Process for catalytic conversion of ethylene to higher hydrocarbons

A method for converting normally gaseous olefins (esp., ethylene) to normally liquid hydrocarbons wherein the olefin feed is contacted with a siliceous molecular sieve at elevated temperatures and short olefin contact times under high severity conditions favorable for substantial conversion of olefins with maximized liquids productivity. ZSM-5 type zeolites and crystalline borosilicate molecular sieves are particularly preferred catalysts.

BACKGROUND OF THE INVENTION 
This invention relates to a method of catalytically converting olefins into 
higher hydrocarbons. This invention more particularly relates to a method 
for converting ethylene to higher hydrocarbons by contact with siliceous 
crystalline molecular sieves. Conversion of various hydrocarbon fractions 
with acidic catalysts generally and more particularly with siliceous 
crystalline molecular sieves is well known in the art. The conversions for 
which such catalysts have been used include cracking, isomerization, 
hydrocracking, etc. Molecular sieves have also been used for the 
conversion of hydrocarbon feeds consisting essentially of C.sub.2 -C.sub.5 
olefins, mixtures thereof, and mixtures thereof with paraffins to higher 
molecular weight products. 
U.S. Pat. No. 3,325,465 teaches a process for polymerizing olefinic 
hydrocarbons over zeolites, the initially present cations of which have 
been partially exchanged with cations selected from the group consisting 
Co,Ni and rare earth cations. Ethylene polymerization at atmospheric 
pressure is described in Examples 3-8 of the patent. At column 6, lines 
41-47, the patent teaches that use of atmospheric pressure is preferred, 
although pressures up to 1000 atmospheres may be used. Higher pressures 
are said to increase throughput but increase the risk of catalyst 
deactivation. Operating temperatures of 25 .degree. to 400 .degree. C. and 
space velocities of 50 to 1000 hr..sup.-1 VHSV (volume hourly space 
velocity), preferably less than 300 hr. .sup.-1 VHSV, are taught. 
Hydrocarbon diluents such as paraffins and/or cycloparaffins may be 
present in the olefinic feedstock, but the patent does not indicate what 
effect such presence may have on selection of operating parameters for the 
process. 
U.S. Pat. No. 3,760,024 teaches preparation of aromatic compounds by 
contacting C.sub.2 -C.sub.4 paraffins and/or olefins with a ZSM-5 type 
zeolite. Operating temperatures of 100.degree.-700.degree. C., operating 
pressures of 0-1000 psig (preferably 0-500 psig), and space velocities of 
0.5-40 hr. .sup.-1 WHSV (weight hourly space velocity) are taught. The 
particular combination of operating parameters employed is selected to 
produce a significant yield of liquid product from a given feedstock, 
which product is substantially aromatic in nature. 
U.S. Pat. No. 3,827,968 discloses an aromatization process wherein the 
olefin content of a C.sub.2 -C.sub.5 olefin-containing feed is first 
oligomerized to produce higher molecular weight olefins over a ZSM-5 type 
zeolite and then contacting the liquid, higher molecular olefins with a 
zeolite catalyst in a second stage to produce aromatic liquids. The first 
step of the '968 process differs from the '024 patent in that less severe 
operating conditions are used to produce a product having a liquid portion 
consisting principally of C.sub.5 -C.sub.9 olefins. Attempting direct 
aromatization of certain feedstocks--especially those containing large 
amounts of paraffins--was apparently found to cause rapid catalyst aging 
and/or deactivation. Operating conditions employed in the first step of 
the '968 patent include temperatures of 290.degree.-450.degree. C., 
pressures up to 800 psig and 0.5-50 hr. .sup.-1 WHSV. The first stage 
oligomerization effluent, in addition to olefinic liquids, contains a gas 
product consisting of a highly paraffinic C.sub.4 - stream. In addition, 
the second stage of the '968 process produces an effluent which may 
contain up to 50% C.sub.4 - paraffins. The C.sub.4 - paraffin streams are, 
according to the '968 patent, preferably recycled to a pyrolysis unit. 
U.S. Pat. No. 3,960,978 discloses the conversion of gaseous C.sub.2 
-C.sub.5 olefins, either alone or in admixture with paraffins, to a 
gasoline fraction having no more than about 20 wt. % aromatics by 
contacting the olefin feed with a ZSM-5 type zeolite having a controlled 
acid activity (i.e., alpha value) of about 0.1-120. Other oligomerization 
conditions include temperatures of 260.degree.-480.degree. C. (preferably 
290.degree.-450.degree. C.), WHSV of 0.1-25 hr..sup.-1 (preferably 
0.5-20), and hydrocarbon partial pressures of 0.5 to 40 atmospheres 
(preferably 0.5-20 atmospheres). An advantage of the process is said to be 
improved catalyst stability. Example 1 of the patent shows oligomerization 
of propylene according to the method of the '978 patent. The gaseous 
product produced was primarily C.sub.4 olefins. The patent suggests 
recycle of the gaseous C.sub.4 olefin byproduct to extinction. 
U.S. Pat. No. 3,972,832 discloses conversion of aliphatic compounds over 
phosphorus-containing zeolites. Example 8 of the patent shows that when 
ethylene is contacted with the phosphorus-containing zeolite at 
500.degree. C. and a WHSV of about 1.5, ethylene is converted into 
propylene and C.sub.5 hydrocarbons as the major products. As compared to a 
zeolite without phosphorus, the olefin/paraffin ratios of the product 
obtained over the phosphorus-containing zeolite were much higher and the 
quantity of aromatics produced was much less. Also see U.S. Pat. No. 
4,044,065 at column 9, lines 32-48. 
U.S. Pat. No. 4,021,502 discloses the conversion of gasesous C.sub.2 
-C.sub.5 olefins or mixtures thereof with C.sub.1 -C.sub.5 paraffins to 
higher molecular weight olefins, over ZSM-4, ZSM-12, ZSM-18, chabazate or 
zeolite beta. The process is operated under conditions selected to give 
low yields of aromatics. Temperatures are about 230.degree.-650.degree. C. 
(preferably 290.degree.-540.degree. C.). WHSV is about 0.2-50 (preferably 
1-25). Hydrocarbon partial pressures are about 0.1-50 atmospheres 
(preferably 0.3-20 atmospheres). An advantage of the process is said to be 
the stability of the zeolite under the conditions employed. 
U.S. Pat. No. 4,070,411 discloses the conversion of lower olefins (e.g., 
ethylene or propylene) over HZSM-11 catalyst to produce a product having a 
significant isobutane content. The conversion is effected at temperatures 
of 300.degree.-500.degree. C. and at space velocities of 0.5-100 WHSV. 
U.S. Pat. No. 4,100,218 discloses a process for converting ethane to LPG 
and gasoline and/or aromatic concentrate by passing olefin effluent from 
the thermal cracking of ethane over a ZSM-5 type zeolite. 
U.S. Pat. No. 4,150,062 discloses the conversion of C.sub.2 -C.sub.4 
olefins over ZSM-5 type zeolites in the presence of co-fed water. 
Temperatures are about 230.degree.-430.degree. C. (preferably 
290.degree.-400.degree. C.). Pressures range from atmospheric to 1000 psig 
(preferably from atmospheric to 450 psig). The WHSV is about 0.2-20 hr. 
.sup.-1. 
U.S. Pat. No. 4,211,640 teaches conversion of olefinic gasoline fractions 
over ZSM-5 type zeolites to produce gasoline (having enhanced gum 
stability) and fuel oil. 
U.S. Pat. No. 4,227,992 discloses a process for selectively reacting 
C.sub.3 and higher olefins from a mixture of the same with ethylene to 
produce products comprising fuel oil and gasoline. Operating conditions 
are selected such that the C.sub.3 and higher olefins are substantially 
converted to products comprising fuel oil and gasoline but such that 
substantially no ethylene will be converted. Generally, operating 
pressures are within the range of about 100-1000 psig, temperatures are 
within the range of about 150.degree.-315.degree. C., and space velocities 
are within the range of about 0.1-10 WHSV (based on the C.sub.3 and higher 
olefins). 
U.S. Pat. No. 4,451,685 teaches conversion of lower olefins to gasoline 
blending stocks over borosilicate catalysts. 
U.S. Pat. No. 4,423,268 teaches oligomerization of normally gaseous olefins 
over essentially alumina-free molecular sieves (e.g., silicalite). 
As noted, conversion of olefins to gasoline and/or distillate products over 
a ZSM-5 type catalyst is known. See the description of U.S. Pat. Nos. 
3,960,978 and 4,021,502, supra. U.S. Pat. No. 4,227,992 discloses 
operating conditions for selective conversion of C.sub.3 +olefins and no 
more than 20% ethylene conversion. Closely related is U.S. Pat. No. 
4,150,062 which discloses a process of converting olefins to gasoline 
components. In such processes for oligomerizing olefins using acidic 
crystalline zeolites, it is known that process conditions may be varied to 
favor the formation of either gasoline or distillate range products. At 
moderate temperatures (i.e., 190.degree.- 315.degree. C.) and relatively 
high pressures (i.e., 42-70 atmospheres) the conversion conditions favor 
distillate range product having a normal point of at least 165.degree. C. 
At moderate temperature and relatively lower pressures (i.e., 7-42 
atmospheres), the conversion conditions favor gasoline and distillate 
range products. See U.S. Pat. No. 4,211,640. 
One object of the present invention is an improved method for converting 
ethylene to high yields of heavier hydrocarbons. A more particular object 
is the production of normally liquid hydrocarbons from ethylene under 
conditions whereby catalyst productivity is maximized, employing a 
siliceous crystalline molecular sieve catalyst. Other objects, aspects and 
the several advantages of the present invention will be apparent to those 
skilled in the art upon consideration of the following description of this 
invention and of the appended claims. 
SUMMARY OF THE INVENTION 
In accordance with the present invention there is provided a process for 
producing normally liquid hydrocarbons which process comprises contacting 
a gas comprising ethylene with a siliceous crystalline molecular sieve 
under high severity conditions including elevated temperatures and short 
olefin contact times, said conditions being selected such that the liquids 
productivity of the catalyst is greater than about 50%, preferably greater 
than about 75%, of the theoretical maximum liquids productivity. In 
addition to ethylene the feed to the process of this invention may contain 
other normally gaseous olefins and may also contain other hydrocarbons 
such as paraffins (e.g. methane and higher alkanes) as well as inorganic 
components. 
Oligomerization of olefins according to the method of this invention has 
been found to allow substantial olefin conversion to normally liquid 
hydrocarbons with maximized liquids productivity. One preferred method for 
carrying the present process comprises continuously recirculating 
molecular sieve catalyst between an ethylene contact zone and a 
regeneration zone.

DETAILED DESCRIPTION OF THE INVENTION 
The feedstock converted to normally liquid hydrocarbons according to this 
invention may contain ethylene and C.sub.3 + olefins. In addition, the 
feedstock may contain other hydrocarbon or non-hydrocarbon components. 
Examples of other hydrocarbon components include the lower alkanes, 
especially C.sub.1 -C.sub.5 alkanes. Examples of non-hydrocarbon 
components include water, carbon oxides (i.e., CO and/or CO.sub.2), 
N.sub.2 and the like. The presence of steam in the catalyst reactor zones 
under the temperature conditions employed is presently believed to 
substantially effect the aging and/or the deactivation characteristics of 
the catalyst employed and, accordingly, it is preferred to avoid the the 
presence of steam in the oligomerization process of this invention. 
Preferably, the olefins are converted in the substantial absence of 
hydrogen. 
One distinct aspect of the present invention involves the use of highly 
dilute olefinic feedstocks. More particularly, according to this aspect of 
the present invention, it has been found that desirable results may be 
obtained even though the feedstock contains major amounts (i.e., more than 
50 vol. %) of lower alkanes. It has further been found that desirable 
results may be obtained even though the feedstock contains major amounts 
(i.e., more than 50 vol. %) of methane. When employing such highly dilute 
olefinic feedstocks in the process of this invention, it has been found 
advantageous to maintain the ethylene partial pressure in the feed 
contacted with the catalyst in the oligomerization zone within the range 
of about 0.5 to 5 atmospheres, preferably within the range of about 1 to 
2.5 atmospheres. Total operating pressure in the first reactor zone is 
thus determined, according to this aspect of the invention, by the 
ethylene content of the feed to the oligomerization zone. According to 
this aspect of the present invention such ethylene content may vary 
broadly, e.g., from less than about 10 vol. % to 50 vol. %. 
As will be apparent to those skilled in the art, the selection of whether 
to employ such highly dilute, olefinic feedstocks or to first isolate an 
olefinic fraction of such feedstock prior to oligomerization according to 
this invention, will be dependent on the cost of processing the highly 
dilute feedstock via oligomerization relative to the cost of isolating an 
olefinic fraction therefrom. In general, it will noted that alkane 
recovery from oligomerization effluents (particularly the second catalyst 
rector zone effluent of the process of this invention) is much easier than 
isolation before oligomerization. 
The process of this invention is particularly suited to oligomerizing 
feedstocks comprising an olefinic fraction which contains a major amount 
(i.e., greater than 50 vol. %, preferably greater than 70 vol. %) of 
ethylene. 
One observation that led to the present invention was that operating modes 
may be selected to maximize the liquids productivity of the molecular 
sieve oligomerization catalyst. By "liquids productivity" is meant weight 
of liquid hydrocarbons produced/weight of catalyst/hour or, alternatively, 
weight of liquid hydrocarbons produced/volume of catalyst/hour. More 
meaningful comparisons between different molecular sieves are possible 
using the latter expression of productivity because the densities of the 
catalysts are widely variable. 
A related observation is that operating modes which maximize liquids 
productivity involve very high severities. Hence, the catalyst deactivates 
rapidly. However, as will be described in more detail below and as 
illustrated in the Examples, it is possible to select operating variables 
to produce the high severities required by the process of this invention 
which result in sufficiently long periods of operation at high catalyst 
productivity such that catalyst regeneration may be used to maintain the 
desired productivities. More specifically, reaction means comprising a 
system comprising a high-severity oligomerization zone and a catalyst 
regeneration zone with catalyst preferably continuously recirculating 
between the two zones is desirably employed to fully exploit the 
advantages of the broader aspects of this invention. 
The broad concept of contacting olefins with a siliceous crystalline 
molecular sieve to oligomerize the olefins is not novel. A key to one 
inventive concept of this invention resides in selecting within a limited 
range of operating conditions such that the following objectives will be 
accomplished: 
(1) ethylene will be substantially converted, i.e., greater than about 50 
and preferably greater than about 80 wt % is converted and 
(2) the products obtained are such that hydrocarbon liquid productivity of 
the catalyst is maximized. 
Maximization of catalyst productivity may be expressed by stating that the 
liquids productivity of the catalyst is greater than about 50%, preferably 
greater than about 75% of the theoretical maximum. The theoretical maximum 
liquids productivity for any given reactor system is obtained by dividing 
the ethylene feedrate (e.g., grams C.sub.2 =/hour) by the volume of 
catalyst present in the reactor. 
The characteristics of the normally liquid hydrocarbons produced are not of 
primary concern in the selection of operating variables. Maintenance of 
catalyst stability over relatively long run times is not an object of this 
invention. Rather such catalyst stability is sacrificed in order to 
maximize liquids productivity. 
The general operating parameters for the oligomerization method of this 
invention can be defined by stating that the conversion is effected at 
short contact times and that the ethylene feed is introduced to the 
oligomerization zone at elevated temperatures. By "short contact times" is 
meant contact times selected within the range of about 0.1-3 seconds, 
preferably within the range of about 0.1-1 second. By "elevated 
temperature" is meant a temperature selected within the range of about 
285.degree.-425.degree. C., preferably 325.degree.-375.degree. C. 
The temperature ranges specified are initial temperatures--the temperatures 
at which the olefin feed is introduced to the oligomerization zone. 
Employing the high severities required by the present invention results in 
highly exothermic reactions. Relatively high exotherms (as much as 
300.degree. C. or higher) will occur during oligomerization. Although 
means (e.g., alkane dilution or staged reactors with interstage cooling) 
may be employed to reduce the magnitude of such exotherms, such means need 
not be employed to attain the results of this invention. 
Having selected an initial temperature and contact time, operating 
pressures and space velocities may be selected. Temperature and contact 
time are considered primary operating variables. Pressure and space 
velocity are considered secondary operating variables. Generally, however, 
it has been found desirable to maintain the ethylene partial pressure of 
the feedstream within the range of about 0.5-5 atmospheres, preferably 
within the range of about 1-2.5 atmospheres. 
These ranges of initial temperature, contact time, pressure and space 
velocity are not intended to be construed as meaning that all operations 
within these limits will accomplish the desired results of this invention. 
What is meant by these units is best expressed in a negative way. 
Operation outside the ranges set forth will not accomplish the desired 
results of the process of this invention. A well-known correlation exists 
between temperature, pressure and space velocity with respect to the 
severity of the reaction. Stated simply, the present method is concerned 
with the conversion of ethylene to normally liquid hydrocarbons at a 
severity such that ethylene is substantially converted and the liquids 
productivity of the catalyst is maximized. The examples below illustrate 
such a severity. 
To further illustrate, it is known that as contact time is decreased, 
higher temperatures are necessary to achieve the desired severity. 
Conversely, as contact time increases, lower temperatures are necessary to 
achieve the desired severities. Contact time varies directly with pressure 
and varies inversely with space velocity. 
Thus, if the pressure remains constant and space velocity is increased, 
then a higher temperature is necessary to achieve the desired severity. 
Conversely, if the space velocity would remain constant and the pressure 
increased, then a lower temperature is necessary to achieve the desired 
severity. The precise contact time (and space velocity and pressure) for 
any given temperature within the broad range previously stated can be 
easily obtained by routine experimentation following the guidelines and 
illustrations set forth herein. 
One feature of the present invention which is of principal significance to 
the design of reaction means for carrying out the present process is the 
relatively rapid deactivation of the catalyst. It has been found that 
initial catalyst activity may be regenerated and maintained by relatively 
frequent regeneration of the catalyst during use. Regeneration means per 
se are conventional and known to those skilled in the art. A preferred 
reaction system for the present process is one comprising an 
oligomerization zone and a regeneration zone. Catalyst particles may be 
provided as fixed, moving, fluidized, ebullating or entrained beds of 
solids. In the preferred embodiment, solids are provided as fluidized, 
ebullating or entrained beds of solids with the solids continuously 
recirculating between the oligomerization and regeneration zones. Average 
solids residence times in the oligomerization zone preferably is less than 
100 minutes, more preferably less than 60 minutes. 
Oligomerization effluent produced by the method of this invention generally 
comprises normally liquid hydrocarbons and will also contain varying 
amounts of gaseous hydrocarbons. It is within the scope of this invention 
to recover all or a portion of such gaseous hydrocarbons and recycle them 
to the oligomerization zone. 
Alternatively, it is also within that particular aspect of this invention 
concerned with oligomerization of olefin feedstocks containing major 
amounts of ethylene (i.e., a hydrocarbon feed having an olefin fraction 
containing a major amount of ethylene) to recover and separately convert 
(e.g. oligomerize) the gaseous hydrocarbon (esp. C.sub.3 + olefins) 
present in the oligomerization effluent of the process of this invention. 
In a preferred embodiment of this particular aspect of this invention, the 
hydrocarbons comprising C.sub.3 + olefins may be converted to normally 
liquid hydrocarbons in a second oligomerization zone by contact with a 
siliceous crystalline molecular sieve. 
Regarding selection of operating conditions which may be employed in the 
second oligomerization zone, the general operating parameters for 
converting C.sub.3 + olefins to heavier hydrocarbons in the gasoline 
and/or distillate boiling range can be defined broadly by stating that the 
conversion is effected at moderate temperature. By "moderate temperature" 
is meant a temperature selected within the range of about 
150.degree.-330.degree. C. The pressure employed in the second 
oligomerization zone may be vary widely, preferably within the range of 
about 1 to 70 atmospheres. Similarly, the space velocity may vary widely, 
preferably within the range of about 0.1 to 50 WHSV. Several alternative 
objectives are within the scope of operation of the second oligomerization 
zone: (1) substantial conversion of C.sub.3 + olefins to normally liquid 
hydrocarbons; (2) substantial conversion of C.sub.3 + olefins to olefinic 
gasoline boiling range hydrocarbons; or (3) substantial conversion of 
C.sub.3 + olefins to distillate boiling range hydrocarbons. By 
"substantial conversion is meant the conversion of at least 80 wt. %, 
preferably 90 wt. %, of the C.sub.3 + olefins to said products. 
Selection of operating parameters suitable to accomplish any of the 
foregoing objectives have previously been described in the particular 
context of oligomerization using ZSM-5 type zeolites. See, for example, 
U.S. Pat. No. 3,760,024 (describes conversion of C.sub.2 -C.sub.4 
paraffins and/or olefins); U.S. Pat. No. 3,960,978 (describes conversion 
of C.sub.2 -C.sub.5 of olefins to a gasoline fraction containing no more 
than about 20 wt. % aromatics); U.S. Pat. No. 4,021,502 (describes 
conversion of gaseous olefins to higher molecular weight olefins over 
ZSM-4, ZSM-12, ZSM-18 chabazite or zeolite beta); and U.S. Pat. No. 
4,227,992 (describes selective oligomerization of C.sub.3 + olefins to 
produce fuel oil and gasoline products). The entire content of each of 
these applications is incorporated by reference. 
The comments made above concerning the effect of varying operating 
temperature, pressure, and space velocity on severity of the first 
oligomerization zone apply generally to the effect of such operating 
conditions on severity in the second oligomerization zone. 
Furthermore, the foregoing descriptions of how to use ZSM-5 type zeolites 
in the process of this invention have been found to also apply to the 
similar use of other siliceous crystalline molecular sieves. Moreover, the 
use of borosilicate, silicoaluminophosphate, and silicalite catalysts in 
the present process constitute distinct aspects of the broader invention 
generally described herein. 
The catalyst employed in the method of this invention are siliceous 
crystalline molecular sieves. Such silica-containing crystalline materials 
include materials which contain, in addition to silica, significant 
amounts of alumina. These crystalline materials are frequently named 
"zeolites", i.e., crystalline aluminosilicates. However, the use of 
materials exemplified by silicoaluminophosphates (see U.S. Pat. No. 
4,440,871) are also within the scope of this invention. Silica-containing 
crystalline materials also include essentially aluminum-free silicates. 
These crystalline materials are exemplified by crystalline silica 
polymorphs (e.g., silica silicalite, disclosed in U.S. Pat. No. 4,061,724 
and organosilicates disclosed in U.S. Pat. No. RE. 29948), 
chromiasilicates (e.g., CZM), ferrosilicates and galliosilicates (see U.S. 
Pat. No. 4,238,318), and borosilicates (see U.S. Pat. Nos. 4,226,420; 
4,269,813; and 4,327,236). 
The term "essentially aluminum-free" is not intended to totally exclude the 
presence of aluminum from the catalyst composition. For example, it has 
been suggested that silicates containing less than 100 ppm. by weight of 
aluminum may not be effective for the oligomerization of olefins. See U.S. 
Pat. No. 4,331,641, especially see column 9, lines 49-52 of that patent. 
Crystalline aluminosilicate zeolites are best exemplified by ZSM-5 (see 
U.S. Pat. Nos. 3,702,886 and 3,770,614), ZSM-11 (see U.S. Pat. No. 
3,709,979) ZSM-12 (see U.S. Pat. No. 3,832,449), ZSM-21 and ZSM-38 (see 
U.S. Pat. No. 3,948,758), ZSM-23 (see U.S. Pat. No. 4,076,842), and ZSM-35 
(see. U.S. Pat. No. 4,016,246). 
The acidic crystalline aluminosilicates are desirably in the hydrogen form, 
although they may also be stabilized or their performance otherwise 
enhanced by ion exchange with rare earth or other metal cations. 
The molecular sieves can be composited with inorganic matrix materials, or 
they can be used with an organic binder. It is preferred to use an 
inorganic matrix since the molecular sieves, because of their large 
internal pore volumes, tend to be fragile, and to be subject to physical 
collapse and attrition in normal loading and unloading of the reaction 
zones as well as during oligomerization processes. 
Preferred siliceous crystalline molecular sieves to be employed in the 
process of this invention are ZSM-5 type zeolites, borosilicates and 
silicalite. ZSM-5 and borosilicates are particularly preferred. 
The present invention is further illustrated by reference to the following 
examples. 
EXAMPLE I 
A crystalline borosilicate catalyst was prepared by dissolving H.sub.3 
BO.sub.3 and NaOH in distilled H.sub.2 O. Then tetra-n-propylammonium 
bromide (TPAB) was added and dissolved. Finally, Ludox AS-30(30% solids) 
was added with vigorous stirring. The addition of Ludox gave a curdy, 
gelatinous, milky solution. This solution was placed in a vessel and 
sealed. The vessel was heated to 329.degree. F. (165.degree. C.) for 7 
days. At the end of this time, it was opened and its contents were 
filtered. The recovered crystalline material was washed with copious 
quantities of H.sub.2 O and was then dried at 329.degree. F. (165.degree. 
C.) in a forced air oven. 
The material was calcined at 1,100.degree. F. (593.degree. C.) in air for 4 
hours to remove the organic base. The calcined sieve was exchanged one 
time with an aqueous solution of NH.sub.4 NO.sub.3 and then a second time 
with an aqueous ammonium acetate solution at 190.degree. C. (88.degree. 
C.) for 2 hours. The exchanged borosilicate was dried and calcined in air 
by heating it to 900.degree. F. (482.degree. C.) in 4 hours, maintaining 
the borosilicate at 900.degree. C. (482.degree. C.) for 4 hours and then 
cooling to 100.degree. F. (38.degree. C.) in 4 hours. 
The X-ray diffraction pattern is presented in Table I below. 
TABLE I 
______________________________________ 
Interplanar Spacing (.ANG.) 
Relative Intensity Spacing 
______________________________________ 
3.34 9 
3.30 10 
3.24 5 
3.04 14 
2.97 15 
2.93 7 
2.72 5 
2.60 7 
2.48 8 
2.00 15 
1.99 17 
1.91 6 
1.86 5 
1.66 5 
______________________________________ 
EXAMPLE II 
An aluminosilicate catalyst was prepared by dissolving 400 grams of N-Brand 
sodium silicate in 300 ml. of water. Then 150 grams of NaCl, 14.2 grams of 
Al.sub.2 (SO.sub.2).sub.3.H.sub.2 O, and 32.9 grams of H.sub.2 SO.sub.4 
was dissolved in 680 ml of H.sub.2 O. Tetrapropyl ammonium bromide (50 
grams) was dissolved in 200 ml of H.sub.2 O. The sodium silicate solution 
was mixed with the sodium chloride solution to form a thick, semi-solid 
mass which was mixed well. The bromide solution was then added to the 
mixture. The mixture (250 ml.) was charged to an autoclave and was 
maintained with stirring at 300.degree. F. for 16 hours. 
The mixture had a pH of about 12. The solids were washed and decanted until 
no positive C1-test was shown with AgNO.sub.3. The solids were calcined at 
500.degree. C. to product a white solid. 
The material was identified by X-ray diffraction as having the typical 
ZSM-5 pattern. The X-ray diffraction pattern is presented in Table 2. 
TABLE 2 
______________________________________ 
Interplanar Spacing (.ANG.) 
Relative Intensity 
______________________________________ 
11.47 21 
10.16 18 
6.80 3 
6.41 6 
6.02 12 
5.64 10 
5.03 6 
4.64 5 
4.29 9 
3.86 100 
3.74 59 
3.67 38 
3.45 12 
3.35 12 
3.07 18 
3.00 18 
2.75 6 
2.61 9 
2.50 9 
2.41 9 
2.01 20 
1.88 5 
1.67 7 
______________________________________ 
EXAMPLE III 
The physical characteristics of the materials of Examples I and II were 
tested and are presented in Table 3 below. 
TABLE 3 
______________________________________ 
Bulk Acidity 
Density Al content, wt % 
meq. NH.sub.3 /gm 
______________________________________ 
Example I 
0.622 0.14 0.4 
Example II 
0.214 1.5 0.5 
______________________________________ 
EXAMPLE IV 
Ethylene-contact runs were made at atmospheric pressure at temperatures 
between 300.degree.-369.degree. C. in a stainless steel tube reactor 
packed with 5 ml. of catalyst. The reactors were brought up to temperature 
under a flow of heated nitrogen which is switched to ethylene at the start 
of the run. The ethylene-contact runs described had a duration as 
indicated. 
Samples were taken during the run after 10 min, 15 min, 30 min, and one 
hour. The samples were analyzed and the results are presented in Table 4 
below. The effluent was collected and measured and analyzed from which a 
cumulative sample was generated. At the end of each ethylene-contact run, 
the reactor was flushed with nitrogen to cool the reactor and catalyst. 
The FIGURE is a plot of instantaneous results obtained during ethylene 
contact runs 2 and 3 described in Table 2. 
TABLE 4 
______________________________________ 
Run 
1 2 3 
______________________________________ 
Catalyst Example II Example II 
Example I 
Run Time (hr) 
1 3 3 
Temp (.degree.C.) 
350-528 350-549 353-507 
Contact Time (sec) 
0.45 0.52 0.53 
WHSV (hr.sup.-1) 
39.2 39.2 12.7 
Pressure, psig 
60 60 60 
C.sub.2 = Conv (%) 
95.1 60.8 57.5 
Wt. % Selectivity 
CH.sub.4 1.3 0.5 0.1 
C.sub.2 4.0 0.01 &lt;0.01 
C.sub.3 = 4.2 10.7 10.8 
C.sub.3 10.9 7.8 4.2 
C.sub.4 = 5.3 10.7 11.0 
C.sub.4 2.9 60 5.9 
C.sub.5 + 68.1 64.2 68.0 
Coke 0.2 0.1 0.02 
Productivity 
(# liq./# Cat-hr) 
27.8 15.5 4.9 
(gm liq./cm.sup.3 cat-hr) 
5.9 3.3 3.2 
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