Professional Documents
Culture Documents
2, 1954
2,671,058 '
Example II—42.5_ _ _
Percent15 Percent50 ‘ Percent35 42. 3 __________________ -_ 1.43 ____________________ __
Example III-42.5," v5 50 as 43.4 43.1 5.4 1.33 4.3 10.1
Example Iii-42.5-- 25 50 35 44.6 48.4 4.7 1.45 4.4 11.0
2,671,058 I
are then subjected to acid-treatment, washing, A sample of the same predried sub-bentonite
. and drying in the manner disclosed hereinbefore as in Example VIII was pugged with 20 dosage and
- in connection with extruded pellets.
The amount 35 %v concentration of sulfuric acid for about 30
of acid added to the clay in the formation of the ~ minutes and the mixture was compacted into
compacted nodules, the amount of acid with nodules, and activated with 30 dosage of sulfuric
which the nodules are contacted during activation acid (total dosage of sulfuric acid of 50%), and
-, (and consequently the total acid dosage); the washed in the same manner as in Example VIII.
‘time and temperature for activation, and the re The nodules, like those of Example VIII,
remained
quired washing are essentially the same as for hard and stable throughout the entire process,
extruded acid-containing pellets. _ 60 and practically no slaking was observed. The
In accordance with this invention, nodules or CAT-A test resultson this product are given in
Table 3. . -
---balls_ of clay containing from 5 to 30, and pref~
erably 5 to 25, dosage sulfuric acid are formed
by pugging or thoroughly mixing the sub-ben
tonite clay with the desired amount of acid for 65 . A sample of the Cheto sub-bentonite dried to a
avtiinev su?icient to product a uniform mixture. V. M. content of about 20% was pugged with 15
.Usually 30 minutes pugging will be su?icient. dosage sulfuric, acid, formed into nodules or balls
The clay-acid mixture is placed in a revolving by tumbling, acid contacted with 35 dosage sul
.cylinder or tumbler wherein the mixture rolls furic acid (total acid dosage of 50%)‘, and washed
over and over. The clay-‘acid mixture is sprayed 70 in the same manner and under the same condi-
with a ?nely atomized water spray as the tumbler tions as described in Example VIII, except the
iscontinuously ‘revolved. The water spray mois activation time (period, during which the com
tens the clay mixture, and the, rolling action, to pacted. nodules were contacted with the second
‘gather with the compaction force. exerted on ma portion of the acid) was 150 minutes, instead of
terial as iti‘alls during the revolving of thedrum, 7 3~hours,, . ,.. _~ .
_ From an examination oi Table 3, it will be seen .-,n per cent of mineral acid based on the volatile
that the activated‘ clay pellets produced in ac- n” vfree weight of the clay, pelleting the clay-acid
'cordance with the present, invention by activat- mixture, and treating the pelleted uncalcined
ingjraw clay pellets hardened by the incorpora- clay-acid mixture with an additional amount of
tion therein of. a portion of the acid required mineral acid su?icient to bring about acid ac
to activate the clay had a catalytic activity well ,r_ "tivation of the pelleted clay.
within the range for commercial operations. "“’ 3. In a process for acid activating an acid
Speci?cally, the activated clay pellets produced; in activatable clay in which raw uncalcined clay in
accordance with the invention as describe-i in the form of’pellets of substantially uniform size
the examples whenrtested by the modi?ed CAT-A and shape is treated with a mineral acid and
method showeda N. LB. gasoline of at least 39.6 M thereafter is washed to remove soluble salts and
and a weight per cent conversion of at least 44.2. ""’ excess acid and dried, the improvement oi‘hard
The results of the above experiments show ening the pellets sui?cient to prevent breakdown
that hard, stable nodules: which will not slake or of the pellets during acid activation of the clay
brealc down. during acid activation and washing with the mineral acid and also during washing
may be prepared by tumbling a clay mixture hav- _ of the activated clay which comprises mixing
ing between 5 and 30 dosage acid, as well as by with the raw unpelleted clay 5 to 30 weight per
extrusion. It is further shown that mere com- cent of mineral acid based on the volatile free
paction without the inclusion of acid in the clay weight of the, clay, extruding the clay-acid mix
is not sufficient and such acid-free nodules badly ture, and treating the extruded uncalcined clay
slake and break down during activation and r acid mixture with an additional amount of min
washing. Moreover, the acid-containing nodules ‘0 er-al‘ acid suiflcient to bring about acid'activation
upon activation yield catalyst of high catalytic oi the extruded clay.
activity and well within the activity range for 4. In, a process for acid activating an acid
commercial catalyst. activatable clay in which raw uncalcined clay
While particular embodiments and examples 75 in the form of pellets of substantially uniiorm
size and shape is treated with a; mineral acid
of this invention have been set forth and‘ de
2,671,058
13
and thereafter is washed to remove soluble salts l4
and excess acid and dried, the improvement of ture is capable of being extruded into hard stable
hardening the pellets sufficient to prevent break pellets, pelleting the mixture, and treating the
down of the pellets during acid activation of the pelleted uncalcined clay-acid mixture with an
clay with the mineral acid and also during wash additional amount of mineral acid suf?cient to
Q:
ing of the activated clay which comprises mix bring about acid activation of the pelleted clay.
ing with the raw unpelleted clay 5 to 30 weight
per cent of concentrated mineral acid based on
the volatile free weight of the clay, adjusting in the form of pellets of substantially uniform
the moisture content of the clay-acid mixture size and shape is treated with a mineral acid
so as to produce a consistency suitable for pellet and thereafter is washed to remove soluble salts
ing of the mixture into hard stable pellets, pellet and excess acid and dried, the improvement of
ing the mixture, and treating the pelleted un hardening the pellets su?icient to prevent break
calcined clay-acid mixture with an additional down of the pellets during acid activation of the
amount of mineral acid su?icient to bring about 15 clay with the mineral acid and also during wash—
acid activation of the pelleted clay.‘ ing of the activated clay which comprises mix
5. In a process for acid activating an acid ing with the raw unpelleted clay 5 to 30 Weight
activatable clay in which raw uncalcined clay per cent of mineral acid based on the volatile
in the form of pellets of substantially uniform free weight of the clay, pelleting the clay-acid
size and shape is treated with a mineral acid 20 mixture, aging the mixture for a period of from
and thereafter is washed to remove soluble salts 1 to 24 hours, and treating the pelleted un
and excess acid and dried, the improvement of calcined clay-acid mixture with an additional
hardening the pellets sumcient to prevent break amount of mineral acid sufficient to bring about
pellets during acid activation of acid activation of the pelleted clay.
9. In a process for acid activating an acid
washing of the activated clay which comprises 25
mixing with the raw unpelleted clay 10 to 20
weight per cent- of concentrated mineral acid
based on the volatile free weight of the clay, ad thereafter is washed to remove soluble salts and
justing the moisture content of the clay-acid excess acid and dried, the improvement of
mixture so as to produce a consistency suitable hardening the pellets su?icient to prevent break
down of the pellets during acid activation of the
pelleted uncalcined clay-acid mixture with an
additional amount of mineral acid su?icient to <
bring about acid activation of the pelleted clay.
6. In a process for acid activating an acid
activatable clay in which raw uncalcined clay
in the form of pellets of substantially uniform
size and shape is treated with a mineral acid and
thereafter is washed to remove soluble salts and
excess acid and dried, the improvement of
hardening the pellets su?‘icient to prevent break
down of the pellets during acid activation of the
clay with the mineral acid and also during wash- .
ing of the activated clay which comprises mix
ing with the raw unpelleted clay 5 to 30 weight
per cent of mineral acid in an aqueous solution
containing su?icient water such that the mix
ture is capable of being extruded into hard stable
pellets, pelleting the mixture, and treating the 50
pelleted uncalcined clay-acid mixture with an
additional amount of mineral acid sufficient to
bring about acid activation of the pelleted clay.
7. In a process for acid activating an acid- H
activatable clay in which raw uncalcined clay
in the form of pellets of substantially uniform
size and shape is treated with a mineral acid and an additional
thereafter is washed to remove soluble salts and amount of mineral acid sufficient to bring about
excess acid and dried, the improvement of hard acid activation of the extruded clay.
_ ening the pellets sufficient to prevent breakdown GRANT A. MICKEL-SON.
of the pellets during acid activation of the clay
with the mineral acid and also during washing References Cited in the ?le of this patent
of the activated clay which comprises mixing UNITED STATES PATENTS
with the raw unpelleted clay 10 to 20 weight Number Name Date
per cent of mineral acid in an aqueous solution U5
2,551,580 Bond _____________ __ May 8, 1951
containing su?'icient water such that the mix 2,582,956 Bond ____________ __ Jan. 22, 1952