CN104628601A - Preparation method of efficient environmental-friendly aniline acetonitrile - Google Patents
Preparation method of efficient environmental-friendly aniline acetonitrile Download PDFInfo
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- CN104628601A CN104628601A CN201510048553.9A CN201510048553A CN104628601A CN 104628601 A CN104628601 A CN 104628601A CN 201510048553 A CN201510048553 A CN 201510048553A CN 104628601 A CN104628601 A CN 104628601A
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Abstract
The invention relates to a preparation method of aniline acetonitrile. The preparation method comprises the following steps: carrying out a condensation reaction on aniline and hydroxyl acetonitrile, wherein the molar ratio of hydroxyl acetonitrile and aniline is 1:(1.1-2.0), and the mass concentration of hydroxyl acetonitrile is not lower than 50%; pre-adjusting the pH to 4.0-7.0 by using a sodium hydroxide before reaction, wherein the reaction temperature of the condensation reaction is 50-100 DEG C and the reaction time is 1-3 hours; and after the condensation reaction, cooling to 15-40 minutes and crystallizing, and after crystallization, centrifugalizing to obtain aniline acetonitrile. According to the method provided by the invention, the yield and purity of aniline acetonitrile can be effectively improved, and the industrial cost can be effectively lowered; moreover, as the process is improved, generation of waste water in the preparation process can be reduced, and the generated waste water is close to neutral, so that the sewage treatment cost is lowered.
Description
Technical field
The present invention relates to a kind of preparation method of aniline-acetonitrile.
Background technology
Aniline-acetonitrile product, it is indigo to be mainly used in synthetic dyestuff, also can be used for other organic synthesis raw materials.Existing aniline-acetonitrile preparation method is more, current normally used method is for raw material condensation reaction preparation with aniline and hydroxyacetonitrile, this reaction belongs to rapid reaction early stage, later stage belongs to middle slow reaction, therefore, two step of reaction are also often adopted to carry out the carrying out of different temperature of reaction accelerated reactions aborning.Disclosed in patent CN102627581A aniline-acetonitrile preparation method in first to control temperature of reaction be 70 ~ 90 DEG C of reactions 0.5 ~ 3 hour, then raised temperature to 90 ~ 110 DEG C reaction 1 ~ 6 hour.
In existing preparation technology, all have employed compared to aniline, add the method preparation of the hydroxyacetonitrile of more amount of substances, the weight ratio as hydroxyacetonitrile in patent CN102627581A and aniline is (1.2 ~ 1.5): 1, is scaled mol ratio and is about (1.96 ~ 2.45): 1; In patent CN101613306A, the weight ratio of hydroxyacetonitrile and aniline is (400 ~ 450): (600 ~ 700), is scaled mol ratio and is about (7 ~ 7.9): (6.45 ~ 7.52).And by the optimization to proportioning raw materials and reaction conditions, yield and the purity of aniline-acetonitrile finished product are increased substantially, aniline-acetonitrile purity prepared by patent CN102627581A is greater than 97%, and yield is greater than 99.5%, the optimal standards prepared of closing chemical product.
Summary of the invention
The object of the present invention is to provide a kind of technique simpler and purity and yield higher, and the preparation method of the aniline-acetonitrile of energy-conserving and environment-protective more.
In order to realize foregoing invention object, the present invention's technical scheme used comprises:
A preparation method for high-efficiency environment friendly aniline-acetonitrile, it is prepared by aniline and hydroxyacetonitrile generation condensation reaction, and the mol ratio of described hydroxyacetonitrile and aniline is 1: (1.1 ~ 2.0); The mass concentration of described hydroxyacetonitrile is not less than 50%, and uses presetting pH to 4.0 ~ 7.0 of sodium hydroxide before the reaction; The temperature of reaction of above-mentioned condensation reaction is 50 ~ 100 DEG C, and the reaction times is 1 ~ 3 hour; 15 ~ 40 DEG C of crystallizations are cooled to, centrifugal acquisition aniline-acetonitrile after crystallization completely after described condensation reaction completes.
Further, the mass concentration of hydroxyacetonitrile described in preparation method of the present invention is 60 ~ 80%.
Further, presetting pH to 6.0 ~ 7.0 of sodium hydroxide are used in preparation method of the present invention before the reaction.
Further, the mol ratio of hydroxyacetonitrile and aniline described in preparation method of the present invention is 1: (1.1 ~ 1.3).
Further, described in preparation method of the present invention, aniline is preheated to 50 ~ 100 DEG C before the reaction.
Further, described in preparation method of the present invention, hydroxyacetonitrile is preheated to 50 ~ 100 DEG C before the reaction.
Further, hydroxyacetonitrile described in preparation method of the present invention and aniline import reaction kettle for reaction after fully being mixed by external mixing tank.
Described hydroxyacetonitrile of the present invention can be commercially available hydroxyacetonitrile, and synthesis technique includes but not limited to iS-One method or edible vegetable oil cracking process.
Aniline of the present invention can be commercially available aniline, and production technique includes but not limited to iron powder reducing method or hydrogenating reduction method.
Sodium hydroxide of the present invention can be commercially available sodium hydroxide; can be that sodium hydrate particle also can for sodium hydroxide solution; its effect is mainly and regulates pH; therefore without the need to specifically limiting its concentration, but sodium hydrate particle or high-concentration sodium hydroxide solution is used to be useful for the volume reducing reaction system.
Beneficial effect of the present invention is:
By adjusting the feed ratio of hydroxyacetonitrile and aniline, adopting the method for the amount of substance increasing aniline, improve purity and the yield of finished product aniline-acetonitrile.Due to the change of above-mentioned feed ratio, make technique of the present invention can complete reaction under the condition of pH 4 ~ 7, preferred adjustment aniline is (1.1 ~ 1.3) with the amount of substance ratio of hydroxyacetonitrile: 1, regulate pH to 6.0 ~ 7.0, under this condition, trade effluent after synthesis without regulating pH again, directly can carry out subsequent disposal.
The present invention adopts the hydroxyacetonitrile of high density to participate in condensation reaction, a large amount of heat release when hydroxyacetonitrile mixes with aniline, the mixing rate of the two can be accelerated after increase mixing tank, the process of condensation reaction can be accelerated, simplify the operation step, react 1 ~ 3 hour at 50 ~ 100 DEG C, can make to react completely.Meanwhile, owing to improve the original concentration of hydroxyacetonitrile, decrease the content of water in reaction system, thus reduce generation and the discharge of trade effluent further, as preferred scheme, the mass concentration of hydroxyacetonitrile is 60% ~ 80%.
The present invention, by carrying out thermal pretreatment to aniline and hydroxyacetonitrile, can add the carrying out of fast response further.Meanwhile, release a large amount of heats when reacting for avoiding the two and make reactor temperature too high, entering again in reactor after making the two fully be mixed by external mixing tank and react, temperature control cost can be reduced and reduce potential safety hazard.
By method of the present invention, effectively can improve yield and the purity of aniline-acetonitrile, reduce industrial cost; Simultaneously due to the improvement to technique, the generation of waste water in preparation process can be reduced, and the waste water produced is close to neutral, reduces the cost of sewage disposal.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is specifically addressed.
Various embodiments of the present invention all use mixing tank to be mixed with aniline by hydroxyacetonitrile, and the two is mixed with the generation being beneficial to reaction fully.Consider exothermic heat of reaction simultaneously; for improving the security of reaction; adopt the mode of external mixing tank; but there is not the impact of essence to the enforcement of technical solution of the present invention in the model of the mixing tank of the modes of emplacement of mixing tank or use; therefore being only the difference of hybrid mode, also should be regard the technical scheme identical with the present invention as and be subject to protection of the present invention.Alternatively, the operable mixing tank of the present invention includes but not limited to: SV type static mixer, line mixer M394223, lining tetrafluoro mixing tank or line mixer GJH.
Embodiment 1
The aniline 102.54g(1.1mol that mass concentration is 99.9% is added in the four-hole bottle of 500mL) be warming up to 50 DEG C; The hydroxyacetonitrile 114.1g(1mol that mass concentration is 50% is added in the four-hole bottle of 250mL), adjust pH to 4 with sodium hydroxide, by SV type static mixer the hydroxyacetonitrile that pH is 4 brought into and added in the four-hole bottle of aniline, with aniline circulating reaction 3h.
DEG C crystallization of reacted feed liquid circulating water cooling to 15 ~ 40, after crystallization terminates, obtain aniline-acetonitrile finished product 134.1g, purity 98.1%, yield 99.54% by centrifugal; Mother liquid recycle.
Embodiment 2 ~ 6 pH value is on the impact of reaction
Embodiment 2 ~ 6 is basically identical with the working method of embodiment 1, and its difference is to regulate the pH of hydroxyacetonitrile and the feed ratio of aniline and hydroxyacetonitrile, specifically as shown in table 1, have detected purity and yield that reaction terminates rear target product aniline-acetonitrile simultaneously.
Table 1 embodiment 2 ~ 6
Wherein the synthesis technique shown in embodiment 4 is the known synthesis technique of aniline-acetonitrile, namely under excessive hydroxyacetonitrile existent condition, the generation that alkaline environment catalyzes and synthesizes, and this synthesis condition can prepare the aniline-acetonitrile of higher concentration and high yield.If embodiment 3 only adjusts the ratio of the amount of substance of aniline and hydroxyacetonitrile under being presented at same pH condition, greatly reduce the speed of reaction, reduce yield and the purity of target product.Embodiment 1 ~ 4 pair of reaction conditions improves, by the feed ratio of feed change, change the pH of reaction simultaneously, facilitate the generation of reaction on the contrary, improve purity and the yield of target product, and the raising of this purity and yield is more difficult realization on the basis of existing technology, wherein the pH of most preferred adjustment hydroxyacetonitrile is 6 rear and aniline hybrid reactions.Under this condition, the purity and the yield that react generation aniline-acetonitrile are the highest.Meanwhile, during reaction and reacted wastewater pH all close to neutral, be conducive to the maintenance to equipment, and save technique and the cost of subsequent wastewater treatment.
The impact of embodiment 7 ~ 10 hydroxyacetonitrile concentration
Embodiment 7 ~ 11 is basically identical with the working method of embodiment 1, and its difference is pH and the concentration difference of hydroxyacetonitrile, specifically as shown in table 2, have detected purity and yield that reaction terminates rear target product aniline-acetonitrile simultaneously.
Table 2 embodiment 7 ~ 11
Pass through above-described embodiment, when other condition is identical, change the concentration of hydroxyacetonitrile, when functional quality concentration is not less than the hydroxyacetonitrile of 50%, the generation of reacting can be promoted, improve purity and the yield of end product, especially when the mass concentration of hydroxyacetonitrile is 60 ~ 80%, facilitation effect is comparatively obvious, and wherein most preferred mass concentration is 70%, and purity and the yield of the aniline-acetonitrile obtained are all the highest.When the hydroxyacetonitrile used mass concentration lower than 50% or higher than 80% time, reaction efficiency declines on the contrary, analyzing may be the too low contact reacts being unfavorable for reaction raw materials of concentration, is unfavorable for mixing causing during excessive concentration.Increase the concentration of hydroxyacetonitrile simultaneously, use the hydroxyacetonitrile of same amount of substance can reduce bringing into of moisture, decrease the generation of trade effluent, save the cost of water treatment.
Embodiment 12 ~ 16
Embodiment 12 ~ 16 is basically identical with the working method of embodiment 1, its difference be feeding intake of hydroxyacetonitrile and aniline and the reaction times different, specifically as shown in table 3, have detected the purity and the yield that react and terminate rear target product aniline-acetonitrile simultaneously.
Table 3 embodiment 12 ~ 16
Pass through above-described embodiment, increase feeding intake of aniline and can increase the speed of reaction, the aniline-acetonitrile of higher degree and yield is obtained within the shorter reaction times, especially compare for (1.1 ~ 1.3) at the amount of substance of aniline and hydroxyacetonitrile: when 1, reaction efficiency is higher, and wherein most preferred condition is aniline is 1.3: 1 with the amount of substance ratio of hydroxyacetonitrile.
Claims (7)
1. a preparation method for high-efficiency environment friendly aniline-acetonitrile, it is characterized in that it is prepared by aniline and hydroxyacetonitrile generation condensation reaction, the mol ratio of described hydroxyacetonitrile and aniline is 1: (1.1 ~ 2.0);
The mass concentration of described hydroxyacetonitrile is not less than 50%, and uses presetting pH to 4.0 ~ 7.0 of sodium hydroxide before the reaction;
The temperature of reaction of above-mentioned condensation reaction is 50 ~ 100 DEG C, and the reaction times is 1 ~ 3 hour;
15 ~ 40 DEG C of crystallizations are cooled to, centrifugal acquisition aniline-acetonitrile after crystallization completely after described condensation reaction completes.
2. the preparation method of a kind of high-efficiency environment friendly aniline-acetonitrile according to claim 1, is characterized in that the mass concentration of described hydroxyacetonitrile is 60 ~ 80%.
3. the preparation method of a kind of high-efficiency environment friendly aniline-acetonitrile according to claim 1, is characterized in that reacting presetting pH to 6.0 ~ 7.0 of front sodium hydroxide.
4. the preparation method of a kind of high-efficiency environment friendly aniline-acetonitrile according to claim 1, is characterized in that the mol ratio of described hydroxyacetonitrile and aniline is 1: (1.1 ~ 1.3).
5. the preparation method of a kind of high-efficiency environment friendly aniline-acetonitrile according to claim 1, is characterized in that described aniline is preheated to 50 ~ 100 DEG C before the reaction.
6. the preparation method of a kind of high-efficiency environment friendly aniline-acetonitrile according to claim 5, is characterized in that described hydroxyacetonitrile is preheated to 50 ~ 100 DEG C before the reaction.
7. the preparation method of a kind of high-efficiency environment friendly aniline-acetonitrile according to claim 1 ~ 6 any one, is characterized in that described hydroxyacetonitrile and aniline import reaction kettle for reaction after fully being mixed by external mixing tank.
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| CN201510048553.9A CN104628601A (en) | 2015-01-30 | 2015-01-30 | Preparation method of efficient environmental-friendly aniline acetonitrile |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033030A (en) * | 2017-05-10 | 2017-08-11 | 大连微凯化学有限公司 | A kind of production technology of continuous aniline-acetonitrile |
| CN109535028A (en) * | 2018-11-15 | 2019-03-29 | 天津科技大学 | The method that levitation melting crystallisation prepares aniline-acetonitrile sterling |
| CN114716348A (en) * | 2022-03-02 | 2022-07-08 | 重庆东庚工程技术有限公司 | Production method and production system of anilinoacetonitrile |
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| DE2748905A1 (en) * | 1977-11-02 | 1979-05-03 | Basf Ag | Phenyl-glycine-nitrile ortho-carboxylic acid prodn. - from anthranilic acid, formaldehyde and hydrogen cyanide, useful as indigo intermediate |
| CN101514170A (en) * | 2009-04-03 | 2009-08-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinonitrile |
| CN102627581A (en) * | 2012-03-20 | 2012-08-08 | 河北诚信有限责任公司 | Preparation technology of N-phenylglycinonitrile |
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2015
- 2015-01-30 CN CN201510048553.9A patent/CN104628601A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2748905A1 (en) * | 1977-11-02 | 1979-05-03 | Basf Ag | Phenyl-glycine-nitrile ortho-carboxylic acid prodn. - from anthranilic acid, formaldehyde and hydrogen cyanide, useful as indigo intermediate |
| CN101514170A (en) * | 2009-04-03 | 2009-08-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinonitrile |
| CN102627581A (en) * | 2012-03-20 | 2012-08-08 | 河北诚信有限责任公司 | Preparation technology of N-phenylglycinonitrile |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033030A (en) * | 2017-05-10 | 2017-08-11 | 大连微凯化学有限公司 | A kind of production technology of continuous aniline-acetonitrile |
| CN107033030B (en) * | 2017-05-10 | 2019-06-14 | 大连微凯化学有限公司 | A kind of production technology of continuous aniline-acetonitrile |
| CN109535028A (en) * | 2018-11-15 | 2019-03-29 | 天津科技大学 | The method that levitation melting crystallisation prepares aniline-acetonitrile sterling |
| CN109535028B (en) * | 2018-11-15 | 2021-10-08 | 天津科技大学 | Method for preparing pure anilinoacetonitrile by suspension melting crystallization method |
| CN114716348A (en) * | 2022-03-02 | 2022-07-08 | 重庆东庚工程技术有限公司 | Production method and production system of anilinoacetonitrile |
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Application publication date: 20150520 |