Note: Descriptions are shown in the official language in which they were submitted.
1~86;~93
. ................................................................. .
This invention relates to the production of synthetic,
crystalline ferrierite, an alumino-silicate zeolite. Ferrierite
is relatively scarce in nature, but has been found in large
deposits in the Western United States. Natural ferrierite has
the general formula
(Na,K)0 5_4 Ca0_1 Mg0.s_3 (A14_7 Fe0_1 Si27_3J 72
18-23 H2O
where the sum of the moles of alkali and alkaline earth oxides
equal the sum of the moles of alumina and ferria,
~(Na2O ~ K2O + CaO +MgO) ~ ~(~12O3 + Fe2O3), and
~ (Si + A1 + Fe) = 36. Natural ferrierite from Kamloops Lake,
British Columbia, Canada has been shown by P. A. Vaughan, Acta
Crystallographica 21, 983 (1966), to be orthorhombic with the
space group I 2/M 2/M 2/M. Natural ferrierites from various
localities do not have exactly the same X-ray powder pattern, but
X-ray powder pattern of ferrierite from each locality fits the
theoretically allowed lines for the space group 2/M, 2/M, 2/M, as
shown below in Table A, and the differences are presumably caused
by variable cation contents. Synthetic strontium ferrierites of
the approximate composition SrO:A12O3: 7-9 SiO2, the X-ray powder
patterns of which also fit the allowed lines, have been described
in the literature by R.M. Barrer and D.J. Marshall, Journal of the
Chemical Society 1964. 485. Synthetic strontium and calcium
ferrierite were made at 350-370C and 1,020-1,632 atmospheres
by D. B. Hawkins, Materials Research Bulletin, 2 951 (1967). Also,
synthetic sodium ferrierite was made by E.E. Senderov, Geochemistry
(English Translation) 9. 848 (1963). Synthesis of strontium
ferrierites by Barrer and Marshall were carried out at tempera-
tures of 260, 340 and 380C at pressures of 39, 144 and 235 ~
30 atmospheres, respectively. Even though such high temperatures ~`
- 2 - _
i
1!D86;~93
as 340 and 380 were employed, the synthesis of strontium fer-
rierite required 2-4 days. Twenty days were required to crystal-
lize strontium ferrierite from a 1.5 SrO:1.0 A12O3: 9SiO2: 500H20
slurry at 260C.
The syntheses of strontium ferrierite, reported by Barrer
and Marshall, at 340 and 380 C are relatively difficult, and
the product ferrierite is frequently contaminated with impurities.
By using the seeding technique, described below, we have reduced
the temperatures, pressures and times required for synthesis;
also we have greatly improved the reliability of the process.
Furthermore, no natural ferrierite has been shown to con-
tain substantial amounts of strontium or lithium or both. Table
B shows that samples of natural ferrierite from five localities
are mainly sodium, potassium, magnesium, calcium aluminosilicate
hydrates, with some possible substitution of iron for aluminum.
The compositions of natural ferrierites have recently been
reviewed by Wise and Tschernich (American Mineralogist (1976),
vol. 61, p. 60-66); they did not find lithium in natural
ferrierite samples~
~186Z93
TABLE A
COMPARISON OF D SPACINGS OF TWO NATURAL AND SYNTHETIC STRONTIUM
FERRIERITES WITH THE ALLOWED LINES
FERRIERITE Ferrierite FERRIERITE, SYNTHETIC
Theoretical Kamloops Lake Agoura, Ca. STRONTIUM *
For I 2/M 2/M 2/~ B.C., Canada FERRIERITE
Where a = 19.16
b = 14.13
and c = 7.49
Relative Relative Relative
hkl dA dA Intensity dA Intensity dA Intensity
11011.37 11.3 20 11.3 3 __ __
2009.58 9.61 100 9.47 50 9.49 75
1016 98 7.00 30 {7 07 38 ~7 07 20
0116.62 6.61 20 6.59 3 6.61 55
3105.82 5.84 50 5.75 15 5.77 15
2205.69 __ __ 5.64 14 __ __
2115.44 __ __ __ __ 5.43 5
1214.964 4.96 10- __ __ 4.96 15 -
3014.860 __ __ __ __ __ __
4004.790 4.80 10- 4.75 2 4.76 15
1304.574 4.58 10- 4.56 1 _ __
3214.004 __ __ __ __ __ __
0313.987 3.99 90 3.98 35 3.99 45
4203.965 __ __ 3.94 35 3.94 35
4113.880 3.88 10 __ __ 3.86 25
3303.791 3.791 20 3.78 65 3.78 50
0023.745 __ __ __ __ 3.74 10
5103 66818 3.69 50 3 66 12 ~ 3.67 30
1123.557 3.54 80 __ __ 3.555 10
0403.532 __ __ 3.54 100 3.536 90
2023.488 3.49 80 3.48 18 3.483 100
5013.411 3.42 20 __ __ 3.389 15
2403.314 3.31 20 3.31 35 3.313 20
6003.193 3.20 10 __ __ __ __
1413.152 3.15 30 __ __ 3.142 55
3123.149 __ __ 3.14 12 __
5213.072 3.07 30 __ __ 3.058 45
4313.064 __ __ 3.05 12 __ __
5302.972 2.97 30 __ __ 2.960 25
4022.950 __ __ 2.9~5 11 2.938 25
6202.910 2.90 20 __ __ 2.897 35
4222.722 2.72 20 __ __ 2.715 30
0512.644 2.64 20 2.644 7 2.646 15
3502.584 2.58 30 2.582 10 2.583 10
7012.571 __ __ __ __ __ __
* Barrier and Marshall, American Mineralogist _, 484 (1965)
. ~
1~)136;~93
,
TABLE B
Chemical Analysis of Natural Ferrierite
. . .
Locality Itomuka, Kamloops Albero ** **
Japan Lake, Bassi, Agoura, Agoura, Sonora**
Yajima, Graham Alietti Calif. Calif. Pass,
et al Calif.
Oxide(1971)(1918) (1967)
SiO271.21 69.13 56.8074.4075.64 66.17
A1239.84 11.44 12.718.51 9.39 10.71
10 Fe2O30 05 3.29 0.04 0.01 0.99
TiO2 - 0.10
Mno
CaO - none 5.52 0.13 0.14 0.55
MgO 1.70 2.92 4.12 1.07 1.02 2.79
Na2O1.59 3.97 0.27 1.91 2.33
K2O 2.85 0.36 0.82 2.48 2.80 1.54
C2 ~ 2.84
H2O(+)4.25) 4.16~
~ 13.05 11.46 8.67 17.25
H2O(-)8.63~ 10.1
-
100.12 100.87 100.79 100 100 100
Chemical Formulae of Ferrierite
(Nal 32K1 57)Mgl og(Si30 gsAL5.03Feo.ol)35-99 72-01 2
(Yajima, et al.)
~ )4 g2(Si30Al6)o72(oH)2-l8H2o (Staples, 1955)
Nal.5Mg2Si30.5A15.s72-1~H2 (Vaughan, 1966)
Ko 51Na0 25Cao g9Mg2 98(Fel 20A17.25si27.50)o72 2
(Alietti, 1967)
N 1.8Kl.4Mgo.6(si3l.6Al4 4)72 18H2O (Wise et al., 1969)
. .
* From S. Yajima, et al., Mineralogical Journal, 6 343 (1971).
** W. S. Wise, et al., American Mineralogist, 54, 887 (1969).
-- 5
-
1~86Z93
Brief Description of the Invention
We have found that the preparation of synthetic
ferrierites having the X-ray diffraction patterns shown
in Table C can be greatly facilitated by promoting the
reaction mixtures, consisting of one or more salts of
Group lA (sodium, potassium, rubidium, and cesium) and/or
salts of Group II A (magnesium, barium, strontium, and
calcium) of the periodic table, with silica, water, and
natural or synthetic ferrierites as seeds, with lithium
hydroxide.
,~, The preparation of the lithium, strontium potassium
ferrierite; the lithium potassium ferrierite; and the
lithium, sodium, potassium ferrierite were discussedin
U.S. Patent 3,966,883. The preferred method of -~
preparing the lithium-promoted ferrierite precursor
reactant mixtures is to mix the hydroxides of the salts
with a source of alumina, a source of silica, water, and
natural or synthetic ferrierite as seeds. Thus, the lithium
magnesium ferrierite reaction mixture is prepared by
mixing lithium hydroxide, magnesium hydroxide, a source
of alumina, a source of silica, water, and natural or
synthetic ferrierite seeds. The seeds are present in
a concentration of 0.1 to 10 percent of the reaction
; mixture of a powdered or natural ferrierite, or a
powdered synthetic ferrierite recovered from previous
reactions.
We have further discovered that good synthetic
ferrierite can be made from natural amorphous volcanic
ash, both with and without seeds of natural ferrierite~
The reactions are carried out at a temperature of
- 6 -
. , - . ., . - :, .
1~6293
90 to 325C. in enclosed vessels at a pressure of 1 to 120
atmospheres.
It is an object of the invention to prepare a highly
siliceous, acid resistant zeolite for sorption, ion exchange,
and catalytic uses, especially in acidic systems.
Thus, in accordance with the present teachings, a
process is provided for preparing synthetic ferrierite which
comprises:
a) preparing an alkaline reaction mixture which
contains group I and/or group II cations, a source of alumina,
a source of silica, water, powdered, natural or synthetic
ferrierite seeds in a concentration of 0.1 to 10% by weight
and promotional amounts of lithium cations; and
b) heating the reaction mixture at a temperature of
about 180 to 325 to form ferrierite.
Detailed Description of the Invention
The first step of the process is the preparation of the
precursor mixture. The particular mixture used, of course,
depends on the desired composition of the product. The lithium,
sodium, potassium, rubidium, cesium, magnesium,barium, strontium,
and calcium salts are preferably added as the hydroxides. The
hydroxides are preferred since it is essential that the reaction
be carried out in an alkaline medium, preferably at a pH of
8 to 14.
The alumina can be added in any hydrated or amorphous
form. Alpha-alumina monohydrate and bauxite give satisfactory
results, in addition to commercially available alumina sols.
The silica can be added in any form that is finely
divided. The silica sols give satisfactory results as do silica
gel powders, such as Hi-Sil 21 ~ (a product of PPG Chemicals).
Part of the silica and all of the sodium may be added as sodium
silicate if the final product is to be a lithium promoted sodium
-7-
~ .
93
containing ferrierite. Also, both the silica and the alumina
may be supplied by pumice or tuff, natural amorphous alumino
silicates. Other alkali silicates may also be used as silica
sources (eg. potassium, or lithium silicates). The ratios of
reactants depends, of course, on the final composition of the
mixture. When the product to be recovered is a lithium-barium
ferrierite the reactant mixture should have the following ratios
of reactants: 0.5-1.5 Li2O: 0.25-1.5 BaO: A12O3: 6-30SiO2:
50-600H20. When the ferrierite is a lithium-potassium ferrierite
,~ :
~ , : .: ' , ~ -
.
10~6~3
the ratios of reactants should be 0.5-1.5 Li2O: 0.5-1.5 K2O:
1 Al2O3: 6-3 SiO2: 50-600 H2O. Thus, the central feature of the
process is the inclusion of a lithium cation in the reaction
mixture together with cations of sodium, potassium, rubidium,
caesium, magnesium, barium, strontium, and calcium preferably in
amounts of 0.1 to 5 times the concentration of other Group I or
the Group II cations.
The ferrierite seeds are usually added as a fine powder,
preferably about minus 200 mesh. The seeds may be the natural
ferrierite mineral, or they may be derived from any portion of a
prior preparation. A sample of the natural ferrierite used as
seeds from Lovelock, Nevada had the following composition in
weight percent:
CaO 1.7
MgO 1.1
Fe23 1.4
TiO2 0.1
2 4.5
Na2O 0.7
A123 10.9
SiO2 79.6
; In the preparation the components of the reaction mixture
are added in the desired ratio of reactants and the reactants
are transferred to a sealed pressure reaction vessel. The tem-
perature is increased to about 180 to 325C. and the reaction
allowed to proceed at autogenous pressure. The synthesis is
normally completed in about 1 to 7 days at 300C., when the
strontium is in the sole alkaline earth component. At 250C. the
synthesis takes two days. However, when the alkali metal com-
ponent is a mixture of strontium and lithium, lithium and sodium,
- 8 -
.
: . . ................... . : .
. - , . . : .. ~ .. ..
293
strontium or sodium and lithium, the reaction is completed in a
period as little as 24 hours at 225C. The reaction time is -
from about 12 hours to 7 days with about 1-2 days being preferred
in most cases. The temperatures of seeds syntheses are in the
- range 180C. to 325C., with 200 to 250C. being preferred.
The other steps in the preparation are conventional. The -
product is removed from the reaction vessel and washed free of
excess reactants and dried. The washing is preferably carxied -
out with deionized water at a temperature of about 20 to 80C.
Drying is immediately carried out at a temperature of about 105C.
for a period of about 1 hour.
Our invention is illustrated by the following specific but
nonlimiting examples.
Example 1
A slurry of the oxide ratio 0.5 SrO:0.5 Li2O:1 A12O3:
10 SiO2: 125 H2O was prepared by blending 51 g. Sr(OH)2-8H2O,
16 g. LiOH-H2O, 149 g.~alumina sol, 445 g. silica sol, 263 g.
water and 12 g. powdered natural ferrierite. The slurry was
heated in a sealed steel reaction vessel for one day at 250C.
The product was found to be good quality ferrierite.
The chemical analysis was as follows:
SrO 4.1%
Li2O 2.3%
K2O 0.2%
A123 14.5%
SiO2 78.9%
_ g _
1~86Z93
Example 2
A slurry of the oxide ratio Li2O:A12O3:10SiO2:125 H2O was
prepared by mixing 12 g. powdered natural ferrierite, 32.5 g.
LiOH-H2O, 150 g. alumina sol, 449 g. silica sol and 302 g. water.
The slurry was heated in a sealed steel reaction vessel at 250C
for one day. The product was ferrierite and had the following
chemical analysis:
Li2O 5.4%
K2O 0.2
A123 13.4
SiO2 81.0%
Example 3
A slurry was prepared by the same procedure as in example
2 to achieve the oxide ratio Li2O A12O3 10 SiO2 125 H2O. The
slurry was reacted in a sealed steel reaction vessel at 225C
for 1 day. The product was found to be ferrierite.
The chemical analysis was as follows:
2 5.3%
K2O 0.2%
A123 15.5%
SiO2 79-0%
Example 4
A slurr~ of the oxide ratio Li2O A12O3 10 SiO2 125 H2O was
prepared using the same ingredients as in Example 2. The slurry
was reacted in a sealed steel reaction vessel at 200C. A good
yield of ferrierite was obtained in 5 days.
Example 5
A slurry was prepared from 17 g. -325 mesh powdered natural
ferrierite, 11 g. NaOH, 34.7 g. LiOH-H2O, 209 g. alumina sol,
636 g. silica sol and 437 g. H2O. The slurry oxide ratio was
-- 10 --
.
Z93
0.75 Li2O: 0.25 Na2O: A12O3: 10 SiO2: 125 H2O. The slurry was -
sealed into a steel reaction vessel, and the vessel heated at
225C for one day. The crystallized product was found to be good
quality ferrierite. The chemical analysis was as follows:
Li2O 3.6%
Na2O 2.5%
K2O 0.2~
2 3 14.8%
SiO2 78.9%
Example 6
A lithium-barium ferrierite was prepared from a slurry
having the following oxide ratio: 0:5Li2o:0.5 BaO:lA12O3:10SiO2:
125H20. The slurry was made by mixing 26g barium hydroxide
actahydrate with a solution of 7g lithium hydroxide monohydrate
in 154g water. This was added with blending to a mixture of 250g
silica sol (commercially available Ludox HS-40~, 40% SiO2 and
60% H2O) and 74 g alumina sol (commercially available Q-Loid
` A-3 ~ from the Philadelphia Ouartz Co.) Finally 2.7g natural
ferrierite from ~ovelock, Nevada, powdered to -325 mesh, was
added as seeds; the seeds supply approximately 2.5% of the slurry
alumina.
The slurry was mixed well in a Hobart~ blender, then
placed in steel reaction vessels. The vessels were sealed and
heated at 250C in an oven. After 48 hours the vessel was
; removed from the oven, cooled and opened. The product, a white
slurry, was washed free of excess alkalinity with hot deionized
water and oven dried at 105C. The dried powder was X-rayed by
the powder diffraction method using copper radiation. The X-ray
powder pattern showed the product to be a high purity ferrierite;
the pattern is shown in Table C.
-- 11 -- .
:' ~ ' ' -' '' ' . '
16~86Z93
This ferrierite was calcined and chemically analyzed and
found to contain the following oxides by weight percent.
Li2O 1.4
K2O 0.2
BaO 8.6
A123 11.7
SiO2 77.4
Na O 0 7
100.O
The small amount of K2O is apparently contributed by the
natural ferrierite seeds which contain 4.5% K2O.
Example 7
This example demonstrates the use of Ludox HS-30 silica
sol, a commercially available product, as a silica source for
ferrierite synthesis. A mixture of 335g of silica sol (Ludox
HS-30)~ and 74 g alumina sol (Q-Loid A-30)~ was blended in a
Hobart mixer. To this were added a solution of llg lithium
hydroxide ~lonohydrate in 76g water and 13g finely powdered
barium hydroxide octahydrate. Lastly 2.7g natural ferrierite
(from Lovelock, Nevada), powdered to -325 mesh was blended into
the slurry which formed a soft paste, having the oxide ratio of
0.75Li20:0.25BaO: lA12O3:10SiO2:125H2O. The paste was trans-
ferred to pressure vessels and heated at 250C. After two days
(48 hours) at 250C the product recovered was shown by its X-ray
powder pattern to be a well crystallized, pure ferrierite.
- 12 -
-- . .
8t~293
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-- 13 --
- . '
1~86293
A chemical analysis gave the following composition of the
calcined ferrierite.
Na20 0.1
Li2O 2.5
; 2 0.1
BaO 4.6
A123 13.0
SiO 79-7
100.0 , ,
Example 8
A lithium-potassium ferrierite resulted from a slurry of
the ratio 0.5Li2O:0.5K2O:lA12O3:10SiO2:125H20 heated in a pres-
sure vessel at 250C for one day (24 hours). The slurry was -~;
prepared by dissolving 7g lithium hydroxide monohydrate and ;
llg potassium hydroxide in 160g water. The solution of bases
was mixed with 250g silica sol (Ludox HS-40)R and 74g alumina
sol (Q-Loid A-30) in a HobartR mixer. Lastly, 2.7g powdered
natural ferrierite, -325 mesh, was blended in as seeds. The
X-ray powder pattern is essentially the same as that found for
the product of Example 6. The chemical analysis of the calcined
ferrierite was:
Li2o 2.0
K2O 6.0
A123 13.1
SiO2 78.9
1'00.0
The X-ray powder pattern is shown in Table C. Examples 9
thru 16 were prepared using the same procedures as described
in Examples 6 thru 8. The data is presented in Table E.
- 14 -
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~ ~86Z93
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1~6;~93
Example 17
A reaction slurry was prepared employing the slurry oxide
ratio of SrO:A12O3:10SiO2:125H2O, seeded with natural ferrierite
powder takes the following times to react at various temperatures. ;
Days for Good Yield
Temp. Cof Ferrierite
190 23
200 ~11
225 5
In contrast the slurries employing the oxide ratio
Li2O:A12O3:10SiO2:125H2O produce a good yield of ferrierite in
the following times at various temperatures.
O Days for Good Yield Example
Temp. C of Ferrierite No.
200 5 23
225 1 22
Thus, the synthesis of lithium ferrierite is much more
rapid than the synthesis of strontium ferrierite at 200 and 225C,
making the synthesis of lithium ferrierite a more commercially
useful process.
Example 18
This example demonstrates the acid stability of lithium
ferrierite. A sample of lithium ferrierite was prepared by the
method of Example 2. This lithium ferrierite was then boiled with
0.6M hydrochloric acid using 20g ferrierite and 200 ml 0.6M hydro-
chloric acid for 1/2 hour. The product was washed free of acid,
dried and calcined at 1400F for 3 hours. The nitrogen
; surface area after the above treatment was 273 m2/g as
- 17a -
. .
,. . ' ' . :, ~ - ' ~ : -
- . ' .: - , : ~ ' ~
- 1~86293
measured on a Perkin-Elmer Shell sorptometer. Another
20g sample of lithium ferrierite was boiled in 200ml
0.6M hydrochloric acid for 1/2 hour, the acid filtered
off and the ferrierite boiled another 1/2 hour in a
fresh portion of 0.6M hydrochloric acid. Then the
ferrierite was washed free of acid, dried and calcined
at 1200F for 3 hours. The nitrogen surface area
was 265 m /g.
The following examples demonstrate that ferrierite
cannot be synthesized by our methods if slurries of the
ratio M2O/~IO:lA12O3:8-10SiO2:100-125H20 are reacted
employing powdered ferrierite as seeds without the
addition of some lithium. Examples 19-24 illustrate
the results obtained without the addition of lithium.
(Table F). Most of the products of these experiments
are der.se phases (quartz, feldspar, and analcine), and
clearly show, by reference to previous examples, that
the addition of lithium to the synthesis slurry clearly
has a promoting effect that directs the synthesis to
ferrierite products.
- 18 -
i~6;~93
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-- 19 -- -
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