CN107790191B - Preparation method of solid acid catalyst for cyclohexanone and ethylene ketal reaction - Google Patents
Preparation method of solid acid catalyst for cyclohexanone and ethylene ketal reaction Download PDFInfo
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- CN107790191B CN107790191B CN201710966510.8A CN201710966510A CN107790191B CN 107790191 B CN107790191 B CN 107790191B CN 201710966510 A CN201710966510 A CN 201710966510A CN 107790191 B CN107790191 B CN 107790191B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
Abstract
The invention discloses a preparation method of a solid acid catalyst for cyclohexanone and ethylene ketal reaction, belonging to the technical field of inorganic nano composite materials. Doping iron ions into the SBA-15 to prepare Fe-SBA-15, synthesizing butyrolactam chloride-zinc chloride ionic liquid, and loading according to the mass ratio of the Fe-SBA-15 to the ionic liquid of 1-0.05: 1. Weighing a certain amount of ionic liquid, adding the ionic liquid into a dispersing agent in a three-neck flask, stirring at 40-50 ℃ until the ionic liquid is completely dissolved, adding Fe-SBA-15 with required amount, continuously stirring for 6-12h, evaporating the dispersing agent after the reaction is finished, washing with diethyl ether, and vacuum drying at 60-100 ℃ for 6-12 h. The catalyst prepared by the invention has various acid sites, the acidity of the catalyst can be adjusted, and the catalyst has excellent catalytic activity for the reaction of cyclohexanone and ethylene ketal.
Description
Technical Field
The invention belongs to the chemical field of inorganic nano materials, and relates to a mesoporous molecular sieve SBA-15 (a mesoporous molecular sieve) carrier doped with metallic iron and butyrolactam chloride-zinc chloride
The (Brewster-Lewis) double-acid ionic liquid is used as an active site, an IL/Fe-SBA-15 solid catalyst with various acid sites is prepared, and the catalyst is applied to the pre-ketal reaction of cyclohexanone and glycol.
Background
The traditional acid catalytic reaction including esterification reaction, alkylation reaction, ketal reaction and the like is an important component of petrochemical industry, and has important promotion effect on national industrial and economic development. These reactions typically require the corresponding acid as a catalyst to accelerate the reaction and reduce the temperature and pressure conditions required for the reaction. The traditional catalysts used for these reactions, including concentrated sulfuric acid, p-toluenesulfonic acid, aluminum chloride, ion exchange resins, have drawbacks in terms of the method, for example, the most common concentrated sulfuric acid has extremely strong corrosivity to equipment and great harm to the environment. Therefore, it is a significant task to find a green, clean and sustainable acid catalyst.
In recent years, ionic liquids have been receiving attention from a great deal of researchers due to their superiority, and are called green solvents, which are composed of anions and cations, can exist as liquids at room temperature, have zero vapor pressure, and are not volatile. At the same time due to its yinThe cation is generally composed of corresponding organic substances, and various useful functional groups can be designed into the structure of the ionic liquid, so that the cation has high designability. According to the characteristic, acidic groups such as sulfonic groups, halides and the like are designed to enter the ionic liquid structure, so that the ionic liquid structure has strong acidity, and the ionic liquid structure is feasible when being applied to the traditional acid catalytic reaction to replace the traditional acid catalyst. In this respect, hydrochloric acid is used to modify chloroaluminate-type ions, and the acidity is proved to reach a super acid level by Deng, which is applied to benzene alkylation reaction to achieve good effect (K.Qiao, Y.Q.Deng, J.mol.Catal.A: chem.,171(2001) 81-84.). Lunagariya et al synthesized compounds containing sulfonic acid group functional groupAcidic ionic liquids and proved to be a very good catalyst for esterification reactions (j.lunagaliya, a.dhar, r.l.vekariya, RSC adv.,7(2017) 5412.).
However, the ionic liquid has certain defects, and firstly, the price of the ionic liquid is mostly expensive, and only a small amount of ionic liquid can be industrially produced so far; secondly, the ionic liquid has larger viscosity, and is applied to large chemical production, and the mass transfer and the heat transfer are very big problems. Thirdly, the presence of a post-treatment portion of its recovery and production stages as a liquid is more difficult than for a solid catalyst. To address this problem, some researchers have proposed the concept of "loading" ionic liquids, i.e., grafting ionic liquids onto corresponding solid supports, such as Mohammad et al loading pyridine sulfate ionic liquids onto nano-scale MCM-41 mesoporous molecular sieves, for synthesizing quinine with high yield (a.a.mohammad, m.p.nanosized, cat.com.2012, 22: 13-18.). The ionic liquid loaded solid carrier makes the composite possess corresponding property, reduces the use of ionic liquid, and the liquid-changed catalyst is solid catalyst and may be used widely.
It is well known that the acidity of the catalyst is an important performance indicator for acid catalyzed ketal reactions. Traditional acids, including inorganic acids such as sulfuric acid, while relatively acidic, have the same relatively large adverse effects including contamination and corrosion. And for common metal composite catalysts, the acidity is poor. Other catalysts such as pure ionic liquids have corresponding problems as with the above analysis.
Disclosure of Invention
Aiming at the problems in the prior art, the invention takes butyrolactam chloride-zinc chloride double-acid ionic liquid as one active site and ferric ion as the other active site, and the two active sites are loaded on an SBA-15 carrier to prepare the IL/Fe-SBA-15 multi-active site composite catalyst. Meanwhile, the ionic liquid is applied to the ketal reaction of cyclohexanone and ethylene glycol.
The technical scheme of the invention is as follows:
the method comprises the following steps: iron doping was as follows: p123: the molar ratio of the ethyl orthosilicate is 250: prepared in a ratio of 0.017: 1. Dissolving ferric nitrate nonahydrate and tetraethyl orthosilicate in an aqueous solution with the pH value of 1.5 at room temperature, and stirring to form a solution A; dissolving P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) in another aqueous solution with the pH value of 1.5, and stirring to dissolve to form a solution B; and (3) placing the solution B into a three-port baked product at 40 ℃, continuously stirring, slowly dropwise adding the solution A, and after dropwise adding, keeping the temperature of the mixed solution at 40 ℃ and stirring for 24 hours. Then the obtained solution is put into a high-temperature reaction kettle of 100ml and crystallized for 24 hours at the temperature of 100 ℃. Taking out, cooling to room temperature, suction filtering with a large amount of cooling water, washing, and drying. The obtained solid is roasted for 6h at 550 ℃,2 ℃/min and air atmosphere. Fe-SBA-15 can be obtained;
the ionic liquid butyrolactam chloride-zinc chloride is prepared according to a molar ratio of zinc chloride to butyrolactam chloride of 2:1, under the condition of ice-water bath, toluene is used for pre-dissolving butyrolactam, then the solution is poured into a three-port baked product, concentrated hydrochloric acid is dropwise added, the mixture is stirred for 30min, the height temperature is between 10 ℃, the reaction solution is continuously stirred for 3h, after the reaction is finished, liquid is separated, the supernatant is removed, the solution is washed by ether, the obtained liquid is dried in vacuum for 12h at 60 ℃, then the obtained product is added into the three-port baked product, the temperature is heated to 80 ℃, zinc chloride with the required content is added according to the principle of a small amount of times, the stirring reaction is carried out for 4h, the obtained liquid is taken out after the reaction is finished, and the obtained liquid is dried in vacuum for 12h at 100 ℃, thus obtaining the product.
Step two: and (3) placing the ionic liquid obtained in the step one into a three-neck flask, keeping the temperature at a certain value, adding a corresponding solvent, and magnetically stirring for a certain time to dissolve the ionic liquid. Keeping the temperature unchanged, adding Fe-SBA-15, continuously stirring for a period of time, evaporating to remove the solvent, and carrying out suction filtration and washing by using a detergent. Then dried under vacuum at a certain temperature.
In the second step, the temperature of the three-neck flask is kept between 40 and 50 ℃;
in the second step, dissolving the ionic liquid for 1 hour or until the solution is clear and transparent;
in the second step, the solvent is a chloroform-methanol mixed solvent (chloroform: methanol: 95: 5);
in the second step, adding Fe-SBA-15 and then continuously stirring for 6-8 h;
in the second step, the washing agent is diethyl ether, the single dosage is 1-2 times of the solid volume, and the washing is carried out for three times;
in the second step, the drying temperature is 60-100 ℃, and vacuum drying is carried out;
in the second step, the drying time is 6-12 h;
in the second step, the mass ratio of Fe-SBA-15 to the ionic liquid is 1:0.025,1:0.5 and 1: 1;
in the second step, the Si/Fe molar ratio of the catalyst is 25:1,50:1
The IL/Fe-SBA-15 prepared by the invention is used for the ketal reaction of cyclohexanone and ethylene glycol.
The invention has the beneficial effects that:
1. the invention combines the advantages of the two materials, can greatly enhance the catalytic activity of the mesoporous material, can improve the defects of the ionic liquid in the aspect of catalysis, and has great application potential. Moreover, the acidity of the surface properties of the catalyst can be controlled by simply changing the ratio of reactants (the ratio of ionic liquid, iron ions and SBA-15), so that the applicability of the catalyst is improved.
2. Surface of catalyst
The ratio of Lewis acid sites can be adjusted by adjusting the content of zinc chloride and butyrolactam chloride and iron ions.
3. The methanol-chloroform mixed solvent is used as a dispersing agent, so that the ionic liquid can be fully dispersed on the inner surface of the carrier material, and the contact area between the active site of the catalyst and a reactant is increased.
4. The ionic liquid is immobilized on the mesoporous material, so that the liquid catalyst is changed into a solid catalyst, the catalyst and a reaction system are easier to separate, and the catalyst can be repeatedly used, thereby reducing the dosage of the ionic liquid and lowering the cost.
5. The catalytic activity of the ionic liquid and the metal ions which are used as main active sites is far higher than that of SBA-15; the catalyst has very excellent catalytic activity for the ketalization reaction of cyclohexanone and ethylene glycol.
Drawings
FIG. 1 is a transmission analysis of the sample of example 1;
FIG. 2 is a BET analysis of the sample of example 1;
FIG. 3 is an XRD analysis of the sample of example 1;
FIG. 4 is a graph of cyclohexanone conversion as a function of time in example 1;
FIG. 5 is a graph of cyclohexanone conversion as a function of time in example 2;
FIG. 6 is a graph of cyclohexanone conversion as a function of time in example 3.
Detailed description of the preferred embodiments
The invention is further illustrated by the following specific examples and the accompanying drawings of the specification.
Example 1:
according to the method of the first step, 2g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), 4.5ml of tetraethyl orthosilicate and 0.3232g of ferric nitrate nonahydrate are used as raw materials, ferric ions are doped into SBA-15, the Si/Fe molar ratio of the obtained material is 25:1, and ionic liquid butyrolactam chloride-zinc chloride is prepared. Then 0.025g of ionic liquid is weighed and added into a three-port baked good, the temperature is heated to 40 ℃, a mixed solvent of chloroform and methanol is added, the mixture is stirred until the solution is clear and transparent, then 1g of Fe-SBA-15 is added, and the stirring is continued for 6 hours. Then, the mixture is filtered and washed by ether, and is dried in vacuum for 12 hours at the temperature of 100 ℃ to obtain the brownish red solid catalyst. The transmission spectrum of the catalyst is shown in figure 1, and the catalyst has a clear and ordered pore channel structure. The BET curve of the catalyst is shown in FIG. 2, which is similar to that of the conventional SBA-15, and has an adsorption curve of type IV and a hysteresis loop of type H1, and the XRD pattern of the catalyst is shown in FIG. 3, wherein three characteristic peaks of 100,110 and 210 are characteristic diffraction peaks of a 2-dimensional hexagonal structure.
Catalytic activity test:
adding 9.8g (0.1mol) of cyclohexanone and 9.3g (0.15mol) of ethylene glycol into a three-neck flask, quickly adding 0.1g of catalyst when the temperature is increased to 90 ℃, installing a reflux condenser tube, and stirring for reaction; sampling every 30min, analyzing the mixture by gas chromatography, and calculating to obtain the cyclohexanone conversion rate.
As shown in FIG. 4, the reaction can reach equilibrium at 120min, and the optimal cyclohexanone conversion rate reaches about 88.5%.
Example 2: Fe-SBA-15 and ionic liquid butyrolactam chloride-zinc chloride were prepared according to example 1, under the condition that other conditions were not changed, the addition amount of the ionic liquid in the catalyst preparation process was changed, and the catalysts were prepared by the addition amount of 0.5g and 1g of the ionic liquid respectively, and named as b and c, and the catalyst named as a in example 1, and the catalyst was applied to the catalytic activity experiment: adding 9.8g (0.1mol) of cyclohexanone and 9.3g (0.15mol) of ethylene glycol into a three-neck flask, quickly adding 0.1g of catalyst when the temperature is increased to 90 ℃, installing a reflux condenser tube, and stirring for reaction; sampling every 30min, analyzing the mixture by gas chromatography, and calculating to obtain the cyclohexanone conversion rate.
As shown in fig. 5, the increase of the content of the ionic liquid increases the cyclohexanone conversion to some extent, and when the amount of the ionic liquid added is 0.5g, the maximum cyclohexanone conversion can reach 92.6%, but this does not mean that the cyclohexanone conversion can be increased continuously by continuously increasing the amount of the ionic liquid, and on the contrary, the cyclohexanone conversion can not be increased any more with the amount of the ionic liquid added being 1g, which is mainly caused by the chemical thermodynamic equilibrium limitation in the ketal reaction.
Example 3:
step 1 the same as example 1, except that the amount of ferric nitrate nonahydrate was changed, 0.1616g of ferric nitrate nonahydrate was used as the starting material to prepare the catalyst. The resulting catalyst had a Si/Fe molar ratio of 50:1, was designated as d, and was applied to a catalytic activity test: adding 9.8g (0.1mol) of cyclohexanone and 9.3g (0.15mol) of ethylene glycol into a three-neck flask, quickly adding 0.1g of catalyst when the temperature is increased to 90 ℃, installing a reflux condenser tube, and stirring for reaction; sampling every 30min, analyzing the mixture by gas chromatography, and calculating to obtain the cyclohexanone conversion rate.
As shown in fig. 6: the reduction of the content of iron ions in the catalyst has some influence on the catalytic activity of the catalyst, and the optimal conversion rate of cyclohexanone is reduced to 82.8%. This is mainly caused by the reduction of active sites.
Claims (1)
1. A preparation method of a solid acid catalyst for cyclohexanone and ethylene ketal reaction is characterized by comprising the following steps:
step 1, doping iron ions into an SBA-15 mesoporous molecular sieve structure, and preparing ionic liquid butyrolactam chloride-zinc chloride
Step 2, loading the ionic liquid into Fe-SBA-15 by referring to the following steps:
weighing the ionic liquid obtained in the step 1, placing the ionic liquid in a three-neck flask, keeping a certain temperature, adding a corresponding solvent, magnetically stirring for a certain time to dissolve the ionic liquid, keeping the temperature unchanged, adding Fe-SBA-15, continuously stirring for a period of time, performing suction filtration and washing by using a detergent, and then performing vacuum drying at a certain temperature;
in the step 2, the temperature of the three-neck flask is kept to be 40-50 ℃;
in the step 2, dissolving the ionic liquid for 1 hour or until the solution is clear and transparent;
in the step 2, the used solvent is a chloroform + methanol mixed solvent, and the chloroform: methanol 95: 5;
in the step 2, continuously stirring for 6-8h after adding Fe-SBA-15;
in the step 2, the washing agent is diethyl ether, the single dosage is 1-2 times of the solid volume, and the washing is carried out for three times;
in the step 2, the drying temperature is 60-100 ℃, and vacuum drying is carried out;
in the step 2, the drying time is 6-12 h;
in the step 2, the mass ratio of the Fe-SBA-15 to the ionic liquid is 1:0.025-1: 1;
in step 2, the Si/Fe molar ratio in the catalyst is 25:1-50: 1.
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