CN107876100B - Preparation method of solid acid catalyst for preparing methylal - Google Patents
Preparation method of solid acid catalyst for preparing methylal Download PDFInfo
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- CN107876100B CN107876100B CN201710997497.2A CN201710997497A CN107876100B CN 107876100 B CN107876100 B CN 107876100B CN 201710997497 A CN201710997497 A CN 201710997497A CN 107876100 B CN107876100 B CN 107876100B
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
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- 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
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Abstract
The invention discloses a preparation method of a solid acid catalyst for preparing methylal, which comprises the following operation steps: (1) putting the activated carbon into an environment of 280-300 ℃, carbonizing for 2-3 hours at constant temperature, and crushing to 200 meshes; (2) adding an additive with the weight of 0.08-0.1 time of that of the powder prepared in the step (1), uniformly mixing, and carrying out ultrasonic treatment for 25-30 min; (3) and (3) adding an acidic mixed solution with the weight 1.1-1.3 times that of the mixture prepared in the step (2), sulfonating for 2-3 hours, filtering to obtain filter residues, fully cleaning the filter residues with clear water until the pH value of the cleaned water is reached, and drying to obtain a finished product. The invention provides a preparation method of a solid acid catalyst, which can effectively reduce the preparation cost of the solid acid catalyst, and the prepared solid acid catalyst has high catalytic activity, stable property and long service life.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a solid acid catalyst for preparing methylal.
Background
Methylal is one of the most important downstream products of methanol and is mainly used as an organic solvent, and researches in recent years show that methylal serving as an additive of methanol gasoline can remarkably improve the octane number of the methanol gasoline and improve the low-temperature starting performance of the methanol gasoline, and the methylal is widely applied to the methanol gasoline. The traditional synthesis method of methylal takes methanol and formaldehyde aqueous solution as raw materials and synthesizes the methylal under the action of an acid catalyst. In the method, a large amount of water exists in the reaction process, so the reaction conversion rate is low, and methylal, methanol and water can form an azeotrope, which causes difficult separation and purification, and large energy consumption and waste liquid discharge. The reactive distillation method is a new developing methylal industrial preparation method, which adopts a solid acid catalyst, has the advantages of high purity of the product methylal, less generation of waste water and the like, and becomes a main industrial production method for synthesizing the methylal. However, the method has the obvious defects that the price of the solid acid catalyst is higher and the effective activity time is short.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a solid acid catalyst for preparing methylal.
The invention is realized by the following technical scheme.
A preparation method of a solid acid catalyst for preparing methylal comprises the following operation steps:
(1) putting the activated carbon into an environment of 280-300 ℃, carbonizing for 2-3 hours at constant temperature, and crushing to 200 meshes;
(2) adding an additive with the weight of 0.08-0.1 time of that of the powder prepared in the step (1), uniformly mixing, and carrying out ultrasonic treatment for 25-30min, wherein the additive is prepared from the following components in parts by weight: 3-6 parts of tetraheptyl ammonium iodide and 7-10 parts of behenamide;
(3) adding an acidic mixed solution with the weight 1.1-1.3 times that of the mixture prepared in the step (2), sulfonating for 2-3 hours, filtering to obtain filter residue, fully cleaning the filter residue with clear water until the pH value of the cleaned water is reached, and drying to obtain a finished product, wherein the mixed acid is prepared from the following components in parts by weight: 85-92 parts of 95% sulfuric acid, 7-10 parts of 70% periodic acid and 1-3 parts of phosphotungstic acid.
Specifically, in the step (2), the frequency of the ultrasonic wave during the ultrasonic treatment is 32 to 36 kHz.
Specifically, the temperature of the drying treatment is 85-90 ℃, and the time of the drying treatment is 2-3 hours.
According to the technical scheme, the beneficial effects of the invention are as follows:
the invention provides a preparation method of a solid acid catalyst, which can effectively reduce the preparation cost of the solid acid catalyst, and the prepared solid acid catalyst has high catalytic activity, stable property and long service life. Active carbon is selected as a raw material in the busy process, and after high-temperature treatment, carbon atoms in the active carbon are in an amorphous state, so that the specific surface area, the activity and the stability of the solid acid catalyst can be effectively improved; after the tetraheptyl ammonium iodide and the docosanamide act synergistically, the hydrophobic property of the solid acid catalyst can be improved, so that the stability and the service life of the solid acid catalyst are effectively improved; after the synergistic effect of periodic acid and phosphotungstic acid, the effect of sulfonation reaction can be effectively improved, so that sulfonic groups in sulfuric acid are connected to a polycyclic aromatic hydrocarbon carbon structure as far as possible, and the connection stability is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following examples further illustrate the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a solid acid catalyst for preparing methylal comprises the following operation steps:
(1) putting the activated carbon into an environment with the temperature of 280 ℃, carbonizing for 2 hours at constant temperature, and crushing to 180 meshes;
(2) adding an additive with the weight 0.08 times that of the powder prepared in the step (1), uniformly mixing, and carrying out ultrasonic treatment for 25min, wherein the additive is prepared from the following components in parts by weight: 3 parts of tetraheptyl ammonium iodide and 7 parts of behenamide;
(3) adding an acidic mixed solution with the weight 1.1 times that of the mixture prepared in the step (2), sulfonating for 2 hours, filtering to obtain filter residue, fully cleaning the filter residue with clear water until the pH value of the cleaned water is reached, and drying to obtain a finished product, wherein the mixed acid is prepared from the following components in parts by weight: 85 parts of 95% sulfuric acid, 7 parts of 70% periodic acid and 1 part of phosphotungstic acid.
Specifically, in the step (2), the frequency of the ultrasonic wave during the ultrasonic treatment is 32 kHz.
Specifically, the temperature of the drying treatment was 85 ℃ and the time of the drying treatment was 2 hours.
Example 2
A preparation method of a solid acid catalyst for preparing methylal comprises the following operation steps:
(1) putting the activated carbon into an environment with the temperature of 290 ℃, carbonizing the activated carbon at a constant temperature for 2.5 hours, and crushing the carbonized activated carbon into 190 meshes;
(2) adding an additive with the weight 0.09 times that of the powder prepared in the step (1), uniformly mixing, and performing ultrasonic treatment for 28min, wherein the additive is prepared from the following components in parts by weight: 5 parts of tetraheptyl ammonium iodide and 8 parts of behenamide;
(3) adding an acidic mixed solution with the weight 1.2 times that of the mixture prepared in the step (2), sulfonating for 2.5 hours, filtering to obtain filter residue, fully cleaning the filter residue with clear water until the pH value of the cleaned water is reached, and drying to obtain a finished product, wherein the mixed acid is prepared from the following components in parts by weight: 90 parts of 95% sulfuric acid, 9 parts of 70% periodic acid and 2 parts of phosphotungstic acid.
Specifically, in the step (2), the frequency of the ultrasonic wave during the ultrasonic treatment is 34 kHz.
Specifically, the temperature of the drying treatment was 88 ℃ and the time of the drying treatment was 2.5 hours.
Example 3
A preparation method of a solid acid catalyst for preparing methylal comprises the following operation steps:
(1) putting the activated carbon into an environment with the temperature of 300 ℃, carbonizing the activated carbon for 3 hours at a constant temperature, and crushing the carbonized activated carbon into 200 meshes;
(2) adding an additive with the weight of 0.1 time of that of the powder prepared in the step (1), uniformly mixing, and carrying out ultrasonic treatment for 25-30min, wherein the additive is prepared from the following components in parts by weight: 6 parts of tetraheptyl ammonium iodide and 10 parts of behenamide;
(3) adding an acidic mixed solution with the weight 1.3 times that of the mixture prepared in the step (2), sulfonating for 3 hours, filtering to obtain filter residue, fully cleaning the filter residue with clear water until the pH value of the cleaned water is reached, and drying to obtain a finished product, wherein the mixed acid is prepared from the following components in parts by weight: 92 parts of 95% sulfuric acid, 10 parts of 70% periodic acid and 3 parts of phosphotungstic acid.
Specifically, in the step (2), the frequency of the ultrasonic wave during the ultrasonic treatment is 36 kHz.
Specifically, the temperature of the drying treatment was 90 ℃ and the time of the drying treatment was 3 hours.
Comparative example 1
Step (2) was carried out in exactly the same manner as in example 1 except that no additive was added.
Comparative example 2
The mixed acid in the step (3) does not contain periodic acid and phosphotungstic acid, and the rest of the operation steps are completely the same as those in the example 2.
The solid acid catalysts obtained in the respective methods of examples and comparative examples were used for industrial catalysis of methanol to methylal, and the conversion of methanol in the reaction was measured, and the experimental results are shown in table 1:
TABLE 1 solid acid catalyst catalytic Activity
| Item | Methanol conversion after 2 months% | Methanol conversion after 4 months% | Methanol conversion after 2 months% |
| Example 1 | 98.6 | 96.7 | 94.1 |
| Comparative example 1 | 92.5 | 86.8 | 72.5 |
| Example 2 | 98.8 | 97.0 | 95.8 |
| Comparative example 2 | 90.1 | 82.1 | 70.1 |
| Example 3 | 99.0 | 97.6 | 96.9 |
| Prior Art | 89.9 | 78.2 | 66.1 |
As shown in Table 1, the solid acid catalyst prepared by the invention has long service life and stable activity.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.
Claims (3)
1. A preparation method of a solid acid catalyst for preparing methylal is characterized by comprising the following operation steps:
(1) putting the activated carbon into an environment of 280-300 ℃, carbonizing for 2-3 hours at constant temperature, and crushing to 200 meshes;
(2) adding an additive with the weight of 0.08-0.1 time of that of the powder prepared in the step (1), uniformly mixing, and carrying out ultrasonic treatment for 25-30min, wherein the additive is prepared from the following components in parts by weight: 3-6 parts of tetraheptyl ammonium iodide and 7-10 parts of behenamide;
(3) adding an acidic mixed solution with the weight 1.1-1.3 times that of the mixture prepared in the step (2), sulfonating for 2-3 hours, filtering to obtain filter residue, fully cleaning the filter residue with clear water, and drying to obtain a finished product, wherein the mixed acid is prepared from the following components in parts by weight: 85-92 parts of 95% sulfuric acid, 7-10 parts of 70% periodic acid and 1-3 parts of phosphotungstic acid.
2. The process for producing a solid acid catalyst for methylal production as claimed in claim 1, wherein in the step (2), the frequency of the ultrasonic wave in the ultrasonic treatment is 32 to 36 kHz.
3. The process for producing a solid acid catalyst for methylal production according to claim 1, wherein in the step (3), the temperature of the drying treatment is 85 to 90 ℃ and the time of the drying treatment is 2 to 3 hours.
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| CN103084187B (en) * | 2012-12-17 | 2015-07-01 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103691484B (en) * | 2013-12-17 | 2016-09-28 | 中国科学院长春应用化学研究所 | A kind of preparation method of solid acid catalyst, its preparation method and double olefin compound |
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