CN107876100A - A kind of preparation method for preparing dimethoxym ethane solid acid catalyst - Google Patents
A kind of preparation method for preparing dimethoxym ethane solid acid catalyst Download PDFInfo
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- CN107876100A CN107876100A CN201710997497.2A CN201710997497A CN107876100A CN 107876100 A CN107876100 A CN 107876100A CN 201710997497 A CN201710997497 A CN 201710997497A CN 107876100 A CN107876100 A CN 107876100A
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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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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The present invention discloses a kind of preparation method for preparing dimethoxym ethane solid acid catalyst, including following operating procedure：（1）In 280 300 DEG C of the environment that activated carbon is put into, constant temperature carbonization treatment is crushed to 180 200 mesh after 23 hours；（2）To step（1）0.08 0.1 times of heavy additives of its weight are added in obtained powder, after being well mixed, using being ultrasonically treated 25 30min；（3）To step（2）1.1 1.3 times of heavy acid mixed solutions of its weight are added in obtained mixture, after sulfonation handles 23 hours, filter to obtain filter residue, after filter residue is fully cleaned with clear water, until after cleaning after the pH of water, after drying process, finished product.The present invention provides the preparation method of solid acid catalyst, can effectively reduce the preparation cost of solid acid catalyst, and obtained solid acid catalyst, and catalytic activity is high, and property is stable, service life length.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of system for preparing dimethoxym ethane solid acid catalyst
Preparation Method.
Background technology
Dimethoxym ethane is one of most important downstream product of methanol, is used mainly as organic solvent, and Recent study is found
Dimethoxym ethane is remarkably improved the octane number of methanol gasoline as the additive of methanol gasoline, improves its low-temperature startup performance, and
The extensive use in methanol gasoline.The prior synthesizing method of dimethoxym ethane is using methanol and formalin as raw material, is urged in acidity
The lower synthesis of agent effect.Due to there is substantial amounts of water in the method, therefore, reaction conversion ratio is relatively low in course of reaction, and first contracts
Aldehyde can form azeotropic mixture with first alcohol and water, cause separation, purification difficult, power consumption and waste liquid discharging amount are larger.Reaction distillation method is
A kind of new dimethoxym ethane industrial making method developed, the method use solid acid catalyst, are the contractings of product first the advantages of the technique
The purity of aldehyde is high, and waste water growing amount is few etc., and has turned into the key industry production method of synthesizing dimethoxym ethane.But such a method
Defect is it is also obvious that the price of solid acid catalyst is higher, and the effective active time is short.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention provides a kind of preparation side for preparing dimethoxym ethane solid acid catalyst
Method.
The present invention is achieved by the following technical solutions.
A kind of preparation method for preparing dimethoxym ethane solid acid catalyst, including following operating procedure：
（1）In 280-300 DEG C of the environment that activated carbon is put into, after constant temperature carbonization treatment 2-3 hours, 180-200 mesh is crushed to；
（2）To step（1）The additive that 0.08-0.1 times of its weight weighs is added in obtained powder, after being well mixed, using super
Sonication 25-30min, wherein additive are made up of the component of following parts by weight：4 heptyl iodide 3-6 parts, two lauramides
7-10 parts；
（3）To step（2）The acid mixed solution that 1.1-1.3 times of its weight weighs is added in obtained mixture, sulfonation processing 2-3 is small
Shi Hou, filter residue is filtered to obtain, after filter residue is fully cleaned with clear water, until after drying process, being made into after the pH of water after cleaning
Product, wherein mixed acid are made up of the component of following parts by weight：Mass fraction is 95% sulfuric acid 85-92 parts, mass fraction is 70% high
Acid iodide 7-10 parts, phosphotungstic acid 1-3 parts.
Specifically, above-mentioned steps（2）In, the frequency of ultrasonic wave is 32-36kHz during supersound process.
Specifically, the temperature of drying process is 85-90 DEG C, and the time of drying process is 2-3 hours.
Technical scheme more than, the beneficial effects of the invention are as follows：
The present invention provides the preparation method of solid acid catalyst, can effectively reduce the preparation cost of solid acid catalyst, and
Obtained solid acid catalyst, catalytic activity is high, and property is stable, service life length.Wherein, it is originally busy to be used as original from activated carbon
Material, after high-temperature process, carbon atom therein is unformed state, can effectively lift the ratio surface of solid acid catalyst
Product, activity and stability；After 4 heptyl iodide, two lauramides synergy, the hydrophobicity of solid acid catalyst can be lifted
Can, and then the effective stability and service life for improving solid acid catalyst；, can after periodic acid, phosphotungstic acid synergy
The effect of effective lifting sulfonating reaction so that the sulfonic group in sulfuric acid is connected on polycyclic aromatic hydrocarbon carbon structure as far as possible, is carried
Rise the stability of connection.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, following examples are carried out to the present invention
It is further described.It should be appreciated that specific embodiment party example described herein is not used to limit only to explain the present invention
The fixed present invention.
Embodiment 1
A kind of preparation method for preparing dimethoxym ethane solid acid catalyst, including following operating procedure：
（1）In 280 DEG C of the environment that activated carbon is put into, constant temperature carbonization treatment is crushed to 180 mesh after 2 hours；
（2）To step（1）0.08 times of heavy additive of its weight is added in obtained powder, after being well mixed, at ultrasound
25min is managed, wherein additive is made up of the component of following parts by weight：3 parts of 4 heptyl iodide, 7 parts of two lauramide；
（3）To step（2）1.1 times of heavy acid mixed solutions of its weight are added in obtained mixture, after sulfonation is handled 2 hours,
Filter residue is filtered to obtain, after filter residue is fully cleaned with clear water, until after cleaning after the pH of water, after drying process, finished product, wherein
Mixed acid is made up of the component of following parts by weight：Mass fraction is 85 parts of 95% sulfuric acid, mass fraction is 7 parts of 70% periodic acid, phosphorus
1 part of wolframic acid.
Specifically, above-mentioned steps（2）In, the frequency of ultrasonic wave is 32kHz during supersound process.
Specifically, the temperature of drying process is 85 DEG C, and the time of drying process is 2 hours.
Embodiment 2
A kind of preparation method for preparing dimethoxym ethane solid acid catalyst, including following operating procedure：
（1）In 290 DEG C of the environment that activated carbon is put into, constant temperature carbonization treatment is crushed to 190 mesh after 2.5 hours；
（2）To step（1）0.09 times of heavy additive of its weight is added in obtained powder, after being well mixed, at ultrasound
28min is managed, wherein additive is made up of the component of following parts by weight：5 parts of 4 heptyl iodide, 8 parts of two lauramide；
（3）To step（2）1.2 times of heavy acid mixed solutions of its weight are added in obtained mixture, sulfonation is handled 2.5 hours
Afterwards, filter residue is filtered to obtain, after filter residue is fully cleaned with clear water, until after cleaning after the pH of water, after drying process, finished product,
Wherein mixed acid is made up of the component of following parts by weight：Mass fraction is 90 parts of 95% sulfuric acid, mass fraction is 70% periodic acid 9
Part, 2 parts of phosphotungstic acid.
Specifically, above-mentioned steps（2）In, the frequency of ultrasonic wave is 34kHz during supersound process.
Specifically, the temperature of drying process is 88 DEG C, and the time of drying process is 2.5 hours.
Embodiment 3
A kind of preparation method for preparing dimethoxym ethane solid acid catalyst, including following operating procedure：
（1）In 300 DEG C of the environment that activated carbon is put into, constant temperature carbonization treatment is crushed to 200 mesh after 3 hours；
（2）To step（1）0.1 times of heavy additive of its weight is added in obtained powder, after being well mixed, using supersound process
25-30min, wherein additive are made up of the component of following parts by weight：6 parts of 4 heptyl iodide, 10 parts of two lauramide；
（3）To step（2）1.3 times of heavy acid mixed solutions of its weight are added in obtained mixture, after sulfonation is handled 3 hours,
Filter residue is filtered to obtain, after filter residue is fully cleaned with clear water, until after cleaning after the pH of water, after drying process, finished product, wherein
Mixed acid is made up of the component of following parts by weight：Mass fraction is 92 parts of 95% sulfuric acid, mass fraction is 10 parts of 70% periodic acid, phosphorus
3 parts of wolframic acid.
Specifically, above-mentioned steps（2）In, the frequency of ultrasonic wave is 36kHz during supersound process.
Specifically, the temperature of drying process is 90 DEG C, and the time of drying process is 3 hours.
Comparative example 1
Step（2）Additive is not added, remaining operating procedure is identical with embodiment 1.
Comparative example 2
Step（3）Mixed acid in do not contain periodic acid, phosphotungstic acid, remaining operating procedure is identical with embodiment 2.
Solid acid catalyst is made with the method for each embodiment and comparative example respectively, then uses it for Industrial Catalysis methanol
The reaction of dimethoxym ethane is generated, measures the conversion ratio of methanol in reaction, experimental result is as shown in table 1：
The solid acid catalyst catalytic activity of table 1
| Project | Methanol conversion after 2 months, % | Methanol conversion after 4 months, % | Methanol conversion after 2 months, % |
| Embodiment 1 | 98.6 | 96.7 | 94.1 |
| Comparative example 1 | 92.5 | 86.8 | 72.5 |
| Embodiment 2 | 98.8 | 97.0 | 95.8 |
| Comparative example 2 | 90.1 | 82.1 | 70.1 |
| Embodiment 3 | 99.0 | 97.6 | 96.9 |
| Prior art | 89.9 | 78.2 | 66.1 |
As shown in Table 1, solid acid catalyst produced by the present invention, service life length are activity stabilized.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the technology of invention
Scheme is modified or equivalent substitution, and without departing from the scope of technical solution of the present invention, it all should cover the power in the present invention
In sharp claimed range.
Claims (3)
1. a kind of preparation method for preparing dimethoxym ethane solid acid catalyst, it is characterised in that including following operating procedure：
（1）In 280-300 DEG C of the environment that activated carbon is put into, after constant temperature carbonization treatment 2-3 hours, 180-200 mesh is crushed to；
（2）To step（1）The additive that 0.08-0.1 times of its weight weighs is added in obtained powder, after being well mixed, using super
Sonication 25-30min, wherein additive are made up of the component of following parts by weight：4 heptyl iodide 3-6 parts, two lauramides
7-10 parts；
（3）To step（2）The acid mixed solution that 1.1-1.3 times of its weight weighs is added in obtained mixture, sulfonation processing 2-3 is small
Shi Hou, filter residue is filtered to obtain, after filter residue is fully cleaned with clear water, until after drying process, being made into after the pH of water after cleaning
Product, wherein mixed acid are made up of the component of following parts by weight：Mass fraction is 95% sulfuric acid 85-92 parts, mass fraction is 70% high
Acid iodide 7-10 parts, phosphotungstic acid 1-3 parts.
2. according to a kind of preparation method for preparing dimethoxym ethane solid acid catalyst described in claim 1, it is characterised in that
Above-mentioned steps（2）In, the frequency of ultrasonic wave is 32-36kHz during supersound process.
3. according to a kind of preparation method for preparing dimethoxym ethane solid acid catalyst described in claim 1, it is characterised in that
Above-mentioned steps（3）In, the temperature of drying process is 85-90 DEG C, and the time of drying process is 2-3 hours.
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| CN201710997497.2A CN107876100B (en) | 2017-10-24 | 2017-10-24 | Preparation method of solid acid catalyst for preparing methylal |
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| CN201710997497.2A CN107876100B (en) | 2017-10-24 | 2017-10-24 | Preparation method of solid acid catalyst for preparing methylal |
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| CN107876100B CN107876100B (en) | 2020-07-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304030A (en) * | 2011-05-24 | 2012-01-04 | 安徽省绩溪三明精细化工有限公司 | Method for preparing dimethoxymethane in presence of active carbon immobilized acid catalyst |
| CN103084187A (en) * | 2012-12-17 | 2013-05-08 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103691484A (en) * | 2013-12-17 | 2014-04-02 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
-
2017
- 2017-10-24 CN CN201710997497.2A patent/CN107876100B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304030A (en) * | 2011-05-24 | 2012-01-04 | 安徽省绩溪三明精细化工有限公司 | Method for preparing dimethoxymethane in presence of active carbon immobilized acid catalyst |
| CN103084187A (en) * | 2012-12-17 | 2013-05-08 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103691484A (en) * | 2013-12-17 | 2014-04-02 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
Non-Patent Citations (4)
| Title |
|---|
| HEESOO KIM ET AL: ""Preparation, characterization, and catalytic activity of H5PMo10V2O40 immobilized on nitrogen-containing mesoporous carbon (PMo10V2/N-MC) for selective conversion of methanol to dimethoxymethane"", 《KOREAN J. CHEM. ENG.》 * |
| 张敏等: "《杂多酸催化精细有机合成反应研究》", 31 October 2008, 吉林大学出版社 * |
| 杨颖: "《碳纳米管的结构、性能、合成及其应用》", 31 August 2013, 黑龙江大学出版社 * |
| 董建勇等: "《天然药物化学》", 31 January 2011, 浙江大学出版社 * |
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