United States Patent (15) 3,679,762

La Hue et al. (45) July 25, 1972

(54) SELECTIVE HYDROGENATION OF 3,155,739 1 1/1964 Fleming............................. 260/677 H
ACETYLENES : 3,549,720 12/1970 Wright et al....................... 260/677 H
72 Inventors: Richard W. La Hue; Nolan A. Smith, both Primary Examiner-Delbert E. Gantz
of Louisville, Ky. Assistant Examiner-Veronica O'Keefe
73) Assignee: Catalysts and Chemicals Inc., Louisville, Attorney-Norman L. Wilson, Jr.
Ky.
22 Filed: June 8, 1970 57) ABSTRACT
21) Appl. No.: 44,567 In view of the exothermic nature of acetylene hydrogenation
reactions it is necessary to effect the hydrogenation of process
gas streams containing larger quantities of acetylenes under
52 U.S.C. .......................................... 260/677 H, 252/463 other than usually practiced conditions. Under such circum
5ll int. Cl............................................................C07c5/08 stances isothermal operation has become the process of cho
(58) Field of Search.............................................. 260/677 H ice. Whereas a multiplicity of palladium catalysts have found
(56) References Cited their place in adiabatic operation, very few of these perform
satisfactorily in isothermal reactors. We have found a palladi
UNITED STATES PATENTS um catalyst which outperforms these known catalysts.
3,075,917 1/1963 Kronig et al....................... 260/677 H 6 Claims, NoDrawings
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3,679,762
2
SELECTIVEHYDROGENATION OF ACETYLENES hydrocarbon or other coolant, since any unsubmerged portion
BACKGROUND OF THE INVENTION would react adiabatically. Coolant circulation on the shell side
must be rapid enough to remove sufficient heat to control the
With the growth of the plastics industry olefins such as exotherm and thus maintain a desired temperature rise or
ethylene and propylene are produced in ever increasing quan delta T during the reaction. It is to be understood, of course,
tities. In fact, ethylene is perhaps the largest volume that theoretically complete isothermal conditions are impossi
petrochemical in terms of production. These olefins are ob ble to achieve. However, the processes nevertheless are
tained in petroleum refineries from refinery off-gases or other referred to as isothermal processes. Isothermal operation for
refinery products. Other quantities are produced by the ther 10 hydrogenating acetylene gas streams is more complex than
mal cracking or pyrolysis of hydrocarbons. Feeds vary from adiabatic operation, which is employed when small quantities
ethane up through naphtha and other oil field condensates. of acetylene are present, i.e., less than 1 percent. Isothermal
It is known that olefins such as ethylene and propylene, as operation is nevertheless the process of choice if more than
commercially produced, frequently contain minor amounts of trace quantities of acetylene are present in the olefin gas
acetylenes, for example acetylene and methylacetylene. Such 5 stream.
commercially available olefins may not be suitable for some
purposes, such as polymerization processes, unless the SUMMARY OF THE INVENTON
acetylenes are first removed.
The most practical method of removing these acetylenes is tion of acetylene inhave
Many catalysts been used for the selective hydrogena
by selective hydrogenation. As pointed outin an article by An 20 tivity is now centered aroundstream.
an olefin
the use
However, most of the ac
of palladium. Palladium
derson et al. in I & EC, Nov. 1960, Vol. 52, No. 11, p. 901, in catalysts are very effective selective hydrogenation catalysts.
a full-scale plant with near-adiabatic reactors, a temperature Such being the case, palladium catalysts are described as
rise of between 52 and 131F. would occur in the bed for 1% hydrogenation catalysts throughout the prior art, for example
C.H. in an ethylene stream containing 3% H at 392 F., de
pending on the extent to which the excess hydrogen reacts 25 in U.S. Pat. Nos. 2,802,889, 2,946,829, 3,075,917, 3,113,980,
with the ethylene. Careful temperature control is thus andIt 3,116,342. is interesting to note that whereas the multiplicity of pal
required in catalytically processing ethylene streams to ladium
prevent excessive hydrogenation of ethylene. Hydrogenation very fewcatalysts have found their place in adiabatic operation,
of acetylenic compounds is highly exothermic. The heats of reactors. ofInthese catalysts perform satisfactorily in isothermal
accordance with this invention we have
hydrogenation of acetylene compounds are much higher than 30
of olefins, the delta H for ethylene being around -60,000 discovered,
all others in
quite unexpectedly, that one catalyst outperforms
isothermal operation. The catalyst is a palladium
BTU/pound mol, whereas for acetylenes the delta His around activated, predominantly alumina, hydrogenation catalyst of
-137,000 BTU/pound mol. improved selectivity having between 0.01 and 5 percent by
In view of the exothermic nature of the acetylene selective weight palladium on a dry basis uniformly distributed
hydrogenation process it is desirable to treat feed or process 35 throughout a support containing at least 70 percent alumina,
gas streams which contain larger quantities of acetylene, say any remainder being clay, the support having a surface area of
one-half to five mol percent, acetylene in a somewhat dif. 80 to 300 square meters per gram, with at least 50 percent of
ferent manner. In other words there is a limit to the concentra
tion of impurity that can be economically processed. This is its pores having average pore diameters in the size range
due to the fact that removal of the impurity is an exothermic 40 below 800 Angstrom units.
reaction resulting in a temperature rise across the catalyst bed. DETALED DESCRIPTION OF THE INVENTION
With high impurity concentrations, the temperature reaches a
level where the catalyst is non-selective and loss of product Olefins produced by cracking processes invariably are con
occurs. Under such conditions one of several methods are taminated with appreciable quantities of acetylenes. When
generally employed. The product stream can be recycled. 45 acetylene quantities are above normal, that is, above 1 volume
However it appears that recycling causes rapid fouling of the percent, the temperature rise becomes more critical during
catalyst, resulting in short operating cycles. Part of the hydrogenation. Careful temperature control is necessary dur
polymer, or green oil, in the recycle stream also tends to ing hydrogenation to minimize the polymer formation by
deposit on the catalyst surface, thus increasing the fouling SO
keeping the temperature rise as low as possible, since it is
rate. Another alternative is to use separate reactors and par known that polymer formation increases with increasing tem
tially hydrogenate the acetylene in each one. For this process perature. Careful temperature control is also required to keep
to be effective the stream must be cooled before injection into the temperatures below that wherein significant quantities of
a subsequent reactor. ethylene are hydrogenated. Another factor to be considered
The importance of isothermal operation will be appreciated 55 when the amount of acetylene is above one volume percent
when the heat of reaction that is, the temperature rise or delta during hydrogenation is that the polymer formation rate is
T, found in adiabatic operation, is compared with the delta T roughly proportional to the acetylene concentration. This
obtained under isothermal conditions sufficient to control the means also that the catalyst is adversely affected since, largely
heat of reaction. Under isothermal conditions 60 to 75 per due topolymer or green oil formation, the life of the catalyst is
cent of the heat of reaction is removed by heat transfer. Con 60 inversely related to acetylene content. The importance of
sider a process gas stream containing 2 mol percent acetylene isothermal operation is thus quite apparent. Unfortunately
to be hydrogenated in an adiabatic reactor to form ethane. If many acetylene hydrogenation catalysts do not perform as
the inlet or initial reaction temperature is 130 F., the delta T well under isothermal conditions as they do in adiabatic reac
will be 232 F. (274,000 BTU per pound mol of acetylene in tors. The temperature range is more narrow, and there is a risk
the feed stream). A 90 F. temperature rise will result if the 65 of a temperature runaway resulting from only a small change
conversion is carried out isothermally. It can be seen therefore in operating conditions. In addition polymer formation ap
that certain quantities of acetylene, say over one-half volume pears to increase in isothermal reactors.
percent, and especially 1 to 3 percent, require isothermal con In considering the effects of isothermal operation catalysts
ditions of operation. In fact an adiabatic reactor will not for the hydrogenation of acetylenic compounds, it must be un
operate if the feed gas stream contains more than 2 mol per 70 derstood that many hydrogenation catalysts are eliminated ab
cent acetylene because of the tremendous temperature rise. initio since there are only a limited number of catalysts effec
Isothermal acetylene hydrogenation generally involves the use tive in hydrogenating acetylene in admixture with ethylene
of a tubular reactor with the catalyst loaded into tubes which and to the exclusion of ethylene hydrogenation. For the most
are surrounded with a liquid coolant such as propylene or bu part these are palladium catalysts such as are disclosed in U.S.
tylene. The tubes must be completely surrounded with the 75 Pat. Nos. 2,802,889, 2,946,829, and 3,113,980. These depend
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3,679,762
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for their success on specific catalytic compositions such as in >800 Angstroms 31
active carriers, distinct pore volumes, mean pore radii and the 800-350 Angstroms
<350 Angstroms
11
S8
like. This invention is based on the discovery that in isother Average Pore Diameter (Angstroms) 210
mal operation one catalyst outperforms the other acetylene
selective hydrogenation catalysts. The catalyst found to be
outstanding in isothermal operations is the subject of U.S. Pat.
No. 3,549,720 and is incorporated herein by reference. This The outstanding efficiency of these catalysts, tested under
catalyst also contains palladium in the range of 0.01 to 5 per isothermal conditions considered severe due to the presence
cent by weight of the total catalysts, preferably 0.02 to 0.5. of greater than 1 mol percent acetylene in the gas stream, is
However, the physical properties of the catalysts of this inven 10 shown by the following data. The isothermal reactor was
tion represent departure from those of U.S. Pat. No. operated at a space velocity of 5,000 VIV/hr, a pressure of
3,113,980. The catalysts of this invention are characterized by 175 psig; and a temperature of 130 F. The process gas con
three desiderata: sisted of a mixture of 2 mol percent acetylene; 4 mol percent
The palladium must be uniformly distributed throughout hydrogen; 35 mol percent ethylene; and 59 mol percent
nitrogen. Percent conversions were determined from the per
the catalyst support. It cannot be only on or near the surface 15 cent
thereof; acetylene in the inlet stream and the percent acetylene in
The major quantity of the pores must have diameters tion the outlet stream. The activity retention, i.e., percent reten
smaller than 800 Angstrom units (A). Preferably more than version of activity, was determined by dividing the percent con
50 percent of the pores have diameters smaller than 350A, say 20 additionafter 100 hours on stream by the initial conversion. In
the polymerformed was quantitatively determined by
29 to 350 Angstroms;
The alumina must have a surface area above 80 square me collecting and measuring the liquid polymer formed during
100 hours on stream. In the appearance of the catalyst, "fou
ters per gram, preferably above 100.
Aluminas having these physical surface area and pore pro led' means the accumulation of polymer and/or carbon on the
dropped catalysts. The activity and polymer data resulting
perties are available, an such aluminas can be made by the 25 from the use of this catalyst were as follows:
process described in U.S. Pat. No. 2,894,898 and in U.S. Pat.
No. 3,539,468 filed Oct. 25, 1968. However, our preferred Activity
alumina is a commercially available active alumina obtained
from pure alumina hydrate. This alumina comes in the shape
of hard balls made by carefully controlled calcination of beta 30 Average of Two Runs
trihydrate. The alumina has a surface area of about 300 square Initial conversion (%) 81.0
Activity Retention (%) 60.7
meters per gram, a pore volume of 0.51 cc, per gram, and Polymer Formed (gm/hr X 10) 4.39
average pore diameters of 50 Angstroms. This alumina has Catalyst Appearance Slightly Fouled
very few pores larger than 800 Angstrom units in diameters.
Calcination redistributes the pore size so that the majority of EXAMPLE 2
pores are in the range below 350 Angstrom units in diameter. 35
As indicated hereinbefore the palladium promoter cannot Results obtained using a catalyst prepared as 4 X % inch
be on the carrier surface only. It must be uniformly distributed tablets in accordance with Example 1 were as follows. Reac
throughout the alumina support. There are two ways of insur tion and test conditions were the same as those given in Exam
ing that the palladium promoter is uniformly distributed 40 ple 1.
throughout the alumina supports. One method is by mixing or
milling a palladium compound into the composition before Physical Properties
forming into catalyst particles. However, the preferred
method of making certain that the palladium is uniformly dis Palladium (%) 0.035
tributed involves the selection of the noble metal salt. It has 45 Surface Area (m/gm) 86
been found, for example, that if PdCl is employed, palladium Pore Volume (cc/gm) 0.62
Pore Volume Distribution
will not be distributed throughout the alumina. If alumina pel (Percent based on pore diameter size)
lets are dipped in a solution of Pdc1, the palladium will >800 Angstrons
800-350 Angstroms 14
2
remain on or near the surface of the alumina carrier. How K350 Angstroms 74
ever, if alumina pellets or tablets are dipped in an aqueous 50 Average Pore Diameter (Angstroms) 292
solution of Pd(NH),Cl, the palladium penetrates the carrier
and will be uniformly distributed throughout the tablets after Activity
drying.
In order to illustrate the preparation of the catalyst in ac Average of Three Runs
cordance with this invention the following example is given. 55 Initial Conversion (%) 79.0
Activity Retention (%) 51.0
EXAMPLE1 Polymer Formed (gm/hr X 10)
Catalyst Appearance
3.22
Alumina prepared according to Example 1 of U.S. Pat. No. Slightly Fouled
3,539,468 was formed into 4 x 8 mesh spheres. Following U.S. 60
Pat. 3,549,720 the resulting particles were then calcined at EXAMPLE3
1,950 F. yielding catalysts having the surface area and pore Results obtained using another catalyst prepared as 6 x 8
properties listed hereinafter. The particles were then dipped in mesh spheres in accordance with Example 1 were as follows.
sufficient aqueous solution of Pd(NH3)Cl. to cover and in Reaction and test conditions were the same as those given in
pregnate them with 0.035 weight percent palladium based on 65 Example 1.
the weight of the catalyst. After being drained and dried at
250 F., the particles were calcined at 700°F. This catalyst Physical Properties
had the following properties:
Physical Properties Palladium (%) 0.035
70 Surface Area (m/gm) 103
Pore Volume (ccigm) 0.68
Pore Volume Distribution
Palladium (%) 0.035 (Percent based on pore diameter size)
Surface Area (m/gm) 122 >800 Angstroms 20
Pore Volume (cc/gm) 0.64 800-350 Angstroms 14
Pore Volume Distribution <350 Angstroms 66
(Percent based on pore diameter size) 75 Average Pore Diameter (Angstroms) 26S
 3,679,762
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pregnated spheres were allowed to stand about 30 minutes
Activity and then dried at 250 F. and calcined at 2,100 F. Then the
catalyst precursor was dipped in a solution of palladium
Average of Five Runs 5 chloride, with sufficient palladium chloride to form a catalyst
Initial Conversion (%)
Activity Retention (%)
82
68
containing 0.035 weight percent palladium. It was then cal
Polymer Formed (gm/hr x 102) 3.50 cined at 700 F. The catalyst was tested as described in Exam
Catalyst Appearance Slightly Fouled ple 1.
Physical Properties
10
To illustrate another method of preparing catalysts em Palladium (%)
ployed herein the following is given:
0.035
EXAMPLE 4 Surface Area (m/gm) 25
5 Pore Volume (cc/gm) 0.60
Alumina trihydrate and sufficient palladium nitrate so that Pore Volume Distribution
the finished catalyst contains 0.035 weight percent palladium (Percent based on pore diameter size)
>800 Angstroms 57
were dry mixed, and then sufficient water was incorporated in 800-350 Angstroms 17
the mix to yield an extrudable mass. The mass was extruded in <350 Angstroms 26
one-eighth inch particles or extrusions. The following are 20 Average Pore Diameter (Angstroms) 960
catalyst properties, and also test results obtained when this
catalyst was used in the process described in Example 1. Activity
Physical Properties
Initial Conversion (%) 85
25 Activity Retention (%) 16.5
Palladium (%) 0.035 Polymer Formed (gm/hr X 10) S.09
Surface Area (m/gm) 280 Catalyst Appearance Medium Fouling
Pore Volume (cc/gm) 0.80
Pore Volume Distribution
(Percent based on pore diameter size) EXAMPLE 6
>800 Angstroms 2
800 - 350 Angstroms 3 A commercially available catalyst closely resembling the
<350 Angstroms 95 catalyst of Example 5 and similarly prepared and in the form
Average Pore Diameter (Angstroms) 14
of 1/8 x 3/16 tablets had the following properties.
Activity
Initial Conversion (%) 87 35 Physical Properties
Activity Retention (%) 63
Polymer Formed (gm/hr X 10) 2.56
Catalyst Appearance Slightly Fouled Palladium (%) 0.032
Surface Area (m/gm) 86
Pore Volume (cc/gm) 0.30
40 Pore Volume Distribution
To further illustrate the invention, results obtained using (Percent based on pore diameter size)
>800 Angstroms 50
different catalysts of the invention are given. These additional 800-350 Angstroms 20
catalysts are other preparations made by Examples 1 and 3. In <350 Angstroms 30
two of the catalysts, however, less palladium salt was em Average Pore Diameter (Angstroms) 42
ployed, sufficient so that the finished catalyst contained only 45
0.020 weight percent palladium. Activity
TABLE 1.
Initial Conversion (%) 81.0
Initial Activity Polymer 50 Activity Retention (%) S0.6
Conversion Retention Formed Polymer Formed (gm/hr x 10) 4.18
Catalyst (Percent) (Percent) (gm/hr x 10') Catalyst Appearance Medium Fouling

Ex. 1 using 0.035 Pd 86 62 4.39 EXAMPLE 7

Ex. 1 using 0.020 Pd 87 51 2.93
Ex.3 using 0.035 Pd 75 72 3.50 55
Ex.3 using 0.020 Pa 65 62 2.20 Alumina was formed into 3 x 8 mesh spheres and calcined
at 950 F. to be used as a carrier. In an amount of water
required to completely cover a given quantity of these pellets,
normally 100 parts by weight of pellets, sufficient palladium
Referring to the foregoing examples, it is to be noted that in 60 chloride was dissolved to form a catalyst coated with 0.035
itial conversions are high and polymer formation is low. How weight percent palladium. The 100 parts by weight of carrier
ever, of particular significance is the face that more than 50 pellets were then submerged in the palladium chloride solu
percent of the activity remains (activity retention) after 100 tion and allowed to stand 30 minutes. The liquid was drained
hours. This generally is not the case with other acetylene off and the pellets dried at 250 F. The pellets were then sub
hydrogenation catalysts. This will be particularly apparent 65 sequently calcined at 700 F. to form a 0.035 weight percent
from results obtained with the following catalysts. palladium catalyst. When tested as set forth in Example 1, this
EXAMPLES catalyst had an initial conversion of 73.0 percent, and only a
28.8 percent activity retention. The catalyst had a surface area
A commercially available catalyst was prepared using 100 of 275; a total pore volume of 0.50; and a pore distribution as
pounds of a purchased active alumina, manufactured by care 70 follows: > 800 Angstroms, 18%; 800-350 Angstroms, 10%;
fully controlled calcination of beta trihydrate having a surface and <350 Angstroms, 72%.
area of 360 m/gm and formed into 3 x 8 mesh spheres. The Examples 5 and 7 illustrate that even well known acetylene
spheres were impregnated with three pounds of nickel nitrate. hydrogenation catalysts do not perform adequately in isother
The nickel nitrate was dissolved in that predetermined quanti mal operation. The catalyst which is described in Example 8
ty of water which would be absorbed by the alumina. The im 75 performed similarly, as reference to Table 2 will show.
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3,679,762
8
EXAMPLE 8 catalysts where possible, such as those of this invention
A catalyst closely resembling the catalyst of Example 7 and characterized by high activity retention values and low
similarly prepared was purchased from another source in the polymer formation.
form of 1/8 inch X 3/16 inch extrusions. Results of reaction Isothermal hydrogenation conditions are well known. It is
and test conditions given in Example 1 are as follows: 5 also known that the particular process conditions employed in
isothermal operation during selective hydrogenation of
Physical Properties acetylenes affect the results. Thus, the rates of reaction,
polymer formation, etc., are functions of temperature, pres
sure, and the like. At the higher temperature levels the
Palladium (%) 0.025 O catalyst has less selectivity, the result being an increase in
Surface Area (m/gm) 281 ethylene hydrogenation. At high temperatures, say those
Pore Volume (cc/gm) 0.66
Pore Volume Distribution above 400 F., the possibility of olefin degradation or cracking
(Percent based on pore diameter size) exists. Temperatures therefore are in the range of 80 to 400
>800 Angstroms 3 F. As pressure is increased the catalyst shows increased activi
800-350 Angstroms 4. 15 ty thus decreasing the quantity of catalyst required by increas
<350 Angstroms 93
Average Pore Diameter (Angstroms) 96 ing the allowable space velocity. Pressures of atmospheric to
800 psig are used. Varying the hydrogen concentration to give
Activity an excess or deficiency of H in relation to the stoichiometric
Initial Conversion (%) 80.0 quantity has an effect on performance as would be expected.
Activity Retention (%) 23.0 20 Excess H, promotes the hydrogenation of olefins rendering a
Polymer Formed (gm/hr X 10) S.34 higher temperature which promotes polymer formation. A
Catalyst Appearance Badly Fouled
deficiency of H limits hydrogenation and conversely reduces
polymer production; however adequate cleanup is normally
not achieved if a significant deficiency exists. Choice of the
The unexpected superiority of the catalysts of this invention 25 correct space velocity at which a reactor should be operated is
can best be seen by comparing the activity retention abilities, important from the economic standpoint during design and
the quantity of polymer formed, and the ultimate appearance form the performance standpoint during operation. Space
of these catalysts with those of other commercial isothermal velocities of 2,000 to 20,000 are employed. Variations in
selective hydrogenation catalysts. Commercial catalysts are these and other aspects of the invention will occur to those
those of Examples 5, 6, 7, and 8. The invention catalysts con 30 skilled in the art. As an example, any of the various catalyst
taining 0.035 percent palladium compared therewith are pellet shapes can be employed. Tablets and extrusions are ill
prepared by following the examples whose numbers are given. lustrated, as well as spheres prepared by U.S. Pat. No.
The test results given are results of different batches than 2,889,576. Other methods of preparing these catalysts will
those previously prepared and tested. Hence these and earlier also be obvious to those engaged in this field.
results are not identical. 35 What is claimed is:
TABLE 2 1. In the process for purifying an olefin gas stream contain
ing acetylene, wherein the acetylene is removed from said
Comparison of Invention with Commercial Hydrogenation olefin stream by selective hydrogenation, the improvement for
Catalysts use when said stream contains 2 to 5 volume percent
40 acetylene, a quantity of acetylene requiring near-isothermal
Initial Activity Polymer operation, which comprises providing a reaction chamber sur
Cata- Conver- Reten- formed Catalyst rounded with a coolant material adapted to remove at least
lyst sion tion% (gm/hrxx10)Appearance sixty percent of the heat of reaction, at a temperature of 80 to
400 F. and at a pressure of atmospheric to 800 psig passing
Ex. 5 (Com) 87 34 5.93 Medium Fouling 45 the olefin gas stream through a mass of a selective hydrogena
Ex. 2 (Inv.) 81 73 3.22 Slightly Fouled tion catalyst within said chamber while concomitantly remov
Ex. 6 (Com) 82 SS 4.05 Medium Fouling ing said quantity of the heat of reaction, the catalyst being a
Ex. 2 (Inv.) 86 72 2.92 Slightly Fouled
Ex. 7 (Com) 87 34 5.93 Badly Fouled palladium activated, predominately alumina hydrogenation
Ex. 3 (Inv.) 88 69 3.50 Slightly Fouled catalyst of improved selectivity having between 0.01 and 5
Ex. 8 (Com) 83 36 5.34 Medium Fouling 50 percent by weight palladium on a dry basis uniformly dis
Ex. 4 (Inv.) 87 63 2.56 Slightly Fouled
tributed throughout a support containing at least seventy per
cent alumina, any remainder being clay, the support having a
surface area of 80 to 300 square meters per gram, with at least
The foregoing data illustrate an improved performance 50 percent of its pores having pore diameters in the size range
catalyst which there is no reason to expect would be any better 55 below 350 Angstrom units.
than the other catalysts, particularly that of Example 6 which 2. The process of claim 1 wherein the stream contains 2 to 3
is a highly commercial catalyst. The catalysts of this invention volume percent acetylene.
have been found to surpass all known catalysts in this particu 3. The process of claim 1 wherein the hydrogenation
lar application. Thus known commercial catalysts have activi catalyst has 50 to 98 percent of its pores having pore diame
ty retention values after 100 hours on stream appreciably less 60 ters in the range of 29 to 350 Angstroms, wherein only 1 to
than 60 percent, that is, about 17 to say 50 or 55 percent, about 30 percent of the pores have a pore diameter larger than
whereas the catalysts of this invention have retention values 800 Angstroms, and wherein its surface area is in the range of
ranging from fifty to 73 percent. It is not to be understood on 90 through 200 square meters per gram.
the basis of these 100 hour tests that the catalysts are effective 4. The process of claim 1 wherein the catalyst contains 30
for only 100 hours. Normally these catalysts in commercial 65 percent kaolin.
isothermal reactors will have cycle lengths of 1 to 4 months. 5. The process of claim 1 wherein the catalyst is devoid of
These catalysts at the end of a cycle are regenerated by steam clay.
ing in the presence of air at elevated temperatures, thereby 6. The process of claim 1 wherein the catalyst is im
restoring the activity to essentially that of new catalysts. How pregnated with 0.002 to 0.5 percent palladium by weight
ever, regeneration procedures are expensive. Therefore it is 70 based on the catalyst.
preferred to minimize the number required by using long life sk sk k sk se

75