United States Patent [191
[11]
Patent Number:
Kukes
[45]
Date ‘of Patent: 7
[54]
CATALYST FOR DEMETALLIZATION OF
HYDROCARBON CONTAINING FEED
3,733,327 5/1973 Vrieland et al.
3,946,079 3/1976 Mizutani et a1.
502/208
502/208
STREAMS
4,059,679 11/1977
502/208
4,400,568
[76]
Inventor:
[21]
and Doescher, P_O_ Box 2443,
4,430,207
2068252
Mar’ 27’ 1984
Division of Ser. No. 538,068, Sep. 30, 1983, Pat. No.
8/1981 United Kingdom .............. .. 502/202
Assistant Examiner-Anthony McFarlane
[ 5 7]
ABSTRACT
Metals contained -in a hydrocarbon containing feed '
3
stream are removed by contacting the hydrocarbon
"""""""""" """""""
° """" ‘T """"""""""""" " 502/349’_ 423/306’
containing feed stream under suitable demetallization
conditions with hydrogen and a catalyst composition
[58] Field of Search ............. .. 502/208, 344,345, 349;
423/306
_
[56]
502/208
2/ 1984 Kukes ................................ .. 502/208
Primary Examiner-Delbert ‘E. Gantz
4,457,835.
' '
502/208
FOREIGN PATENT DOCUMENTS
Reae
l t d U . S . Appicaion
l_ f Data
[62]
Clear?eld .......... ..
4,409,418 10/1983 Johnson et a1.
APPL No" 593,742
[22] Flled:
Mar. 263 1985
8/1983 Hofmann et al.
Simon G. Kukes, c/o French, Hughes
Bamesvlne’ Okla' 74°05
4,507,402
c°mpfising zircfmlum Phmphate and °°PPeF Pmsphate
The Me and act1v1ty of the catalyst compositlon may be
increased by introducing a decomposable metal com
References Clted
pound selected from the group consisting of the metals
U.s. PATENT DOCUMENTS
QfIEYI'OFPhV-IP,
Gaougrvll-B, Grollllp lYII-B and Group
0 t e erio ic ab e intot e ydrocarbon con
gitgzreétai'l """"""""""" "
3:271:447 9/1966 Naylor _____
5o2/2o8
3,431,311
3/1969 Cooper et al.
3,555,105
1/1971
taining feed stream prior to contacting the hydrocarbon
containing feed stream with the catalyst composition.
502/208
Nolan et a1. ...................... .. 502/208
5 Claims, N0 Drawings
1
4,507,402
2
are generally regarded as being too heavy to be dis
CATALYST FOR DEMETALLIZATION OF
HYDROCARBON CONTAINING FEED STREAMS
This application is a division of application Ser. No.
538,068, ?led Sept. 30, 1983, now U.S. Pat. No.
LII
4,457,835.
pyrophosphates, metaphosphates and polyphosphates.
This invention relates to a process for removing met
als from a hydrocarbon containing feed stream and a
catalyst therefor.
tilled. These materials will generally contain the highest
concentrations of metals such as vanadium and nickel.
The demetallization catalyst employed in the process
of the present invention is a composition comprising
zirconium phosphate and copper phosphate. As used
herein, the term phosphate includes orthophosphates,
10
It is well known that crude oil as well as products
The catalyst composition can be prepared by any
suitable method. coprecipitation is preferred because
the catalyst composition is more effective when pre
from extraction and/or liquifaction of coal and lignite,
products from tar sands, products from shale oil and
pared by coprecipitation. The catalyst is generally pre
similar products may contain metals such as vanadium,
pared by coprecipitating any suitable zirconium salt and
any suitable copper salt with any suitable phosphate.
nickel and iron. When these hydrocarbon containing
15 The coprecipitation may be carried out in any suitable
feeds are fractionated, the metals tend to concentrate in
solvent such as water or alcohol with water being the
the heavier fractions such as the topped crude and resid
uum. The presence of the metals make further process
preferred solvent. The metal salts and the phosphate
must be soluble in the solvent used to be suitable.
If a phosphate such as diamonium phosphate is uti
ing of these heavier fractions difficult since the metals
generally act as poisons for catalysts employed in pro
lized, the pH of the solution will generally be such that
precipitation will occur. However, if other phosphates
cesses such as catalytic cracking, hydrogenation or
hydrodesulfurization.
are used, it may be necessary to add a base such as
It is thus an object of this invention to provide a
process for removing metals from a hydrocarbon con
taining feed stream so as to improve the processability
ammonia to achieve a pH which will result in the de
sired precipitation.
The precipitant formed is washed, dried and calcined
in the presence of a free oxygen containing gas such as
cially improve the processability of heavier fractions
air to form the catalyst.
such as topped crude and residuum. It is also an object
The drying of the precipitant may be accomplished at
of this invention to provide a catalyst composition
any suitable temperature. Generally a temperature of
which is useful for demetallization.
30 about 20° C. to about 200° C., preferably about 100° C.
In accordance with the present invention, a hydro
to about 150° C., is utilized for a time in the range of
carbon containing feed stream, which also contains
about 1 hr. to about 30 hrs.
metals, is contacted with a catalyst composition com
The calcining step is utilized to remove traces of
prising zirconium phosphate and copper phosphate in
nitrates, traces of carbon, and water and to make the
the presence of hydrogen under suitable demetallization 35 structure of the catalyst composition harder. Any suit
conditions. It is believed that the metals contained in
able calcining temperature can be utilized. Generally,
heterocyclic compounds such as porphyrines are re
the calcining temperature will be in the range of about
moved from the heterocyclic compounds by the combi
300° C. to about 800° C. with a temperature in the range
nation of heat, hydrogen and the catalyst composition
of about 500° C. to about 650° C. being preferred for a
of the present invention and are trapped in pores in the 40 time in the range of about 1 to about 24 hours, prefera
catalyst composition. Removal of the metals from the
bly about 2 to about 6 hours.
hydrocarbon containing feed stream in this manner
The catalyst composition can have any suitable sur
of such hydrocarbon containing feed stream and espe
provides for improved processability of the hydrocar
face area and pore volume. In general, the surface area
bon containing feed stream in processes such as cata
Other objects and advantages of the invention will be
apparent from the foregoing brief description of the
will be in the range of about 2 to about 400 m2/g, prefer
ably about 10 to about 200 m2/g, while the pore volume
will be in the range of about 0.2 to about 4.0 cc/g, pref
erably about 0.4 to about 2.0 cc/g.
Any suitable phosphates may be utilized to prepare
invention and the appended claims as well as the de
the catalyst composition. Suitable phosphates include
lytic cracking, hydrogenation and hydrodesulfuriza
tion.
45
tailed description of the invention which follows.
50 (NH4)H2P04, (NH4)zHP04, (NH4)sP04, (NH4)4P207,
Any metal which can be trapped in the pores of the
corresponding phosphates and pyrophosphates of lith
catalyst composition of the present invention can be
ium, sodium, potassium, rubidium, and cesium, and
removed from a hydrocarbon containing feed stream in
H3PO4. Phosphonic acids such as phenyl phosphonic
accordance with the present invention. The present
acids and the metal salts of phosphonic acids may also
invention is particularly applicable to the removal of 55 be used to derive phosphates for the catalyst composi
vanadium and nickel.
tion if desired.
Metals may be removed from any suitable hydrocar
Any suitable zirconium and copper to phosphorus
bon containing feed streams. Suitable hydrocarbon con
ratio in the catalyst composition may be used. The ratio
taining feed streams include petroleum products, coal
will generally be about stoichiometric. Any suitable
pyrolyzates, products from extraction and/or liquifac- 60 ratio of zirconium to copper may be used. The molar
tion of coal and lignite, products from tar sands, prod
ratio of zirconium to copper will generally be in the
ucts from shale oil and similar products. Suitable hydro
range of about 10:1 to about 1:10 and more preferably in
carbon feed streams include gas oil having a boiling
the range of about 3:1 to about 1:2.
range from about 205° C. to about 538° C., topped crude
The demetallization process of this invention can be
having a boiling range in excess of about 343° C. and 65 carried out by means of any apparatus whereby there is
residuum. However, the present invention is particu
achieved a contact of the catalyst composition with the
larly directed to heavy feed streams such as heavy
topped crudes and residuum and other materials which
hydrocarbon containing feed stream and hydrogen
under suitable demetallization conditions. The process
3
4,507,402
4
is in no way limited to the use of a particular apparatus.
The process of this invention can be carried out using a
The time in which the catalyst composition will
maintain its activity for removal of metals will depend
?xed catalyst bed, ?uidized catalyst bed or a moving
upon the metals concentration in the hydrocarbon con
taining feed streams being treated. It is believed that the
catalyst composition may be used for a period of time
long enough to accumulate 20-200 wt.% of metals,
reactor or may be used in combination with essentially
mostly Ni and V, based on the weight of the catalyst
inert materials such as alumina, silica, titania, magnesia,
composition, from oils.
silicates, aluminates, alumina silicates, titanates and
It is believed that the life of the catalyst composition
phosphates. A layer of the inert material and a layer of
and
the ef?ciency of the demetallization process can be
10
the catalyst composition may be used or the catalyst
improved by introducing a decomposable metal com
composition may be mixed with the inert material. Use
pound into the hydrocarbon containing feed stream. It
of the inert material provides for better dispersion of the
is believed that the metal in the decomposable metal
hydrocarbon containing feed stream. Also, other cata
compound
could be selected from the group consisting
lyst such as known hydrogenation and desulfurization
of the metals of Group V-B, Group VI-B, Group VII-B
catalysts may be used in the reactor- to achieve simulta
and Group VIII of the Periodic Table. Preferred metals
neous demetallization, desulfurization and hydrogena
are
molybdenum, tungsten, manganese, chromium,
tion or hydrocracking if desired.
nickel and iron. Molybdenum is a particularly preferred
Any suitable reaction time between the catalyst com
metal which may be introduced as a carbonyl, acetate,
position and the hydrocarbon containing feed stream
acetylacetonate, octoate (octanoate), naphthenate or
may be utilized. In general, the reaction time will range 20 dithiocarbamate.
Molybdenum hexacarbonyl is a partic
from about 0.1 hours to about 10 hours. Preferably, the
ularly preferred additive.
catalyst bed. Presently preferred is a ?xed catalyst bed.
The catalyst composition may be used alone in the
reaction time will range from about 0.4 to about 4 hours.
Thus, the ?ow rate of the hydrocarbon containing feed
stream should be such that the time required for the
passage of the mixture through the reactor (residence
time) will preferably be in the range of about 0.4 to
about 4 hours. This generally requires a liquid hourly
space velocity (LHSV) in the range of about 0.10 to
Any suitable concentration of the additive may
added to the hydrocarbon containing feed stream.
general, a suf?cient quantity of the additive will
added to the hydrocarbon containing feed stream
be
In
be
to
result in a concentration of the metal in the range of
about 1 to about 1000 parts per million and more prefer
ably in the range of about 5 to about 100 parts per mil
about 10 cc of oil per cc of catalyst per hour, preferably
lion.
from about 0.2 to about 2.5 cc/cc/hr.
The following examples are presented in further illus
The demetallization process of the present invention
tration of the invention.
can be carried out at any suitable temperature. The
EXAMPLE I
temperature will generally be in the range of about 150°
to about 550° C. and will preferably be in the range of 35
In this example the preparation and pertinent proper
about 350° to about 450° C. Higher temperatures do
ties of various phosphates employed as heavy oil deme
improve the removal of metals but temperatures should
tallization catalysts are described.
not be utilized which will have adverse effects on the
Zr3(PO4)4 was prepared by ?rst dissolving 301 grams
hydrocarbon containing feed stream, such as coking,
and also economic considerations must be taken into
account. Lower temperatures can generally be used for
lighter feeds.
of zirconyl nitrate, ZrO(NO3)2, in 1 liter of hot water
and then adding to this solution, with stirring, a solution
of 151 grams of (NH4)2HPO4 in 400 cc of hot water.
The resulting solution was ?ltered to obtain the zirco
Any suitable pressure may be utilized in the demetall
nium phosphate precipitate. The precipitate was
ization process. The reaction pressure will generally be
washed with 2 liters of water, dried at about 120° C.
in the range of about atmospheric to about 5,000 psig. 45 overnight, and calcined in air at 550° C. for 5 hours. The
Preferably, the pressure will be in the range of about
calcined Zr3(PO4)4 had a surface area of 64.9 mZ/gram,
100 to about 2500 psig. Higher pressures tend to reduce
a pore volume of 0.76 cc/gram, a bound Zr content of
coke formation but operation at high pressure may have
43.5 weight-%, a bound P content of 15.9 weight-%, a
adverse economic consequences.
bound 0 content of 42.3 weight-%, and was essentially
Any suitable quantity of hydrogen can be added to
amorphous as indicated by X-ray diffraction measure
the demetallization process. The quantity of hydrogen
ment. This zirconium phosphate catalyst was employed
used to contact the hydrocarbon containing feed stock
in Runs 1, 2, 4 and 5.
will generally be in the range of about 100 to about
Mixed zirconium phosphate-nickel phosphate was
10,000 standard cubic feet per barrel of the hydrocar
prepared by dissolving 116.5 grams (0.5 mole) of
bon containing feed stream and will more preferably be
ZrOCl2.4H2O and 145 grams (0.5 mole) of Ni(NO3)2.6
in the range of about 1000 to about 6000 standard cubic
H2O in 1.5 liters of hot water. A solution of 150 grams
feet per barrel of the hydrocarbon containing feed
of (NH4)2HPO4 in 0.7 liter of warm water was added to
the ?rst solution (containing zirconyl chloride and
stream.
In general, the catalyst composition is utilized for
nickel nitrate) with stirring for 30 minutes. The result
demetallization until a satisfactory level of metals re
ingmixture was ?ltered to obtain the precipitate. The
moval fails to be achieved which is believed to result
zirconium phosphate-nickel phosphate (Zr-Ni-PO4)
from the coating of the catalyst composition with the
?lter cake was washed with 1 liter of warm water. The
?lter cake was then slurried in 2 liters of hot water,
metals being removed. It is possible to remove the met
stirred for 1 hour, ?ltered and washed with 1 liter of hot
als from the catalyst composition by certain leaching
procedures but these procedures are expensive and it is 65 water. The washed nickel phosphate-zirconium phos
phate was dried for about 16 hours in a vacuum oven at
generally contemplated that once the removal of metals
120° C. and calcined in air at about 560° C. for 4 hours.
falls below a desired level, the used catalyst will simply
The resulting catalyst’s surface area was 56 m2/grams,
be replaced by a fresh catalyst.
4,507,402
5
6
its pore volume (determined by mercury porosimetry)
was 0.90 cc/gram, and the yolume of pores having a
was moved within the axial thermocouple well. The
liquid product was collected in a receiver, ?ltered
diameter smaller than 300 A (calculated from BET
through a glass frit and analyzed. Exiting hydrogen gas
nitrogen adsorption) was 0.16 cc/gram. This catalyst
was vented. Vanadium and nickel content in oil was
was employed in runs 15 and 16.
determined by plasma emission analysis.
The catalyst of this invention, coprecipitated
The feed was a mixture of 26 weight-% toluene and
Zr3(PO4)4-Cu3(PO4)2, was prepared as follows: 47
grams of cupric nitrate and 27 grams of ZrO(NO3)2
74 weight-% Venezuelan Monagas pipeline oil having
an API gravity of about 17-18 with the exception of
runs 15 and 16 in which undiluted Monagas pipeline oil
were dissolved in 1 liter of hot water. Then a solution of
83 grams of (NH4)2HPO4 in 400 mL of water was added - O was used. The hydrogen pressure was maintained at
to the ?rst solution with stirring. The formed precipi
about 1000 psig in all experiments (with the exception of
Runs 15 and 16) which generally lasted from about 2-6
hours. The reactor temperature (average of thermo
couple readings at four reactor locations) was about
tate was ?ltered from the mixture of the two solutions,
washed twice with 1.5 liter of hot water, dried at about
120° C. overnight, and calcined in air at 550° C. for 4
hours. The surface area of this coprecipitated Cu3(
375°—435° C. The liquid hourly space velocity (LHSV)
PO4)2-Zr3(PO4)4 (determined by BET with N2) was
73.4 mz/g, and its pore volume (determined by mercury
porosimetry) was 1.05 cc/g. Elemental analysis data
were: 29.0 weight-% Zr, 11.3 weight-% Cu, 16.7
weight-% P and 42.3 weight-% 0. The atomic ratio of
ZrzCu was about 1.8:1. This coprecipitated phosphate
of the feed ranged from about 0.5 cc/cc catalyst/hour
to about 2 cc/cc catalyst/hour.
20
was employed in runs 3, 6-14.
EXAMPLE III
Results of heavy oil demetallization runs at 425° C. in
accordance with the procedure described in Example II
are summarized in Table I.
TABLE I
Feed
LHSV
Run
1
2
3
4
5
6
7
8
9
10
(Control)
(Control)
(Invention)
(Control)
(Control)
(Invention)
(Invention)
(Invention)
(Invention)
(Invention)
(c/cc/hr) Catalyst
0.99
0.96
1.02
1.60
1.53
1.48
1.48
1.98
2.00
2.01
Zr3(PO4)4
Zr3(PO4)4
Zr—Cu—PO4
Zr3(PO4)4
Zr3(PO4)4
Zr—-Cu—PO4
Zr—Cu——PO4
Zr—Cu—PO4
Zr—Cu—PO4
Zr—Cu—PO4
Product
Pore
Run
Vana-
Total
Vana-
Volume
Time
dium
Nickel (V + Ni)
dium
Nickel (V + Ni)
Total
(cc/g)
(Hours)
(ppm)
(mm)
(mm)
(ppm)
(ppm)
0.76
0.76
1.05
0.76
0.76
1.05
1.05
1.05
1.05
1.05
3.0
4.0
3.4
2.5
2.1
3.0
2.0
3.9
5.5
5.7
269
217
296
269
217
296
296
296
296
296
62.6
39.2
73.5
62.6
39.2
92.1
92.1
73.5
73.5
73.5
331.6
256.2
369.5
331.6
256.2
388.1
388.1
369.5
369.5
369.5
81.8
74.1
26.8
148.0
113.0
126.0
98.7
165.0
198.0
201.0
27.0
19.4
21.2
42.7
27.1
43.2
35.7
57.4
63.4
62.9
Removal
of Metals
(ppm)
(%)
109.8
93.5
48.0
190.7
140.1
169.2
134.4
222.4
261.4
263.9
77
64
87
42
45
56
65
40
29
29
Data in Table I show that at com arable LHSV co
p
precipitated Zr3(PO4)4-Cu3(PO4)2 was more effective
EXAMPLE II
This example illustrates the experimental setup for 40 than Zr3(PO4)4 in removing Ni and V from heavy oil at
investigating the demetallization of heavy oils by em
425° C. (compare run 3 with runs 1 and 2; runs 6, 7 with
ploying various phosphate catalysts. Oil, with or with
runs 4, 5).
out a dissolved decomposable molybdenum compound,
was pumped by means of a LAPP Model 211 (General
Electric Company) pump to a metallic mixing T-pipe 45
where it was mixed with a controlled amount of hydro
EXAMPLE IV
Results of the demetallization of heavy oils at 400° C.
in accordance with the procedure described in Example
gen gas. The oil/hydrogen mixture was pumped down
II are summarized in Table II.
TABLE II
Feed
Pore
LHSV
Run
11
12
13
14
(Invention)
(Invention)
(Invention)
(Invention)
(c/cc/hr) Catalyst
0.45
1.05
1.49
1.52
Zr-Cu-P04
Zr—Cu—PO4
Zr—Cu-—P04
Zr—Cu—PO4
Run
Vana-
Product
Total
Vana-
Total
Removal of
Volume
Time
dium
Nickel (V + Ni)
dium
Nickel (V + Ni)
(cc/g)
(Hours)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
‘(V + Ni)
(%)
1.05
1.05
1.05
1.05
6.0
3.0
3.0
2.0
296
296
296
296
73.5
73.5
92.1
73.5
369.5
369.5
388.1
369.5
16.9
64.9
213.0
89.8
14.7
36.0
60.0
43.7
31.6
100.9
273.0
133.5
91
73
30
64
ward through a stainless steel trickle bed reactor, 28.5
inches long and 0.75 inches in diameter, ?tted inside
Data in Table II show that, at 400° C., the coprecipi
with a 0.25 O.D. axial thermocouple well. The reactor 60 tated Zr3(PO4)4-Cu3(PO4)z catalyst was quite effective
was ?lled with a top layer (3.5 inches below the oil/H2
in removing Ni and V from heavy oil, especially at a
feed inlet) of 50 cc of low surface area (less than 1
low liquid hourly space velocity of about 0.5-1.1.
m2/gram) a-alumina, a middle layer of 50 cc of a phos
EXAMPLE V
phate catalyst, and a bottom layer of 50 cc of a-alumina.
The reactor tube was heated by a Thermcraft (Winston 65
In this example, the results of extended demetalliza
Salem, NC.) Model 211 3-zone furnace. The reactor
temperature was usually measured in four locations
tion runs of up to 3 months in an automated reactor
along the reactor bed by a traveling thermocouple that
the coprecipitated catalyst (Zr-Ni-PO4) similar to the
similar to the one described in Example II employing
4,507,402
7
8
Data in Table III show that the catalyst of this exam
inventive one (Zr-Cu-PO4) are described. Undiluted,
heavy Monagas pipeline oil was used as the feed. It
ple, Zr3(PO4)4-Ni3(PO4)2, essentially retained its activ
contained 88. ppm of Ni, 337 ppm of V, 2.73 weight-%
ity after about 2 months on stream. However, when the
feed oil contained about 70 ppm of Mo (as dissolved
S, 73.7 volume‘-% residual oil (boiling point higher than
650° F.), 24.7 volume-% of distillate (boiling range of 5 Mo(CO)6, the demetallization activity of the zirconium
phosphate-nickel phosphate increased about 10% after
400°-650° F .); and it had an API gravity of 12.3°.
almost 500 hours (3 weeks) on stream. The removal of
In this demetallization run, the reactor temperature
V and Ni was consistently higher, especially after about
was 407° C. (765' F.), the oil feed LHSV was 0.9-1.1
200 hours on-strearn, than a system without Mo(CO)6
cc/cc catalyst/hr, the total pressure was 2250 psig, and
the hydrogen feed rate was 4800 SCF/bbl (standard
cubic feet of Hz per barrel of oil). The metal removal
achieved with zirconium-nickel phosphate was greater
when Mo(CO)6 was added as an additional demetalliza
tion agent to the feed oil. Results are summarized in
Table III.
(compare Runs 15 and 16). Substantially all iron (ap
proximately 56 ppm in oil) was also removed with zir
conium phosphate-nickel phosphate with and without
added Mo(CO)5. Based on these results, it is believed
that the addition of molybdenum to the feed oil would
15 also be bene?cial when the inventive zirconium phos
phate-copper phosphate catalyst is used.
TABLE III
M0 in
Run
15
16
Feed
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
70
70
70
70
70
70
70
70
Hours
Catalyst
Zr-Ni--PO4
Zr--Ni—PO4
Zr—-Ni-—PO4
Zr—Ni—P04
Zr-—Ni—-PO4
Zr—-Ni--PO4
Zr—Ni—PO4
Zr-—Ni-PO4
Zr—Ni—-PO4
Zr—~Ni—PO4
Zr--Ni—PO4
Zr—Ni—PO4
Zr-—Ni—PO4
Zr--Ni—-PO4
Zr-Ni-PO4
Zr-Ni—-PO4
Zr—Ni—PO4
Zr-Ni—PO4
Zr—Ni-PO4
Zr—Ni—PO4
Zr—-Ni--PO4
That which is claimed is:
Metals in
on
Mpg-L V+Ni
Stream
V Ni V+Ni
(%)
117
233
257
303
390
436
532
789
1008
1228
1416
1717
2189
124
220
244
327
375
423
471
495
93
114
109
104
113
108
109
89
118
108
110
135
135
90
92
68
78
81
74
68
64
49
55
54
51
50
45
49
47
42
46
42
48
49
40
42
36
38
37
36
35
34
142
I69
163
155
168
153
158
136
160
154
152
183
184
130
134
104
116
118
110
103
98
1. A catalyst composition comprising a coprecipi
tated mixture of zirconium phosphate and copper phos
Removal
of
66
60
61
63
60
64
63
68
62
64
64
57
57
69
68
75
73
72
74
76
77
phate.
2. A composition in accordance with claim 1 wherein
said catalyst composition has a surface area in the range
of about 2 to about 400 m2/gram and has a pore volume
in the range of about 0.2 to about 4.0 cc/gram.
3. A composition in accordance with claim 2 wherein
25
said catalyst composition has a surface area in the range
of about 2 to about 400 m2/gram and has a pore volume
in the range of about 0.4 to about 2.0 cc/gram.
4. A composition in accordance with claim 1 wherein
30 the ratio of zirconium and copper to phosphorus in said
catalyst composition is about stoichiometric and
wherein the molar ratio of zirconium to copper is in the
range of about 10:1 to about 1:10.
5. A composition in accordance with claim 4 wherein
35 the ratio of zirconium and copper to phosphorus in said
catalyst composition is about stoichiometric and
wherein the molar ratio of zirconium to copper is in the
range of about 3:1 to about 1:2.
*
45
55
65
*
*
*
=1!