CN111847477B - Preparation method and application of HZSM-5/HMS composite molecular sieve - Google Patents
Preparation method and application of HZSM-5/HMS composite molecular sieve Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an HZSM-5/HMS composite molecular sieve and application thereof, wherein the method comprises the following steps: step S1: mixing dodecylamine, absolute ethyl alcohol and water to obtain mixed feed liquid A; step S2: dropping a mixed solution of a silicon source and absolute ethyl alcohol into the mixed feed liquid A and violently stirring to obtain a mixed feed liquid B; step S3: after the dropwise addition is finished, adding an HZSM-5 molecular sieve into the mixed material liquid B, and then stirring and crystallizing to obtain a glue liquid C; step S4: and standing and aging the obtained glue solution C at normal temperature, centrifugally washing until the pH is neutral, drying and roasting to obtain the glue solution C. Compared with the traditional molecular sieve, the composite molecular sieve HZSM-5/HMS not only has the acid catalysis and shape-selective effects of HZSM-5, but also has larger specific surface area, higher hydrothermal stability and superior mass transfer diffusion characteristics of HMS, and has a promoting effect on the oxidation reaction of alcohol compared with a single molecular sieve catalyst.
Description
Technical Field
The invention relates to the field of alcohol oxidation, in particular to a preparation method and application of an HZSM-5/HMS composite molecular sieve.
Background
HZSM-5 is a commonly used mesoporous zeolite molecular sieve, has better hydrothermal property and shape-selective action due to the unique pore structure and active center, and has wide application in the fields of adsorption, catalysis and the like, and the HZSM-5 structure contains Al element which can provide certain acidity, so that the catalytic oxidation reaction is favorably carried out. The hexagonal mesoporous molecular sieve HMS is a three-dimensional cross arrangement wormhole structure, has the excellent characteristics of large specific surface area, thicker pore wall, high thermal stability and excellent diffusion performance, has larger specific surface area and is beneficial to the rapid diffusion of reactant molecules into the molecular sieve pore channels.
However, the HZSM-5 has a small pore diameter, so that the diffusion of reactant and product molecules is limited, carbon deposition is easy to occur in the reaction process, the catalyst is inactivated, the catalytic performance is reduced, the acidity, the specific surface area, the pore volume, the active sites and the like of the catalyst are obviously reduced, and the service cycle of the catalyst is greatly shortened. As a pure silicon molecular sieve, HMS has poor catalytic performance in alcohol oxidation due to low acidity. Therefore, a composite molecular sieve which can not only keep the excellent surface acidity distribution and shape-selective action of HZSM-5, but also has larger specific surface area of HMS, higher hydrothermal stability and mass transfer diffusion characteristics is urgently needed.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a preparation method of an HZSM-5/HMS composite molecular sieve, which comprises the following steps:
step S1: mixing dodecylamine, absolute ethyl alcohol and water to obtain mixed feed liquid A;
step S2: dropwise adding a mixed solution of a silicon source and absolute ethyl alcohol into the mixed feed liquid A and violently stirring to obtain a mixed feed liquid B;
step S3: after the dropwise addition is finished, adding an HZSM-5 molecular sieve into the mixed material liquid B, and then stirring and crystallizing to obtain a glue liquid C;
step S4: and standing and aging the obtained glue solution C at normal temperature, centrifugally washing until the pH is neutral, drying and roasting to obtain the glue solution C.
The invention also has the following technical characteristics:
optionally, the molar ratio of dodecylamine, absolute ethyl alcohol and water in the mixed feed liquid A is 1: (0.13-0.15): (12.7-12.9).
Optionally, the silicon source is silicate ester or silane compound.
Optionally, the step S2 of dropping the mixed solution of the silicon source and the absolute ethyl alcohol into the mixed material liquid a and vigorously stirring to obtain the mixed material liquid B specifically includes: the dropping speed is 0.6mL/min, and the stirring time is 20-60 min.
Optionally, the stirring crystallization temperature in the step S3 is controlled to be 40-50 ℃, and the stirring time is controlled to be 4-5 hours.
Optionally, in the step S4, the standing time is 6-18 hours, the drying temperature is 60-100 ℃, the drying time is 8-9 hours, the roasting temperature is 600-700 ℃, and the roasting time is 5-7 hours.
The invention also discloses the HZSM-5/HMS composite molecular sieve obtained by the preparation method.
The invention also discloses an application of the HZSM-5/HMS composite molecular sieve for oxidizing isooctyl alcohol.
Specifically, in the oxidation process of isooctyl alcohol, the HZSM-5/HMS composite molecular sieve is used as a catalyst, the adding amount is 0.3-0.7 g, the adding amount of the isooctyl alcohol is 10-20 mL, the reaction time is 6-12 h, and the ratio of the volume flow rate of the isooctyl alcohol to the volume flow rate of oxygen is 3/5 mL/(mL/min).
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the invention adopts roasting treatment, on one hand, the template agent of the composite molecular sieve can be removed, on the other hand, the interaction between the molecular sieve and metal can be enhanced, and the influence on the stability of the catalyst caused by the template agent separated from the molecular sieve carrier and entering into reactants in the reaction process is avoided.
(2) The method adopts dimethylamine as a template agent to directly synthesize the HZSM-5/HMS composite molecular sieve product, has easily controlled preparation process and cheap raw materials, is suitable for large-scale industrial production, and has higher industrial utilization value.
(3) The HZSM-5/HMS composite molecular sieve prepared by the invention is used for the oxidation catalysis process of isooctyl alcohol, and has the advantages of high efficiency, environmental protection, high selectivity and the like.
The present invention will be explained in further detail with reference to examples.
Drawings
FIG. 1 is an XRD pattern of the HZSM-5/HMS composite molecular sieve synthesized in example 2 of the present invention;
FIG. 2 is a NH3-TPD spectrum of the molecular sieves synthesized in examples 1-3 of the present invention and comparative examples 1-2;
FIG. 3 shows FT-IR spectra of molecular sieves synthesized in examples 4 to 6 of the present invention and comparative examples 1 to 2.
Detailed Description
The present invention will be described in detail below with reference to the drawings and embodiments, and the embodiments of the present invention are not to be considered limited to the description. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
In the specific implementation mode of the invention, an IRaffinity-1S WL type infrared spectrometer of Shimadzu corporation in Japan is adopted for characterization; scanning analysis was performed by SmartLab SE type XRD instrument manufactured by japan physical corporation; the specific surface area is measured and analyzed by using a NOVA 2200e type full-automatic specific surface analyzer produced by Congta instruments of America; the product was quantitatively analyzed for its components by GC900A model of shanghai scientific and creation, and the acidic sites on the surface of the material were analyzed by a TP-5080 model ammonia TPD analyzer of pioneer trade development ltd, tianjin. HZSM-5 was purchased from catalyst works of southern Kai university.
Example 1
A preparation method of an HZSM-5/HMS composite molecular sieve comprises the following steps:
(1) fully mixing 15ml of absolute ethyl alcohol and 25ml of distilled water, and then adding 1.7265g of dodecylamine to obtain mixed feed liquid A; where dodecylamine is used as the templating agent.
(2) Dropwise adding a mixed solution consisting of 8mL of tetraethyl silicate and 5mL of absolute ethyl alcohol into the mixed material liquid A at the speed of 0.6mL/min, and violently stirring for 20-60 min to obtain a mixed material liquid B;
(3) after completion of the dropwise addition, 0.07477g of SiO were added to the mixed feed liquid B2/Al2O3A 52 HZSM-5 molecular sieve, controlling the temperature at 45 ℃, and stirring and crystallizing by magnetic stirring for 4 hours to obtain a glue solution C;
(4) and standing and aging the obtained glue solution C for 12h at normal temperature, centrifuging and washing for 6 times until the pH value is 6-8, drying for 8h at 80 ℃, and roasting for 6h at 600 ℃ through a muffle furnace to remove the template agent to obtain the HZSM-5/HMS composite molecular sieve.
Performance analysis experiments:
the BET specific surface area analysis of the prepared HZSM-5/HMS composite molecular sieve shows that the specific surface area of the prepared HZSM-5/HMS composite molecular sieve is 895m2/g。
Respectively adding 0.5-1.0 g of the prepared HZSM-5/HMS composite molecular sieve and 15-30 mL of isooctanol into a 100mL three-neck flask, connecting the three-neck flask with a 300mm snake-shaped condenser tube, setting the reaction pressure to be normal pressure, heating an oil bath pot until the temperature of reactants is 120 ℃, keeping the temperature constant, introducing high-purity oxygen at the speed of 25mL/min, continuing to react for 8 hours, cutting off oxygen and stopping heating. The catalyst of the obtained product is removed by a needle tube filter head, and the supernatant is taken by a microsyringe and added into the chromatogram for component detection. Wherein isooctanol is the reactant, isooctanoic acid is the product, the selectivity of isooctanoic acid is calculated according to the following formula (1), and the value with the highest selectivity in the whole reaction process is taken as the selectivity of isooctanoic acid in the present example. The results show that the isooctanol conversion was 18.5% and the selectivity to isooctanoic acid was 33.9%.
Selectivity%
Example 2
This example shows an HZSM-5/HMS composite molecular sieve, which is different from example 1 in that SiO in the example2/Al2O3HZSM-5 at 52 was added in an amount of 0.2243g, and the other preparation steps and the amounts of the drugs were the same as in example 1.
Performance analysis experiments:
the BET specific surface area analysis is carried out on the prepared HZSM-5/HMS composite molecular sieve, and the result shows that the specific surface area of the prepared HZSM-5/HMS composite molecular sieve is 882m2(ii) in terms of/g. The HZSM-5/HMS composite molecular sieve is used for preparing isooctanoic acid by isooctanol oxidation, and the result shows that the conversion rate of isooctanol is 26 percent and the selectivity of isooctanoic acid is 39 percent.
Example 3
This example shows an HZSM-5/HMS composite molecular sieve, which is different from example 1 in that SiO in this example2/Al2O3HZSM-5 at 52 was added in an amount of 0.3738g, and the other preparation steps and the amounts of the drugs were the same as in example 1.
Performance analysis experiments:
the BET specific surface area analysis is carried out on the prepared HZSM-5/HMS composite molecular sieve, and the result shows that the specific surface area of the prepared HZSM-5/HMS composite molecular sieve is 831m2(ii) in terms of/g. The HZSM-5/HMS composite molecular sieve is used for preparing isooctanoic acid by isooctanol oxidation, and the result shows that the conversion rate of isooctanol is 17.3 percent, and the selectivity of isooctanoic acid is 32 percent.
Example 4
This example shows an HZSM-5/HMS composite molecular sieve, which is different from example 1 in that SiO is used in this example2/Al2O3HZSM-5 of 27 was added in an amount of 0.2g, and other preparation steps and the amounts of the drugs were the same as those in example 1.
Performance analysis experiments:
the BET specific surface area analysis is carried out on the prepared HZSM-5/HMS composite molecular sieve, and the result shows that the specific surface area of the prepared HZSM-5/HMS composite molecular sieve is 840m2(ii) in terms of/g. The HZSM-5/HMS composite molecular sieve is used for preparing isooctanoic acid by isooctanol oxidation, and the result shows that the conversion rate of isooctanol is 15.3 percent, and the selectivity of isooctanoic acid is 32.3 percent.
Example 5
This example shows an HZSM-5/HMS composite molecular sieve, which is different from example 1 in that SiO is used in this example2/Al2O3HZSM-5 at 52 was added in an amount of 0.2g, and the other preparation steps and the amount of the drug were the same as in example 1.
Performance analysis experiments:
the BET specific surface area analysis is carried out on the prepared HZSM-5/HMS composite molecular sieve, and the result shows that the specific surface area of the prepared HZSM-5/HMS composite molecular sieve is 865m2(ii) in terms of/g. The HZSM-5/HMS composite molecular sieve is used for preparing isooctanoic acid by isooctanol oxidation, and the result shows that the conversion rate of isooctanol is 24.3 percent, and the selectivity of isooctanoic acid is 35.6 percent.
Example 6
This example shows an HZSM-5/HMS composite molecular sieve, which is different from example 1 in that SiO is used in this example2/Al2O3HZSM-5 of 85 was added in an amount of 0.2g, and other preparation steps and the amount of the drug were the same as those in example 1.
Performance analysis experiments:
the BET specific surface area analysis is carried out on the prepared HZSM-5/HMS composite molecular sieve, and the result shows that the specific surface area of the prepared HZSM-5/HMS composite molecular sieve is 879m2(ii) in terms of/g. The HZSM-5/HMS composite molecular sieve is used for preparing isooctanoic acid by isooctanol oxidation, and the result shows that the conversion rate of isooctanol is 10.2 percent, and the selectivity of isooctanoic acid is 31.7 percent.
Comparative example 1
In the comparative example, HZSM-5 is not added, and other preparation steps and the addition amount of the medicine are the same as those in example 1.
Performance analysis experiments:
the BET specific surface area analysis is carried out on the prepared HMS molecular sieve, and the result shows that the specific surface area of the prepared HMS molecular sieve is 900m2(ii) in terms of/g. The HMS molecular sieve is used for preparing isooctanoic acid by oxidizing isooctanol, and the result shows that the conversion rate of isooctanol is 2.3 percent, and the selectivity of isooctanoic acid is 31.3 percent.
Comparative example 2
This comparative example usesThe molecular sieve is a directly purchased HMS molecular sieve, and BET specific surface area analysis is carried out on the HZSM-5 molecular sieve, and the result shows that the specific surface area of the obtained HZSM-5 molecular sieve is 215m2/g。
Performance analysis experiments:
the HZSM-5 molecular sieve is used for preparing isooctanoic acid by isooctanol oxidation, the conversion rate of isooctanol is 5.5 percent, and the selectivity of isooctanoic acid is 16.3 percent.
And (3) analyzing an experimental result:
according to the performance experiment results, the HZSM-5/HMS composite molecular sieve disclosed by the invention has the advantages that 0.5-1.0 g of the HZSM-5/HMS composite molecular sieve is added into 15-30 ml of isooctanol, oxygen is introduced into a reactant, and the isooctanol is highly selective under the condition of reacting for 8 hours at 120 ℃, namely the selectivity of the isooctanol can be effectively improved compared with a traditional zeolite catalyst when the HZSM-5/HMS composite molecular sieve disclosed by the invention is added with a corresponding amount.
0.5g of the HZSM-5/HMS composite molecular sieve prepared in the experimental example 2 of the invention is added with 15ml of isooctanol, oxygen is introduced into a reactant, and when the reactant reacts for 8 hours at 120 ℃, the isooctanol has the highest conversion rate and the isooctanoic acid has the highest selectivity. Namely, when a certain amount of the HZSM-5/HMS composite molecular sieve is added in the isooctanol oxidation reaction, the selectivity of the product isooctanoic acid can be obviously improved compared with the traditional zeolite catalyst.
FIG. 2 shows NH3-TPD curves for examples 1-3 and comparative examples 1-2, and it can be seen from FIG. 2 that weak acid and strong acid centers are present in examples 1-3 at both temperatures of 150 deg.C to 300 deg.C and 300 deg.C to 500 deg.C. The acid centers of the HZSM-5/HMS composite molecular sieves prepared in examples 1-3 are all larger than the HMS prepared in comparative example 1, but smaller than the HZSM-5(52) molecular sieve prepared in comparative example 2. As the amount of HZSM-5(52) composite silica prepared in comparative example 2 increased, the weak acid and strong acid centers of the HZSM-5/HMS composite molecular sieve both shifted to high temperatures, indicating that the amount of weak acid and strong acid of the HZSM-5/HMS composite molecular sieve increased, and the addition of HZSM-5(52) may help to increase the acidity of the composite. The prepared HZSM-5/HMS composite molecular sieve shows higher activity to the catalytic reaction of isooctyl alcohol by combining the specific surface area and the average pore diameter.
FIG. 3 shows examples 4 to 6 and comparative examplesFT-IR spectra of examples 1 to 2. As can be seen in FIG. 3, 3738cm-1The nearby absorption peak was attributed to tensile vibration of Si-OH groups at the terminal of the molecular sieve and adsorbed water molecules, 1604cm-1The nearby absorption peak is then due to the O-H bending vibration peak of the water adsorbed on the molecular sieve sample. In addition, all samples were at 435cm-1、804cm-1、1046cm-1The absorption peaks are generated by Si-O bending vibration peaks and asymmetric and symmetric stretching vibration peaks of Si-O-Si bonds in silicon tetrahedron. It is noted that comparative example 2 is 534cm-1There is a characteristic absorption peak of MFI zeolite due to the presence of five-and six-membered ring tetrahedral vibration peaks of T-O-T (T ═ Si or Al) in HZSM-5 zeolite. While comparative example 1 was at 968cm-1There is a smaller diffraction peak, which is attributed to the absorption vibration of Si-OH on the surface of HMS of the mesoporous molecular sieve. Since comparative example 1 and comparative example 2 both have their specific characteristic absorption peaks and the above-mentioned series of characteristic absorption peaks appear in examples 4 to 6, it is demonstrated that the HZSM-5 microporous molecular sieve and the HMS mesoporous molecular sieve are successfully composited, which is consistent with the characterization result of fig. 1.
Claims (4)
1. A preparation method of HZSM-5/HMS composite molecular sieve is characterized by comprising the following steps:
step S1: mixing dodecylamine, absolute ethyl alcohol and water to obtain mixed feed liquid A;
step S2: dropwise adding a mixed solution of a silicon source and absolute ethyl alcohol into the mixed feed liquid A and violently stirring to obtain a mixed feed liquid B;
step S3: after the dropwise addition is finished, adding an HZSM-5 molecular sieve into the mixed material liquid B, and then stirring and crystallizing to obtain a glue liquid C;
step S4: standing and aging the obtained glue solution C at normal temperature, centrifugally washing until the pH is neutral, drying and roasting to obtain the glue solution C;
the molar ratio of the dodecylamine to the absolute ethyl alcohol to the water in the mixed feed liquid A is 1:
(0.13～0.15)：(12.7～12.9)；
step S2, the molar ratio of the silicon source to the absolute ethyl alcohol in the mixed solution of the silicon source and the absolute ethyl alcohol is 1 (0.53-0.55);
the silicon source is silicate ester or silane compound;
step S2, adding the mixture of the silicon source and the absolute ethyl alcohol dropwise into the mixed material liquid a, and vigorously stirring to obtain a mixed material liquid B, specifically including: the dropping speed is 0.6mL/min, and the stirring time is 20-60 min;
the stirring crystallization temperature in the step S3 is controlled to be 40-50 ℃, and the stirring time is controlled to be 4-5 h;
in the step S4, the standing time is 6-18 hours, the drying temperature is 60-100 ℃, the drying time is 8-9 hours, the roasting temperature is 600-700 ℃, and the roasting time is 5-7 hours.
2. An HZSM-5/HMS composite molecular sieve obtained by the method of claim 1.
3. Use of the HZSM-5/HMS composite molecular sieve as claimed in claim 2 for the oxidation of isooctyl alcohol.
4. The use according to claim 3, wherein the HZSM-5/HMS composite molecular sieve is used as a catalyst in the oxidation process of isooctanol, the dosage is 0.3-0.7 g, the dosage of isooctanol is 10-20 mL, the reaction time is 6-12 h, and the ratio of the volume flow rate of isooctanol to the volume flow rate of oxygen is 3/5 mL/(mL/min).
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