CN112028788A - Preparation method for continuously preparing tert-butyl hydrazine hydrochloride - Google Patents
Preparation method for continuously preparing tert-butyl hydrazine hydrochloride Download PDFInfo
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- CN112028788A CN112028788A CN202010942422.6A CN202010942422A CN112028788A CN 112028788 A CN112028788 A CN 112028788A CN 202010942422 A CN202010942422 A CN 202010942422A CN 112028788 A CN112028788 A CN 112028788A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/16—Hydrazine; Salts thereof
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Abstract
The invention discloses a method for continuously preparing tert-butyl hydrazine hydrochloride by using a microchannel reactor, which comprises the following steps: the first step is as follows: carrying out primary reaction and mixing on hydrazine hydrate with the mass concentration of 40-80% and hydrochloric acid with the concentration of 25-36% in the microchannel reactor to obtain a hydrazine hydrochloride solution; the second step is that: mixing the hydrazine hydrochloride solution and a tert-butyl alcohol solution in the microchannel reactor for later use; the third step: and carrying out secondary reaction on the mixed materials in the second step to obtain a product water solution, continuously concentrating the product water solution to a certain concentration, cooling, crystallizing, filtering and drying to obtain the tert-butyl hydrazine hydrochloride. The method improves the reaction rate and the utilization rate of raw materials, avoids the side reaction of producing the olefin compounds by dehydrating the tertiary butanol, has easy control of the reaction, short production period, less discharge of three wastes, high total yield of over 85 percent and high automation degree of the reaction process.
Description
Technical Field
The invention relates to a preparation method of tert-butyl hydrazine hydrochloride, in particular to a method for continuously preparing tert-butyl hydrazine hydrochloride by using a microchannel reactor.
Background
Tert-butyl hydrazine hydrochloride is an important pesticide intermediate, and can be used for synthesizing benzoyl hydrazine pesticide-such as food-inhibiting hydrazine, bishydrazide, methoxyfenozide and chromafenozide, and acaricide pyridaben. And can be used as raw material for synthesizing medicine and material.
In the prior art, a kettle type batch preparation method is generally adopted to produce tert-butyl hydrazine hydrochloride, hydrazine hydrate is acidified by hydrochloric acid, and then the hydrazine hydrate reacts with tert-butyl alcohol at high temperature, and the tert-butyl hydrazine hydrochloride is prepared by concentration and recrystallization. However, the yield of the method is low, and the main reason is that the tertiary butanol and hydrazine hydrate hydrochloride are not fully contacted in a tank reactor, the hydrochloric acid is too strong to cause dehydration reaction of the tertiary butanol, olefin byproducts are produced, and the byproducts are discharged into the air in the form of VOC in the reflux reaction process. The method has the defects of low raw material utilization rate, low product yield, high VOC emission and the like, and simultaneously, the kettle type reaction has low production efficiency and higher production cost.
Disclosure of Invention
In order to overcome the above-mentioned defects of the prior art, the present invention aims to provide a method for continuously preparing tert-butylhydrazine hydrochloride by using a microchannel reactor.
The method of the invention increases the operation safety, reduces the production cost, and overcomes the defects of high labor intensity, long production period, high three-waste discharge amount and the like in the traditional production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for continuously preparing tert-butyl hydrazine hydrochloride by using a microchannel reactor comprises the following steps:
the first step is as follows:
carrying out primary reaction and mixing on hydrazine hydrate with the mass concentration of 40-80% and hydrochloric acid with the concentration of 25-36% in the microchannel reactor to obtain a hydrazine hydrochloride solution;
the second step is that:
mixing the hydrazine hydrochloride solution and a tert-butyl alcohol solution in the microchannel reactor for later use;
the third step:
and carrying out secondary reaction on the mixed materials in the second step to obtain a product water solution, continuously concentrating the product water solution to a certain concentration, cooling, crystallizing, filtering and drying to obtain the tert-butyl hydrazine hydrochloride.
In a preferred embodiment of the invention, the crystallization mother liquor obtained after the third step of temperature reduction crystallization is recycled and reacted with hydrazine hydrate.
In a preferred embodiment of the invention, the molar ratio of hydrazine hydrate to hydrochloric acid in the first step is 1: 1 to 2.
In a preferred embodiment of the present invention, the reaction temperature in the first step is 40 to 70 ℃.
In a preferred embodiment of the present invention, the mixing temperature in the second step is 50 to 80 ℃.
In a preferred embodiment of the invention, the temperature in the secondary reaction is 70-100 ℃.
In a preferred embodiment of the present invention, the concentration in the third step is performed to a concentration of 50 to 75% by mass and a crystallization temperature of 0 to 10 ℃.
In a preferred embodiment of the invention, a plurality of mixing modules and a plurality of reaction modules are arranged in the microchannel reactor, a material mixing channel is arranged in each mixing module, and a reaction material channel is arranged in each reaction module; the inner diameter of the reaction material channel is 0.5-5 mm.
The invention has the beneficial effects that:
the invention takes hydrazine hydrate, tertiary butanol and hydrogen chloride as raw materials to prepare tertiary butyl hydrazine hydrochloride through continuous reaction in a microchannel reactor. The method has the advantages of improving the reaction rate and the utilization rate of raw materials, avoiding the side reaction of producing olefin compounds by dehydrating tert-butyl alcohol, easily controlling the reaction, short production period, less discharge of three wastes, high automation degree of the reaction process and being beneficial to realizing the automatic whole-process operation, and the total yield can reach more than 85 percent.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1
The embodiment provides a method for continuously synthesizing tert-butyl hydrazine hydrochloride by using a microchannel reactor, which is implemented by the following steps:
pumping 50% hydrazine hydrate solution with mass concentration into a first reaction zone of the microchannel reactor at a flow rate of 15ml/min, and simultaneously pumping 20% hydrochloric acid with mass concentration into the first reaction zone of the microchannel reactor at a flow rate of 3.7ml/min, wherein the temperature of the first reaction zone is set to 45 ℃, and the residence time of the hydrazine hydrate solution and the hydrochloric acid solution is 5.0 s.
Pumping the hydrazine hydrochloride solution obtained in the first reaction zone into a mixing zone of the microchannel reactor at the flow rate of 15 ml/min; preparing 75% aqueous solution of tert-butyl alcohol at a concentration of 18 ml/min; the flow rate was pumped into the mixing zone of the microchannel reactor, which was set at 55 ℃ for a residence time of 5 s. The mixed solution enters a second reaction zone of the microchannel reactor at the flow rate of 16.5ml/min, and the temperature of the second reaction zone is set to be 90 ℃.
And continuously distilling the reacted solution, concentrating until the mass concentration is 50%, allowing the solution to enter a crystallization standing kettle, standing and crystallizing at 5 ℃ for 2 hours, filtering, and vacuum-drying at 75 ℃ to obtain the tert-butylhydrazine hydrochloride with the purity of 98.7% (HPLC), wherein the hydrazine hydrate selectivity is 98.4% and the conversion rate is 95.3% in the reaction process.
Example 2
Pumping 70% hydrazine hydrate solution with mass concentration into a first reaction zone of the microchannel reactor at the flow rate of 10ml/min, and simultaneously pumping 30% hydrochloric acid with mass concentration into the first reaction zone of the microchannel reactor at the flow rate of 2.0ml/min, wherein the temperature of the first reaction zone is set at 50 ℃, and the residence time of the hydrazine hydrate solution and the hydrochloric acid solution is 4.0 s.
Pumping the hydrazine hydrochloride solution obtained in the first reaction zone into a mixing zone of the microchannel reactor at the flow rate of 11 ml/min; preparing 60% aqueous solution of tertiary butanol at a concentration of 24 ml/min; the flow rate was pumped into the mixing zone of the microchannel reactor, which was set at 55 ℃ for a residence time of 6 s. The mixed solution was fed into the second reaction zone of the microchannel reactor at a flow rate of 17.5ml/min, and the temperature of the second reaction zone was set to 85 ℃.
And continuously distilling the reacted solution, concentrating until the mass concentration is 60%, allowing the solution to enter a crystallization standing kettle, standing and crystallizing at 10 ℃ for 2 hours, filtering, and vacuum-drying at 75 ℃ to obtain the tert-butylhydrazine hydrochloride with the purity of 99.3% (HPLC), wherein the selectivity of hydrazine hydrate is 97.5% and the conversion rate is 97.5% in the reaction process.
Example 3
Pumping a hydrazine hydrate solution with the mass concentration of 80% into a first reaction zone of the microchannel reactor at the flow rate of 10ml/min, and simultaneously pumping hydrochloric acid with the mass concentration of 30% into the first reaction zone of the microchannel reactor at the flow rate of 1.4ml/min, wherein the temperature of the first reaction zone is set to be 45 ℃, and the residence time of the hydrazine hydrate solution and the hydrochloric acid solution is 5.0 s.
Pumping the hydrazine hydrochloride solution obtained in the first reaction zone into a mixing zone of the microchannel reactor at the flow rate of 11 ml/min; preparing 80% aqueous solution of tert-butyl alcohol at a concentration of 15.5 ml/min; the flow rate was pumped into the mixing zone of the microchannel reactor, which was set at a steady state temperature of 60 ℃ and a residence time of 5 s. The mixed solution enters a second reaction zone of the microchannel reactor at a flow rate of 26.5ml/min, and the temperature of the second reaction zone is set to be 90 ℃.
And continuously distilling the reacted solution, concentrating until the mass concentration is 55%, allowing the solution to enter a crystallization standing kettle, standing and crystallizing at 5 ℃ for 2 hours, filtering, and vacuum-drying at 75 ℃ to obtain the tert-butylhydrazine hydrochloride with the purity of 98.8% (HPLC), wherein the hydrazine hydrate selectivity is 99.5% and the conversion rate is 98.3% in the reaction process.
The product obtained in the above example is analyzed for content by High Pressure Liquid Chromatography (HPLC), and area comparison is performed with a standard sample with the tert-butylhydrazine hydrochloride content of 99.5% or more.
Comparative example 1 kettle batch preparation of Tert-butylhydrazine hydrochloride
In a 1000L glass lined reactor 219 kg of 46.5% (wt%) hydrazine hydrate were pumped in, the stirring was switched on and 300kg of 36% hydrochloric acid were pumped in and the temperature was raised to 80-95 ℃. 155kg of tertiary butanol is diluted by 155kg of water and then is dripped into a reaction kettle for 4 hours, after the dripping is finished, the temperature is raised for 4 hours, the solution after the reaction is continuously distilled and concentrated to 50 percent of mass concentration, the solution enters a crystallization standing kettle for 5 ℃, standing and crystallization are carried out for 2 hours, filtration and vacuum drying are carried out at 75 ℃ to obtain the tertiary butyl hydrazine hydrochloride with the purity of 98.9 percent (HPLC), the selectivity of hydrazine hydrate is 97.8 percent in the reaction process, and the conversion rate is 65.9 percent.
The product obtained in the comparative example is subjected to content analysis by using a High Pressure Liquid Chromatograph (HPLC), and area comparison is carried out by using a standard sample with the tert-butyl hydrazine hydrochloride content of more than 99.5%.
Claims (9)
1. A method for continuously preparing tert-butyl hydrazine hydrochloride by using a microchannel reactor is characterized by comprising the following steps:
the first step is as follows:
carrying out primary reaction and mixing on hydrazine hydrate with the mass concentration of 40-80% and hydrochloric acid with the concentration of 25-36% in the microchannel reactor to obtain a hydrazine hydrochloride solution;
the second step is that:
mixing the hydrazine hydrochloride solution and a tert-butyl alcohol solution in the microchannel reactor for later use;
the third step:
and carrying out secondary reaction on the mixed materials in the second step to obtain a product water solution, continuously concentrating the product water solution to a certain concentration, cooling, crystallizing, filtering and drying to obtain the tert-butyl hydrazine hydrochloride.
2. The method for continuously preparing tert-butylhydrazine hydrochloride by using the microchannel reactor as claimed in claim 1, wherein the crystallization mother liquor after the third step of temperature reduction crystallization is recycled and reacted with hydrazine hydrate.
3. The continuous process for preparing tert-butylhydrazine hydrochloride using a microchannel reactor as claimed in claim 1, wherein the molar ratio of hydrazine hydrate to hydrochloric acid in the first step is 1: 1 to 2.
4. The continuous process for preparing tert-butylhydrazine hydrochloride using a microchannel reactor as claimed in claim 1, wherein the reaction temperature in the first step is 40 to 70 ℃.
5. The continuous process for preparing tert-butylhydrazine hydrochloride using a microchannel reactor as claimed in claim 1, wherein the mixing temperature in the second step is 50 to 80 ℃.
6. The method for continuously preparing tert-butylhydrazine hydrochloride by using the microchannel reactor as claimed in claim 1, wherein the temperature of the secondary reaction is 70-100 ℃.
7. The method for continuously preparing tert-butylhydrazine hydrochloride by using the microchannel reactor as claimed in claim 1, wherein the concentration in the third step is to a mass concentration of 50 to 75% and the crystallization temperature is 0 to 10 ℃.
8. The method for continuously preparing tert-butyl hydrazine hydrochloride by using the microchannel reactor as claimed in claim 1, wherein a plurality of mixing modules and a plurality of reaction modules are arranged in the microchannel reactor, a material mixing channel is arranged in each mixing module, and a reaction material channel is arranged in each reaction module.
9. The method for continuously preparing tert-butylhydrazine hydrochloride by using the microchannel reactor as claimed in claim 1, wherein the inner diameter of the reaction material channel is 0.5-5 mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135838A (en) * | 2021-04-25 | 2021-07-20 | 济南同路医药科技发展有限公司 | Method for continuous flow synthesis of benserazide hydrochloride |
| CN114133339A (en) * | 2021-11-12 | 2022-03-04 | 东力（南通）化工有限公司 | Methyl hydrazine continuous flow microchannel alkylation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435600A (en) * | 1983-01-25 | 1984-03-06 | Japan Hydrazine Co., Inc. | Process for preparation of tertiary butyl hydrazine |
| CN106316879A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrazinobenzene in continuous micro-channel reactor |
| CN108569981A (en) * | 2018-06-07 | 2018-09-25 | 上海试四化学品有限公司 | A kind of preparation method of Tertiary butyl hydrazine hydrochloride |
| CN109574870A (en) * | 2018-12-25 | 2019-04-05 | 维思普新材料（苏州）有限公司 | A kind of continuous preparation method of hydrazides |
-
2020
- 2020-09-09 CN CN202010942422.6A patent/CN112028788A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435600A (en) * | 1983-01-25 | 1984-03-06 | Japan Hydrazine Co., Inc. | Process for preparation of tertiary butyl hydrazine |
| CN106316879A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrazinobenzene in continuous micro-channel reactor |
| CN108569981A (en) * | 2018-06-07 | 2018-09-25 | 上海试四化学品有限公司 | A kind of preparation method of Tertiary butyl hydrazine hydrochloride |
| CN109574870A (en) * | 2018-12-25 | 2019-04-05 | 维思普新材料（苏州）有限公司 | A kind of continuous preparation method of hydrazides |
Non-Patent Citations (3)
| Title |
|---|
| 吴迪 等: "微反应器技术及其研究进展", 《中国陶瓷工业》 * |
| 曹顺民 等: "叔丁基肼的合成", 《江苏化工》 * |
| 朱梅 等: "微通道反应器在合成工艺改进中的应用研究进展", 《合成化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135838A (en) * | 2021-04-25 | 2021-07-20 | 济南同路医药科技发展有限公司 | Method for continuous flow synthesis of benserazide hydrochloride |
| CN113135838B (en) * | 2021-04-25 | 2022-03-15 | 济南同路医药科技发展有限公司 | Method for continuous flow synthesis of benserazide hydrochloride |
| CN114133339A (en) * | 2021-11-12 | 2022-03-04 | 东力（南通）化工有限公司 | Methyl hydrazine continuous flow microchannel alkylation method |
| CN114195675A (en) * | 2021-11-12 | 2022-03-18 | 东力（南通）化工有限公司 | Method for preparing ethyl hydrazine by continuous flow of microreactor |
| CN114195675B (en) * | 2021-11-12 | 2023-02-28 | 东力（南通）化工有限公司 | Method for preparing ethyl hydrazine by continuous flow of microreactor |
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