 2013
10

TABLE 2-continued
Lab Investigation - Effect of TiO-based scrubbing granules on Product
Performance

Interior Interior
high-gloss high-gloss
latex paint latex paint Exterior
Sample Mean IEP Brightness Gloss Tint base
Description GSD pH 9.6 L Ab 2O 60° 96 L Ab
-TIONA595 TM O.274f1.401 7.52 100.1 O.OS 5 5 100.2 -0.2
oxidizer base as

ote:
GSD is Geometric Standard Deviation;
EP is Isoelectric Point

0.136 Each of the patents, published patent applications, 7. A method of making TiO-based scrubbing granules
references and articles cited herein is hereby expressly incor comprising:
porated herein by reference in its entirety. i.combining TiO, particles with sodium aluminate binder
0.137 It will be apparent to those skilled in the art that to form a TiO-binder mixture comprising from about
various modifications and variations can be made in the 0.5% to about 20% dry weight binder; and
method and system of the present invention without departing ii. granulating the TiO-binder mixture;
from the spirit or scope of the invention. Thus, it is intended iii. drying the granulated TiO-binder mixture to form
that the presently disclosed and/or claimed inventive concept TiO-based scrubbing granules.
(s) includes modifications and variations that are within the 8. The method of claim 7, wherein the binder further com
Scope of the appended claims and their equivalents. prises an inorganic metal salt.
0138 While the presently disclosed and/or claimed inven 9. The method of claim 7, wherein the binder further com
tive concept(s) has been described in detail in connection with prises an inorganic metal salt selected from the group con
only a limited number of aspects, it should be understood that sisting of sodium sulfate, sodium phosphate, sodium silicate,
the presently disclosed and/or claimed inventive concept(s) is Sodium chloride, Sodium hexametaphosphate, aluminum Sul
not limited to Such disclosed aspects. Rather, the presently fate, and combinations thereof.
disclosed and/or claimed inventive concept(s) can be modi 10. The method of claim 7, further comprising compacting
fied to incorporate any number of variations, alterations, Sub the TiO-binder mixture under pressure to form the TiO
stitutions, or equivalent arrangements not heretofore binder mixture into compacted briquettes.
described but which are commensurate with the scope of the 11. The method of claim 10, further comprising breaking
claims. Additionally, while various embodiments of the pres the compacted briquettes into TiO2-binder granules having
ently disclosed and/or claimed inventive concept(s) have an average size in a range of from about 1 mm to about 25 mm.
been described, it is to be understood that aspects of the 12. The method of claim 7, wherein drying the TiO-binder
presently disclosed and/or claimed inventive concept(s) may mixture comprises heating at a temperature in a range of from
include only some of the described embodiments. Accord about 100° C. to about 700° C.
ingly, the presently disclosed and/or claimed inventive con
cept(s) is not to be seen as limited by the foregoing descrip 13. The method of claim 7, wherein the TiO, particles are
tion but is only limited by the scope of the appended claims. produced by a chloride or sulfate TiO, manufacturing pro
CCSS,
What is claimed is:
1. TiO-based scrubbing granules comprising: 14. The method of claim 7, wherein the TiO-based scrub
i. granulated TiO, bing granules are unsintered.
ii. sodium aluminate binder comprising from about 0.5% to 15. A method comprising:
about 20% by dry weight of the TiO-based scrubbing i. introducing TiClinto a TiO reaction Zone of a reactor to
granules. form TiO, particles;
2. TiO-based scrubbing granules of claim 1, wherein the ii. introducing TiO-based scrubbing granules into the
TiO-based scrubbing granules are dispersible in a TiO, reactor or a heat exchanger, thereby resulting in a TiO,
slurry during a process of making finished TiO2 pigment. product stream comprising the TiO-based scrubbing
3. TiO-based scrubbing granules of claim 1, wherein the granules and formed TiO particles;
TiO-based scrubbing granules are unsintered. wherein the TiO, based scrubbing granules comprise:
4. TiO2-based scrubbing granules of claim 1, further com a. granulated TiO, and
prising an inorganic salt. b. sodium aluminate binder comprising from about 0.5%
5. TiO-based scrubbing granules of claim 1, further com to about 20% by dry weight of the TiO-based scrub
prising an inorganic metal salt selected from the group con bing granules; and
sisting of sodium sulfate, Sodium phosphate, sodium silicate, iii. cooling the TiO product stream via the heat exchanger,
Sodium chloride, Sodium hexametaphosphate, aluminum Sul wherein the TiO-based scrubbing granules in the TiO,
fate, and combinations thereof. product stream removes deposits on an inner Surface of
6. TiO-based scrubbing granules of claim 1, wherein the the heat exchanger as the TiO product stream compris
TiO-based scrubbing granules have an average size from ing the TiO-based scrubbing granules passes through
about 1 mm to about 25 mm. the heat exchanger.
US 2013/0283703 A1 Oct. 31, 2013

16. The method of claim 15, wherein the introduced TiO 28. The method of claim 27, further comprising increasing
based scrubbing granules are unsintered. or decreasing the amount of introduced TiO, based scrubbing
17. The method of claim 15, further comprising introduc granules in response to a change in the predetermined scrub
ing TiO-based scrubbing granules comprising an inorganic bing efficiency.
salt selected from the group consisting of Sodium Sulfate, 29. The method of claim 15, wherein the TiO-based scrub
Sodium phosphate, Sodium silicate, Sodium chloride, sodium bing granules are introduced in an amount in range from
hexametaphosphate, aluminum Sulfate, and combinations about 1% to 10% weight percent of the total TiO production
thereof. rate in the reactor.
18. The method of claim 15, further comprising recovering 30. TiO-based scrubbing granules of claim 1, wherein the
the cooled TiO particles and TiO-based scrubbing granules TiO-based scrubbing granules have a bulk density in a range
from the heat exchanger.
19. The method of claim 18, further comprising finishing of from about 800 to about 1800 kg/m.
the recovered TiO, particles into finished TiO, pigment via a 31. TiO-based scrubbing granules comprising:
wet finishing process. i.granulated TiO,
20. The method of claim 19, comprising finishing the ii. binder comprising from about 0.5% to about 20% by dry
recovered TiO, particles by introducing the recovered TiO, weight of the TiO-based scrubbing granules; and
particles and recovered TiO-based scrubbing granules into a
slurry tank to form the finished TiO, pigment. iii. wherein the TiO-based scrubbing granules are unsin
21. The method of claim 19, further comprising not remov tered.
ing the TiO-based scrubbing granules from the finished TiO, 32. TiO-based scrubbing granules of claim 31, wherein
pigment. the TiO-based scrubbing granules are dispersible in TiO,
22. The method of claim 15, further comprising introduc slurry during a process of making finished TiO2 pigment.
ing a nucleating agent to the TiO reaction mixture before, 33. TiO-based scrubbing granules of claim 31, wherein
during, or after the TiO-based scrubbing granules are intro the binder comprises an inorganic metal salt selected from the
duced.
23. The method of claim 22, wherein the nucleating agent group consisting of sodium aluminate, Sodium sulfate,
comprises a salt or halide of a group IA metal. Sodium phosphate, Sodium silicate, sodium chloride, sodium
24. The method of claim 22, wherein the nucleating agent hexametaphosphate, aluminum Sulfate, and combinations
thereof.
is selected from the group consisting of potassium, cesium,
and combinations thereof. 34. TiO-based scrubbing granules of claim 31, wherein
25. The method of claim 22, wherein the nucleating agent the binder comprises sodium aluminate.
is selected from a group consisting of KC1, CsCl, and com 35. TiO-based scrubbing granules of claim 31, wherein
binations thereof. the TiO-based scrubbing granules have an average size in a
26. The method of claim 15, wherein the TiO-scrubbing range of from about 1 mm to about 25 mm.
granules are free flowing.
27. The method of claim 15, further comprising altering a 36. TiO-based scrubbing granules of claim 31, wherein
selected characteristic of the introduced TiO, based scrub the TiO-based scrubbing granules have a bulk density in a
bing granules in response to a change in a predetermined range of from about 800 to about 1800 kg/m.
scrubbing efficiency. k k k k k