Patented Nov.

15, 1949
2,488,439

' UNITED STATES_ PATENT OFFICE

2,488,439
PRODUCTION OF TITANIUM OXIDE
PIGMENTS
Holger Heinrich Schaumann, Newark, Del., 'as
signor to E. I. du Pont de Nemours & Com
pany, Wilmington, Del., a corporation of Del
aware

No Drawing. ‘Application March 9, 1946,

Serial No. 653,428
10 Claims. (Cl. 23-202)
1 2
This invention relates to the production of pig between oxygen and the titanium tetrachloride
ment-useful titanium dioxide and to novel meth 1S e?ected in such manner that the use of large
ods for obtaining that product. More particu excesses of oxygen is effectively avoided and sub
larly it relates to the production of T102 pig stantially complete conversion of the tetrachlof
ments by the oxidation under controlled condi ride is obtained; and the provision of a process
tions of titanium tetrachloride while in the gase wherein the chlorine produced in the reaction is
ous phase. substantially free from oxygen and other im
Titanium dioxide has been prepared in the purities to become suitable for direct use and
laboratory by reacting titanium tetrachloride in recycling in the process to obtain .further quanti
the vapor phase with an oxygen~containing gas 10 ties of the titanium tetrachloride reactant or
and by a so-called steam-splitting reaction. otherwise. Further objects and advantages will
However, these prior oxidation processes lack become apparent from the following, more de
technical importance and are neither adaptable tailed description of the invention.
to nor feasible for commercial exploitation. These and other objects are accomplished in
Thus, such methods entail a very di?icult, costly this invention which comprises producing pig
and discontinuous type of operation, while the ment-quality titanium dioxide, in either the rutile
titanium dioxide resulting therefrom is decided or anatase crystalline form, by decomposing ti
ly .lacking in essential pigment properties, e. g., tanium tetrachloride in the vapor phase under
its tinting strength is so poor and its particle size controlled oxidation conditions in the presence
so coarse and of such wide, non-uniform distribu 20 of small, regulated amounts of water vapor.
tion that it completely fails to meet the stringent In a more speci?c and preferred embodiment,
requirements and demands of the trade with re the invention comprises producing pigment
spect to T102 pigments. Furthermore, these quality T102, more especially rutile, by reacting
methods fail to afford a process in which the at an elevated temperature in the vapor phase
crystalline form of-the titanium dioxide pro 25 and over a controlled time period relatively pure
duced can be controlled at will,-and require the titanium tetrachloride with an oxygen-contain
use of large excesses of oxygen to convert the ing gas, and effecting said reaction in the pres
tetrachloride. This results in undesired con ence of from 0.1% to 5% by volume (based on
tamination of the gaseous chlorine simultaneous the total volume of gases) of water vapor to con
ly formed with the TiOz to render such chlorine 30 tinuously form in situ of said reactants small
un?t for reuse in the process. amounts of an effective TiOz nucleating agent
It has been found that the above and other which promotes and insures production of a high
disadvantages of prior vapor phase oxidation quality TiOz pigment.
methods for TiOz preparation can be effectively In producing pigment-quality rutile in accord
remedied, and a principal object of this inven 35 ance with one preferred, practical adaptation
tion, therefore, is to provide novel methods and of the invention, su?icient pure, vaporized, an
means for. attaining that result. Particular ob hydrous titanium tetrachloride and an oxygen
jects of the invention include: the provision of containing gas, such as air, suitably enriched
auseful and ei?cient method for obtaining titan with from .1 %-3% of water vapor, are separately
ium oxide, through vapor phase oxidation of 40 and continuously introduced into an oxidation
titanium tetrachloride, of controlled, uniform zone wherein their rapid, thorough admixture
particle size and other necessary pigment quali and reaction is effected at substantially constant
ties, including essential color, tinting strength, temperatures ranging from 900-1200° C., with
opacity, hiding power, etc., and which is directly substantially complete oxidation of the titanium
useful as an excellent, high-quality type of pig 45 tetrachloride occurring as a result, Prior to in
ment; the provision of a novel method for obtain troduction, either or both reactants are preheated
ing such pigment-useful titanium dioxide in to a temperature su?‘icient to insure the prev
either the rutile or anatase crystalline form and alence von their admixture and reaction of a
by an accelerated, controlled oxidation reaction; temperature within the range mentioned. Any
the provision of a process wherein the reaction 50 conventional corrosion-resistant type of reaction
/
 9,488,480
3
vessel can be employed in the process, but such streams entering the reaction chamber converged
vessel should be of such design, construction and immediately to become rapidly mixed together in
dimension that it will afford a continuous ?ow of the upper portion of said chamber. Flow rates
the reactants and products within and through suflicient to provide an average retention time of
its oxidation chamber and permit of such con, gases and products in the reaction zone of about
trol over the velocities, mixing rates, tempera .5 second were utilized. The gaseous suspension
tures and retention times that, on the average, of titanium dioxide reaction product, issuing
said reactants and products will remain in said from the bottom of the reaction chamber at a
chamber for only a limited, relatively short pe temperature of approximately 1000° C., _was
riod of time, e. g., long enough to effect a sub 10 quickly cooled by introducing su?icient cold
stantially complete reaction but insumciently long' chlorine gas therein to drop its temperature to
to permit undesired particle size growth of the 300° C. in less than 2 seconds. The titanium di
TiO: to occur. Usually; a. retention time of from oxide pigment product was then separated and .
about .1 to 1 second, using the indicated tem recovered in ?lter containers. The process was
. peratures induces substantially complete conver 15 operated continuously with over 99% conversion
sion of the titanium tetrachloride to titanium di of‘ the titanium tetrachloride taking place. The
oxide. ’ I ' titanium dioxide product was determined to be in '
The gaseous reaction products which contain the rutile crystal structure and possessed essen-'
I the TiO: product in suspension, upon discharge tial particle size uniformity and other pigment
from the oxidation chamber are subjected to quick 20 properties, as shown by its possession of a tinting
cooling, such as by quenching, or otherwise, to < strength value of 182, a color value of 19, and an
reduce their temperature below 600‘ C. and pre average particle size radius of 0.17 micron.
vent any' undesired growth taking place of the Duplication of the foregoing example, except
pigment particles by cementation or sintering of that air substantially free from moisture was em
loosely-bound TiOa aggregates. One useful and 25 ployed, failed to result in a satisfactory ?nal
effective method for accomplishing this rapid titanium dioxide product, being of lower refrac
cooling comprises recirculating cooled product tive index (anatase) and having an average par
gases from the system and directly commingling ticle size radius of 0.60, a tinting strength value
them with the gaseous T102 suspension as it issues of 75, and a color value of 17. It was too coarsely
from the oxidation chamber. The quantity of. 30 crystalline, non-uniform, and de?cient in essen
cooled products thus employed should be suflicient tial properties to be useful as a pigment.
to drop the temperature of the pigment suspen
sion preferably below 600° C., in about 1 second Example II
' and not to exceed 10 seconds’ time. The rutile In the same type of apparatus as that employed
T102 pigment can be recovered from such cooled 35 in Example I, titanium tetrachloride vapor was
gaseous products of reaction by means of conven preheated to about 865° C. and admitted to the,
tional separatory treatments, including cyclonic reaction chamber at a continuous rate of 100 parts
or electrostatic separation, ?ltration through by weight per hour. Oxygen gas, to which water,
porous media, or the like. Said pigment will have equivalent to .33% by volume of the total ?ow of
' an average particle size radius ranging from .05 to 40 reactants, had been added was likewise separately
.5 micron, and preferably will range in average preheated to 865° C. and'continuously admitted
particle size radius from .1 to .25 micron. Such to the reaction chamber'wherein it was rapidly
uniform, small particle size and the inherently admixed with the tetrachloride vapor. The
high tinting strength, color, opacity, and other metered oxygen flow was maintained at a rate of
essential pigment properties possessed by the 45 19 parts by weight of 02 per hour, and the flow
product render the pigment adaptable for use in rate of the total reactants was so controlled that
all types of pigment application, including paints, their average retention time in the reaction
enamels, ?nishes and other types of coating com chamber was .47 second. The temperature in the
positions, as a delusterant for rayon orvother arti 50 reaction chamber was maintained at about 1065°
?cial ?bers or silks, in printing inks, rubber, etc. C. ‘and the gaseous, TiOz-containing reaction
To a clearer understanding of the invention, products, upon issuing therefrom, were cooled to
the following speci?c examples are given. each below 600° C. in less than 10 seconds by passing
being merely illustrative in character and not in the reaction products so discharged at high
tended to limit the scope of the invention: velocity through cooled tubes. Thereafter, the
55 pigment was removed from the gas stream by
Example I means of a glass cloth ?lter bag.
Liquid titanium tetrachloride was ?ash evapo From this operation-it was found that sub
rated and preheated to 800° C. in a corrosion stantially complete conversion of the titanium
resistant tubular preheater and the preheated. tetrachloride to titanium dioxide resulted, with
vapor. admitted continuously at a rate equivalent coincident formation of a gaseous product of
to 100 parts by weight of TiCh per hour to the about 94% C12 by volume. The recovered tita
upper portion of a vertical, corrosion-resistant re nium dioxide was in the rutile crystalline struc
action chamber maintained at a temperature of ture and exhibited excellent particle size uni
1050° C. Simultaneously therewith, air preheated 05 formity, having an average particle size of 0.175
in a similar fashion to about‘ 800° C., and to which micron radius. Its tinting strength value was 179,
sumcient water vapor had been added to give its color was 23, and its hiding power was equal to
.95% H2O content by volume, was continuously the highest quality commercially obtainable rutile
admitted through a separate inlet adjacent the titanium dioxide pigments.
TiCh inlet to the upper portion of the reaction 70 ‘ Duplication of this example, but Without re
chamber. The metered, humidi?ed air flow was course to addition of water vapor to the oxygen,
maintained at a‘rate equivalent to 20 parts by resulted in an anatase product which was too
weight of ' 02 per. hour. coarse in particle size and too poor in uniformity
The separate inlets
and other properties to be acceptable for such use
"through which the reactants were admitted to the
reaction zone were so arranged that the gas 75 as a pigment. Its tinting strength was but 88, its
 2,488,489 ,
color was 15, and its hiding power was wholly
deficient. . '
Example III
In an apparatus similar to that used in Exam
ples I and II, titanium tetrachloride vapor heated 5 it into the gas stream in the form of liquid or
to 170° C. was admitted continuously at a rate of
1045 grams per hour to the oxidation chamber
maintained at about 1000“ C. by external heating.
Air preheated to 170° C. and to which water vapor
had been added to give a water content equiva
lent to 1.0% by volume was separately admitted
to the oxidation chamber at a rate of about 640
liters per hour, measured at room temperature.
The two gas streams were rapidly mixed in the
upper portion of the oxidation chamber, and such 15 sure the presence of controlled amounts thereof
flow rates of reactants were resorted to that the
average retention time of reactants within the
oxidation zone was about .99 second. The prod
ucts of reaction, upon issuing from the lower por
tion of said chamber, were cooled in less than 10 20 not exceeding 10% (based on the total volume of
seconds to below 600° C. Substantially complete
conversion of the titanium tetrachloride was ob
tained with production of a high-quality anatase
pigment having an optimum average particle size
range and other essential pigment properties.
Duplication of this example, using the same
flow rates and temperatures, etc., but employing
moisture-freeair, resulted in an extremely coarse
grained T102 product wholly unsuitable for use
as a pigment.
The TiOz pigment values given herein were de
termined in accordance with the methods de
scribed or referred to in U. S. Patents 2,253,551
and 2,046,054.
Although it is essential in producing pigment
quality TiOz under the invention that the tem
peratures, concentrations, and retention times re
sorted to must be controlled and correlated, it will
be understood that the reactants, concentrations,
volumes, ratios, temperatures, velocities, reten
tion times, etc. used in the above examples are
not to be taken as critical. Hence, due variation
therefrom may be made without departing from
the underlying principles and scope of the in
vention. .
While air, humidi?ed to the extent indicated,
comprises a preferred type of useful oxygen-con
taining gas, other types and amounts of oxidizing
gases containing free oxygen (02) and similarly
moisture-enriched, can also be used, as can mix
tures thereof. Examples of other useful gases in
' elude oxygen, oxygen-enriched air, or mixtures of
oxygen or air with various inert gases.
Again, while I prefer to introduce the required
concentration of water vapor into the reaction
zone via the oxidizing agent, if desired other
methods for insuring the presence of a sufficient
H2O concentration during the vapor phase reac—
tion can be resorted to. Since it isessential and
critical to the invention that the water vapor be
present in controlled amounts, any method de
signed to introduce the required quantity (or
lower the amount, if too high) into the oxidizing
gas or reaction zone is contemplated as useful in
practicing the invention. For example, the re
quired amount of water vapor can be continu
ously added, either directly to the reaction zone
itself, or as a component of the oxidizing medium
being fed thereto. Alternatively, it may be intro '0 afforded. While a continuous type of process is
duced with either or both reactants, or by ?rst
,- mixing part or all of the gaseous reactants and
then incorporating the desired quantity of water
vapor therein prior to feeding the mixture into
the reaction zone. Incorporation of the requisite 75 invention, especially in the production of pig
amount of water in the reactants being fed to the
reaction zone can be e?ected in any desired man
ner, as by bubbling the oxidizing gas through the ‘
aqueous liquid body or by conveniently spraying
vapor (steam). For instance, a portion of the
oxidizing gas can be saturated in this manner
with water, in either the liquid or vaporized state,
following which the saturated portion can be
10 blended with the remaining dry portion of the
reactant. _ Alternatively, the desired amount of
water, in liquid or vapor state, or both, can be
injected into or otherwise fed, intermittently or
continuously, directly to the reaction zone to in
during the oxidation reaction. _
While water vapor in amounts ranging from
.1-3% has been mentioned as preferred for use,
other amounts ranging from, say, .05% to 5%, but
gaseous reactants being fed to the reaction zone)
can also be used, and comprise the contemplated
practical limits of operation hereunder.
As noted, reaction zone temperatures ranging
25 from 900—1200° C. are preferred for use herein,
because optimum results have been found to ac
. crue by reason thereof. If desired, higher or
lower orders of temperature, say, from 800° C. to
1350° C., are also employable. These reaction
30 zone temperatures can be readily obtained in a
large scale or commercial type of operation by
either separately preheating one or both reactants
to an extent sufficient to insure on their admix
ture and reaction temperatures of the order indi
_
cated and are maintained by means of the heat
generated from the oxidation reaction or through
external heating of the reaction zone or vessel,
whichever method is preferred. The tempera
tures mentioned above comprise those measured
by arthermocouple extending through the walls
of the reaction vessel and into the reacting gases.
Preheating the reactants can be effected by
separately subjecting each to an equivalent heat
ing temperature, or,-if desired, the oxidizing gas
“ may be preheated to a temperature above or be
low that to which the tetrachloride is subjected,
whichever method is preferred. Any conven
tional equipment can be used in the preheating
step, including any suitable type of electrical re
sistance apparatus or devices adapted‘ to pass the
reactants in direct or indirect heat exchange re
lationship with a heat-imparting medium. A
useful type of heating apparatus comprises one
in which the reactants pass over heat transfer
surfaces heated directly by combustion of fuels or
indirectly by circulation of a suitable‘ heat trans
fer medium.
Normally, the titanium tetrachloride oxidation
is eifected under atmospheric pressures, but it
may be carried out, if desired, under super or
subatmospheric pressures. Similarly, any type
or size of reaction vessel conforming to the scale
vof operation intended can be used in adapting
the invention, equipment of such design and di
mension as will permit a continuous flow of re
actants through the reaction ’vessel, especially
the oxidation chamber thereof, being preferred,
whereby a continuous, as distinguished from a
discontinuous or batch, type of operation, will be
preferred, the process can also be carried out as a
batch or semi-continuous type of operation. The
time of retention of reactants within the reac
tion zone is quite important and critical in the
 asaassc
7 .
meat-quality T102, ‘as herein de?ned In gen ore, such as ilmenite, ‘followed by puri?cation
eral, such retention time must not exceed about ‘. through careful fractional distillation to obtain‘
5 seconds nor be less than about..0l of a second. the desired ‘product. _ Examples of other utilizable
Kpreferred time, to obtain an-optimum quality titanium tetrachloride reactants. comprise the
pigment, ranges from'.1 to 1 second. _ _ > 1 pure, anhydrous titanium tetrachloride ‘(freed of
As already noted, both anatase and rutile T10: copper, vanadium, iron,-and other impurities)
pigments can be produced in accordance with this contemplated in U. 8. Patent 2,062,133, or the
invention. ' ‘ j product which results from soya bean oil treat
In producing pigment rutile of optimum qual ment disclosed in U. 8. Patent 2,230,538.
ities, it is usually desirable to operate the Tick 10 Although chemically-equivalent concentrations
oxidation reaction under such combination. of of reactants are used herein and substantially
conditions that there will be employed complete conversion of the chloride to T10: .ob
(a) a minimum moisture concentration in the tained as a result, .in general I prefer to operate
reacting gases to insure formation of rutile crystal with amounts of oxidizing gas, su?lcient to pro
structure TiOz pigment; 15 vide about 10% excess oxygen over the theoretical
(b) minimum preheating temperatures for the so as \to obtain a product gas containing about
reactants and thorough, rapid mixing of such 30% C]: by volume, when air is used as the source
reactants; . of oxygen, and 90-95% Ch when gaseous oxygen
(0) minimum retention time of reactants and is employed, with but small or minor amounts of
products in the oxidation chamber sumcient only 20 O2 and HCl. The use of oxygen-enriched air
to effect substantially complete conversion of the will produce chlorine concentrations intermediate ,
T1014 to T102 and growth of the T102 pigment between 30 and 90% Cl: gas in the oxidation ,
particles to the desired size; and ' products. However, the invention is not limited
(d) quickly cool the products from the oxida thereto, since it is susceptible of operation using
tion after ‘formation of the desired particle size '25 either excess or de?cient concentrations of the
T10: to prevent over-growth of the pigment par oxidizing or titanium tetrachloride reactant. In
ticles. " , event an excess of the chloride is used, it can be
These variables are interdependent and opti . separated from the oxidation products and reused
mum values, within the limits speci?ed, for mois int-the system. Occasionally it may be desirable
ture content in the reacting gases, preheating 30 to operate the process with incomplete titanium
' and reaction zone temperatures and retention tetrachloride conversion and such type of opera
time in the oxidation chamber must be predeter .tion is likewise contemplated within the scope of
mined for a particular apparatus to obtain there the invention. Satisfactory titanium dioxide pig
from the desired particle size rutile pigment. ments have been produced hereunder with tetra- "
The preferred relationship between these critical 35 chloride conversions as low as 50% of theoretical.
variables is dependent upon such factors as man As already noted, inthe commercial application
I " ner and speed of mixing of the reactants, size of the invention any chlorine produced simultane
and shape of the oxidation chamber, etc., as well ously with the'titanium dioxide pigment can be
as upon the particle size desired in the pig conveniently recycled to produce more titanium
ment TiOz. 40 chloride for oxidation. Consequently, a continu
It has been found, as already indicated, that , ous, as distinguished from a non-continuous, type
the temperature to which the reactants are sub of operation is hereby afforded. The gaseous
jected in the preheating operation has an im chlorine formed may be recycled directly from the
portant bearing upon the ultimate type, crystal pigment recovery operation or, if desired, may be
linity, and character of the TiO: pigment. In concentrated prior to reuse in the chlorination
producing anatase, it is usually desirable to em operation. Such by-product chlorine can also be
ploy lower preheating temperatures with result used for purposes other than chlorinating titani- '
ing lower reaction chamber temperatures than ferous materials, if that should be desired.
are resorted to and necessary in the production The products of reaction are most conveniently
of rutile. The preferred, most useful tempera subjected to quick, rapid cooling by the recircu
ture will depend upon such‘lfactor/s as the scale lation of su?lcient cooled product gases to in
of the involved operation, the size and shape of stantaneously drop the temperature of the pig
the reaction chambenand the rapidity with which ment suspensionissuing from the reaction zone
gas mixing is effected. In producing rutile, pre well below 800° C., and preferably below 600° C.
heating temperatures adequate to insure a mixed Such cooling should be e?ected in less than 30,
gas temperature of at least 350° C., and prefer and preferably in less than 10, seconds’ time.
ably above 400“v C., are usually necessary, while Other means for accomplishing cooling can be
in anatase production preheating temperatures resorted to, such as quick quenching by spraying
sufficient to afford a mixed gas temperature rang. liquid chlorine into the oxidation products; im
ing from below 350° C. to not lower than 100° C. 00 pingement of the gaseous suspension on cold
can be resorted to. While a preheating tem surfaces; rapid ?ow through cooled tubes, etc.
perature of at least 350° C. is suggested in rutile Similarly, quenching with other gases, such as
production, in general, and as already indicated, air, or with liquids other than chlorine can also
it will be found that as the size of a given opera be resorted to. The latter methods are less prac
tion increases, the amount or degree of preheat f? tical and hence are not preferred because unde
ing temperature required to effect such decreases. sired ‘dilution may occur of the chlorine content
Hence, temperatures below that recommended of the gaseous products. ,
and to as low as, say, 250° C., may be employed. The precise manner by which the use and pres
The titanium tetrachloride reactant preferred ence of the contemplated amounts of water va
for use herein comprises a high-purity material 70 por'during the reaction induce production of the
to insure production of a product exhibiting ex high-quality TiOz pigment obtainable hereunder
ceptionally high pigment whiteness and bright is presently not clearly understood. It does ap
ness characteristics. This reactant can be ob pear, however, that under the controlled and reg
tained from any convenient source, as for in ulated conditions of the reaction which prevail
stance through the chlorination of a tltaniferous 76 herein, the water vapor introduced into the reac
 ' 2,488,489
10 ~
tion zone ?rst forms extremely minute T10: crys of the titanium tetrachloride. In such instances
tallites‘which are well dispersed throughout the the nuclei are formed in a first stage and con
gaseous mixture according to the reaction: tinuously carried into a second stagefor thorough
incorporation in and admixture with the major
reactants. ‘ -

Control over the size, crystalline form, and num By the terms "pigment quality" or “essential
ber of these nucleating particles is effected by the pigment properties," as used herein and in the
amount of water present during the oxidation re appended claims, is meant a T102 product pos
action and the temperature conditions under sessing satisfactory properties in respect to color,
which they are ‘permitted to form. Under the 10 tinting strength, texture, particle size, and other
prevailing, controlled conditions of reaction, nu requisite pigment properties which render the
clear T102 or oxychloride particles of such minute - product commercially useful in coating composi
size, number and type form continuously in the tions (paints, enamels, varnishes, ?nishes, etc),
reaction chamber to provide throughout the oxi pigmenting paper, linoleum; the production of
dation of the titanium tetrachloride a continuous, shoe cleaner preparation or as a delusterant for
fresh supply of seeding material onto which the arti?cial silks, nylon, etc. Such titanium dioxide
T102 from such oxidation precipitates to build up‘ is considered as being at least substantially equal
or grow into T102 particles of desired pigment to the quality obtained from a titanium sulphate
dimension, uniformity and crystalline structure. process used in the production of either commer
Low temperatures favor the formation of anatase 20 cial anatase or rutile. Such properties as color,
nuclei while high temperatures promote rutile tinting strength, hiding power, texture, and par
formation, and the nucleating particles function ticle size are referred to in the above-mentioned
as "centers” for subsequent growth by T102 dep U. S. Patents 2,253,551 and 2,046,054. An addi
osition in the same crystalline form as the "cen tionally important property quite signi?cant in
ters" by the oxidation reaction: 25 the manufacture of rutile pigment is that com
monly referred to as carbonblack undertone.
The effect of the addition of carbon black to a
The average ?nal particle size is then an inverse white paint is found to vary considerably and in
function of the number of nuclei, and the crystal some cases a gray of bluish undertone is produced
variety (rutile or anatase) is determined by the while in other instances a gray of reddish under
type of seed crystallite formed in the ?rst stages 30
tone results. The paints may be identical in
of the reaction. The present method of nuclea content of the carbon black and white pigment
tion also serves to greatly accelerate the velocity such as titanium dioxide. but yet appear quite
of the oxidation rate at temperatures below 1000° di?erent to the eye, due to the difference in un
C., which effect appears to be due to the large dertone. This is considered as due to a di?er
number of active “centers" present in the react 35
ence in particle size and/or particle structure.
ing mixture and resulting from the presence of The bluish undertone appears to be character
controlled, small amounts of moisture. Hence, istic of pigments of small particle size, while the
ultimate at-will production is assured of a high reddish undertone is characteristic of pigments
quality T102 pigment exhibiting either the ana of larger and less uniform particle size, although
tase or rutile crystalline diffraction pattern on 40 the structure of the pigment particle may also
X-ray analysis. Quite surprisingly, this nucleat exert an in?uence. In order to give numerical '
ing function and the production of a satisfac gradings or values to this property, an arbitrary
tory T102 product fails to exist when no control scale has been set up by assigning a grading of
is exercised over the amount of H20 present dur
ing the reaction, nor can a rutile type of product 45 zero to a commercial pigment produced by the
process of U. S. Patent 2,253,551, which shows ex
be obtained in the absence of such control and cellent durability in outside house paints and
the combination therewith of the indicated tem other exterior coating compositions, but is rela
perature and reaction zone retention times. tively large in particle size and exhibits a reddish
In producing pigment-quality rutile, the nu undertone. Another pigment produced in ac
clei formed or employed in the reaction zone pref 50 cordance with the process of U. S. Patent
erably consist of minute, ?nely-divided rutile 2,224,987, having a relatively small particle size
crystallites or particles. In the production of and exhibiting a bluish undertone, was given a
anatase, the nucleating particles may be either rating of 100. These pigments serve as the basis
true anatase crystallites or particles, such as hy for an arbitrary scale for rating by comparison
drated oxychlorides or the like, adapted to read 55 the pigments produced by the present invention.
ily convert to anatase crystallites during the oxi The paint trade in general desires the pigment
dation. of bluish undertone, i. e., pigments rated in the
The nuclein employed herein are preferably upper part of the range or having numerical
formed, as shown in the examples, as the gases
become mixed in the reactor. If desired, such gradings in excess of about 50. It is obvious that
nuclei may be formed externally of and prior to some pigments may be graded over 100 if they
their admission into the oxidation reactor. The are more blue in undertone than the based pig
moisture or water vapor reacts with the chloride ment rated 100.
to form solid particles of titanium oxide or oxy The carbon black undertones of pigments best
halide and the limitation of the amount of water 65 suited for optimum durability in, exterior paints
admitted causes a suspension of solids which are in general rated-low and are found to have
passes on as a gaseous ?uid into the oxidation ratings in the lower half of the indicated range.
chamber, and which appear to serve as nuclei Such pigments are more chalk-resistant and
centers on which the titanium oxide grows. In therefore desired even though a sacri?ce in pig
forming the nuclei outside the reaction zone, a 70 ment properties, such as tinting strength and
two-step operation may be resorted to, i. e., the hiding power, due to a growth in particle size,
nucleating particles of the desired crystalline may have resulted. These superior pigments are
form, size and number may be separately pre adapted to exterior use and may be rated low in
pared and then dispersed in the reactant gases. some pigment properties in order to provide the
prior to the oxidation of any substantial quantity 75 desired durability but would not be desired for
 2,488,489
a - 12
- - ' 1.1 .

consumption in the manufacture of the highest tetrachloride, which comprises reacting in the
quality interior finishes. It therefore follows that vapor phase and at temperatures ransi?g from ,
theoptim'um pigment properties for a given pig 900-1200° C. pure, anhydrous titanium tetrachlo
ment depend, in some measure, onthe type of ride, and an oxygen-containing gas after the
application in’ which it is to be used. separate preheating of at least one of said re-_
I claim as my invention: ‘ actants to a temperature su?icient to provide a'
1. A process'for producing a titanium oxide gas temperature on their admixture of at least
pigment which comprises reacting at an elevated 400° C., effecting said reaction in the presence .
temperature ranging from about 800-1350“ C..and of fromv 0.05% to 10% of added water vapor, by
in the vapor phase titanium tetrachloride with 10 volume, based on the total volume of gaseous re
an oxygen-containing gas in an oxidation zone, actants, and in a reaction zone wherein said re
e?ecting said reaction within said zone ‘over ‘a actants remain for a period of from .05 to not to
reaction zone retention time period ranging from exceed 5 seconds, cooling the reaction products
.01 to 5 seconds and in the presence of controlled, immediately upon their discharge from‘ said re
added amounts of water vapor ranging from .05% action zone to a temperature below 600° C., and
to 10% by volume, based on the total volume of thereafter recovering the T10: pigment from said
gases being reacted, and recovering the resulting reaction-cooled products. I _

T10: pigment. ' ' -

7. A process for producing pigment-quality
2. A process for obtaining a titanium oxide rutile which comprises continuously reacting in
pigment having an average particle size radius the vapor phase T1014 and an oxygen-containing‘
ranging from .05 to .5 micron and exhibiting on gas in the presence of a controlled quantity rang-'
X-ray analysis the di?raction pattern of rutile, ing from .1 to 10% by volume, based on the total
comprising reacting in the vapor phase in a re volume of gases being reacted of added H2O,‘
action zone and, over a reaction zone retention preheating at least one of said gases to a tempera'-'-i
time period not to exceed 5 seconds at a tempera- - ture su?icient to provide a gas temperature on
ture of at least 800° C. titanium tetrachloride and their admixture of at least 350° C. but below 1000°~
an oxygen-containing gas, effecting said reaction‘ C., effecting said reaction in a zone maintained by
in the presence of controlled, added amounts of the exothermal heat of the reaction at a tempera-~
water vapor ranging from .05% to 10% by vol ture of above 1000” C. and wherein the reactants-
ume, based on the total volume of gases being re 30 are retained for a period of time ranging from‘;
acted, and'recovering the resulting rutile TiOz about .01 to 5 seconds, promptly removing the re-‘
pigment. sulting reaction products from said zone, cooling
3. A continuous process for producing pigment the same to below 600° C. within from 1 to'notk
quality titanium oxide which comprises reacting to exceed 10 seconds .after such removal, and"
titanium tetrachloride with an oxygen-contain 35 recovering the T103 pigment therefrom. ~1
ing gas in the vapor phase and in a reaction zone 8. A process for producing pigment-quality.
maintained at temperatures above 1000° C., ef rutile which comprises continuously reacting
fecting said reaction over a reaction zone reten TiCl4 and an oxygen-containing gas in the vapor
' tion period 01' time ranging from .1 to 1 second, phase in a reaction zone maintained at a tem-:
and in the presence of controlled added amounts 40 perature above 1000° C., in the presence of an
of watervapor ranging from 0.1% to 3% by vol-v amount of added H20 ranging from .1 to 10% by a
ume, based on the total volume of gases being volume based on the total volume of gases‘being
reacted, promptly cooling the reaction products, reacted and su?icient to effect a substantially"
and recovering the resulting T102 pigment from complete reaction with development of essentialv
the products of reaction. ‘ 45 properties in the TiOa reaction product within.
' 4. A process for producing a titanium oxide less than 1 second of retention time of reactants
pigment through the controlled vapor phase re in said reaction zone, and then promptly remov
action of titanium tetrachloride with an oxygen ing the reaction products from said zone, cooling
containing gas, comprising effecting said reaction the same, and recovering the TiOz product there-:
at temperatures ranging from 800-1350" C. in the .30 from.
presence of from 0.05% to 10% of added water 9. A process for producing pigment-quality
vapor by volume, based on the reactants, and in rutile which comprises continuously reacting
a reaction zone in which said reactants are al TiCl4 and an oxygen-containing gas in the vapor
lowed to remain for a period of from .01 to not to phase in a reaction zone maintained at a tem-'
exceed 5 seconds, promptly removing the prod perature above 1000? C., in the presence of an
ucts of reaction from said zone and quickly cool amount of added water vapor ranging from .1 to‘
ing them to below 600° C., and then recovering. 10% by volume based on the total volume of gases
the resulting T102 pigment. being reacted and su?icient to effect a substan
5. A process for producing pigment-quality tially complete reaction with development of es-~
titanium oxide through a controlled‘ vapor phase 6 sential properties in the T102 reaction product‘
reaction of titanium tetrachloride with an oxy within less than .2 of a second of retention time of
gen-containing gas, comprising effecting said re reactants in said reaction zone, and then 'prom'pt~
action at a temperature above 1000° C. in the pres ly removing the reaction products from said zone,
ence of from 0.05% to 10% by volume, based on cooling the same, and recovering the T102 prod
the reactants, of added water vapor,'in a reac ‘35 uct therefrom.
tion zone wherein the reactants remain for a 10. A process‘ for producing pigment-quality
period of from .01 to not to exceed Sseconds, titanium oxide which comprises reacting in the
quickly removing and cooling to below' 600° C. vapor phase, and at temperatures above 1000° C.,'
the products from the hot reaction zone after titanium tetrachloride with oxygen to which has'
the reaction is substantially complete and before 70 been added an amount of H20 equivalent to from‘
particle size growth of TiOz progresses outside .01% to 10% by volume, based on the total vol-'
the-range of .1-.5 micron average radius, and ume of gases being reacted, effecting said "reac
then recovering the resulting TiOz pigment. tion within a reaction zone over a time period of
6. A process for producing pigment-quality reactant retention ranging from .01 to 5 seconds‘,
rutile through controlled oxidation of titanium 75 cooling the resulting reaction products to a tem-‘
 2,488,489
13 14
perature below 600° C. within not to exceed 10 UNITED STATES PATENTS
seconds from the time of their discharge from
Number Name Date
said zone, and then separating and recovering
the resulting TiOz pigment from the cooled prod 1,931,380 Haber et a1 _______ __ Oct. 1'7, 1933
ucts of reaction. _ 2,347,496 Muskat et a1 ______ __ Apr. 25, 1944
HOLGER HEINRICH SCHAUMANN. U 2,394,633 Pechukas et a1 ____ _; Feb. 12, 1946
2,462,978 Krchma _________ __ Mar. 1, 1949
REFERENCES CITED FOREIGN PATENTS‘
The following references are of record in the Number Country Date
?le of this patent: 541,343 Great Britain ____ __ Nov. 24, 1941