CN108855207A - Hetero atom Beta zeolite catalyst of alkali metal containing and its preparation method and application - Google Patents
Hetero atom Beta zeolite catalyst of alkali metal containing and its preparation method and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention belongs to catalysis material technical fields, and in particular to a kind of hetero atom Beta zeolite catalyst of alkali metal containing and its preparation method and application.The method of the present invention is the defective bit using Beta zeolite itself, carries out dealumination treatment without using concentrated acid and the hetero atom Beta zeolite of alkali metal containing is prepared by liquid-phase reflux, roasting and alkali process three-step approach.The zeolite catalyst can be used for hydrogen transfer reduction reaction, present good catalytic activity and stability.Method provided by the invention is easy to operate, mild condition, hetero atom is applied widely, generates without a large amount of acid waste waters, is environmental-friendly, has comparable application prospect.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of hetero atom Beta zeolite catalyst of alkali metal containing
And preparation method thereof and the application in hydrogen transfer reaction.
Background technique
Zeolitic material has become important because of its regular cellular structure, adjustable acid-base property and good thermal stability
Catalysis material, be widely used in petrochemical industry and field of fine chemical.Heteroatom zeolite, as TS-1, Ti-MOR, Sn-Beta,
Zr-Beta, Sn-MCM-41 and Zr-SBA-15 etc. selective oxidation, ketoxime, hydrogen migration, carbohydrate isomerization, aldol condensation,
Superior catalytic performance is shown in etherificate and ester exchange reaction（J. Catal., 2014, 320, 160-169; Chem. Rev. Soc. 2016, 45, 584-611）.Wherein, hydrogen transfer reaction is in biomass derived platform chemicals, as glyceraldehyde,
It is played an important role in the catalyzed conversion of furfural, 5 hydroxymethyl furfural, levulic acid, glycerol etc.（ACS Catal. 2016,
6, 1420-1436）.For example, the zeolites such as Sn-Beta and Zr-Beta are reacted in the hydrogen transfer reduction of furfural and 5 hydroxymethyl furfural
In present good catalytic effect.
By taking Sn-Beta and Zr-Beta zeolite as an example, the preparation method of heteroatom zeolite is broadly divided into hydrothermal synthesis method with after
Two kinds of modified synthesis method（Chem. Rev. Soc. 2015, 44, 7025-7043; Angew. Chem. Int. Ed.
2012, 51, 11736 –11739; J. Phys. Chem. C2011, 115, 3663–3670）.Hydrothermal synthesis method be by
Silicon species, hetero atom species, template and mineralizer are mixed with to form gel, to carry out hydrothermal crystallizing, synthesis obtains miscellaneous
Atom zeolite.Hydrothermal synthesis method has the disadvantages that, such as fluorine-containing mineralizer（Hydrofluoric acid or ammonium fluoride）Use, hydrothermal crystallizing when
Between it is longer（Greater than 40 days）, hetero atom introduction volume is less, gained zeolite grain size is larger, synthesis step is complicated and collimation compared with
Difference etc..Modified synthesis method is to remove the aluminium in zeolite in the zeolite base with crystal phase structure by acid and form defective bit afterwards,
Then hetero atom is introduced into zeolite skeleton by means such as gas-solid reaction, liquid-solid reaction and solid-phase grindings（Chem. Soc. Rev., 2015, 44, 7025—7043, CN106694027A, CN104310425B, CN104860329B, CN103252252B, CN103920527B）.The shortcomings that modified synthesis method, is to carry out zeolite using a large amount of concentrated nitric acid afterwards
Dealuminzation, burn into are seriously polluted.On the one hand the part for causing zeolite skeleton collapses, and reduces the hydrothermal stability of zeolite；It is another
Aspect needs to wash dealuminated zeolite, generates a large amount of acid waste water, is unfavorable for the industrial applications of this method.However,
Beta zeolite is the symbiotic structure of three kinds of polymorphs, contains a large amount of accumulation defective bit（CrystEngComm, 2016, 18,
1782–1789）.Therefore, it can use the defective bit that Beta zeolite contains itself, be used for introducing hetero-atoms, be heteroatom zeolite
Preparation a kind of more green method is provided.
Summary of the invention
The purpose of the present invention is to provide hetero atom Beta zeolite catalyst of a kind of alkali metal containing and preparation method thereof and
Application in hydrogen transfer reaction.
The preparation method of the hetero atom Beta zeolite catalyst of alkali metal containing provided by the invention is a kind of rear modification side
Method carries out dealumination treatment without using concentrated acid, by liquid-phase reflux, roasting and alkali process three using industrial Beta zeolite as raw material
Footwork is made, the specific steps are：
（1）Hetero atom transition metal inorganic salts are dissolved in alcoholic solvent, it is molten that industrial Beta zeolite is then added to above-mentioned alcohol
It in liquid, is placed in oil bath or microwave applicator and flows back, reflux temperature is 78-120 DEG C, 10 min-5 h of return time；
（2）Decompression filters and obtains filter cake, and the dry 12-24 h in air dry oven, temperature is 60-120 DEG C, is subsequently placed in Muffle
It is roasted in furnace：With the heating rate of 1-5 DEG C/min, it is warming up to 150-250 DEG C, constant temperature 4-8 h, then with 1-5 DEG C/min's
Heating rate is heated to 450-650 DEG C, then constant temperature 4-8 h, obtains hetero atom Beta zeolite, is labeled as M-Beta, M ride instead of walk
Suddenly（1）In hetero atom kinds of transition metals；
（3）Hetero atom Beta zeolite is placed in the alcoholic solution of alkali metal compound, 5-30 min is stirred at room temperature, is then centrifuged for,
And washed for several times with corresponding alcoholic solvent, in 60-100 DEG C of dry 12-24 h, the hetero atom Beta zeolite of alkali metal containing is obtained,
Labeled as X-N-M-Beta, wherein X represents the molar concentration of alkali metal compound solution；N represents the type of alkali metal ion, is
Li, Na, K, Rb or Cs, M represent step（1）In hetero atom kinds of transition metals.
Step of the present invention（1）In, the hetero atom transition metal inorganic salts be manganese, cobalt, nickel, copper, zinc, zirconium, tin, hafnium,
One kind of the nitrate or chlorate of lanthanum and cerium；The introduction volume of hetero atom transition metal is the 0.5- of industry Beta zeolite quality
5%；The alcohol is methanol, ethyl alcohol or isopropanol, and the feed ratio of industry Beta zeolite and the alcoholic solution is 1:15~1:100
(g/mL)。
Step of the present invention（3）In, the alkali metal compound is lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium carbonate
Or one kind of potassium carbonate；The alcohol is one kind of methanol, ethyl alcohol or isopropanol；The molar concentration of alkali metal compound solution is
5-100 mmol/L, and the feed ratio of hetero atom Beta zeolite and alkali metal compound solution is 1:15~1:60 (g/mL).
In the present invention, the hetero atom Beta zeolite catalyst for the alkali metal containing being prepared using the above method is applied to hydrogen
In transfer reaction, good catalytic activity and stability are shown：
The zeolite catalyst that synthesis obtains is added in the aqueous isopropanol of furfural, the hydrogen transfer reduction for furfural reacts,
Product uses gas phase analysis；The molar ratio of furfural and isopropanol is 1:5~1:100, reaction temperature is 80-140 DEG C, the reaction time
For 10 min-5 h.Experiment shows the choosing of hetero atom Beta zeolite the furfural conversion ratio and product with higher of alkali metal containing
Selecting property.
The hetero atom Beta zeolite catalyst preparation method of alkali metal containing provided by the invention compared with prior art, process
Simple to operation, mild condition, hetero atom are applied widely, environmental-friendly, and gained zeolite catalyst is in hydrogen transfer reaction
Good catalytic activity and stability have been embodied, there is comparable application prospect.
Detailed description of the invention
Fig. 1 is the XRD spectra of Zr-Beta zeolite catalyst prepared by embodiment 1.
Fig. 2 is the UV-vis spectrogram of Zr-Beta zeolite catalyst prepared by embodiment 1.
Fig. 3 is the SEM figure of Zr-Beta zeolite catalyst prepared by embodiment 1.
Specific embodiment
Illustrate technical solution of the present invention below with reference to specific example, but the scope of the present invention is not limited thereto.
Industry Beta zeolite of the present invention is commercial samples, is purchased from Shanghai Xinnian Petrochemical Aids Co., Ltd, sial
Molar ratio（Si/Al）It is 14.2.
Embodiment 1
The synthesis step and hydrogen migration performance evaluation of the Zr-Beta zeolite catalyst of alkali metal containing provided by the present embodiment are such as
Under：
（1）By 0.0716 g Zr (NO3)4•5H2O is dissolved in the dehydrated alcohol of 100 mL, and 30 min are stirred at room temperature；Then plus
Enter 1.0 g industry Beta zeolites, is placed in 5 h of atmospheric pressure reflux in oil bath heater；
（2）Decompression filters and obtains filter cake, and in 60 DEG C of dry 12 h, roasting obtains Zr-Beta.Roasting condition is at 200 DEG C and 550
DEG C 6 h of difference constant temperature, heating rate are 1 DEG C/min；
（3）Alkali metal compound solution is lithium hydroxide, sodium hydroxide or the hydrogen-oxygen of 6.25,12.5,25,50,100 mmol/L
Change the methanol solution of potassium；0.5 g Zr-Beta zeolite is placed in the alkali metal compound solution of the above-mentioned various concentration of 15 mL,
10 min are stirred at room temperature, and are washed 4 times with methanol, in 65 DEG C of dry 12 h, obtain the Zr-Beta zeolite catalysis of alkali metal containing
Agent is labeled as X-N-Zr-Beta；Wherein, X=6.25,12.5,25,50,100, N Li, Na or K；25-Na-Zr-Beta boiling
XRD, UV-vis map and SEM photograph of stone are shown in Fig. 1, Fig. 2 and Fig. 3 respectively；
（4）The hydrogen transfer reduction of furfural reacts：0.48 g furfural is dissolved in 3.0 g isopropanols, 0.1 g catalyst is added,
It is placed in microwave reactor, in 120 DEG C of 3 h of reaction.The product of the reaction is the etherification product of furfuryl alcohol and furfuryl alcohol and isopropanol（2-
I-propoxymethyl furans）.Product uses 2010 plus gas chromatograph of Shimadzu, carries FFAP capillary column and fid detector
It is analyzed.By chromatographic work station, the conversion ratio of furfural and the selectivity of product are calculated using internal standard method.Wherein, X-Li-
Zr-Beta zeolite catalysis Evaluation results and element composition are shown in Table 1.
It can be seen that the increase with lithium hydroxide concentration from hydrogen migration catalytic performance test result, furfural conversion ratio is in
Downward trend after now first rising, there are a Best Points.25-Li-Zr-Beta zeolite presents highest furfural conversion
Rate, up to 96.2%.From the point of view of the selectivity of product, with the increase of lithium hydroxide concentration, product is gradually by 2- isopropoxy first
Base furans is gradually transitions furfuryl alcohol.The furfuryl alcohol selectivity of product of 25-Li-Zr-Beta zeolite is 100.0%.Meanwhile by the member of table 1
Element composition can be seen that the silica alumina ratio of different Zr-Beta zeolite samples（Si/Al）With silicon zirconium ratio（Si/Zr）Do not become significantly
Change, illustrates to can be obtained the Zr-Beta zeolite of the alkali metal containing of high activity without carrying out dealuminzation.The content of Li element（Li/Al）
Increase, the lithium aluminium ratio of 25-Li-Zr-Beta zeolite with the increase of lithium hydroxide concentration（Li/Al）It is 0.74.Lithium hydroxide
The processing of methanol solution can be distributed with the hydrogen transfer reaction catalytic activity of modulation Zr-Beta zeolite sample and product.
1 X-Li-Zr-Beta zeolite catalysis Evaluation results of table and element composition
X-Na-Zr-Beta zeolite catalysis Evaluation results and element composition are shown in Table 2.As can be seen from Table 2, sodium hydroxide first
The catalytic activity and element composition of the Zr-Beta zeolite of alcoholic solution processing also present similar rule.25-Na-Zr-Beta
When zeolite is as catalyst, for the high conversion rate of furfural up to 96.1%, the selectivity of furfuryl alcohol is 100.0%.At this point, 25-Na-Zr-
The sodium aluminium ratio of Beta zeolite（Na/Al）It is 0.89.
2 X-Na-Zr-Beta zeolite catalysis Evaluation results of table and element composition
X-K-Zr-Beta zeolite catalysis Evaluation results and element composition are shown in Table 3.As can be seen from Table 3, methanolic potassium hydroxide
The catalytic activity and element composition of the Zr-Beta zeolite of solution processing also present similar rule.25-K-Zr-Beta boiling
When masonry is catalyst, for the high conversion rate of furfural up to 91.9%, the selectivity of furfuryl alcohol is 100.0%.At this point, 25-K-Zr-Beta boils
The potassium aluminium ratio of stone（K/Al）It is 0.84.
It is 0.5 h between when reacted, as can be seen from Table 4 under same concentrations, different alkali metal hydroxide methanol solutions
There is apparent differences for the Zr-Beta zeolite catalysis performance of processing.Wherein, corresponding catalytic activity order is Li > Na
> K.
3 X-K-Zr-Beta zeolite catalysis Evaluation results of table and element composition
The comparison of 4 25-N-Zr-Beta zeolite catalysis performance of table
。
Embodiment 2
It is tested with method similar to Example 1, but by 1 step of embodiment（3）In methanol be changed to ethyl alcohol, it is obtained
Zr-Beta zeolite has similar catalytic activity and rule.
Embodiment 3
It is tested with method similar to Example 1, but by 1 step of embodiment（3）In methanol be changed to isopropanol, it is acquired
Zr-Beta zeolite have similar catalytic activity and rule.
Embodiment 4
It is tested with method similar to Example 1, but by 1 step of embodiment（1）In dehydrated alcohol be changed to isopropanol, institute
Obtained Zr-Beta zeolite has similar catalytic activity and rule.
Embodiment 5
It is tested with method similar to Example 1, but by 1 step of embodiment（1）In roasting condition be changed at 150 DEG C and
600 DEG C of 4 h of difference constant temperature, heating rate are 2 DEG C/min, and obtained Zr-Beta zeolite has similar catalytic activity and rule
Rule.
Embodiment 6
It is tested with method similar to Example 1, but by 1 step of embodiment（1）In Zr (NO3)4•5H2O is changed to
ZrCl4, obtained Zr-Beta zeolite is with similar catalytic activity and rule.
Embodiment 7
By 0.0716 g Zr (NO3)4•5H2O is dissolved in the dehydrated alcohol of 15 mL, and 30 min are stirred at room temperature；Then 1.0 are added
G industry Beta zeolite is placed in microwave applicator in 120 DEG C of 10 min of reflux, and other conditions are identical as example 1, acquired
25-Na-Zr-Beta zeolite after 120 DEG C of 3 h of reaction, furfural conversion ratio be 96.0%, furfuryl alcohol is selectively 100.0%.
Embodiment 8
It is tested with method similar to Example 1, but by 1 step of embodiment（3）In alkali metal compound solution be changed to
The rubidium carbonate ethanol solution of 25 mmol/L, is prepared 25-Rb-Zr-Beta zeolite.After 120 DEG C of 3 h of reaction, 25-Rb-
The furfural conversion ratio that Zr-Beta zeolite shows is 85.0%, and furfuryl alcohol is selectively 100.0%.
Embodiment 9
It is tested with method similar to Example 1, but by 1 step of embodiment（3）In alkali metal compound solution be changed to
The cesium carbonate ethanol solution of 25 mmol/L, is prepared 25-Cs-Zr-Beta zeolite.After 120 DEG C of 3 h of reaction, 25-Cs-
The furfural conversion ratio that Zr-Beta zeolite shows is 80.0%, and furfuryl alcohol is selectively 100.0%.
Embodiment 10
Circulation of the 25-Na-Zr-Beta zeolite prepared in this case expedition embodiment 1 in the reaction of furfural hydrogen transfer reduction
Using effect.Catalyst passes through after one cycle, is centrifugated catalyst, fresh raw material is then added, into next time
Reaction.Reaction condition is same as Example 1, and the reaction time is 3 h, and catalyst circulation use the results are shown in Table 5.
Effect is recycled in 5 25-Na-Zr-Beta zeolite of table
。
As can be seen from Table 5, after recycled 5 times, furfural conversion ratio is kept not 25-Na-Zr-Beta zeolite substantially
Become, illustrates that 25-Na-Zr-Beta zeolite has quite stable catalytic activity.
Embodiment 11
It is tested with method similar to Example 1, but by the Zr (NO in embodiment 13)4•5H2O input amount doubles,
For obtained 25-Na-Zr-Beta zeolite after 120 DEG C of 0.5 h of reaction, furfural conversion ratio is 80.0%, furfuryl alcohol selectivity
100.0%。
Embodiment 12
This example has expanded the scope of application of hetero atom Beta zeolite, is tested with method similar to Example 1, but will
0.0716 g Zr(NO3)4•5H2O is changed to the nitrate of the manganese of identical hetero atom amount, cobalt, nickel, copper, zinc, tin, lanthanum and cerium, gained
To 25-Na-M-Beta zeolite furfural hydrogen transfer reduction reaction in have certain catalytic activity.Reaction time is 3 h
Catalytic performance test the results are shown in Table 6.
As can be seen from Table 6, the synthesized hetero atom Beta zeolite for obtaining alkali metal containing is anti-in the hydrogen transfer reduction of furfural
Ying Zhong has certain catalytic activity, illustrates that preparation method provided by the present invention has certain universality.
6 25-Na-M-Beta zeolite catalysis Evaluation results of table
。
The present invention utilize Beta zeolite itself defective bit, without using concentrated acid carry out dealumination treatment, by liquid-phase reflux,
Roasting and alkali process three-step approach, synthesis have obtained the hetero atom Beta zeolite of alkali metal containing.Also, prepared alkali metal containing
Hetero atom Beta zeolite presents good catalytic activity and stability in hydrogen transfer reduction reaction.Side provided by the invention
Method is easy to operate, mild condition, hetero atom are applied widely, environmental-friendly, has comparable application prospect.
Claims (5)
1. the preparation method of the hetero atom Beta zeolite catalyst of alkali metal containing is a kind of rear method of modifying, which is characterized in that tool
Body step is：
（1）Hetero atom transition metal inorganic salts are dissolved in alcoholic solvent, it is molten that industrial Beta zeolite is then added to above-mentioned alcohol
It in liquid, is placed in oil bath or microwave applicator and flows back, reflux temperature is 78-120 DEG C, and return time is 10 min-5 h；
（2）Decompression filters and obtains filter cake, and the dry 12-24 h in air dry oven, temperature is 60-120 DEG C, is subsequently placed in Muffle
It is roasted in furnace, heating rate obtains miscellaneous original respectively in 150-250 DEG C and 450-650 DEG C of constant temperature 4-8 h for 1-5 DEG C/min
Sub- Beta zeolite, is labeled as M-Beta, and M represents step（1）In hetero atom kinds of transition metals；
（3）Hetero atom Beta zeolite is placed in the alcoholic solution of alkali metal compound, 5-30 min is stirred at room temperature, is then centrifuged for,
And washed for several times with corresponding alcoholic solvent, in 60-100 DEG C of dry 12-24 h, the hetero atom Beta zeolite of alkali metal containing is obtained,
Labeled as X-N-M-Beta, wherein X represents the molar concentration of alkali metal compound solution；N represents the type of alkali metal ion,
For Li, Na, K, Rb or Cs, M represents step（1）In hetero atom kinds of transition metals.
2. preparation method according to claim 1, which is characterized in that step（1）Described in hetero atom transition metal without
Machine salt is the nitrate of manganese, cobalt, nickel, copper, zinc, zirconium, tin, hafnium, lanthanum and cerium or one kind of chlorate；Hetero atom transition metal draws
Enter the 0.5-5% that amount is industry Beta zeolite quality；The alcohol is one kind of methanol, ethyl alcohol or isopropanol, and industry Beta boils
The feed ratio of stone and the alcoholic solution is 1:15~1:100 (g/mL).
3. preparation method according to claim 1 or 2, which is characterized in that step（3）Described in alkali metal compound object
For one kind of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium carbonate or cesium carbonate, the alcohol is methanol, ethyl alcohol or isopropanol
One kind；The molar concentration of alkali metal compound solution is 5-100 mmol/L, and hetero atom Beta zeolite and alkali metal chemical combination
The feed ratio of object solution is 1:15~1:60 (g/mL).
4. a kind of hetero atom Beta zeolite catalyst for the alkali metal containing that the preparation method as described in one of claim 1-3 obtains.
5. the hetero atom Beta zeolite catalyst of alkali metal containing as claimed in claim 4 is in the hydrogen transfer reduction reaction of furfural
Using.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529912A (en) * | 2018-12-28 | 2019-03-29 | 湘潭大学 | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof |
| CN110683557A (en) * | 2019-11-20 | 2020-01-14 | 中山大学 | Synthesis method of Sn-Beta zeolite molecular sieve under fluorine-free condition |
| CN112939006A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Modification method of framework silicon-rich zeolite molecular sieve |
| CN114210362A (en) * | 2021-11-30 | 2022-03-22 | 大连理工大学 | Preparation method and application of zinc ion modified Sn-Beta zeolite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011010104A1 (en) * | 2010-02-01 | 2011-08-04 | Johnson Matthey Public Ltd. Co. | Three-way catalyst comprising an extruded solid body |
| CN103920527A (en) * | 2014-04-24 | 2014-07-16 | 南开大学 | Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof |
| CN104549453A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Zirconium-containing beta zeolite and preparation method thereof |
-
2018
- 2018-06-17 CN CN201810625060.0A patent/CN108855207B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011010104A1 (en) * | 2010-02-01 | 2011-08-04 | Johnson Matthey Public Ltd. Co. | Three-way catalyst comprising an extruded solid body |
| CN104549453A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Zirconium-containing beta zeolite and preparation method thereof |
| CN103920527A (en) * | 2014-04-24 | 2014-07-16 | 南开大学 | Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| LI GANG ET AL.: "A Scalable Upgrading of Concentrated Furfural in Ethanol: Combining Meerwein–Ponndorf–Verley Reduction with in Situ Cross Aldol Condensation", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| ROMAN-LESHKOV YURIY ET AL.: "Activation of Carbonyl-Containing Molecules with Solid Lewis Acids in Aqueous Media", 《ACS CATALYSIS》 * |
| WANG JIE ET AL.: "Post-synthesized zirconium-containing Beta zeolite in Meerwein–Ponndorf–Verley reduction: Pros and cons", 《APPLIED CATALYSIS A-GENERAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529912A (en) * | 2018-12-28 | 2019-03-29 | 湘潭大学 | Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof |
| CN109529912B (en) * | 2018-12-28 | 2021-09-24 | 湘潭大学 | Composite nano-structure copper catalyst for preparing furfuryl alcohol by furfural hydrogenation and preparation method thereof |
| CN110683557A (en) * | 2019-11-20 | 2020-01-14 | 中山大学 | Synthesis method of Sn-Beta zeolite molecular sieve under fluorine-free condition |
| CN112939006A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Modification method of framework silicon-rich zeolite molecular sieve |
| CN114210362A (en) * | 2021-11-30 | 2022-03-22 | 大连理工大学 | Preparation method and application of zinc ion modified Sn-Beta zeolite |
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