CN109894152B - Preparation method of catalyst for synthesizing tetrahydrofuran, catalyst obtained by preparation method and application of catalyst - Google Patents
Preparation method of catalyst for synthesizing tetrahydrofuran, catalyst obtained by preparation method and application of catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for synthesizing tetrahydrofuran, and the obtained catalyst and application thereof, and relates to the field of catalyst synthesis. The choline chloride and the zinc chloride form eutectic ionic liquid between the bentonite layers, and the eutectic ionic liquid can optimize the acidic active center of the catalyst, improve the tolerance of the catalyst, improve the selectivity and the conversion rate of the synthetic reaction and prolong the service life of the catalyst by regulating and controlling the loading proportion of the choline chloride and the zinc chloride.
Description
Technical Field
The invention relates to the field of catalyst synthesis, in particular to a preparation method of a catalyst for synthesizing tetrahydrofuran, and the obtained catalyst and application thereof.
Background
Tetrahydrofuran is an important organic chemical raw material, has wide application as a solvent in the fields of fine chemical engineering, organic synthesis, pharmacy and the like, and is also an important raw material for producing downstream chemical products such as polytetramethylene ether glycol and the like. At present, tetrahydrofuran is mainly produced by a furfural method, a 1, 4-butanediol dehydration cyclization method, a maleic anhydride hydrogenation method, a butadiene oxidation method, a dichlorobutene method and the like. The method for producing tetrahydrofuran by dehydrating 1, 4-butanediol by using acid as a catalyst has the advantages of simple process, mature technology and relatively high yield of tetrahydrofuran.
However, sulfuric acid is mostly used as a catalyst, so that equipment is easy to corrode, the environment is polluted, and coking byproducts are easy to form in a reaction system. To overcome these disadvantages, researchers have attempted to develop various solid catalysts instead of liquid sulfuric acid. Earlier solid catalyst systems used include alumina, silica gel, silica-alumina composite oxides, etc., and related catalysts and technical processes are disclosed in patents SU1426973, JP48-1075, etc., but the space time yield of these catalysts is generally low.
Various molecular sieves with large specific surface area show better catalytic effect than the above, such as patent CN1283620A, 1, 4-butanediol is contacted with H-ZSM-5 molecular sieve catalyst, and the method keeps plateauUnder the conditions of material conversion rate and tetrahydrofuran selectivity, the processing capacity of the 1, 4-butanediol is improved. Supported solid super acidic catalysts have also been used in this reaction, for example, CN1793133A discloses a method for synthesizing tetrahydrofuran by using a granular solid super acidic catalyst, the catalyst is SO4 2-/MxOyThe solid-like superacid is subjected to dehydration cyclization reaction of 1, 4-butanediol under atmospheric pressure gas phase condition by adopting a fixed bed.
However, in industrial production, the acid sites of the above two catalysts are gradually lost in the aqueous reaction system, resulting in slow decrease of catalytic performance. The strong acid ion exchange resin is a kind of catalyst which is applied more at present. However, ion exchange resins have poor heat resistance, are easily deactivated at high temperatures, are easily pulverized during stirring reaction, and have not high enough product purity.
In summary, the existing catalysts also have the main problems of low production capacity, high catalyst preparation cost, large influence of byproducts on conversion rate, easy coking and inactivation, and the like, and the performance of the catalyst needs to be further improved.
Disclosure of Invention
In view of the problems of the prior art, the present invention aims to provide a catalyst for synthesizing tetrahydrofuran, which catalyzes dehydration cyclization reaction of 1, 4-butanediol by Lewis acid acidity of zinc chloride. The invention also aims to provide a preparation method and a catalytic application of the catalyst, which can improve the combination effect with zinc chloride by inserting choline chloride between bentonite sheets. The invention also aims to provide an application of the catalyst in catalytic synthesis of tetrahydrofuran, which can improve the selectivity and the conversion rate of the synthesis reaction by improving the tolerance of the catalyst.
The preparation method of the catalyst for synthesizing tetrahydrofuran is characterized in that choline chloride is adsorbed in a layered structure of sodium bentonite by utilizing the layered structure of the bentonite and the exchangeability of cations among layers, and then zinc chloride is added for loading.
The preparation method of the catalyst for synthesizing tetrahydrofuran provided by the invention comprises the following steps:
1) and (3) carrier treatment: after impurity removal and purification, the bentonite raw soil is subjected to sodium modification to obtain sodium bentonite with the cation exchange capacity of more than 60mmol/100g, and the sodium bentonite is used as a catalyst carrier;
2) modifying choline: mixing (10-100) mmol of choline chloride with 1000mL of water, completely dissolving, adding (100-200) g of the sodium bentonite obtained in the step 1), and heating and stirring for reacting for 3-24 hours; and (4) carrying out suction filtration, washing a filter cake, and drying in vacuum to obtain the modified bentonite.
3) Loading and activating: dissolving anhydrous zinc chloride to prepare a (0.2-0.6) mol/L solution, taking 200mL of the solution, adding (50-100) g of modified bentonite treated by choline chloride obtained in the step 2), cooling, stirring, reacting for 3-15 hours, and filtering to obtain a powdery solid; and then, drying the powdery solid in a nitrogen atmosphere, heating to 200-260 ℃, treating for 3h, and cooling to room temperature to obtain the catalyst.
According to the invention, choline chloride is intercalated into the bentonite nanosheet layer through physical adsorption and ion exchange processes, the interlayer framework structure is modified, and then after zinc chloride is loaded, choline chloride and zinc chloride are combined to form eutectic ionic liquid, so that anions and cations stably exist between the bentonite layers, and the stability and water resistance of the obtained catalyst are improved. In addition, the strength and the acid amount of the Lewis acid of the catalyst are controlled by adjusting the loading ratio of choline chloride and zinc chloride, so that the catalytic activity of the catalyst is effectively improved. Preferably, in step 3), the molar ratio of zinc chloride to choline chloride is (1-20):1, more preferably (2-5): 1.
Preferably, in step 1), the bentonite sodium modification step comprises: adding a certain amount of purified bentonite into deionized water to enable the solid-liquid mass ratio of the purified bentonite to be 1:10, then adding sodium carbonate accounting for 5% of the mass of the bentonite, continuously stirring and reacting for 2 hours in a constant-temperature water bath at 90 ℃, then performing suction filtration to obtain a filter cake, drying and grinding, and preferably selecting the cation exchange capacity of the sodium bentonite to be more than 100mmol/100g after sodium modification.
Preferably, the reaction temperature is 30-60 ℃ by heating and stirring in step 2).
Preferably, the vacuum drying temperature of the filter cake is 40-105 ℃, and the time is 12-36 h.
Preferably, the reaction temperature in step 3) is (3-5) ° c, and the solvent for dissolving the anhydrous zinc chloride is at least one of methanol, ethanol, glycerol, acetone, and diethyl ether, preferably diethyl ether.
Further provides a catalyst prepared by the preparation method.
Further provides a method for synthesizing tetrahydrofuran by dehydrating and cyclizing 1, 4-butanediol by using the catalyst, and the reaction process comprises the following steps: adopting a fixed bed reactor for reaction, filling a catalyst bed layer, introducing nitrogen, raising the temperature of the bed layer to 150 ℃, and keeping the temperature for 1 hour; then raising the temperature of the bed layer to (200-; wherein the volume ratio of the 1, 4-butanediol to the water is (1-5):1, the gauge pressure is (0-0.5) MPa, and the mass space velocity of the 1, 4-butanediol is (20-100) h-1。
In the preferred embodiment of the invention, the catalyst for synthesizing tetrahydrofuran provided by the invention is used for catalyzing dehydration and cyclization of 1, 4-butanediol mainly through Lewis acid acidity of zinc chloride; secondly, zinc chloride is loaded on a bentonite carrier and combined with an interlayer anion framework to achieve high dispersion; and, compared with non-loaded zinc chloride, the zinc chloride has better stability.
Of particular importance are: before the zinc chloride is loaded on the bentonite, the choline chloride is exchanged between the bentonite nanosheets by utilizing the cation exchange performance of the bentonite, the sodium bentonite is modified, and then the anhydrous zinc chloride is loaded, so that the choline chloride and the zinc chloride are combined in situ between the bentonite layers to form eutectic ionic liquid, and the stability and the water resistance of the obtained catalyst to the dehydration cyclization reaction of the 1, 4-butanediol are obviously enhanced.
The comprehensive effects brought by the invention comprise:
the catalyst for synthesizing tetrahydrofuran can efficiently produce tetrahydrofuran by using 1, 4-butanediol as a raw material, adopts a fixed bed reaction process, has strong water resistance, and is suitable for large-scale continuous production. The catalyst has good stability and is not easy to coke. The selectivity of tetrahydrofuran reaches 99%, and the conversion rate of 1, 4-butanediol can be kept above 90% for a long time. And the catalyst takes bentonite as a main carrier, is cheap and easy to obtain, and has simple preparation process and low cost.
Detailed Description
The invention is further illustrated by the following examples, but it will be understood that the scope of the invention is not limited thereto.
Example 1
1) And (3) carrier treatment: after raw bentonite is subjected to impurity removal and purification, a certain amount of purified bentonite is added into deionized water to enable the solid-liquid mass ratio of the purified bentonite to be 1:10, then sodium carbonate accounting for 5% of the mass of the bentonite is added, the mixture is continuously stirred and reacts for 2 hours in a constant-temperature water bath at 90 ℃, then a filter cake is obtained through suction filtration, and the sodium bentonite is obtained after drying and grinding. Taking sodium bentonite with cation exchange capacity of 100mmol/100g as a catalyst carrier;
2) modifying choline: mixing 30mmol of choline chloride with 1000mL of water, adding 120g of the sodium bentonite carrier obtained in the step after completely dissolving, and heating and stirring at 40 ℃ for reaction for 12 hours; and (4) carrying out suction filtration, washing a filter cake, and drying in vacuum to obtain the modified carrier.
3) Loading and activating: dissolving anhydrous zinc chloride in diethyl ether to prepare a solution of 0.225mol/L, taking 200mL of the solution, adding 60g of modified bentonite treated by choline chloride obtained in the step 2), cooling at 4 ℃, stirring, reacting for 3 hours, and filtering to obtain a powdery solid; and then, drying the powdery solid in a nitrogen atmosphere, heating to 200 ℃ for treatment for 3h, and cooling to room temperature to obtain the catalyst.
The 1, 4-butanediol dehydration cyclization synthesis of tetrahydrofuran by using the catalyst comprises the following steps: adopting a fixed bed reactor for reaction, filling a catalyst bed layer, introducing nitrogen, raising the temperature of the bed layer to 150 ℃, and keeping the temperature for 1 hour; then raising the temperature of the bed layer to 280 ℃, starting to introduce a reaction raw material 1, 4-butanediol aqueous solution, completely vaporizing by a preheater, and then entering a catalyst bed layer along with nitrogen; wherein the volume ratio of the 1, 4-butanediol to the water is 1:1, the reaction pressure is 0.1MPa,the mass space velocity of the 1, 4-butanediol is 20h-1. After the reaction was carried out for 6 hours, the composition of the product was checked by gas chromatography to obtain 1, 4-butanediol having a conversion of 93% and tetrahydrofuran selectivity of 99%.
Example 2
This example followed the three steps described in example 1 to prepare a catalyst, which differed from example 1 in that: the addition amount of choline chloride in the step 2) is 60mmol, the concentration of the zinc chloride solution in the step 3) is 0.3mol/L, and the treatment is carried out for 3 hours at 260 ℃ after the loading is finished. The obtained catalyst was subjected to dehydration cyclization reaction of 1, 4-butanediol by the reaction process described in example 1, wherein the reaction temperature was 300 ℃ and the volume ratio of 1, 4-butanediol to water was 3:1, the mass space velocity of 1, 4-butanediol was 60 hours-1. After the reaction was carried out for 6 hours, the composition of the product was checked by gas chromatography to obtain 1, 4-butanediol having a conversion of 95% and tetrahydrofuran having a selectivity of 99%. The product composition was then checked every 6 hours, and no reduction in conversion and selectivity (± 0.3) was observed after 120 hours of reaction time.
Example 3
This example followed the three steps described in example 1 to prepare a catalyst, which differed from example 1 in that: the addition amount of choline chloride in the step 2) is 100mmol, the modification time is 36 hours, the concentration of the zinc chloride solution in the step 3) is 0.5mol/L, and the solvent is acetone. The obtained catalyst was subjected to dehydration cyclization reaction of 1, 4-butanediol by the reaction process described in example 1, wherein the reaction temperature was 300 ℃ and the volume ratio of 1, 4-butanediol to water was 2:1, and the mass space velocity of 1, 4-butanediol was 100 hours-1. After the reaction was carried out for 6 hours, the composition of the product was checked by gas chromatography to obtain 1, 4-butanediol having a conversion of 91% and tetrahydrofuran selectivity of 99%.
Comparative example 1
This comparative example was carried out using the catalyst prepared by the method of example 1 and applied to tetrahydrofuran synthesis, except that bentonite was not modified by sodium treatment, nor treated with choline chloride, and the catalyst obtained had a corresponding tetrahydrofuran selectivity of 95% and a conversion of 1, 4-butanediol of 76%, with the conversion being lower due to the loss of the catalytic center being too fast.
Comparative example 2
This comparative example was conducted using the catalyst prepared by the method of example 2 and applied to tetrahydrofuran synthesis, except that the sodium bentonite was not modified with choline chloride and the performance of the resulting catalyst was plotted against reaction time as shown in the following table:
| reaction time (h) | 6 | 12 | 24 | 36 | 48 | 60 |
| Conversion (%) | 93 | 92 | 91 | 89 | 72 | 57 |
| Selectivity (%) | 98 | 99 | 99 | 97 | 97 | 90 |
As can be seen from the data in the table, although the catalyst without choline modification has higher initial activity, the activity decreases faster as the reaction proceeds, and the ratio of raw materials and byproducts increases.
After choline modification, as described in example 2, no decrease in catalytic performance was observed after the reaction was carried out for 120 hours, indicating that choline modification plays an important role in improving the stability of the catalyst.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (9)
1. A preparation method of a catalyst for synthesizing tetrahydrofuran is characterized in that choline chloride is inserted between bentonite lamella to improve the structure between bentonite layers, so that the combination of zinc chloride and bentonite is facilitated, and zinc chloride can be stably immobilized with high dispersion by forming eutectic ionic liquid in situ;
the preparation steps are as follows:
1) and (3) carrier treatment: after impurity removal and purification, the bentonite raw soil is subjected to sodium modification to obtain sodium bentonite with the cation exchange capacity of more than 60mmol/100g, and the sodium bentonite is used as a catalyst carrier;
2) modifying choline: mixing 10-100mmol of choline chloride with 1000mL of water, adding 100-200g of sodium bentonite obtained in the step 1) after completely dissolving, and heating and stirring for reacting for 3-24 hours; carrying out suction filtration, washing a filter cake, and drying in vacuum to obtain modified bentonite;
3) loading and activating: dissolving anhydrous zinc chloride to prepare 0.2-0.6mol/L solution, taking 200mL of the solution, adding 50-100g of modified bentonite treated by choline chloride obtained in the step 2), cooling, stirring, reacting for 3-15 hours, and filtering to obtain powdery solid; then, drying the powdery solid in a nitrogen atmosphere, heating to 200-260 ℃, treating for 3h, and cooling to room temperature to obtain a catalyst;
in the step 3), the molar ratio of zinc chloride to choline chloride is (1-20): 1.
2. The preparation method according to claim 1, wherein in step 3), the molar ratio of zinc chloride to choline chloride is (2-5): 1.
3. The preparation method according to claim 1, wherein in step 1), the bentonite sodification modification step comprises: adding a certain amount of purified bentonite into deionized water to enable the solid-liquid mass ratio of the purified bentonite to be 1:10, then adding sodium carbonate accounting for 5% of the mass of the bentonite, continuously stirring and reacting for 2 hours in a constant-temperature water bath at 90 ℃, then performing suction filtration to obtain a filter cake, drying and grinding, and performing sodium modification to obtain the sodium bentonite with the cation exchange capacity of more than 100mmol/100 g.
4. The method according to claim 1, wherein the reaction temperature is 30 to 60 ℃ by heating and stirring in the step 2).
5. The process of claim 1, wherein the cake is vacuum dried at a temperature of 40 to 105 ℃ for 12 to 36 hours.
6. The preparation method according to claim 1, wherein the reaction temperature is 3-5 ℃ with cooling and stirring in step 3), and the solvent for dissolving the anhydrous zinc chloride is at least one of methanol, ethanol, glycerol, acetone and diethyl ether.
7. The method according to claim 6, wherein the solvent for dissolving the anhydrous zinc chloride is diethyl ether.
8. A catalyst obtained by the method according to any one of claims 1 to 7, wherein choline chloride and zinc chloride are combined to form a eutectic ionic liquid, and anions and cations are stably present between layers of bentonite.
9. Use of a catalyst obtainable by a process according to any one of claims 1 to 7 or a catalyst according to claim 8 in a catalytic synthesis reaction for the preparation of tetrahydrofuran, wherein the reaction process comprises the steps of: adopting a fixed bed reactor for reaction, filling a catalyst bed layer, introducing nitrogen, raising the temperature of the bed layer to 150 ℃, and keeping the temperature for 1 hour; then raising the temperature of the bed layer to 200-300 ℃, starting to introduce a reaction raw material 1, 4-butanediol aqueous solution, completely vaporizing by a preheater, and then entering the catalyst bed layer along with nitrogen; wherein the volume ratio of 1, 4-butanediol to water is (1-5):1, the gauge pressure is 0-0.5MPa, and the mass space velocity of 1, 4-butanediol is 20-100h-1。
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