CN1137082C - Catalyst for synthesizing N,N-dimethylphenylamine - Google Patents
Catalyst for synthesizing N,N-dimethylphenylamine Download PDFInfo
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- CN1137082C CN1137082C CNB021290814A CN02129081A CN1137082C CN 1137082 C CN1137082 C CN 1137082C CN B021290814 A CNB021290814 A CN B021290814A CN 02129081 A CN02129081 A CN 02129081A CN 1137082 C CN1137082 C CN 1137082C
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- Prior art keywords
- accelerine
- reaction
- catalyzer
- aniline
- zro
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a catalyst for synthesizing N, N-dimethylaniline, which is characterized in that ZrO2 is loaded on gamma-Al2 O3 by an isometric immersion method or a collosol deposition method, wherein the content of the ZrO2 is from 1 wt% to 40 wt%. The catalyst for synthetizing N, N-dimethylaniline from aniline and methanol with a gas-phase method has the advantages of favorable catalytic performance, high conversion rate of aniline, high selectivity of N, N-dimethylaniline, relatively mild reaction conditions and easy industrial production.
Description
Affiliated technical field
The present invention relates to N, synthesizing of accelerine particularly used by ZrO
2To γ-Al
2O
3N, the method for preparing catalyst of accelerine and reaction process technology are synthesized in the solid acid catalyst catalysis of modification.
Background technology
N, accelerine are a kind of important chemical intermediates, are widely used in dyestuff, explosive, plastics and medicine etc. and manufacture industry, and its production status and people's productive life has very close getting in touch.Raising day by day along with development of science and technology and human consumption's demand, the synthetic double challenge that is faced with quality and quantity of various functional materialss, and as the N of important intermediate, the accelerine synthetic is broken through will provide the solid platform of a science and technology leap with economic growth.
N, the traditional synthesis of accelerine is divided into liquid phase method and vapor phase process, and liquid phase method is catalyzer with the mineral acid mainly, and this method is serious to equipment corrosion, the spent acid difficult treatment, contaminate environment, by product is many, and the energy consumption height.Vapor phase process mainly is catalyzer with the solid acid, and some solid acid catalysts and the effect thereof of existing document are listed in table 1.Though this method has been avoided the unfavorable factor of many liquid phase methods, but the catalytic performance of existing catalyzer can not be satisfactory as can be seen from Table 1, be difficult to make the transformation efficiency and the N of aniline, the selectivity of accelerine all reaches a higher level, so the development of effective catalyst has very important significance.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic N, the method for accelerine, it is to be applied in γ-Al
2O
3Last load has ZrO
2Catalyzer, this catalyzer is synthesized by vapor phase process by aniline and methyl alcohol, it shows extraordinary catalytic activity and very high N, the selectivity of accelerine, and reaction conditions gentleness are easy to industry's enlarging production.
The present invention is at γ-Al
2O
3Last load has the ZrO of 1%-40wt%
2And make catalyzer.
The present invention specifically comprises the steps: a γ-Al
2O
3Impregnated in ZrOCl
28H
24 hours (equi-volume impregnating) or γ-Al in the O solution
2O
3With ZrOCl
28H
2The colloidal sol that O solution made under boiling state in reflux distillation 24-96 hour (sol deposition method); By centrifugal or suction filtration solid is separated, placed the ammoniacal liquor of proper concn again, filter after a while, wash solid with water up to using AgNO
3Solution detects less than Cl
-, use absolute ethanol washing again three times, after in air, fully drying, 110 ℃ of oven dry 3 hours, 500 ℃ of roastings are 4 hours then.Three kinds of solution of corresponding dipping usefulness or colloidal sol obtain t-ZrO
2/ γ-Al
2O
3, h-ZrO
2/ γ-Al
2O
3And m-ZrO
2/ γ-Al
2O
3Catalyst series.
The present invention is to synthesizing N by aniline and methyl alcohol by vapor phase process, and accelerine has extraordinary catalytic performance, aniline transformation efficiency height, and N, the accelerine selectivity is good, and reaction conditions is gentle relatively, is easy to industrial production.
Substantive distinguishing features of the present invention and unusual effect can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
Embodiment
Embodiment 1
Weighing ZrOCl
28H
2O 13.1 grams are dissolved in the deionized water, add water to 700ml, and reflux keeps 103 ℃ of boilings, stop after 24 hours refluxing, and after cooling, add 45 gram γ-Al
2O
3, at room temperature stirred dipping 4 hours, join in the diluted ammoniacal liquor of about 50ml, pH=9.3 forms gel, and suction filtration is washed to no Cl
-(with the AgNO of 0.1M
3Solution detects), give a baby a bath on the third day after its birth time with dehydrated alcohol again, after fully drying in the air, 110 ℃ of oven dry 3 hours, 500 ℃ of roastings 4 hours promptly obtain 50 gram h-ZrO
2/ γ-Al
2O
3, ZrO wherein
2Content 10wt%.When catalyzer uses, compressing tablet, fragmentation, be screened into the 20-60 order.
Reaction conditions:
Continuous flow reactor of fixed bed is adopted in this reaction.300 ℃ of temperature of reaction, with methyl alcohol and aniline 2.5～3: 1 (ratio of amount of substance) charging, the liquid volume air speed is 0.5h
-1, reaction result sees Table 2. these catalyzer and makes aniline transformation efficiency and N, and the selectivity of accelerine has all reached very high level.
Embodiment 2
With the ZrOCl among the embodiment 1
28H
2The return time of O solution is increased to 96 hours, and other is with embodiment 1.Make the m-ZrO of 10wt%
2/ γ-Al
2O
3Catalyzer.Reaction conditions is with embodiment 1.Reaction result sees Table 2.
Embodiment 3
Weighing 13.1 gram ZrOCl
28H
2O is dissolved in the 135ml deionized water, adds 45 gram γ-Al
2O
3Dipping is 4 hours under the room temperature, and all the other steps are with embodiment 1.Make the t-ZrO of 10wt%
2/ γ-Al
2O
3Catalyzer.Reaction conditions is with embodiment 1.Reaction result sees Table 2.
Embodiment 4
With the ZrOCl among the embodiment 1
28H
2O changes 26.2 grams into, adds γ-Al
2O
3Amount change into 40 the gram, other makes the h-ZrO of 20wt% with embodiment 1
2/ γ-Al
2O
3Reaction conditions is with embodiment 1.Reaction result sees Table 2.
Embodiment 5
With the ZrOCl among the embodiment 1
28H
2O changes 39.3 grams into, adds γ-Al
2O
3Amount change into 35 the gram, other makes the h-ZrO of 30wt% with embodiment 1
2/ γ-Al
2O
3Reaction conditions is with embodiment 1.Reaction result sees Table 2.
Embodiment 6
Catalyzer is with embodiment 1, and temperature of reaction is 280 ℃, and all the other conditions are with embodiment 1, and reaction result sees Table 2.Have table 2 as seen, 280 ℃ this with relatively low temperature under, aniline transformation efficiency and N, the selectivity of accelerine is still very high.
Embodiment 7
Catalyzer is with embodiment 1, and the liquid volume air speed is 0.8h in the reaction
-1, all the other conditions are with embodiment 1, and reaction result sees Table 2.By table 2 as seen, under higher air speed, aniline transformation efficiency and N, the selectivity of accelerine is still very high, on industrial production, can enhance productivity.
Embodiment 8
Catalyzer is with embodiment 1, changes the raw material among the embodiment 1 into methyl alcohol and aniline 2.5: 1, and all the other conditions are all with embodiment 1.Reaction result sees Table 2.By table 2 as seen, under the lower situation of methanol usage, still can keep good reaction effect.
Embodiment 9
Catalyzer reacts as raw material with the reaction product among the embodiment 1 with embodiment 1, and reaction conditions is with embodiment 1.Reaction result sees Table 2.By table 2 as seen, through behind the second-stage reaction, aniline is transformed fully, and product almost is N entirely, accelerine.
Embodiment 10
Catalyzer is with embodiment 1, and temperature of reaction is 280 ℃, and all the other conditions are with embodiment 7.Reaction result sees Table 2.As seen under 280 ℃, reaction result is still satisfactory.Table 1. synthesizes N, the basic condition of the catalyzer of accelerine
Reaction result under table 2. different catalysts and the different condition
| Catalyzer | Temperature of reaction (℃) | Aniline transformation efficiency (%) | N, accelerine selectivity (%) |
| X type molecular sieve | 300 | 97 | 75 |
| γ-Al 2O 3 | 320 | 98.5 | 85.53 |
| AlPO 4-Al 2O 3 | 250 | 85.1 | 26.8 |
| Modification on Al 2O 3 | 280 | 99 | 92 |
| Sequence number | Aniline transformation efficiency (%) | N, accelerine selectivity (%) |
| Embodiment 1 | 99.81 | 94.22 |
| Embodiment 2 | 99.80 | 93.54 |
| Embodiment 3 | 99.81 | 93.46 |
| Embodiment 4 | 99.65 | 94.06 |
| Embodiment 5 | 99.59 | 93.27 |
| Embodiment 6 | 99.80 | 94.14 |
| Embodiment 7 | 99.80 | 92.80 |
| Embodiment 8 | 99.80 | 92.50 |
| Embodiment 9 | 100 | 97.44 |
| Embodiment 10 | 100 | 97.94 |
Claims (2)
1, a kind of γ-Al
2O
3Loaded catalyst is at synthetic N, and the application in the accelerine is characterized in that this catalyzer is at γ-Al
2O
3Last load has ZrO
2, ZrO wherein
2Content be: 1wt%-40%.
2, a kind of synthetic N, the method for accelerine is characterized in that it has used catalyzer as claimed in claim 1, reaction conditions is: adopt continuous flow reactor of fixed bed, 300 ℃ of temperature of reaction are 2.5-3 with methyl alcohol and aniline mass ratio: 1 charging, liquid volume air speed are 0.5h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021290814A CN1137082C (en) | 2002-09-03 | 2002-09-03 | Catalyst for synthesizing N,N-dimethylphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021290814A CN1137082C (en) | 2002-09-03 | 2002-09-03 | Catalyst for synthesizing N,N-dimethylphenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1395989A CN1395989A (en) | 2003-02-12 |
| CN1137082C true CN1137082C (en) | 2004-02-04 |
Family
ID=4746133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021290814A Expired - Fee Related CN1137082C (en) | 2002-09-03 | 2002-09-03 | Catalyst for synthesizing N,N-dimethylphenylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1137082C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393413C (en) * | 2006-05-19 | 2008-06-11 | 河北工业大学 | Method for preparing load-type zirconium oxide and its using method |
| CN103012159B (en) * | 2011-09-27 | 2014-06-11 | 北大方正集团有限公司 | Preparation method of N, N-diethyl aniline |
| CN102728367B (en) * | 2012-06-09 | 2014-10-08 | 浙江大学 | Method and catalyst for synthesizing N,N-dimethylaniline |
| CN105399637A (en) * | 2015-12-01 | 2016-03-16 | 南京师范大学 | Continuous preparation method of N,N-dimethylaniline |
-
2002
- 2002-09-03 CN CNB021290814A patent/CN1137082C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1395989A (en) | 2003-02-12 |
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