CN114345294B - Zinc-manganese-zirconium modified mesoporous molecular sieve, preparation method and application - Google Patents
Zinc-manganese-zirconium modified mesoporous molecular sieve, preparation method and application Download PDFInfo
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Abstract
The invention discloses a zinc-manganese-zirconium modified mesoporous molecular sieve, a preparation method and application thereof, wherein the structure of the zinc-manganese-zirconium modified mesoporous molecular sieve comprises the following components: mesoporous molecular sieve and zinc, manganese and zirconium metals loaded in pore canals of the mesoporous molecular sieve; wherein, the content ratio of zinc, manganese and zirconium is 1 (1-10): 0.5-5, preferably 1 (1-5): 0.5-2.5 based on the molar weight of metal elements. The zinc-manganese-zirconium modified mesoporous molecular sieve provided by the invention is used for refining a crude geraniol product, and trace amine impurities with unpleasant smell can be removed, so that the product purity and the aromatic smell are improved, and the application is wider.
Description
Technical Field
The invention relates to a modified mesoporous molecular sieve, in particular to a zinc-manganese-zirconium modified mesoporous molecular sieve, a preparation method and application thereof.
Background
Geraniol is an important acyclic monoterpene compound, is widely applied to the food and cosmetic industry, is a main component of rose oil, and is an important aromatic chemical for manufacturing rose fragrance. The unique fragrance and the mellow fruit taste become indispensable flavoring raw materials in various flower fragrance essences. In addition, geraniol can also be used as advanced fuel, medicine, bactericide, etc.
At present, the industrialized synthesis method route of geraniol is basically divided into two routes, namely a myrcene route and a citral route. The myrcene route is limited in mass production due to the fact that raw materials mainly originate from natural products, and production is periodic. Thus, the current production of geraniol is mainly through the hydrogenation of citral.
In the preparation of geraniol by hydrogenation of citral, a tertiary amine is typically added as an additive to enhance the selective adsorption of the carbonyl c=o groups in the substrate by the active components of the catalyst, as disclosed for example in publication CN1304112C, CN 109503327B. However, due to the introduction of the auxiliary agent, tertiary amine auxiliary agent residues exist in the prepared crude geraniol, so that the fragrance of the product used as a spice product is affected. On the one hand, tertiary amine has bad smell, and trace residue at ppb level can influence the fragrance of the product; on the other hand, the tertiary amine inevitably contains trace primary amine and secondary amine impurities, and the impurities react with citral to generate amine substances in the hydrogenation reaction process, so that the tertiary amine is difficult to separate from the geraniol product, and the fragrance of the product is also influenced.
Therefore, it is desirable to invent a purification method of crude geraniol that can achieve efficient removal of product impurities to improve the aroma quality of the product while achieving high yield and green low cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zinc-manganese-zirconium modified mesoporous molecular sieve, a preparation method and application. The zinc-manganese-zirconium modified mesoporous molecular sieve provided by the invention is used for purifying crude geraniol, so that a geraniol product with high quality and pure fragrance can be obtained.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a zinc manganese zirconium modified mesoporous molecular sieve, the structure of which comprises: mesoporous molecular sieve and zinc, manganese and zirconium metals loaded in pore canals of the mesoporous molecular sieve;
wherein, the content ratio of zinc, manganese and zirconium is 1 (1-10): 0.5-5, preferably 1 (1-5): 0.5-2.5 based on the molar weight of metal elements.
Further, the total loading of zinc, manganese and zirconium metal elements in the mesoporous molecular sieve is 0.1-5%, preferably 0.5-2%.
Further, the mesoporous molecular sieve is one or more of MCM-41, MCM-48, SBA-15, KIT-5 and KIT-6, preferably MCM-41.
The preparation method of the zinc-manganese-zirconium modified mesoporous molecular sieve is characterized by comprising the following steps of: the zinc, manganese and zirconium components are loaded into the pore canal of the mesoporous molecular sieve in the in-situ synthesis process of the mesoporous molecular sieve.
Further, the zinc, manganese and zirconium components are one or more of metal simple substances, oxides, hydroxides or nitrates, hydrochlorides, sulfates, acetates, isooctanoates and naphthenates of zinc, manganese and zirconium.
Further, the in-situ synthesis method of the mesoporous molecular sieve is a microwave radiation synthesis method, a room temperature dynamic synthesis method, a dry powder synthesis method or a hydrothermal crystallization synthesis method.
Taking hydrothermal crystallization synthesis method for preparing zinc-manganese-zirconium modified MCM-41 as an example, the specific preparation method comprises the following steps:
mixing hexadecyl trimethyl ammonium bromide with NaOH in a mass ratio of (1-5) in a three-neck flask, adding deionized water, stirring for 10-30min, sequentially adding zinc nitrate solution, manganese nitrate solution and zirconium nitrate solution with mass concentration of 0.5-3%, wherein the addition amount is 1 (1-10) to (0.5-5) according to the molar ratio of zinc, manganese and zirconium, and the total amount of metal elements is 2-15% of the mass of hexadecyl trimethyl ammonium bromide. After stirring, dripping tetraethoxysilane, wherein the dosage of the tetraethoxysilane is 0.5-4 times of the mass of the cetyltrimethylammonium bromide. Adding NaOH solution to adjust the pH value to about 11, aging and crystallizing in a reaction kettle, adjusting the pH value of the solution to be neutral, drying and roasting under the following conditions: roasting for 1-5h at 500-700 ℃ to finally obtain the zinc-manganese-zirconium modified mesoporous molecular sieve with good crystallinity, which is named as ZnMnZr-MCM-41.
The use of a zinc manganese zirconium modified mesoporous molecular sieve as described hereinbefore or as prepared by a method as described hereinbefore in the purification of a crude geraniol product, wherein the crude geraniol product is subjected to a purification reaction in the presence of the zinc manganese zirconium modified mesoporous molecular sieve.
Further, in the purification reaction, the zinc-manganese-zirconium modified mesoporous molecular sieve is used in an amount of 1-5%, preferably 2-3% of the mass of the crude geraniol product.
Further, the purification reaction condition is that the reaction temperature is 10-40 ℃, preferably 20-30 ℃, the reaction time is 15-60min, preferably 20-40min, and the normal pressure is adopted.
Further, the content of the amine compound in the crude geraniol product is 1-1000ppm.
In the present invention, the purification of the crude geraniol product is preferably carried out in a discontinuous manner in a tank reactor.
According to the invention, the mesoporous molecular sieve which is not modified has only a physical adsorption effect and a poor adsorption effect, and after hetero atoms are introduced into a mesoporous molecular sieve skeleton, the surface acidity is enhanced and the specific surface area is increased, so that the hetero atom mesoporous molecular sieve not only enhances the physical adsorption, but also enhances the pi bond complexation of the hetero atoms and amine substances and the coordination bond complexation of the nitrogen atoms and metal ions, and the adsorption effect on amine impurities is greatly enhanced. The zinc, manganese and zirconium metals are introduced into the mesoporous molecular sieve framework to cause the pore diameter, pore volume, specific surface area and other structural parameters of the molecular sieve to change, and the three atoms have different properties, so that the mesoporous molecular sieve has different properties, and the combined action has good adsorption effect on different amine impurities, thereby producing the effect of improving the fragrance of the crude geraniol product.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The analysis method comprises the following steps: gas chromatograph: agilent7820A, column DB-5 (30 m×320 μm×0.25 μm), sample inlet temperature: 200 ℃, and the split ratio is 80:1; carrier gas flow rate: 1.5ml/min; heating program: maintaining at 50deg.C for 2min, heating to 120deg.C at 10deg.C/min, heating to 180deg.C at 5deg.C/min, heating to 280 deg.C at 20deg.C/min, and maintaining for 5min; detector temperature: 280 ℃.
Atomic absorption elemental analyzer: monochromatic monochromator of Shandong Guokang Co., ltd.): aberration-eliminating Czerny-Turner monochromator, detector: photomultiplier tube with wide spectral range, resolution: manganese lamp 279.5nm, burner: 100mm full titanium metal burner, atomizer: high-efficient glass atomizer of metal covering, atomizing room: corrosion-resistant plastic atomizing chamber.
Fragrance rating of refined geraniol: according to the evaluation of whether the fragrance has natural feeling, fresh feeling and aromatic alcohol feeling, the score of 'full score' is 40, the score of 'pure' is 39.1-40, the score of 'pureness' is 36.0-39.0, the score of 'can' is 32.0-35.9, the score of 'can' is 28.0-31.9, the score of 'pass' is 24.0-27.9, and the score of 'fail' is less than 24.
The raw materials used in the examples or comparative examples except for the protecting agent were all commercially available raw materials.
Preparation of citral hydrogenation catalyst
110g of activated carbon were introduced without further pretreatment into a stirred flask with 2L of water, suspended and heated to 80 ℃ under reflux. The pH was then raised to 9 by adding aqueous NaOH (1 mol/L). After stirring for 1 hour, 300mL of a solution of ruthenium nitrosylnitrate and ferric nitrate (corresponding to a concentration of 5.85g Ru and 1.17g Fe) were added dropwise at 80℃while maintaining the pH at about 9 by adding aqueous NaOH. Stirring was continued for 1 hour at 80℃and the mixture was then cooled. The cold suspension was filtered and washed with 40L of water and then dried in a vacuum oven at 80℃for 16 hours. The dried powder was then transferred to a rotary sphere furnace for reduction in a stream consisting of 70% hydrogen and 30% nitrogen at 500 ℃ for 3 hours. After the reduction was completed, the catalyst was cooled under nitrogen and passivated with a gas mixture of 1% oxygen in nitrogen. The Ru content in the catalyst is 5.0%, the Fe content is 1.0%, and the Na content is 0.036%, and the catalyst is used as a citral hydrogenation catalyst.
Preparation example 2 geraniol is prepared by hydrogenating citral
The hydrogenation catalyst prepared in preparation example 1 was activated in a hydrogen stream for 30 minutes and then added to the reaction autoclave. To a 1000mL autoclave containing 2.4g of the hydrogenation catalyst prepared in preparation example 1, 240g of citral, 2.4g of trimethylamine and 250g of methanol were continuously added. Hydrogen was then immediately introduced into the autoclave until a pressure of 50 bar was reached, after which the hydrogen flow was initially set to 16 standard liters per hour (sl/h). At the same time, the stirrer was turned on and the internal temperature was adjusted to 70 ℃. Excess hydrogen is continuously released through the vent valve. After one hour the hydrogen flow was reduced to 6sl/h and after a further six hours the hydrogenation was terminated by removing the reaction mixture from the autoclave by frit filtration. Volatile components are removed by evaporation to give the crude geraniol product. The geraniol content in the product was 99.4% and the amine content was 550ppm (mainly trimethylamine) as measured by gas chromatography.
Preparation of Zinc manganese zirconium modified mesoporous molecular sieves with different Metal ratios or loadings by examples 1-5
[ example 1 ]
Mixing 72g of hexadecyl trimethyl ammonium bromide with 20g of NaOH in a three-neck flask, adding 500mL of deionized water, stirring for 15min, sequentially adding 10mL of zinc nitrate solution (1 moL/L), 10mL of manganese nitrate solution (1 moL/L) and 5mL of zirconium nitrate solution (1 moL/L), stirring, dropwise adding 245g of ethyl orthosilicate, adding NaOH solution to adjust the pH value to about 11, aging and crystallizing in a reaction kettle to neutral, roasting at 500 ℃ for 2.5 hours, and finally obtaining a modified molecular sieve ZnMnZr-MCM-41-1 with good crystallinity, wherein the molar ratio of zinc to manganese to zirconium is 1:1:0.5, and the loading amount of zinc to manganese to zirconium metal in the modified molecular sieve is 1 percent measured by an atomic absorption element analyzer. The molecular sieve has a pore diameter of 2.6nm and a pore volume of 1.1cm 3 Per gram, a specific surface area of 834cm 2 /g。
[ example 2 ]
Mixing 72g of hexadecyl trimethyl ammonium bromide with 20g of NaOH in a three-neck flask, adding 500mL of deionized water, stirring for 15min, sequentially adding 20mL of zinc nitrate solution (1 moL/L), 100mL of manganese nitrate solution (1 moL/L) and 40mL of zirconium nitrate solution (1 moL/L), stirring, dropwise adding 122g of tetraethoxysilane, adding NaOH solution to adjust the pH value to about 11, aging and crystallizing in a reaction kettle to neutral, roasting at 500 ℃ for 2.5 hours, and finally obtaining a modified molecular sieve ZnMnZr-MCM-41-2 with good crystallinity, wherein the molar ratio of zinc, manganese and zirconium is 1:5:2, and the loading amount of zinc, manganese and zirconium metal in the modified molecular sieve is 2% measured by an atomic absorption element analyzer. The molecular sieve has a pore diameter of 2.4nm and a pore volume of 1.2cm 3 Per gram, specific surface area 757cm 2 /g。
[ example 3 ]
Mixing 72g of cetyl trimethyl ammonium bromide and 20g of NaOH in a three-necked flask, adding 500mL of deionized water, stirring for 15min, sequentially adding 10mL of zinc nitrate solution (1 moL/L), 20mL of manganese nitrate solution (1 moL/L) and 40mL of zirconium nitrate solution (1 moL/L), stirring, dripping 2450g of ethyl orthosilicate, adding NaOH solution to adjust the pH value to about 11, and stirring in a reaction kettleAnd (3) regulating the pH value of the aged and crystallized solution to be neutral, roasting at 500 ℃ for 2.5 hours, and finally obtaining the modified molecular sieve ZnMnZr-MCM-41-3 with good crystallinity, wherein the molar ratio of zinc to manganese to zirconium is 1:2:4, and the loading amount of zinc, manganese and zirconium metal in the modified molecular sieve is 0.1 percent as measured by an atomic absorption element analyzer. The molecular sieve has a pore diameter of 2.5nm and a pore volume of 1.0cm 3 /g: specific surface area of 765cm 2 /g。
[ example 4 ]
Mixing 72g of hexadecyl trimethyl ammonium bromide with 20g of NaOH in a three-neck flask, adding 500mL of deionized water, stirring for 15min, sequentially adding 5mL of zinc nitrate solution (1 moL/L), 35mL of manganese nitrate solution (1 moL/L) and 5mL of zirconium nitrate solution (1 moL/L), stirring, dropwise adding 490g of tetraethoxysilane, adding NaOH solution to adjust the pH value to about 11, aging and crystallizing in a reaction kettle to neutral, roasting at 500 ℃ for 2.5 hours, and finally obtaining a modified molecular sieve ZnMnZr-MCM-41-4 with good crystallinity, wherein the molar ratio of zinc to manganese to zirconium is 1:7:1, and the loading amount of zinc to manganese to zirconium metal in the modified molecular sieve is 0.5 percent measured by an atomic absorption element analyzer. The molecular sieve has a pore diameter of 2.8nm and a pore volume of 1.2cm 3 Per gram, specific surface area 875cm 2 /g。
[ example 5 ]
Mixing 72g of hexadecyl trimethyl ammonium bromide with 20g of NaOH in a three-neck flask, adding 500mL of deionized water, stirring for 15min, sequentially adding 5mL of zinc nitrate solution (1 moL/L), 35mL of manganese nitrate solution (1 moL/L) and 5mL of zirconium nitrate solution (1 moL/L), stirring, dropwise adding 49g of tetraethoxysilane, adding NaOH solution to adjust the pH value to about 11, aging and crystallizing in a reaction kettle to neutral, roasting at 500 ℃ for 2.5 hours, and finally obtaining a modified molecular sieve ZnMnZr-MCM-41-5 with good crystallinity, wherein the molar ratio of zinc to manganese to zirconium is 1:7:1, and the loading amount of zinc to manganese to zirconium metal in the modified molecular sieve is 5% measured by an atomic absorption element analyzer. The molecular sieve has a pore diameter of 2.3nm and a pore volume of 1.3cm 3 Per gram, specific surface area 784cm 2 /g。
Comparative example 1
According to and implementExample 1 mesoporous molecular sieves were prepared in essentially the same manner except that: and (3) adding no metal precursor (namely zinc nitrate, manganese nitrate and zirconium nitrate) in the preparation process to prepare the MCM-41 molecular sieve. The molecular sieve has a pore diameter of 2.3nm and a pore volume of 0.9cm 3 Per gram, specific surface area of 634cm 2 /g。
Comparative example 2
Mesoporous molecular sieves were prepared in substantially the same manner as in example 1, except that: zirconium nitrate solution is not added in the preparation process, and the ZnMn-MCM-41-2' molecular sieve is prepared. The molecular sieve has a pore diameter of 2.4nm and a pore volume of 1.1cm 3 Per gram, specific surface area of 717cm 2 /g。
[ comparative example 3 ]
Mesoporous molecular sieves were prepared in substantially the same manner as in example 1, except that: and (3) preparing the ZnZr-MCM-41-3' molecular sieve without adding a manganese nitrate solution in the preparation process. The molecular sieve has a pore diameter of 2.3nm and a pore volume of 1.2cm 3 Per gram, specific surface area of 697cm 2 /g。
[ comparative example 4 ]
Mesoporous molecular sieves were prepared in substantially the same manner as in example 1, except that: and zinc nitrate solution is not added in the preparation process, so that the MnZr-MCM-41-4' molecular sieve is prepared. The molecular sieve has a pore diameter of 2.2nm and a pore volume of 0.9cm 3 Per gram, a specific surface area of 659cm 2 /g。
Comparative example 5
Mesoporous molecular sieves were prepared in substantially the same manner as in example 1, except that: the dosage of the zirconium nitrate solution in the preparation process is 2mL, and the ZnMnZr-MCM-41-5' molecular sieve is prepared. The molecular sieve has a pore diameter of 2.4nm and a pore volume of 1.1cm 3 Per gram, specific surface area of 737cm 2 /g。
[ comparative example 6 ]
Mesoporous molecular sieves were prepared in substantially the same manner as in example 1, except that: the dosage of the zirconium nitrate solution in the preparation process is 60mL, and the ZnMnZr-MCM-41-6' molecular sieve is prepared. The molecular sieve has a pore diameter of 2.2nm and a pore volume of 1.1cm 3 Per gram, a specific surface area of 626cm 2 /g。
[ example 7 ]
100g of the crude geraniol product prepared in preparation example 2 was taken and added to a 500mL reaction kettle; the molecular sieve prepared in the previous examples or comparative examples was added to a reaction vessel, stirred at normal pressure, and then filtered to obtain purified geraniol.
The amounts of the medium molecular sieves used and the stirring conditions in each example or comparative example are shown in Table 1. The purified geraniol product was tested for purity and impurity amine content, as well as aroma, and the results are reported in table 1.
TABLE 1 refining conditions and Performance test of crude geraniol
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (11)
1. The zinc-manganese-zirconium modified mesoporous molecular sieve is characterized by comprising the following structure: mesoporous molecular sieve and zinc, manganese and zirconium metals loaded in pore canals of the mesoporous molecular sieve;
wherein, the content ratio of zinc, manganese and zirconium is 1 (1-10) (0.5-5) based on the molar weight of metal elements;
the mesoporous molecular sieve is MCM-41;
the preparation method of the zinc-manganese-zirconium modified mesoporous molecular sieve comprises the following steps: the zinc, manganese and zirconium components are loaded into the pore canal of the mesoporous molecular sieve in the in-situ synthesis process of the mesoporous molecular sieve;
the in-situ synthesis method is a microwave radiation synthesis method, a room temperature dynamic synthesis method, a dry powder synthesis method or a hydrothermal crystallization synthesis method.
2. The zinc-manganese-zirconium modified mesoporous molecular sieve according to claim 1, wherein the content ratio of zinc, manganese and zirconium is 1 (1-5): 0.5-2.5 based on the molar amount of metal elements.
3. The zinc-manganese-zirconium modified mesoporous molecular sieve according to claim 1, wherein the total loading of zinc, manganese and zirconium metal elements in the mesoporous molecular sieve is 0.1-5%.
4. A zinc-manganese-zirconium modified mesoporous molecular sieve according to claim 3, wherein the total loading of zinc, manganese and zirconium metal elements in the mesoporous molecular sieve is 0.5-2%.
5. The zinc-manganese-zirconium modified mesoporous molecular sieve according to claim 1, wherein said zinc, manganese, zirconium component is one or more of elemental zinc, manganese, zirconium, oxides, hydroxides or nitrates, hydrochlorides, sulfates, acetates, isooctanoates, naphthenates.
6. Use of a zinc manganese zirconium modified mesoporous molecular sieve according to any of claims 1 to 5 for purifying a crude geraniol product, wherein the crude geraniol product is subjected to a purification reaction in the presence of the zinc manganese zirconium modified mesoporous molecular sieve.
7. The use according to claim 6, wherein the amount of zinc-manganese-zirconium modified mesoporous molecular sieve used in the purification reaction is 1-5% of the mass of the crude geraniol product.
8. The use according to claim 7, wherein the amount of zinc manganese zirconium modified mesoporous molecular sieve used in the purification reaction is 2-3% of the mass of the crude geraniol product.
9. The use according to claim 7, wherein the purification reaction conditions are a reaction temperature of 10-40 ℃, a reaction time of 15-60min, and an atmospheric pressure.
10. The use according to claim 9, wherein the purification reaction conditions are a reaction temperature of 20-30 ℃, a reaction time of 20-40min, and an atmospheric pressure.
11. The use according to any one of claims 6 to 10, characterized in that the content of amine compounds in the crude geraniol product is 1 to 1000ppm.
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