CN109133015A - A kind of preparation method of hydroxylamine hydrochloride - Google Patents
A kind of preparation method of hydroxylamine hydrochloride Download PDFInfo
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- CN109133015A CN109133015A CN201811232021.0A CN201811232021A CN109133015A CN 109133015 A CN109133015 A CN 109133015A CN 201811232021 A CN201811232021 A CN 201811232021A CN 109133015 A CN109133015 A CN 109133015A
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- temperature
- hydroxylamine hydrochloride
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- butanone
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of hydroxylamine hydrochloride.Steps are as follows: diacetylmonoxime, hydrochloric acid being put into the autoclave with rectifying column, closed system is warming up to certain temperature and pressure, the butanone that recycling reaction generates, and clout decrease temperature crystalline filters to obtain hydroxylamine hydrochloride.Reaction temperature is to influence the key factor of diacetylmonoxime conversion ratio in the present invention, conversion ratio can be improved by improving temperature, but there is the risk decomposed in excessively high more than the 150 degree hydroxylamine hydrochlorides of temperature, therefore the present invention selects 80 ~ 135, and system pressure influences the temperature of reaction and the separation of material in the present invention, due to having water and butanone in material, temperature can be improved by increasing pressure, reaction speed is improved, the separating degree of butanone and water is improved, is removed convenient for butanone.
Description
Technical field
The present invention relates to a kind of preparation methods of hydroxylamine hydrochloride, belong to pesticide reagent preparation technical field.
Background technique
There are mainly three types of synthetic methods at present for hydroxylamine hydrochloride, the first is nitromethane and acid-hydrolysis method, and second is biography
System acetone oximate method, the third is the acid catalyzed hydrolysis of ketoxime.
The first nitromethane acid-hydrolysis method, the preparation of nitromethane mainly have dimethyl sulfate method and natural gas act two
Kind, dimethyl suflfate is more toxic, and preparation condition is harsh, and it is at high cost, and natural gas act side reaction is more, the synthesis of nitromethane
Yield is low, at high cost.
Second method is traditional acetone oximate method, which is reacted with sodium pyrosulfite, sodium nitrite and acetone generates
Acetoxime raw material consumption is big, equipment seriously corroded, and three wastes discharge amount is big.
The third is ketoxime Hydrolyze method, and ketoxime hydrolyzes under the conditions of sour water, generates ketone and hydroxylamine hydrochloride, ketone recycling in
The synthesis of ketoxime has reached recycling for material, and therefore, this method meets the primary condition of friendly process, causes both at home and abroad
The attention of scientist, and the key point of technique is how to select suitable process conditions, reaches least consumption of raw materials, maximum
Yield.
Using under ketoxime and inorganic acid reduced pressure 40 ~ 100, overhead reflux is steamed than 1 ~ 6 to nothing patent CN101497433A
Ketone evaporates, and then crystallization obtains hydroxylamine hydrochloride, and patent CN105776160A is using butanone oxime hydrochloride and water in 70 ~ 100 conditions
It hydrolyzes within lower 3 ~ 7 hours, then condensing crystallizing obtains hydroxylamine hydrochloride.
These methods all use to be hydrolyzed under lower temperature normal pressure or negative pressure, and one side temperature low reaction speed is slow, separately
On the one hand with the inferior separating effect of water under normal pressure or condition of negative pressure, ketone comes out slow the ketone that reaction generates, and reaction speed is slow, raw
Produce it is inefficient, the reaction time length also has an impact to the quality and yield of product.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, provide that a kind of simple process, reaction efficiency is high, production cost is lower
Environmentally protective hydroxylamine hydrochloride preparation method.
In order to reach this purpose, the technical solution adopted by the present invention are as follows: a kind of preparation method of hydroxylamine hydrochloride, step is such as
Under: diacetylmonoxime, hydrochloric acid are put into the autoclave with rectifying column, closed system is warming up to certain temperature and pressure, recycling reaction
The butanone of generation, clout decrease temperature crystalline filter to obtain hydroxylamine hydrochloride.
The molar ratio of diacetylmonoxime and hydrochloric acid is 1:1.5 ~ 10, and reaction temperature is 80 ~ 135 degree, and reaction pressure is 0 ~ 0.2Mp,
Reaction time is 0.5 ~ 3 hour.
Recovered overhead butanone after reaction, tower reactor discharging concentration decrease temperature crystalline obtain hydroxylamine hydrochloride product.
Reaction temperature is to influence the key factor of diacetylmonoxime conversion ratio in the present invention, and conversion ratio can be improved by improving temperature, but
There is the risk decomposed, therefore present invention selection 80 ~ 135. in excessively high more than the 150 degree hydroxylamine hydrochlorides of temperature
System pressure influences the temperature of reaction and the separation of material in the present invention, due to having water and butanone in material, increases pressure
Temperature can be improved, reaction speed is improved, improves the separating degree of butanone and water, is removed convenient for butanone.
The present invention has the advantage that 1) reaction speed is fast compared with prior art, high production efficiency, and production cost is low；2)
Reaction yield is high, and superior product quality, yield is 98% or more, and 99.5% or more product purity, product appearance is good.
Specific embodiment
The present invention is described in further detail with reference to embodiments, but the present invention is not limited solely to following embodiment.
Embodiment 1:
Diacetylmonoxime 150g, 30% hydrochloric acid 250g are put into the autoclave with rectifying column, then closed system, is warming up to 100
DEG C heat preservation 2 hours, then condensing crystallizing obtains hydroxylamine hydrochloride 117g, yield 97.2%, hydroxylamine hydrochloride purity 99.4%.
Embodiment 2:
Diacetylmonoxime 150g, 30% hydrochloric acid 250g are put into the autoclave with rectifying column, then closed system, is warming up to 110
DEG C, pressure 0.06Mpa keeps the temperature 1.5 hours, and then condensing crystallizing obtains hydroxylamine hydrochloride 118g, and yield 98.2%, hydroxylamine hydrochloride is pure
Degree 99.6%.
Embodiment 3:
Diacetylmonoxime 150g, 30% hydrochloric acid 250g are put into the autoclave with rectifying column, then closed system, is warming up to 120
DEG C, pressure 0.07Mpa keeps the temperature 1 hour, and then condensing crystallizing obtains hydroxylamine hydrochloride 118.2g, and yield 98.3%, hydroxylamine hydrochloride is pure
Degree 99.6%.
Embodiment 4:
Diacetylmonoxime 150g, 30% hydrochloric acid 250g are put into the autoclave with rectifying column, then closed system, is warming up to 130
DEG C, pressure 0.09Mpa keeps the temperature 0.5 hour, and then condensing crystallizing obtains hydroxylamine hydrochloride 118.4g, yield 98.6%, hydroxylamine hydrochloride
Purity 99.8%.
Embodiment 5:
Diacetylmonoxime 150g, 30% hydrochloric acid 250g are put into the autoclave with rectifying column, then closed system, is warming up to 135
DEG C, pressure 0.09Mpa keeps the temperature 0.5 hour, and then condensing crystallizing obtains hydroxylamine hydrochloride 118.2g, yield 98.3%, hydroxylamine hydrochloride
Purity 99.8%.
Claims (3)
1. a kind of preparation method of hydroxylamine hydrochloride, which is characterized in that steps are as follows: diacetylmonoxime, hydrochloric acid investment with rectifying column
Autoclave, closed system are warming up to certain temperature and pressure, the butanone that recycling reaction generates, and clout decrease temperature crystalline filters
Hydroxylamine hydrochloride.
2. the preparation method of hydroxylamine hydrochloride according to claim 1, which is characterized in that the molar ratio of diacetylmonoxime and hydrochloric acid is
1:1.5 ~ 10, reaction temperature are 80 ~ 135 degree, and reaction pressure is 0 ~ 0.2Mp, and the reaction time is 0.5 ~ 3 hour.
3. the preparation method of hydroxylamine hydrochloride according to claim 2, which is characterized in that recovered overhead fourth after reaction
Ketone, tower reactor discharging concentration decrease temperature crystalline obtain hydroxylamine hydrochloride product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811232021.0A CN109133015A (en) | 2018-10-22 | 2018-10-22 | A kind of preparation method of hydroxylamine hydrochloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811232021.0A CN109133015A (en) | 2018-10-22 | 2018-10-22 | A kind of preparation method of hydroxylamine hydrochloride |
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| CN109133015A true CN109133015A (en) | 2019-01-04 |
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| CN201811232021.0A Pending CN109133015A (en) | 2018-10-22 | 2018-10-22 | A kind of preparation method of hydroxylamine hydrochloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436425A (en) * | 2019-05-20 | 2019-11-12 | 山东理工大学 | The solvent-free green synthesis process for preparing hydroxylamine hydrochloride |
| CN112535999A (en) * | 2020-12-16 | 2021-03-23 | 江苏长青农化股份有限公司 | Synthesis process of hydroxylamine hydrochloride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497433A (en) * | 2009-03-08 | 2009-08-05 | 宁波欧迅化学新材料技术有限公司 | Method for preparing hydroxylammonium salt |
| CN103159191A (en) * | 2013-03-25 | 2013-06-19 | 浙江圣安化工有限公司 | Preparation method of hydroxylamine salt |
| CN103395756A (en) * | 2013-07-05 | 2013-11-20 | 天津市化学试剂研究所 | Preparation method of hydroxylamine hydrochloride |
| CN105776160A (en) * | 2016-03-25 | 2016-07-20 | 巨化集团技术中心 | Preparation method of hydroxylammonium chloride |
| CN108584893A (en) * | 2018-06-15 | 2018-09-28 | 中触媒新材料股份有限公司 | A kind of hydroxylamine hydrochloride synthetic method |
-
2018
- 2018-10-22 CN CN201811232021.0A patent/CN109133015A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497433A (en) * | 2009-03-08 | 2009-08-05 | 宁波欧迅化学新材料技术有限公司 | Method for preparing hydroxylammonium salt |
| CN103159191A (en) * | 2013-03-25 | 2013-06-19 | 浙江圣安化工有限公司 | Preparation method of hydroxylamine salt |
| CN103395756A (en) * | 2013-07-05 | 2013-11-20 | 天津市化学试剂研究所 | Preparation method of hydroxylamine hydrochloride |
| CN105776160A (en) * | 2016-03-25 | 2016-07-20 | 巨化集团技术中心 | Preparation method of hydroxylammonium chloride |
| CN108584893A (en) * | 2018-06-15 | 2018-09-28 | 中触媒新材料股份有限公司 | A kind of hydroxylamine hydrochloride synthetic method |
Non-Patent Citations (1)
| Title |
|---|
| 刘忠喜等: "《中学教师手册﹒化学》", 31 August 2000, 南方出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436425A (en) * | 2019-05-20 | 2019-11-12 | 山东理工大学 | The solvent-free green synthesis process for preparing hydroxylamine hydrochloride |
| CN112535999A (en) * | 2020-12-16 | 2021-03-23 | 江苏长青农化股份有限公司 | Synthesis process of hydroxylamine hydrochloride |
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