Process for producing vanadium chlorides

Product yields are increased and effluent streams purified for disposal by an improved process for producing vanadium chlorides. The process comprises reacting vanadium oxide with chlorine and reactant carbon to produce substantially pure vanadium chlorides and an effluent stream containing vanadium chlorides and unreacted chlorine. The effluent stream is contacted with adsorptive carbon whereby the vanadium chlorides and chlorine are adsorbed thereon. The adsorptive carbon is subsequently recycled and used as the reactant carbon.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a process for producing vanadium chlorides by 
chlorinating vanadium oxides. More particularly, this invention relates to 
a process for producing vanadium oxytrichloride (VOCl.sub.3) and vanadium 
tetrachloride (VCl.sub.4) by reacting chlorine and carbon with vanadium 
pentoxide (V.sub.2 O.sub.5) wherein the effluent stream from the process 
is substantially free of vanadium chlorides and chlorine. 
2. Description of the Prior Art 
Vanadium chlorides, such as vanadium oxytrichloride (VOCl.sub.3), vanadium 
tetrachloride (VCl.sub.4) and mixtures thereof, are used as components of 
co-catalyst systems for olefin polymerization. 
Various methods are known for preparing vanadium oxytrichloride. According 
to Inorganic Syntheses, Volume 4, New York, 1953 page 80, vanadium 
pentoxide is reduced with hydrogen or carbon at a temperature in the range 
of from 600.degree. C. to 1000.degree. C. to vanadium trioxide, which is 
then transformed into vanadium oxytrichloride by a treatment with chlorine 
at a temperature of 500.degree.-600.degree. C. The final product obtained 
is strongly contaminated with vanadium tetrachloride and chlorine and, 
therefore repeated distillation over sodium is recommended for 
purification. 
U.S. Pat. No. 3,355,244 to Carter et al., describes a process for preparing 
vanadium oxytrichloride by maintaining vanadium oxide, a carbon and an 
inert diluent in a fluidized bed and fluidizing the bed with chlorine. The 
gaseous reaction products recovered overhead from the fluidized bed are 
initially passed into a cyclone separator to remove any entrained solids. 
The resulting crude vanadium oxytrichloride gases are then fed to a quench 
condenser wherein they are quenched in a counter current circulating 
stream of liquid vanadium oxytrichloride. The condensed vanadium 
oxytrichloride product is then subsequently treated, e.g. by fractional 
distillation, to obtain a highly purified vanadium oxytrichloride product. 
The gaseous effluent stream, from this process, however, contains 
unrecovered vanadium chlorides and unreacted chlorines, necessitating the 
use of expensive auxiliary equipment to remove these products and reducing 
yields by wasting chlorine, vanadium and vanadium chlorides. 
The production of vanadium tetrachloride and vanadium oxytrichloride 
mixtures by the intereaction of vanadium pentoxide, carbon and chlorine at 
elevated temperatures is known from Z. Chem. 2, 376-7, (1962). The basic 
reaction is known from U.S. Pat. No. 1,415,028 to 
Methods are known for producing vanadium tetrachloride. British Pat. No. 
1,308,738 describes the chlorination of vanadium pentoxide in a fluidized 
bed of particulate vanadium pentoxide and carbon at 425.degree. C. The 
resultant product stream containing predominantly vanadium oxytrichloride 
is then chlorinated in a second fluidized bed at 600.degree. C. in the 
presence of activated carbon to produce a product stream containing 
predominantly vanadium tetrachloride and minor quantities of vanadium 
oxytrichloride. The vanadium oxytrichloride and vanadium tetrachloride are 
then separated by fractional distillation. 
Thus, generally, vanadium chlorides, such as vanadium oxytrichloride and 
vanadium tetrachloride are prepared by subjecting a vanadium oxide or 
vanadium oxide ore to the action of chlorine at elevated temperatures in 
the presence of a reactant carbon to produce a gas stream containing 
gaseous vanadium chlorides. Usually this gas stream contains, in addition 
to vanadium chlorides, carbon dioxide, carbon monoxide and unreacted 
chlorine. The bulk of the vanadium chlorides are separated from the gas 
mixture by condensation. However, as a result of the comparatively high 
vapor pressures of the vanadium chlorides, substantial amounts thereof 
will remain in the effluent stream along with the carbon dioxide and 
unreacted chlorine. 
The vanadium chlorides remaining in the effluent stream after condensation, 
will generally amount to from about 2 to about 10% of the total vanadium 
chlorides produced, but most likely about 2 to about 4%. Obviously, such 
amounts of vanadium chlorides in the effluent stream along with the loss 
of unreacted chlorine represents a large economic loss as well as a 
pollution problem. 
All of the prior art processes suffer from the fact that the effluent 
stream from the process must be treated to remove the pollutants 
therefrom, e.g. chlorine, vanadium tetrachloride etc. Such treatment is 
typically accomplished with complicated and expensive apparatus and with 
no increase in yields or process efficiency. 
For example, the effluent stream from the reaction of vanadium oxide with 
chlorine and carbon typically can contain carbon dioxide, carbon monoxide, 
chlorine vanadium oxytrichloride and minor quantities of vanadium 
tetrachloride. Known prior art methods of purifying such a gaseous 
effluent stream would consist of a caustic scrubbing process or absorption 
by CCl.sub.4. Caustic scrubbing is costly in energy requirements and 
capital equipment and only converts an air pollution problem into a water 
pollution problem. Absorption of chlorine and vanadium oxytrichloride 
using CCl.sub.4, besides being costly in energy requirement and capital 
equipment, affords only a partial solution to the problem, for excessive 
amounts of CCl.sub.4 will be added to the gas effluent stream. Neither of 
these methods of purifying the effluent stream would increase product 
yields. 
SUMMARY OF THE INVENTION 
It is an object of this invention to provide a process for preparing 
vanadium chlorides wherein product yields are substantially increased over 
known prior art processes. 
It is a further object of this invention to provide a process for preparing 
vanadium chlorides wherein the effluent stream therefrom is substantially 
free from vanadium chlorides and chlorine. 
It has now been found that the foregoing objects can be attained by the 
process of this invention. The process is of the type wherein vanadium 
oxide is reacted with chlorine and reactant carbon to produce 
substantially pure vanadium chlorides and an effluent stream containing 
vanadium chlorides and unreacred chlorine, wherein the improvement 
comprises: 
(a) contacting the effluent stream with adsorptive carbon whereby the 
vanadium chlorides and chlorine are removed from the effluent stream and 
adsorbed on the adsorptive carbon; and subsequently 
(b) recycling and using the adsorptive carbon as the reactant carbon.

DETAILED DESCRIPTION OF THE INVENTION 
Vanadium chlorides are produced by reacting vanadium oxide with chlorine 
and reactant carbon. 
The use of the term "vanadium chlorides" is meant to include all the 
chlorides of vanadium, including vanadium oxytrichloride (VOCl.sub.3) and 
mixtures thereof. The vanadium chlorides of primary interest are however, 
vanadium oxytrichloride, vanadium tetrachloride and mixtures thereof. 
For example, these vanadium chlorides can be produced by the following 
reactions: 
REACTION I 
EQU v.sub.2 o.sub.5 +3cl.sub.2 +1.5C.fwdarw.2VOCl.sub.3 +1.5CO.sub.2 
reaction ii 
EQU v.sub.2 o.sub.5 +4cl.sub.2 +5C.fwdarw.2VCl.sub.4 +5CO 
it is highly preferred that the reaction be accomplished in a fluidized bed 
system of the type well known in the art (see for example, U.S. Pat. No. 
3,355,244 to Carter), or in a plurality of reaction zones (as in British 
Pat. No. 1,308,738). 
Referring to FIG. 1, in a preferred embodiment reactant carbon (including 
the recycled adsorptive carbon) is introduced by feed line (26) into 
reactor (22). 
The reactant carbon employed herein can be any carbonaceous reducing agent 
(including adsorptive carbon) which can effectively convert vanadium 
oxides to vanadium chlorides. It is believed that any amorphous carbon or 
any carbon containing amorphous carbon can be used as the reactant carbon. 
Although the particular type of reactant carbon is not critical, it is 
preferred to utilize coke, calcined petroleum coke and activated carbon. 
In a preferred embodiment of this invention the reactant carbon is the 
same type carbon as the adsorptive carbon, which is preferably an 
activated carbon. When employing a fluid bed system, as is preferred 
herein, it is necessary to employ a powdered reactant carbon. 
While any type reactant carbon can be employed for the production of 
vanadium oxytrichloride, it has been found that material such as calcined 
petroleum coke is not sufficiently reactive for the production of vanadium 
tetrachloride. It has been discovered that if high yields of vanadium 
tetrachloride are required, an activated carbon is a preferred reactant 
carbon. 
In the preferred embodiment depicted in FIG. 1, vanadium oxide is 
introduced by feed line (24) into reactor (22). 
Although it will be understood that various vanadium oxides (with the 
vanadium metal having different valences) and vanadium oxide containing 
ores may be employed in the present process, the use of vanadium 
pentoxides or ores containing vanadium pentoxides are the preferred 
reactant materials. 
It is particularly preferred that a high purity vanadium pentoxide be 
employed as the reactant material, particularly when a fluidized bed 
system is being used. For convenience therefore, the invention will be 
specifically described and illustrated with respect to the use of vanadium 
pentoxide as the reactant material. 
Chlorine, preferably dry gaseous chlorine, is introduced into reactor (22) 
by feed line (20). The upflowing chlorine and the gaseous reaction 
products i.e. carbon dioxide, carbon monoxide and vanadium chlorides 
maintain fluidization of the carbon in the bed of reactor (22). 
It is preferred to use up to about 5.% excess chlorine, i.e. about 5.% over 
that which is stoichiometrically required to convert the vanadium 
pentoxide to the desired vanadium chlorides. During periods of upset, 
however, as much as 25% excess chlorine may be present. 
The reaction temperatures are from about 350.degree. C. to about 
800.degree. C. High temperatures within the aforementioned range favor 
vanadium tetrachloride formation. Temperatures below 600.degree. C. are 
preferred in order to permit the employment of a metallic reactor, e.g. 
nickel or INCONEL (International Nickel Co., Inc.). At temperatures 
substantially above 600.degree. C. refractory or graphite lined reactors 
should be used. 
The reaction temperature for producing vanadium chlorides is higher than 
the temperature at which adsorption of the vanadium chlorides and chlorine 
occur. This permits the vanadium chlorides and chlorine, which are 
adsorbed on the adsorptive carbon, to efficiently desorb from the carbon. 
Again, referring to FIG. 1, the gaseous reaction mixture produced in 
reactor (22) (primarily vanadium chloride, unreacted chlorine, carbon 
dioxide, carbon monoxide and entrained solids) is passed by exit line (28) 
to cyclone (34). The entrained solids are separated from the gaseous 
reaction mixture and sent to waste or recycled to reactor (22) by cyclone 
exit line (32). 
The gaseous mixture from cyclone (34) is passed by feed line (30) to 
condenser (36) wherein a substantial portion of the vanadium chlorides are 
condensed. Some chlorine may also be dissolved in the condensed liquid. 
The residual gaseous material from condenser (36) is then passed by feed 
line (38) to condenser (40), i.e. an "after cooler," wherein a portion of 
the remaining vanadium chlorides are further condensed. 
The residual gaseous material from condenser (40) is passed by exit line 
(46) to form a part of effluent stream (66). 
The condensed liquid from condenser (36) and condenser (40) are passed to 
feed line (44) by exit lines (41) and (42). The condensed liquid in feed 
line (44) is passed into distillation column (48) wherein vanadium 
oxytrichloride and vanadium tetrachloride are separated. 
The higher boiling vanadium tetrachloride is withdrawn by exit line (50) 
and sent to storage. The lower boiling vanadium oxytrichloride and 
unreacted chlorine are withdrawn by exit line (52) and passed to reflux 
condenser (54). 
The residual gaseous material from reflux condenser (54) is passed by exit 
line (58) to form a part of effluent stream (66). 
The condensed liquid from reflux condenser (54) is passed to reflux drum 
(60) by exit line (56). 
At reflux drum (60) a portion of the condensed liquid, i.e. vanadium 
oxytrichloride, is returned by return line (64) to distillation column 
(48) and a portion is withdrawn by exit line (62) and sent to storage. 
The residual gaseous material from condenser (40) and reflux condenser (54) 
are collected by lines (58) and (46) and passed to effluent stream (66). 
Generally, this effluent stream contains carbon dioxide, carbon monoxide, 
chlorine and vanadium chlorides. Typically, the effluent stream contains 
about 90-93% carbon dioxide and/or carbon monoxide, about 6-9% chlorine 
and about 4 to 0.5% vanadium chlorides, predominantly vanadium 
oxytrichloride. 
The effluent stream is then contacted with adsorptive carbon whereby the 
vanadium chlorides and chlorine are removed from the effluent stream and 
adsorbed on the adsorptive carbon. 
Referring to FIG. 1, the effluent stream (66) is passed through an adsorber 
column (68) which contains adsorptive carbon. The adsorptive carbon is 
introduced into column (68) by feed line (70). In adsorber column (68), 
the vanadium chlorides and chlorine are adsorbed on the carbon and the 
remaining gases (predominantly CO.sub.2) are vented to the atmosphere by 
vent line (74). 
The adsorptive carbon employed can be any carbonaceous reducing agent which 
can effectively adsorb vanadium chlorides and chlorine. It has been found 
that it is highly preferred that the adsorptive carbon have a high surface 
area, that is to say be an activated carbon. 
Activated carbon is a well known material, and numerous descriptions of its 
preparation are given in the literature. Literature references which 
adequately describe the preparation of the activated carbon used in this 
invention may be found in "Industrial Chemistry" by E. R. Riegel, 3rd 
edition, p. 589 (1937); "Industrial Chemistry of Colloidal and Amorphous 
Materials," by Lewis, Squires, and Broughton (1943), pp. 74, 75 or in the 
"Encyclopedia of Chemical Technology," by Kirk-Othmer volume 2, pp. 
881-898 (1948). The preparation of activated carbon consists essentially 
of removing adsorbed hydrocarbons from a porous amorphous-base carbon 
which is usually obtained by simple low-temperature distillation of a 
carbon-containing material, such as nutshells, wood, coal or peat. The 
removal of adsorbed hydrocarbons is usually accomplished at elevated 
temperatures by a combined oxidation and distillation involving the use of 
steam or the use of steam and air. As a result of such treatment internal 
pores are developed within the carbon material. In active carbons the 
surface area of these pores typically constitutes a major portion of the 
total surface area, which is in excess of 200 square meters per gram. 
A preferred activated carbon is BARNABY CHENEY No. 346 activated charcoal 
of Barnaby Cheney Co., Inc. and WITCO Type 235 by Witco Chemical Co. Inc. 
It is preferred that the quantity of adsorptive carbon used be no greater 
than and preferably about equal to the quantity of reactant carbon 
consumed. In order to accomplish this the unit adsorptive capacity of the 
adsorptive carbon for adsorbing vanadium chlorides and chlorine i.e. grams 
of vanadium chlorides and chlorine adsorbed per gram of adsorptive carbon, 
must be equal to or greater than the quantity of vanadium chlorides and 
chlorine in the effluent stream per unit weight, i.e. gram, of reactant 
carbon consumed. 
The capacity of carbons to adsorb vanadium chlorides and chlorine are 
highly dependent on the unit surface area of the carbon, i.e. square 
meters/grams. The higher the unit surface area, the greater is the 
capacity for adsorbing vanadium chlorides and chlorine per unit weight 
carbon. Thus, knowing the quantities of vanadium chlorides and chlorine in 
the effluent stream and the quantity of reactant carbon consumed in the 
process, one skilled in the art can readily determine the type of 
adsorptive carbon to utilize so that the quantity of adsorptive carbon 
utilized is less than or, preferably, about equal to the quantity of 
reactant consumed. 
The temperature of the effluent stream entering the adsorber should 
preferably be from about -30.degree. C. to about 160.degree. C., and most 
preferably from about -10.degree. C. to about +10.degree. C. 
It has been found that a preferred manner of contacting the effluent stream 
with the adsorptive carbon is to pass the effluent stream through a bed of 
adsorptive carbon. 
The adsorptive carbon, having adsorbed thereon the vanadium chlorides and 
chlorine is then recycled and used as the reactant carbon. 
Referring to FIG. 1, the adsorptive carbon, is passed from adsorber (68) by 
exit line (72) to mixing and storage area (78) where this adsorptive 
carbon is mixed with makeup reactant carbon. This makeup reactant carbon 
is introduced into the mixing and storage area (78) by feed line (76). 
The reactant carbon (including the recycled adsorbent carbon) is then 
passed from the storage and mixing area (78) into reactor (22) by feed 
line (26). 
It has been found that when the adsorptive carbon is recycled and used as 
reactant carbon, the presence of vanadium chlorides and chlorine adsorbed 
thereon do not adversely effect the ability of the carbon to react with 
chlorine and vanadium oxide to produce vanadium chlorides. 
The process of this invention has the flexibility of producing a broad 
range of concentrations of vanadium oxytrichloride and/or vanadium 
tetrachloride, i.e., a broad range of vanadium oxytrichloride to vanadium 
tetrachloride molar ratios. In the broadest sense, by varying the 
appropriate parameters and equipment, the process is capable of producing 
substantially all vanadium oxytrichloride or vanadium tetrachloride and 
producing only minor quantities of the other vanadium chloride. 
Generally, the molar ratio of vanadium oxytrichloride to vanadium 
tetrachloride produced by the process of this invention is primarily 
dependent on four factors: 
1. Reaction temperature--generally, higher temperatures, e.g. above 
550.degree. C. favor higher conversions to vanadium tetrachloride, i.e. 
decreased molar ratios of vanadium oxytrichloride to vanadium 
tetrachloride. 
2. Type of reactant carbon--generally the greater the surface area per unit 
weight of carbon the greater the conversion to vanadium tetrachloride. 
Thus, for example, calcined coke is suitable for the production of high 
concentrations of vanadium oxytrichloride but is not sufficiently reactive 
for producing high concentrations of vanadium tetrachloride. To favor the 
production of vanadium tetrachloride an activated carbon is required. 
3. Excess chlorine--the use of greater quantities of excess chlorine favors 
the production of higher conversions to vanadium tetrachloride. 
4. Space velocity--space velocity is the volume of feed per hour divided by 
the unit volume of the reactant carbon bed. Generally, lower space 
velocities favor higher conversions to vanadium tetrachloride. A preferred 
range of space velocities for producing predominantly vanadium 
tetrachloride is from about 700 to about 2500 Hours.sup.-1. Space 
velocities from about 900 hours.sup.-1 to about 2000 hours are most 
preferred. A preferred range of space velocities for producing 
predominantly vanadium oxytrichloride is from about 450 to about 900 
Hours.sup.-1. Space velocities from about 600 to about 700 Hours.sup.-1 
are most preferred. 
Pressure is not a critical factor in the process of this invention. 
Pressure either below or above atmospheric can be employed, however, for 
economic reasons operation at atmospheric pressure is preferred. 
Although the preferred method of practicing the present invention involves 
a continuous operation, it is also possible to operate the system on a 
semi-continuous or batch basis. 
The following non-limiting examples will serve to illustrate the invention. 
EXAMPLE 1 
CHLORINE CAITY OF ADSORPTIVE CARBON 
Several carbons were tested for use as adsorptive carbons to determine the 
capacity of carbons to adsorb chlorine. 
The following carbons were tested: 
______________________________________ 
Carbon Surface Area (M.sup.2 /grams) 
______________________________________ 
Amax Carbon.sup.(1) 
5-8 
Barnaby-Cheney No. 346.sup.(2) 
350-400 
Witco-Type 235.sup.(3) 
850 
______________________________________ 
.sup.(1) Sold by Amax Co., Inc. 
.sup.(2) Sold by Barnaby-Cheney Co., Inc. 
.sup.(3) Sold by Witco Chemical Corp., Inc. 
400 grams of the indicated carbon was placed in a glass adsorption column. 
Chlorine gas from a cylinder was metered and directed into the windbox of 
the column and distributed through a porous support place to the carbon 
bed. The chlorine feed temperature was maintained at about 20.degree. C. 
Gas samples were periodically taken from the top of the column and 
analyzed for chlorine. When chlorine first appeared at the top of the 
column ("breakthrough") the test was terminated. The carbon was removed 
from the adsorber and weighed. The gain in weight was the amount of 
chlorine adsorbed by the carbon. 
The results are indicated below, in table form. and graphically in FIG. 2: 
______________________________________ 
WITCO - Type 235 Carbon (850 M.sup.2 /gm.) 
Chlorine:Carbon "G" Mass 
Chlorine Feed 
Wt. Ratio at Flow Velocity 
(gms/min) "Breakthrough" (lb./hr.-ft.sup.2) 
______________________________________ 
7.5 .173 45.3 
6.75 .25 40.8 
4.5 .28 27.2 
2.5 .34 15.4 
______________________________________ 
BARNEBY - CHENEY No. 346 Carbon (350-400 M.sup.2 /gm.) 
Chlorine:Carbon "G" Mass 
Chlorine Feed 
Wt. Ratio at Flow Velocity 
(gms./min.) "Breakthrough" (lb./hr.-ft.sup.2 
______________________________________ 
7.5 .09 45.3 
6.75 .13 40.8 
4.5 .15 27.2 
2.5 .16 15.4 
______________________________________ 
AMAX COKE (5-8 M.sup.2 /gm.) 
No chlorine adsorbed at "Breakthrough". 
______________________________________ 
The foregoing tests indicate that as the surface area of the adsorptive 
carbon is increased the capacity of the carbon to adsorb chlorine 
increases. Additionally as the mass flow velocity of the chlorine through 
the adsorption column decreases, the capacity of the carbon to adsorb 
chlorine increases. 
By the use of the foregoing procedure and with knowledge of the amount of 
chlorine in the effluent stream one can select a carbon, i.e. unit surface 
area, such that the quantity of adsorptive carbon used is less than the 
quantity of reactant carbon consumed in the reaction, or as may be 
preferred, make such quantities about equal to each other. 
EXAMPLE 2 
ADSORPTION OF VANADIUM CHLORIDE AND CHLORINE 
400 grams of WITCO Type 235 carbon (850 M.sup.2 /gm) was placed in a glass 
adsorption column. Chlorine gas, vanadium oxytrichloride gas and nitrogen 
were metered and directed into the windbox of the column and distributed 
through a porous support plate to the carbon bed. The temperature of the 
feed stream was maintained at a temperature of about 20.degree. C. Gas 
samples were periodically taken from the top of the column and analyzed 
for chlorine and vanadium oxytrichloride and the quantity of chlorine and 
vanadium oxytrichloride adsorbed on the carbon determined. The results are 
indicated below: 
TABLE I 
__________________________________________________________________________ 
Cumulative 
Feed Rate VOCl.sub.3 
VOCl.sub.3 
Time (gms/min) Out Absorbed 
(Min.) N Cl VOCl.sub.3 
gms/min 
gms/min 
__________________________________________________________________________ 
0 3.77 .61 .44 -- -- 
15 .dwnarw. 
.dwnarw. 
.dwnarw. 
.0057 .4343 
21 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
27 .dwnarw. 
.dwnarw. 
.dwnarw. 
.005 .435 
33 .dwnarw. 
.dwnarw. 
.527 .dwnarw. 
.522 
39 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
45 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
48 .dwnarw. 
.dwnarw. 
.507 .dwnarw. 
.502 
54 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.502 
57 .dwnarw. 
.dwnarw. 
.527 .dwnarw. 
.522 
78 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
90 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
100 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
115 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
120 .dwnarw. 
.dwnarw. 
.dwnarw. 
.006 .521 
130 .dwnarw. 
.dwnarw. 
.dwnarw. 
.007 .52 
142 .dwnarw. 
.dwnarw. 
.dwnarw. 
.0173 .509 
148 .dwnarw. 
.dwnarw. 
.dwnarw. 
.0115 .515 
154 .dwnarw. 
.dwnarw. 
.dwnarw. 
.023 .504 
160 .dwnarw. 
.dwnarw. 
.dwnarw. 
.0519 .475 
162 .dwnarw. 
.dwnarw. 
.dwnarw. 
.0577 .469 
164 .dwnarw. 
.dwnarw. 
.dwnarw. 
.075 .452 
166 .dwnarw. 
.dwnarw. 
.dwnarw. 
.075 .452 
169 .dwnarw. 
.dwnarw. 
.dwnarw. 
.08 .447 
__________________________________________________________________________ 
Adsorption 
Cumulative 
Chlorine 
Chlorine 
Adsorption 
Cumulative 
Time Out Adsorbed 
Eff.(%) Wt. (gms) 
(min.) 
gms/min 
gms/min 
VOCl.sub.3 
Cl VOCl.sub.3 
Cl.sub.2 
__________________________________________________________________________ 
0 -- -- -- -- -- -- 
15 0 .61 98.7 
100. 
6.51 
9.15 
21 .dwnarw. 
.dwnarw. 
98.7 
.dwnarw. 
9.13 
12.81 
27 .dwnarw. 
.dwnarw. 
98.8 
.dwnarw. 
11.75 
16.47 
33 .dwnarw. 
.dwnarw. 
99.0 
.dwnarw. 
14.63 
20.13 
39 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
17.758 
23.79 
45 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
20.89 
27.45 
48 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
22.396 
29.28 
54 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
25.408 
32.94 
57 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
26.974 
34.77 
78 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
37.936 
47.58 
90 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
44.2 
54.9 
100 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
49.42 
61.0 
115 .dwnarw. 
.dwnarw. 
.dwnarw. 
.dwnarw. 
57.25 
70.5 
120 .dwnarw. 
.dwnarw. 
98.8 
.dwnarw. 
59.88 
73.55 
130 .dwnarw. 
.dwnarw. 
96.6 
.dwnarw. 
65.15 
79.65 
142 .0084 .602 96.6 
98.7 
71.47 
86.97 
148 .0078 .602 96.6 
98.7 
74.63 
90.63 
154 .0113 .598 93.4 
98 77.79 
94.29 
160 .0253 .585 89.1 
95.9 
80.95 
97.95 
162 .0282 .582 85.8 
95.4 
82 99.17 
164 .0366 .573 85.8 
93.9 
83.058 
100.39 
166 .0366 .573 85.8 
93.9 
84.11 
101.6 
169 .04 .57 84.9 
93.4 
85.69 
103.44 
__________________________________________________________________________ 
EXAMPLE 3 
REACTION OF VANADIUM OXIDE CHLORINE AND REACTANT CARBON 
600 grams of WITCO 235 carbon having adsorbed thereon 0.22 grams Cl.sub.2 
/gram of carbon and 0.05 VOCl.sub.3 /gram of carbon was used as the bed in 
a 15 inch high 3 inch diameter electrically heated fluid bed reactor. 
Reactor temperature was maintained at 410.degree.-415.degree. C., vanadium 
pentoxide feed rate at 22.4 gms./min. providing about 3% excess chlorine 
and a superficial velocity of 0.28 ft./sec. 
The results of this test were as follows: 
______________________________________ 
Chlorine Vanadium 
Efficiency.sup.(1) 
Efficiency.sup.(2) 
Time (min.) % % 
______________________________________ 
30 78 77 
60 97.5 100 
90 95.8 96 
120 98.7 98 
150 96.5 98 
210 98.0 98 
______________________________________ 
600 grams of WITCO 235 carbon having adsorbed thereon, 0.28 grams Cl.sub.2 
/gram carbon and 0.12 grams VOCl.sub.3 /gram carbon was used as the bed in 
a 15 inch high 3 inch diameter electrically heated fluid bed reactor. 
Reactor temperature was maintained at 410.degree.-415.degree. C., vanadium 
pentoxide feed rate was 100 grams/10 minutes and chlorine feed rate at 24 
grams/minute providing about 3% excess chlorine and a superficial velocity 
of 0.30 ft./sec. 
The results of the test were as follows: 
______________________________________ 
Chlorine Vanadium 
Efficiency.sup.(1) 
Efficiency.sup.(2) 
Time (min.) (%) (%) 
______________________________________ 
30 77 68 
60 95.7 97 
90 97.8 96 
120 98.1 98.5 
______________________________________ 
##STR1## 
##STR2## 
Although the present invention has been disclosed in connection with a few 
preferred embodiments thereof, variations and modifications may be 
resorted to by those skilled in the art without departing from the 
principles of this invention. All of these variations and modifications 
are considered to be within the spirit and scope of the present invention 
as disclosed in the foregoing description and defined by the appended 
claims.