Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~h~ ~ '
This application is a division o~ Canadian application
no. 273,972 filed March 15, 1977 for "Hydrogenation Process
of Olefin Polymers for Producing White Oils".
BACKGROUND OF THE INVENTION
The present invention relates to a process for hydro
genating polymers derived from olefin units having 4 carbon atoms
and thereby preparing products which are colorless, odorless,
stable to heat and storage and which fulfill the requirements for
white oils and medicinal oils.
White oils usually are mineral oils which are prepared
by high purification of petroleum fractions boiling in the
lubricating oil boiling range. This process usually comprises two
steps: a desulfurization followed by hyd~ogenation under very
severe~.operating conditions. ~hite oils are allowed to be used
in or in contact with food, only if they fulfill the official
requirements for foodstuffs. The most widely applied standards
are the official'requirements in the U.S. regulations promulgated
by the FDA, the German regulations set forth in DAB VII and the
British regulations set forth in the s.P. acid test.
It has already been proposed to purify polymers which
are prepared from olefin units having 4 carbon atoms, particulaxly
polybutenes by means of a hydrogenation process/ in order to
obtàin a colorless and substantially odorless polybutene which can
be used, for example, as a substitute for natural squalane in
cosmetic formulas. However, the product obtained does not come
close to fulfilling the white oils requirements. Indeed, the
iodine value of the hydrogenated product, which charactexizes the
unsaturation degree of the product, is much too high.
German Patent Application No. 2,360,306 teaches the
30 ` hydrogenation of polybutene at a temperature o~ between 150 and
230C and at a pressure of between 15 and 35 atmospheres, in the
presence o~ nickel or palladium on kieselguhr, but the iodine value
of the hydrogenated product is about 1.
: : ,
. ,, . . , . : ~
U.S. Patent No. 3,100,808 teaches the hydrogenation of
polybutene at a temperature of between 60 and 350C, at a pressure
of bet~Jeen 3.5 and 210 kg/cm2 in the presence of nickel, palladium
or platinum on an alumina support/ but the iodine value of the
hydrogenated product is higher than 1. Such an iodine value is
absolutely too high in order for the hydrogenated product to fulfill
the white oils requirements.
SUMMARY OF THE INVENTION
It is an object o the present invention to provide a
process for producing high quality white oils, especially white
oils exhibiting a relatively low iodine value.
It is a further objec~ to provide a hydrogenation process,
especially a one step process for producing such white oils from
polymers der~ed from olefin units containing 4 carbon atoms.
It is a further object of this invention to provide a
process which permits hydrogenation under relatively mild reaction
conditions. It is a further object to provide such a process
which allows preparation of hydrogenated products, the iodine value
of which is less than 0.26.
In order to accomplish the foregoing objects, there has
been provided, according to the present invention, a process for
hydrogenating a liquid polymer derived from olefin units containing
4 carbon atoms which comprises the step of hydrogenating said
pol~mer at a suitabie pressure and temperature, in the presence of
a catalyst comprising a noble metal selected from the group of
platinum and palladium on an alumina support exhibi~ing a total pore
volume of at least about 0.25 ml/g wherein, if the noble metal is
platinum, hydrogenation is at a hydrogen pressure of between about
40 and about 120 kg/cm2 and a temperature of between about 200
~o and about 250C, and about 90 to about 98~ of the pore volume is
provided by pores the mean size of which is distributed around a
mean size of less than 100A and, if the noble metal i5 palladium,
hydrogenation is at a hydrogen pressure of between about 20 and
~$~
about 120 kg/cm2 and a temperature of between about 130 and about
250C, a~d abou~ 35 to a~out 50% of the pore volume is provided by
small si~e pores the mean size o~ which is distribu~ed around a
m~an size of less than 300A + 50A and about 25 to about 35~ of the
pore volume is provided by large size pores the mean size of which
is distributed around a mean size of about 300A ~ 50A with the mean
size of the large size pores being at least 1.5 times the mean
siz~ of the small siz~ pores.
If the noble metal in the catalyst is platinum, the
reaction temperature preferably is at least about 200C and
the hydrogen pressure is at least about 40 kg/cm2.
The space velocity of the liquid may be between about
~.25 and 4 hr 1 A suitable hydrogen:polymer ratio is between
about 250 and 6000 Nl/l. Preferably the reaction is effected
undar reaction conditions which are sufficient `to yield a hydro-
genated product, the iodine value of which is below U.26.
It is really unexpected that such a low iodine value
is achieved under such rela$ively mild conditions. It is well
known that until now, in order to obtain low iodine values, a
0 much higher temperature had to be applied. Moreover, such a low
iodine value has never been reached by hydrogenating polybutenes
in such known hydrogenation processes.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The term "a liquid polymer derived from olefin units
containing 4 carbon atoms" not only comprises butene polymers,
but also isobutene polymers and ~utene and isobutene copolymers,
whereby all these homopolymers and copolymers are liquid or oily
products. Such polymers generally ha~e a molecular weight of
between about 300 and 2000.
The hydrogenation catalyst of the present invention
comprises platinum or palladium on an alumina support. The
alumina support must be a support having a total pore volume of
a-t least 0.25 ml/g, preferably of about 0.25 to about 2.5, most
- 3 --
preferably of about 0.25 to 1 ml/g. If the catalyst comprise.s
platinum, the support is a monomodal support wherein about 90 to
about 98~ of this total pore volume are provided by pores the
general size of which is distributed around a mean pore size lower
than 100~. Generally the pore size is between about 50 and about
90A~
The mean pore sizes and the recommended percentages of
pores within these size ranges are dependent upon each other and
are essential operating conditions, and if either of these
conditions is not met, the resulting produc~ does not fulfill the
white oils requirements as is shown in the comparative examples
below.
The amount of platinum which is present in the catalyst
is generally between about 0.1 and about 1.0% by weight and,
more particularly, between about 0.3 and about 0.7% by weight,
based on the total weight of the catalyst.
If the catalyst comprises palladium, the alumina suppoxt
must be a bimodul support having a to~al pore volume of at least ...
0.25 ml/g, preferably of about 0.25 to about 2.5, most preferably
~0 of about 0.25 to 1 ml/mg, wherein 35 to 50% of this total volume
are provided by small pores the general size of which is distributed
around a mean size lower than 300A + 50~ and 25 to 35% of this
total volume are provided by large pores the general size of which
is distributed around a mean size above 300A 50A, whereby the
mean size of the latter is at least about 1.5 times, preferably
about l.S to about 5,000 times, the mean size of the former~
The mean pore sizes and the recommended percentages of
pores for each size are dependent on each other and are essential
operating conditions, and if either of these conditions is not met,
the resulting produc-t does not fulfill. the white oil requi.rements,
as is shown in the comparative examples below.
Prefera~ly mean si~e of the small pores is between about
30 and about 300A, and particularly between about 50 and about 150A,
_ ~ _
hereas that of the larger pores is between 300A - 50A and about
150,000 A, and the mean size of the larger pores always is at
least 1.5 times, more particularly between about 10 and 1,000,
most preferably between 10 and 200, that of the small pores.
~oreover, the percentage of pore volume which is provided by the
small pores must always be a~ least equal to that which is provided
by the large pores.
The amount of palladium which is present in the catalyst
is generally between about 0.25 and about 1.5% by weight, and
more particularly between about 0.4 and about 0.9% by weight,
based on the total catalyst weight.
The catalyst composition which is used according to the
present invention may be prepared according to conventional
impregnation techniques. ~ypically, the support material is
impregnated with an aqueous solution of a soluble noble metal
compound. The soluble compound is used as a precursor of the
metal itself and the desired metal is iormed on the support by a
chemical or a thermal treatment of the impregnated support material.
The impregnation may al50 be carried out by other conventional
processes according to which the support particles are impregnated
with, immersed, or suspended in, or otherwise introduced into an
impregnation solution in order to absorb a soluble noble metal
compound. On the other hand, the catalyst may be shaped in various
forms and particulaxly in the form of granules, extrudates, cylinders,
particles, beads or powder. The hydrogenation process according to
the present invention may be carried out by using any catalytic
hydrogenation technique, e.g., batchwise or in a continuous process
and in the latter case, either a fixed bed, or a moving bed or a
~luidized bed procedure may be used.
The reaction temperature and pressure at which the
hydrogenation process is carried out, are dependent on each other
and the above-defined ranges should be observed. Moreover, it is
well known that the higher the temperature and the pressure are,
" 1-.
, , ..... . :
~3~
,he more complete the hydrogenation is, and thus the lower the
iodine value of the hydrogenated product. According to the p~ocess
of the presen~ invention, poiybutene may be hydrogenated a-t a
temperature of between about 130 and about 250C in the presence
of a palladium catalyst or at a temperature of between about 200
and about 250C in the presence of a platinum catalys-t in order to
obtain a hydrogenated product having an iodine value as low as 0.26
while the appl ed pressure is not very high, this pressure being
about 75 kg/cm . On the other hand, a hydrogenated product having
a very low iodine value may be obtained with a pressure as low
as 20 kg/cm2 at a temperature which does not exceed 250C.
Naturally, the temperature and the hydrogen pressure depend on the
kind o~ starting material and the type of catalyst which is used.
Usually the temperature is between about 200 and about 250C in
case of a platinum catalyst and between about 130 and about
250C in case of a palladium catalyst, and the pressure is between
about 40 and about 120 kg/cm2 in case of a platinum catalyst and
between about 20 and about 120 kg/cm2 in case of a palladium
catalyst. Both these variables can be selected in order to obtain
a hydrogenated product having an iodine value lower than or equal
to 0.26. Such temperature and pressure conditions are consider-
ably milder than those which are used in conventional processes
~or obtaining white oils wherein the pressure must be at least
130 kg/cm2.
~he other operating conditions such as the hourly space
velocity of tha liquid and the hydrogen:polymer ratio also have
an influence on the iodine value and therefore on the degree of
hydrogenation of the resulting product, but this influence is not
so important as that due to temperature or pressure. Generally the
space velocity of the liquid is between about 0.25 and about 4 hr 1
and particularly between about 0.5 and about 2 hr . The hydrpgen:
polymer ratio usually varies between about 250 and about 6000 Nl/l*
and still higher ratios may be used, but without any significant
*(li-ter per liter under normal conditions, i.e., 0C and
atmospheric pressure) 6
,
~dvantage.
The obtained hydrogenated products have been submitted
to "BP acid test", DAB VI~ test and F.D.~. tests in order to
determine their usefulness as white oils and medicinal oils.
According to the ~AB VII requirements, the product must
be tested for the absorption of ultraviolet light at 275, 295 and
300 nanometers, in a cell of 1 cm size. The maximum of absorption
at each wavelength must be lower than 1.6, 0.2, and 0.15,
respectively.
The "BP acid test" consists oE a colorimetric deter-
mination of carbonizable matters in a liquid paraffins using an
extraction with sulfuric acid. The colorimetric indices according
to the Lovibond scale which may not be ~xceeded are 2.5 in the red
r~nge and 6.5 in the yellow range, when the eXperimentS are
performed in a cell of 10 mm size.
The F.D.A. tes~ consists of three tests, the first of
which concerns the determination of the carbonizable matters
according to a colorimetric method. The colorimetric indices
according to the Lovibond scale which may not be exceeded are 2.1
in the red range and 9 in the yellow range. The second test concerns
the analysis of the sulfurized products and the third consists ~f
the determination of the absorbance of ultraviolet light of the ;;;
extract with D.U.SØ of the test product, whereby this absorbance
must not exceed 0.1 at wavelengths of between 260 and 350 nanometers
when the experiment is performed in a cell of l cm size.
The following examples are given in order to bettex
illustrate the features and advan-tages of the present invention
but without limitin~ it.
Example l
A hydrogenation catalyst the support of which consists
of alumina beads having a diameter 1~5 mmt iS prepared. The
specific surface is 209 m /g. The total pore volume is 0.51 ml/g,
and 0.5Q ml/g, or 98% of this total pore volume is provided by
-- 7 --
. - - -: . . . .. . , . . . . " .. , .. ..... .. ., .. -- .
;......... .
~3~
o
_,ores the size of which is distributed around a rnean size oE 65A.
100 g of the hereabove described alumina support is
dried at 120C and then impregnated with 100 ml of an aqueous
solution of chloroplatinic acid con~aining 3 g of chloroplatinic
acid. After 1 hour of impregnation, the catalyst is placed on a
buchner funnel in order to quickly eliminate ~he excess of the
impregnating solution. The wet catalyst is -~hen dried at 120C.
Thereafter, the catalyst is calcined at the air at 500C
and reduced with hydrogen a~ 500C. The reduced catalyst contains
0~59~ by wèight of platinum.
With this catalyst, the continuous hydrogenation of a
polybutene the characteristics of which are given in Table I i'
below, is performed.
T A B L E
Characteristic Method of determination
.. . . .
Specific gravity 15/4C ASTM D 1298 0.838
- v~ScOSity
at 37.8C (Cstokes) ASTM D 445 27.34
at 98.9C (Cstokes) ASTM D 445 4.88
~0 at 37.8C (SSU) 127
Viscosity index ASTM D 2270 110-111
Molecular weight 650
Saybolt color ASTM D 156 ~18
Iodine value IP 84 128~3
The operating conditions under which the hydxogenation
is perfonmed, and the properties of the hydrogenated product
obtained in each experiment, are indicated in Table II below.
By way of comparison, hydrogenation of a polybutene the
characteristics of which are described in Table I, is carried out
in the presence of catalysts wherein the support of which or the
metal which is deposited thereon is outsicle the scope oE the
present invention.
In a comparative experiment A, the support of the catalyst
.3~ ~
consists of alumina beads of 1.5 mm diameter, having a total pore
volume of 0.87 ml/g and wherein O.58 ml/g, or 67% of this pore
volume, is provided by pores the size of which is distributed
around a mean size of 200A. Platinum is deposited on this support
according to a known process and the final catalyst contains 0.78%
by weight of platinumO
In a comparative experiment B, the support of the catal~st
consists of alumina granules having a total pore volume is 0.40 ml/g
and wherein 0.25 ml/g, or 62% of this pore volume is provided by
pores thè size of which is distributed around a mean size of 60A.
Palladium is deposited on this support according to a known
process, and the final catalyst contains 0.55~ by weight of
palladium.
~ n a comparative experiment C, a catalyst is tested the
suppoxt of which.consists of alumina granules having a total pore
volume of 0.58 ml/g and wherein 0.53 ml/g, or 91% of thîs pore
volume, is provided by pores the size of which is distributed
around a mean size of 55A. Palladium is deposited on this support
according to a known process and the final catalyst contains 0.6% :~
by weight of palladium.
In a comparative experiment D, the hydrogenation is
carried out in the presence of 10% by weight of black palladium.
The operating conditions under which the comparative
experiments A, B, C and D are carried out and the properties of
the resulting hydrogenated products are indicated in Table II `~
below.
_ 9 _
T A B L E I I
Characteristic Experiment
1* 2* A B C D
Temperature (C) 230 200 200 230 230 200
Li~uid
Space velocity(hr
Pressure~kg/cm ~ 100 75 75 100 100 75
Hydrogen: Polymer
ra~iotNl/l) 300 300 300 300 300 300
10 Specific gravity
15~DsC . 0.838 0.838~0.83~ Q.8380083~0.838
Viscosity . r
at 37.8C(Cstokes~27. 34 27. 34 27. 34 27.34 27.34 27. 34
at 98.9~CtCstokes)4.88 4.88 4.884.88 4.g8 4.88
at 37.8C(SSU) 127 127 127 127 127 127
Viscosity Inde~ 110-111 110-111 110~ 110-111. 110-111 110-111
Saybolt color ~30 ~30 +30 ~30 ~30 ~Z7
Iodine value 0.12 0.26 0O78 3.5 1.8 10
BP acid test conorm conform n o t c o n f o r m
[1.5R [2.5R
[3.6Y [6.5Y
D~B VII - UV absorption
cell.lcm 275 nm ~.05 0.12 0.15 0.5 0.2 not co~form
295 nm 0.01 0Ø2 Q.~3 0.~7 a .. ~5
30Q nm a.ol 0.Ql Q.Q2 . Q.04 Q.Q3
FDA
-sulfuri~ed compounds c o n ~ a r m
-polynuclear aroma
tics cell 1 cm
260 - 350 nm c o n ~ o r m
-USP acid test c o n f o r m n o t c o n ~ o r m
~1.4R ~2.1R
~3.6Y [8.5Y
Odor o d o r 1 e s ~ u n s a t i s ~ a c t o r y
1~ yellow range, ~=red range]:
Example 2
.
The process descri~ed în Example l.is repeated in order
to obtain a catalyst containing 0.64% ~y weight o platinum on a
support consisting o alumina beads having a total pore volume o~
0.53 ml/g and wherein 0.49 ml/g or 92% of this pore volume is
provided by pores the size of wh.ich is distributed around a mean
* catalyst in both experiments as described in Example 1~
-- 10 --
size of 70A.
With this catalyst, the hydrogenation of polybutene,
thP characteristics of which axe given in Table III below, is
ca~ried out.
T A B L E I I I
Characteristic Determination method
_.
Specific gxavity 15/4C AST~ D. 1248 0.831
Viscosity a~ 98.9C (SSU) 1067
Iodine value IP 84* 60
10 Saybolt color ASTM D. lS6 + 18
The operating conditions under which the hydroyenation r
iS carried out and the properties of the resulting hydrogenated
product are indicated in Table IV below.
* IP = Institute of Petroleum method.
~ T A B L E I V
Temperature - . 240C
Pressure 115 k ~cm2
Liquid hourly space velocity 1 hr 1
- Hydrogen: Pol~mer ratio 500 Nl/l
Iodine value 0.16
Saybolt color +30
BP acid test conform
~1.6R
f4.1Y
D~B VII - W absorption
Cell 1 cm 275 nm O.Q5
295 nm 0.01
300 nm - 0.01
FDA
-Sulfurized compounds conform
-Polynuclear aromatics
cell 1 cm - 260-350 nm con~orm
- Example 3
. The cataIyst described in Example 1 is used to
hydrogenate a polybutene, the characteristics of which are
indicated in Table III of Example 2. The hydrogenation is carried
~ut unaer the following opera~ing conditions:
Temperature 230C
Pressure 100 kg/cm2
Liquid hourly space velocity 2 hr 1
Hydrogen: Polymer ratio 5000 Nl/l
The properties of the resulting hydrogenated
product are the ~ollowing: . ;
Saybolt color + 30
Iodine value . 0.20
10 BP acid tes~ conform
~1.7R
[4.2Y
DAB VII - W abs~rptio~
cell 1 cm 275 nm 0.1
295 nm `- 0.~2
300 nm 0.01
FDA
-Sulfurized compounds conform
-polynuclear aromatics
cell 1 cm - 260-350 nm conform
-USP acid test con~orm
[1.9R
[6.5Y
Odor ~ . Odorless
Example 4
According to the process described in Example 1 there
i~.preparea a catalyst containing 0.44~ by weight of platinum on
the same support as that described in Exampla 1 and co~sisking of
alumina beads having a total pore volume of 0.51 ml~g wherein
0.50 ml/g or 98~ of this total pore volume is provided ~y pores
the size o which is distributed around a mean size of 65A.
With this catalyst, hydrogenation of the polybutene the
characteristics of which are described in Table I of Example 1, is
carried out under the ~ollowing operating conditions:
Temperature 230C
Pressure50 kg/cm
Liquid hourly space velocity 0.5 hr 1
Hydrogen5000 Nl/l
The properties of the resulting hydrogenated product
- 12 -
?~
are the following:
Saybolt color ~30
Iodine value 0.24
"BP acid test" conform
r2.2R
[6.5y
DAB VII - W absorption
cell 1 cm 275 nm 0.12
295 nm 0.02
300 nm a . ol
FDA
-Sulfurized compounds conform
: -Polynuclear aromatics
cell 1 cm 260-350 nm conform
~USP acid test conform
[2.lR
. :[7.0~
Odor Odorless .
The polybutenes which are hydrogenated according to the
~0 process of the present invention, are characterized by a remarkable
heat and storage stabilityi
The product obtained in experiment 1 of Example 1 is
heated at ~00C during 48 hours. After these 48 hours of heating,
the.product is odorless and has a Saybolt color of ~30. :
~ he product which is obtained in experiment 1 of Example
1 is introduced into a steel vessel.. The vessel is closed and
stored at room temperature.
After one week, the product is still odorless and its
Saybolt color is ~30.
Example 5
A hydrogenation catalyst the support of whîch consists
o~ alumina extrudates having a diameter o~ 1.5 mm, is pxepared.
The specific surface is 174 m2/g. The total pore. volume is
0.81 ml/g. This pore volume has the following distri~ution:
- 0.37 ml/g, or 45.7% of the total pore volume are
provided by small pores, the size of which is distri~uted around
a mean size of 65A,
0.25 ml/g, or 30.9% of the total pore volume are
provided by large pores the size of which is distributed around
~ 13 -
~ ~3~,ft.
o
a mean size of 6,000A.
Therea~ter a palladium chlo~ide solution is prepared ,
by introducing 3.05 g of PdCl2 into 145 g of distilled water and
adjusting the pH to l by add.ition of concentrated hydrochloric
acid. The mixture is heated to about 60C until the dissolution
of the salt is substantially completed and then filtered after
cooling. Analysis shows that the solution contains 1.24 g Pd
pex lO0 g solution. To 95.31 g solution, distillated ~ater is
added to obtain a total weight of 324 g. Thereafter this solution
is poured on 162 g of alumina support which is previously calcineaat 500C and cooled. The mixtu.re is allowed to stand during 16
hours and the solution is decanted. The humid catalyst.is
introduced into a store and dried at 120.C. The catalyst is then
calcined at the air at sao ~c and reduced with hydrogen at 5~Q~C.
The reduced catalyst contains 0.7% by weiyht of palladium.-
With this catalyst, the continuous hydrogenation of abutene polymer the characteristics of which are given in Ta~le V
below, is performed: .
T ~ B ~ E V
20 Characteristic . Met~od o~ deter~n'at~on
Speci~ic gravity ls/4oc ASTM D 12~8 0.838
Viscosit~
at 37.8C (C stokesl ASTM D 445 27.34
' at 98.8C CC stokesl ASTM D 445 4.88
at 37.8C (SSU) . 1~7
Viscosity Index ASTM D 227Q llQ-lll
Molecular weight ' 65Q
Saybolt color . ASTM D 156 ~18
Iodine value IP 84 128~3
'The operating cond.~tions under w.hich the hydrogenation
is performed and the properties of the hydrogenaked product
obtained in each experiment are indicated in Tahle VI herein~elow.
- 14 -
T A B L E V I
Characteristics Experiments
5.1 5.2 5.35.4 5.55.6
Temperature (C) 130 240 178156 178230
Liquid hourly1space
velocity (hr
Pressure (kg/cm2) 75 75 75 50 75 35
Hydrogen:polvmer
ratio ~Nl/l~ 300 300 300 30050005000
Specific gravity 15/4C0.838 0.838 0.838 0.838 0.838 0.838
Viscosity
at 37.8C (C stokes)27.34 27.34 27~3427.3427.34 27.34
at 98.9C (C stokes) 4.88 4.88 4.88 4.884.88 4.88
at 37.8C (SSU) 127 127 127 127 127 127
Viscosity Index 110/111 110/111 110/111 110flll 110/111 110/111 :
Saybolt color ~30 ~+30 ~+30 ~+30 ~ 30 ~+30 `~
Iodine value 0.14 0.06 0.08 0.24 0.07 0.26
"BP acid test" conform conform conform conform conform conform
1.7R 0.6R 0.9R 2.2R0.9R2.5R
4.0Y 1.3Y 2.1Y 6.5Y2.1Y6.5Y
DAB VII - W absorption
Cell 1 cm 275 nm0.050.04 0.04 0.080.040.14
295 nm0.010.01 0.01 0.020.010.02
300 nm0.010.01 0.01 0.010.010.01
FDA
Sulfurized compound conform conform conform conform conform conform
Polynuclear aromatics
Cell 1 cm 260/350 nm conform conform conform conform conform conform :
USP acid test conform conform conform conform conform conform
1.6R 0.5R 0.8R 2~0R 0.8R2.1R
4.0Y 1.3Y 2.0Y 6.5Y 2.0Y8~5Y
Odor o d o r 1 e s s
Y = Yellow range of the I.ovibond scale.
R = Red range of the Lovibond scale.
- 15 -
~r
3¢~
By way of comparison, hydrogenation of a polybutene
the characteristics of which are described in Table v, is per~ormed
with catalysts wherein the support on which the metal is deposi~ed
iS outside the scope of the present invention.
In a comparative experiment E, the support of the
catalyst consists of alumina yranul~s having a total pore volume
of 0.39 ml/g, wherein 0.24 ml~g or 61% of that to~al poxe volume
is provided by small pores the size o which is distributed around
a mean size of 55A. The remainder of the total pore volume is
provided by pores the size of which is substantially uniformly
distributed ~etween sizes varyLng he~een 1~0 and lO,QQGA.
Palladium is deposited on this support according to a known proce~s
and the final catalyst contalns Q.57% by ~eLght of palladium.
In the comparati~Te experiment F, the support of the
catalyst consists of kieselguhr on which palla~ium is deposited
acçording to a known proces~! and t~e ~inal catalyst contains Q.6%
by weight of palladium.
In the comparat;Ve experLment G, a c~taly~t is tested
the support of which cons;sts of alumina granules h~ving a totàl
pore volume of 0.77 ml/g, wherein ~.32 ml~s or 42% of t~at total
volume i5 provided ~y pores the size of ~h~ch i~ distri~uted
around a mean size of 65A and Q.25 ml/y or 32% of that are provided
by pores the size of which is distributed around a mean size o~
6,OOOA. Platinum is deposited on this support according to a
known process and the final catalyst contains 0..64% by weight of
platinum.
The herein~elow Table VII indicates the operat1ng
conditions under which the hydrogenation is~performed, and the
properties of the hydrogenated product.
- 16 -
L~
T A B L E V I I
Characteristics Comparative Experiment
_ _
' E F G
Temperature (CJ 240 160 180
Liquid hourly
Space velocity ~hr ~1 1 1
Pressure ~kg/cm2) 100 17 75
Hydrogen: polymer ratio(N1/1~ 3Qa 3aQ 30Q
Density 15/4C a.838 Q.83~ ~.83
10 Viscosity
at 37.8~C ~C stokes~ 27.34 27.34 27.34
at 98.9~C ~C stokes~ 4.88 4.88 4.88
at 37.8C CSSU~ 127 127 127
Viscosity IndexllQ/lll11~/111llQ~110
Saybolt color ~30 ~3Q ~3Q
Iodine value 2.3 l.Q 4.4
"BP acid test" n o t c o n ~ o r m
DAB VII-UV ab,sorption
cell 1 cm 275 nm 0.30 Q.15 ~.60
295 nm ~.05 0 03 Q 0
300 nm 0.03 0 02 0 04
FDA
Sulfurlzed compounds c o n ~ o x m
Polynuclear aromatics
cell 1 cm -260-350 nm c o n ~ o r m
USP acid test n o t c o n f o r m
Odor - u n s a t i s f a c t o r y
Example 6
The process which is described in Example 5 is repeated
in order to obtain a catalyst containing 0.41% by weight of
palladium based on the weight of the catalyst, on a support
consisting of alumina granules having a total pore volume of
O.32 ml/g wherein 45% of that total pore volume is provided by
pores the size of which is distributed around a mean size o~ 125A
and 27.5%, distributed around a mean size of 600A.
In the presence of this cataly.st, a polybutene whose
characteristics are described in Table V of Example 5, was
hydrogenated under the following operating condi~ions.
...... . . ..
~emperature 160C
Pressure 75 kg/cm
Liquid space velocity 2 hr 1
Hydrogen: pol~mer ratio S00 Nl/l
` The hydrogenated product has the follo~ing propertie~:
Saybolt color ~30
Iodine value 0,15
BP acid test conform 1.7R
4.lY
DAB VII - W absorption
Cell 1 cm - 275 nm O.Q5
295 nm ~.Ql
300 nm
FDA
Sulfurized compounds conorm
Polynuclear aromatics
Cell 1 cm - 260-350 nm conform
- USP acid test con~orm 1.6R .
4.lY
By way of comparison, a catalyst is prepared according
to the process described in Example 5, which contains 0.49~ by
weight based on the total weight of catalyst, of palladium on an
alumina support having a total pore volume of 0.34 ml/g wherein
16% of that total pore volume is provided ~y pores the size o~
which is distributed around a mean size of 3S~ and 74% o that
total pore ~olume is provided by pores the size of which is
distributed around a mean size of 300A.
In the presence o~ this catalyst, a poly~utene, the
characteristics of which are descrihed in Table V o~ Example 5,
is hydrogenated under the hereinabove described operating
conditions.
The hydrogenated product ha~ the followin~ propsrties:
` Saybolt color ~30
Iodine value 1.2
BP acid test not con~orm
18 -
DAs VII - uv absorption
Cell 1 cm 275 nm 0.18
295 0.03
300 mn 0 . 02
FDA
Sulfurized compounds conform
Polynuclear aromatic~ -
cell l cm - 260-350 nm conform
USP acid test not conform
10 Odor unsatisfactory
Example 7
The process de~cribed in Example S is repeàted ln order :
to obtain a catalyst containing Q.q2~ by ~eight hased on the total
weight of catalyst, of palladium on an alumina support havin~ a
total pore volume of 0.32 ml~g wherein 45% o~ that total pore
volume is provided ~y pores the size of ~hich is dlstributed
around a mean size of 125A and 27.5% o~ that total pore volume is
provided by pores the size of which is distri~uted around a mean .
size of 600A.
In t~e presence o~ thi5 catal~st, a poly~uten~ the
characteristics of which are descrihed în Table V o~ Example 5,
is hydrogenated under thR following operating conditions:
Temperature 2QQC
P.ressure 75 k~/cm2
Liquid-Space velocity -l !
Hydrogen:polymer ratio 5~Q Nl~l
The hydrogenated product ~a~ the ~ollo~ing ~xopert;es:
Saybolt color ~3Q
Iodine value Q.~8
30 BP acid test con~orm a . 9R
2.1Y
DAB VII - UV absorption
Cell l cm 275.nm 0.04
295 nm 0.01
300 nm 0.01
-- 19 --
. .
FDA
Sulfurize~ compounds conform
Polynuclear aromatics
Cell 1 cm 260-350 nm con~orm
USP acid test conform 0.8R
2~0Y
Odor Odorless
While the invention has now been described in texms of
certain preferred embodiments, and exemplîfied with respect
ther~to, the skilled artisan ~îll appreciate that various
modifications, changes, su~stitutions, and omissions ma~ ~e
made without dèparting fro~ the spirit thereof~ ~ccordingly, it
is intended that the scope of the present invention ~e limîted
solely by that of the follo~ing claim~.
~ 2a -
