CN114057602A - Preparation method for producing ethyl hydrazine by hydrazine hydrate method - Google Patents
Preparation method for producing ethyl hydrazine by hydrazine hydrate method Download PDFInfo
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- CN114057602A CN114057602A CN202010789412.3A CN202010789412A CN114057602A CN 114057602 A CN114057602 A CN 114057602A CN 202010789412 A CN202010789412 A CN 202010789412A CN 114057602 A CN114057602 A CN 114057602A
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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
Abstract
The invention discloses a preparation method for producing ethyl hydrazine by a hydrazine hydrate method, which is characterized in that under the protection of inert gas, hydrazine hydrochloride reacts with ethanol to obtain ethyl hydrazine hydrochloride, hydrazine hydrate dissociates the ethyl hydrazine hydrochloride, and the ethyl hydrazine is obtained by distillation and rectification processes. In the synthesis process, the selectivity of the catalyst is high, the purity of the product is higher than or equal to 99.0 percent, the side reaction is less, the yield can reach more than 90 percent, the energy consumption is low, the synthesis reaction pressure is reduced by 0.5-0.7Mpa, the internal circulation and continuous production are realized, the labor intensity is reduced, and the method has the advantages of energy conservation, environmental protection, safety, convenience and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method for producing ethyl hydrazine by a hydrazine hydrate method.
Background
Ethyl hydrazine is a basic raw material for synthesizing medicines and pesticides, is particularly used for synthesizing and developing new patents and medicines, and at present, some international famous pharmaceutical enterprises, such as German Merck, Bayer, Switzerland Nowa, bring the product into a purchase catalogue and seek manufacturers for the needs of developing new medicines. So far, domestic published documents report that no mature synthesis process of the product is found. For this reason, a relatively mature technical scheme is required for the synthesis of ethyl hydrazine.
Disclosure of Invention
The invention aims to provide a preparation method for producing ethyl hydrazine by a hydrazine hydrate method, which aims to solve the problem of immature synthesis process of the existing ethyl hydrazine in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method for producing ethyl hydrazine by a hydrazine hydrate method is characterized in that under the protection of inert gas, hydrazine hydrochloride reacts with ethanol to obtain ethyl hydrazine hydrochloride, hydrazine hydrate dissociates the ethyl hydrazine hydrochloride, and ethyl hydrazine is obtained by distillation and rectification processes.
Under the protection of inert gas, the preparation method comprises the following specific steps:
a. preparation of hydrazine hydrochloride: hydrazine hydrate is used as initial raw material, stirred in a salt-forming kettle, then hydrochloric acid with a certain proportion is dripped in, the temperature is controlled at 30-50 DEGoC, adjusting the pH value to 3-5, after the reaction is finished, heating to 70-80 ℃, and performing reduced pressure dehydration to prepare hydrazine hydrochloride;
b. preparation of ethyl hydrazine hydrochloride solution: transferring hydrazine hydrochloride into an alkylation reaction kettle, adding ethanol in a certain proportion, sealing the alkylation reaction kettle, heating to 90-120 ℃ for alkylation reaction, cooling to 45-55 ℃ after the reaction is finished, putting the reaction kettle into a distillation kettle, and distilling out the ethanol to prepare ethyl hydrazine hydrochloride solution;
c. preparation of a crude product: transferring the ethyl hydrazine hydrochloride solution into a dissociation kettle, adding hydrazine hydrate in a certain proportion for dissociation, sucking a mixture obtained by dissociation into a distillation kettle, and carrying out reduced pressure distillation to prepare a crude product and a kettle substrate hydrazine hydrochloride;
d. preparation of ethyl hydrazine: and transferring the crude product into a rectifying still, slowly heating to boil, collecting the 1, 1-diethylhydrazine and the 1, 2-diethylhydrazine evaporated at 60-65 ℃, continuously heating to 100-130 ℃, collecting the ethylhydrazine with the concentration of 42-44%, cooling after the rectification is finished, adding water into the collected ethylhydrazine to prepare an aqueous solution with the required concentration, and hermetically packaging to obtain the final product of the ethylhydrazine.
In the step a, the molar ratio of hydrazine hydrate to hydrochloric acid is 1: 1.01-1.10.
In the step a, the pressure of the reduced pressure dehydration is-0.09 to-0.1 Mpa.
In the step b, the ratio of the hydrazine hydrochloride to the ethanol is 1: 3-4.
In the step b, the pressure of the alkylation reaction kettle is 0.5-0.7Mpa, and the reaction lasts 2-3 hours.
In the step c, the ratio of the ethyl hydrazine hydrochloride to the hydrazine hydrate is 1: 1.1-1.5.
In step c, the still substrate hydrazine hydrochloride is transferred to an alkylation process, i.e., transferred to step b.
In the step d, the temperature is cooled to 40-45 ℃ to obtain a kettle substrate hydrazine hydrate, and the kettle substrate hydrazine hydrate is sucked into the free kettle in the step c.
Compared with the prior art, the invention has the beneficial effects that:
1. in the synthesis process, the selectivity of the catalyst is high, the purity of the product is higher than or equal to 99.0 percent, the side reaction is less, the yield can reach more than 90 percent, the energy consumption is low, the pressure of the synthesis reaction is reduced by 0.5-0.7Mpa, the internal circulation and the continuous production are realized, and the labor intensity is reduced.
2. Under the protection of inert gas, hydrazine hydrochloride reacts with ethanol to obtain ethyl hydrazine hydrochloride, hydrazine hydrate dissociates the ethyl hydrazine hydrochloride, and ethyl hydrazine is obtained through distillation and rectification processes, so that the method has the advantages of energy conservation, environmental protection, safety, convenience and the like; the waste water of unit product is reduced from 12 tons to 2 tons, the waste gas is reduced from 0.012 ton to 0.002 ton, and the waste residue is reduced from 0.3 ton to 0 ton.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
referring to FIG. 1, under the protection of inert gas
Step one, preparing hydrazine hydrochloride:
firstly putting 480 parts by mass of hydrazine hydrate with the concentration of 75% into a salt forming kettle, starting stirring, and controlling the temperature to be 30oC, then 1120 parts by mass of hydrochloric acid with the concentration of 25% is dripped to adjust the pH to 4-5, and after the reaction is finished, the temperature is heated to 70 DEGoAnd C, carrying out reduced pressure dehydration under the pressure of-0.09 MPa to obtain hydrazine hydrochloride.
Step two, preparing an ethyl hydrazine hydrochloride solution:
transferring the obtained hydrazine hydrochloride into an alkylation reaction kettle, adding 1067 parts by mass of 95% ethanol, and then sealing the alkylation reaction kettle and heating to 110%oC, performing alkylation reaction, controlling the pressure of the reaction kettle to be 0.5MPa, reacting for 2 hours, and cooling to 45 ℃ after the reaction is finishedoAnd C, transferring the mixture into a distillation kettle to distill out ethanol to obtain the ethyl hydrazine hydrochloride solution.
Step three, preparation of a crude product:
transferring the obtained ethyl hydrazine hydrochloride solution into a dissociation kettle, adding 624 parts by mass of hydrazine hydrate with the concentration of 75% for dissociation, sucking the mixture obtained by dissociation into a distillation kettle, carrying out reduced pressure distillation to obtain a crude product and a kettle substrate hydrazine hydrochloride, and transferring the hydrochloride into an alkylation process.
Step four, preparing ethyl hydrazine:
transferring the obtained crude product into a rectifying still, slowly heating to boil, and heating to 60 deg.CoCollecting the 1, 1-diethylhydrazine and the 1, 2-diethylhydrazine evaporated under the condition of C, and continuously heating to 100 DEGoC, collecting 42% ethyl hydrazine, cooling to 40% after rectificationoAnd C, absorbing hydrazine hydrate serving as a kettle substrate into a free position, adding water into the collected ethyl hydrazine to prepare a 40% aqueous solution, and hermetically packaging the aqueous solution to obtain a final product of ethyl hydrazine.
The purity of the collected ethyl hydrazine is detected to be more than or equal to 99.0 percent, and through measurement and calculation, the waste water of a unit product is reduced from 12 tons to 2 tons, the waste gas is reduced from 0.012 tons to 0.002 tons, and the waste residue is reduced from 0.3 tons to 0 tons.
Example 2:
referring to FIG. 1, under the protection of inert gas
Step one, preparing hydrazine hydrochloride:
firstly, 500 parts by mass of hydrazine hydrate with the concentration of 75 percent are put into a salt forming kettle, the stirring is started, and the temperature is controlled to be 40oC, then adding 1040 parts by mass of hydrochloric acid with the concentration of 28% dropwise, adjusting the pH to 3.5-4.5, and heating to 75 ℃ after the reaction is finishedoAnd C, carrying out reduced pressure dehydration under the pressure of-0.09 MPa to obtain hydrazine hydrochloride.
Step two, preparing an ethyl hydrazine hydrochloride solution:
transferring the obtained hydrazine hydrochloride into an alkylation reaction kettle, adding 1296 parts by mass of 95% ethanol, and then sealing the alkylation reaction kettle to raise the temperature to 115 DEG CoC, carrying out alkylation reaction, controlling the pressure of the reaction kettle to be 0.6MPa, reacting for 2.5 hours, and cooling to 50 ℃ after the reaction is finishedoAnd C, transferring the mixture into a distillation kettle to distill out ethanol to obtain the ethyl hydrazine hydrochloride solution.
Step three, preparation of a crude product:
transferring the obtained ethyl hydrazine hydrochloride solution into a dissociation kettle, adding 623 parts by mass of 78% hydrazine hydrate for dissociation, sucking the mixture obtained by dissociation into a distillation kettle, carrying out reduced pressure distillation to obtain a crude product and a kettle substrate hydrazine hydrochloride, and transferring the hydrochloride into an alkylation process.
Step four, preparing ethyl hydrazine:
transferring the obtained crude product into a rectifying still, slowly heating to boil, and cooling at 65 deg.CoC, collecting the 1, 1-diethylhydrazine and the 1, 2-diethylhydrazine evaporated out, and continuing to heat to 110 DEGoC, collecting 43% ethyl hydrazine, cooling to 42% after rectificationoAnd C, absorbing hydrazine hydrate serving as a kettle substrate into a free position, adding water into the collected ethyl hydrazine to prepare a 40% aqueous solution, and hermetically packaging the aqueous solution to obtain a final product of ethyl hydrazine.
The purity of the collected ethyl hydrazine is detected to be more than or equal to 99.0 percent, and through measurement and calculation, the waste water of a unit product is reduced from 12 tons to 2 tons, the waste gas is reduced from 0.012 tons to 0.002 tons, and the waste residue is reduced from 0.3 tons to 0 tons.
Example 3:
referring to FIG. 1, under the protection of inert gas
Step one, preparing hydrazine hydrochloride:
firstly, 520 parts by mass of the mixture isPutting 80% hydrazine hydrate into a salt forming kettle, starting stirring, and controlling the temperature to be 50 DEGoC, then 1100 parts by mass of hydrochloric acid with the concentration of 30% are dripped, the PH is adjusted to 3-4, and the temperature is heated to 80 ℃ after the reaction is finishedoAnd C, carrying out reduced pressure dehydration, and controlling the pressure to be-0.9 MPa to obtain hydrazine hydrochloride.
Step two, preparing an ethyl hydrazine hydrochloride solution:
transferring the obtained hydrazine hydrochloride into an alkylation reaction kettle, adding 1594 parts by mass of 98% ethanol, and then sealing the alkylation reaction kettle to raise the temperature to 110 DEG CoC, performing alkylation reaction, controlling the pressure of the reaction kettle to be 0.7MPa, reacting for 3 hours, and cooling to 55 ℃ after the reaction is finishedoAnd C, transferring the mixture into a distillation kettle to distill out ethanol to obtain the ethyl hydrazine hydrochloride solution.
Step three, preparation of a crude product:
transferring the obtained ethyl hydrazine hydrochloride solution into a dissociation kettle, adding 728 parts by mass of 80% hydrazine hydrate for dissociation, sucking the mixture obtained by dissociation into a distillation kettle, carrying out reduced pressure distillation to obtain a crude product and kettle substrate hydrochloride, and transferring the hydrochloride into an alkylation process.
Step four, preparing ethyl hydrazine:
transferring the obtained crude product into a rectifying still, slowly heating to boil, and cooling at 65 deg.CoCollecting the 1, 1-dimethylhydrazine and 1, 2-dimethylhydrazine evaporated under the condition of C, and continuously heating to 130 DEGoC, collecting 44% ethyl hydrazine, cooling to 45% after rectificationoAnd C, absorbing hydrazine hydrate which is a kettle substrate into free positions, adding water into the collected ethyl hydrazine to prepare a 40% aqueous solution, and hermetically packaging the aqueous solution to obtain the final product of ethyl hydrazine.
The purity of the collected ethyl hydrazine is detected to be more than or equal to 99.0 percent, and through measurement and calculation, the waste water of a unit product is reduced from 12 tons to 2 tons, the waste gas is reduced from 0.012 tons to 0.002 tons, and the waste residue is reduced from 0.3 tons to 0 tons.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method for producing ethyl hydrazine by a hydrazine hydrate method is characterized in that under the protection of inert gas, hydrazine hydrochloride reacts with ethanol to obtain ethyl hydrazine hydrochloride, hydrazine hydrate dissociates the ethyl hydrazine hydrochloride, and ethyl hydrazine is obtained by distillation and rectification processes.
2. A preparation method of ethyl hydrazine produced by hydrazine hydrate method according to claim 1, characterized in that under the protection of inert gas, the specific preparation steps are as follows:
a. preparation of hydrazine hydrochloride: hydrazine hydrate is used as initial raw material, stirred in a salt-forming kettle, then hydrochloric acid with a certain proportion is dripped in, the temperature is controlled at 30-50 DEGoC, adjusting the pH value to 3-5, after the reaction is finished, heating to 70-80 ℃, and performing reduced pressure dehydration to prepare hydrazine hydrochloride;
b. preparation of ethyl hydrazine hydrochloride solution: transferring hydrazine hydrochloride into an alkylation reaction kettle, adding ethanol in a certain proportion, sealing the alkylation reaction kettle, heating to 90-120 ℃ for alkylation reaction, cooling to 45-55 ℃ after the reaction is finished, putting the reaction kettle into a distillation kettle, and distilling out the ethanol to prepare ethyl hydrazine hydrochloride solution;
c. preparation of a crude product: transferring the ethyl hydrazine hydrochloride solution into a dissociation kettle, adding hydrazine hydrate in a certain proportion for dissociation, sucking a mixture obtained by dissociation into a distillation kettle, and carrying out reduced pressure distillation to prepare a crude product and a kettle substrate hydrazine hydrochloride;
d. preparation of ethyl hydrazine: and transferring the crude product into a rectifying still, slowly heating to boil, collecting the 1, 1-diethylhydrazine and the 1, 2-diethylhydrazine evaporated at 60-65 ℃, continuously heating to 100-130 ℃, collecting the ethylhydrazine with the concentration of 42-44%, cooling after the rectification is finished, adding water into the collected ethylhydrazine to prepare an aqueous solution with the required concentration, and hermetically packaging to obtain the final product of the ethylhydrazine.
3. A preparation method of ethyl hydrazine by hydrazine hydrate method as claimed in claim 2, wherein in step a, the molar ratio of hydrazine hydrate to hydrochloric acid is 1: 1.01-1.10.
4. A preparation method of ethyl hydrazine by hydrazine hydrate method as claimed in claim 2, characterized in that in step a, the pressure of reduced pressure dehydration is-0.09 MPa to-0.1 MPa.
5. A preparation method of ethyl hydrazine by hydrazine hydrate method as claimed in claim 2, wherein in step b, the ratio of hydrazine hydrochloride to ethanol is 1: 3-4.
6. A method as claimed in claim 2, wherein in step b, the pressure of the alkylation reaction kettle is 0.5-0.7MPa, and the reaction time is 2-3 hours.
7. A preparation method of ethyl hydrazine hydrate according to claim 2, wherein in step c, the ratio of ethyl hydrazine hydrochloride to hydrazine hydrate is 1: 1.1-1.5.
8. A method as claimed in claim 2, wherein in step c, the still substrate hydrazine hydrochloride is transferred to the alkylation step, i.e. step b.
9. A method as claimed in claim 2, wherein in step d, the temperature is cooled to 40-45 deg.C to obtain hydrazine hydrate as a kettle substrate, and the hydrazine hydrate is sucked into the free kettle in step c.
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Citations (3)
| 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 |
| JPS60237059A (en) * | 1984-05-09 | 1985-11-25 | Nippon Carbide Ind Co Ltd | Preparation of monoalkylhydrazine |
| CN102516117A (en) * | 2011-12-06 | 2012-06-27 | 东力（南通）化工有限公司 | Process for producing methyl hydrazine with hydrazine hydrate method |
-
2020
- 2020-08-07 CN CN202010789412.3A patent/CN114057602A/en active Pending
Patent Citations (3)
| 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 |
| JPS60237059A (en) * | 1984-05-09 | 1985-11-25 | Nippon Carbide Ind Co Ltd | Preparation of monoalkylhydrazine |
| CN102516117A (en) * | 2011-12-06 | 2012-06-27 | 东力（南通）化工有限公司 | Process for producing methyl hydrazine with hydrazine hydrate method |
Non-Patent Citations (1)
| Title |
|---|
| ENDERS, D. 等: "烷基肼化合物的合成方法研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 4, pages 014 - 59 * |
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