Molecular sieve abstract
Described is a process for selectively converting xylene in the
gas phase with an ethylating agent under hydrocarbon conversion
conditions to a highly pure 34-dimethylethylbenzene product in
the presence of a catalyst composition comprising a metal-ion-modified,
crystalline borosilicate molecular sieve in which the metal is intimately
associated with the framework silica lattice, composited in an inorganic
matrix.
Molecular sieve claims
What is claimed is:
1. A process comprising contacting xylene and an ethylating agent
under hydrocarbon conversion conditions to selectively form 34-dimethylethylbenzene
in the presence of a catalyst composition comprising a crystalline
metalloborosilicate molecular sieve containing between about 0.1
weight percent of about 6 weight percent of metal ion selected from
the group consisting of manganese, cobalt, nickel, copper, zinc,
and ytterbium ions, composited in an inorganic matrix, said sieve
made by crystallization from an aqueous solution containing ammonia
or an organic base, an organic template compound, a metal ion-affording
compound selected from soluble compounds of said metal ion, and
sources of an oxide of silicon and boron and providing an X-ray
pattern comprising the following X-ray diffraction lines and assigned
strengths:
2. The process of claim 1 wherein the amount of said metal ion
in said sieve is between about 0.5 and about 4 weight percent.
3. The process of claim 1 wherein said metal ion-affording compound
is selected from the group consisting of compounds of manganese,
cobalt, nickel, and zinc.
4. The process of claim 2 wherein said metal ion-affording compound
is selected from the group consisting of soluble compounds of manganese,
cobalt, nickel, and zinc.
5. The process of claim 1 wherein said inorganic matrix is silica,
silica-alumina, or alumina.
6. The process of claim 2 wherein said inorganic matrix is silica,
silica-alumina, or alumina.
7. The process of claim 3 wherein said inorganic matrix is silica,
silica-alumina, or alumina.
8. The process of claim 4 wherein said inorganic matrix is silica,
silica-alumina, or alumina.
9. The process of claim 1 wherein said inorganic matrix is alumina.
10. The process of claim 2 wherein said inorganic matrix is alumina.
11. The process of claim 3 wherein said inorganic matrix is alumina.
12. The process of claim 4 wherein said inorganic matrix is alumina.
Molecular sieve description
BACKGROUND OF THE INVENTION
This invention relates to the selective gas phase ethylation of
xylene to form a highly isomerically-pure dimethylethylbenzene product
and to the use of catalyst compositions comprising metal-modified,
crystalline borosilicate molecular sieves, incorporated into an
inorganic matrix, for carrying out such selective ethylation. More
particularly, this invention relates to the selective gas phase
conversion of xylene to highly isomerically pure 34-dimethylethylbenzene
by contacting xylene, pure or in a mixture, with an ethylating agent
under hydrocarbon conversion conditions in the presence of a catalyst
composition comprising a metal-ion-modified, crystalline borosilicate
molecular sieve incorporated in an inorganic matrix in which the
metal ion is intimately associated with the silica framework lattice.
The process offers a simple route from xylene to a highly isomerically-pure
34-dimethylethylbenzene product having reduced isomer purification
problems.
Catalyst compositions, generally useful for hydrocarbon conversion,
based upon AMS-1B crystalline borosilicate molecular sieves have
been described in U.S. Pat. Nos. 4268420 4269813 4285919
and published European Application No. 68796 all of which are incorporated
herein by reference.
In U.K. Pat. No. 2024790B, catalyst compositions containing high
specific surface area crystalline silica based materials modified
by boron, which have been impregnated by Pt, Pd, Ni, Co, W, Cu,
and Zn, are taught, which materials have catalytic usefulness in,
inter alia, the alkylation of toluene with methanol. European Pat.
No. 38682 teaches methanol-to-synthesis-gas conversion catalysts
comprising a crystalline silica modified by inclusion of cobalt
in the crystal lattice in place of a proportion of the silicon atoms.
The catalyst is prepared by mixing in water or alcohol a source
of silicon, a source of cobalt, a nitrogenous base such as a quaternary
ammonium compound and, optionally, a mineralizing agent, and/or
an inorganic base like sodium hydroxide. Also, European Pat. No.
63436 describes a methanol or olefin conversion catalyst of general
formula 0-9 M.sub.2 O:aY.sub.2 O.sub.3 :at least 100XO.sub.2 :0-35H.sub.2
O, where M is a monovalent cation or 1/n of a cation of valency
n, a is from 0-9 X is silicon and Y can be one or more of aluminum,
iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese,
gallium, or boron.
Selective production of 34-dimethylethylbenzene by alkylation
of xylene over zeolite catalysts having a silica-to-alumina ratio
of at least about 12 and a Constraint Index of greater than 2 and
up to about 12 is taught in European Patent Application No. 0021600.
The class of zeolites is exemplified by ZSM-5 ZSM-11 ZSM-23 and
ZSM-35.
Catalyst compositions made using crystalline borosilicate molecular
sieves have shown a great utility for hydrocarbon conversion reactions
such as aromatic isomerization and alkylation reactions. While excellent
for many purposes, it is desirable to fine-tune the borosilicate
family of catalysts to perform more selectively in a particular
type of hydrocarbon conversion reaction. Now it has been found that
by incorporating a small amount of metal ion in the formation of
a HAMS-1B molecular sieve, crystalline borosilicate-based molecular
sieves, metalloborosilicates, can be produced which are very selective
for producing the 34-dimethylethylbenzene isomer during the gas
phase ethylation of a xylene alone or in a mixture.
SUMMARY OF THE INVENTORY
Described herein is a process comprising contacting xylene and
an ethylating agent under hydrocarbon conversion conditions to selectively
form 34-dimethylethylbenzene with a catalyst composition comprising
a crystalline metalloborosilicate molecular sieve containing between
about 0.1 weight percent and about 6 weight percent of metal ion
selected from the group consisting of manganese, cobalt, nickel,
copper, zinc, and ytterbium ions, said sieve made by crystallization
from an aqueous solution containing ammonia or an organic base,
an organic templating material, a metal ion-affording compound selected
from soluble compounds of said metal ion, and sources of an oxide
of silicon and boron and providing an X-ray pattern comprising the
X-ray diffraction lines and assigned strengths to be found in Table
A below.
These metalloborosilicates are made in such a way that the metal
ion content of the sieve, while small, is incorporated differently
in the crystalline lattice than metal ion-containing sieves made
by ion exchange or impregnation processes. It is believed that the
metal ion may be incorporated in the silica lattice of the crystalline
metalloborosilicate sieve.
DETAILED DESCRIPTION OF THE INVENTION
Ethylation of xylene in the presence of the catalyst compositions
according to this invention is effected by contact of xylene with
an ethylating agent, preferably in the gas phase, at a temperature
between about 200.degree. and about 600.degree. C. and preferably
between about 250.degree. and about 400.degree. C. The reaction
generally takes place at atmospheric pressure, but the pressure
may be within the approximate range of about 1 atmosphere to about
2000 psig. The molar ratio of xylene to ethylating agent employed
is within the approximate range of about 0.5 to about 50 more preferably
about 2 to about 20. Reaction is suitably accomplished utilizing
a weight hourly space velocity of between about 0.1 and about 100
and preferably between about 0.5 and about 50. The reaction product
consisting primarily of the 34-dimethylethylbenzene isomer together
with comparatively smaller amounts of other isomers may be separated
from the other isomers and any unconverted feed materials by any
suitable means such as fractionation.
Alkylating agents useful in this invention are ethylene and ethanol
and more preferably ethylene is the alkylating agent of choice.
The xylene feed to the instant process can be a single isomer such
as ortho-, meta-, or paraxylene or a mixture of such isomers. The
feed can be either pure xylene or xylenes, or a xylene or xylenes
in mixture with other materials such as ethylbenzene. Too much of
an impurity which is ethylatable, however, wastes ethylation agent
and should be pre-separated.
The crystalline metalloborosilicate molecular sieves of this invention
are characterized by the representative X-ray pattern listed in
Table A below and by the composition formula:
wherein M is hydrogen and one cation selected from the group manganese,
cobalt, nickel, copper, zinc, and ytterbium, n is the valence of
the cation, x is between about 2 and about 8 except for Yb where
it is between about 0.2 and 0.8 y is between about 25 and about
600 and z is between 0 and about 160.
TABLE A ______________________________________ Interplanar Interplanar
Spacing (1) Assigned Spacing (1) Assigned d, .ANG. Strength d, .ANG.
Strength ______________________________________ 11.18 .+-. 0.20
VS 3.84 .+-. 0.10 MS 10.03 .+-. 0.20 MS 3.81 .+-. 0.10 M 9.75 .+-.
0.20 W 3.74 .+-. 0.10 W 6.35 .+-. 0.20 W 3.71 .+-. 0.10 M 5.98 .+-.
0.15 W 3.63 .+-. 0.10 W ______________________________________ (1)
Copper K alpha radiation (2) VW = very weak; W = weak; M = medium;
MS = medium strong; VS = very strong
It is believed that the small metal ion content of the sieves is
at least in part incorporated in the silica lattice. Various attempts
to remove the metal ion from the metalloborosilicate sieves by exhaustive
exchange with sodium, ammonium, and hydrogen ions, although in some
cases removing a small amount of metal ion, leaves a definite, residual,
nonexchangeable metal percentage, maybe incorporated in the silica
lattice.
The metalloborosilicate molecular sieve useful in this invention
can be prepared by crystallizing an aqueous mixture, at a controlled
pH, of a metal ion-affording compound, sources of an oxide of boron
and an oxide of silicon, and an organic template compound.
By regulation of the quantity of metal ion (represented as MO)
and the quantity of boron (represented by B.sub.2 O.sub.3) in the
reaction mixture, it is possible to vary the SiO.sub.2 /MO and the
SiO.sub.2 /B.sub.2 O.sub.3 molar ratios in the final product. In
general it is desirable to have the metal ion content of the metalloborosilicate
sieve of this invention between about 0.1 and about 6 percent by
weight of metal ion. More preferably, the amount of metal ion should
be between about 0.5 and about 4 weight percent metal ion. Too much
metal ion in the reaction mixture can reduce the sieve crystallinity
which can reduce the catalytic usefulness of the sieve.
The metal ion is selected from the group consisting of manganese,
cobalt, nickel, copper, zinc, and ytterbium ions and more preferably
from the group consisting of manganese, cobalt, nickel, and zinc
ions. It is conveniently introduced into the molecular sieve synthesis
mixture as a soluble metal salt such as the metal nitrate, acetate,
chloride, etc.
More specifically, the material useful in the present invention
is prepared by mixing a base, a boron oxide source, a metal ion-affording
substance, an oxide of silicon, and an organic template compound
in water (preferably distilled or deionized). The order of addition
usually is not critical although a typical procedure is to dissolve
the metal ion-affording substance in an excess of complexing organic
or inorganic base such as ethylenediamine or ammonia in water, add
the boric acid and then the template compound. Generally, the silicon
oxide compound is added with stirring and the resulting slurry is
transferred to a closed crystallization vessel for a suitable time.
After crystallization, the resulting crystalline product can be
filtered, washed with water, dried, and calcined.
During preparation, acidic conditions should be avoided. Advantageously,
the pH of the reaction mixture falls within the range of about 8.0
to about 12.0 more preferably between about 9.0 and about 11.0
and most preferably between about 9.5 and 10.5.
Examples of oxides of silicon useful in this invention include
silicic acid, sodium silicate, tetraalkyl silicates, and Ludox,
a stabilized polymer of silicic acid manufactured by E. I. DuPont
de Nemours & Co. Typically, the oxide of boron source is boric
acid although equivalent species can be used such as sodium borate
and other boron-containing compounds.
Organic templates useful in preparing the crystalline metalloborosilicate
include alkylammonium cations or precursors thereof such as tetraalkylammonium
compounds, especially tetra-n-propylammonium compounds. A useful
organic template is tetra-n-propylammonium bromide. Diamines, such
as hexamethylenediamine, can be used.
Organic bases useful in the process described herein are amines
and substituted amines, particularly those compounds which are able
to keep the metal ion in solution during formation of the sieve
without tying up the metal ion so completely so as not to allow
some of it to be incorporated in the sieve.
The crystalline metalloborosilicate molecular sieve can be prepared
by crystallizing a mixture of sources for an oxide of silicon, an
oxide of boron, an oxide of a metal, an alkylammonium compound and
an organic base or ammonia such that the initial reactant molar
ratios of water to silica range from about 5 to about 80 preferably
from about 10 to about 50 and most preferably from about 20 to
about 40. The silica-to-boron oxide molar ratio is preferably about
5 to about 400 more preferably about 10 to about 150 and most preferably
about 10 to about 80. In addition, preferable molar ratios for initial
reactant silica to oxide of metal range from about 4 to about 200
more preferably from about 10 to about 150 and most preferably
from about 20 to about 100. The molar ratio of organic base or ammonia
to silicon oxide should be about above about 0.05 typically below
about 5 preferably between about 0.05 and about 1.0 and most preferably
between about 0.1 and about 0.5. The molar ratio of alkylammonium
compound, such as tetra-n-propylammonium bromide, to silicon oxide
can range from 0 to about 1 or above, typically above about 0.005
preferably about 0.01 to about 0.2 and most preferably about 0.02
to about 0.1.
The resulting slurry is transferred to a closed crystallization
vessel and reacted usually at a pressure at least the vapor pressure
of water for a time sufficient to permit crystallization which usually
is about 0.25 to about 20 days, typically is about one to about
ten days, and preferably is about one to about seven days, at a
temperature ranging from about 100.degree. to about 250.degree.
C., preferably about 125.degree. to about 200.degree. C. The crystallizing
material can be stirred or agitated as in a rocker bomb. Preferably,
the crystallization temperature is maintained below the decomposition
temperature of the organic template compound. Especially preferred
conditions are crystallizing at about 150.degree. C. for about three
to about seven days. Samples of material can be removed during crystallization
to check the degree of crystallization and determine the optimum
crystallization time.
The crystalline material formed can be separated and recovered
by well-known means such as filtration with aqueous washing. This
material can be mildly dried for anywhere from a few hours to a
few days at varying temperatures, typically about 50.degree. to
about 225.degree. C., to form a dry cake which can then be crushed
to a powder or to small particles and extruded, pelletized, or made
into forms suitable for its intended use. Typically, materials prepared
after mild drying contain the organic template compound and water
of hydration within the solid mass and a subsequent activation or
calcination prodecure is necessary, if it is desired to remove this
material from the final product. Typically, the mildly dried product
is calcined at temperatures ranging from about 260.degree. to about
850.degree. C. and preferably from about 420.degree. to about 600.degree.
C. Extreme calcination temperatures or prolonged crystallization
times may prove detrimental to the crystal structure or may totally
destroy it. Generally, there is no need to raise the calcination
temperature beyond about 600.degree. C. in order to remove organic
material from the originally formed crystalline material. Typically,
the molecular sieve material is dried in a forced draft oven at
165.degree. C. for about 4 hours and is then calcined in air in
a manner such that the temperature rise does not exceed 125.degree.
C. per hour until a temperature of about 540.degree. C. is reached.
Calcination at this temperature usually is continued for about 4
to 16 hour. The metalloborosilicate sieves thus made generally have
a surface area greater than about 300 sq. meters per gram as measured
by the BET procedure.
The metalloborosilicate sieve useful in this invention is admixed
with or incorporated within various binders or matrix materials
depending upon the intended process use. The crystalline metalloborosilicates
are combined with active or inactive materials, synthetic or naturally-occurring
zeolites, as well as inorganic or organic materials which would
be useful for binding the metalloborosilicate. Well-known materials
include silica, silica-alumina, alumina, magnesia, titania, zirconia,
alumina sols, hydrated aluminas, clays such as bentonite or kaolin,
or other binders well-known in the art. Typically, the metalloborosilicate
is incorporated within a matrix material by blending with a sol
of the matrix material and gelling the resulting mixture or slurrying
the sieve with the matrix material and drying. Also, solid particles
of the metalloborosilicate and matrix material can be physically
admixed. Typically, such metalloborosilicate compositions can be
pelletized or extruded into useful shapes. The crystalline metalloborosilicate
content can vary anywhere from a few up to 100 wt.% of the total
composition. Catalytic compositions can contain about 0.1 wt.% to
about 100 wt.% crystalline metalloborosilicate material and preferably
contain about 10 wt.% to about 95 wt.% of such material and most
preferably contain about 20 wt.% to about 80 wt.% of such material.
More specifically, catalytic compositions comprising the crystalline
metalloborosilicate material of this invention and a suitable matrix
material are formed by adding a finely-divided crystalline metalloborosilicate
sieve to an aqueous sol or gel of the matrix material, such as PHF
Alumina made by American Cyanamid Co. The resulting mixture is thoroughly
blended and gelled, typically by adding a material such as ammonium
hydroxide. The resulting gel is dried below about 200.degree. C.,
more preferably between about 100.degree. and about 150.degree.
C. and calcined between about 350.degree. and about 700.degree.
C. to form a catalyst composition in which the crystalline metalloborosilicate
sieve is distributed throughout the matrix material.
Alternatively, the sieve and a suitable matrix material like alpha-alumina
monohydrate such as Conoco Catapal SB Alumina can be slurried with
a small amount of a dilute weak acid such as acetic acid, dried
at a suitable temperature under about 200.degree. C., preferably
about 100.degree. to about 150.degree. C., and then calcined at
between about 350.degree. and about 700.degree. C., more preferably
between about 400.degree. to about 650.degree. C.
The catalyst compositions of this invention appear to be more selective
for the ethylation of xylene when matrixed by the gel technique
rather than the slurry technique, so the gel technique of making
the catalyst compositions of this invention is preferred.
The catalyst compositions of this invention can be impregnated
with a magnesium compound or a phosphorus compound or both, which
can be accomplished using the catalyst composition in powder form
or already in extrudate or pellet form.
To make the impregnated catalyst compositions, a composition comprising
the acid form of the crystalline metalloborosilicate molecular sieve
in an inorganic matrix is contacted with a phosphorus compound-containing
solution. The resulting mass is then dried at temperatures up to
about 150.degree. C. removing in this step essentially all of the
impregnation solvent. The resulting composition is then activated
by calcination for 3 hours to about 24 hours at about 350.degree.
to about 650.degree. C., more preferably about 4 hours to about
24 hours at about 400.degree. to about 600.degree. C. Care should
be taken to avoid catalyst degradation during calcination.
The amount of phosphorus incorporated with the catalyst composition
should be from about 1 to about 15 percent by weight, especially
from about 2 to about 10 percent by weight, with the percents calculated
as percent of the element.
Representative phosphorus compounds useful in the impregnation
step include primary, secondary, or tertiary phosphines; tertiary
phosphine oxides; primary and secondary phosphonic acids; esters
of phosphonic acids; the dialkyl alkyl phosphonates; alkyl dialkyl
phosphonates phosphinous acids, primary, second, and tertiary phosphites
and esters thereof; alkyl dialkylphosphinites, dialkyl alkylphosphonites,
their esters, phosphoric acid, phosphite esters such as triethylphosphite
and ammonium phosphate salt. Preferred phosphorus-containing compounds
include phosphoric acid, phosphite esters such as triethylphosphite,
ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Magnesium compounds can be incorporated with the catalyst compositions
in a manner similar to that employed with the phosphorus compounds
above. Magnesium impregnation should result in about 4% to 20% by
weight magnesium, preferably from about 8% to about 15% by weight
magnesium, percent calculated as percent of the element. As with
phosphorus, magnesium compound incorporation is effected by contacting
the catalyst composition with the solution of an appropriate magnesium
compound followed by drying and calcining to substantially convert
impregnated magnesium compound to its oxide form. Preferred magnesium-containing
compounds include most soluble magnesium salts, more preferably
magnesium nitrate or acetate. Drying and calcination times and temperatures
are generally the same as recited hereinbefore for drying the calcination
of phosphorus-containing catalyst compositions.
The solutions of phosphorus or magnesium compounds used in impregnation
may be made from polar or nonpolar solvents, including water and
organic solvents generally. Solvents that are destructive of either
the zeolite or matrix should be avoided. Water and alcohols are
preferred solvents.
When both phosphorus and magnesium impregnation is used, the phosphorus
compound and the magnesium compound are impregnated in the catalyst
composition sequentially with phosphorus impregnation preceding
magnesium impregnation.
The following Examples will serve to illustrate certain embodiments
of the hereindisclosed invention. These Examples should not, however,
be construed as limiting the scope of the novel invention as there
are many variations which may be made thereon without departing
from the spirit of the disclosed invention, as those of skill in
the art will recognize.
EXAMPLES
General
The reactions in the hydrocarbon conversion Examples below were
carried out in a stainless steel reactor of plug-flow design. Reactants
were mixed and then fed into a preheater packed with inert Denstone
packing and passed into a 1/2-inch O.D..times.5-inch reactor tube
filled with a 3-5 g catalyst composition charge. The entire reactor
and preheater assembly was supported in a fluidized sand bath maintained
at reaction temperature. Product was collected in a cooled vessel
as it dripped from the reactor and analyzed by gas chromatography
on a 60-meter fused silica capillary column. All hydrocarbon isomer
amounts are given in percents by weight. In the case of use of mixed
xylenes as feed, the xylenes contain about 20% ethylbenzene, the
reaction products of which are not included in the data for the
table below.
All reaction runs were at ambient pressure and 4-6 hours in length
and the system was lined out for at least an hour before collecting
conversion and selectivity data. These runs wwee made with ethylene
by feeding 0.21 ml/min of aromatic compound together with 5.5 ml/min
of ethylene (an 8:1 molar aromatic/ethylene ratio), or in the case
of the ethanol runs, feeding a 8:1 molar aromatic/ethanol liquid
mixture to the preheater from the feed reservoir. Each run used
a 3-5 g catalyst charge and, due to variations in catalyst density,
the WHSV are not always constant so that the % conversion values
are not strictly comparable.
EXAMPLE 1
A 14.76 g portion of manganese acetate and a 29.45 g portion of
boric acid were dissolved in 1000 ml of water. A 23.96 g portion
of tetrapropylammonium bromide was dissolved in the solution and
the pH raised to 9.8 with 35.05 g of ethylenediamine. Ludox AS-40
supplied by E. I. DuPont in the amount of 300.94 g was then added.
The resulting mixture was stirred at room temperature for 15 minutes
before recording the final pH and charging to a stainless steel
autoclave. Digestion in the autoclave was allowed to proceed at
150.degree. C. for a minimum of 3 days. The result was cooled, filtered,
washed well with distilled water, and dried at 165.degree. C. for
4 hours. The dried material was then calcined at 500.degree. C.
for 12 hours. The resulting solid was exchanged twice with ammonium
acetate solutions and dried at 165.degree. C. The product contained
2.09% by weight manganese.
EXAMPLE 2
A 17.77 g portion of nickel nitrate and a 24.73 g portion of boric
acid were dissolved in 1000 ml of water. A 23.98 g portion of tetrapropylammonium
bromide was dissolved in the solution and the pH raised to 9.5 with
24.74 g of ethylenediamine. Ludox AS-40 supplied by E. I. DuPont
in the amount of 300.94 g was then added. The resulting mixture
was stirred at room temperature for 15 minutes before recording
the final pH and charging to a stainless steel autoclave. Digestion
in the autoclave was allowed to proceed at 150.degree. C. for a
minimum of 3 days. The result was cooled, filtered, washed well
with distilled water, and then dried at 165.degree. C. for 4 hours.
The dried material was then calcined at 500.degree. C. for 12 hours.
The resulting solid was exchanged twice with ammonium acetate solutions
and dried at 165.degree. C. The product contained 0.91% by weight
nickel.
EXAMPLE 3
A 15.42 g portion of cobalt nitrate and a 24.55 g portion of boric
acid were dissolved in 1000 ml of water. A 40.55 g portion of tetrapropylammonium
bromide was dissolved in the solution and the pH raised to 9.9 with
40.41 g of ethylenediamine. Ludox AS-40 supplied by E. I. DuPont
in the amount of 300.94 g was then added. The resulting mixture
was stirred at room temperature for 15 minutes before recording
the final pH and charging to a stainless steel autoclave. Digestion
in the autoclave was allowed to proceed at 150.degree. C. for a
minimum of 3 days. The result was cooled, filtered, washed well
with distilled water, and then dried at 165.degree. C. for 4 hours.
The dried material was then calcined at 500.degree. C. for 12 hours.
The resulting solid was exchanged twice with ammonium acetate solutions
and dried at 165.degree. C. The product contained 1.01% by weight
cobalt. Surface analysis of this sieve using XPS indicates that
the cobalt is present in the +2 oxidation state and the Co(II) is
incorporated in the sieve lattice rather than present as CoO.
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