CN103159191B - A kind of preparation method of hydroxylammonium salt - Google Patents
A kind of preparation method of hydroxylammonium salt Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of hydroxylammonium salt.Existing hydroxylammonium salt complicated process of preparation, production security have to be strengthened, product stability is poor.The present invention takes the first oxime (C=NOH) in molar ratio of following technical scheme: acid (H) is 1:(1 ~ 1.3), get out appropriate acid solution and oxime, the massfraction of acid solution is (10% ~ 35%), again ready for the first step solution is added in rectifying tower, control rectifying tower to distill at absolute pressure 0.095 ~ 0.1MPa and bottom temperature are 20 ~ 130 DEG C, controlling tower top reflux ratio is 0 ~ 4, timely separate fraction, controlling tower reactor reflux ratio is 0 ~ 100, cyclic part still liquid, finally product is concentrated, crystallization, filter, drying obtains the solid hydroxylammonium salt of high-quality.Invention increases efficiency of rectification tower, facilitate speed of reaction, saved raw material dosage, optimize thick final product quality, overcome organic residue.This technical process is short, and raw material is economized, and yield is high, constant product quality, and aftertreatment is simple, and environmental friendliness.<!--1-->
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, particularly a kind of preparation method of hydroxylammonium salt.
Background technology
Hydroxylammonium salt is purposes Chemicals widely.Oxammonium sulfate and phosphatic hydroxylamine mainly for the production of hexanolactam, agricultural chemicals etc.; Oxammonium hydrochloride is mainly used as the raw material of the compound probabilities such as medicine, spices, dyestuff.
At present, the method preparing oxammonium sulfate mainly contains nitric oxide reduction method, acetoxime method, hydrolysis method etc.; The method preparing phosphatic hydroxylamine mainly contains hydrogenation catalyst reduction method and hydrolysis method etc.; The method preparing oxammonium hydrochloride mainly contains Nitromethane 99Min. hydrolysis method, acetoxime method, disulfonic acid ammonium salt hydrolysis method etc.This class methods ubiquity technical process is numerous and diverse, unstable product quality, post-processed difficulty, the drawbacks such as yield is low.
Publication number is the production technique being described to a kind of route based on Raschig process in the application documents " preparing the method for solid hydroxylamine hydrochloride " of CN1751986A, the hydroxylamine sulfate solution utilizing oxammonium sulfate, ammonium sulfate, sulfuric acid, water to form is raw material, azanol complex compound is obtained by extraction agent complexometric extraction, use that the oxammonium hydrochloride aqueous solution (or hydroxylamine sulfate solution) neutralizes, dilute hydrochloric acid back extraction above-mentioned azanol complex compound obtains the new oxammonium hydrochloride aqueous solution more successively, after evaporative crystallization, obtain product solid oxammonium hydrochloride.Use this technology effectively can utilize Raschig process fluid sulphuric acid azanol, but technical process is complicated, add auxiliary agent many, finished product hydroxylammonium salt contains organic residue, and waste liquid contains a large amount of acid and organism, and post-processed is complicated.
Publication number is be described in the application documents " oxime hydrolysis reaction and infiltration evaporation membrane sepn lotus root conjunction technology preparation of hydroxylamine by one-step method " of CN101100293A to utilize oxime hydrolysis reaction and infiltration gasification film separation coupling technique preparation of hydroxylamine by one-step method, although use this technology to make oxime hydrolysis efficiency be 80%, but infiltration vaporization membrane module is complicated, cost is higher, restricted lifetime, and owing to using excessive strong acid and toluene, actual industrial feasibility is not high.
Publication number is be described in rectifying tower in the application documents " method of hydroxylammonium salt " of CN101497433A, the reaction that is hydrolyzed in an acidic solution by ketoxime generates hydroxylammonium salt and ketone, discharge in time from the ketone of rectifying tower tower top output, the crystallization of cooling reactor liquid, filter, washing, drying obtains hydroxylammonium salt solid.Use this technical matters flow process simple, but this method cannot prepare high-quality oxammonium sulfate, the hydroxylammonium salt obtained contains organic residue, and acid-utilising rate excessive in system is low again cannot reuse.
Above-mentioned document shows, technique is simple, production safety, product are stable, trash is few, environmental friendliness, and save energy is the direction that following hydroxylammonium salt preparation technology probes into.Therefore, be badly in need of improving or develop new production line to existing hydroxylammonium salt preparation technology.
Summary of the invention
The present invention is directed to above-mentioned defect, a kind of preparation method of hydroxylammonium salt is provided, utilize a kind of rectification and hydrolization technology containing backflow at the bottom of tower, according to raw material oxime and reflux ratio at the bottom of the proportioning adjusting tower of acid, reflux ratio increases, cyclic part still liquid along with sour increment, improve acid-utilising rate, thus improve the column efficiency of rectifying tower operate continuously, facilitate speed of reaction, optimize thick final product quality.This operational path is simple, flow process is short, and product purity is high, and aftertreatment is light, the high and advantage of lower cost of yield.
For this reason, the present invention takes following technical scheme, a kind of preparation method of hydroxylammonium salt, oxime and acid are added in rectifying tower with certain proportioning, controls the pressure and temperature of rectifying tower and to be hydrolyzed reaction, distinguish adjusting tower head tower still reflux ratio, knockout tower tops, circulation tower reactor liquid, extraction bottom product, this product obtains the hydroxylammonium salt of high-quality through concentrated, crystallization, filtration, drying.
Concrete steps are as follows:
The first step: oxime (C=NOH) in molar ratio: acid (H) is 1:(1 ~ 1.3), get out appropriate acid solution and oxime.Described oxime is acetoxime, Diacetylmonoxime, methyl-propyl ketoxime, methyl isobutyl ketoxime, described acid is phosphoric acid, sulfuric acid, hydrochloric acid, and the massfraction of acid solution is (10% ~ 35%).
Second step: ready for the first step solution is added in rectifying tower, control rectifying tower to distill at absolute pressure 0.095 ~ 0.1MPa and bottom temperature are 20 ~ 130 DEG C, controlling tower top reflux ratio is 0 ~ 4, timely separate fraction, controlling tower reactor reflux ratio is 0 ~ 100, cyclic part still liquid, circulation fluid entrance can at feed position co-altitude or upper-lower position, extraction bottom product.
3rd step: the solid hydroxylammonium salt that product carries out concentrating, crystallization, filtration, drying obtain high-quality.
Described ketoxime is acetoxime, Diacetylmonoxime, methyl-propyl ketoxime, methyl isobutyl ketoxime.
Described mineral acid is hydrochloric acid, sulfuric acid or phosphoric acid.
Described proportioning is molar ratio: oxime (C=NOH): acid (H) is 1:(1 ~ 1.3).
Reflux ratio at the bottom of described tower is tower reactor circulation fluid and the ratio of tower reactor Produced Liquid, and span of control is (0 ~ 100), with proportioning raw materials acid be controlled to direct ratio, namely sour increment reflux ratio increases.
The pressure of described control rectifying tower is normal pressure or decompression, and decompression refers to that absolute pressure is (0.095 ~ 0.1MPa).
Hydroxylammonium salt preparation method of the present invention, use a kind of rectification and hydrolization technology containing backflow at the bottom of tower, according to reflux ratio size at the bottom of raw material oxime and sour proportioning adjusting tower, cyclic part tower reactor liquid, raw material is fully hydrolyzed in rectifying tower and obtains hydroxylammonium salt and ketone, to achieve in rectifying tower acid little excessive greatly reaction-ure conversion-age high, Reaction Separation is carried out simultaneously.Improve efficiency of rectification tower, facilitate speed of reaction, saved raw material dosage, optimize thick final product quality, overcome organic residue.This technical process is short, and raw material is economized, and yield is high, constant product quality, and aftertreatment is simple, and environmental friendliness.
Compared with prior art, the technology of the present invention has following remarkable advantage:
1. the present invention innovates a kind of rectification and hydrolization technology containing backflow at the bottom of tower, and according to reflux ratio at the bottom of the proportioning adjusting tower of raw material oxime and acid, reflux ratio is tower reactor circulation fluid and the ratio of tower reactor Produced Liquid, and span of control is (0 ~ 100), increases along with the increment of acid.Cyclic part still liquid, improves acid-utilising rate, thus improves the column efficiency of rectifying tower operate continuously, facilitates speed of reaction, optimizes thick final product quality.
2. this technique adopts the backflow of tower reactor part still liquid to coordinate top portion from carrying out simultaneously, for the feature that this technique hydrolysis reaction is reversible, by controlling the reflux ratio of tower top and tower reactor, cyclic part still liquid while separate fraction, achieve the speed of reaction when acid is little excessive greatly fast, transformation efficiency is high, hydrolysis degree is complete, thick finished product purity is good, constant product quality, process operation safety.
3. the aftertreatment of this technique is simple, and through suitably processing, ketone can reuse oxime, and azanol mother liquor can use derived product processed, and acid solution can use agricultural chemicals processed, energy-saving and emission-reduction, environmental friendliness.
4. finished product purity is high, not containing organic detritus.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
Embodiment 1
By oxime with 10% sulfuric acid molar ratio than for 1:0.5, take the acetoxime 73.2 grams that purity is 99.9%, 490 grams, the sulfuric acid of 10%, use dropping funnel to add rectifying tower from middle part with the speed of 2ml/s to distill, control temperature is 50 ~ 60 DEG C, and absolute pressure is 0.09MPa simultaneously, controlling tower top reflux ratio is 100(and total reflux), after 15 minutes, then regulate tower top reflux ratio to be 1, tower reactor reflux ratio is 5, part still liquid returns the rectifying section of rectifying tower, circulation hydrolysis, collects, sampling analysis respectively.Recording liquid of top of the tower PH is 7, and tower bottoms is 0.1% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid sulphuric acid azanol 160 grams after crystallization, filtration, drying.Yield is 97%, and transformation efficiency is 95%.
Embodiment 2
By oxime with 10% sulfuric acid molar ratio than for 1:0.5, take the acetoxime 73.2 grams that purity is 99.9%, 490 grams, the sulfuric acid of 10%, use dropping funnel to add rectifying tower from middle part with the speed of 2ml/s simultaneously and distill, control temperature is 50 ~ 60 DEG C, absolute pressure is 0.09MPa, and controlling tower top reflux ratio is 100(and total reflux), after 15 minutes, tower top reflux ratio is regulated to be 1 again, tower reactor reflux ratio is that namely 0(does not circulate), collect respectively, sampling analysis.Recording liquid of top of the tower PH is 7, and tower bottoms is 2.8% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid sulphuric acid azanol 151.2 grams after cooling, crystallization, filtration, drying.Yield is 97%, and transformation efficiency is 92%.
Embodiment 3
By oxime with 20% hydrochloric acid mol ratio than for 1:1, take the acetoxime 73.2 grams that purity is 99.9%, the hydrochloric acid of 20% 365 grams, use dropping funnel to add rectifying tower from middle part with the speed of 2ml/s to distill, control temperature is 50 ~ 60 DEG C, and absolute pressure is 0.09MPa simultaneously, controlling tower top reflux ratio is 100(and total reflux), after 15 minutes, then regulate tower top reflux ratio to be 0.5, tower reactor reflux ratio is 8, part still liquid returns the rectifying section of rectifying tower, circulation hydrolysis, collects, sampling analysis respectively.Recording liquid of top of the tower PH is 6.5, and tower bottoms is 0.3% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid hydroxylamine hydrochloride 66.6 grams after cooling, crystallization, filtration, drying.Yield is 96%, and transformation efficiency is 95.7%.
Embodiment 4
By oxime with 20% hydrochloric acid mol ratio than for 1:1, take the acetoxime 73.2 grams that purity is 99.9%, the hydrochloric acid of 20% 365 grams, use dropping funnel to add rectifying tower from middle part with the speed of 2ml/s simultaneously and distill, control temperature is 50 ~ 60 DEG C, absolute pressure is 0.09MPa, and controlling tower top reflux ratio is 100(and total reflux), after 15 minutes, tower top reflux ratio is regulated to be 0.5 again, tower reactor reflux ratio is that namely 0(does not circulate), collect respectively, sampling analysis.Recording liquid of top of the tower PH is 6.8, and tower bottoms is 2.8% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid hydroxylamine hydrochloride 62.9 grams after cooling, crystallization, filtration, drying.Yield is 90.5%, and transformation efficiency is 91.8%.
Embodiment 5
By oxime with 20% phosphoric acid molar ratios than for 1:0.35, take the acetoxime 73.2 grams that purity is 99.9%, the phosphatase 11 of 20% 71.5 grams, use dropping funnel to add rectifying tower from middle part with the speed of 2ml/s to distill, control temperature is 70 ~ 80 DEG C, and absolute pressure is 0.08MPa simultaneously, controlling tower top reflux ratio is 100(and total reflux), after 25 minutes, then regulate tower top reflux ratio to be 2, tower reactor reflux ratio is 4, part still liquid returns the feed zone of rectifying tower, circulation hydrolysis, collects, sampling analysis respectively.Recording liquid of top of the tower PH is 7.0, and tower bottoms is 0.4% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid phosphoric acid azanol 166.5 grams after cooling, crystallization, filtration, drying.Yield is 97.3%, and transformation efficiency is 97%.
Embodiment 6
By oxime with 20% phosphoric acid molar ratios than for 1:0.35, take the acetoxime 73.2 grams that purity is 99.9%, the phosphatase 11 of 20% 71.5 grams, use dropping funnel to add rectifying tower from middle part with the speed of 2ml/s simultaneously and distill, control temperature is 70 ~ 80 DEG C, absolute pressure is 0.08MPa, and controlling tower top reflux ratio is 100(and total reflux), after 25 minutes, tower top reflux ratio is regulated to be 2 again, tower reactor reflux ratio is that namely 0(does not circulate), collect respectively, sampling analysis.Recording liquid of top of the tower PH is 6.4, and tower bottoms is 3.9% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid phosphoric acid azanol 178.2 grams after cooling, crystallization, filtration, drying.Yield is 90.5%, and transformation efficiency is 90.2%.
Embodiment 7
Be 1:1.02 by the hydrochloric acid mol ratio of oxime and 33%, take the Diacetylmonoxime 87.2 grams that purity is 99.9%, the hydrochloric acid of 33% 110.6 grams, use dropping funnel to add rectifying tower from middle part with the speed of 3ml/s to distill, control temperature is 90 ~ 100 DEG C, and absolute pressure is 0.8MPa simultaneously, controlling tower top reflux ratio is 100(and total reflux), after 30 minutes, then regulate tower top reflux ratio to be 1, tower reactor reflux ratio is 3, part still liquid returns the feed zone of rectifying tower, circulation hydrolysis, collects, sampling analysis respectively.Recording liquid of top of the tower PH is 7.0, and tower bottoms is 0.5% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid hydroxylamine hydrochloride 67.8 grams after cooling, crystallization, filtration, drying.Yield is 97.5%, and transformation efficiency is 97%.
Embodiment 8
Be 1:1.02 by the hydrochloric acid mol ratio of oxime and 33%, take the Diacetylmonoxime 87.2 grams that purity is 99.9%, the hydrochloric acid of 33% 110.6 grams, use dropping funnel to add rectifying tower from middle part with the speed of 3ml/s simultaneously and distill, control temperature is 90 ~ 100 DEG C, absolute pressure is 0.8MPa, and controlling tower top reflux ratio is 100(and total reflux), after 30 minutes, tower top reflux ratio is regulated to be 1 again, tower reactor reflux ratio is that namely 0(does not circulate), collect respectively, sampling analysis.Recording liquid of top of the tower PH is 6.5, and tower bottoms is 4.2% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid hydroxylamine hydrochloride 64.1 grams after cooling, crystallization, filtration, drying.Yield is 92.1%, and transformation efficiency is 91.5%.
Embodiment 9
Be 1:1.03 by the hydrochloric acid mol ratio of oxime and 25%, take the methyl isobutyl ketoxime 115.4 grams that purity is 99.8%, the hydrochloric acid of 25% 150.39 grams, use dropping funnel to add rectifying tower from middle part with the speed of 4ml/s to distill simultaneously, control temperature is 90 ~ 100 DEG C, absolute pressure is 0.09MPa, controlling tower top reflux ratio is 100(and total reflux), after 40 minutes, then regulate tower top reflux ratio to be 1.5, tower reactor reflux ratio is 3, part still liquid returns the stripping section of rectifying tower, circulation hydrolysis, collects, sampling analysis respectively.Recording liquid of top of the tower PH is 7.0, and tower bottoms is 0.2% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid hydroxylamine hydrochloride 68.3 grams after cooling, crystallization, filtration, drying.Yield is 98.3%, and transformation efficiency is 98%.
Embodiment 10
Be 1:1.03 by the hydrochloric acid mol ratio of oxime and 25%, take the methyl isobutyl ketoxime 115.4 grams that purity is 99.8%, the hydrochloric acid of 25% 150.39 grams, use dropping funnel to add rectifying tower from middle part with the speed of 4ml/s simultaneously and distill, control temperature is 90 ~ 100 DEG C, absolute pressure is 0.09MPa, and controlling tower top reflux ratio is 100(and total reflux), after 40 minutes, tower top reflux ratio is regulated to be 1.5 again, tower reactor reflux ratio is that namely 0(does not circulate), collect respectively, sampling analysis.Recording liquid of top of the tower PH is 6.0, and tower bottoms is 3.9% through dehydrated alcohol extraction post analysis organic phase oxime content.Final concentration kettle liquid, obtains solid hydroxylamine hydrochloride 65.1 grams after cooling, crystallization, filtration, drying.Yield is 93.7%, and transformation efficiency is 93%.
Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (3)
1. the preparation method of a hydroxylammonium salt, oxime and acid is it is characterized in that to add in rectifying tower with certain proportioning, control the pressure and temperature of rectifying tower to be hydrolyzed reaction, adjusting tower head tower still reflux ratio respectively, knockout tower tops, circulation tower reactor liquid, extraction bottom product, this product obtains the hydroxylammonium salt of high-quality through concentrated, crystallization, filtration, drying, is specially:
The first step: in molar ratio in the oxime of C=NOH: in the acid of H for 1:(1 ~ 1.3), get out appropriate acid solution and oxime, the massfraction of described acid solution is (10% ~ 35%);
Second step: ready for the first step solution is added in rectifying tower, control rectifying tower to distill at absolute pressure 0.095 ~ 0.1MPa and bottom temperature are 20 ~ 130 DEG C, controlling tower top reflux ratio is 100, after 15 minutes, then tower top reflux ratio is regulated to be 1, timely separate fraction, controlling tower reactor reflux ratio is 5, cyclic part still liquid, circulation fluid entrance can at feed position co-altitude or upper-lower position, extraction bottom product;
3rd step: the solid hydroxylammonium salt that product carries out concentrating, crystallization, filtration, drying obtain high-quality.
2. the preparation method of a kind of hydroxylammonium salt according to claim 1, is characterized in that described oxime is acetoxime, Diacetylmonoxime, cyclohexanone-oxime, methyl isobutyl ketoxime.
3. the preparation method of a kind of hydroxylammonium salt according to claim 1, is characterized in that described acid is hydrochloric acid, sulfuric acid or phosphoric acid.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925768A (en) * | 2014-03-19 | 2015-09-23 | 湖北航天化学技术研究所 | Hydroxylamine nitrate crystal preparation method |
| CN105314610A (en) * | 2014-08-04 | 2016-02-10 | 余立新 | Preparation method for hydroxylammonium chloride |
| CN105315139B (en) * | 2014-08-04 | 2017-08-29 | 余立新 | A kind of processing method of ketoxime type silane by-products ketoxime salt |
| CN105384656B (en) * | 2015-10-23 | 2017-08-25 | 中石化南京工程有限公司 | A kind of method of cyclohexanone oximate |
| CN105776159B (en) * | 2016-01-28 | 2017-08-25 | 张玲 | A kind of method that continuity method produces hydroxylamine hydrochloride |
| CN105540559A (en) * | 2016-01-28 | 2016-05-04 | 苏州市吴赣药业有限公司 | Method for improving quality of oxammonium hydrochloride and raising yield of oxammonium hydrochloride |
| CN105752954A (en) * | 2016-03-25 | 2016-07-13 | 巨化集团技术中心 | Method for purifying hydroxylamine hydrochloride |
| CN105731401B (en) * | 2016-03-25 | 2018-01-30 | 巨化集团技术中心 | A kind of method for producing hydroxylamine hydrochloride |
| CN106946234B (en) * | 2017-03-09 | 2019-07-30 | 北京化工大学 | A kind of preparation method of hydroxyl sulfate |
| CN106829893A (en) * | 2017-03-20 | 2017-06-13 | 临沭县华盛化工有限公司 | The method that HAS is produced using continuous vacuum distillation |
| CN107539966B (en) * | 2017-09-29 | 2019-02-01 | 江苏艾科维科技有限公司 | The preparation method of hydroxyl sulfate |
| CN109250694B (en) * | 2018-08-24 | 2020-12-11 | 北京化工大学 | Method for preparing hydroxylamine hydrochloride by using hydrogen chloride dry gas |
| CN109133015A (en) * | 2018-10-22 | 2019-01-04 | 江苏长青农化股份有限公司 | A kind of preparation method of hydroxylamine hydrochloride |
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| CN101250112A (en) * | 2008-03-18 | 2008-08-27 | 台州市知青化工有限公司 | Method for producing 1-p-methylphenyl ethylamine |
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