Molecular sieve abstract
The present invention relates to a composition of metal-incorporated
VSB-5 molecular sieve with nanopores and its preparation method,
in particular, to a composition of a metal-incorporated VSB-5 molecular
sieve with a framework of VSB-5 molecular sieve comprising nickel,
phosphorous, oxygen and metal, which is useful in various fields
such as a hydrogen storage material, an optical and electric/electronic
material, a sensor, a catalyst, a catalyst supporter and an adsorbent,
and its preparation method performed in such a manner that a specific
metal component is added in a predetermined mole ratio to a reaction
mixture comprised of nickel and phosphorous compounds and the resultant
mixture is crystallized in the presence of inorganic or organic
base as a pH modifier to yield a metal-incorporated VSB-5 molecular
sieves in an economical and efficient manner.
Molecular sieve claims
What is claimed is:
1. A composition of a metal-incorporated VSB-5 molecular sieve
prepared using 1 mole of a nickel compound, 0.3-3.0 mole of a phosphorous
compound, 0.001-1.0 mole of at least one metal selected from the
group consisting of a transition metal, a main-group metal, a noble
metal of Group VIII and lanthanide, and 1.0-10.0 mole of a base.
2. The composition according to claim 1 wherein said metal is
at least one selected from the group consisting of titanium, vanadium,
chromium, manganese, iron, silicon, magnesium, palladium, lanthanum,
and cerium.
3. The composition according to claim 1 wherein said metal is
at least one selected from the group consisting of vanadium, manganese,
iron, and zinc.
4. The composition according to claim 2 wherein said metal is
added as a metal source in the form of nitrate, chloride, acetate,
sulfate or oxide.
5. The composition according to claim 1 wherein said base is an
inorganic base or organic base.
6. The composition according to claim 4 wherein said inorganic
base is selected from the group consisting of ammonia, aqueous ammonia,
sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium
hydroxide.
7. The composition according to claim 4 wherein said organic base
is selected from the group consisting of 13-diaminopropane, triethyl
amine, tri-n-propyl amine, diisopropylethyl amine, triethanol amine,
morpholine, cyclohexyl amine and tetraethylethylene diamine.
8. A method for preparing a metal-incorporated VSB-5 molecular
sieve, which comprises the steps of: (a) adding at least one metal
compound selected from the group consisting of a transition metal,
a main-group metal, a noble metal of Group VIII and lanthanide to
a mixture comprised of a nickel compound and a phosphorous compound;
(b) adding an inorganic base or organic base to the resultant of
(a); and (c) heating and crystallizing the resultant of (b) at a
temperature of 50-350.degree. C. and pH 7.0-12.0.
9. The method according to claim 7 wherein said heating is carried
out using a microwave or electric heater.
10. The method according to claim 7 wherein during said crystallization,
the reactants are agitated at a rate of 100-1000 rpm.
11. The method according to claim 7 wherein said inorganic base
is selected from the group consisting of ammonia, aqueous ammonia,
sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium
hydroxide.
12. The method according to claim 7 wherein said organic base
is selected from the group consisting of 13-diaminopropane, triethyl
amine, tri-n-propyl amine, diisopropylethyl amine, triethanol amine,
morpholine, cyclohexyl amine and tetraethylethylene diamine.
13. A metal-incorporated VSB-5 molecular sieve, characterized in
that said molecular sieve form a framework of VSB-5 molecular sieve
and metals are positioned on the inner and outer surfaces of said
molecular sieve.
Molecular sieve description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a composition of a metal-incorporated
VSB-5 molecular sieve with nanopores and its preparation method,
in particular, to a composition of a metal-incorporated VSB-5 molecular
sieve with a framework of VSB-5 molecular sieve comprising nickel,
phosphorous, oxygen and metal, which is useful in various fields
such as a hydrogen storage material, an optical and electric/electronic
material, a sensor, a catalyst, a catalyst supporter and an adsorbent,
and its preparation method performed in such a manner that a specific
metal component is added in a predetermined mole ratio to a reaction
mixture comprised of nickel and phosphorous compounds and the resultant
mixture is crystallized in the presence of inorganic or organic
base as a pH modifier to yield metal-incorporated VSB-5 molecular
sieves in an economical and efficient manner.
[0003] 2. Description of the Related Art
[0004] A nanoporous material of nickel and phosphorous, the so-called
VSB-5 molecular sieve with pore openings composed of 24-membered
ring of oxygen atoms has pores of about 6.4 .ANG., exhibits a catalytic
activity for selective hydrogenation and dehydrogenation, and shows
relatively higher thermal stability. Therefore, the VSB-5 molecular
sieve has been highlighted as a porous solid inorganic material
as compared to conventional zeolitic molecular sieves.
[0005] However, the procedure for synthesizing VSB-5 molecular
sieve containing metal has not reported yet. Furthermore, the procedure
for synthesizing VSB-5 molecular sieve not containing metal has
not been well known. The only process reported so far for producing
VSB-5 molecular sieve comprises the utilization of the diamine bases
from 12-ethylene diamine to 18-octane diamine and nickel and phosphorous
compounds (J. Am. Chem. Soc., 125:1309-1312(2003); and Angew. Chem.
Int. Ed., 40:2831-2834(2001)). As the diamine base, 13-diaminopropane
(DAP) is mainly used. The composition of VSB-5 molecular sieve includes
as mole ratio of about 1.0 Ni: 2.1 P: 5.0 DAP: 140 H.sub.2O, which
undergoes a hydrothermal reaction for 5-6 days at 180.degree. C.
to yield VSB-5 molecular sieve. However, the diamines used as a
base are generally expensive and require heat treatment for its
removal after the synthesis of the VSB-5 molecular sieve. Furthermore,
the heat treatment results in the destruction or occlusion of pore
structures of the VSB-5 molecular sieve, which highly decreases
the surface area of the VSB-5 molecular sieve thus reducing efficiency
of its applications.
[0006] Meanwhile, the molecular sieve of metal aluminophosphate
prepared by incorporating metal into the molecular sieve of aluminophosphate
has been applied to various catalytic reactions and the properties
of its metal have been very likely to be utilized (Chemical review,
99:635-663(1999). In this regard, it could be recognized that the
metal-incorporated VSB-5 molecular sieve shows improved applicability
and usefulness. However, there has been no publication on the metal-incorporated
VSB-5 molecular sieve.
[0007] Therefore, there remains a need in the art for developing
a VSB-5 molecular sieve containing metal and a novel method for
preparing a VSB-5 molecular sieve containing metal in an economical
manner.
SUMMARY OF THE INVENTION
[0008] The present inventors have made intensive researches to
develop a metal-incorporated VSB-5 molecular sieve, and as a result,
found that a suitable amount of certain metal precursor is added
to a composition of VSB-5 molecular sieve comprising nickel and
phosphorous compounds as a raw precursors and a base as a pH modifier,
in order to produce a metal-incorporated VSB-5 molecular sieve exhibiting
redox, optical and electric/electronic properties which are not
found in conventional VSB-5 molecular sieves. In addition, the present
inventors have found that a commercially-available low-cost inorganic
base or organic base such as monoamine works as good as expensive
diamines during crystallization for producing a VSB-5 molecular
sieve. In particular, it has been surprisingly found that the inorganic
base enables to avoid post-heat treatment, so that the process for
producing a VSB-5 molecular sieve may be very cost-effective.
[0009] Accordingly, the object of this invention is to provide
a metal-incorporated VSB-5 molecular sieve and a process for producing
metal-incorporated VSB-5 molecular sieves in an economical and efficient
manner.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 represents the XRD spectrum of metal-incorporated
VSB-5 molecular sieves produced from Examples 1-4 (a-d) and Comparative
Example 1 (e).
[0011] FIG. 2 shows the ratios of the unit cell volume depending
on vanadium concentration of Examples 1 2 5 12 and 13 and Comparative
Example 1.
DETAILED DESCRIPTION OF THIS INVETNION
[0012] In one aspect of this invention, there is provided a composition
of a metal-incorporated VSB-5 molecular sieve prepared using 1 mole
of a nickel compound, 0.3-3.0 mole of a phosphorous compound, 0.001-1.0
mole of at least one metal component selected from the group consisting
of a transition metal, a main-group metal, a noble metal of Group
VIII and lanthanide, and 1.0-10.0 mole of a base.
[0013] In another aspect of this invention, there is provided a
method for preparing a metal-incorporated VSB-5 molecular sieve,
which comprises the steps of: (a) adding at least one metal selected
from the group consisting of a transition metal, a main-group metal,
a noble metal of Group VIII and lanthanide to a reaction mixture
comprised of a nickel compound and a phosphorous compound; (b) adding
an inorganic base or organic base to the resultant of (a); and (c)
heating and crystallizing the resultant of (b) at a temperature
of 50-350.degree. C. and pH 7.0-12.0.
[0014] The present invention will be described in more detail as
follows.
[0015] The present invention is directed to a composition of a
metal-incorporated VSB-5 molecular sieve prepared by adding a specific
metal to a reaction mixture comprised of nickel and phosphorous
compounds followed by crystallization, and a method for preparing
the metal-incorporated VSB-5 molecular sieve. The composition of
the metal-incorporated VSB-5 molecular sieve of this invention shows
redox, optical and electric/electronic properties, which are not
found in conventional VSB-5 molecular sieves, so that it has an
extremely wide range of applications. Further, the method of the
present invention is economical and effective in the sense that
it extends the range of a base useful to a low-cost inorganic base
or monoamine to replace the very expensive diamine.
[0016] The composition of metal-incorporated VSB-5 molecular sieve
of the present invention will be described in more detail as follows.
[0017] Examples of a nickel compound to be used as a raw material
having a certain degree of solubility to a given solvent, for example,
include an inorganic nickel compound such as nickel chloride hydrate
and nickel nitrate hydrate, and an organic nickel compound such
as nickel oleate and nickel oxalate. Of them, nickel chloride hexahydrate
is most preferred. Another raw material, the phosphorous compound
also exhibits the solubility to solvent to some extent, for example,
including inorganic and organic phosphorous compounds such as phosphoric
acid and tri-butylphosphate. Of them, phosphoric acid is most preferred.
[0018] As to the amount of the nickel and phosphorous compounds
as raw materials, it is preferred that the phosphorous compound
be used in the mole ratio of 0.3-3.0 to 1 mole of the nickel compound
to maintain the mole ratio of (P/Ni) to 0.3-3.0. If the mole ratio
is less than 0.3 the materials without pore structures may be obtained
due to excess nickel; and if it is more than 3.0 the preparation
of nanoporous materials becomes difficult because, under excess
phosphorous, the material crystallizable may be dissolved to makes
it difficult to obtain materials in solid-state.
[0019] The technical feature of this invention lies in the addition
of a specific metal to a reaction mixture comprised of nickel and
phosphorous compounds. The metals used are incorporated in the framework
of VSB-5 molecular sieve and are positioned on the inner and outer
surfaces of the molecular sieve, so that the molecular sieve exhibits
the inherent characteristics of metal, e.g., redox, ion-exchange,
optical and electric/electronic properties. Therefore, the molecular
sieve of this invention may be applied to a wider range of applications
compared to a VSB-5 molecular sieve without incorporated metals.
[0020] The metal added to the reaction mixture containing nickel
and phosphorous is at least one selected from the group consisting
of a transition metal, a main-group metal, a noble metal of Group
VIII and lanthanide. In particular, at least one selected from the
group consisting of a transition metal such as titanium, vanadium,
chromium, manganese and iron, a main-group metal such as silicon
and magnesium, a noble metal such as palladium, and lanthanide such
as lanthanum and cerium. The transition metal is more preferred.
The metal-incorporated VSB-5 molecular sieves produced exhibit various
characteristics depending on the type of metals incorporated. For
example, the molecular sieves containing vanadium, chromium, manganese,
palladium, lanthanum or cerium with redox properties show a catalytic
activity in redox reactions; and those containing silicon or magnesium
to show ion-exchange capacity are useful in ion exchange and removal
of harmful ions.
[0021] It is preferred that the metal be used in the amount of
0.001-1.0 mole to 1 mole of nickel compound. If the amount is less
than 0.001 mole, the function of the metal component becomes negligible;
and if it exceeds 1.0 mole, the aggregation between metals occurs
to occlude the pores of the molecular sieve, so that the inherent
properties of a molecular sieve may not be expected. Examples of
the metal that may be used as a metal precursor having a certain
degree of solubility to a given solvent, for example, include at
least one selected from nitrate, chloride, acetate, sulfate and
oxide. More preferably, nitrate, chloride or acetate is used. The
metal precursor may be dissolved in solvent or phosphoric acid.
In addition, the metal precursor may be dissolved and added at the
time of preparing the reaction mixture for VSB-5 molecular sieve
containing base.
[0022] According to the present invention, at least one selected
from low-cost inorganic base and organic base such as monoamine
as a pH modifier may be used instead of high-cost diamines used
in the conventional method to produce VSB-5. The inorganic base
includes hydroxides or oxides of alkaline metal and alkaline earth
metal, and ammonia. For example, sodium hydroxide, potassium hydroxide,
calcium hydroxide, cesium hydroxide, ammonia, aqueous ammonia and
the like may be used. The organic base includes a tertiary amine
such as triethyl amine, tripropyl amine, diisopropylethyl amine
and triethanol amine, a secondary amine such as dibutyl amine and
dipropyl amine, a primary amine such as heptyl amine, octyl amine
and nonyl amine and amine with ring structure such as morpholine,
cyclohexyl amine and pyridine. More preferably, the inorganic base
is employed because it does not require the heat treatment after
synthesis. Most preferably, aqueous ammonia or sodium hydroxide
is used.
[0023] The inorganic base and monoamine used in this invention
serve as a pH modifier to maintain the raw material favorable to
produce metal-incorporated VSB-5 molecular sieve. It is preferred
that the inorganic base or monoamine be employed in the mole ratio
of 1.0-10.0 to 1 mole of the nickel compound.
[0024] Meanwhile, another technical feature of this invention is
a process for producing metal-incorporated VSB-5 molecular sieve
performed in such a manner that a specific metal is added to a reaction
mixture comprised of nickel and phosphorous compounds and crystallized
in the presence of a base, wherein a low-cost inorganic base or
organic base such as monoamine can be used as a base instead of
the most frequently used expensive diamine.
[0025] The present process for preparing metal-incorporated VSB-5
molecular sieve as a porous solid inorganic material will be described
in more detail hereunder.
[0026] First, nickel and phosphorous compounds, a metal compound,
a base and a solvent are mixed in a predetermined mole ratio. The
mole ratio is adjusted to obtain the composition of 1.0 Ni: (0.3-3.0)
P: (0.001-1.0) metal: (1.0-10.0) base: (10-1000) solvent and pH
of 7.0-12.0 more preferably, the composition of 1.0 Ni: (0.5-1.0)
P: (0.005-0.5) metal: (2.0-8.0) base: (50-150) solvent and pH of
7.0-11.0. pH is adjusted by the addition of the base. If pH is beyond
or below the above range, materials without micropores is obtained.
The solvent is at least one selected from the group consisting of
water, alcohols such as ethylene glycol, isopropanol and butanol,
hydrocarbons such as benzene and n-hexane, carbon tetrachloride
and chloroform. More preferably, the solvent is water or butanol,
most preferably, water.
[0027] Thereafter, the mixture is heated at a high temperature
to be crystallized. The crystallization is performed generally at
50-300.degree. C., preferably, 100-250.degree. C., and more preferably,
150-200.degree. C. If the reaction temperature is lower than 50.degree.
C., the reaction proceeds extremely slowly to require a longer period
of time for synthesis; but in the case of exceeding 300.degree.
C., the material containing nickel and phosphorous without pores
is obtained. As a reactor for heating, a microwave or an electric
heater is used. If the electric heater is used as a heat source,
the reaction time ranges from several hours to several days; and
if the microwave is used as a heat source, the reaction time ranges
from several minutes to several hours.
[0028] During the crystallization, the agitation may be performed
additionally. However, for the convenience of the process, agitation
may be omitted. The agitation is usually performed at a rate of
100-1000 rpm, preferably, at 300-750 rpm. The present process may
be carried out in a continuous or batch manner. If the process is
performed for small-scale production, the batch reactor is appropriate;
and if the process is performed for large-scale production, the
continuous reactor is suitable. Where the evaporation of the solvent
occurs significantly, the pressurized reactor is required to prevent
the loss of the solvent.
[0029] Finally, the reaction resultant crystallized under the conditions
described above is then cooled and subject to solid liquid separation
to yield dried VSB-5 molecular sieve. The cooling is generally performed
at 0 to 100.degree. C. The separation of solid product from liquid
may be carried out using a centrifuge or a vacuum filter.
[0030] If organic amine is used as a base, the heat treatment is
performed under gas containing air and oxygen or vacuum to remove
organic materials contained in pores, so that VSB-5 molecular sieve
with high adsorption capacity may be produced. The heat treatment
is preferably performed at 200-500.degree. C., more preferably,
at 300-450.degree. C. If the temperature for heat treatment is lower
than 200.degree. C., the removal of organic materials is not sufficient
to give VSB-5 molecular sieve with lower adsorption capacity; and
if the temperature is higher than 500.degree. C., the framework
of VSB-5 molecular sieve produced is very likely to be destroyed.
When the inorganic base is used, the heat treatment is not required.
This is because the inorganic base is not strongly bound to a VSB-5
molecular sieve enough to remain in the VSB-5 molecular sieve produced
and is well dissolved in water. Therefore, the inorganic base is
easily removed from molecular sieve during washing step. In this
regard, where the inorganic base is used, the production of pure
VSB-5 molecular sieve may be accomplished by performing only washing
and drying without the heat treatment required in the process using
the organic amine.
[0031] The metal-incorporated VSB-5 molecular sieve produced according
to this invention is nanoporous and very useful as a hydrogen storage
material, an ion exchanger, an optical and electric/electronic material,
a sensor, a catalyst, a catalyst supporter and an adsorbent.
[0032] The following specific examples are intended to be illustrative
of the invention and should not be construed as limiting the scope
of the invention as defined by appended claims.
EXAMPLE 1
[0033] Nickel chloride hexahydrate (NiCl.sub.2.cndot.6H.sub.2O)
and vanadyl sulfate (VOSO.sub.4) were dissolved in distilled water.
To the mixed solution, was added 85% phosphoric acid dropwisely
and then aqueous ammonia was added. The reaction proceeded under
the conditions described in Table 1 to obtain the reactant composition
of 1.0 Ni: 0.63 P: 0.017 V: 3.0 NH.sub.3: 100 H.sub.2O (pH 7.7).
30 g of the reactant yielded thus were loaded into a Teflon reactor
and the reactor was sealed and heated in a microwave oven for 4
hr at 180.degree. C. to be crystallized. The reactor was cooled
to room temperature (25.degree. C.) and the solid liquid separation
was performed to yield V-VSB-5 molecular sieve.
[0034] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained V-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are shown in Table
1 and its XRD spectrum is represented in FIG. 1.
[0035] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., V.sup.4+: 0.63 .ANG.), it could be understood
that vanadium ions are present in the molecular sieve.
EXAMPLE 2
[0036] The synthesis was carried out as Example 1 under the conditions
described in Table 1 except that the amount of vanadyl sulfate
was increased 4-fold in mole ratio.
[0037] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained V-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1 and its XRD spectrum is represented in FIG. 1.
[0038] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., V.sup.4+: 0.63 .ANG.), it could be understood
that vanadium ions are present in the molecular sieve.
EXAMPLE 3
[0039] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that manganese acetate hexahydrate
was used instead of vanadium to give Mn-VSB-5 molecular sieve.
[0040] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Mn-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1 and its XRD spectrum is represented in FIG. 1.
[0041] Comparing the unit cell volume and the size of metal ions,
it could be understood that manganese ions are present in the molecular
sieve.
EXAMPLE 4
[0042] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that 13-diaminopropane (DAP) was used
as a base instead of aqueous ammonia, chromic acid (CrO.sub.3) was
used instead of vanadium and aqueous chromic acid solution was added
to the mixed solution of nickel, phosphoric acid and DAP to yield
Cr-VSB-5 molecular sieve.
[0043] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Cr-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1 and its XRD spectrum is represented in FIG. 1.
[0044] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., Cr.sup.6+: 0.52 .ANG.), it could be understood
that chromium ions are present in the molecular sieve.
EXAMPLE 5
[0045] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that 13-diaminopropane was used as
a base instead of aqueous ammonia and vanadium pentoxide (V.sub.2O.sub.5)
dissolved in phosphoric acid was used instead of vanadium sulfate
to yield V-VSB-5 molecular sieve.
[0046] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained V-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0047] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., V.sup.4+: 0.63 .ANG.), it could be understood
that vanadium ions are present in the molecular sieve.
EXAMPLE 6
[0048] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that silica sol (SiO.sub.2) was used
instead of vanadium and silica sol was added to the mixed solution
of nickel compound, phosphoric acid and aqueous ammonia to yield
Si-VSB-5 molecular sieve.
[0049] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Si-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0050] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., Si.sup.4+: 0.42 .ANG.), it could be understood
that silicon ions are present in the molecular sieve.
EXAMPLE 7
[0051] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that magnesium nitrate hexahydrate
was used instead of vanadium sulfate to give Mg-VSB-5 molecular
sieve.
[0052] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Mg-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0053] Comparing the unit cell volume and the size of metal ions,
it could be understood that magnesium ions are present in the molecular
sieve.
EXAMPLE 8
[0054] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that palladium chloride was used instead
of vanadium sulfate and DAP was used instead of aqueous ammonia
to give Pd-VSB-5 molecular sieve.
[0055] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Pd-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
EXAMPLE 9
[0056] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that palladium chloride was used instead
of vanadium sulfate to yield Pd-VSB-5 molecular sieve.
[0057] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Pd-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0058] Comparing the unit cell volume and the size of metal ions,
it could be understood that palladium ions are present in the molecular
sieve.
EXAMPLE 10
[0059] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that lanthanum chloride hexahydrate
was used instead of vanadium sulfate and lanthanum compound was
added to the mixture of nickel, phosphorous compound and aqueous
ammonia to give La-VSB-5 molecular sieve.
[0060] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained La-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0061] Comparing the unit cell volume and the size of metal ions,
it could be understood that lanthanum ions are present in the molecular
sieve.
EXAMPLE 11
[0062] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that cerium nitrate hexahydrate was
used instead of vanadium sulfate and cerium compound was added to
the mixture of nickel, phosphorous compound and aqueous ammonia
to produce Ce-VSB-5 molecular sieve.
[0063] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Ce-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0064] Comparing the unit cell volume and the size of metal ions,
it could be understood that cerium ions are present in the molecular
sieve.
EXAMPLE 12
[0065] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that DAP was used instead of aqueous
ammonia and an electric heater instead of the microwave heater was
used for the heat treatment for 4 days at 180.degree. C. to give
V-VSB-5 molecular sieve.
[0066] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained V-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0067] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., V.sup.4+: 0.63 .ANG.), it could be understood
that vanadium ions are present in the molecular sieve.
EXAMPLE 13
[0068] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that an electric heater instead of
the microwave heater was used for the heat treatment for 4 days
at 180.degree. C. and the agitation at 750 rpm was carried out.
[0069] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained V-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal ate indicated in Table
1.
[0070] Comparing the unit cell volume and the size of metal ion
(P.sup.5+: 0.35 .ANG., V.sup.4+: 0.63 .ANG.), it could be understood
that vanadium ions are present in the molecular sieve.
EXAMPLE 14
[0071] The synthesis was carried out as Example 1 under the conditions
indicated in Table 1 except that iron (III) chloride was used instead
of vanadium to give Fe-VSB-5 molecular sieve.
[0072] The BET surface area and the ratio of Me/(P+Ni+Me) of thus
obtained Fe-VSB-5 molecular sieve, and the ratio of the unit cell
volume to that of VSB-5 not containing metal are indicated in Table
1.
[0073] Comparing the unit cell volume and the size of metal ion
(Ni.sup.2+: 0.69 .ANG., Fe.sup.3+: 0.64 .ANG.), it could be understood
that iron ions are present in the molecular sieve.
COMPARATIVE EXAMPLE 1
[0074] The synthesis of VSB-5 molecular sieve was carried out as
Example 1 not using metal.
[0075] The BET surface area of thus obtained VSB-5 molecular sieve
is indicated in Table 1 and its XRD spectrum is represented in FIG.
1.
COMPARATIVE EXAMPLE 2
[0076] The synthesis of Co-VSB-5 was carried out as Example 4
except that cobalt acetate tetrahydrate was used instead of chromic
acid. However, it was revealed from XRD spectrum that amorphous
solid material was obtained instead of the target product of Co-VSB-5.
In addition, the BET 10 surface area of thus obtained material was
measured to be less than 10 m.sup.2/g, indicating that the material
yielded was without micropore structures.
1 TABLE 1A Reaction conditions Temp. Time Example Metal Composition
(mole)* pH (.degree. C.) (h) Exa. 1 V 1.0Ni:0.63P:0.017V: 7.7 180
4 3.0NH.sub.3:100H.sub.2O Exa. 2 V 1.0Ni:0.63P:0.068V: 7.8 180 4
3.0NH.sub.3:100H.sub.2O Exa. 3 Mn 1.0Ni:0.63P:0.033Mn: 8.3 180 4
3.0NH.sub.3:100H.sub.2O Exa. 4 Cr 1.0Ni:0.63P:0.033Cr: 8.5 180 4
2.0DAP:100H.sub.2O Exa. 5 V 1.0Ni:0.63P:0.033V: 10.0 180 4 3.5DAP:100H.sub.2O
Exa. 6 Si 1.0Ni:0.63P:0.033Si: 8.3 180 4 3.0NH.sub.3:100H.sub.2O
Exa. 7 Mg 1.0Ni:0.63P:0.033Mg: 8.3 180 4 3.0NH.sub.3:100H.sub.2O
Exa. 8 Pd 1.0Ni:2.4P:0.034Pd: 10.7 180 4 5.9DAP:13EG:88H.sub.2O
Exa. 9 Pd 1.0Ni:0.63P:0.034Pd: 8.0 180 4 3.0NH.sub.3:100H.sub.2O
Exa. 10 La 1.0Ni:0.63P:0.033La: 8.0 180 4 3.0NH.sub.3:100H.sub.2O
Exa. 11 Ce 1.0Ni:0.63P:0.033Ce: 8.1 180 4 3.0NH.sub.3:100H.sub.2O
Exa. 12 V 1.0Ni:0.63P:0.033V: 10.0 180 96 3.0NH.sub.3:100H.sub.2O
Exa. 13 V 1.0Ni:0.63P:0.033V: 8.0 180 96 3.0NH.sub.3:100H.sub.2O
Exa. 14 Fe 1.0Ni:0.63P:0.185Fe: 7.9 180 96 3.0NH.sub.3:100H.sub.2O
Com. Exa. 1 -- 1.0Ni:0.63P: 7.7 180 4 3.0NH.sub.3:100H.sub.2O Com.
Exa. 2 Co 1.0Ni:0.63P:0.033Cr: 8.5 180 4 2.0DAP:100H.sub.2O *13-diaminopropane;
EG, ethylene glycol
[0077]
2 TABLE 1B Reaction results Composition Unit cell BET surface area
(Me/(P + Ni + Me), volume Example pH (m.sup.2/g) atom %) (%).sup.e
Exa. 1 8.4 436.sup.d 0.58 100.25 Exa. 2 8.2 334.sup.d 1.91 100.63
Exa. 3 8.6 ND.sup.a 1.31 100.70 Exa. 4 9.2 250.sup.c 1.44 100.40
Exa. 5 10.1 ND.sup.a 1.19 100.46 Exa. 6 8.7 ND.sup.a 2.10 100.42
Exa. 7 8.6 ND.sup.a 0.50 100.40 Exa. 8 10.9 300.sup.c ND 100.30
Exa. 9 8.7 397.sup.d 0.40 100.51 Exa. 10 8.8 425.sup.d 1.40 100.85
Exa. 11 8.7 385.sup.d 0.50 100.68 Exa. 12 10.2 260.sup.c 1.20 100.46
Exa. 13 8.0 ND.sup.a 1.10 100.40 Exa. 14 8.0 ND.sup.a 5.90 99.78
Com. Exa. 1 7.8 400d 0.0 100.00 Com. Exa. 2 9.7 <10 1.50 -- ND.sup.a,
not determined; .sup.cBET surface area of an activated sample .sup.dBET
surface area of an as-synthesizwd sample, .sup.eratio of the unit
cell volume of a metal-incorporated VSB-5 to that of a metal-unincorporated
VSB-5
[0078] As indicated in Table 1 it could be appreciated that Examples
1-14 according to the present invention provided pure metal-incorporated
VSB-5 molecular sieves, which is demonstrated with high BET surface
area values and Me/(P+Ni+Me) and XRD spectrum of FIG. 1. Compared
to BET surface area of the molecular sieve not containing metal,
those of the molecular sieves from Examples 1-14 show comparable
BET surface area. Referring to FIG. 2 representing the ratio of
the unit cell volume depending on vanadium concentration, which
are the results of Examples 1 2 5 12 and 13 and 15 Comparative
Example 1 the unit cell volume shows a linear increase with the
increase in vanadium concentration, which shows the successful production
of vanadium-incorporated VSB-5 molecular sieve.
[0079] In addition, Examples using low-cost inorganic base or monoamine
are more economic than Examples 4 8 and 12 using conventional diamines;
particularly, the cases using inorganic base can simplify the process
for producing VSB-5 molecular sieve because they do not require
heat treatment at high temperature. The molecular sieves produced
show various properties depending on the type of metals incorporated.
For example, the molecular sieves containing V, Cr, Mn, Pd, La or
Ce show a catalytic activity in redox reactions; and those containing
Si or Mg show ion-exchange capability and are therefore useful in
ion exchange and removal of harmful ions.
[0080] As described above, the present invention using a suitable
metal and a base renders the process to be simplified and also enables
to provide a metal-incorporated VSB-5 molecular sieve in an economical
and efficient manner. The metal-incorporated VSB-5 molecular sieve
is very useful in various industrial fields such as a hydrogen storage
material, optical and electric/electronic materials, a sensor, a
catalyst, a catalyst supporter and an adsorbent. |