CN106984356A - A kind of method that utilization Sn β classes catalyst prepares methallyl alcohol and acetal simultaneously - Google Patents
A kind of method that utilization Sn β classes catalyst prepares methallyl alcohol and acetal simultaneously Download PDFInfo
- Publication number
- CN106984356A CN106984356A CN201710311988.7A CN201710311988A CN106984356A CN 106984356 A CN106984356 A CN 106984356A CN 201710311988 A CN201710311988 A CN 201710311988A CN 106984356 A CN106984356 A CN 106984356A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetal
- calcined
- class catalyst
- methallyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J29/7049—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method that utilization Sn β classes catalyst prepares methallyl alcohol and acetal simultaneously, using H beta-molecular sieves as parent, it is calcined to being ground after its dealuminzation with tin acetate, obtains Sn β class catalyst Sn β；The method pre-processed again with Ar with the Na post processings exchanged obtains Sn β class catalyst Sn β Ar and Sn β Ar Na, can reduce the B acid contents in tin species and the catalyst outside skeleton, further lifting catalytic activity and selectivity；Followed by above-mentioned Sn β class catalyst, using MAL as substrate, ethanol is solvent and hydrogen source, can prepare two kinds of important chemicals of methallyl alcohol and acetal simultaneously at a lower temperature.The Sn β classes catalyst activity of the present invention is high, can obtain methallyl alcohol and acetal that yield is 90% and 96%；Catalyst stability is high, is recycled multiple non-inactivation；Reaction is carried out at a lower temperature, without HTHP；React for multiphase reaction system, the separation simplicity of catalyst and product.
Description
Technical field
The invention belongs to methallyl alcohol and acetal preparing technical field, and in particular to one kind utilizes Sn- β class catalyst
The method for preparing methallyl alcohol and acetal simultaneously.
Background technology
Methallyl alcohol is a kind of important organic intermediate, for synthetic perfume, resin etc..With methallyl alcohol and ring
Oxidative ethane is Material synthesis methyl allyl alcohol polyoxyethylene ether (HPEG), for high performance concrete water reducer of new generation.Methyl
Allyl alcohol can also synthesize the ester containing pi-allyl with synthesizing methyl acrylicacidandesters with other organic acids, polymerized monomer,
There is important application in terms of surfactant.
The method that tradition prepares methallyl alcohol is, using 2- methallyl chlorides as initiation material, to be given birth to using alkaline water solution
Produce methallyl alcohol.US2072015, US2323781, US2313767 etc. are that certain improvement is carried out to the conventional method.Alkali
Property Hydrolyze method turn into one of method of topmost production methallyl alcohol, but the problem of exist certain：Needed in hydrolytic process
Substantial amounts of base reagent and organic solvent are added, it is necessary to higher temperature and pressure, the pollution to environment are larger, and due to pair
The presence of product ether causes yield relatively low.
It is a kind of environment-friendly and economic method to obtain unsaturated alcohol through reduction reaction using unsaturated aldehyde as substrate,
JP-B56-36176, US2779801, which are disclosed, uses aluminium alcoholates to prepare unsaturated alcohol, but isopropanol demand for the reaction of catalyst
It is larger, and homogeneous system is difficult to separate.US2767221 can avoid above mentioned problem using magnesia as catalyst preparation unsaturated alcohol,
But reaction temperature requires higher, energy consumption is big.
US4072727, CN102167657 prepare unsaturated alcohol with the method for catalytic hydrogenation reduction unsaturated aldehyde, but due to
Need optionally to reduce C=O without reducing C=C alkali, often need noble metal as catalyst, catalyst preparation process is more
Complexity, catalyst cost is larger, and selectivity is difficult to control to.Therefore Development of Novel MAL is reduced to methallyl alcohol
Method has great importance.
Acetal is also a kind of important chemicals, is mainly used as solvent, and for organic synthesis and cosmetics, spices
Manufacture, also can reduce NO as diesel fuel additivesxDischarge.The preparation condition of acetal is more harsh,
CN104478844, CN103717564 describe the preparation method of acetal and ketal, but temperature conditionss, raw material selection all compared with
For harshness.Therefore exploitation acetal preparation method is also an important problem.And so far, not yet have one kind without high temperature
The method that high pressure, separation prepare methallyl alcohol and acetal while easy.
The content of the invention
It is an object of the invention to overcome in place of the deficiencies in the prior art there is provided one kind using Sn- β classes catalyst simultaneously
The method for preparing methallyl alcohol and acetal, using Sn- β class catalyst, using MAL as substrate, ethanol be solvent and
Hydrogen source can prepare two kinds of important chemicals of methallyl alcohol and acetal simultaneously at a lower temperature.
One of the technical solution adopted for the present invention to solve the technical problems is：
A kind of method that utilization Sn- β classes catalyst prepares methallyl alcohol and acetal simultaneously, including：
1) with 65~68% HNO under 370~375K3Dealuminzation 18~22h, described 65~68% HNO are carried out to H- β3
Formula rate with H- β is 18~22ml：1g, obtained powder washing and drying, with tin acetate carry out physical grinding 15~
25min, the ratio of the powder and tin acetate is 4~6:1, then using air as flowing atmosphere 820~825K be calcined 2.5~
3.5h, obtains Sn- β class catalyst, is Sn- β；
2) using MAL as substrate, ethanol adds the Sn- β class catalyst, 67~87 as solvent and hydrogen source
DEG C, carry out liquid phase under counterflow condition and pass 1~3h of hydrogen reduction reaction, obtain methallyl alcohol and acetal；The MAL,
The formula rate of ethanol and Sn- β class catalyst is 0.8~3.0mmol：78~82mmol：0.05~0.5g.
In one embodiment：The step 1) in, by the powder washing and drying and tin acetate carry out physical grinding 15~
After 25min, 2.5~3.5h first is calcined in 820~825K by flowing atmosphere of argon gas, then carry out described using air as flowing atmosphere
The step of 820~825K is calcined 2.5~3.5h, Sn- β class catalyst is obtained, is Sn- β-Ar.
In one embodiment：The step 1) in, by the powder washing and drying and tin acetate carry out physical grinding 15~
After 25min, 2.5~3.5h first is calcined in 820~825K by flowing atmosphere of argon gas, then carry out described using air as flowing atmosphere
The step of 820~825K is calcined 2.5~3.5h, Sn- β class catalyst is obtained, is Sn- β-Ar；It will be obtained under 350~355K
Sn- β-Ar and 0.8~1.2M NaNO3Carry out ion exchange 10~14h, the Sn- β-Ar and 0.8~1.2M NaNO3Match somebody with somebody
Square ratio is 1g：4~6h is calcined in 770~775K after 45~55ml, obtained product centrifuge washing, the catalysis of Sn- β classes is obtained
Agent, is Sn- β-Ar-Na.
In one embodiment：The step 1) in, the mol ratio of MAL and methanol is 0.9:80.
In one embodiment：The step 1) in, the formula rate of MAL, ethanol and Sn- β class catalyst is 0.9
~2.8mmol：80mmol：0.5g.
In one embodiment：The step 2) in, it is 77 DEG C that liquid phase, which passes hydrogen reduction reaction temperature,.
The two of the technical solution adopted for the present invention to solve the technical problems are：
A kind of preparation method of Sn- β class catalyst, with 65~68% HNO under 370~375K3Dealuminzation is carried out to H- β
18~22h, described 65~68% HNO3Formula rate with H- β is 18~22ml：1g, obtained powder washing and drying, with
Tin acetate carries out 15~25min of physical grinding, and the ratio of the powder and tin acetate is 4~6:1, then using air as flowing gas
Atmosphere is calcined 2.5~3.5h in 820~825K, obtains Sn- β class catalyst, is Sn- β.
In one embodiment：After the powder washing and drying and tin acetate are carried out into 15~25min of physical grinding, first with argon
Gas is calcined 2.5~3.5h for flowing atmosphere in 820~825K, then carry out it is described using air be flowing atmosphere in 820~825K roastings
The step of burning 2.5~3.5h, obtains Sn- β class catalyst, is Sn- β-Ar.
In one embodiment：The step 1) in, by the powder washing and drying and tin acetate carry out physical grinding 15~
After 25min, 2.5~3.5h first is calcined in 820~825K by flowing atmosphere of argon gas, then carry out described using air as flowing atmosphere
The step of 820~825K is calcined 2.5~3.5h, Sn- β class catalyst is obtained, is Sn- β-Ar；It will be obtained under 350~355K
Sn- β-Ar and 0.8~1.2M NaNO3Carry out ion exchange 10~14h, the Sn- β-Ar and 0.8~1.2M NaNO3Match somebody with somebody
Square ratio is 1g：4~6h is calcined in 770~775K after 45~55ml, obtained product centrifuge washing, the catalysis of Sn- β classes is obtained
Agent, is Sn- β-Ar-Na.
The three of the technical solution adopted for the present invention to solve the technical problems are：
A kind of Sn- β class catalyst according to prepared by above-mentioned preparation method.
The present invention prepares methallyl alcohol with MPV reduction mechanisms reduction MAL, and ethanol is reduced to after passing hydrogen
Acetaldehyde, the acetaldehyde of generation obtains high valuable chemicals acetal by aldolisation.
Sn- β class catalyst of the present invention is prepared by the solid liposome nanoparticle method post-processed.By to mother
After the dealumination treatment of body H- beta-molecular sieves, tin acetate is subjected to solid liposome nanoparticle with it, the substitution to aluminium is carried out.It is pre- by Ar
The quantity of Sn species, reduces the outer Sn species quantities of skeleton, lifting selectivity in the method increase skeleton of processing.Exchanged by Na
Method is further removed in catalystSour site, lifting selectivity.
The technical program is compared with background technology, and it has the following advantages that：
The advantage of the method for the present invention is that Sn- β classes catalyst activity is high, can obtain the methyl alkene that yield is 90% and 96%
Propyl alcohol and acetal；Catalyst stability is high, is recycled multiple non-inactivation；Reaction can be carried out at a lower temperature, without high temperature
High pressure；React for multiphase reaction system, the separation simplicity of catalyst and product.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is Sn- β class catalyst Sn- β, Sn- β-Ar, Sn- β-Ar-Na X-ray diffractogram.
Fig. 2 is Sn- β class catalyst Sn- β, Sn- β-Ar, Sn- β-Ar-Na UV-vis DRS collection of illustrative plates.
Fig. 3 is Sn- β class catalyst Sn- β, Sn- β-Ar, Sn- β-Ar-Na pyridine adsorption infared spectrum in situ.
Fig. 4 is the Activity evaluation of different catalysts addition in embodiment 7 to 11, and conversion is methyl in figure
The conversion ratio of methacrylaldehyde, Mol is methallyl alcohol, and Dal is acetal.
The recycling Activity evaluation that Fig. 5 is Sn- β class catalyst Sn- β-Ar-Na in embodiment 15.
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1
1) Sn- β preparation methods：With 65~68% HNO under 373K3To H- β progress dealuminzations 20h, described 65~68%
HNO3Formula rate with H- β is 20ml：1g, obtained powder washing and drying carries out physical grinding 20min with tin acetate,
The ratio of the powder and tin acetate is 5:1,3h then is calcined in 823K using air as flowing atmosphere in tube furnace, is obtained
Sn- β class catalyst, is Sn- β.
2) Sn- β-Ar preparation methods：With 65~68% HNO under 373K3Carry out dealuminzation 20h to H- β, described 65~
68% HNO3Formula rate with H- β is 20ml：1g, obtained powder washing and drying carries out physical grinding with tin acetate
20min, the mass ratio of the powder and tin acetate is 5:1, first it is calcined in tube furnace by flowing atmosphere of argon gas in 823K
3h, then 3h is calcined in 823K using air as flowing atmosphere, Sn- β class catalyst is obtained, is Sn- β-Ar.
3) Sn- β-Ar-Na preparation methods：Sn- β-Ar are prepared according to the method described above, then by obtained Sn- under 353K
β-Ar and 1.0M NaNO3Carry out ion exchange 12h, the Sn- β-Ar and 1.0M NaNO3Formula rate be 1g：50ml, is obtained
To product centrifuge washing after in Muffle furnace 773K be calcined 5h, obtain Sn- β class catalyst, be Sn- β-Ar-Na.
X-ray diffraction sign, UV-vis DRS sign, original are carried out to above-mentioned Sn- β, Sn- β-Ar, Sn- β-Ar-Na
Position Adsorption of Pyridine IR Characterization, characterization result is shown in Fig. 1,2,3 respectively.
Embodiment 2
Prepare methallyl alcohol and the method for acetal simultaneously and can be carried out in 10ml round-bottomed flasks, and be configured with and condense back
Flow tube, thermocouple, agitator, heater etc..Specifically, 2.8mmol MALs are added in 10ml round-bottomed flasks,
80mmol ethanol, add 0.2g Sn- β class catalyst Sn- β, using MAL as substrate, ethanol as solvent and hydrogen source, plus
Heat is to 77 DEG C, and back flow reaction 2h obtains methallyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 1.On the basis of MAL, the conversion of MAL
Rate is 69.9%, and the yield of methallyl alcohol and acetal is respectively 35.4% and 41.0%.
Embodiment 3
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.2g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 2h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 1.On the basis of MAL, the conversion of MAL
Rate is 76.6%, and the yield of methallyl alcohol and acetal is respectively 42.8% and 50.6%.
Embodiment 4
0.9mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.2g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 2h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 1.On the basis of MAL, the conversion of MAL
Rate is 88.8%, and the yield of methallyl alcohol and acetal is respectively 53.6% and 59.4%.
Embodiment 5
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.2g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 67 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 2.On the basis of MAL, the conversion of MAL
Rate is 51.2%, and the yield of methallyl alcohol and acetal is respectively 18.4% and 26.7%.
Embodiment 6
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.2g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 2.On the basis of MAL, the conversion of MAL
Rate is 61.6%, and the yield of methallyl alcohol and acetal is respectively 28.4% and 37.7%.
Embodiment 7
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.05g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Fig. 4.On the basis of MAL, the conversion of MAL
Rate is 41.5%, and the yield of methallyl alcohol and acetal is respectively 0.7% and 10.0%.
Embodiment 8
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.1g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Fig. 4.On the basis of MAL, the conversion of MAL
Rate is 49.5%, and the yield of methallyl alcohol and acetal is respectively 14.7% and 21%.
Embodiment 9
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.2g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Fig. 4.On the basis of MAL, the conversion of MAL
Rate is 61.6%, and the yield of methallyl alcohol and acetal is respectively 28.4% and 37.7%.
Embodiment 10
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.3g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Fig. 4.On the basis of MAL, the conversion of MAL
Rate is 73.7%, and the yield of methallyl alcohol and acetal is respectively 40.9% and 48.8%.
Embodiment 11
1.8mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.5g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 1h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Fig. 4.On the basis of MAL, the conversion of MAL
Rate is 80.3%, and the yield of methallyl alcohol and acetal is respectively 52.4% and 58.7%.
Embodiment 12
0.9mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.5g Sn- β classes
Agent Sn- β, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 2h obtains methyl alkene as solvent and hydrogen source
Propyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 3.On the basis of MAL, the conversion of MAL
Rate is 97.2%, and the yield of methallyl alcohol and acetal is respectively 71.3% and 94.7%.
Embodiment 13
0.9mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.5g Sn- β classes
Agent Sn- β-Ar, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 2h obtains first as solvent and hydrogen source
Base allyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 3.On the basis of MAL, the conversion of MAL
Rate is 99.5%, and the yield of methallyl alcohol and acetal is respectively 85.0% and 99.1%.
Embodiment 14
0.9mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.5g Sn- β classes
Agent Sn- β-Ar-Na, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 3h is obtained as solvent and hydrogen source
Methallyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.The Activity evaluation of catalyst is shown in Table 3.On the basis of MAL, the conversion of MAL
Rate is 98.9%, and the yield of methallyl alcohol and acetal is respectively 90.2% and 96.6%.
Embodiment 15
0.9mmol MALs are added in 10ml round-bottomed flasks, 80mmol ethanol adds the catalysis of 0.5g Sn- β classes
Agent Sn- β-Ar-Na, using MAL as substrate, ethanol is heated to 77 DEG C, back flow reaction 3h is obtained as solvent and hydrogen source
Methallyl alcohol and acetal.
Reacted product, qualitative point is carried out after filtering with GC-MS (HP-5 capillary columns 30m × 0.25mm × 0.25 μm)
Analysis, gas-chromatography (Thermo Trace 1310, HP-5 capillary column 30m × 0.25mm × 0.25 μm) hydrogen flame ionization detection
Device carries out quantitative analysis.Detect that catalyst uses the activity after 1 time.
The catalyst after activity rating will be carried out and centrifuge recovery, be dried overnight in 110 DEG C of baking ovens, and in Muffle furnace
550 DEG C of roasting 5h；Then the synthesis that catalyst carries out methallyl alcohol and acetal is reused according to above-mentioned steps, detection is urged
Agent recycles 2 times, 3 times, 4 times, the activity of 5 times, and the Activity evaluation of catalyst is shown in Fig. 5.
The substrate of table 1., the Activity evaluation of solvent molar ratio
Reaction condition：Backflow：77 DEG C, 2h, 80mmol ethanol, 0.2g Sn- β
The Activity evaluation of the reaction temperature of table 2.
Reaction condition：Backflow：1.8mmol MALs, 1h, 80mmol ethanol, 0.2g Sn- β
The Activity evaluation of the catalyst of table 3. difference post-processing approach
Reaction condition：Backflow：0.9mmol MALs, 77 DEG C, 80mmol ethanol, 0.5g Sn- β
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of method that utilization Sn- β classes catalyst prepares methallyl alcohol and acetal simultaneously, it is characterised in that：Including：
1) with 65~68% HNO under 370~375K3Dealuminzation 18~22h, described 65~68% HNO are carried out to H- β3With H-
β formula rate is 18~22ml：1g, obtained powder washing and drying carries out 15~25min of physical grinding, institute with tin acetate
The ratio for stating powder and tin acetate is 4~6:1,2.5~3.5h then is calcined in 820~825K using air as flowing atmosphere, is obtained
It is Sn- β to Sn- β class catalyst；
2) using MAL as substrate, ethanol adds the Sn- β class catalyst as solvent and hydrogen source, 67~87 DEG C,
Liquid phase is carried out under counterflow condition and passes 1~3h of hydrogen reduction reaction, methallyl alcohol and acetal is obtained；The MAL, second
The formula rate of alcohol and Sn- β class catalyst is 0.8~3.0mmol：78~82mmol：0.05~0.5g.
2. the method that utilization Sn- β classes catalyst according to claim 1 prepares methallyl alcohol and acetal simultaneously, its
It is characterised by：The step 1) in, after the powder washing and drying and tin acetate are carried out into 15~25min of physical grinding, first
Be calcined 2.5~3.5h in 820~825K by flowing atmosphere of argon gas, then carry out it is described using air for flow atmosphere 820~
The step of 825K is calcined 2.5~3.5h, obtains Sn- β class catalyst, is Sn- β-Ar.
3. the method that utilization Sn- β classes catalyst according to claim 1 prepares methallyl alcohol and acetal simultaneously, its
It is characterised by：The step 1) in, after the powder washing and drying and tin acetate are carried out into 15~25min of physical grinding, first
Be calcined 2.5~3.5h in 820~825K by flowing atmosphere of argon gas, then carry out it is described using air for flow atmosphere 820~
The step of 825K is calcined 2.5~3.5h, obtains Sn- β class catalyst, is Sn- β-Ar；Under 350~355K by obtained Sn- β-
Ar and 0.8~1.2M NaNO3Carry out ion exchange 10~14h, the Sn- β-Ar and 0.8~1.2M NaNO3Formula rate
For 1g：4~6h is calcined in 770~775K after 45~55ml, obtained product centrifuge washing, Sn- β class catalyst is obtained, is Sn-
β-Ar-Na。
4. the method that utilization Sn- β classes catalyst according to claim 1 prepares methallyl alcohol and acetal simultaneously, its
It is characterised by：The step 1) in, the mol ratio of MAL and methanol is 0.9:80.
5. the method that utilization Sn- β classes catalyst according to claim 1 prepares methallyl alcohol and acetal simultaneously, its
It is characterised by：The step 1) in, the formula rate of MAL, ethanol and Sn- β class catalyst is 0.9~2.8mmol：
80mmol：0.5g.
6. the method that utilization Sn- β classes catalyst according to claim 1 prepares methallyl alcohol and acetal simultaneously, its
It is characterised by：The step 2) in, it is 77 DEG C that liquid phase, which passes hydrogen reduction reaction temperature,.
7. a kind of preparation method of Sn- β class catalyst, it is characterised in that：With 65~68% HNO under 370~375K3To H- β
Carry out dealuminzation 18~22h, described 65~68% HNO3Formula rate with H- β is 18~22ml：1g, obtained powder washing
Drying, carries out 15~25min of physical grinding, the ratio of the powder and tin acetate is 4~6 with tin acetate:1, then with air
2.5~3.5h is calcined in 820~825K for flowing atmosphere, Sn- β class catalyst is obtained, is Sn- β.
8. the preparation method of Sn- β class catalyst according to claim 7, it is characterised in that：Dried the powder is washed
It is dry to be carried out with tin acetate after 15~25min of physical grinding, 2.5~3.5h first is calcined in 820~825K using argon gas as flowing atmosphere,
Sn- β class catalyst is obtained, is the step of 820~825K is calcined 2.5~3.5h by flowing atmosphere of air described in carrying out again
Sn-β-Ar。
9. the preparation method of Sn- β class catalyst according to claim 7, it is characterised in that：The step 1) in, inciting somebody to action
The powder washing and drying is carried out after 15~25min of physical grinding with tin acetate, is first to flow atmosphere in 820~825K using argon gas
It is calcined 2.5~3.5h, then it is flowing atmosphere the step of 820~825K, 2.5~3.5h of roasting using air to carry out described, is obtained
Sn- β class catalyst, is Sn- β-Ar；By obtained Sn- β-Ar and 0.8~1.2M NaNO under 350~355K3Carry out ion
Exchange 10~14h, the Sn- β-Ar and 0.8~1.2M NaNO3Formula rate be 1g：45~55ml, obtained product from
4~6h is calcined in 770~775K after heart washing, Sn- β class catalyst is obtained, is Sn- β-Ar-Na.
10. the Sn- β class catalyst prepared by a kind of preparation method according to any one of claim 7 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710311988.7A CN106984356B (en) | 2017-05-05 | 2017-05-05 | Method for simultaneously preparing methyl allyl alcohol and acetal by using Sn- β catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710311988.7A CN106984356B (en) | 2017-05-05 | 2017-05-05 | Method for simultaneously preparing methyl allyl alcohol and acetal by using Sn- β catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106984356A true CN106984356A (en) | 2017-07-28 |
| CN106984356B CN106984356B (en) | 2020-07-03 |
Family
ID=59417466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710311988.7A Active CN106984356B (en) | 2017-05-05 | 2017-05-05 | Method for simultaneously preparing methyl allyl alcohol and acetal by using Sn- β catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106984356B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833904A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of difunction catalyst, preparation method and the application in ethyl alcohol conversion reaction |
| CN114702373A (en) * | 2022-05-10 | 2022-07-05 | 东南大学 | Method for preparing acetal by molecular sieve pore-enlarging adsorption lanthanide series trimesylate catalyst |
| CN114950540A (en) * | 2022-05-18 | 2022-08-30 | 福建农林大学 | Acid-modified H-Beta zeolite catalyst and preparation method and application thereof |
| CN115212917A (en) * | 2021-04-21 | 2022-10-21 | 天津师范大学 | Catalyst for preparing alkyl lactate by chemical catalysis of 1, 3-dihydroxyacetone and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
-
2017
- 2017-05-05 CN CN201710311988.7A patent/CN106984356B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278814A (en) * | 2015-06-10 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method simultaneously preparing methallyl alcohol and cyclododecanone |
Non-Patent Citations (4)
| Title |
|---|
| CERI HAMMOND ET AL.: "Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis", 《CHEMCATCHEM》 * |
| M. UESHIMA ET AL.: "Vapor phase hydrogen transfer reaction between methacrolein and ethanol over MgO based catalysts", 《CATALYSIS LETTERS》 * |
| 高滋等: "《固体碱催化》", 31 May 2013, 复旦大学出版社 * |
| 高滋等: "《固体酸催化》", 31 May 2016, 复旦大学出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833904A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of difunction catalyst, preparation method and the application in ethyl alcohol conversion reaction |
| CN109833904B (en) * | 2017-11-29 | 2020-08-11 | 中国科学院大连化学物理研究所 | Acid-base bifunctional catalyst, preparation method thereof and application thereof in ethanol conversion reaction |
| CN115212917A (en) * | 2021-04-21 | 2022-10-21 | 天津师范大学 | Catalyst for preparing alkyl lactate by chemical catalysis of 1, 3-dihydroxyacetone and preparation method and application thereof |
| CN115212917B (en) * | 2021-04-21 | 2023-11-14 | 天津师范大学 | Catalyst for preparing alkyl lactate by chemical catalysis of 1, 3-dihydroxyacetone as well as preparation method and application thereof |
| CN114702373A (en) * | 2022-05-10 | 2022-07-05 | 东南大学 | Method for preparing acetal by molecular sieve pore-enlarging adsorption lanthanide series trimesylate catalyst |
| CN114702373B (en) * | 2022-05-10 | 2023-11-28 | 东南大学 | Method for preparing acetal by molecular sieve reaming adsorption of lanthanide series trimellitic salt catalyst |
| CN114950540A (en) * | 2022-05-18 | 2022-08-30 | 福建农林大学 | Acid-modified H-Beta zeolite catalyst and preparation method and application thereof |
| CN114950540B (en) * | 2022-05-18 | 2023-11-03 | 福建农林大学 | Acid modified H-Beta zeolite catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106984356B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106984356A (en) | A kind of method that utilization Sn β classes catalyst prepares methallyl alcohol and acetal simultaneously | |
| CN107376997B (en) | Preparation and application of catalyst for preparing benzaldehyde by oxidizing benzyl alcohol | |
| CN108586392A (en) | A kind of method that 5 hydroxymethyl furfural add in-place hydrogen prepares 2,5- dimethyl furans | |
| CN106866589B (en) | A kind of preparation method of gamma-valerolactone | |
| CN102728380B (en) | Application of catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis | |
| CN105968075B (en) | A kind of method that photochemical catalytic oxidation HMF prepares DFF | |
| CN105693659B (en) | A kind of preparation method of tetrahydrofurfuryl alcohol | |
| CN104262120B (en) | A kind of vanillin food grade,1000.000000ine mesh catalytic hydrodeoxygenation prepares the method for 4-methyl guaiacol and 4 | |
| CN106008414B (en) | The method that 5 hydroxymethylfurfurals catalysis transfer hydrogenation prepares 2,5 dihydroxymethyl furans | |
| CN104277017B (en) | 2,5-dihydroxymethyl furans prepares the method for 2,5-dimethylin furans | |
| CN103990473A (en) | Sulfate radical composite oxide solid acid catalyst, its preparation method, and method for catalyzing conversion of xylan to furfural through using it | |
| CN104190401B (en) | Molybdenum based composite metal oxidate catalyst for glycerine synthesizing propylene alcohol and preparation method thereof | |
| CN103232418A (en) | Homogeneous catalytic preparation method of gamma-valerolactone | |
| CN104138753B (en) | A kind of tinbase montmorillonite catalyst is the application of furfural with preparation method and catalysis xylose thereof | |
| CN106187752A (en) | A kind of method that in near-critical methanol medium, Zr SBA 15 mesopore molecular sieve catalysis furfural one kettle way prepares methyl ester levulinate | |
| CN103709196A (en) | Complex containing 2-aminopyridine tetradentate ligand and application thereof | |
| CN103007943A (en) | Catalyst used for preparing ethanol by hydrogenation of acetic ester as well as preparation method and application of catalyst | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| CN107903225B (en) | A method of 5 hydroxymethyl furfural is prepared with glucose | |
| CN103755529B (en) | A kind of method preparing pyrogallol and Phloroglucinol monomethyl ether | |
| CN102755901A (en) | Preparation and application of composite solid acid catalyst used for condensation reaction | |
| CN108250165A (en) | A kind of method for preparing N- (5- methyl furfuryl group) aniline and derivative using biomass carbohydrates | |
| CN102010309B (en) | Method for preparing benzaldehyde by catalytic oxidation of benzyl alcohol over supported palladium chloride | |
| CN103657653B (en) | A kind of solid acid catalyst C/Fe3O4The method of MWCNTs and catalyzing cellulose hydrolysis thereof | |
| CN109622031A (en) | The preparation method of 2- hydroxyphosphonoacetic acid zirconium and its application in furfuryl alcohol synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |