Fixed bed catalyst for oxychlorination

The present invention provides a fixed bed catalyst for the oxychlorination of ethene, alpha olefins and aromatics. More specifically, this invention relates to a catalyst having an impeded center which excludes reactants, or prevents products from forming in the interior of the catalyst. The impeded center may be made inaccessible or it may be inert to reaction. Thin layers of high specific surface area carrier material cover the outer surface of the impeded center. An agent capable of catalyzing oxychlorination reactions is added to the layered catalytic carrier material.

DESCRIPTION 
TECHNICAL FIELD 
The present invention relates to catalysts for the oxidative chlorination 
of olefins and aromatic compounds. The production of chlorinated 
hydrocarbons by oxidative chlorination of hydrocarbons is well known in 
the art. The process normally consists of catalytically reacting olefinic 
or aromatic hydrocarbons, hydrogen chloride, and oxygen. Hydrogen chloride 
is employed as a source of chlorine for the hydrocarbon which is the 
chlorine acceptor in the reaction thereby producing chlorinated 
hydrocarbons as the product. 
BACKGROUND AND SUMMARY OF THE INVENTION 
Representative but nonexhaustive examples of art in this area include U.S. 
Pat. No. 4,123,467, which describes a catalyst comprising a spherical, 
high surface area, activated alumina impregnated with the catalytic agent, 
copper chloride, and the modifier, potassium chloride. The process 
described in this patent utilizes catalyst beds in two sections, with the 
more active catalyst in the lower section. 
Other U.S. patents describe catalysts made by impregnating carrier material 
with catalytic material. These catalysts are useful in fixed bed 
operations, but are more suited for fluid bed operations. U.S. Pat. No. 
4,172,052 describes a catalyst prepared by treating particulate carrier 
material with aluminum halide, copper halide, and optionally an alkali 
metal halide. Impregnation may be carried out in either one step with a 
single aqueous solution, or in several steps with aqueous solutions of the 
single reagent which is to be loaded onto the solid carrier. U.S. Pat. No. 
4,123,389 describes a catalyst wherein the carrier is formed from 
colloidal sized particles adhering to each other in structures resembling 
chains and loops. The carrier employed has a low bulk density, a surface 
area of a minimum 50 square meters per gram, and nonporous particles with 
pore diameters in the range of 50 to 1,000 Angstroms. Impregnation with 
the active catalyst ingredients is carried out in steps so that there is a 
first layer or deposit of copper chloride which is partially covered with 
a second layer of at least one alkali metal chloride. 
U.S. Pat. No. 3,427,359 describes a catalyst prepared from a carrier having 
a high pore volume and low surface area, but is more suitable for a fluid 
bed system. 
None of these prior art catalysts are entirely satisfactory, whether used 
in fluidized bed or fixed bed processes. Fluidized bed reactor processes 
are much more difficult to operate on a commercial basis. The catalysts 
used in those processes tend to suffer severe attrition, and must be 
continuously replaced. The fixed bed process, on the other hand, has 
disadvantages such as activity control. 
Another disadvantage found in the production of chlorinated aliphatic and 
aromatic hydrocarbons by oxychlorination are the undesired by-products 
produced in the reaction. In ethylene oxychlorination a major by-product 
is ethyl chloride. Coke is responsible for catalyst deactivation and 
fracturing, which accelerates the need to replace the catalyst. 
It would therefore be of great benefit to provide a catalyst which provides 
the advantages of a fixed bed catalyst process, is capable of improved 
selectivity to the desired product, has longer catalyst life, and provides 
better activity control. It is an object of the present invention to 
provide an improved fixed bed catalyst which is more selective to desired 
oxychlorination products, has a long life, and improved activity control. 
Other objects will become apparent to those skilled in the art as this 
description proceeds. 
The present invention provides a structured catalyst which, in addition to 
offering the advantages inherent to a fixed bed catalyst, requires less 
active catalytic material per gram, is more selective to desired products, 
delivers excellent activity control with/or without the use of modifiers 
or physical catalyst diluents, and has a longer catalytic life because of 
less coke formation. Specifically, this catalyst comprises a structured 
catalyst for oxychlorination of ethylene, alpha olefins, and aromatics 
comprising: (a) an impeded center; (b) a layer of catalyst carrier 
material having a thickness in the range of about 0.001 millimeters to 1 
millimeter disposed on (a); (c) a catalytic agent for oxychlorination 
disposed on or dispersed in the layer of catalyst carrier material in an 
amount that said catalytic agent is present at a concentration of from 
about 0.01 to 20% (by wt.) of the finished catalyst. 
In this invention the "impeded" center is a center which prevents the 
oxychlorination reaction due to physical inaccessibility of the center 
and/or due to the absence of catalytic sites in the central portions of 
the catalyst. The absence of these necessary sites may be insured by the 
exclusion of the catalyst carrier material or the catalytic agent, since 
it is the union of the proper catalyst carrier material with the catalytic 
agent for oxychlorination that creates active sites which promote the 
reaction. Since the center area of the structured catalyst of the present 
invention is, by its inert character and/or its inaccessibility, excluded 
from the oxychlorination reaction, the reaction is forced to take place in 
the layered carrier material. Conditions in this layered area insure 
better diffusivity and higher concentrations of reactants. This 
arrangement encourages production of desired oxychlorination products. 
This is at the direct expense of by-products, (such as ethyl chloride in 
the case of ethylene), since by-product formation preferentially takes 
place toward the central area of the conventional fixed bed 
oxychlorination catalyst. The catalysts of the present invention are 
therefore more selective to desired products. 
Coke formation also occurs preferentially in the central areas of the usual 
fixed bed oxychlorination catalyst. Impeded centers inside the catalysts 
of the present invention exclude coke-forming reactions in these areas, 
thus increasing catalyst life. 
Oxychlorination activity is controlled without resorting to conventional 
methods such as catalyst modifiers or physical catalyst diluents such as 
graphite, clay, or SiO.sub.2, although these may be used also if an 
additional control parameter is desired. Control is achieved, with or 
without accompanying conventional methods, by varying the depth of the 
layered catalytic carrier to specifically desired amounts, thereby 
inducing the desired change in activity. The structured nature of the 
present invention decreases, if not virtually eliminates, hot spot 
problems in commercial reactors. 
DETAILED DESCRIPTION OF THE INVENTION 
The structured catalysts of the instant invention have an impeded center. 
The type of material used for this center is not critical provided that it 
is stable under oxychlorination reaction conditions. This center is 
inaccessible to reactants and/or inert for reaction due to the substantial 
absence of catalytic sites. This effectively eliminates the reaction from 
the interior volume, and is done through the catalyst preparation method, 
or by having a center with a low specific surface area and/or a low 
porosity. A layered catalyst carrier material covers the impeded center 
and can be used to make the center inaccessible to reactants. The 
oxychlorination reaction takes place in this carrier layer. The thickness 
of this layer may vary between 0.001 mm and 1 mm. The catalyst is 
completed by any catalytic agent capable of promoting oxychlorination. 
This agent is either dispersed in, or preferably, is placed on the layer 
of catalytic carrier material. The amount of catalytic agent added to the 
surface of this structured catalyst is not critical. Generally any amount 
practical for the catalysis of the oxychlorination reaction is used. Such 
a range would be from about 0.1 to about 20 % by weight based on the 
weight of the finished catalyst. 
The reactant feed material which may be used with these catalysts are 
ethylene, alpha olefins, and aromatics. Representative but nonexhaustive 
examples of the alpha olefin feed are propene, butene, and pentene. An 
example of the aromatic feed which is preferred is benzene. The most 
preferable olefinic feed for this reaction is ethylene. 
It should be noted that these catalysts are especially successful with 
regard to ethylene oxychlorination. Reduced ethyl chloride formation, and 
increased concentrations of ethylene di chloride (EDC) and carbon 
tetrachloride have been noted. This is desirable since CCl.sub.4 is a 
useful initiator when combined with ethylene di chloride (EDC) in the 
production of vinyl chloride. 
The shape of the impeded center will largely determine the geometric shape 
of the overall finished catalyst. Any geometric shape capable of use in a 
fixed bed system is suitable. Particulate shaped impeded centers may even 
be hollow as long as the center is truly impeded, thus preventing 
reactions in that area. Examples of some suitable shapes are spheres, 
tablets, extrudates, rings, and honeycomb catalyst monoliths. Various 
factors influence the choice of which shaped center to use, including ease 
of coating it with layered catalytic carrier material, and the amount of 
specific and geometric surface area which the chosen geometric shape 
delivers. 
Fixed bed catalytic systems in general should contain catalyst particles 
arranged such that there will be no pressure drop problem during the 
reaction, while simultaneously preventing "channeling" of reactants 
through the catalyst bed. Suitable catalyst shapes and sizes will depend 
on the particular reactor used. For most commercial fixed bed processes 
(excluding honeycomb catalyst monoliths) sizes from about 1/8" to 3/8" in 
average diameter will be used, although this size range can vary widely. 
Considerable latitude is available in determining the size of the impeded 
center, limited by a minimum size necessary for a fixed bed system. The 
impeded center and the covering layer combined should approximately equal 
the size desired for the finished fixed bed catalyst. Impeded centers of 
particulate, non-monolithic catalysts, (for example, spherical), should 
have average diameters in the range of about 1 mm to about 10 mm. The 
impeded center, considered by itself, should be large enough to deliver a 
packed, bulk geometric (external) surface area in the range of about 2-50 
cm.sup.2 /cm.sup.3, (including honeycomb catalyst monoliths). The extreme 
values in this range correspond to spherical centers. Monolithic centers 
tend to show geometric surface areas toward the middle of the range (about 
25 cm.sup.2 /cm.sup.3 for a 400 hole/in.sup.2 variety). In the case where 
the impeded center is a honeycomb catalyst monolith, the center should be 
formed into a size and shape so that the finished catalyst slides freely 
into the usual fixed bed reactor tube, while filling the reactor chamber 
well enough to prevent significant channeling of reactants between the 
catalyst and the wall. Holes in the honeycomb lattice of the finished 
catalyst should parallel the reactor tube axis. Suitably any honeycomb 
adequate for a fixed bed system may be used. Preferred honeycombs are 
those with about 100 to 800 holes per square inch of cross-sectional area. 
The use of material inert to oxychlorination reactions having a low 
specific surface area is a convenient method of sealing the interior 
region of the catalyst from availability to the oxychlorination reaction. 
A suitable range for low specific surface areas would be less than 50 
m.sup.2 /g, but more preferably the specific surface area should be less 
than 25 m.sup.2 /g. The invention is also effective when the center 
material has a low porosity and is even more effective when the center 
material has both a low specific surface area and a low porosity. The 
latter is extremely advantageous since it creates an impeded center that 
eliminates reactions due to both the absence of catalytic sites and the 
substantial exclusion of reagents. Representative, but nonexhaustive 
examples of materials suitable for the impeded center are glass, quartz, 
clay, metal, plastics, magnesia alumina, silica alumina, alpha alumina, 
silica, or bauxite. In the case of substances such as clay, silica 
alumina, or silica, similar material may be used for the layered catalytic 
carrier as long as the impeded center is made substantially inaccessible 
to the reactants, and/or the active catalytic agent. 
When the impeded center is made of a material of low porosity, instead of 
or in combination with low surface area, substantially all the pores 
should be greater than about 150 Angstroms (.ANG.) in diameter, as 
measured by Brunauer, Emmett and Teller porosymmetry. Most preferably, 
however, substantially all the pores should be greater than 1000 Angstroms 
in diameter. 
The material used for the layered catalyst carrier material is not critical 
as long as it is suitable for the oxychlorination reaction and conditions 
contemplated, and is capable of retaining the catalytic agent in a manner 
which will create an active site for promoting oxychlorination. In 
general, any oxychlorination carrier material can be used. Representative 
but nonexhaustive examples of suitable materials include gamma, eta, or 
delta aluminas, silica aluminas, titania, silica, niobia, clay, magnesia 
alumina (spinel), or combinations of the above such as alumina-niobia, 
silica-titania, and the like. 
The carrier material used will have a high specific surface area, in the 
range of about 50 to about 300 square meters per gram, preferably from 
about 100 square meters per gram to about 200 square meters per gram 
(m.sup.2 /g), when it is dry and not disposed on the impeded center. The 
thickness of this layer on the impeded center will range from about 0.001 
millimeter (mm) to about 1 millimeter, preferably from about 0.005 
millimeter to about 0.4 millimeter. 
Any catalytic agent for oxychlorination reactions can be used in union with 
the layered catalytic support material to create active sites in the outer 
layer which will promote oxychlorination. This catalytic agent may be 
placed on or dispersed in the layered catalytic support material. 
The amount of active catalytic agent used can vary widely. Some factors 
influencing the quantative amount of catalytic agent used include type of 
coating material, surface area of the coating, layer thickness and 
porosity of the coating, and the specific catalytic agent used. In 
general, a catalytic agent in a range from about 0.01 to about 20% by 
weight, based on the weight of the finished catalyst will be used, but 
from about 0.5 to about 15% by weight of the finished catalyst is 
preferred. 
The present invention requires less active catalytic agent per catalyst 
gram than prior art catalysts, when these active agents are excluded from 
interior areas. A preferred catalytic agent is copper chloride (CuCl.sub.2 
or Cupric chloride). Copper chloride will normally comprise from about 0.1 
to about 9 weight percent of copper based on the total weight of the 
finished catalyst. Preferably from about 1 to about 7 weight percent 
copper based on the total weight of the finished catalyst is used. 
Optionally, a Group 1 or Group 2 metal salt catalyst modifier such as 
potassium chloride may be added. Examples of these modifiers are salts of 
lithium, sodium, potassium, magnesium, calcium, strontium, barium, cesium, 
or rubidium. The preferred modifier is potassium chloride. Amounts of 
these metal salts will range from about 0.05 to 1.0 on a molar basis 
relative to copper. A preferred metal to Cu mole ratio range is about 0.05 
to 0.4 respectively. Maintaining this ratio at the optimum value while at 
the same time varying carrier layer thickness will result not only in 
superior activity gradation in the reactor but also optimum selectivity to 
desired product. If desired, however, modifiers may be eliminated, and 
activity gradation controlled solely by varying layer thickness. 
Copper compounds suitable for use as active catalytic agents in 
oxychlorination reactions are cuprous chloride, cupric chloride, copper 
oxychloride, copper aluminate, copper titanate, copper niobate, copper 
silicate, copper nitrate, copper bromide, copper sulfate, or copper oxide, 
or copper salts of organic acids. Examples of other active catalytic 
agents known to catalyze oxychlorination reactions useful in the present 
invention are ferric chloride and manganese chloride. 
The catalysts of the instant invention can be prepared by a variety of 
methods. Normally, the impeded center is immersed in a dispersion of 
finely divided active carrier material, preferably, while using a center 
impeded by its low porosity. The coated centers are then removed from the 
dispersion, dried, and optionally calcined. Additional immersion steps are 
carried out until the desired shell thickness of carrier material is 
achieved. When using the immersion method to make this catalyst, 
preferably, a viscous dispersion is used so that the impeded centers will 
not be wetted, and a thicker layer is deposited per immersion. The 
catalyst can also be made by filling the pores of the impeded center with 
an inert liquid or other inert material, thereby closing this area to the 
carrier material and/or the catalytic agent. 
Methods of applying the catalytic agents themselves to carrier material are 
well known in catalyst art. Any method not destructive to the impeded 
center and surrounding carrier can be used. Usually simply immersing the 
carrier in a suitable solution of the catalytic agent is sufficient. The 
impregnated solid is then dried and optionally calcined. Alternatively, 
the carrier may be sprayed with a solution of the catalytic agents. 
Sequential stepwise applications of catalytic agents are also effective. 
The active catalytic agent may also be mixed with the coating material. 
When this method is used, however, a limited amount of carrier coating 
material should be used so as not to bury the active catalytic agents, and 
the impeded interior should have low porosity, with substantially all the 
pores greater than 150 Angstroms (.ANG.) in diameter. 
The catalysts of the instant invention may be used under any conditions or 
in any process suitable for a fixed bed oxychlorination catalyst. Some of 
the processes which may be used in conjunction with the instant invention 
are described in U.S. Pat. Nos. 3,867,469; 3,720,723; 3,564,066; 
4,025,461; 4,046,821; 3,892,816; Great Britain Patent No. 2,007,522A; and 
German Patent No. 26 51 974. Also, U.S. Pat. Nos. 4,123,467; 4,206,180; 
and Great Britain Patent Specifications Nos. 1,548,303; 1,548,304; and 
1,104,666. 
In the processes taught by these patents or in processes suitable for the 
catalysts of the instant invention, the organics should be in the vapor 
phase along with a gaseous source of oxygen and a gaseous source of 
chlorine, when contact is made with the structured catalyst. The organic 
reactants used may be alpha olefins in the range of C.sub.3 to C.sub.16, 
ethylene, or aromatic hydrocarbons. The temperature and pressure 
conditions used should therefore be adequate to insure this gaseous state. 
Temperature ranges preferred are from about 220.degree. C. to about 
320.degree. C.; most preferably the temperature range is about 250.degree. 
C. to about 280.degree. C. The pressure is preferably in the range of from 
about 0.29 pounds per square inch (PSI) to 150 pounds per square inch 
gauge (PSIG), the lower pressures being used for alpha olefins having from 
12 to 16 carbon atoms per molecule. The most preferable reactant is 
ethylene. A preferable source of chlorine is HCl. 
The oxychlorination process contemplated by the instant invention comprises 
contacting a gaseous mixture of an oxygen source, a chlorine source, and 
the hydrocarbon with one of the structured catalysts of the instant 
invention under conditions capable of promoting oxychlorination, and then 
collecting the chlorinated product. Preferably, the chlorine source is 
either HCl or a mixture of HCl and Cl.sub.2. 
In any oxychlorination process for fixed bed catalysts, the unique 
properties of the structured catalysts of the instant invention may be 
taken advantage of. For example, setting the modifier metal: copper mole 
ratio in the preferred range of from about 0.05 to about 0.4, while 
varying the thickness of the layered catalytic carrier material will 
achieve optimum catalyst activity gradation in the reaction. Catalysts so 
prepared are sufficiently resistant to deleterious heat effects on EDC 
selectivity that a reactor system packed throughout with a single zone of 
undiluted catalyst will produce commercially attractive production rates 
and selectivity. Savings in production lost during catalyst change-out 
would be gained from the speed which a single (instead of a multi-zone) 
catalyst can be charged. These catalysts also enable the total elimination 
of modifier which would increase conversion capabilities and result in the 
elimination of modifier-caused undesirables from the product, while still 
maintaining some activity gradation (reactor temperature) control by 
controlling carrier loading.

The following examples are presented to illustate the invention and not to 
limit it. In the examples, all parts and percentages are by weight unless 
otherwise specified. Example 1 is comparative while the subsequent 
examples illustrate the present invention. 
EXAMPLE 1 
A vertical 1" I.D..times.4' long nickel reactor was set up to simulate the 
first of a series of 3 oxychlorination reactors. Silicone oil at 
.about.200.degree. C. was pumped through the reactor jacket in upflow. All 
tubing exposed to HCl was nickel. All fittings exposed to HCl were monel. 
Feed gases were metered to the top of the reactor at 110 psig head 
pressure. The first .about.8.5" of reactor was used as a gas preheater. 
Reactor temperatures were measured by traveling thermocouple in a central 
vertical 1/8" O.D. nickel thermowell. 
The reactor was packed in 2 zones (as shown in FIG. 2) with catalysts made 
according to U.S. Pat. No. 4,206,180. Catalyst, A, in the top zone was 3-6 
mesh gamma alumina spheres impregnated with 5.6% CuCl.sub.2 and 2.8 weight 
percent (w/o) KCl based on the weight of the finished catalyst. Catalyst, 
B, in the bottom zone was 3-6 mesh gamma (.gamma.) alumina spheres 
impregnated with a nominal 18 w/o CuCl.sub.2 and 1.8 w/o KCl based on the 
weight of the finished catalyst. 
During reaction, the crude liquid contents of a knock-out pot were 
periodically collected, weighed, and analyzed by gas liquid chromatography 
(glc). A slipstream of offgas from the knock-out pot was scrubbed with 
dilute caustic solution. Periodic samples of the scrubbed offgas were 
analyzed by glc for organics. A slipstream of this scrubbed offgas was 
passed through an oxygen analyzer for measurements of unconverted oxygen. 
Table 1 indicates the gas feed rates. FIG. 1 shows the reactor temperature 
profile under the test conditions. Table 2 summarizes the glc analysis of 
crude liquid EDC. 
EXAMPLE 2 
A 615.0 gram (g) sample of 1/4" diameter alpha (.alpha.)-alumina spheres 
having a specific surface area of 15.5 m.sup.2 /g was saturated with 
distilled water, drained, and dipped into a dispersion of gamma 
(.gamma.)-alumina. The dipped spheres were drained and dried on stainless 
steel screens at 110.degree. C. for 1 hr., then calcined 1 hour at 
400.degree. C. 
The cooled spheres were rewet with distilled water, redipped in the 
.gamma.-alumina dispersion, redried at 110.degree. C. for 1 hour, and 
calcined at 500.degree. C. for 3 hours to produce 654.0 g of coated 
spheres. 
A 230.0 g sample of these coated spheres was impregnated with a 90 
milliliters (ml) solution of 33.6 g of CuCl.sub.2.2H.sub.2 O and 8.8 g of 
KCl in distilled water over 30 minutes. The spheres were drained and then 
dried at 170.degree. C. for about 16 hours to produce 262.0 g of 
tan-tinged magenta spheres. Analyses of these spheres showed 4.40 w/o Cu, 
1.72 w/o K, 5.95 weight percent (w/o) Cl.sup.-, and 475 parts per million 
(ppm) Fe. Surface area of the finished catalyst was about 14.5 m.sup.2 /g. 
and the .gamma.-Al.sub.2 O.sub.3 coating was about 5.2 wt.% of the total 
catalyst. 
The reactor was packed with these spheres as indicated in FIG. 2. The 
spheres were tested under the same conditions as in Example 1. Analytical 
results from the crude liquid EDC are shown in Table 2. The reactor 
thermal profile is shown in FIG. 2. 
EXAMPLE 3 
To a 230 g sample of 1/4" diameter .alpha.-alumina spheres having a 
specific surface area of 15.5 m.sup.2 /g was added a 360 ml solution of 
240.0 g of Al(NO.sub.3).sub.3.9H.sub.2 O in distilled water. After 15 
minutes, the excess liquid was drained and bottled. The spheres were dried 
overnight at 170.degree. C. and then calcined for 2 hours at 500.degree. 
C. to yield 237.4 g of coated spheres. 
These spheres were resoaked in the Al(NO.sub.3).sub.3 solution for 15 
minutes. The excess solution was rebottled. The spheres were re-dried at 
170.degree. C. and then calcined for 2 hours at 500.degree. C. to yield 
247.2 g of coated spheres. 
These spheres were similarly resoaked in the Al(NO.sub.3).sub.3 solution, 
drained, dried, and calcined in 4 more cycles to yield 286.5 g of coated 
spheres. 
A 266.5 g sample of the coated spheres was impregnated by soaking with a 
147 ml solution of 78.0 g of CuCl.sub.2.2H.sub.2 O and 20.48 g of KCl in 
distilled water for 10 minutes. The spheres were drained and dried 
overnight at 170.degree. C. to yield 307.9 g of mainly tan spheres. 
Analyses showed that these spheres contained 4.29 w/o Cu, 1.60 w/o K, 5.45 
w/o Cl.sup.-, and 270 ppm Fe. Surface area was 10.4 m.sup.2 /g and 
.gamma.-Al.sub.2 O.sub.3 coating was about 17.1 wt% of the total catalyst. 
The spheres were charged into the test reactor as shown in FIG. 3 and 
tested under the conditions of Example 1. Glc data on the crude liquid EDC 
product are indicated in Table 2. A broad reactor hotspot (285.degree. C.) 
was located at the bottom of the catalyst zone. 
EXAMPLE 4 
A 230.0 g sample of 1/4" diameter .alpha.-alumina spheres having a specific 
surface area of 15.5 m.sup.2 /g was soaked 5 minutes in a 836 ml solution 
of 800 g of Al(NO.sub.3).sub.3.9H.sub.2 O in distilled water. Excess 
liquid was drained and bottled. The drained spheres were dried for 2 hours 
at 170.degree. C. and then calcined for 2 hours at 500.degree. C. to yield 
241.6 g of coated spheres. 
These spheres were resoaked, dried, and calcined through 5 more cycles to 
yield 309.4 g of coated spheres. 
A 292.1 g sample of the coated spheres was impregnated with a 143 ml 
solution of 85.5 g of CuCl.sub.2.2H.sub.2 O and 22.4 g of KCl in distilled 
water for 5 minutes. The spheres were drained and then dried overnight at 
170.degree. C. to yield 332.4 g of mainly tan spheres. Analyses showed 
that these spheres contained 3.90 w/o Cu, 1.45 w/o K, 5.28 w/o Cl.sup.-, 
110 ppm NO.sup.-.sub.3, and 180 ppm Fe. Surface area was about 5.3 m.sup.2 
/g and the .gamma.-Al.sub.2 O.sub.3 coating was about 22.6% by wt. of the 
finished catalyst. 
These spheres were charged into the test reactor and tested under the 
conditions of Example 1. Glc data on the crude liquid EDC product are 
listed in Table 2, The reactor temperature profile is shown in FIG. 4. 
TABLE 1 
______________________________________ 
TEST CONDITIONS 
Gas Feeds, moles/hr. 
% O.sub.2 
Crude Liquid,g/hr 
Example # 
O.sub.2 
HCl C.sub.2 H.sub.4 
N.sub.2 
Conv. EDC H.sub.2 O 
______________________________________ 
1 4.0 18.4 56.7 98 97 518.0 170.1 
2 4.0 18.4 56.7 98 34 94.3 60.8 
3 4.0 18.4 56.7 98 62 320.1 130.2 
4 4.0 18.4 56.7 98 51 187.2 94.6 
______________________________________ 
TABLE 2 
______________________________________ 
Glc DATA FROM CRUDE LIQUID EDC 
NORMALIZED TO EXCLUDE C.sub.2 H.sub.4 
Organic 
Components, 
Example 
Mole Percent 
1 Example 2 Example 3 
Example 4 
______________________________________ 
Vinyl Chloride 
0.0734 0.0808 0.0046 0.0035.sup.c 
Ethyl Chloride 
0.7386 0.1257 0.1237 0.0759.sup.c 
(undesired) 
trans-Dichloro- 
0.1342 0.1631 0.1907 0.1545 
ethylene 
Carbon Tetra- 
0.0722 0.5923 0.3622 0.3342 
chloride 
(desired) 
Trichloro- 
0.1617 0.1778 0.2166 0.2138 
ethylene.sup.a 
Chloroform.sup.a 
0.0370 0.0409 0.0496 0.0489 
cis-Dichloro- 
0.0139 0.0153 0.0186 0.0184 
ethylene.sup.a 
Ethylene Di- 
98.6828 98.5740 98.9767 99.0462 
chloride 
(desired) 
1,1,2-Trichloro- 
0.0289 0.0259 0.0245 0.0239 
ethane 
Chloral 0.0000 0.0000 0.0000 0.0000 
2-Chloral- 
0.0000 0.0000 0.0000 0.0000 
ethanol 
Unknown.sup.b 
(0.0573 0.2042 0.0328 0.0809) 
______________________________________ 
.sup.a Chart traces ordinarily show cisdichloroethylene and chloroform 
shoulders estimated to be 5-10% each of the peak area computerintegrated 
as trichloroethylene. 
.sup.b Assumed to have molecular weight of 100 and glc response factors 
identical to that of ethylene dichloride. 
.sup.c Combined peak was assumed to contain VCM similar to that in Exampl 
3. 
EXAMPLE 5 
To indicate activity and the effectiveness of the .alpha.-Al.sub.2 O.sub.3 
impeded centers, a CuCl.sub.2 catalyst on .alpha.-Al.sub.2 O.sub.3 
spheres, was prepared as follows: 
500 ml of 1/4".alpha.-Al.sub.2 O.sub.3 spheres (same as used for the 
impeded centers in Examples 2-4) were soaked overnight in a solution of 
124.7 g of CuCl.sub.2.2H.sub.2 O and 19.8 g of KCl in 400 ml of distilled 
water in a covered beaker. The drained spheres were then dried for 2 hours 
at 160.degree. C. to yield a catalyst with the following properties: 
specific surface area=21.0 m.sup.2 /g 
weight percent Cu=4.77 
weight percent K=0.94 
weight percent Cl.sup.- =5.43 
K:Cu molar ratio=0.32 
The previously described reactor was charged with a 36" zone of this 
catalyst, and was heated to 200.degree. C., as usual, fed with 12.7 
moles/hr of ethylene, 11.8 moles/hr of HCl, 2.4 moles/hr of O.sub.2, and 
107 moles/hr of N.sub.2. The catalyst was inactive. For the catalyst 
described in Example 1, these conditions were sufficient to generate 
304.degree. C. hotspot temperature and 97% O.sub.2 conversion. 
DISCUSSION OF EXAMPLES 
Examples 1 through 4 and FIGS. 1 through 4 taken comparatively show that 
the catalysts of the present invention have superior selectivity to carbon 
tetrachloride and ethylene di-chloride. Lower amounts of the undesired 
ethyl chloride are also shown relative to the conventional catalysts of 
Example 1. (See mole percent data in Table 2) 
Since the structured catalysts' activity may be controlled by varying the 
coating of thickness, the modifiers used in Examples 2 through 4 are not 
necessary. Catalyst activity is controllable by varying the added 
parameters not available in conventional catalysts. More specifically this 
is achieved by varying the coating thickness via carrier loading in 
conjunction with the particular impeded center involved. With regard to 
the specific catalysts involved in Examples 2 through 4, an added benefit 
is achieved in eliminating the potassium modifier. With lower potassium 
concentrations in the catalysts, the production of undesired 
potassium-caused impurities would decrease. Such imputities are, for 
example, transdichloroethylene, trichloroethylene, chloroform, and 
cis-dichloroethylene. 
Another capability demonstrated by the examples given is a more moderate 
temperature gradation in the reactor. (See FIGS. 1, 2 and 4.) These data 
compare the conventional catalysts of Example 1 and the structural 
catalysts depicted in Examples 2 through 4, and indicate that reactor 
temperature can be more evenly distributed, if desired, through the use of 
structured catalysts without adversely affecting catalyst selectivity. 
FIG. 5 demonstrates the effects of these structured catalysts on activity. 
In these reactions oxygen was the limiting reactant so activity is 
expressed in terms of percent oxygen conversion. Note that values in 
parenthesis on FIG. 5 represent the corresponding values of specific 
surface area in meters squared per gram (m.sup.2 /g). 
The catalytic activity of the structured catalysts depicted in FIG. 5 was 
due to the gamma-alumina (.gamma.-Al.sub.2 O.sub.3) and active catalytic 
agent CuCl.sub.2 with KCl modifier. This is demonstrated by the fact that 
no activity was shown where there was no gamma-alumina coating. (See FIG. 
5-0% gamma-Al.sub.2 O.sub.3 and 0% activity for the catalyst described in 
Example 5.) 
The two distinct characteristics of this coating (carrier) material that 
influenced the oxygen conversion (activity) of this particular system 
were: (1) the amount, and, hence, thickness of the gamma Al.sub.2 O.sub.3, 
and (2) the resulting specific surface area of the catalysts surface after 
the coating was affixed to it (given on FIG. 5). Coating thickness has a 
stronger influence for the values found along line A. Line B indicates 
that at a certain point the loss of surface area, occurring simultaneously 
with increasing amounts of layered catalytic material will become the 
stronger influence and cause activity to decrease. This is probably due to 
the filling of large pores. Of course, the point intersection of these two 
lines will be different for each separate system since the characteristics 
of different materials and the characteristics of their inter-related 
state will change and will influence both porosity and specific surface 
area of the resulting structured catalyst. For the system disclosed in 
Examples 2 through 4 and depicted in the pertinent Figures, the maximum 
activity that may be expected is at approximately 13% gamma-Al.sub.2 
O.sub.3 coating. For that point, the percent conversion would be expected 
to be at around 74%. It is naturally expected that if the KCl modifier 
were eliminated, that the point of maximum conversion would increase 
considerably, most probably to nearly 100% conversion at even less gamma 
Al.sub.2 O.sub.3 coating. The beneficial use achieved by recognition of 
the nature of this relationship is that reactor activity may be 
specifically planned. For example, since catalyst activity can be planned, 
catalyst batches of varying activity can be prepared by changing the 
loading amounts of the layered carrier. Thus the thickness of the active 
coating would change. For a 3 zone system, if our structured catalysts 
were used, a less active catalyst is prepared for an initial zone, an 
intermediately active catalyst for a central zone, and the most active 
catalyst for the finishing reactor zone. This is achieved by varying the 
combined parameters delivered exclusively by the catalysts of this 
invention. Thus, one can tailor a fixed bed oxychlorination catalyst for 
individual circumstances and desires. 
While certain details have been shown for the purposes of illustrating this 
invention, it will be apparent to those skilled in this art that various 
changes and modifications may be made herein without departing from the 
script or scope of the invention. 
Having described our invention, what we desire to secure by Letters Patent 
are: