U.S. patent application number 16/361693 was filed with the patent office on 2020-09-24 for method of using biopolymer to synthesize titanium-containing silicon oxide material and applications thereof.
The applicant listed for this patent is ORIENTAL UNION CHEMICAL CORP.. Invention is credited to Ying-Shih CHANG, Chien-Chang CHIANG, Yu-Chuan HSU, Pin-Hsuan HUANG, Hong-Ping LIN, Hsi-Chin TSAI.
Application Number | 20200298218 16/361693 |
Document ID | / |
Family ID | 1000005073981 |
Filed Date | 2020-09-24 |
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United States Patent
Application |
20200298218 |
Kind Code |
A1 |
HSU; Yu-Chuan ; et
al. |
September 24, 2020 |
METHOD OF USING BIOPOLYMER TO SYNTHESIZE TITANIUM-CONTAINING
SILICON OXIDE MATERIAL AND APPLICATIONS THEREOF
Abstract
A method of using biopolymer to synthesize titanium-containing
silicon oxide material and applications thereof are disclosed. The
method comprises steps: mixing a titanium source, a silicon source,
an acid source, a base source, a biopolymer and a solvent to form
an aqueous solution, and letting the aqueous solution react to form
a semi-product; performing aging, solid-liquid separation and
drying of the semi-product to obtain a dried solid; and performing
calcination or extraction of the dried solid to obtain a
titanium-containing silicon oxide material with a high specific
surface area. The present invention adopts a biopolymer as the
templating agent, which makes the fabrication process of
titanium-containing silicon oxide material more
environment-friendly. After calcination or extraction, the product
still has superior catalytic activity, able to catalyze epoxidation
of olefins and favorable for the production of epoxide.
Inventors: |
HSU; Yu-Chuan; (Kaohsiung,
TW) ; HUANG; Pin-Hsuan; (Taipei, TW) ; CHIANG;
Chien-Chang; (Taipei, TW) ; CHANG; Ying-Shih;
(Taipei, TW) ; TSAI; Hsi-Chin; (Kaohsiung, TW)
; LIN; Hong-Ping; (Tainan City, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ORIENTAL UNION CHEMICAL CORP. |
Taipei |
|
TW |
|
|
Family ID: |
1000005073981 |
Appl. No.: |
16/361693 |
Filed: |
March 22, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01B 37/005 20130101;
B01J 37/04 20130101; B01J 35/1071 20130101; B01J 35/1066 20130101;
B01J 29/89 20130101; B01J 37/08 20130101; C01P 2006/17 20130101;
C07D 303/04 20130101; B01J 37/0018 20130101; C01P 2006/14 20130101;
B01J 35/1038 20130101; B01J 35/1076 20130101 |
International
Class: |
B01J 29/89 20060101
B01J029/89; B01J 37/04 20060101 B01J037/04; B01J 37/00 20060101
B01J037/00; B01J 37/08 20060101 B01J037/08; B01J 35/10 20060101
B01J035/10; C01B 37/00 20060101 C01B037/00; C07D 303/04 20060101
C07D303/04 |
Claims
1. A method for fabricating titanium-containing silicon oxide
material, comprising steps: mixing a titanium source, a silicon
source, an acid source, a base source, a biopolymer, and a solvent
to form an aqueous solution; letting said aqueous solution react to
form a first resultant liquid, aging said first resultant liquid to
form a second resultant liquid, performing a solid-liquid
separation process on said second resultant liquid, and drying a
solid obtained from said solid-liquid separation process to obtain
a dried solid; and performing a calcination process on said dried
solid to obtain said titanium-containing silicon oxide material or
performing an extraction process on said dried solid with an
extracting agent to obtain said titanium-containing silicon oxide
material, wherein said titanium-containing silicon oxide material
meets following conditions: pores of said titanium-containing
silicon oxide material have an average diameter of greater than 10
.ANG.; more than 90% of total volume of said pores of said
titanium-containing silicon oxide material have diameters of 5-200
.ANG.; and said titanium-containing silicon oxide material has a
specific pore volume of more than 0.2 cm.sup.3/g, wherein said
biopolymer is selected from a group consisting of chitosan,
collagen, gelatin, agarose, polyhydroxyalkanoates, pullulan,
starch, hyaluronic acid, and combinations thereof.
2. The method for fabricating titanium-containing silicon oxide
material according to claim 1, wherein said titanium source is a
titanate, an inorganic titanium source, or a combination thereof;
said silicon source is an amorphous silicon dioxide, an
alkoxysilane, a silicate, or a combination thereof said acid source
is an organic acid, an inorganic acid, or a combination thereof;
said base source is an organic base, an inorganic base, an organic
molecule whose counter ion is an anion with hydroxyl groups, or a
combination thereof said biopolymer is a polymer generated by
organisms; said solvent is an alcohol solvent; said extracting
agent is a solution containing said solvent and said acid
source.
3. The method for fabricating titanium-containing silicon oxide
material according to claim 2, wherein said titanate is selected
from a group consisting of tetramethyl titanate, tetraethyl
titanate, tetra n-propyl titanate, tetra iso-propyl titanate, tetra
n-butyl titanate, tetra sec-butyl titanate, tetra iso-butyl
titanate, tetra tert-butyl titanate, tetra (2-ethyl-1-hexanol)
titanate, tetra n-octadecane titanate and combinations thereof;
said inorganic titanium source is selected from a group consisting
of titanium trichloride, titanium tetrachloride, titanium
tribromide, titanium tetrabromide, titanium triiodide, titanium
tetraiodide, titanium sulfate, and combinations thereof.
4. The method for fabricating titanium-containing silicon oxide
material according to claim 2, wherein said amorphous silicon
dioxide is selected from a group consisting of silica fume, white
carbon, silica gel, silica sol, and combinations thereof; said
alkoxysilane is selected from a group consisting of
tetramethylorthosilicate, tetraethylorthosilicate,
tetrapropylorthosilicate, alkyltrialkoxysilanes,
dialkyldialkoxysilanes, trialkylmonoalkoxysilanes, and combinations
thereof; said silicate is selected from a group consisting of
sodium silicate, potassium silicate, magnesium silicate, calcium
silicate, and combinations thereof.
5. The method for fabricating titanium-containing silicon oxide
material according to claim 2, wherein said organic acid is
selected from a group consisting of formic acid, acetic acid,
propionic acid, sulfonic acid, sulfinic acid, thionocarboxylic
acids, citric acid, malic acid, tartaric acid, oxalic acid,
succinic acid, lactic acid, and combinations thereof; said
inorganic acid is selected from a group consisting of hydrochloric
acid, hypochlorous acid, chlorous acid, chloric acid, perchloric
acid, nitric acid, hydrazoic acid, hyponitrous acid, nitroxyl,
nitrous acid, peroxynitric acid, sulfuric acid, hydrogen sulfide,
hydrogen disulfide, thiosulfuric acid, sulfoxylic acid, persulfuric
acid, phosphoric acid, hypophosphorous acid, phosphorous acid,
metaphosphoric acid, metaphosphorous acid, diphosphonic acid,
hypophosphoric acid, pyrophosphoric acid, boric acid, metaboric
acid, tetraboric acid, fluoroboric acid, peroxyboric acid, carbonic
acid, hydrocyanic acid, cyanic acid, fulminic acid, isocyanic acid,
thiocyanic acid, isothiocyanic acid, selenocyanic acid,
trithiocarbonic acid, hydrogen peroxide, hydrofluoric acid,
hypofluorous acid, bromic acid, hydrobromic acid, chromic acid,
dichromic acid, permanganic acid, and combinations thereof.
6. The method for fabricating titanium-containing silicon oxide
material according to claim 2, wherein said organic base is
selected from a group consisting of sodium methoxide, potassium
ethoxide, potassium tert-butoxide, butyllithium, phenyllithium,
lithium diisopropylamide, lithium hexamethyldisilazide, pyridine,
imidazole, benzimidazole, histidine, and combinations thereof; said
inorganic base is selected from a group consisting of lithium
hydroxide, sodium hydroxide, potassium hydroxide, magnesium
hydroxide, calcium hydroxide, strontium hydroxide, barium
hydroxide, aluminum hydroxide, ammonium hydroxide, zinc hydroxide,
copper hydroxide, nickel hydroxide, chromium hydroxide, sodium
carbonate, sodium hydrogen carbonate, potassium carbonate,
potassium hydrogen carbonate, and combinations thereof; said
organic molecule whose counter ion is an anion with hydroxyl groups
is selected from a group consisting of trimethyloctadecylammonium
hydroxide, cetyltrimethylammonium hydroxide, dodecyl trimethyl
ammonium hydroxide, and combinations thereof.
7. (canceled)
8. The method for fabricating titanium-containing silicon oxide
material according to claim 2, wherein said alcohol solvent is
selected from a group consisting of methanol, ethanol, n-propanol,
isopropanol, vinyl butanol, allyl butanol, n-butanol, sec-butyl
alcohol, tert-butyl alcohol, pentanol, cyclohexanol, benzyl
alcohol, diol compounds, and combinations thereof.
9. The method for fabricating titanium-containing silicon oxide
material according to claim 1, wherein a molar ratio of said
titanium source to said silicon source in said aqueous solution is
0.00001-0.5; a weight ratio of said biopolymer to said silicon
source is 0.005-5; a molar ratio of said acid source to said
silicon source is 0.01-6; a molar ratio of said base source to said
silicon source is 0.01-6; a weight ratio of said biopolymer to
water is 0.0001-1; a weight ratio of said solvent to water is
0-5.
10. The method for fabricating titanium-containing silicon oxide
material according to claim 9, wherein said molar ratio of said
titanium source to said silicon source in said aqueous solution is
0.0001-0.1; said molar ratio of said acid source to said silicon
source is 0.1-3; said molar ratio of said base source to said
silicon source is 0.1-3; said weight ratio of said solvent to water
is 0.01-3.
11. The method for fabricating titanium-containing silicon oxide
material according to claim 1, wherein said aqueous solution reacts
at a temperature ranging from -20 to 200.degree. C. for 0.5-5 hours
to form said first resultant liquid; said first resultant liquid is
aged at a temperature ranging from 60 to 200.degree. C. for 6-48
hours to form said second resultant liquid; said solid obtained
from said solid-liquid separation process is dried at a temperature
ranging from 30 to 120.degree. C. for 0.5-6 hours.
12. The method for fabricating titanium-containing silicon oxide
material according to claim 1, wherein a calcination temperature of
said calcination process is 300-800.degree. C.; a calcination time
of said calcination process is 1-9 hours; a ratio of weights of a
solvent, an acid source and water in said extracting agent used by
said extraction process is 3-10:0.01-5: 0-10; an extraction
temperature of said extraction process is 25-150.degree. C.; an
extraction time of said extraction process is 0.5-6 hours; a weight
ratio of said extracting agent to said dried solid is 1000-10.
13. The method for fabricating titanium-containing silicon oxide
material according to claim 12, wherein said calcination
temperature of said calcination process is 450-750.degree. C.; said
calcination time of said calcination process is 3-6 hours; said
ratio of weights of said solvent, said acid source and water in
said extracting agent used by said extraction process is
5-8:0.05-3: 0-3; said extraction temperature of said extraction
process is 40-90.degree. C.; said extraction time of said
extraction process is 1-3 hours.
14. The method for fabricating titanium-containing silicon oxide
material according to claim 1 further comprising at least one of
following steps: performing a silylation treatment on said
titanium-containing silicon oxide material at a reaction
temperature of 25-200.degree. C. for a reaction time of 0.5-3
hours; and merging a transition metal into said titanium-containing
silicon oxide material, wherein a concentration of said transition
metal in said titanium-containing silicon oxide material is
0.001-10 wt %.
15. The method for fabricating titanium-containing silicon oxide
material according to claim 14, wherein said concentration of said
transition metal in said titanium-containing silicon oxide material
is 0.005-5 wt %.
16-22. (canceled)
Description
BACKGROUND OF THE INVENTION
Field of the Invention
[0001] The preset invention relates to a method of using a template
method to synthesize titanium-containing silicon oxide material and
applications thereof, particularly to a method of using biopolymer
as the template agent to synthesize titanium-containing silicon
oxide material and using the titanium-containing silicon oxide
material as a catalyst to directly oxidize olefins into
epoxides.
Description of the Related Art
[0002] The titanium-containing silicon oxide materials usually have
porous structures with high-specific surface area, favorable to
function as absorptive agents, catalysts, and catalyst carriers. At
present, the synthesis of titanium-containing materials is often
realized by hydrothermal processes using surfactants as template
agents. It is the most well-known example among them: a
positively-charged quaternary ammonium salt surfactant is used as
the template agent. U.S. Pat. Nos. 7,018,950, 688,782 and 6,512,128
all disclosed the methods for fabricating titanium-containing
silicon oxide catalysts, comprising steps: dissolving a silicon
source, a titanium source and a quaternary ammonium salt
(functioning as a template agent) in a solvent and agitating them
to obtain a solid containing a catalyst and a template agent; and
removing the templating agent to obtain a titanium-containing
silicon oxide catalyst with a special pore diameters, a pore
diameter distribution and a special specific volume ratio. In the
template method for fabricating titanium-containing silicon oxide
material, titanium is introduced into the silicon dioxide material
with a high specific surface area to diversify the catalytic
activity of the material. In the fabrication process, the
templating agent generates micelles, and the added silicon compound
aggregates around the micelles and forms silicon oxide substrates
on the micelles. The templating agent (i.e. the surfactant) may be
removed by a high-temperature calcination process or an extraction
process, whereby is created a material having porous structures
whose size and shape is similar to that of the templating agent.
The advantages of the fabrication process are that the pore volume
of the resultant material can be controlled via modifying the size
of the molecules of the templating agent and that the pore size can
be controlled via modifying the size of the micelles of the
template agent. However, the surfactant, which functions as the
template agent, is expensive and likely to generate toxicity and
pollute the environment.
[0003] In order to overcome the abovementioned problems, the
applicant of the present invention has developed a low-cost
non-toxic green material as the templating agent for fabricating
titanium-containing silicon oxide material to reduce pollution to
the environment. Further, the titanium-containing silicon oxide
material fabricated by the present invention has high catalytic
activity in epoxidation.
SUMMARY OF THE INVENTION
[0004] The primary objective of the present invention is to provide
a method of using biopolymer to synthesize titanium-containing
silicon oxide material and applications thereof, wherein an aqueous
solution, which is formulated with a titanium source, a silicon
source, an acid source and a base source, a biopolymer and a
solvent, is aged, filtered, dried, calcined (or extracted) to
obtain a titanium-containing silicon oxide material with a
high-specific surface area and a high catalytic activity, which may
function as a catalyst to catalyze epoxidation of olefins and
generate epoxides.
[0005] In order to achieve the abovementioned objective, the
present invention proposes a method for fabricating
titanium-containing silicon oxide material, wherein an aqueous
solution, which is formulated with a titanium source, a silicon
source, an acid source and a base source, a biopolymer, and a
solvent, is agitated uniformly; next, the aqueous solution is kept
at a temperature ranging from -20 to 200.degree. C. and agitated
persistently for 0.5-5 hours; next, the aqueous solution is aged at
a temperature ranging from 60-200.degree. C. for 6-48 hours; next,
a solid-liquid separation process is undertaken; next, the solid
obtained in the solid-liquid separation process is dried; next, a
calcination process or an extraction process of the dried solid is
undertaken to obtain a titanium-containing silicon oxide material
with a high specific surface area.
[0006] The titanium-containing silicon oxide material fabricated by
the present invention meets the following conditions: [0007] 1. The
average diameter of the pores of the titanium-containing silicon
oxide material is greater than 10 .ANG.; [0008] 2. The pores with
diameters ranging from 5-200 .ANG. have a volume of more than 90%
of the total pore volume. [0009] 3. The titanium-containing silicon
oxide material has a specific pore volume greater than 0.2
cm.sup.3/g.
[0010] In the method of the present invention, the titanium source
may be sourced from titanates, inorganic titanium sources, or
combinations thereof. The silicon source may be amorphous silicon
dioxide, alkoxysilanes, silicates, or combinations thereof. The
acid source may be sourced from any material able to lower the pH
value of the system, such as organic acids, inorganic acids, or
combinations thereof. The base source may be sourced from any
material able to increase the pH value of the system, such as
organic bases, inorganic bases, organic molecules whose counter
ions are anions with hydroxyl groups, or combinations thereof. The
biopolymers may be sourced from the polymers generated by
organisms. The solvent may be sourced from alcohol solvents. The
extracting agent used in the extraction process may be sourced from
aqueous solutions of solvents and acid sources.
[0011] The present invention also proposes a method for fabricating
epoxide, wherein the titanium-containing silicon oxide, which is
fabricated by the abovementioned method of the present invention,
is used as the catalyst to enable the reaction of the olefins and
oxides and generate epoxides.
[0012] In one embodiment of the present invention, a silylation
method is used to increase the catalytic activity of the catalyst
before the catalytic reaction.
[0013] In the abovementioned methods, the quantity of the used
catalyst is not strictly limited as long as the quantity of the
used catalyst is sufficient to enable the epoxidation reaction to
be completed in the shortest time. The molar ratio of the olefin to
the oxide, which is used in the reaction, is 1:100-100:1,
preferably 1:10-10:1. The reaction temperature is not particularly
limited, normally 0-200.degree. C., preferably 25-150.degree. C.
The reaction pressure is not particularly limited as long as the
pressure is higher than a pressure able to keep the reactants in
the liquid state, preferably 1-100 atm. The reaction time is 1
minute-48 hours, preferably 5 minutes-8 hours. The methods of the
present invention are applicable to any reactor or device. For
example, the methods of the present invention may be applied to a
fixed bed reactor, a conveyor reactor, a fluidized bed reactor, a
slurry agitation reactor, or a continuous stirred-tank reactor in a
batch way, a continuous way, or a semi-continuous way.
[0014] The methods of the present invention are simple, low-cost,
environment-friendly and thus favorable for industrial
application.
[0015] Below, embodiments are described in detail to make easily
understood the objectives, technical contents, characteristics, and
accomplishments of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows a flowchart of a method of fabricating
titanium-containing silicon oxide material according to one
embodiment of the present invention.
[0017] FIG. 2 shows a flowchart of using a titanium-containing
silicon oxide material fabricated by the present invention can
fabricate epoxide according to one embodiment of the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Refer to FIG. 1 for a flowchart of a method of fabricating
titanium-containing silicon oxide material according to one
embodiment of the present invention. The flowchart includes 5
steps: Steps S100-S140, wherein Steps S100-S120 relates to a method
of fabricating titanium-containing silicon oxide material; Step
S130 and Step S140 are two steps that may be used in the
fabrication process where the titanium-containing silicon oxide
material with a high specific surface area is involved. In
practical application, a single fabrication process may adopt one
or more of Step S130 and Step S140. However, the two steps are
presented on the single flowchart simultaneously for conciseness,
wherein dashed-line frames are used to indicate that these steps
are optional.
[0019] In Step S100, formulate a titanium source, a silicon source,
an acid source and a base source, a biopolymer, and a solvent into
an aqueous solution, and agitate the aqueous solution uniformly. In
Step S110, place the aqueous solution at a temperature of
-20-100.degree. C. for reaction, and agitate the aqueous solution
persistently for 0.5-5 hours; next, age the reactants at a
temperature of 60-200.degree. C. for 6-48 hours; next, undertake a
solid-liquid separation process to separate the solid from the
reaction solution; next, dry the solids separated in the
solid-liquid separation process at a temperature of 30-120.degree.
C. for 0.5-6 hours persistently. In Step S120, calcine the dried
solid to obtain a titanium-containing silicon oxide material with a
high specific surface area; alternatively, use the mixed aqueous of
a solvent and an acid source as an extracting agent to undertake an
extraction process of the dried solid to obtain a
titanium-containing silicon oxide material with a high specific
surface area.
[0020] The titanium-containing silicon oxide material fabricated by
the present invention meets the following conditions:
1. The average diameter of the pores of the titanium-containing
silicon oxide material is greater than 10 .ANG.; 2. The pores with
diameters ranging from 5-200 .ANG. have a volume of more than 90%
of the total pore volume. 3. The titanium-containing silicon oxide
material has a specific pore volume greater than 0.2
cm.sup.3/g.
[0021] The titanium sources used by the present invention include
but are not limited to be titanates, inorganic titanium sources,
and combinations thereof. In details, the titanate may be selected
from a group including tetramethyl titanate, tetraethyl titanate,
tetra n-propyl titanate, tetra iso-propyl titanate, tetra n-butyl
titanate, tetra sec-butyl titanate, tetra iso-butyl titanate, tetra
tert-butyl titanate, tetra (2-ethyl-1-hexanol) titanate, tetra
n-octadecane titanate and combinations thereof. The inorganic
titanium sources may be titanium halides, titanium sulfate, or
combinations thereof. The titanium halides may be selected from a
group including titanium trichloride, titanium tetrachloride,
titanium tribromide, titanium tetrabromide, titanium triiodide, and
titanium tetraiodide. The abovementioned titanium sources may be
used singly, or several thereof are used jointly.
[0022] The silicon sources used by the present invention include
but are not limited to be amorphous silicon dioxide, alkoxysilanes,
silicates, and combinations thereof. In details, the amorphous
silicon dioxide has a general formula: SiO.sub.2. The amorphous
silicon dioxide may be but is not limited to be sourced from powder
materials or bulky materials of silicon dioxide. The amorphous
silicon dioxide may be but is not limited to be silica fume, white
carbon, silica gel, or silica sol. The alkoxysilanes may be silanes
containing 4 alkoxy groups, including tetramethylorthosilicate,
tetraethylorthosilicate, tetrapropylorthosilicate, and the likes.
The alkoxysilanes containing different functional groups may also
be used as the silicon sources, including alkyltrialkoxysilanes,
dialkyldialkoxysilanes, trialkylmonoalkoxysilanes, and the likes.
The silicates may be but are not limited to be sodium silicate,
potassium silicate, magnesium silicate, calcium silicate, and the
likes. The abovementioned silicon sources may be used singly, or
several thereof are used jointly.
[0023] The acid sources used by the present invention include but
are not limited to be organic acids, inorganic acids, and any
material able to decrease the pH value of the system. In details,
the organic acids may be materials containing carboxyl groups or
sulfonic acid groups. The organic acid sources may be selected from
a group including formic acid, acetic acid, propionic acid,
sulfonic acid, sulfinic acid, thionocarboxylic acids, citric acid,
malic acid, tartaric acid, oxalic acid, succinic acid, lactic acid,
and the likes. The inorganic acids may be materials releasing
hydrogen ions and conjugate basic ions. The inorganic acids may be
selected from a group including hydrochloric acid, hypochlorous
acid, chlorous acid, chloric acid, perchloric acid, nitric acid,
hydrazoic acid, hyponitrous acid, nitroxyl, nitrous acid,
peroxynitric acid, sulfuric acid, hydrogen sulfide, hydrogen
disulfide, thiosulfuric acid, sulfoxylic acid, persulfuric acid,
phosphoric acid, hypophosphorous acid, phosphorous acid,
metaphosphoric acid, metaphosphorous acid, diphosphonic acid,
hypophosphoric acid, pyrophosphoric acid, boric acid, metaboric
acid, tetraboric acid, fluoroboric acid, peroxyboric acid, carbonic
acid, hydrocyanic acid, cyanic acid, fulminic acid, isocyanic acid,
thiocyanic acid, isothiocyanic acid, selenocyanic acid,
trithiocarbonic acid, hydrogen peroxide, hydrofluoric acid,
hypofluorous acid, bromic acid, hydrobromic acid, chromic acid,
dichromic acid, permanganic acid, and the likes. The abovementioned
acid sources may be used singly, or several thereof are used
jointly.
[0024] The base sources used by the present invention include but
are not limited to be organic bases, inorganic bases, organic
molecules whose counter ions are anions with hydroxyl groups, and
any material able to increase the pH value of the system. In
details, the organic bases may be alcohols containing alkali
metals, organic metal compounds, or organic materials containing
nitrogen. The organic bases may be selected from a group including
sodium methoxide, potassium ethoxide, potassium tert-butoxide,
butyllithium, phenyllithium, lithium diisopropylamide, lithium
hexamethyldisilazide, pyridine, imidazole, benzimidazole,
histidine, and the likes. The organic bases may be hydroxides
containing metal ions or carbonates containing metal ions. The
inorganic bases may be selected from a group including lithium
hydroxide, sodium hydroxide, potassium hydroxide, magnesium
hydroxide, calcium hydroxide, strontium hydroxide, barium
hydroxide, aluminum hydroxide, ammonium hydroxide, zinc hydroxide,
copper hydroxide, nickel hydroxide, chromium hydroxide, sodium
carbonate, sodium hydrogen carbonate, potassium carbonate,
potassium hydrogen carbonate, and the likes. The organic molecules
whose counter ions are anions with hydroxyl groups may be
trimethyloctadecylammonium hydroxide, cetyltrimethylammonium
hydroxide, dodecyl trimethyl ammonium hydroxide, and the likes. The
abovementioned base sources may be used singly, or several thereof
are used jointly.
[0025] The biopolymers used by the present invention are polymers
generated by organisms. The biopolymers may be selected from a
group including chitosan, collagen, gelatin, agarose, chitin,
polyhydroxyalkanoates, pullulan, starch, cellulose, hyaluronic
acid, and the likes, wherein the starch includes amylose and
amylopectin. The abovementioned biopolymers may be used singly, or
several thereof are used jointly.
[0026] The solvents used by the present invention include but are
not limited to be alcohol solvents. In details, the alcohol
solvents are alcohols containing 1-10 carbon atoms. The alcohol
solvents may be selected from a group including methanol, ethanol,
n-propanol, isopropanol, vinyl butanol, allyl butanol, n-butanol,
sec-butyl alcohol, tert-butyl alcohol, pentanol, cyclohexanol,
benzyl alcohol, and diol compounds. The abovementioned solvents may
be used singly, or several thereof are used jointly.
[0027] The molar ratio of the titanium source to the silicon source
in the aqueous solution is 0.00001-0.5, preferably 0.0001-0.1. The
weight ratio of the biopolymer to the silicon source is 0.005-5.
The molar ratio of the acid source to the silicon source is 0.01-6,
preferably 0.1-3. The molar ratio of the base source to the silicon
source is 0.01-6, preferably 0.1-3. The weight ratio of the
biopolymer to water is 0.0001-1. The weight ratio of the solvent to
water is 0-5, preferably 0.01-3. The temperature of calcination is
300-800.degree. C., preferably 450-750.degree. C. The time of
calcination is 1-9 hours, preferably 3-6 hours. The ratio of the
weights of the solvent, the acid source and water in the extracting
agent is 3-10:0.01-5: 0-10, preferably 5-8:0.05-3: 0-3. The
temperature of extraction is 25-150.degree. C., preferably
40-90.degree. C. The time of extraction is 0.5-6 hours, preferably
1-3 hours. The weight ratio of the extracting agent to the dried
solid is 1000-10.
[0028] The titanium-containing silicon oxide material may function
as a catalyst. Before undertaking catalyzation, the catalyst may be
silylated to decrease the number of silanol groups, as in Step
S130. Thereby is decreased the intrinsic acidity of the catalyst,
improved the surface characteristic of the catalyst, and enhanced
the catalytic activity of the catalyst.
[0029] The silylation treatment may be performed in a gas phase
method or a liquid phase method. In the gas phase method, the
titanium-containing silicon oxide material reacts with a gas-phase
silylation agent. In the liquid phase method, the
titanium-containing silicon oxide material reacts with a
liquid-phase silylation agent. The silylation treatment may be
performed according to an ordinary method, using one or more kinds
of organic silanes. The organic silanes for silylation may be
halogenosilanes (the general formula thereof is
R.sup.1R.sup.2R.sup.3SiX), silazanes (the general formula thereof
is [R.sup.4R.sup.5R.sup.6Si].sub.2NH), methylsilyllimidazoles (the
general formula thereof is
R.sup.7R.sup.8R.sup.9Si[N.sub.2C.sub.3H.sub.3]), or
methylsilyllamines (the general formula thereof
is)(R.sup.10).sub.3SiN(R.sup.11).sub.2), wherein R.sup.1, R.sup.2
and R.sup.3 are identical or different and may be respectively a
saturated alkyl group containing 1-6 carbon atoms, and a saturated
phenyl group, and wherein R.sup.4, R.sup.5, and R.sup.6 are
identical or different and may be respectively an alkyl group
containing 1-6 carbon atom, a haloalkyl group containing 1-6 carbon
atoms, and a phenyl group, and wherein R.sup.7-R.sup.11 are
respectively saturated alkyl groups containing 1-3 carbon atoms.
The preferred organic silane is hexamethyldisilazane,
methylsilyllamine, trimethylchlorosilane,
N-trimethylformamimidazole, or a combination thereof. The solvent
used in silylation may be one or more kinds of aromatic
hydrocarbons containing 6-16 carbon atoms, or one or more kinds of
alkanes containing 6-16 carbon atoms. The preferred solvent is
toluene, benzene, isopropylbenzene-cyclohexane, or a combination
thereof.
[0030] In silylation, the weight ratio of the organic silane to the
titanium-containing silicon oxide material is 0.01-1, preferably
0.1-0.8; the weight ratio of the solvent to the titanium-containing
silicon oxide material is 1-200, preferably 1-100; the reaction
temperature of silylation is 25-200.degree. C., preferably
50-150.degree. C.; the reaction temperature is 0.5-3 hours,
preferably 1-2 hours.
[0031] The present invention also has an alternative step (Step
S140), wherein transition metals are merged into the
titanium-containing silicon oxide material to enhance the catalytic
activity of the material.
[0032] According to the requirement, transition metals may be
merged into the titanium-containing silicon oxide material in an
impregnation method, a deposition method, a blending method, or a
like method. In the impregnation method, a solution of transition
metals is dispersed in a suitable solvent to form a mixed solution;
the mixed solution is further mixed with the titanium-containing
silicon oxide material to form a titanium-containing silicon oxide
material impregnated with transition metals; the
titanium-containing silicon oxide material impregnated with
transition metals is further dried or calcined according to
requirement, wherein the concentration of the transition metals in
the titanium-containing silicon oxide material is 0.001-10 wt. %,
preferably 0.005-5 Wt %. In the titanium-containing silicon oxide
material impregnated with transition metals, transition metals are
inside or outside the skeletons of the titanium-containing silicon
oxide material.
[0033] In the present invention, the titanium-containing silicon
oxide material may be granulated before calcination, after
calcination, before extraction, after extraction, before
silylation, after silylation, . . . , in any stage of the process.
The granulation may be undertaken in a suitable process, such as
the compression molding process or the extrusion molding process,
to fabricate the titanium-containing silicon oxide material into
granules having a specified range of diameters.
[0034] Because of having a high specific surface area and
highly-dispersed active-titanium sites, the titanium-containing
silicon oxide material fabricated by the present invention can be
used as a catalyst for oxidation or selective oxidation of organic
compounds. If a third group of components (such as aluminum, etc.)
is added to the titanium-containing silicon oxide material
fabricated by the present invention to promote the acidic
positions, the titanium-containing silicon oxide material can be
used to catalyze alkylation, reforming, etc.
[0035] The titanium-containing silicon oxide material fabricated by
the present invention can be used to fabricate epoxide. Refer to
FIG. 2 for a flowchart of using the titanium-containing silicon
oxide material fabricated by the present invention to fabricate
epoxide. The flowchart includes three steps: Steps S200-S220. Step
S220 describes a method for fabricating an epoxide. Step S200 and
Step S210 are two steps that may be added to the process of
fabricating epoxide, used to enhance the catalytic activity of the
catalyst. In practical application, a single fabrication process
may adopt one or more of Step S200 and Step S210. However, the two
steps are presented on the single flowchart simultaneously for
conciseness, wherein dashed-line frames are used to indicate that
these steps are optional.
[0036] In Step S200 and Step S210, before catalytic reaction, the
catalytic activity can be enhanced via silylation and/or merging
transition metals into the titanium-containing silicon oxide
material. The other details of these steps are similar to those of
Step S130 and Step S140 and will not repeat herein. The granulation
treatment may also be adopted herein.
[0037] In Step S220, the titanium-containing silicon oxide material
fabricated by the present invention is used as a catalyst to
catalyze the reaction of olefins and oxides to form epoxides.
[0038] The titanium-containing silicon oxide material used in the
abovementioned epoxidation may be fabricated into the form of
powder, lumps, microbeads, or a single bulk via extrusion-molding,
compression-molding, or another method. The olefins used in the
epoxidation may be but are not limited to be aliphatic compounds
and cyclic compounds (including monocyclic compounds, bicyclic
compounds, and polycyclic compounds). The olefins may be
mono-olefins, di-olefins, and poly-olefins. While the olefin has
more than two double bonds, the double bonds may be conjugated
double bonds or non-conjugated double bonds. The mono-olefins may
be but are not limited to be olefins containing 2-60 carbon atoms.
The olefin may have a substituent, preferably a substituent stable
relatively. The mono-olefins may be but are not limited to be
ethylene, propylene, 1-butylene, isobutylene, 1-hexene, 2-hexene,
3-hexene, 1-octene, 1-decene, styrene, or cyclohexene. The
di-olefins may be but are not limited to be butadiene or
isoprene.
[0039] The oxides used in the epoxidation may be organic peroxides
having a general formula: R--O--O--H, wherein R denotes a
hydrocarbon group. The hydrocarbon group is a group containing 3-20
carbon atoms, preferably 3-10 carbon atoms. The hydrocarbon group
may be but are not limited to be a secondary alkyl group, a
tertiary alkyl group, or an aryl alkyl group, such as tertiary
butyl, tertiary pentyl, cyclopentane, and 2-phenyl-2-propyl. The
organic peroxide may be but is not limited to be ethylbenzene
hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, or
cyclohexyl hydroperoxide. While the hydroperoxide is cumene
hydroperoxide, the product of the reaction is alpha-cumyl alcohol.
Via dehydration, alpha-cumyl alcohol is converted into alpha-methyl
styrene, which has many applications in industry. Via
hydrogenation, alpha-methyl styrene is converted into cumene. Via
oxidization, cumene is converted into cumene hydroperoxide. The
other organic peroxides also have the same recycling characteristic
and thus can be used repeatedly.
[0040] The oxide used in the epoxidation may be hydrogen peroxide
having a general formula: H--O--O--H. Hydrogen peroxide can be
obtained from the aqueous solution thereof. The reaction of
hydrogen peroxide and olefin generates epoxide and water.
[0041] The oxide used as a reactant may be a concentrated or
diluted pure/impure substance.
[0042] While epoxidation is undertaken to generate epoxide, a
solvent or diluent may be added to let the reaction be undertaken
in a liquid state. The solvent or diluent is in the form of a
liquid and inert to all the reactants and products in the
epoxidation reaction. The solvent may be but is not limited to be
methanol, acetone, ethylbenzene, cumene, isobutene, cyclohexane, or
a combination thereof. The abovementioned solvent is a material
that may exist in the oxide solution ready for use. For example,
while the mixed solution of cumene hydroperoxide and cumene is used
as the oxide source, cumene may function as the solvent required by
the epoxidation reaction. In such a case, the addition of another
type of solvent is unnecessary.
[0043] In the abovementioned methods, the amount of the used
catalyst is not strictly limited as long as the epoxidation
reaction can be completed in the shortest time. The molar ratio of
the olefin to the oxide is 1:100-100:1, preferably 1:10-10:1. The
reaction temperature is not strictly limited, normally
0-200.degree. C., preferably 25-150.degree. C. The reaction
pressure is not strictly limited as long as the pressure is
sufficient to keep all the reactants in a liquid state. The
reaction pressure is preferably 1-100 atm. The reaction time is the
time able to achieve the highest yield of epoxide, normally 1
minute-48 hours, preferably 5 minutes-8 hours. The methods of the
present invention may be applied to a fixed bed reactor, a conveyor
reactor, a fluidized bed reactor, a slurry agitation reactor, or a
continuous stirred-tank reactor in a batch way, a continuous way,
or a semi-continuous way.
[0044] Below, several embodiments are used to further demonstrate
how the titanium-containing silicon oxide material is effectively
fabricated by the present invention and how the material is used as
a catalyst to catalyze the epoxidation reaction of olefin and oxide
to generate epoxide.
Embodiment I
[0045] Fabrication of titanium-containing silicon oxide material:
Add 2.9 kg ammonia water (28%) to a first mixture liquid containing
0.26 kg tetraisopropyl orthotitanate, 3.6 kg sodium silicate, 0.54
kg gelatin, 2.7 kg sulfuric acid (98%), 3 kg isopropanol, and 45 kg
water to form a second mixture liquid; agitate the second mixture
liquid at an ambient temperature for 2 hours to form a first
semi-product; age the first semi-product at a temperature of
100.degree. C. persistently for 16 hours to generate a second
semi-product; filter the second semi-product to remove the solution
thereof and obtain a powder; dry the powder at a temperature of
70.degree. C.; heat the dried powder to a temperature of
550.degree. C. at a temperature rising rate of 5.degree. C./min and
calcine the dried powder at the temperature of 750.degree. C.
persistently for 6 hours; let the powder cool down naturally and
thus obtain a titanium-containing silicon oxide material with a
high specific surface area. In this embodiment, more than 97%
organic compounds are removed in the calcination process.
Embodiment II
[0046] Fabrication of titanium-containing silicon oxide material:
The fabrication process is basically the same as that in Embodiment
I except the calcination process is replaced by an extraction
process. Use 10 kg sulfuric acid, 70 kg ethanol, and 20 kg water to
prepare an extracting liquid. Agitate the mixture liquid containing
100 kg of the extracting liquid and 1 kg of the dried powder, which
is acquired after the aging, filtering and drying processes, at a
temperature of 80.degree. C. for 2 hours to form a semi-product.
Next, filter the semi-product. Next, further repeat the extraction
process twice. Next, remove the solution to obtain a powder. Next,
dry the powder at a temperature of 70.degree. C. Thus, obtain a
titanium-containing silicon oxide material with a high specific
surface area. In this embodiment, more than 90% organic compounds
are removed in the extraction process.
Embodiment III
[0047] Fabrication of propylene epoxide: Use 15 g of the
titanium-containing silicon oxide material fabricated in Embodiment
I as the catalyst. Mix uniformly the catalyst, 225 g cumene
hydroperoxide solution (25 wt %) (the solvent thereof is cumene),
and 125 g propylene in a 1-liter high-pressure airtight reactor
(autoclave), and heat them to enable reaction at a temperature of
95.degree. C. for less than 1.5 hours. The results of the reaction
are shown in Table.1.
Embodiment IV
[0048] Fabrication of titanium-containing silicon oxide material:
The fabrication process is basically the same as that in Embodiment
I except the titanium-containing silicon oxide material with a high
specific surface area, which is obtained after the calcination
process, is silylated. Mix uniformly 16.5 g of the
titanium-containing silicon oxide material, 165 g toluene, and 11.2
g hexamethyldisilazane; next, agitate them at a temperature of
120.degree. C. for 1 hour; next filter and dry the product. The
titanium-containing silicon oxide material obtained in this
embodiment has a specific surface area of 353 m.sup.2/g, a pore
volume of 0.752 ml/g and an average pore diameter of 5.5 nm.
[0049] Fabrication of propylene epoxide: The fabrication process is
basically the same as that in Embodiment III except the catalyst is
replaced by the titanium-containing silicon oxide material
fabricated in Embodiment IV. The results of the reaction are shown
in Table.1.
TABLE-US-00001 TABLE 1 Embodiment 3 Embodiment 4 Conversion rate of
cumene 83 98 hydroperoxide(%) (Note.sup.1) Selectivity of propylene
77 95 epoxide(%)(Note.sup.2) (Note.sup.1) Conversion rate of cumene
hydroperoxide = Consumption of cumene hydroperoxide/Addition of
cumene hydroperoxide .times. 100% (Note.sup.2) Selectivity of
propylene epoxide = Generation of propylene epoxide/Consumption of
cumene hydroperoxide .times. 100%
[0050] Embodiment I and Embodiment II show that a calcination
process or an extraction process can remove the biopolymer from the
titanium-containing silicon oxide material fabricated by the
present invention--a method of using biopolymer to synthesize
titanium-containing silicon oxide material. According to Table.1,
Embodiment III shows that the titanium-containing silicon oxide
material fabricated by the present invention has a superior
catalytic activity in catalyzing the epoxidation of olefins;
Embodiment IV shows that silylation can significantly increase the
catalytic activity of the titanium-containing silicon oxide
material fabricated by the present invention in catalyzing the
epoxidation of olefins.
[0051] In conclusion, the present invention proposes a method of
using biopolymer to synthesize titanium-containing silicon oxide
material and applications thereof, wherein the present invention
uses an environment-friendly biopolymer as a templating agent to
fabricate a titanium-containing silicon oxide material with a high
specific surface area in an ordinary simple template method. The
titanium-containing silicon oxide material fabricated by the
present invention has high catalytic activity, able to function as
a catalyst to successfully catalyze the epoxidation of olefins.
[0052] The embodiments described above are only to exemplify the
present invention but not to limit the scope of the present
invention. Any equivalent modification or variation according to
the spirit of the present invention is to be also included by the
scope of the present invention, which is based on the claims stated
below.
* * * * *